USOO9453128B2

(12) United States Patent (10) Patent No.: US 9.453,128 B2

Sybert et al. (45) Date of Patent: *Sep. 27, 2016

(54) RAIL COMPONENT COMPRISING FLAME 8.33 E: 3. SR

chottland etalal.
RETARDANT COMPOSITIONS, AND 6,833,422 B2 12/2004 Silva et al.
METHODS OF MANUFACTURE 7.253,223 B2 8/2007 Kawato et al.
7,309,730 B2 12/2007 Kim
(75) Inventors: Paul Dean Sybert, Evansville, IN (US); 7,652,107 B2 1/2010 Gallucci et al.
7,790,292 B2 9/2010 Colborn et al.
first gy, Eyville
(US); Thomas L. Evans, Mt.
7,928, 168 B2
2005/0085580 A1
4/2011 Li et al.
4/2005 Marugan et al.
Vernon, IN (US) 2006/0030664 A1 2/2006 Kim .............................. 524,588
2007/0135569 A 6/2007 DeRudder
(73) Assignee: SABIC GLOBAL TECHNOLOGIES 2008, 0230751 A1 9, 2008 Li et al.
B.V.,
e was Bergen op Zoom (NL) 588. A 1338 R.S., a
ogunova et al.
- 2010.0075,125 A1 3, 2010 Maas et al.
(*) Notice: Subject to any disclaimer, the term of this 2011/0098.386 Al 4, 2011 Krauter et al.
patent is extended or adjusted under 35 2012fO248102 A1 10/2012 Van De Wetering et al.

This patent is Subject to a terminal dis- FOREIGN PATENT DOCUMENTS

claimer.
DE 102O08054329 A1 5, 2010
EP O524731 A1 1/1993
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WO 2005037.921 A1 4, 2005
(65) Prior Publication Data WO 2010005486 A3 1, 2010
US 2012/O273.738 A1 Nov. 1. 2012 OTHER PUBLICATIONS

(51) Int. Cl. SABIC Innovative Plastics Purity+ Permformance Specialty Addi
COSL 83/10 (2006.01) tives & Intermediates, 2013, pp. 1-20, www.sabic-ip.com.
COSL 69/00 (2006.01) U.S. Appl. No. 13/251,137, filed Sep. 30, 2011.
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ooisol). Cook 500-11 (2013.01). Cook Evonik Industries, EUROPLEX PPSU 99470 CF130, 2010, 8
2003/2337 (2013.0). Cosi 300 (2013.01), Ps
Y10T 428/1352 (2015.01); Y10T 428/31507 (Continued)
(2015.04): Y10T 428/31663 (2015.04)
(58) Field of classists, so coooo Primary Examiner Margaret Moore
See application file for complete search history. (74) Attorney, Agent, or Firm — Cantor Colburn LLP
(56) References Cited (57) ABSTRACT
U.S. PATENT DOCUMENTS A railway vehicle component, wherein the component is a
partition or a light cover, and wherein the component is
3,539,655 A 11/1970 Strachan et al. molded or formed from a thermoplastic polymer composi
3,539,657 A 11/1970 Noshay et al. tion comprising: a siloxane-containing copolymer in an
3,751,400 A 8, 1973 Crennan et al.
3,929.908 A 12/1975 Orlando et al. amount effective to provide a total of 0.2 to 6.5 wt % of
4,170,711 A 10, 1979 Orlando et al. siloxane units based on the total weight of the polymers in
4.404,350 A 9/1983 Ryang the thermoplastic polymer composition, a bromine-contain
4,443,581 A 4, 1984 Robeson et al. ing polymer in an amount effective to provide 9 to 13 wt %
4,690,997 A 9, 1987 Cella et al.
4,808,686 A 2f1989 Cella et al. of bromine, based on the total weight of the polymers in the
4,814,392 A 3, 1989 Shea et al. thermoplastic polymer composition, and optionally a third
4,923,933 A * 5/1990 Curry ............................ 525,439 polymer, wherein the wt % of the siloxane-containing copo
5,204,438 A 4, 1993 Snow et al. lymer, the bromine-containing polymer, and the optional
5,451,632 A 9, 1995 Okumura et al.
5,596,048 A 1/1997 Blohm et al. third polymer, sum to 100 wt %, and 0.05 to 10 wt % of a
5,981,661 A 11/1999 Liao et al. light diffuser additive, based on the total weight of polymers
6,031,036 A * 2/2000 Rosenquist et al. .......... 524, 164 in the thermoplastic polymer composition.
6,140,399 A 10, 2000 Munro
6.462,111 B1 10/2002 Singh et al.
6,723,864 B2 4/2004 Silva et al. 73 Claims, 3 Drawing Sheets
 US 9,453,128 B2
Page 2

(56) References Cited International Search Report for International Application No. PCT/
US2012/031132, International Filing Date Mar. 29, 2012, Date of
OTHER PUBLICATIONS Mailing Jun. 13, 2012, 5 pages.
“Federal Aviation Administration Section 25.853'. Federal Aviation Written Opinion for International Application No. PCT/US2012/
Regulations online), retrieved on Nov. 18, 2011; from http://www.
gpo.gov/fdsys/pkg/CFR-2011-title14-vol1/pdf CFR-2011-title14 031132, International Filing Date Mar. 29, 2012, Date of Mailing
voll-sec25-853.pdf, 51 pages. Jun. 13, 2012, 7 pages.
“Federal Aviation Regulations Section 25, Appendix F. Part IV”. International Search Report of the International Searching Author
Federal Aviation Regulations online), retrieved on Nov. 18, 2011; ity; International Application No. PCT/US2012/031729; Interna
from http://www.gpo.gov/fdsys/pkg/CFR-2011-title14-vol1/pdf tional Filing Date: Mar. 30, 2012; Date of Mailing: Jul. 23, 2012; 7
CFR-2011-title14-vol1-part25-appF.pdf, 51 pages. Pages.
Innes et al., “Flame retardants for polycarbonate new and classical Written Opinion of the International Searching Authority; Interna
solutions'. Plastics Additives & Compounding, Jan.-Feb. 2006:26
26. tional Application No. PCT/US2012/031729; International Filing
LEXAN EXL9930 Catalog, 2004, pp. 1-6. Date: Mar. 30, 2012; Date of Mailing: Jul. 23, 2012; 4 Pages.
LEXAN Resin FST9705 Datasheet. Last updated Jan. 6, 2011, 2
pageS. * cited by examiner
U.S. Patent Sep. 27, 2016 Sheet 1 of 3 US 9,453,128 B2

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U.S. Patent Sep. 27, 2016 Sheet 3 of 3 US 9,453,128 B2

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 US 9,453,128 B2
1. 2
RAIL COMPONENT COMPRISING FLAME Such as toughness (high impact strength and high ductility).
RETARDANT COMPOSITIONS, AND It would be a further advantage if such materials could be
METHODS OF MANUFACTURE manufactured to be colorless and transparent. Still other
advantageous features include good processability for form
CROSS-REFERENCE TO RELATED ing articles, Smooth Surface finish, and light stability.
APPLICATION
BRIEF SUMMARY OF THE INVENTION
This application claims priority to India Patent Applica
tion No. 920/DEL/2011, India Patent Application No. 921/ Disclosed herein is a railway vehicle component wherein
DEL/2011 and India Patent Application No. 922/DEL/2011, 10 the component is a partition or a light cover, and wherein the
all filed Mar. 31, 2011, the contents of all applications being component is molded or formed from a thermoplastic poly
incorporated by reference in their entirety. mer composition comprising: a siloxane-containing copoly
mer in an amount effective to provide a total of 0.2 to 6.5 wt
BACKGROUND OF THE INVENTION % of siloxane units based on the total weight of the polymers
15 in the thermoplastic polymer composition, a bromine-con
This disclosure generally relates to rail components, and taining polymer in an amount effective to provide 9 to 13 wit
more particularly to rail components comprising flame retar % of bromine, based on the total weight of the polymers in
dant compositions containing specific combinations of the thermoplastic polymer composition, and optionally a
siloxane block copolymers. third polymer, wherein the wt % of the siloxane-containing
Flame retardant (FR) polymers and polymer blends, for copolymer, the bromine-containing polymer, and the
example polycarbonates and polycarbonate blends with UL optional third polymer, sum to 100 wt %, and 0.05 to 10 wt
VO and 5VA and B Underwriters Laboratories flammability % of a light diffuser additive, based on the total weight of
ratings are widely prepared and used, especially in a wide polymers in the thermoplastic polymer composition;
variety of electrical and electronic applications. Conversely, wherein a molded or formed sample of the thermoplastic
only a very limited set of polycarbonates are used in certain 25 polymer composition has a transmission of 20% to 90% or
railway applications, particularly interior parts for passenger a haze of 70% to 99.9%, each measured using the color
rail cars Such as windows, partition walls, ceiling panels, space CIE 1931 (Illuminant C and a 2° observer) at a
cabinet walls, storage compartments, galley Surfaces, light thickness of 3.2 mm, an OSU integrated 2 minute heat
panels, and the like. All of these applications have stringent release test value of less than 65 kW-min/m and a peak heat
flammability safety requirements that the polycarbonates 30 release rate of less than 65 kW/m, each measured using the
must meet. Particular requirements include Smoke density, method of FAR F25.4, in accordance with Federal Aviation
flame spread, and heat release values. Furthermore, it is Regulation FAR 25.853 (d), and an E662 smoke test DsMax
anticipated that rail requirements will approach or align with value of less than 200 when measured at a thickness of 1.6
current aircraft standards. In the United States, Federal .
Aviation Regulation (FAR) Part 25.853 sets forth the air 35 Disclosed herein is a railway vehicle component, wherein
worthiness standards for aircraft compartment interiors. The the component is a trolley sidewall, an access door, or an
safety standards for transportation systems used in the access panel, and wherein the component is molded or
United States include a smoke density test specified in FAR formed from a thermoplastic polymer composition compris
25.5 Appendix F, Part V Amdt 25-116. Flammability ing: a siloxane-containing copolymer in an amount effective
requirements include the “60 second test” specified in FAR 40 to provide a total of 0.2 to 6.5 wt % of siloxane units based
25.853(a) Appendix F. Part I, (a), 1.(i) and the heat release on the total weight of polymers in the thermoplastic polymer
rate standard (referred to as the OSU 65/65 standard) composition, a bromine-containing polymer in an amount
described in FAR F25.4 (FAR Section 25, Appendix F, Part effective to provide 9 to 13 wt % of bromine based on the
IV), or the French flame retardant tests such as, NF-P-92 total weight of the polymers in the thermoplastic polymer
504 (flame spread) or NF-P-92-505 (drip test). In another 45 composition, and optionally a third polymer, wherein the wt
example, the aircraft manufacturer Airbus has Smoke density % of the siloxane-containing copolymer, the bromine-con
and other safety requirements set forth in ABD0031. In the taining polymer, and the optional third polymer, Sum to 100
event of a fire, components made from materials having wt %; wherein a molded or formed sample of the thermo
these properties can increase the amount of time available plastic polymer composition has a transmission of 70% to
for escape and provide for better visibility during a fire 50 87% or a haze of 2% to 10%, each measured using the color
Despite extensive investigation, current materials that space CIE 1931 (Illuminant C and a 2° observer) at a
meet these FAR standards (and thus potential rail standards) thickness of 3.2 mm, an OSU integrated 2 minute heat
could be further improved with respect to other properties. release test value of less than 65 kW-min/m2 and a peak heat
Thus, there is a perceived need for polysulfones having release rate of less than 65 kW/m2, each measured using the
improved melt flow, improved ultraviolet (UV) stability, and 55 method of FAR F25.4, in accordance with Federal Aviation
improved light transmission. Siloxane-polyestercarbonates Regulation FAR 25.853 (d), and an E662 smoke test DsMax
have low melt flow and good color stability to indoor light, value of less than 200 when measured at a thickness of 1.6
but may shift in color upon exposure to UV light. Certain .
polycarbonate-polyetherimide blends also have low melt Disclosed herein is a railway vehicle component, wherein
flow, but can be difficult to formulate so as to provide bright 60 the component is a window, window dust cover, partition,
white compositions. light cover, electronics screen, display cover, or plastic
In view of the current interior material safety standards, mirror, and wherein the component is molded or formed
and in anticipation of more stringent standards in the future, from a thermoplastic polymer composition comprising: a
materials that exceed governmental and aircraft or train siloxane-containing copolymer in an amount effective to
manufacturer flame safety requirements are sought for cur 65 provide a total of 0.2 to 1.5 wt % of siloxane units based on
rent and anticipated rail applications. Such materials should the total weight of polymers in the thermoplastic polymer
also advantageously maintain excellent physical properties, composition; a bromine-containing polymer in an amount
 US 9,453,128 B2
3 4
effective to provide 9 to 13 wt % of bromine, based on the Disclosed herein is a railway vehicle component, wherein
total weight of the polymers in the thermoplastic polymer the component is an access door panel, a seat component, a
composition, and optionally, a third polymer, wherein the wt component of a stow bin, a magazine rack, a seat compo
% of the siloxane-containing copolymer, the bromine-con nent, a component of a trolley cart, an access door panel call
taining polymer, and the optional third polymer Sum to 100 button, a light bezel, a door pull, a door handle, an arm rest,
wt %; wherein a molded or formed sample of the thermo a foot rest, or a trolley cart, wherein the component is
plastic polymer composition has a transmission of 87% or molded or formed from a thermoplastic polymer composi
more or a haze of 2% or less, each measured using the color tion comprising a first siloxane-containing copolymer in an
space CIE 1931 (Illuminant C and a 2° observer) at a amount effective to provide a total of 2.5 to 6.0 wt % of
thickness of 3.2 mm, an OSU integrated 2 minute heat 10 siloxane units based on the total weight of polymers in the
release test value of less than 65 kW-min/m and a peak heat thermoplastic polymer composition, and wherein the silox
release rate of less than 65 kW/m, each measured using the ane-containing copolymer comprises siloxane blocks having
method of FAR F25.4, in accordance with Federal Aviation 10 to 200 siloxane units per block; a bromine-containing
Regulation FAR 25.853 (d), and an E662 smoke test DsMax polymer in an amount effective to provide 9 to 13 wt % of
value of less than 200 when measured at a thickness of 1.6
15 bromine, based on the total weight of the polymers in the
.
thermoplastic polymer composition, and optionally a third
polymer, wherein the wt % of the siloxane-containing copo
Disclosed herein is a railway vehicle component, wherein lymer, the bromine-containing polymer, and the optional
the component is an access door panel, a seat component and third polymer, sum to 100 wt %; and wherein a molded or
a component of a trolley cart, wherein the component is formed sample of the thermoplastic polymer composition
molded or formed from a thermoplastic polymer composi has a notched Izod impact strength of 2.0 ft-lb/in or greater,
tion comprising: a siloxane-containing copolymer in an measured according to ASTM D 256-10 at a 3.2 mm
amount effective to provide a total of 2.5 to 6.0 wt % of thickness at room temperature, an OSU integrated 2 minute
siloxane units based on the total weight of polymers in the heat release test value of less than 65 kW-min/m and a peak
thermoplastic polymer composition, optionally a second 25 heat release rate of less than 65 kW/m, each measured using
siloxane-containing copolymer, a bromine-containing poly the method of FAR F25.4, in accordance with Federal
mer in an amount effective to provide 9 to 13 wt % of Aviation Regulation FAR 25.853 (d), and an E662 smoke
bromine, based on the total weight of the polymers in the test DsMax value of less than 200 when measured at a
thermoplastic polymer composition, and optionally, a third thickness of 1.6 mm.
polymer wherein the wt % of the siloxane-containing copo 30 Disclosed herein is a railway vehicle component, wherein
lymer, the bromine-containing polymer, and the optional the component is a window, window dust cover, partition,
third polymer, sum to 100 wt %; and wherein a molded or light cover, electronics screen, display cover, or plastic
formed sample of the thermoplastic polymer composition mirror, and wherein the railway vehicle component is
has a notched IZod impact strength of 480 J/m or greater, molded or formed from a thermoplastic polymer composi
measured according to ASTM D 256-10 at a 3.2 mm 35 tion comprising a siloxane-containing copolymer in an
thickness at 0°C., an OSU integrated 2 minute heat release amount effective to provide a total of 0.2 to 1.5 wt % of
test value of less than 65 kW-min/m and a peak heat release siloxane units based on the total weight of polymers in the
rate of less than 65 kW/m, each measured using the method thermoplastic polymer composition, wherein a molded
of FAR F25.4, in accordance with Federal Aviation Regu plaque of the siloxane-containing copolymer has a percent
lation FAR 25.853 (d), and an E662 smoke test DsMax value 40 haze value of 3% or less measured using the color space CIE
of less than 200 when measured at a thickness of 1.6 mm. 1931 (Illuminant C and a 2° observer) at a thickness of 3.2
Disclosed herein is a colored railway vehicle component, mm, a bromine-containing polymer in an amount effective to
wherein the component is a stow bin component, a magazine provide 9 to 13 wt % of bromine, based on the total weight
rack, a seat component, a component of a trolley cart, and an of the polymers in the thermoplastic polymer composition,
access door panel, wherein the component is molded or 45 and optionally a third polymer, wherein the wt % of the
formed from a thermoplastic polymer composition compris siloxane-containing copolymer, the bromine-containing
ing a first siloxane-containing copolymer in an amount polymer and the optional third polymer sums to 100 wt %,
effective to provide a total of 2.5 to 5.3 wt % of siloxane wherein a molded or formed sample of the thermoplastic
units based on the total weight of polymers in the thermo polymer composition has a transmission of 87% or more or
plastic polymer composition. a bromine-containing polymer 50 a haze of 2% or less, each measured using the color space
in an amount effective to provide 9 to 13 wt % of bromine, CIE 1931 (Illuminant C and a 2° observer) at a thickness of
based on the total weight of the polymers in the thermo 3.2 mm, an OSU integrated 2 minute heat release test value
plastic polymer composition, and optionally, a third polymer of less than 65 kW-min/m and a peak heat release rate of
wherein the wt % of the siloxane-containing copolymer, the less than 65 kW/m2, each measured using the method of
bromine-containing polymer, and the optional third polymer, 55 FARF25.4, in accordance with Federal Aviation Regulation
sum to 100 wt %; and 0.00002 to 5.0 wt % of a colorant FAR 25.853 (d), and an E662 smoke test DsMax value of
based on the total weight of the polymers in the thermo less than 200 when measured at a thickness of 1.6 mm.
plastic polymer composition, wherein a molded or formed The above described and other features are exemplified by
sample of the thermoplastic polymer composition has a the following Detailed Description, Figures, and Examples.
notched iZod impact strength of 400 J/m or greater, mea 60
sured at 10° C. according to ASTM D 256-10 at a 3.2 mm BRIEF DESCRIPTION OF THE FIGURES
thickness, an OSU integrated 2 minute heat release test value
of less than 65 kW-min/m and a peak heat release rate of A description of the Figures, which are meant to be
less than 65 kW/m, each measured using the method of exemplary and not limiting, is provided below.
FAR F25.4, in accordance with Federal Aviation Regulation 65 FIG. 1 is a diagram of a hard coated sheet:
FAR 25.853 (d), and an E662 smoke test DsMax value of FIG. 2 is a diagram of a hard coated sheet:
less than 200 when measured at a thickness of 1.6 mm. FIG. 3 is a diagram of a window article for a rail;
 US 9,453,128 B2
5 6
FIG. 4 is a diagram of a window article for a rail; standard are required to have a 2-minute integrated heat
FIG. 5 is a diagram of a multilayer article: release rate of less than or equal to 65 kilowatt-minutes per
FIG. 6 is a diagram of a multilayer article; and square meter (kW-min/m) and a peak heat release rate of
FIG. 7 is a diagram of a plastic mirror. less than 65 kilowatts per square meter (kW/m) determined
using the Ohio State University calorimeter, abbreviated as
DETAILED DESCRIPTION OF THE OSU 65/65 (2 min/peak). In applications requiring a more
INVENTION stringent standards, where a better heat release rate perfor
mance is called for, a 2-minute integrated heat release rate
The inventors hereofhave discovered that flame retardant, of less than or equal to 55 kW-min/m and a peak heat
low Smoke compositions comprising specific siloxane block 10 release rate of less than 55 kW/m (abbreviated as OSU
copolymers can unexpectedly be obtained when certain 55/55) may be required.
siloxane-containing copolymer compositions and bromine Without being bound by theory, it is believed that the
containing compositions, neither of which meets strict low unexpected combination of low Smoke density and low heat
density Smoke standards, are used in combination. In par release values obtained is achieved by careful selection and
ticular, certain poly(siloxane) block copolymer composi 15 balancing of the absolute and relative amounts of the first
tions and certain bromine-containing compositions, do not polymer, the second polymer, and the optional one or more
by themselves meet strict low smoke density standards when third polymers, including selecting an amount of first poly
burned. However, specific combinations of these two com mer, block size (i.e., length) of the siloxane blocks, and
positions can meet low Smoke density standards, and have number of siloxane blocks such that at least 0.3 wt %
very low heat release properties. Achieving very low Smoke polysiloxane units are present in the composition; and
density and very low flammability ratings are conflicting selecting the type and amount of the second polymer and the
requirements. Halogenated, specifically brominated, flame amount of bromine in the second polymer Such that at least
retardants are used in poly(siloxane) copolymer composi 7.8 wt % bromine is present in the composition. The
tions for their effectiveness in improving flame spread compositions therefore include amounts of the first and
properties and satisfying stringent rail (e.g., railcar or train 25 second polymers effective, i.e., Sufficient, to provide the
car) interior flammability standards. Brominated flame retar desired amount of polysiloxane units and bromine, which in
dant additives, however, cause an increase in Smoke when turn yields compositions having the an OSU-integrated 2
the sheet compositions are ignited. It is therefore Surprising minute heat release test value of less than 65 kW-min/m and
that a brominated flame retardant can be added to a poly a peak heat release rate of less than 65 kW/m as measured
(siloxane) block or graft copolymer and lower the Smoke 30 using the method of FARF25.4, in accordance with Federal
density of the poly(siloxane) copolymer. Aviation Regulation FAR 25.853 (d), and an E662 smoke
The compositions can further have excellent mechanical test DSMax value of less than 200 when tested at a thickness
properties, including at least one of high impact strength, of 1.6 mm.
low brittleness (high ductility) as well as favorable process In an embodiment, an effective amount of the siloxane
ing characteristics, such as low melt viscosity. In a further 35 containing copolymer is at least 1 wt %, specifically 1 to 85
advantageous feature, the combinations can be transparent. wt % of the siloxane-containing copolymer, and an effective
In another advantageous feature, the compositions can have amount of the brominated polymer is at least 15 wt %,
low density. Such compositions are especially useful in the specifically 15 to 95 wt %, each based on the total weight of
manufacture of flame retardant, low Smoke poly(siloxane) the first polymer, second polymer, and optional one or more
copolymer sheets that can be used in railway vehicle appli 40 third polymers. The precise amount of the first polymer
cations. effective to provide at least 0.3 wt % of the polysiloxane
The compositions contain a first polymer comprising first units depends on the selected copolymer, the length of the
repeating units and blocks of repeating polysiloxane units; a siloxane block, the number the siloxane-containing blocks,
brominated second polymer different from the first polymer; and the desired properties, such as Smoke density, heat
and optionally, one or more third polymers different from the 45 release values, transparency, impact strength, melt viscosity,
first polymer and second polymer, wherein the weight and/or other desired physical properties. In general, to be
percent (wt %) of the first polymer, second polymer, and effective, when a block copolymer is used, the smaller the
optional one or more third polymers sum to 100 wt %, and block size and/or the lower the number of blocks in the first
the polysiloxane units are present in the composition in an polymer, the higher the fractional concentration of the first
amount of at least 0.3 wt %, based on the sum of the wt % 50 polymer, based on the total weight of the first, second and
of the first, second, and optional third polymers, and bro optionally one or more third polymers. When a graft copo
mine is present in the composition in an amount of at least lymer is used, the lower the number of branches and/or the
7.8 wt %, based on the sum of the wt % of the first, second, shorter the branches, the higher is the fractional concentra
and optional third polymers; and further wherein an article tion of the first polymer based on the total weight of the first,
molded from the composition has an OSU integrated 2 55 second and optionally one or more third polymers. Similarly,
minute heat release test value of less than 65 kW-min/m and for the brominated polymer, the precise amount depends on
a peak heat release rate of less than 65 kW/m as measured the type of polymer, the amount of bromine in the polymer,
using the method of FARF25.4, in accordance with Federal and other desired characteristics of the compositions. The
Aviation Regulation FAR 25.853 (d), and an E662 smoke lower the weight percent of bromine in the second polymer,
test DsMax value of less than 200 when measured at a 60 the higher the fractional concentration of the second poly
thickness of 1.6 mm. For simplicity, this test can be referred mer, based on the total weight of the first, second and
to herein as the “smoke density test.” optionally one or more third polymers. Thus, an effective
The first, second, and optionally one or more third poly amount of the siloxane-containing copolymer in some
mers are further selected and used in amounts effective to embodiments can be at least 5 wt %, specifically 5 to 80 wt
satisfy the requirements for heat release rates described in 65 %, or at least 10 wt %, specifically 10 to 70 wt %, or at least
FAR F25.4 (Federal Aviation Regulations Section 25, 15 wt %, specifically 15 to 60 wt %, and an effective amount
Appendix F. Part IV). Materials in compliance with this of the brominated polymer in Some embodiments can be at
 US 9,453,128 B2
7 8
least 20 wt %, specifically 20 to 85 wt %, or 20 to 75 wt %, Excellent transparency can also be obtained when the
each based on the total weight of the first polymer, second thermoplastic composition comprises the first polymer in an
polymer, and optional one or more third polymers. amount effective to provide at least 0.3 wt % siloxane and
As stated above, the first polymer comprises first repeat the second polymer in an amount effective to provide at least
ing units and blocks of repeating polysiloxane units. In a 5.0 wt % bromine, each based on total weight of the first
particularly advantageous feature, the first repeating units polymer, second polymer, and optional one or more third
can be a variety of different units, which allows manufacture polymers, and the siloxane blocks or grafts have an average
of low Smoke, low heat release compositions having a of 5 to 75, specifically 5 to 15 units. Effective amounts can
variety of properties. The first repeating units can be poly be at least 30 wt %, specifically 30 to 80 wt % of the first
carbonate units, etherimide units, ester units, Sulfone units, 10 polymer, and at least 20 wt %, specifically at least 20 to 50
ether sulfone units, arylene ether sulfone units, arylene ether wt % of the second polymer (the TBBPA copolymer), and 0
units, and combinations comprising at least one of the to 50 wt % of the optional one or more third polymers, each
foregoing, for example resorcinol-based aryl ester-carbonate based on the total weight of the first, second, and optionally
units, etherimide-Sulfone units, and arylene ether-Sulfone one or more third polymers. An article molded from the
units. 15 composition has a haze of less than 3% and a transmission
In a specific embodiment, the first, second, and optional greater than 85%, each measured using the color space
third polymers are polycarbonates, that is, polymers con CIE 1931 (Illuminant C and a 2° observer), or according to
taining repeating carbonate units. Thus the first polymer is a ASTM D1003 (2007) using illuminant C at a 0.062 inch
poly(siloxane-carbonate) copolymer, the second polymer is (1.5 mm) thickness.
a brominated polymer containing repeating carbonate units, In still other embodiments, it has been found that limiting
and the one or more optional third polymers are polycar the amount of the optional third polymer, together with use
bonate homopolymers or copolymers. In an embodiment, of specific first and second polycarbonates can produce
the thermoplastic composition comprises at least 5 wt %, compositions with advantageous properties. In one Such
specifically 5 to 85 wt % of the first poly(siloxane-carbon embodiment, the thermoplastic composition comprises the
ate) copolymer, at least 15 wt %, specifically 15 to 95 wt % 25 first polymer (the poly(siloxane-carbonate)), the second
of the second brominated polycarbonate, Such as a bromi polymer (the TBBPA copolymer or brominated oligomer),
nated polycarbonate derived from 2,2',6,6'-tetrabromo-4,4'- and 8 to 12 wt % of the one or more third polymers, wherein
isopropylidenediphenol (2.2-bis(3,5-dibromo-4-hydroxy the wt % of the first polymer, second polymer, and one or
phenyl)propane (TBBPA) and carbonate units derived from more third polymers sum to 100 wt % based on the total
at least one dihydroxy aromatic compound that is not 30 weight of the first, second and optionally one or more third
TBBPA (“TBBPA copolymer), and 0 to 70 wt % of the polymers. The siloxane blocks have an average value of 20
optional one or more third polymers, based on the total to 85 units. At least 0.4 wt % of siloxane and at least 7.8 wit
weight of the first, second, and optional one or more third % of bromine is present, each based on total weight of the
polymers, i.e., the wt % of the first polymer, second polymer, first polymer, second polymer, and one or more third poly
and optional one or more third polymers sum to 100 wt %. 35 mers. In an embodiment, the thermoplastic composition
The siloxane blocks present in the first polymer have an comprises 5 to 60 wt % of the first poly(siloxane-carbonate)
average of 5 to 200 units, specifically 5 to 100, or 20 to 65 30 to 60 wt % of the second polymer (the TBBPA copoly
units. At least 0.3 wt % siloxane and at least 7.8 wt % mer).
bromine is present, each based on total weight of the first In an alternative embodiment of the thermoplastic com
polymer, second polymer, and optional one or more third 40 positions, it has been found that other brominated oligomers
polymers. can be used in place of the TBBPA copolymer, such as other
Further in this embodiment, when the siloxane blocks brominated polycarbonate oligomers or brominated epoxy
have an average of 25 to 75 units, specifically 25 to 50 units, oligomers. In this embodiment, the thermoplastic composi
and at least 2.0 wt % siloxane is present based on total tions contain the first poly(siloxane-carbonate), a bromi
weight of the first polymer, second polymer, and optional 45 nated oligomer, and an optional additional polycarbonate
one or more third polymers, excellent toughness is obtained, different from the first polymer and the brominated oli
in particular an article molded from the composition further gomer. The optional additional polycarbonate can be the
has a room temperature notched Izod impact of greater than same as the optional one or more third polymers described
500 J/m as measured according to ASTM D 256-10 at a in the above embodiments. The first polymer, the bromi
0.125 inch (3.2 mm) thickness. The articles can further have 50 nated oligomer, and the optional additional polycarbonate
100% ductility. The amount of siloxane in the composition are present in amounts effective to provide at least 0.4 wt %
can be varied by controlling the length of units per block, the of siloxane and at least 7.8 wt % of bromine, each based on
number of blocks and the tacticity of the blocks along the total weight of the first polymer, brominated oligomer, and
backbone. additional polycarbonate, and thus satisfy at least the Smoke
Still further in this embodiment, when the polysiloxane 55 density test and the heat release OSU 65/65 test. In particu
units of the first polymer is present in an amount of at least lar, the thermoplastic compositions comprise at least 5 wt %,
2.0 wt % and the composition has 35 to 50 wt % of the specifically 5 to 85 wt % of the first poly(siloxane-carbon
second polymer (the TBBPA copolymer), each based on ate), at least 15 wt %, specifically at least 15 to 95 wt % of
total weight of the first polymer, second polymer, and the brominated oligomer, and 0 to 60 wt % of the optional
optional one or more third polymers, and the siloxane blocks 60 additional polycarbonate, each based on the total weight of
have an average length of 25 to 50 units, excellent trans the first polymer, brominated oligomer, and optional addi
parency can be obtained, in particular an article molded from tional polycarbonate. The siloxane blocks have an average
this composition has a haze of less than 10% and a trans of 5 to 200, or 5 to 100 units.
mission greater than 70%, each measured using the color While the smoke density and OSU tests demonstrate the
space CIE 1931 (Illuminant C and a 2° observer), or accord 65 ability of the poly(siloxane) copolymer compositions
ing to ASTM D1003 (2007) using illuminant C at a 0.125 described herein to comply with both the smoke generation
inch (3.2 mm) thickness. and heat release requirements for railway vehicle interiors,
 US 9,453,128 B2
9 10
any of the above-described compositions can advanta -continued
geously comply with other related flammability and safety Re
(5)
tests as described above.
In certain embodiments, the first, second, and optional -C o
|
one or more third polymers, as well as the brominated
polycarbonates (including the TBBPA copolymer and bro wherein each R and R is independently hydrogen, C-12
minated polycarbonate oligomers) have repeating structural alkyl, C-2 cycloalkyl, C7 arylalkyl, C. heteroalkyl, or
carbonate units of formula (1) cyclic C-2 heteroarylalkyl, and R is a divalent C.
10 hydrocarbon group. In particular, R and R are each the
same hydrogen or C. alkyl, specifically the same C
(3) alkyl, even more specifically, methyl.
(R) (R'), In an embodiment, R and R' taken together is a Cs20
cyclic alkylene or a heteroatom-containing Co cyclic
15
alkylene comprising carbon atoms and heteroatoms with a
Valency of two or greater. These groups can be in the form
of a single Saturated or unsaturated ring, or a fused polycy
clic ring system wherein the fused rings are Saturated,
wherein at least 60%, specifically at least 80%, and specifi unsaturated, or aromatic. A specific heteroatom-containing
cally at least 90% of the total number of R' groups contains cyclic alkylene group comprises at least one heteroatom
aromatic organic groups and the balance thereof are ali with a Valency of 2 or greater, and at least two carbon atoms.
phatic or alicyclic groups. In particular, use of aliphatic Heteroatoms in the heteroatom-containing cyclic alkylene
groups is minimized in order to maintain the flammability group include —O— —S , and —N(Z)—, where Z is a
performance of the polycarbonates. In an embodiment, at Substituent selected from hydrogen, hydroxy, C. alkyl,
C-12 alkoxy, or C-12 acyl.
least 70%, at least 80%, or 95 to 100% of the R' groups are 25 In a specific embodiment, X* is a substituted Cls
aromatic groups. In an embodiment, each R" is a divalent cycloalkylidene of formula (6)
aromatic group, for example derived from an aromatic
dihydroxy compound of formula (2)
HO-A-Y-A-OH (2) RP Ra (6)
30
wherein each of A' and A is independently a monocyclic
divalent arylene group, and Y is a single bond or a bridging
group having one or two atoms that separate A" from A. In IR-trils (C)--R"),
an embodiment, one atom separates A' from A. In another /\
embodiment, when each of A' and A is phenylene, Y is 35
para to each of the hydroxyl groups on the phenylenes. wherein each R. R. R. and R is independently hydrogen,
Illustrative non-limiting examples of groups of this type are halogen, oxygen, or C-12 organic group: I is a direct bond,
a carbon, or a divalent oxygen, Sulfur, or —N(Z)— wherein
O— —S— —S(O)— —S(O) , —C(O)—, methyl Z is hydrogen, halogen, hydroxy, C-12 alkyl, C-12 alkoxy,
ene, cyclohexyl-methylene, 2-2.2.1-bicycloheptylidene, 40 or C-acyl: h is 0 to 2, j is 1 or 2, i is an integer of 0 or
ethylidene, isopropylidene, neopentylidene, cyclohex 1, and k is an integer of 0 to 3, with the proviso that at least
ylidene, cyclopentadecylidene, cyclododecylidene, and ada two of R. R. R. and R taken together are a fused
mantylidene. The bridging group Y can be a hydrocarbon cycloaliphatic, aromatic, or heteroaromatic ring. It will be
group, specifically a saturated hydrocarbon group Such as understood that where the fused ring is aromatic, the ring as
methylene, cyclohexylidene, or isopropylidene. shown in formula (6) will have an unsaturated carbon
Included within the scope of formula (2) are bisphenol 45 carbon linkage where the ring is fused. When k is 1 and i is
0, the ring as shown in formula (6) contains 4 carbon atoms,
compounds of formula (3) when k is 2, the ring as shown contains 5 carbon atoms, and
when k is 3, the ring contains 6 carbon atoms. In an
embodiment, two adjacent groups (e.g., R and R taken
(3) together) form an aromatic group, and in another embodi
(R) (R'), 50 ment, R and R taken together form one aromatic group and
R and R taken together form a second aromatic group.
When k is 3 and i is 0, bisphenols containing substituted
or unsubstituted cyclohexane units are used, for example
bisphenols of formula (7)
55
wherein each of R" and R is independently a halogen atom (7)
or a monovalent hydrocarbon group; p and q are each
independently integers of 0 to 4; and X represents a single Rf Rf
bond or one of the groups of formulas (4) or (5)
60
== ==
HO ) tG
(4)
-( / R8 R8
R8 \ XOH
R8
Rf Rf

65
R4 R
 US 9,453,128 B2
11 12
wherein R is each independently hydrogen, C-2 alkyl, or 5-phenyl resorcinol, 5-cumyl resorcinol, 2,4,5,6-tetrafluoro
halogen; and R is each independently hydrogen or C. resorcinol. 2,4,5,6-tetrabromo resorcinol, and the like; cat
alkyl. The Substituents can be aliphatic or aromatic, straight echol; hydroquinone; and Substituted hydroquinones such as
chain, cyclic, bicyclic, branched, saturated, or unsaturated. 2-methyl hydroquinone, 2-ethyl hydroquinone, 2-propyl
Such cyclohexane-containing bisphenols, for example the 5 hydroquinone, 2-butyl hydroquinone, 2-t-butyl hydroqui
reaction product of two moles of a phenol with one mole of none, 2-phenyl hydroquinone, 2-cumyl hydroquinone, 2.3,
a hydrogenated isophorone, are useful for making polycar 5,6-tetramethyl hydroquinone, 2,3,5,6-tetra-t-butyl hydro
bonate polymers with high glass transition temperatures (T) quinone, 2,3,5,6-tetrafluoro hydroquinone, 2,3,5,6-
and high heat distortion temperatures (HDT). Cyclohexyl tetrabromo hydroquinone, and the like. Combinations
bisphenol-containing polycarbonates, or a combination 10 comprising at least one of the foregoing dihydroxy com
comprising at least one of the foregoing with other bisphenol pounds can be used.
polycarbonates, are supplied by Bayer Co. under the Specific examples of bisphenol compounds that can be
APEC(R) trade name. represented by formula (3) include 1,1-bis(4-hydroxyphe
Other useful dihydroxy compounds having the formula nyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 2.2-bis(4-
HO-R-OH include aromatic dihydroxy compounds of 15 hydroxyphenyl)propane (bisphenol A or BPA), 2.2-bis(4-
formula (8) hydroxyphenyl)butane, 2.2-bis(4-hydroxyphenyl)octane,
1,1-bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphe
nyl)n-butane, 2.2-bis(4-hydroxy-1-methylphenyl)propane,
(8) 1,1-bis(4-hydroxy-t-butylphenyl)propane, 3.3-bis(4-hy
droxyphenyl)phthalimidine, 2-phenyl-3,3-bis(4-hydroxy
phenyl)phthalimidine (PPPBP), and 1,1-bis(4-hydroxy-3-
methylphenyl)cyclohexane (DMBPC). Combinations
comprising at least one of the foregoing dihydroxy com
pounds can also be used.
wherein R" is each independently a halogen atom, a C-lo 25 “Polycarbonate' as used herein includes homopolycar
hydrocarbyl Such as a Co alkyl group, a halogen Substi bonates, copolymers comprising different R' moieties in the
tuted Co hydrocarbyl Such as a halogen-substituted Co carbonate ("copolycarbonates'), and copolymers compris
alkyl group, and h is 0 to 4. The halogen is usually bromine. ing carbonate units and other types of polymer units. Such as
Some illustrative examples of dihydroxy compounds polysiloxane units or ester units. In a specific embodiment,
include the following: 4,4'-dihydroxybiphenyl, 1,6-dihy 30 the one or more optional third polymers is a linear homopo
droxynaphthalene, 2,6-dihydroxynaphthalene, bis(4-hy lymer or copolymer comprising units derived from bisphe
droxyphenyl)methane, bis(4-hydroxyphenyl)diphenylmeth nol A, in which each of A' and A is p-phenylene and Y is
ane, bis(4-hydroxyphenyl)-1-naphthylmethane, 1.2-bis(4- isopropylidene in formula (2). More specifically, at least
hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)-1- 60%, particularly at least 80% of the R' groups in the
phenylethane, 2-(4-hydroxyphenyl)-2-(3-hydroxyphenyl) 35 polycarbonate homopolymer or copolymer are derived from
propane, bis(4-hydroxyphenyl)phenylmethane, 2.2-bis(4- bisphenol A. In an embodiment, the first polymer is a block
hydroxy-3-bromophenyl)propane, 1,1-bis (hydroxyphenyl) or graft copolymer comprising carbonate units of formula
cyclopentane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1- (1) and blocks of polysiloxane units, i.e., a poly(siloxane
bis(4-hydroxyphenyl)isobutene, 1,1-bis(4-hydroxyphenyl) co-carbonate), referred to herein as a "poly(siloxane-carbon
cyclododecane, trans-2,3-bis(4-hydroxyphenyl)-2-butene, 40 ate). Block poly(siloxane-carbonate) copolymers comprise
2.2-bis(4-hydroxyphenyl)adamantine, alpha, alpha'-bis(4- siloxane blocks and carbonate blocks in the polymer back
hydroxyphenyl)toluene, bis(4-hydroxyphenyl)acetonitrile, bone. Graft poly(siloxane-carbonate) copolymers are non
2.2-bis(3-methyl-4-hydroxyphenyl)propane, 2.2-bis(3- linear copolymers comprising the siloxane blocks connected
ethyl-4-hydroxyphenyl)propane, 2.2-bis(3-n-propyl-4-hy to linear or branch polymer backbone comprising carbonate
droxyphenyl)propane, 2.2-bis(3-isopropyl-4-hydroxyphe 45 blocks.
nyl)propane, 2.2-bis(3-sec-butyl-4-hydroxyphenyl)propane, In addition to the first repeating units in the first polymer
2.2-bis(3-t-butyl-4-hydroxyphenyl)propane, 2.2-bis(3-cy (for example polycarbonate units (1) as described above),
clohexyl-4-hydroxyphenyl)propane, 2.2-bis(3-allyl-4-hy the first polymer comprises blocks of polysiloxane units of
droxyphenyl)propane, 2.2-bis(3-methoxy-4-hydroxyphe formula (9)
nyl)propane, 2.2-bis(4-hydroxyphenyl)hexafluoropropane, 50
1,1-dichloro-2,2-bis(4-hydroxyphenyl)ethylene, 1,1-di
bromo-2,2-bis(4-hydroxyphenyl)ethylene, 1,1-dichloro-2,2-
bis(5-phenoxy-4-hydroxyphenyl)ethylene, 4,4'-dihydroxy
benzophenone, 3.3-bis(4-hydroxyphenyl)-2-butanone, 1.6-
bis(4-hydroxyphenyl)-1,6-hexanedione, ethylene glycol bis
(4-hydroxyphenyl)ether, bis(4-hydroxyphenyl)ether, bis(4-
55 jo
R
E.
hydroxyphenyl)sulfide, bis(4-hydroxyphenyl)sulfoxide, bis
(4-hydroxyphenyl)sulfone, 9.9 to bis(4-hydroxyphenyl)
fluorine, 2,7-dihydroxypyrene, 6,6'-dihydroxy-3,3,3',3'- wherein R is each independently a C-C hydrocarbon
tetramethylspiro(bis)indane (“spirobiindane bisphenol), 60 group, specifically a C-1 alkyl group, C2-alkenyl group.
3.3-bis(4-hydroxyphenyl)phthalide, 2,6-dihydroxydibenzo C. cycloalkyl group, C. aryl group, C7 arylalkyl
p-dioxin, 2,6-dihydroxythianthrene, 2,7-dihydroxyphenox group, or C7-1 alkylaryl group. The foregoing groups can be
athin, 2.7-dihydroxy-9,10-dimethylphenazine, 3,6-dihy fully or partially halogenated with fluorine, chlorine, bro
droxydibenzofuran, 3,6-dihydroxydibenzothiophene, and mine, or iodine, or a combination comprising at least one of
2,7-dihydroxycarbazole, resorcinol, substituted resorcinol 65 the foregoing. Combinations of the foregoing R groups can
compounds such as 5-methyl resorcinol, 5-ethyl resorcinol, be used in the same copolymer. In an embodiment, the
5-propyl resorcinol, 5-butyl resorcinol, 5-t-butyl resorcinol, polysiloxane comprises R groups that have minimum hydro
 US 9,453,128 B2
13 14
carbon content. In yet another embodiment, the foregoing R droxybenzene, 5-methyl-1,3-dihydroxybenzene, 4,6-dim
groups are functionalized wherein at least one methyl group ethyl-1,3-dihydroxybenzene, 1,4-dihydroxybenzene, 1,1-bis
has been replaced by another group, which is preferably not (4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)
hydrogen, or wherein the functionalized R groups incorpo ethane, 2.2-bis(4-hydroxyphenyl)propane, 2.2-bis(4-
rate reactive functional groups such as anhydrides and 5 hydroxyphenyl)butane, 2.2-bis(4-hydroxyphenyl)octane,
epoxides that can react with other components by, for 1,1-bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphe
example, covalent bonding. In a specific embodiment, R is nyl)n-butane, 2.2-bis(4-hydroxy-1-methylphenyl)propane,
each the same and is a methyl group. 1,1-bis(4-hydroxyphenyl)cyclohexane, bis(4-hydroxyphe
The average value of E in formula (9) can vary from 5 to nyl sulfide), and 1,1-bis(4-hydroxy-t-butylphenyl)propane.
200. In an embodiment, E has an average value of 5 to 100, 10 Combinations comprising at least one of the foregoing
10 to 100, 10 to 50, 25 to 50, or 35 to 50. In another dihydroxy compounds can also be used. In an embodiment,
embodiment, E has an average value of 5 to 75, specifically the dihydroxy aromatic compound is unsubstituted, or is not
5 to 15, specifically 5 to 12, more specifically 7 to 12. The Substituted with non-aromatic hydrocarbon-containing Sub
siloxane blocks can be atactic, isotactic, or syndiotactic. In stituents such as alkyl, alkoxy, or alkylene Substituents.
an embodiment, the tacticity of the siloxane can affect the 15
effective amount of each copolymer used as well as the In a specific embodiment, where Ar is derived from
physico-chemical characteristic of the thermoplastic com resorcinol, the polydiorganosiloxane repeating units are
positions formed (e.g., crystallinity, transparency, impact derived from polysiloxane bisphenols of formula (12)
resistance and the like). The siloxane containing copolymer
can be a graft copolymer wherein the siloxane-containing 20
blocks are branched from a polymer backbone having blocks
of the first repeating units, for example carbonate units of
formula (1). (12)
In an embodiment, for example in poly(siloxane-carbon
ates), the polysiloxane units can be derived from polysilox- 25
ane bisphenols of formula (10) or (11)

(10) HO OH
30

HO-Air - O o Air-OH
R or, where Aris derived from bisphenol A, from polysiloxane
E.
bisphenols of formula (13)

(13)
CH CH st CH

to-K) ()-Ho-Ho-K) ()-on CH3 CH3 CH3

-continued 45 wherein E is as defined in formula (9) above.

(11) Where R is C, so arylenealkylene in formula (11), the
polysiloxane units can be derived from polysiloxane bisphe
HO-R--SiO Si-R-OH
nols of formula (14)
50
(14)

wherein E is as defined in formula (9); each R can be the N 21

same or different, and is as defined in formula (9); each Ar
can be the same or different, and is a substituted or unsub
stituted Clso arylene group; and each R is the same or
55
in-O-
X4 ||SO | --Gor
(M)
sex (E-1) (M)
different, and is a divalent Clso alkylene or C, so arylene
alkylene wherein the bonds of the hydroxyl groups are wherein R and E are as defined in formula (9). R is each
directly bonded to the arylene moiety or the alkylene moiety. 60 independently a divalent Cls aliphatic group. Each M can
The Argroups informula (10) can be derived from a C-so be the same or different, and can be a halogen, cyano, nitro,
dihydroxy aromatic compound, for example a dihydroxy Cs alkylthio. Cls alkyl, Cs alkoxy, C2-s alkenyl, C2-s
aromatic compound of formula (2), (3), (6), (7), or (8) alkenyloxy group, C.s cycloalkyl, C.s cycloalkoxy, Co
above. Combinations comprising at least one of the forego aryl, Cao aryloxy, C7-12 arylalkyl, C7-12 arylalkoxy, C7-12
ing dihydroxy aromatic compounds can also be used. Illus- 65 alkylaryl, or C7-2 alkylaryloxy, wherein each n is indepen
trative examples of dihydroxy aromatic compounds are dently 0, 1, 2, 3, or 4. In an embodiment, M is bromo or
resorcinol (i.e., 1,3-dihydroxybenzene), 4-methyl-1,3-dihy chloro, an alkyl Such as methyl, ethyl, or propyl, an alkoxy
 US 9,453,128 B2
15 16
Such as methoxy, ethoxy, or propoxy, or an aryl Such as polysiloxane units are present in an amount of 5 to 30 wt %
phenyl, chlorophenyl, or tolyl; R is a dimethylene, trim based on the total weight of the poly(siloxane-carbonate); or
ethylene or tetramethylene group; and R is a Cls alkyl, E can have an average value of 30 to 50, or 40 to 50, wherein
haloalkyl Such as trifluoropropyl, cyanoalkyl, or aryl Such as the polysiloxane units are present in an amount of 4 to 8 wit
phenyl, chlorophenyl or tolyl. In another embodiment, R is % based on the total weight of the poly(siloxane-carbonate);
methyl, or a combination of methyl and trifluoropropyl, or a or E can have an average value of 5 to 12, wherein the
combination of methyl and phenyl. In still another embodi polysiloxane units are present in an amount of 0.5 to 7 wt %
ment, M is methoxy, n is 0 or 1, R is a divalent Caliphatic based on the total weight of the poly(siloxane-carbonate). In
group, and R is methyl. 10
other embodiments, specifically those used in translucent,
In a specific embodiment, the polysiloxane units are high clarity, medium clarity, high impact, and colored rail
derived from a polysiloxane bisphenol of formula (15) way vehicle articles, E can have an average value of 5 to
200, or 8 to 100, wherein the polysiloxane units are present
in an amount of 0.5 to 25 wt % based on the total weight of
(15) the poly(siloxane-carbonate); or, in other embodiments, E
15
HO can have an average value of 25 to 65, wherein the polysi
loxane units are present in an amount of 15 to 25 wt % based
CHO SH: SH: on the total weight of the poly(siloxane-carbonate); or E can
have an average value of 20 to 65, or 40 to 65, wherein the
j-o polysiloxane units are present in an amount of 4 to 25 wt %
CH E
CH OCH based on the total weight of the poly(siloxane-carbonate); or
OH
E can have an average value of 5 to 12, wherein the
polysiloxane units are present in an amount of 0.5 to 7 wt %
based on the total weight of the poly(siloxane-carbonate).
wherein E is as described in formula (9). 25 In another embodiment, the first polymer is a poly(silox
In another specific embodiment, the polysiloxane units ane-etherimide) copolymer comprising siloxane blocks (9)
are derived from polysiloxane bisphenol of formula (16) and polyetherimide units of formula (17)

(16) 30 (17)
O O

H. H. OH N 21
—o N-R-N -HO-Z-O
HO CH3 CH3 21 N
E
O O

wherein E is as described in formula (9).

The relative amount of carbonate and polysiloxane units 40 wherein a is 1 or greater than 1, for example 5 to 1,000 or
in the poly(siloxane-carbonate) will depend on the desired more, or more specifically 10 to 500. In this embodiment,
properties, and are carefully selected using the guidelines the first polymer is a block or graft copolymer comprising
provided herein. In particular, as mentioned above, the block etherimide units of formula (17) and blocks of polysiloxane
or graft poly(siloxane-carbonate) copolymer is selected to units, i.e., a poly(siloxane-co-etherimide), referred to herein
have a certain average value of E, and is selected and used 45 as a “(polyetherimide-siloxane).” Block poly(siloxane
in amount effective to provide the desired wt % of polysi etherimide) copolymers comprise siloxane blocks and ether
loxane units in the composition. In an embodiment, the imide blocks in the polymer backbone. The siloxane blocks
poly(siloxane-carbonate) can comprise polysiloxane units in and the polyetherimide units can be present in random order,
an amount of 0.3 to 30 weight percent (wt %), specifically as blocks (i.e., AABB), alternating (i.e., ABAB), or a
0.5 to 25 wt %, or 0.5 to 15 wt %, or even more specifically 50 combination thereof. Graft poly(siloxane-etherimide) copo
0.7 to 8 wt %, or 0.7 to 7 wt %, based on the total weight lymers are non-linear copolymers comprising the siloxane
of the poly(siloxane-carbonate), with remainder being car blocks connected to linear or branch polymer backbone
bonate units. In another embodiment, the poly(siloxane comprising etherimide blocks.
carbonate) can comprise polysiloxane units in an amount of The group R in formula (17) is a divalent hydrocarbon
0.5 to 25 weight percent (wt %), specifically 0.5 to 20 wt %, 55 group. Such as a Co aromatic hydrocarbon group or
or 0.5 to 10 wt % based on the total weight of the poly halogenated derivative thereof, a straight or branched chain
(siloxane-carbonate), with remainder being carbonate units. Co alkylene group or halogenated derivative thereof, a
In an embodiment, the poly(siloxane-carbonate) com Co cycloalkylene group or halogenated derivative thereof,
prises units derived from polysiloxane bisphenols (14) as or a divalent group of formula (18)
described above, specifically wherein M is methoxy, n is 0 60
or 1, R is a divalent Caliphatic group, and R is methyl, (18)
still more specifically a polysiloxane bisphenol of formula
(15) or (16). In these embodiments, E can have an average
value of 5 to 200, or 8 to 100, wherein the polysiloxane units
are present in an amount of 0.3 to 25 wt % based on the total
weight of the poly(siloxane-carbonate); or, in other embodi
65 CH3 ( ) ( )
ments, E can have an average value of 25 to 100, wherein the
 US 9,453,128 B2
17 18
-continued As is known, polyetherimides can be obtained by polym
erization of an aromatic bisanhydride of the formula (20)

(20)
O

21
O --O-z-O- O
10
N
O O

wherein Z is as described in formula (17), with a diamine of

H3C CH3 15
the formula (21)
H2N-R-NH2 (21)
( ) ( ) sO wherein R is as described in formula (17). Illustrative
examples of the aromatic bisanhydrides (20) include 3.3-
HC CH bis4-(3,4-dicarboxyphenoxy)phenylpropane dianhydride;
HC CH 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl ether dianhydride:
4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhy
t s
dride: 4,4'-bis(3,4-dicarboxyphenoxy)benzophenone dian
hydride; 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfone
25 dianhydride; 2.2-bis(4-(2,3-dicarboxyphenoxy)phenylpro
CH pane dianhydride: 4,4'-bis(2,3-dicarboxyphenoxy)diphenyl
HC CH ether dianhydride; 4,4'-bis(2,3-dicarboxyphenoxy)diphenyl
sulfide dianhydride; 4,4'-bis(2,3-dicarboxyphenoxy)benzo
phenone dianhydride: 4,4'-bis(2,3-dicarboxyphenoxy)di
30 phenyl sulfone dianhydride: 4-(2,3-dicarboxyphenoxy)-4-
(3,4-dicarboxyphenoxy)diphenyl-2.2-propane dianhydride;
4-(2,3-dicarboxyphenoxy)-4-(3,4-dicarboxyphenoxy)di
wherein Q' is -O-, -S , C(O)—, -SO. , -SO , phenyl ether dianhydride: 4-(2,3-dicarboxyphenoxy)-4-(3.
and —CH2— and a halogenated derivative thereof (which 4-dicarboxyphenoxy)diphenyl sulfide dianhydride: 4-(2,3-
includes perfluoroalkylene groups) wherein y is an integer 35 dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)
from 1 to 5. In a specific embodiment R is a m-phenylene or benzophenone dianhydride and 4-(2,3-dicarboxyphenoxy)-
p-phenylene. 4'-(3,4-dicarboxyphenoxy)diphenyl sulfone dianhydride.
The group Z in formula (17) is also a divalent hydrocar Combinations comprising at least one of the foregoing
bon group, and can be an aromatic C-2 monocyclic or aromatic bisanhydrides (20) can be used.
polycyclic moiety optionally Substituted with 1 to 6 C's 40 Illustrative examples of diamines (21) include ethylene
alkyl groups, 1 to 8 halogenatoms, or a combination thereof, diamine, propylenediamine, trimethylenediamine, diethyl
provided that the valence of Z is not exceeded. Exemplary enetriamine, triethylenetetramine, hexamethylenediamine,
groups Z include groups derived from a dihydroxy com heptamethylenediamine, octamethylenediamine, nonameth
pound of formula (3). A specific example of a group Z is a ylenediamine, decamethylenediamine, 1,12-dodecanedi
divalent group of formula (19) 45 amine, 1,18-octadecanediamine, 3-methylheptamethylene
diamine, 4,4-dimethylheptamethylenediamine,
4-methylnonamethylenediamine, 5-methylnonamethylene
(19) diamine, 2,5-dimethylhexamethylenediamine, 2,5-dimeth
ylheptamethylenediamine, 2,2-dimethylpropylenediamine,
50 N-methyl-b is (3-aminopropyl)amine, 3-methoxyhexameth
ylenediamine, 1.2-bis(3-aminopropoxy)ethane, bis(3-
aminopropyl)sulfide, 1,4-cyclohexanediamine, bis-(4-
aminocyclohexyl)methane, m-phenylenediamine,
wherein Q is —O— —S , C(O)— —SO. , —SO—, p-phenylenediamine, 2,4-diaminotoluene, 2,6-diaminotolu
and —CH2— and a halogenated derivative thereof (in 55 ene, m-xylylenediamine, p-xylylenediamine, 2-methyl-4,6-
cluding a perfluoroalkylene group) wherein y is an integer diethyl-1,3-phenylene-diamine, 5-methyl-4,6-diethyl-1,3-
from 1 to 5. In a specific embodiment Z is derived from phenylene-diamine, benzidine, 3,3'-dimethylbenzidine, 3,3'-
bisphenol A wherein Q is 2.2-isopropylidene. dimethoxybenzidine, 1.5-diaminonaphthalene, bis(4-
aminophenyl)methane, bis(2-chloro-4-amino-3,5-
More specifically, the first polymer comprises blocks of diethylphenyl)methane, bis(4-aminophenyl)propane, 2.4-bis
10 to 1,000 or 10 to 500 structural units of formula (17) (amino-t-butyl)toluene, bis(p-amino-t-butylphenyl)ether,
wherein R is a divalent group of formula (19) wherein Q' is bis(p-methyl-o-aminophenyl)benzene, bis(p-methyl-o-
—CH2— wherein y is an integer from 1 to 5 or a aminopentyl)benzene, 1,3-diamino-4-isopropylbenzene, bis
halogenated derivative thereof, and Z is a group of formula (4-aminophenyl)sulfide, bis (4-aminophenyl)sulfone, bis(4-
(19). In a specific embodiment, R is m-phenylene, p-arylene 65 aminophenyl)ether and 1,3-bis(3-aminopropyl)
diphenylsulfone, or a combination thereof, and Z is 2.2-(4- tetramethyldisiloxane. Combinations comprising at least
phenylene)isopropylidene. one of the foregoing aromatic bisanhydrides can be used.
 US 9,453,128 B2
19 20
Aromatic diamines are often used, especially m- and p-phe The sequential intercondensation of the polysiloxane
nylenediamine, Sulfonyl dianiline and combinations thereof. diamine (22) and the diamine (21) with the aromatic bisan
The poly(siloxane-etherimide)s can be formed by polym hydride (20) can be achieved in either a single container or
erization of an aromatic bisanhydride (20) and a diamine in multiple containers. In the 'single pot” procedure, an off
component comprising an organic diamine (21) or mixture Stoichiometric amount of either the polysiloxane diamine
of diamines (21), and a polysiloxane diamine of formula (22) or the diamine (21), is intercondensed with the aromatic
(22) bisanhydride (20) in the presence of an inert organic solvent
to produce a mixture of polyimide oligomer chain stopped
(22) 10
with either intercondensed diamine or aromatic bisanhy
R R dride. An excess of aromatic bisanhydride (2) or diamine
(21) corresponding to the chain stopping units also can be
NH-R jo -R-Ni, present. The oligomer can be either a silicone polyimide, or
R R an oligomer of intercondensed aromatic bisanhydride and
E
15 diamine. There is then added to the same pot, after the initial
period of oligomer formation, the remaining diamine, which
wherein R and E are as described in formula (9), and R is can be either the polysiloxane diamine (22) or the diamine
each independently a C-Co hydrocarbon, in particular a (21) and optionally sufficient aromatic bisanhydride (20) to
C-C arylene, alkylene, or arylenealkylene group. In an achieve stoichiometry. There also can be added to the
embodiment R is a C-C alkyl group, specifically a resulting intercondensation mixture, chain stoppers, such a
C-C alkyl group Such as propylene, and E has an average phthalic anhydride or monofunctional arylamine Such as
value of 5 to 100, 5 to 75, 5 to 60, 5 to 15, or 15 to 40. aniline to control the molecular weight of the 55 final
Procedures for making the polysiloxane diamines of formula silicone polyimide. In the multiple pot procedure, diamine
oligomer and polysiloxane diamine oligomer can be inter
(22) are well known in the art. For example, an aminoor 25 condensed with aromatic bisanhydride in separate contain
ganotetraorganodisiloxane can be equilibrated with an octa ers. The multiple pot procedure can achieve satisfactory
organocyclotetrasiloxane, Such as octamethylcyclotetrasi results in instances where two or more oligomers are
loxane, to increase the block length of the required providing a Substantially stoichiometric balance
polydiorganosiloxane. maintained between total aromatic bisanhydride and
In some poly(siloxane-etherimide)s the diamine compo 30 diamine.
nent can contain 20 to 50 mole percent (mol%), or 25 to 40 Oligomer block size can vary depending upon the pro
mol % of polysiloxane diamine (22) and about 50 to 80 mol portions of polysiloxane diamine (22) and the diamine (21)
%, or 60 to 75 mol % of diamine (21), for example as used, per mole of aromatic bisanhydride (20). For example,
described in U.S. Pat. No. 4,404.350. The diamine compo for a “three block, oligomer, a 4/3 ratio can be used, i.e. 4
nents can be physically mixed prior to reaction with the 35
moles of diamine for 3 moles of bisanhydride. Reaction can
bisanhydride(s), thus forming a Substantially random copo continue until the intercondensation of anhydride and amine
lymer. Alternatively, block or alternating copolymers can be functional groups are achieved and the water of reaction is
formed by selective reaction of (21) and (22) with aromatic completely removed. Such as by azeotroping from the reac
dianhydrides (20), to make polyimide blocks that are sub tion mixture.
sequently reacted together. Thus, the poly(siloxane-imide) 40 Examples of Such poly(siloxane-etherimide) are
copolymer can be a block, random, or graft copolymer. described in U.S. Pat. Nos. 4,404,350, 4,808,686 and 4,690,
In an embodiment, the poly(siloxane-etherimide) is made 997. In an embodiment, the poly(siloxane-etherimide) has
by sequentially intercondensing attemperatures in the range units of formula (23)

(23)
O O O O

21 N 21 N
R-N -HO-Z-O-H- N-R-HSO Si-R-N -HO-Z-O-H- N
N 21 N 2
E
O O O O pi

of 100° C. to 300° C., the polysiloxane diamine (22) and the wherein E is as in formula (9), R and Z are as in formula
diamine (21) with aromatic bisanhydride (20). A substan (17), R is as in formula (22), and n is an integer from 5 to
tially inert organic solvent can be used to facilitate inter 60 100.
condensation, for example, dipolar aprotic solvents such as It is also possible to incorporate polysiloxane units into a
dimethylformamide, N-methyl-2-pyrrolidone, cresol, ortho poly(siloxane-etherimide) by reaction of diamine (21) with
dichlorobenzene, and the like. A polymerization catalyst can an anhydride component comprising aromatic anhydride
be used at 0.025 to 1.0% by weight, based on the weight of
the reaction mixture. Such as an alkali metal aryl phosphi 65 (20) and a polysiloxane dianhydride of formula (24), a
nate or alkali metal aryl phosphonate, for example, sodium siloxane dianhydride of formula (25), or a combination
phenylphosphinate. thereof
 US 9,453,128 B2
21
(27)

wherein R and W are as defined in formula (26). In an

10 embodiment, n, m, and q are each 0 and W is isopropylidene.
These poly(siloxane-Sulfone) copolymers may be made by
reaction of arylene Sulfone-containing, arylene ether-con
(25) taining, or arylene ether Sulfone-containing oligomers with
O O
functionalized polysiloxanes to form random or block copo
1 fill
O Air jo - O
15 lymers. Examples of the poly(siloxane-Sulfones and their
manufacture, in particular poly(siloxane-arylene Sulfone)S
and poly(siloxane-arylene ether Sulfone)S. are disclosed in
Y O
R E R Y
O
U.S. Pat. Nos. 4,443,581, 3,539,657, 3,539,655 and 3,539,
655.
The relative amount of polysiloxane units and arylene
wherein R and E are as described in structure (9) and each sulfone units or arylene ether sulfone units in the poly
Ar is independently a C-C aromatic group. In some (siloxane-Sulfone) copolymers depends on the desired prop
poly(siloxane-etherimide)s the dianhydride component can erties, and are carefully selected using the guidelines pro
contain 20 to 50 mole percent (mol%), or 25 to 40 mol % vided herein. In particular, the block or graft poly(siloxane
25 sulfone) is selected and used in amount effective to provide
of polysiloxane dianhydride (24) and/or (25) and about 50 to
80 mol %, or 60 to 75 mol % of dianhydride (20), for the desired wt % of polysiloxane units in the composition.
example as described in U.S. Pat. No. 4,404.350. The In an embodiment the poly(siloxane-arylene ether Sulfone)
anhydride components can be physically mixed prior to comprises 10 to 50 wt %, 10 to 35 wt %, or 10 to 30 wt %
reaction with the diamine(s), thus forming a substantially polysiloxane units, based on the total weight of the poly
random copolymer. Alternatively, block or alternating copo 30 (siloxane-arylene ether Sulfone).
lymers can be formed by selective reaction of anhydrides Other poly(siloxane) copolymers include poly(siloxane
(20) and (24) and/or (25) with diamine (21), to make arylene ether)s wherein the first repeating units are blocks of
polyimide blocks that are subsequently reacted together. units of formula (28)
The relative amount of polysiloxane units and etherimide 35
units in the poly(siloxane-etherimide) depends on the
desired properties, and are carefully selected using the (28)
guidelines provided herein. In particular, as mentioned
above, the block or graft poly(siloxane-etherimide) copoly
mer is selected to have a certain average value of E, and is 40
selected and used in amount effective to provide the desired
wt % of polysiloxane units in the composition. In an
embodiment the poly(siloxane-etherimide) comprises 10 to
50 wt %, 10 to 40 wt %, or 20 to 35 wt % polysiloxane units,
based on the total weight of the poly(siloxane-etherimide).
Other poly(siloxane) copolymers include poly(siloxane 45
wherein Z' is each independently halogen or C-C2 hydro
Sulfone) copolymers such as poly(siloxane-arylene Sulfone)S carbon group with the proviso that that the hydrocarbon
and poly(siloxane-arylene ether sulfone)s wherein the first group is not tertiary hydrocarbon group; and Z is each
repeating units are units of formula (26) independently hydrogen, halogen, or C-C hydrocarbon

(26)

wherein R', R, and R are each independently a halogen 60 group with the proviso that that the hydrocarbon group is not
atom, a nitro group, a cyano group, a Caliphatic radical, tertiary hydrocarbyl. In an embodiment, Z is hydrogen and
C. cycloaliphatic radical, or a C-2 aromatic radical, n, Z' is methyl.
m, q are each independently 0 to 4; and W is a Co Poly(siloxane-arylene ether)s and methods for the manu
facture of poly(siloxane-arylene ether)s have been described
cycloaliphatic radical or a C-C aromatic radical. In an 65 in U.S. Pat. No. 5,204,438, which is based on the conversion
embodiment, the first units (26) contain at least 5 mol % of of phenol-siloxane macromers to a silicone polyphenylene
aromatic ether units of formula (27) ether graft copolymer; and in U.S. Pat. No. 4,814,392. U.S.
 US 9,453,128 B2
23 24
Pat. No. 5,596,048 discloses reaction of a polyarylene ether
with a hydroxyaromatic terminated siloxane in the presence O O
(29)
of an oxidant.
The relative amount of polysiloxane units and arylene |
-C-T-C-O-D-O-
ether units in the poly(siloxane-arylene ether) depends on
the desired properties, and are carefully selected using the wherein D is a divalent group derived from a dihydroxy
guidelines provided herein. In particular, the block or graft compound, and can be, for example, a C2-lo alkylene group.
poly(siloxane-arylene ether) copolymer is selected and used a C-2 alicyclic group, a C-2 aryl, or a polyoxyalkylene
in amount effective to provide the desired wt % of polysi 10 group in which the alkylene groups contain 2 to 6 carbon
loxane units in the composition. In an embodiment the atoms, specifically 2, 3, or 4 carbon atoms. In an embodi
poly(siloxane-arylene ether) comprises 1 to 80 wt %, 5 to 50 ment, D is a C-so alkylene having a straight chain, branched
wt %, 10 to 35 wt %, or 10 to 30 wt % polysiloxane units, chain, or cyclic (including polycyclic) structure. In another
based on the total weight of the poly(siloxane-arylene ether). embodiment, D is derived from an aromatic dihydroxy
Other poly(siloxane) copolymers include poly(siloxane 15 compound of formula (3), an aromatic dihydroxy compound
arylene ether ketone)s wherein the first repeating units are of formula (8), or a combination thereof. T in formula (29)
units of formula (29) is a divalent group derived from a dicarboxylic acid, and can
be, for example, a C2-io alkylene group, a C-20 alicyclic
(29) group, a C-2 alkyl aromatic group, or a C-2 aromatic
group. Examples of aromatic dicarboxylic acids that can be
used to prepare the polyester units include isophthalic or
terephthalic acid, 1,2-di(p-carboxyphenyl)ethane, 4,4'-dicar
boxydiphenyl ether, 4,4'-bisbenzoic acid, and combinations
25 comprising at least one of the foregoing acids. Acids con
taining fused rings can also be present, such as in 1,4-, 1.5-,
or 2,6-naphthalenedicarboxylic acids. Specific dicarboxylic
acids are terephthalic acid, isophthalic acid, naphthalene
wherein Z' is each independently halogen or C-C2 hydro dicarboxylic acid, cyclohexane dicarboxylic acid, or com
carbon group with the proviso that that the hydrocarbon 30 binations comprising at least one of the foregoing. A specific
group is not tertiary hydrocarbon group; and Z is each dicarboxylic acid comprises a combination of isophthalic
independently hydrogen, halogen, or C-C hydrocarbon acid and terephthalic acid wherein the weight ratio of
group with the proviso that that the hydrocarbon group is not isophthalic acid to terephthalic acid is 100:0 to 0:100, or
tertiary hydrocarbyl. In an embodiment Zi and Z' are hydro 99:1 to 1:99, or 91:9 to 2:98.
gen. The arylene ether units and arylene ketone units can be 35 In another specific embodiment, D is a C- alkylene and
present in random order, as blocks (i.e., AABB, or alternat T is p-phenylene, m-phenylene, naphthalene, a divalent
ing (i.e., ABAB), or a combination thereof. cycloaliphatic group, or a combination comprising at least
The relative amount of polysiloxane units and arylene one of the foregoing. Alternatively, the ester unit can be an
ether ketone units in the poly(siloxane-arylene ether ketone) arylate ester unit derived from the reaction of an aromatic
depends on the desired properties, and are carefully selected 40 dihydroxy compound of formula (8) (e.g., resorcinol) with a
using the guidelines provided herein. In particular, the block combination of isophthalic and terephthalic diacids (or
or graft poly(siloxane-arylene ether ketone) copolymer is derivatives thereof). In another specific embodiment, the
selected and used in amount effective to provide the desired ester unit is derived from the reaction of bisphenol A with a
wt % of polysiloxane units in the composition. In an combination of isophthalic acid and terephthalic acid. A
embodiment the poly(siloxane-arylene ether ketone) com 45 specific poly(siloxane-ester-carbonate) comprises siloxane
prises 5 to 50 wt %, 10 to 35 wt %, or 10 to 30 wt % blocks (9), ester units derived from resorcinol and
polysiloxane units, based on the total weight of the poly isophthalic and/or terephthalic diacids, and carbonate units
(siloxane-arylene ether ketone). (1) derived from resorcinol, bisphenol A, or a combination
Poly(siloxane-esters), including poly(siloxane-ester-car of resorcinol and bisphenol A in a molar ratio of resorcinol
bonate) copolymers can be used provided that the ester units 50 carbonate units to bisphenol A carbonate units of 1:99 to
are selected so as to not significantly adversely affect the 99:1, specifically 20:80 to 80:20. The molar ratio of ester
desired properties of the poly(siloxane) copolymer compo units to carbonate units in these copolymers can vary
sitions, in particular low Smoke density and low heat release, broadly, for example 1:99 to 99:1, specifically 10:90 to
as well as other properties such as stability to UV light. For 90:10, more specifically 25:75 to 75:25, depending on the
example, aromatic ester units can diminish color stability of 55 desired properties of the final composition. Poly(siloxane
the poly(siloxane) copolymer compositions during process ester-carbonate)s of this type can include siloxane blocks
ing and when exposed to UV light. Aromatic ester units can (9), and blocks comprising 50 to 99 mol% arylate ester units
also decrease the melt flow of the thermoplastic composi (e.g., resorcinol ester units) and 1 to 50 mol % aromatic
tion. On the other hand, the presence of aliphatic ester units carbonate units including resorcinol carbonate units and
can diminish the heat release values. In an embodiment the 60 optionally bisphenol A carbonate units. Such copolymers are
poly(siloxane-esters), including poly(siloxane-ester-carbon described in U.S. Pat. No. 7,605,221.
ate) copolymers comprise 10 to 50 wt %, 10 to 35 wt %, or Any of the foregoing poly(siloxane) copolymers can have
10 to 30 wt % polysiloxane units. an Mw of 5,000 to 250,000, specifically 10,000 to 200,000
The first repeating units in the poly(siloxane-esters) or grams per mole (Daltons), even more specifically 15,000 to
poly(siloxane-ester-carbonate)s further contain, in addition 65 100,000 Daltons, as measured by gel permeation chroma
to the siloxane blocks of formula (9), repeating units of tography (GPC), using a crosslinked styrene-divinylbenzene
formula (29) column and calibrated to polycarbonate references. GPC
 US 9,453,128 B2
25 26
samples are prepared at a concentration of 1 mg/ml, and are dihydroxy aromatic compound, specifically bisphenol A. In
eluted at a flow rate of 1.5 ml/min. an embodiment, no other monomers are present in the
Melt volume flow rate (often abbreviated “MVR) mea TBBPA copolymer.
Sures the rate of extrusion of a poly(siloxane) copolymer Combinations of different TBBPA copolymers can be
through an orifice at a prescribed temperature and load. The 5 used. Specifically, a TBBPA copolymer can be used having
foregoing poly(siloxane) copolymers can have an MVR, phenol endcaps. Also specifically, a TBBPA carbonate can
measured at 300° C. under a load of 1.2 kg, of 0.1 to 200 be used having 2,4,6-tribromophenol endcaps can be used.
cubic centimeters per 10 minutes (cm/10 min), specifically The TBBPA copolymers can have an Mw from 18,000 to
1 to 100 cm/10 min. 30,000 Daltons, specifically 20,000 to 30,000 Daltons as
In some embodiments a combination of two or more 10 measured by gel permeation chromatography (GPC) using
different poly(siloxane) copolymers are used to obtain the polycarbonate standards.
desired properties. The poly(siloxane) copolymers can differ Alternatively, the poly(siloxane) copolymer is used with
in one or more of a property (e.g., polydispersity or molecu a brominated oligomer. Thus, instead of a TBBPA copoly
mer as the second polymer in certain embodiments, a
lar weight) or a structural feature (e.g., the value of E, the 15 brominated oligomer having an Mw of 18,000 Daltons or
number of blocks of E, or the identity of the first repeating less is used. The term “brominated oligomer' is used herein
unit). For example, a poly(siloxane-carbonate) having a for convenience to identify a brominated compound com
relatively lower weight percent (e.g., 3 to 10 wt %, or 6 wit prising at least two repeat units with bromine Substitution,
%) of relatively longer length (E having an average value of and having an Mw of less than 18,000 Daltons. The bromi
30-60) can provide a composition of lower colorability, nated oligomer can have an Mw of 1,000 to 18,000 Daltons,
whereas a poly(siloxane-carbonate) having a relatively specifically 2,000 to 15,000 Daltons, and more specifically
higher weight percent of siloxane units (e.g., 15 to 25 wt %, 3,000 to 12,000 Daltons.
or 20 wt %) of the same length siloxane units, can provide In certain embodiments the brominated oligomer has a
better impact properties. As another example, For example, bromine content of 40 to 60 wt %, specifically 45 to 55 wt
a poly(siloxane-carbonate) having a relatively lower weight 25 %, more specifically 50 to 55 wt %. The specific brominated
percent (e.g., 3 to 10 wt %, or 6 wt %) of relatively longer oligomer and the amount of brominated oligomer are
length (E having an average value of 30-60) can provide a selected to provide at least 7.8 wt % bromine, specifically
composition of lower colorability, whereas a poly(siloxane 7.8 to 14 wt % bromine, more specifically 8 to 12 wt %
carbonate) having a relatively higher weight percent of bromine, each based on the total weight of first polymer, the
siloxane units (e.g., 15 to 25 wt %, or 20 wt %) of the same 30 brominated oligomer, and the optional additional polycar
length siloxane units, can provide better impact properties. bonate. In other embodiments, the specific brominated oli
Use of a combination of these two poly(siloxane-carbonate)S gomer and the amount of brominated oligomer are selected
can provide a composition having both good colorability and to provide at least 9.0 wt % bromine, specifically 9.0 to 13
impact properties. Similarly, a poly(siloxane-carbonate) can wt % bromine based on the total weight of first polymer, the
be used with a poly(siloxane-etherimide) to improve impact.
35 brominated oligomer, and the optional additional polycar
bonate.
The first polymer, i.e., the poly(siloxane) copolymer, is The brominated oligomer can be a brominated polycar
used with a second brominated polymer, wherein the type bonate oligomer derived from brominated aromatic dihy
and amount of the brominated polymer is selected so as to droxy compounds (e.g., brominated compounds of formula
provide at least 7.8 wt., or at least 9.0 wt.% bromine to the 40 (1)) and a carbonate precursor, or from a combination of
composition as described above. As used herein, a "bromi brominated and non-brominated aromatic dihydroxy com
nated polymer is inclusive of homopolymers and copoly pounds, e.g., of formula (1), and a carbonate precursor.
mers, and includes molecules having at least 2, at least 5, at Brominated polycarbonate oligomers are disclosed, for
least 10, or at least 20 repeat units with bromine substitution, example, in U.S. Pat. Nos. 4,923,933, 4,170,711, and 3,929,
and an Mw of at least 1,000 Daltons, for example 1,000 to 45 908. Examples of brominated aromatic dihydroxy com
50,000 Daltons. pounds include 2.2-bis(3,5-dibromo-4-hydroxyphenyl)pro
In certain embodiments, the second polymer is a specific pane, bis(3,5-dibromo-4-hydroxyphenyl)menthanone, and
brominated polycarbonate, i.e., a polycarbonate containing 2,2',6,6'-tetramethyl-3,3',5,5'-tetrabromo-4,4'-biphenol.
brominated carbonate units derived from 2,2',6,6'-tetra Examples of non-brominated aromatic dihydroxy com
bromo-4,4'-isopropylidenediphenol (TBBPA) and carbonate 50 pounds for copolymerization with the brominated aromatic
units derived from at least one dihydroxy aromatic com dihydroxy compounds include bisphenol A, bis(4-hydroxy
pound that is not TBBPA. The dihydroxy aromatic com phenyl)methane, 2.2-bis(4-hydroxy-3-methylphenyl)pro
pound can be one of formula (5), (6), (7), (8), (9), or (10). pane, 4.4-bis(4-hydroxyphenyl)heptane, and (3,3'-dichloro
In a specific embodiment the dihydroxy aromatic compound 4,4'-dihydroxydiphenyl)methane. Combinations of two or
is of formula (5), more specifically dihydroxy aromatic 55 more different brominated and non-brominated aromatic
compound (5) containing no additional halogenatoms. In an dihydroxy compounds can be used. If a combination of
embodiment, the dihydroxy aromatic compound is Bisphe aromatic dihydroxy compounds is used, then the combina
nol A. tions can contain 25 to 55 mole percent of the brominated
The relative ratio of TBBPA to the dihydroxy aromatic aromatic dihydroxy compounds and 75 to 65 mole percent
compound used to manufacture the TBBPA copolymer will 60 of a non-brominated dihydric phenol. Branched brominated
depend in some embodiments on the amount of the TBBPA polycarbonate oligomers can also be used, as can composi
copolymer used and the amount of bromine desired in the tions of a linear brominated polycarbonate oligomer and a
thermoplastic composition. In an embodiment, the TBBPA branched brominated polycarbonate oligomer. Combina
copolymer is manufactured from a composition having 30 to tions of different brominated copolycarbonate oligomers can
70 wt % of TBBPA and 30 to 70 wt % of the dihydroxy 65 be used. Various endcaps can be present, for example
aromatic compound, specifically Bisphenol A, or specifi polycarbonates having phenol endcaps or 2,4,6-tribro
cally 45 to 55 wt % of TBBPA and 45 to 55 wt % of the mophenol endcaps can be used.
 US 9,453,128 B2
27 28
Other types of brominated oligomers can be used, for that is not same as the first poly(siloxane-carbonate) or the
example brominated epoxy oligomers. Examples of bromi TBBPA copolymer. Specifically in certain embodiments, the
nated epoxy oligomers include those derived from Bisphe one or more third polymers do not contain either polysilox
nol A, hydrogenated Bisphenol A, Bisphenol-F, Bisphenol ane units or bromine. In the alternative thermoplastic com
S. novolak epoxies, phenol novolac epoxies, cresol novolac positions comprising the poly(siloxane-carbonate) and the
epoxies, N-glycidyl epoxies, glyoxal epoxies dicyclopenta brominated oligomer, an additional polycarbonate that is not
diene phenolic epoxies, silicone-modified epoxies, and epsi the same as the first poly(siloxane) or the brominated
lon-caprolactone modified epoxies. Combinations of differ oligomer is present. Specifically, the additional polycarbon
ent brominated epoxy oligomers can be used. Specifically, a ate does not contain polysiloxane units or bromine When the
tetrabromobisphenol A epoxy be used, having 2,4,6-tribro 10 optional one or more third polymer is a polycarbonate, the
mophenol endcaps. An epoxy equivalent weight of 200 to polymer comprises units of formula (1) as described above,
3000 can be used. specifically wherein R' is derived from the dihydroxy aro
In some embodiments a combination of two or more matic compound (2) (3), (8), or a combination thereof, and
different brominated polymers are used to obtain the desired more the specifically dihydroxy aromatic compound (3)
properties. The brominated polymers can differ in one or 15 containing no additional halogen atoms. In an embodiment,
more of a property (e.g., polydispersity or molecular weight) at least 60%, at least 80%, or at least 90% of the R' units are
or a structural feature (e.g., the identity of the repeating bisphenol A units. In an embodiment, the optional one or
units, the presence of copolymer units, or the amount of more third polymer (including the additional polycarbonate)
bromine in the polymer). For example, two different TBBPA is a homopolymer with bisphenol A carbonate units. It is also
copolymers can be used, or a combination of a TBBPA possible for the one or more third polycarbonates or addi
copolymer and a brominated epoxy oligomer. Of course, two tional polycarbonates to contain units other than polycar
or more different poly(siloxane) copolymers can be used bonate units, for example ester units (29), provided that the
with two or more different brominated polymers. ester units are selected so as to not significantly adversely
The poly(siloxane) copolymer compositions can further affect the desired properties of the poly(siloxane) copolymer
optionally comprise one or more polymers additional to the 25 compositions as described above. In an embodiment, the
poly(siloxane) copolymer and the brominated polymer, ester units are arylate ester unit derived from the reaction of
which can be referred to herein as "one or more third an aromatic dihydroxy compound of formula (8) (e.g.,
polymers' for convenience. The one or more third polymers resorcinol) with a combination of isophthalic and
can be homopolymers or copolymers and can have repeating terephthalic diacids (or derivatives thereof). In another spe
units that are the same or different from first repeating units 30 cific embodiment, the ester unit is derived from the reaction
of the poly(siloxane) copolymer. The one or more third of bisphenol A with a combination of isophthalic acid and
polymers can comprise different types of repeating units, terephthalic acid. A specific poly(ester-carbonate) comprises
provided that the type and amount of repeating units does ester units derived from resorcinol and isophthalic and/or
not significantly adversely affect the desired properties of terephthalic diacids, and carbonate units (1) derived from
the compositions, in particular low Smoke density and low 35 resorcinol, bisphenol A, or a combination of resorcinol and
heat release. The one or more third polymers can comprise bisphenol A in a molar ratio of resorcinol carbonate units to
carbonate units (1), imide units, etherimide units (17), bisphenol A carbonate units of 1:99 to 99:1, specifically
arylene ether sulfone units (26), arylene ether units (28), 20:80 to 80:20. The molar ratio of ester units to carbonate
ester units (29), or a combination of units comprising at least units in these copolymers can vary broadly, for example 1:99
one of the foregoing. However, in an embodiment, the one 40 to 99:1, specifically 10:90 to 90:10, more specifically 25:75
or more third polymers do not contain either polysiloxane to 75:25, depending on the desired properties of the final
units or bromine. The one or more third polymers can have composition.
an Mw, for example, of 5,000 to 500,000 Daltons, specifi In addition to the poly(siloxane) copolymer, brominated
cally 10,000 to 250,000 Daltons, or 10,000 to 100,000 polymer, and one or more optional third polymers, the
Daltons, as measured by gel permeation chromatography 45 poly(siloxane) copolymer compositions can include various
(GPC), using a crosslinked styrene-divinylbenzene column additives ordinarily incorporated into flame retardant com
and calibrated to polycarbonate references. GPC samples are positions having low Smoke density and low heat release,
prepared at a concentration of 1 mg/ml, and are eluted at a with the proviso that the additive(s) are selected so as to not
flow rate of 1.5 ml/min. The one or more third polymers can adversely affect the desired properties of the poly(siloxane)
have an MVR, measured at 300° C. under a load of 1.2 kg, 50 copolymer composition significantly, in particular low
of 0.1 to 200 cubic centimeters per 10 minutes (cm/10 min), smoke density low heat release. Such additives can be mixed
specifically 1 to 100 cm/10 min. at a Suitable time during the mixing of the components for
The one or more third polymers is selected and used in an forming the composition. Exemplary additives include fill
amount to provide the desired characteristics to the compo ers, reinforcing agents, antioxidants, heat stabilizers, light
sitions. The amount of the one or more third polycarbonates 55 stabilizers, ultraviolet (UV) light stabilizers, plasticizers,
can be 0 to 85 wt %, 1 to 80 wt %, 5 to 75 wt %, 8 to 60 lubricants, mold release agents, antistatic agents, colorants
wt %, 20 to 50 wt %, or 30 to 40 wt %, based on the total Such as Such as titanium dioxide, carbon black, and organic
weight of the first polymer, the second polymer, and the one dyes, surface effect additives, radiation stabilizers, addi
or more third polymers. In a specific embodiment the third tional flame retardants, and anti-drip agents. A combination
polymer is present in an amount of 8 to 50 wt %, the 60 of additives can be used. In general, the additives are used
polysiloxane unit is present in an amount of 1.5 to 3.5 wt %, in the amounts generally known to be effective. The total
and the bromine is present in an amount of 7.8 to 13 wt %, amount of additives (other than any filler or reinforcing
each based on the sum of the wt % of the first, second, and agents) is generally 0.01 to 25 parts per parts per hundred
third polymers. parts by weight of the combination of the first, second, and
In a specific embodiment, in the thermoplastic composi 65 optional one or more third polymers (PHR).
tions comprising a poly(siloxane-carbonate) and the TBBPA In an advantageous embodiment, it has been found that
copolymer, an optional third polycarbonate can be present certain important additives can be used without adversely
 US 9,453,128 B2
29 30
affecting the heat release and low smoke properties of the Plasticizers, lubricants, and/or mold release agents can
poly(siloxane) copolymer compositions significantly, in par also be present in the compositions. There is considerable
ticular UV stabilizers, heat stabilizers (including phosphi overlap among these types of materials, which include
tes), other flame retardants (such as Rimar salts) and certain phthalic acid esters such as dioctyl-4,5-epoxy-hexahy
colorants. The use of pigments such as titanium dioxide 5 drophthalate: tris-(Octoxycarbonylethyl)isocyanurate;
produces white compositions, which are commercially tristearin; di- or polyfunctional aromatic phosphates Such as
desirable. Pigments such as titanium dioxide (or other min resorcinol tetraphenyl diphosphate (RDP), the bis(diphenyl)
eral fillers) can be present in the poly(siloxane) copolymer phosphate of hydroquinone and the bis(diphenyl)phosphate
compositions in amounts of 0 to 12 PHR, 0.1 to 9 PHR, 0.5 of bisphenol A; poly-alpha-olefins; epoxidized soybean oil;
to 5 PHR, or 0.5 to 3 PHR.
10 silicones, including silicone oils; esters, for example, fatty
Exemplary antioxidant additives include organophosphi acid esters such as alkyl Stearyl esters, e.g., methyl Stearate,
tes such as tris(nonyl phenyl)phosphite, tris(2,4-di-t-butyl Stearyl Stearate, pentaerythritol tetrastearate, and the like;
phenyl)phosphite, bis(2,4-di-t-butylphenyl)pentaerythritol combinations of methyl Stearate and hydrophilic and hydro
diphosphite, distearyl pentaerythritol diphosphite; alkylated phobic nonionic Surfactants comprising polyethylene glycol
15 polymers, polypropylene glycol polymers, poly(ethylene
monophenols or polyphenols; alkylated reaction products of glycol-co-propylene glycol) copolymers, or a combination
polyphenols with dienes, such as tetrakismethylene(3,5-di comprising at least one of the foregoing glycol polymers,
tert-butyl-4-hydroxyhydrocinnamate)methane; butylated e.g., methyl Stearate and polyethylene-polypropylene glycol
reaction products of para-cresol or dicyclopentadiene; alky copolymer in a solvent, waxes such as beeswax, montan
lated hydroquinones: hydroxylated thiodiphenyl ethers: wax, and paraffin wax. Such materials are used in amounts
alkylidene-bisphenols; benzyl compounds; esters of beta-(3. of 0.1 to 1 PHR.
5-di-tert-butyl-4-hydroxyphenyl)-propionic acid with Additional monomeric flame retardants include organic
monohydric or polyhydric alcohols; esters of beta-(5-tert compounds that include phosphorus, bromine, and/or chlo
butyl-4-hydroxy-3-methylphenyl)-propionic acid with rine. Non-brominated and non-chlorinated phosphorus-con
monohydric or polyhydric alcohols; esters of thioalkyl or 25 taining flame retardants can be added for certain applica
thioaryl compounds such as distearylthiopropionate, dilau tions, for example organic compounds containing
rylthiopropionate, ditridecylthiodipropionate, octadecyl-3- phosphorus-nitrogen bonds.
(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, pentaeryth Inorganic flame retardants can also be used, for example
rityl-tetrakis3-(3,5-di-tert-butyl-4-hydroxyphenyl) salts of C alkyl Sulfonate salts such as potassium per
propionate; amides of beta-(3,5-di-tert-butyl-4- 30 fluorobutane Sulfonate (Rimar salt), potassium perfluorooc
hydroxyphenyl)-propionic acid, or combinations comprising tane Sulfonate, tetraethylammonium perfluorohexane Sul
at least one of the foregoing antioxidants. Antioxidants are fonate, and potassium diphenylsulfone sulfonate; salts such
used in amounts of 0.01 to 0.1 PHR. as NaCO, KCO, MgCO, CaCO, and BaCO, or fluoro
Exemplary heat stabilizer additives include organophos anion complexes such as LiAlF, BaSiF6, KBF. K. AlF.
phites such as triphenyl phosphite, tris-(2,6-dimethylphenyl) 35 KAIF, KSiF, and/or NaAlF. When present, inorganic
phosphite, tris-(mixed mono- and di-nonylphenyl)phos flame retardant salts are present in amounts of 0.01 to 10
phite; phosphonates such as dimethylbenzene phosphonate, PHR, more specifically 0.02 to 1 PHR.
phosphates such as trimethyl phosphate, or combinations Anti-drip agents in most embodiments are not used in the
comprising at least one of the foregoing heat stabilizers. poly(siloxane) copolymer compositions. Anti-drip agents
Heat stabilizers are used in amounts of 0.01 to 0.1 PHR. 40 include a fibril-forming or non-fibril forming fluoropolymer
Light stabilizers and/or ultraviolet light (UV) absorbing such as polytetrafluoroethylene (PTFE). The anti-drip agent
additives can also be used. Exemplary light stabilizer addi can be encapsulated by a rigid copolymer, for example
tives include benzotriazoles such as 2-(2-hydroxy-5-meth styrene-acrylonitrile copolymer (SAN). PTFE encapsulated
ylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)- in SAN is known as TSAN. Antidrip agents are substantially
benzotriazole and 2-hydroxy-4-n-octoxy benzophenone, or 45 absent or completely absent from the poly(siloxane) copo
combinations comprising at least one of the foregoing light lymer compositions in some embodiments.
stabilizers. Light stabilizers are used in amounts of 0.01 to Colorants can be used in the thermoplastic compositions.
5 PHR. The term “colorant’ as used herein includes pigments (gen
Exemplary UV absorbing additives include hydroxyben erally, particulate colorants that can be inorganic or organic)
Zophenones; hydroxybenzotriazoles; hydroxybenzotriaz 50 and dyes (generally organic colorants that are soluble in the
ines; cyanoacrylates; oxanilides; benzoxazinones; 2-(2H compositions, including fluorescent compounds). The colo
benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)-phenol rant can also have further properties such as electrical
(CYASORB(R) 5411): 2-hydroxy-4-n-octyloxybenzophe conductivity, or may be magnetically shielding. Examples of
none (CYASORB.R. 531): 2-4,6-bis(2,4-dimethylphenyl)-1, inorganic pigments are white pigments such as titanium
3,5-triazin-2-yl)-5-(octyloxy)-phenol (CYASORB(R) 1164); 55 dioxide in its three modifications of rutile, anatase or
2,2'-(1,4-phenylene)bis(4H-3,1-benzoxazin-4-one) (CYAS brookite, lead white, Zinc white, Zinc sulfide or lithopones:
ORB(R) UV-3638); 1,3-bis(2-cyano-3,3-diphenylacryloyl) black pigments such as carbon black, black iron oxide, iron
oxy-2.2-bis(2-cyano-3,3-diphenylacryloyl)oxymethyl manganese black or spinel black; chromatic pigments such
propane (UVINUL(R) 3030): 2,2'-(1,4-phenylene)bis(4H-3, as chromium oxide, chromium oxide hydrate green, cobalt
1-benzoxazin-4-one); 1,3-bis(2-cyano-3,3- 60 green or ultramarine green, cobalt blue, iron blue, Milori
diphenylacryloyl)oxy-2.2-bis(2-cyano-3.3- blue, ultramarine blue or manganese blue, ultramarine violet
diphenylacryloyl)oxymethylpropane; nano-size inorganic or cobalt and manganese violet, red iron oxide, cadmium
materials such as titanium oxide, cerium oxide, and Zinc sulfoselenide, molybdate red or ultramarine red; brown iron
oxide, all with particle size less than or equal to 100 oxide, mixed brown, spinel phases and corundum phases or
nanometers; or combinations comprising at least one of the 65 chromium orange; yellow iron oxide, nickel titanium yellow,
foregoing UV absorbers. UV absorbers are used in amounts chromium titanium yellow, cadmium sulfide, cadmium Zinc
of O.O1 to 5 PHR. sulfide, chromium yellow, Zinc yellow, alkaline earth metal
 US 9,453,128 B2
31 32
chromates, Naples yellow; bismuth vanadate, and effect Plastics Co. under the trade name TECHPOLYMERMBSR),
pigments such as interference pigments and luster pigments. low levels of TiO. A combination comprising at least one of
Other specific inorganic pigments include Pigment White 6, the foregoing types of light diffuser additives can be used.
Pigment White 7, Pigment Black 7, Pigment Black 11, Such diffuser particles can be added to high clarity or
Pigment Black 22, Pigment Black 27/30, Pigment Yellow medium clarity compositions to provide light-diffusive com
34, Pigment Yellow 35/37, Pigment Yellow 42, Pigment positions, for example in an amount of 0.05 to 10.0 wt %, 0.2
Yellow 53, Pigment Brown 24, Pigment Yellow 119, Pig to 3.0 wt %, 0.2 to 2.0 wt %, or 0.25 to 1.00 wt % of the light
ment Yellow 184, Pigment Orange 20, Pigment Orange 75, diffuser additives, based on the total weight of the polymers
Pigment Brown 6, Pigment Brown 29, Pigment Brown 31, in the in the thermoplastic compositions. In general, greater
Pigment Yellow 164, Pigment Red 101, Pigment Red 104, 10 amounts of light diffuser additive is used in the manufacture
Pigment Red 108, Pigment Red 265, Pigment Violet 15, of thinner articles to obtain the same degree of light diffu
Pigment Blue 28/36, Pigment Blue 29, Pigment Green 17, sion. In an embodiment the light diffuser additives are
and Pigment Green 26/50. A combination comprising at silicone particles. The light diffuser additives can also be
least one of the foregoing pigments can be used. Pigments, PMMA. Likewise, the light diffuser additives can be a
when present, can be used in amounts of about 0.1 to 9 PHR, 15 combination of silicone particles and PMMA particles.
0.5 to 5 PHR, or 0.5 to 3 PHR. Methods for forming the poly(siloxane) copolymer com
Exemplary dyes are generally organic materials and positions can vary. In an embodiment, the poly(siloxane)
include coumarin dyes such as coumarin 460 (blue), cou copolymer, brominated polymer, and optional one or more
marin 6 (green), nile red or the like; lanthanide complexes; third polymers are combined (e.g., blended) with any addi
hydrocarbon and Substituted hydrocarbon dyes; polycyclic tives (e.g., a mold release agent) Such as in a screw-type
aromatic hydrocarbon dyes; Scintillation dyes Such as extruder. The poly(siloxane) copolymer, brominated poly
oxazole or oxadiazole dyes; aryl- or heteroaryl-substituted mer, optional one or more third polymers and any additives
poly (Cs) olefin dyes; carbocyanine dyes; indanthrone can be combined in any order, and in form, for example,
dyes; phthalocyanine dyes; oxazine dyes; carbostyryl dyes; powder, granular, filamentous, as a masterbatch, and the
napthalenetetracarboxylic acid dyes; porphyrin dyes; bis 25 like. The composition can then be foamed, extruded into a
(styryl)biphenyl dyes; acridine dyes; anthraquinone dyes; sheet or optionally pelletized. Methods of foaming a ther
cyanine dyes; methine dyes; arylmethane dyes; azo dyes; moplastic composition using frothing or physical or chemi
indigoid dyes, thioindigoid dyes, diazonium dyes; nitro cal blowing agents are known and can be used. The pellets
dyes; quinone imine dyes; aminoketone dyes; tetrazolium can be used for molding into articles, foaming, or they can
dyes; thiazole dyes; perylene dyes, perinone dyes; bis 30 be used in forming a sheet of the flame retardant poly
benzoxazolylthiophene (BBOT); triarylmethane dyes; xan (siloxane) copolymer composition. In some embodiments,
thene dyes; thioxanthene dyes; naphthalimide dyes; lactone the composition can be extruded (or co-extruded with a
dyes; fluorophores such as anti-Stokes shift dyes which coating or other layer) in the form of a sheet and/or can be
absorb in the near infrared wavelength and emit in the processed through calendaring rolls to form the desired
visible wavelength, or the like; luminescent dyes such as 35 sheet.
7-amino-4-methylcoumarin: 3-(2-benzothiazolyl)-7-dieth As discussed above, the poly(siloxane) copolymer com
ylaminocoumarin: 2-(4-biphenylyl)-5-(4-t-butylphenyl)-1, positions are formulated to meet strict flammability require
3,4-oxadiazole; 2.5-bis-(4-biphenylyl)-oxazole; 2,2'-dim ments. The poly(siloxane) copolymer compositions have an
ethyl-p-quaterphenyl: 2,2-dimethyl-p-terphenyl: 3.5.3". E662 smoke test DsMax value of less than 200 when tested
5"-tetra-t-butyl-p-quinquephenyl; 2.5-diphenylfuran; 2.5- 40 at a thickness of 1.6 mm, and in Some embodiments can
diphenyloxazole; 4,4'-diphenylstilbene: further have a value of less than 150, less than 100, less than
4-dicyanomethylene-2-methyl-6-(p-dimethylaminostyryl)- 80, or 70 to 72. The poly(siloxane) copolymer compositions
4H-pyran: 1,1'-diethyl-2,2'-carbocyanine iodide; 3,3'-di can have an E662 Smoke test DSMax value of 70 to 200, 70
ethyl-4,4,5,5'-dibenzothiatricarbocyanine iodide; 7-dimeth to 150, 70 to 100, or 70 to 80.
ylamino-1-methyl-4-methoxy-8-azaquinolone-2, 45 The poly(siloxane) copolymer compositions further have
7-dimethylamino-4-methylduinolone-2: 2-(4-(4-dimethyl an OSU integrated 2 minute heat release test value of less
aminophenyl)-1,3-butadienyl)-3-ethylbenzothiazolium per than 65 kW-min/m and a peak heat release rate of less than
chlorate: 3-diethylamino-7-diethyliminophenoxazonium 65 kW/m as measured using the method of FAR F25.4, in
perchlorate: 2-(1-naphthyl)-5-phenyloxazole; 2,2'-p-phe accordance with Federal Aviation Regulation FAR 25.853
nylen-bis(5-phenyloxazole); rhodamine 700; rhodamine 50 (d). In some embodiments the poly(siloxane) copolymer
800; pyrene, chrysene, rubrene, coronene, or the like; or compositions can have an OSU integrated 2 minute heat
combinations comprising at least one of the foregoing dyes. release test value of less than 55 kW-min/m and a peak heat
Dyes can be used in amounts of 0.001 to 5 PHR. release rate of less than 55 kW/m as measured using the
Specific colorants include Solvent Red 135, Solvent Red method of FAR F25.4, in accordance with Federal Aviation
52, Pigment Blue 28, Pigment Blue 29:77007, Pigment Blue 55 Regulation FAR 25.853 (d).
60, and Solvent Violet 36. The poly(siloxane) copolymer compositions can further
Compositions used to form light-diffusive articles, for beformulated to have a haze less than 3% and a transmission
example light-diffusive railway vehicle components, can greater than 85%, each measured using the color space
further comprise a light diffuser additive, i.e., a plurality of CIE 1931 (Illuminant C and a 2° observer) or according to
light-diffusive particles to provide the light-diffusive effect. 60 ASTM D1003 (2007) using illuminant C at a 0.062 inch
Such particles are generally insoluble in the polymers of the (1.5 mm) thickness. In some embodiments, the poly(silox
thermoplastic compositions. Light-diffuser additives include ane) copolymer compositions can be formulated Such that an
silicone particles, e.g., polymethylsilsesquioxanes available article molded from the composition has all three of a haze
from GE Silicones under the trade name Tospearl R, cross less of than 15% and a transmission of greater than 75%,
linked poly(methyl methacrylate) (PMMA) and other 65 each measured using the color space CIE 1931 (Illuminant C
organic polymer particles, e.g., methyl methacrylate/ethyl and a 2° observer) or according to ASTM D1003 (2007)
eneglycol dimethacrylate copolymers available from Sekisui using illuminant C at a 0.125 inch (3.2 mm) thickness, and
 US 9,453,128 B2
33 34
a room temperature notched Izod impact of greater than 500 specifically 0 to 10%, 0.5 to 10%, and more specifically 1 to
J/m as measured according to ASTM D 256-10 at a 0.125 10%, and transparency as measured by % transmission can
inch (3.2 mm) thickness. be 70% or greater, specifically 80% or greater, greater than
Density (or specific gravity) is a critical factor in certain or equal to 75%, more specifically, greater than or equal to
railway vehicle components, such as components for high 5 90%, as measured using the color space CIE 1931 (Illumi
speed or high-performance railway vehicles, and the poly nant C and a 2° observer), or in accordance with ASTM
(siloxane) copolymer compositions can be formulated to D1003-07, Procedure A, illuminant C. These values can be
have lower densities, in particular a density of 1.31 g/cc or obtained even when average value of E in the poly(siloxane
less, 1.30 g/cc or less, or 1.29 g/cc or less. Such densities can carbonate) is higher, i.e., 25 to 200, 25 to 100, or 25 to 50.
generally be obtained when the amount of bromine is less 10 Such compositions often have higher siloxane levels, i.e., at
than 15 wt %, 13 wt %, 12 wt %, 11 wt %, 10 wt %, 9 wit least 2.0 wt %, specifically 2.0 to 8 wt %, 2.0 to 5 wt %, 2.0
%, 8 wt %, or 7.8 wt %, each based on the total weight of to 4 wt %, or 2.0 to 3.5 wt %, based on the total weight of
the first polymer, second polymer, and optional one or more the polymers in the thermoplastic compositions. The
third polymers. TBBPA copolymer can be present in an amount from 35 to
The poly(siloxane-carbonate) compositions can further be 15 50 wt %, and the bromine can be present in an amount of at
formulated to have a hydrogen to carbon ratio of 0.81:1 to least 7.8 wt %, specifically 8 to 25 wt %, more specifically
O.88:1. 8 to 13 wt %, or 10 to 13 wt %, each based on the total
The compositions can further have good melt viscosities, weight of the poly(siloxane-carbonate), TBBPA copolymer,
which aids processing. The poly(siloxane) copolymer com and optional one or more third polymers. The bromine
positions can have a melt volume flow rate (MVR, cubic containing oligomer can be present in an amount from 15 to
centimeter per 10 minutes (cc/10 min), according to ASTM 30 wt %, and the bromine can be present in an amount
D 1238) of less than 20, less than 19, less than 18, less than greater than 8 wt %, specifically 8 to 25 wt %, more
17, less than 16, less than 15, or less than 12, measured at specifically 8 to 13 wt %, based on the total weight of the
300° C./1.2 Kg at 360 second dwell. poly(siloxane-carbonate), the brominated oligomer, and the
In a specific embodiment, the thermoplastic compositions 25 additional polycarbonate.
(i.e., compositions containing poly(siloxane-carbonate), In another embodiment, even greater transparency can be
brominated polymer, and one or more optional third poly obtained when the poly(siloxane-carbonate) has an average
mers) are formulated to meet strict flammability require value of E that is lower, i.e., 5 to 75, 5 to 50, or 5 to 15,
ments. The compositions have an E662 smoke test DsMax specifically 7 to 13, or 8 to 12. Such compositions further
value of less than 200 when tested at a thickness of 1.6 mm, 30 have at least 30 wt %, specifically 30 to 80 wt %, or 30 to
and in some embodiments can further have a value of less 60 wt % of the poly(siloxane-carbonate), at least 20 wt %,
than 150, less than 100, less than 80, or 70 to 72. specifically 20 to 70 wt %, or 20 to 65 wt % of the TBBPA
The thermoplastic compositions can further have an OSU copolymer, and 0 to 50 wt %, specifically 0 to 30 wt %, or
integrated 2 minute heat release test value of less than 65 5 to 20 wt % of the optional third copolymer; lower siloxane
kW-min/m and a peak heat release rate of less than 65 35 levels, i.e., at least 0.3 wt %, specifically 0.3 to 2 wt %, 0.3
kW/m as measured using the method of FAR F25.4, in to 1 wt %, 0.3 to 0.8 wt %; and at least 5 wt %, specifically
accordance with Federal Aviation Regulation FAR 25.853 5 to 20 wt % bromine, 5 to 10 wt %, or 7.8 to 13 wt % of
(d). In some embodiments the thermoplastic compositions bromine, each based on the total weight of the first polymer,
can have an OSU integrated 2 minute heat release test value TBBPA copolymer, and optional one or more third poly
of less than 55 kW-min/m and a peak heat release rate of 40 CS.
less than 55 kW/m as measured using the method of FAR Density (or specific gravity), is a critical factor in certain
F25.4, in accordance with Federal Aviation Regulation FAR railway vehicle components, such as components for high
25.853 (d). speed or high-performance railway vehicles, and the ther
The thermoplastic compositions can further have excel moplastic compositions can be formulated to have lower
lent impact strength, particularly when the average value of 45 densities, in particular a density of 1.31 gram per cubic
E is higher, i.e., 25-200, 25-100, or 25 to 50. Such compo centimeter (g/cc) or less, 1.30 g/cc or less, or 1.29 g/cc or
sitions often have higher siloxane levels, i.e., at least 2.0 wt less. Such densities can generally be obtained when the
%, specifically 2.0 to 8 wt %, 2.0 to 5 wt %, 2.0 to 4 wt %, amount of bromine is less than 15 wt %, 13 wt %, 12 wt %,
or 2.0 to 3.5 wt %, each based on the total weight of the 11 wt %, 10 wt %, 9 wt %, 8 wt %, or 7.8 wt %, each based
poly(siloxane-carbonate), brominated copolymer, and 50 on the total weight of the poly(siloxane-carbonate), TBBPA
optional one or more third polymers, or based on the total copolymer, and optional one or more third polymers, or
weight of the first polymer, the brominated oligomer, and the based on the total weight of the poly(siloxane-carbonate),
optional additional polycarbonate. An article molded from the brominated oligomer, and the additional polycarbonate.
the thermoplastic compositions can have a notched Izod The compositions can further have good melt viscosities,
impact of greater than 500 J/m as measured according to 55 which aids processing. The thermoplastic compositions can
ASTM D 256-10 at a 0.125 inch (3.2 mm) thickness. In have a melt volume rate (MVR, cc/10 min. ASTM D 1238)
some embodiments the articles have 80% or 100% ductility. of less than 20, less than 19, less than 18, less than 17, less
In some applications, it can be desirable to have a than 16, less than 15, or less than 12, measured at 300°
transparent article. Haze values, as measured using the color C./1.2 Kg at 360 second dwell.
space CIE 1931 (Illuminant C and a 2° observer), or by 60 The thermoplastic compositions can advantageously be
ANSI/ASTM D1003 (2007), Procedure A, illuminant C, can formulated to have high clarity, medium clarity, to be
be a useful determination of the optical properties of the transparent, and/or to be light diffusive by adjusting the type
transparent flame retardant polycarbonate sheet. The lower and amount of the poly(siloxane-carbonate) and the addition
the haze levels, the better the transparency of the finished of light diffusive additives where light diffusivity is desired.
sheet. In an embodiment, haze levels for an article compris 65 Light-diffusive compositions can be used to manufacture
ing the thermoplastic composition, when measured at a articles that have good luminance, in which the article
thickness of 1.5 millimeters (mm), can be less than 10%, provides a high level of transmission of incident light (Such
 US 9,453,128 B2
35 36
as natural light through a window or skylight, or artificial value of 5 to 150, 5 to 65, or 5 to 20, for example 10. For
light) with a minimum light loss by reflectance or scattering, example, the siloxane-containing copolymer comprises a
where it is not desirable to either see the light source or other first siloxane-containing copolymer comprising an average
objects on the other side of the article. An article e.g., a sheet siloxane block length from 25 to 65, and a siloxane content
having a high degree of hiding power (i.e., luminance) 5 of 2 to 10 wt % based on the weight of the siloxane
allows a significant amount of light through, but is Sufi containing copolymer, wherein the first siloxane-containing
ciently diffusive so that a light source or image is not copolymer contributes 0.3 to 4.0 wt.% of the total siloxane
discernible through the panel. The terms “high clarity.” units, and an optional second siloxane-containing copolymer
“transparent,” “medium clarity,” and the like are simply for comprising an average siloxane block length from 5 to 20,
convenience, and refer to the level of transmission/haze 10 and a siloxane content of 0.5 to 2 wt %, based on the weight
before any light diffusive additives are added to the com of the siloxane-containing copolymer, wherein the optional
positions. second siloxane-containing copolymer contributes 0 to 0.4
Such thermoplastic compositions comprise an amount of wt.% of the total siloxane units. For example, based on the
bromine-containing polymer effective to provide 9 to 13 wit total weight of the polymers in the thermoplastic polymer
% of bromine, based on the total weight of the polymers in 15 composition, 5 to 65 wt.% of the first siloxane-containing
the thermoplastic composition. Specifically, these thermo copolymer, wherein the first siloxane-containing copolymer
plastic compositions comprise 35 to 50 wt % of the bromine has an average siloxane block length of 35 to 55; and 0 to
containing polymer based on the total weight of polymers in 60 wt % of the optional second siloxane-containing copo
the thermoplastic composition; and 10 to 65 wt %, 20 to 65 lymer, wherein the second siloxane-containing copolymer
wt %, 30 to 65 wt %, 40 to 65 wt %, or 50 to 65 wt % of 20 has an average siloxane block length from 5 to 15 are
the siloxane-containing copolymer based on the total weight present. The foregoing poly(carbonate-siloxane) copoly
of the polymers in the thermoplastic composition, wherein mers can have carbonate units derived from bisphenol A and
the siloxane-containing copolymer comprises siloxane poly(siloxane) block units derived from a polysiloxane
blocks having from 5 to 200 siloxane units per block. In bisphenol of formula (15), (16), or a combination thereof.
Some embodiments a third, optional polymer is present, Such 25 In another embodiment, the light transmissive thermo
that the weight percents of the bromine-containing polymer, plastic compositions can be formulated to be of high clarity.
the siloxane-containing polymer, and the optional third Such compositions have less haze than medium clarity
polymer total 100 wt %. In a specific embodiment, the articles, and are transparent. For example, a sample molded
siloxane-containing copolymer contains carbonate units or formed from a high clarity composition can have a
derived from bisphenol A and poly(siloxane) block units 30 transmission of 87% or more or a haze of 2% or less, each
derived from a polysiloxane bisphenol of formula (15), (16), measured using the color space CIE 1931 (Illuminant C and
or a combination thereof wherein E has an average value of a 2° observer) at a thickness of 3.2 mm. Such compositions
5 to 200; specifically E has an average value of 5 to 150, 5 often have relatively lower siloxane levels, i.e., 0.2 to 1.5 wt
to 65, or 5 to 20; or E has an average value of 25 to 200, 25 %, specifically 0.5 wt % siloxane, based on the total weight
to 150, 25 to 65, or 35 to 55. In this embodiment, the 35 of the polymers in the thermoplastic compositions. A com
optional third polymer is a polycarbonate, specifically bis bination of poly(carbonate-siloxane) copolymers can be
phenol-A homopolycarbonate. One or both of the tube used. For example, a first poly(carbonate-siloxane) copoly
reactor processes described in U.S. Patent Application No. mer can have average E value of 25 to 200, specifically, 25
2004/0039145A1 or the process described in U.S. Pat. No. to 150, more specifically 25 to 65, for example 30, while the
6,723,864 may be used to synthesize the poly(siloxane 40 second poly(carbonate-siloxane) copolymer can have aver
carbonate) copolymers. age E value of 5 to 150, specifically 5 to 65, more specifi
An article molded from these thermoplastic compositions cally, 5 to 20, for example 10. The foregoing poly(carbon
has an OSU integrated 2 minute heat release test value of ate-siloxane) copolymers can have carbonate units derived
less than 65 kW-min/m and a peak heat release rate of less from bisphenol A and poly(siloxane) block units derived
than 65 kW/m as measured using the method of FARF25.4, 45 from a polysiloxane bisphenol of formula (15), (16), or a
in accordance with Federal Aviation Regulation FAR 25.853 combination thereof.
(d), and an E662 smoke test DSMax value of less than 200 In still another embodiment, the foregoing light transmis
when measured at a thickness of 1.6 mm. Solely for con sive compositions can be formulated to be transparent. Such
venience herein, these compositions are referred to collec compositions have a transmission of 87% or more or a haze
tively herein as “light transmissive' thermoplastic compo 50 of 2% or less, each measured using the color space CIE 1931
sitions, which includes the light diffusive embodiments. (Illuminant C and a 2° observer) at a thickness of 3.2 mm.
Medium clarity composition can be formulated from the Further, such compositions have low siloxane levels, on the
light transmissive thermoplastic compositions that can order of 0.2 to 1.5 wt %, specifically 0.5 wt %, of siloxane
optionally be made light diffusive by the addition of a light units based on the total weight of polymers in the compo
diffuser additive. For example, a sample molded or formed 55 sition. These compositions can be obtained using siloxane
from a medium clarity composition can have a transmission containing copolymers wherein a molded plaque of the
of 70% to 87% or a haze of 2% to 10%, each measured using siloxane-containing copolymer has a % haze value of 3% or
the color space CIE 1931 (Illuminant C and a 2° observer) less measured using the color space CIE 1931 (Illuminant C
at a thickness of 3.2 mm. Such compositions can have and a 2° observer) at a thickness of 3.2 mm Advantageously,
relatively higher siloxane levels, i.e., 0.2 to 6.5 wt %, or 0.2 60 a wide variety of different siloxane-containing copolymers
to 5.3 wt %, based on the total weight of the polymers in the and combinations thereof can be used, provided that a
light transmissive thermoplastic compositions. A combina molded plaque of the siloxane-containing copolymer(s)
tion of first and second poly(carbonate-siloxane) copoly have a % haze value of 3% or less measured using the color
mers can be used. For example, the first poly(carbonate space CIE 1931 (Illuminant C and a 2° observer) at a
siloxane) copolymer can have average E value of 25 to 200, 65 thickness of 3.2 mm. In an embodiment the siloxane
25 to 150, or 25 to 65, for example 45, while the second containing copolymer is a poly(carbonate-siloxane) copoly
poly(carbonate-siloxane) copolymer can have average E mer having an average E value of 2 to 200; or 25 to 200, to
 US 9,453,128 B2
37 38
150, or 25 to 65, for example 30 or 45; or 5 to 150, 5 to 65, a colorant where color is desired. As used herein, the terms
or 5 to 20, for example 10. The foregoing poly(carbonate “high impact,” “medium impact', and “good colorability”
siloxane) copolymers can have carbonate units derived from are simply for convenience.
bisphenol A and poly(siloxane) block units derived from a Such thermoplastic compositions comprise an amount of
polysiloxane bisphenol of formula (15), (16), or a combi bromine polymer effective to provide 9 to 13 wt % of
nation thereof. bromine, based on the total weight of the polymers in the
The foregoing medium-clarity, high-clarity, and transpar thermoplastic composition. Specifically, these thermoplastic
ent compositions can be formulated to be light diffusive by compositions comprise 35 to 50 wt % of the bromine
the addition of a plurality of light diffuser additives as containing polymer based on the total weight of polymers in
described above. For example, the light diffuser additives 10 the thermoplastic composition; and 10 to 65 wt %, 20 to 65
can comprise silicone, polymethylsilsesquioxane, cross wt %, 30 to 65 wt %, 40 to 65 wt %, or 50 to 65 wt % of
linked poly(methyl methacrylate), methyl methacrylate/eth the siloxane-containing copolymer based on the total weight
yleneglycol dimethacrylate copolymer, TiO, or a combina of the polymers in the thermoplastic composition, wherein
tion comprising at least one of the foregoing additives. The the siloxane-containing copolymer comprises siloxane
additives, in the form of particles, can be present in an 15 blocks having from 5 to 200 siloxane units per block. In
amount of 0.05 to 10 wt %, based on the total weight of Some embodiments a third, optional polymer is present, Such
polymers in the thermoplastic composition. Alternatively, or that the weight percents of the bromine-containing polymer,
in addition, the medium-clarity or high-clarity formulations the siloxane-containing polymer, and the optional third
can include 0.00002 to 5.0 wt % of a colorant based on the polymer total 100 wt %. In a specific embodiment, the
total weight of the polymers in the light diffusive thermo siloxane-containing copolymer contains carbonate units
plastic composition. For example, the high clarity formula derived from bisphenol A and poly(siloxane) block units
tion can comprise 0.0001 to 0.001 wt % of a blue colorant derived from a polysiloxane bisphenol of formula (15), (16),
and 0.0001 to 0.001% of violet colorant; a phosphite heat or a combination thereof wherein E has an average value of
stabilizer; and a UV absorber. The blue colorant can be 5 to 200; specifically E has an average value of 5 to 150, 5
Pigment Blue 60 and the violet colorant can be Solvent 25 to 65, or 5 to 20; or E has an average value of 25 to 200, 25
Violet 36. the UV absorber is 2,2'-(1,4-phenylene)bis-2,2'- to 150, 25 to 65, or 35 to 55. In this embodiment, the
(1,4-phenylene)bis(4H-3,1-benzoxazin-4-one); 2-(2hy optional third polymer is a polycarbonate, specifically bis
droxy-5-t-octylphenyl)-benzotriazole: 2-(2H-benzotriazol phenol-A homopolycarbonate. An article molded from these
2-yl)-4,6-bis(1-ethyl-1-phenylethylphenol; or a combination thermoplastic compositions has an OSU integrated 2 minute
comprising at least one of the forgoing. 30 heat release test value of less than 65 kW-min/m and a peak
Other light diffusive compositions can be formulated from heat release rate of less than 65 kW/m as measured using
the light transmissive thermoplastic compositions comprise the method of FAR F25.4, in accordance with Federal
0.05 to 10 wt %, based on the total weight of polymers in the Aviation Regulation FAR 25.853 (d), and an E662 smoke
thermoplastic composition, wherein a sample molded or test DsMax value of less than 200 when measured at a
formed from the light-diffusive composition can have a 35 thickness of 1.6 mm. Solely for convenience herein, these
transmission of 20% to 90%, or a haze of 40% to 99.9%, compositions are referred to collectively herein as “impact
each measured using the color space CIE 1931 (illuminant thermoplastic compositions, which includes the embodi
C and a 2° observer) at a thickness of 3.2 mm. Such ments having high impact, optionally with good colorability
compositions often have relatively higher siloxane levels, and medium impact optionally with good colorability.
i.e., 0.2 to 6.5 wt %, or 0.2 to 5.3 wt %, based on the total 40 In an embodiment the impact thermoplastic composition
weight of the polymers in the thermoplastic compositions. In can be formulated to be high impact. A sample molded or
an embodiment, the light diffusive composition can com formed from a high impact composition has a notched Izod
prise a combination of two poly(carbonate-siloxane) copo impact of greater than 480 J/m as measured on a 3.2
lymers, i.e., a first poly(carbonate-siloxane) copolymer that mm-thick molded article according to ASTM D256-10 at 0°
can have average E value of 25 to 200, specifically, 25 to 45 C. These high impact values can be obtained when average
150, more specifically 25 to 65, for example 45, and a value of E in the poly(siloxane-carbonate) copolymers is
second poly(carbonate-siloxane) copolymer that can have higher, i.e., 25 to 200, 25 to 100, or 25 to 65. Such
average E value of 5 to 150, specifically 5 to 65, more compositions often have relatively higher siloxane levels,
specifically, 5 to 20, for example 10. The foregoing poly i.e., at least 2.5 wt %, specifically 2.5 to 6.0 wt %, based on
(carbonate-siloxane) copolymers can have carbonate units 50 the total weight of the polymers in the thermoplastic com
derived from bisphenol A and poly(siloxane) block units positions. A combination of poly(siloxane-carbonate) copo
derived from a polysiloxane bisphenol of formula (15), (16), lymers can be used, for example, a first poly(carbonate
or a combination thereof. siloxane) copolymer having an average E value of 25 to 200,
The thermoplastic compositions can advantageously be 25 to 150, or 25 to 65, for example 45 and comprising 15 to
formulated to high impact, including high impact with good 55 25 wt % siloxane, or 20 wt %; and a second poly(carbonate
colorability and medium impact with good colorability. siloxane) copolymer having an average E value of 25 to 200,
Compositions having good colorability generally show no or 25 to 150, for example 45. and having 4.0 to 10% siloxane,
minimal flow lines, Swirls or gate blush when injection for example 6.0%. The poly(carbonate-siloxane) copolymer
molded. The color is visually uniform across the molded can be one having carbonate units derived from bisphenol A
part. It is also advantageous for the base color (color of the 60 and poly(siloxane) block units derived from a polysiloxane
composition without pigments) to have a low yellowness bisphenol of formula (15), (16), or a combination thereof.
index (YI). Most useful compositions have a base color In addition, the impact thermoplastic composition can be
below a YI of 12, below 8, or most below 5. Compositions formulated to be high impact, together with good colorabil
with a high base color mitigate the ability to bright white and ity. For example, a sample molded or formed from a high
other light colors. The impact and colorability properties of 65 impact composition can have a notched IZod impact of
the compositions are obtained by adjusting the type and greater than 400 J/m as measured on a 3.2 mm-thick molded
amount of the poly(siloxane-carbonate) and the addition of article according to ASTM D256-10 at 10°C. The thermo
 US 9,453,128 B2
39 40
plastic compositions can be tinted or colored as needed, and and poly(siloxane) block units derived from a polysiloxane
have good color stability when exposed to UV light. These bisphenol of formula (15), (16), or a combination thereof.
characteristics can be obtained at relatively higher siloxane As mentioned throughout, the poly(siloxane) copolymer
levels, i.e., at least 2.5 wt %, specifically 2.5 to 5.3 wt % compositions can be used in a wide variety of applications,
siloxane, based on the total weight of the polymers in the particularly those requiring low Smoke and low heat release
thermoplastic compositions. In addition, the average value values. Articles comprising the poly(siloxane) copolymer
of E in the poly(siloxane-carbonate) copolymers is higher, compositions can be manufactured by foaming, molding,
i.e., 25 to 200, 25 to 100, or 25 to 65. For example, a first thermoforming, extruding, or casting the poly(siloxane)
poly(carbonate-siloxane) copolymer can have average E copolymer compositions. Thus the poly(siloxane) copoly
value of 25 to 200, 25 to 150, or 25 to 65, for example 45, 10 mer compositions can be used to form a foamed article, a
and comprise 15 to 25% siloxane, for example, 20 wt % molded article, a thermoformed article, an extruded film, an
siloxane based on the weight of the copolymer; and a second extruded sheet, one or more layers of a multi-layer article, a
poly(carbonate-siloxane) copolymer can have an average E substrate for a coated article, or a substrate for a metallized
article.
value of 25 to 200, 25 to 100, or to 65, for example 65, and 15 The thermoplastic compositions can be used to form a
comprise 4.0 to 10 wt % siloxane, for example 6 wt %, based sheet. A “sheet' (which includes a film, layer, and the like)
on the weight of the copolymer. The foregoing poly(carbon can be a shaped or unshaped, and is a molded, formed, or
ate-siloxane) copolymers can have carbonate units derived extruded article of Substantially uniform thickness (e.g.,
from bisphenol A and poly(siloxane) block units derived 0.001 to 10.0 cm) and which is unshaped or is further
from a polysiloxane bisphenol of formula (15), (16), or a shaped. For example in an operation to make a sheet, the
combination thereof. The high impact, good colorability molten thermoplastic composition (e.g., a thermoplastic
compositions can further comprise 0.00002 to 5.0 wt % of composition that has been heated to a temperature greater
a colorant, based on the total weight of the polymers in the than a glass transition temperature (Tg) of the thermoplastic
thermoplastic composition. composition) can be extruded from a slot die. Twin or single
In yet another embodiment, the impact thermoplastic 25 screw extruders and be used. Single or multi-manifold dies
compositions can be formulated to be medium impact, can be used. The extrusion temperatures of 200 to 320°C.,
together with good colorability. For example, a sample specifically 260 to 310° C., and more specifically 270 to
molded or formed from a medium impact composition can 290° C. The molten thermoplastic composition can then be
have a notched Izod impact of greater than or equal to 400 passed through a nip (e.g., a space formed between two
J/m as measured on a 3.2 mm-thick molded article according 30 calendaring rolls), which when cooled can form the sheet.
to ASTM D256-10 at 23° C. Such compositions often have The temperature for the cooling rolls can be the same or
relatively higher siloxane levels, i.e., at least 2.5 wt %, different, for example the temperature of the rolls can be
specifically 2.5 to 5.3 wt %, based on the total weight of the from 80 to 175° C., specifically 100 to 160° C., and more
polymers in the thermoplastic compositions. These impact specifically 105 to 150° C. After passing through the nip, the
values and good colorability can be obtained when the 35 thermoplastic composition can be cooled (e.g., to a tempera
average value of E in the poly(siloxane-carbonate) copoly ture less than the Tg of the thermoplastic composition), and
mers is higher, i.e., 25 to 200, 25 to 100, or 25 to 65. For can then be passed through pull rolls. A mask can optionally
example, a first poly(carbonate-siloxane) copolymer can be applied to the cooled sheet to protect the sheet 60 from
have average E value of 25 to 200, 25 to 150, or 25 to 65, damage or contamination. The sheet can be cut into lengths
for example 45 and comprise 15 to 25 wt % siloxane, for 40 suitable for handling.
example, 20 wt %, based on based on the weight of the In various embodiments, the calendaring roll(s) can com
copolymer, and a second poly(carbonate-siloxane) copoly prise a polished roll (e.g., a chrome or chromium plated roll)
mer can have average E value of 25 to 150, specifically 25 or a textured roll (e.g., a roll comprising an elastomeric
to 50, for example 45 and have 4.0 to 10% siloxane, for material (e.g., an EPDM (ethylene propylene diamine mono
example 6.0 wt %, based on the weight of the copolymer. 45 mer) based rubber)). Suitable materials for the rolls include
The foregoing poly(carbonate-siloxane) copolymers can plastic, metal (e.g., chrome, stainless steel, aluminum, and
have carbonate units derived from bisphenol A and poly the like), rubber (e.g., EPDM), ceramic materials, and the
(siloxane) block units derived from a polysiloxane bisphenol like. The size of the rolls, material of the rolls, number of
of formula (15), (16), or a combination thereof. rolls, the film wrap around the rolls, and the like, can vary
In still another embodiment, the impact compositions can 50 with the system employed. Processing conditions (e.g., the
be formulated to be high or medium impact, optionally with temperature of the calendaring rolls, the line speed, nip
good colorability. These compositions can have a notched pressure, and the like) can also be varied, depending on the
IZod impact of greater than or equal to a notched IZod impact properties of the thermoplastic compositions used.
of 2.0 ft-lb/in or greater, measured according to ASTM D The sheet can comprise a cap layer to provided additional
256-10 at a 3.2 mm thickness at room temperature (e.g., 23° 55 properties desirable in the sheet. In an embodiment, the cap
C.). Such compositions have relatively higher siloxane lev layer can be a hard coat, defined herein as a coating applied
els, i.e., 2.5 to 6.0 wt %, based on the total weight of the to the sheet to enhance Scratch and abrasion resistance,
polymers in the thermoplastic compositions and siloxane chemical resistance, or other desirable Surface properties.
blocks having 10 to 200 siloxane units per block. Advanta Cap layers can also include a UV blocking layer applied to
geously, a wide variety of different siloxane-containing 60 provide optical properties such as enhanced weatherability
copolymers and combinations thereof can be used. In an for underlying layers.
embodiment, the siloxane-containing copolymer is a poly In an embodiment, the sheet comprising the thermoplastic
(carbonate-siloxane) copolymer, specifically having an aver composition further comprises as a cap layer, a hard coat
age E value of 2 to 200; or 25 to 200, 25 to 150, or 25 to 65, disposed on a surface of the sheet layer. In another embodi
for example 30 or 45; or 5 to 150, 5 to 65, or 5 to 20, for 65 ment, the sheet comprises as a cap layer, a UV blocking
example 10. The foregoing poly(carbonate-siloxane) copo layer disposed on a Surface of the sheet. Alternatively, a
lymers can have carbonate units derived from bisphenol A multilayer article comprises the sheet comprising the ther
 US 9,453,128 B2
41 42
moplastic compositions, a first layer a UV blocking cap cure retardants which bind the platinum at room temperature
layer disposed on a first side of the sheet, and a second layer to prevent early cure, but release the platinum at higher
a UV blocking layer cap layer disposed on a second, temperatures to affect cure; ultraviolet absorbers (UVAs)
opposite side of the sheet. In another embodiment, a mul Such as benzotriazoles and hydroxybenzophenones, sily
tilayer article comprises the sheet comprising the thermo lated UVAs such as 4,6-dibenzoyl-2-(trialkoxysilylalkyl)
plastic compositions, a first hard coat cap layer disposed on resorcinols and 4-(triethoxysilane)propoxy-2-hydroxyben
a first side of the sheet, and a second hard coat cap layer Zophenone.
disposed on a second, opposite side of the sheet. A first UV In another embodiment, a coating composition is a UV
blocking layer can optionally further be disposed between absorbing layer comprising polycarbonate, and additional
the sheet and the first cap layer, and a second UV blocking 10 polymer such as PCCD. Additives, where used, can be
layer can further be optionally disposed between the oppo present in an amount of 0.1 to 20 wt %, based on the total
site side of the sheet and the second hard coat cap layer. weight of the polymer. In an embodiment, the sheet or
Where more than one hard coat or UV blocking cap layer is multilayer sheet can have a color shift of less than or equal
disposed on the sheet, each layer can be the same or different to 4 yellowness index (YI) units when exposed to UV light,
from the cap layer on the opposing Surface. 15 or in other words, the change in yellowness index dYI can
Other layers can be present in the multilayer sheets. In an be less than or equal to 4, as 40 measured according to
embodiment, in FIG. 1, a hard coated sheet 100 comprises ASTM D1 1925-70.
a sheet layer 110 comprising the thermoplastic composition, The hard coat composition further comprises a solvent,
and a layer 120 comprising a hard coat. In another embodi Such as water, or a branched or straight chain C-2 alcohol,
ment, in FIG. 2, a hard coated sheet 200 comprises a sheet ether alcohol, diol, polyol, or ethyl acetate, or other C.
layer 210 comprising the thermoplastic composition, a hard organic solvent miscible with these alcohols. Once coated,
coat layer 220, and a primer layer 240 disposed between the the hard coat layer is dried to form the uncured hard coat,
sheet layer 210 comprising the thermoplastic composition and can be cured thermally, or by photoinitiation, for
and the hard coat layer 220. As used herein, where a layer example wherein the hard coat composition comprises a
is disposed on another layer it will be understood that the 25 photolytic cure catalyst and curable groups reactive with the
layers are in at least partial contact with each other. cure catalyst.
While any suitable method of forming a multilayer article A primer layer can be disposed on the article to be coated
comprising the thermoplastic composition can be used (e.g., prior to the hard coat layer. Useful primer layers include
thermoforming, vacuum forming, pressure forming, coex those based on copolymers comprising C-2 alkyl(meth)
trusion, laminating, profile extrusion, blow molding, com 30 acrylates, (meth)acrylic acid, Substituted methacrylates Such
pression molding, injection molding, and the like), in an as hydroxyalkyl(meth)acrylates, silane Substituted meth
embodiment the multilayer articles can be formed by coex acrylates including alkoxysilane substituted methacrylates,
trusion or thermoforming. The term “thermoforming refers epoxy-substituted methacrylates, and the like. Other non
to a method comprising the sequential or simultaneous (meth)acrylate monomers co-polymerizable with the (meth)
heating and forming of a material onto a mold, wherein the 35 acrylate monomers including styrenes, C-2 olefins, C
material is originally in the form of a sheet, and can then be vinyl ethers, C-2 (meth)acrylamides, methcacrylonitrile),
formed into a desired shape, for example a window. Once and the like.
the desired shape has been obtained, the formed article (e.g., Multi-layered shaped articles can alternatively be formed
a component of a window) is cooled below its Tg. Thermo by injection molding the thermoplastic composition onto a
forming methods that can be used include mechanical form 40 single or multi-layer film or sheet substrate as follows: (a)
ing (e.g., matched tool forming), membrane assisted pres providing a single or multi-layer thermoplastic Substrate
Sure? vacuum forming, membrane assisted pressure? vacuum optionally having a color on the Surface, for instance, using
forming with a plug assist, and the like. screen printing or a transfer dye; (b) conforming the Sub
Hard coats are manufactured from a hard coat composi strate to a mold configuration Such as by forming and
tion that has a hardness after cure that is harder than the 45 trimming the Substrate into a three-dimensional shape and
hardness of the over-coated article. Desirably, hard coats are fitting the Substrate into a mold having a Surface which
also transparent and colorless, and still more desirably, can matches the three dimensional shape of the Substrate; (c)
protect the underlying coated article from exposure to ultra injecting the thermoplastic composition into the mold cavity
violet radiation. In an embodiment, the hard coat provides behind the Substrate to produce a one-piece, permanently
scratch resistance. Hard coats are generally thermosetting, 50 bonded three-dimensional productor (ii) to transfer a pattern
but can be thermoformable or non-thermoformable. A non or aesthetic effect from a printed substrate to the injected
thermoformable hard coat can be applied after the article to resin and (d) removing the printed Substrate, thus imparting
be hard coated has been shaped to its final shape, whereas a the aesthetic effect to the molded thermoplastic composition.
thermoformable hard coat can be applied prior to shaping The article comprising the thermoplastic compositions
(e.g., thermoforming, etc.) by coextruding, coating, or other 55 can be a metallized article, for example a Substrate com
Suitable methods, and is Subsequently cured to its desired prising the thermoplastic compositions, having a first side
final hardness during or after shaping to form the article. and a second side opposite the first side, with a metal layer
Hard coats can be a single layer hard coat having Sufficient disposed on the first side of the substrate. The substrate can
scratch resistance. Hard coats comprise curable (i.e., cross be of any shape, for example a film. Examples of metals that
linkable) polymers, and can be based on hydroxy-containing 60 can be deposited on the Substrate include aluminum, copper,
organic polymers such as novolacs, organosilioxane poly silver, gold, Steel, brass, tin or alloys comprising at least one
mers such as polysilsesquioxane copolymers, acrylates, or a of the foregoing. Metallizing typically involves a two-step
combination comprising at least one of the foregoing. Addi process, comprising creating a metallized transfer layer, and
tives can be included in the coating composition can be applying metallized layer of the transfer layer to a side of the
included to add or enhance the properties of the hard coat, 65 substrate. For example, a transfer layer can be coated with
for example a filler Such as silica can be used to increase a protective layer. Metallic particles are then deposited onto
hardness. Other additives include methyl vinyl cycloalkyl the protective layer by vacuum deposition, for example, or
 US 9,453,128 B2
43 44
other methods. In a second step, an adhesive coating is and outer window pane 310 are separated by a space 301,
applied to the Substrate comprising the thermoplastic com and inner window 320 and dust cover 330 are also separated
positions, whereupon the transfer layer coated with the by a space 302. The outer window pane 310, inner window
metal, is adhered to the substrate, with the metallic layer pane 320, and dust cover 330 are each contacted by their
adjacent the adhesive coating. After heating the various edges to a frame 340, such that the frame 340 provides
layers, the transfer layer is removed to provide a metallic support for and holds in place the outer window pane 310,
coated Substrate comprising the thermoplastic compositions, inner window pane 320, and dust cover 330. In another
and having a protective layer. The metal layer resulting from embodiment, windows structures for commercial railway
the metallizing process (e.g., by vapor deposition) can be vehicles can also further contain a moveable shade (not
broaden this range 0.001 to 50 micrometers (Lm) thick. The 10 shown) that allows the passenger to block outside light.
metallized Substrate can have a protective layer disposed on In another embodiment, a window for a railway vehicle,
the second side of the substrate. e.g., a commercial passenger train can comprise at least four
Those skilled in the art will also appreciate that common major elements as shown in FIG. 4. The window comprises
curing and Surface modification processes including heat an outer window pane 410 comprising a transparent mate
setting, texturing, embossing, corona treatment, flame treat 15 rial, an inner window pane 420 comprising a transparent
ment, plasma treatment, and vacuum deposition can further material, and dust cover 430. The outer window pane 410
be applied to the above articles to alter Surface appearances and inner window pane 420 are thicker and are engineered
and impart additional functionalities to the articles. to be load bearing, where at least the outer window element
In an embodiment, the thermoplastic composition is used a part of the structure of the cabin, for example. The dust
to prepare a window article for a railway vehicle, such as a cover 430 can be prepared from the thermoplastic compo
window for a passenger train, comprising a frame and a sition. It can be advantageous to hard coat the dust cover 430
sheet comprising the thermoplastic composition Supported to increase the scratch resistance of the dust cover 430, and
by the frame. “Supported by means the window article is in to thereby increase the interior transparency, hardness, and
contact with and is fixed or movable with respect to the smoke release capability of the dust cover 430. Inner win
frame, and where the frame can be fixed or movable with 25 dow 420 and outer window 410 are separated by a space
respect to a Surrounding element (such as, for example, a 401, and inner window pane 420 and dust cover 430 are also
cabin of a passenger train). Such that the frame is intervening separated by a space 402. The outer window pane 410, inner
between the window article and Surrounding element, and window pane 420, and dust cover 430 are each contacted by
the sheet does not directly contact the Surrounding element. their edges to a frame 440, such that the frame 440 provides
In an embodiment, a window comprises the window article. 30 support for and holds in place the outer window pane 410.
In an embodiment, window article can be a component of a inner window pane 420, and dust cover 430. The frame 440
window for a railway vehicle, for example a windshield, or holding the outer window pane 410 and the inner window
a window for passenger cabin. Window articles can be pane 420 can be the same as or different from the frame
transparent, translucent, or opaque, and can be fixed or holding the dust cover 430. The dust cover protects the inner
movable relative to the window. In an embodiment, a 35 and outer element from damage. In lieu of a moveable shade
window article can be a transparent or opaque interior to block the light, an electrochromic element 450 can be
covering for a railcar window. An exemplary transparent included. In an example, the electrochromic element 450 can
window article is a “dust cover, which is fixed relative to be inserted between the inner window pane 420 and the dust
the window. In another embodiment, an opaque window cover 430, in space 402.
article that is movable relative to the window is a window 40 The thermoplastic composition for use in the window
shade. In an embodiment, a transparent window article is an panes or dust covers can further be tinted using standard
interior covering, also referred to herein as a “dust cover for dyes and pigments. The thermoplastic composition can be
the interior section of a railway vehicle window. The dust formed into the window pane or dust cover by extrusion of
cover can be used for windows for a passenger or non a sheet (followed by optionally thermoforming) or injection
passenger (i.e., freight) railway vehicle as desired. 45 molding. Optionally where needed the window pane or dust
Railway vehicle windows, e.g., windows for a passenger cover can be hard coated one or both sides using the hard
train, can comprise at least three elements: an outer window coat and primer layers described above. The hard coats can
pane, an inner window pane, and the dust cover. In an be applied to the sheet after extrusion or to the formed
embodiment, in FIG. 3, a window for a passenger train 300 window. The dust cover can have a thickness of about 1 to
comprises an outer window pane 310, an inner window pane 50 about 4 mm.
320, and a dust cover 330. The outer window pane 310 and In another embodiment, a multilayer article 500 com
inner window pane 320 are generally thicker than the dust prises a sheet 510 comprising the thermoplastic composition
cover 330 and are thus engineered to be load bearing where and a UV blocking layer 530 disposed on a surface of the
the outer window 310 and the inner window 320 may be sheet 510 as shown in FIG. 5. UV blocking layer 530 is UV
structural members of the cabin of the train. The outer 55 stable such that it does not substantially shift in color on
window pane 310 can be a part of the train's structure. The exposure to UV light of a wavelength of 275 to 410 nm. In
dust cover 330 protects the inner window pane 320 and outer addition, the UV blocking layer 530 is of a sufficient
window pane 310 from damage. thickness to provide the desired UV protection to substan
Also in FIG. 3, the inner window pane 320 and outer tially prevent the incident light from causing a photo deg
window pane 310 can be formed from the thermoplastic 60 radation in the sheet layer 510 comprising the thermoplastic
composition or another composition, for example an acrylic composition, but is present in a film thickness that does not
polymer composition. The dust cover 330 can be manufac cause the multilayer article 500 to fail the heat release or
tured the thermoplastic composition described herein. It can Smoke testing requirements set forth herein. In a specific
be advantageous to hard coat the dust cover 330 to increase embodiment, a second UV blocking layer is optionally
the scratch resistance of the dust cover 330, and to thereby 65 co-extruded on the side of the sheet comprising the thermo
increase the interior transparency, hardness, and Smoke plastic composition opposite the first UV blocking layer. In
release capability of dust cover 330. Inner window pane 320 another embodiment, the multilayer article can comprise an
 US 9,453,128 B2
45 46
additional layer (not shown) on a side of the sheet layer include CYASORBTM UV-3638 (Cytec), CYASORBTM
comprising the thermoplastic composition 510 opposite UV UV-1164 (Cytec), CYASORBTM 5411 (Cytec), TINUVINTM
blocking layer 530. In a specific embodiment, the additional 1577 (Ciba), TINUVINTM 360 (Ciba), TINUVINTM 234
layer is a UV blocking layer. In another embodiment, the (Ciba), UVINULTM 3030 (BASF) and 4,6-dibenzoylresor
article comprising the sheet layer comprising the thermo cinol. Optionally, the UV blocking layer can contain an
plastic composition 510 has a reflective layer disposed on a effective amount of a flame retardant. In a specific embodi
side opposite the UV blocking layer 530. In another embodi ment, where improved chemical resistance is needed, the
ment, the sheet layer comprising the thermoplastic compo UV blocking layer comprises a blend with a polyester, such
sition 510 has a reflective layer disposed between the sheet as poly(1,4-cyclohexylene dimethylenel, 4cyclohexanedi
layer comprising the thermoplastic composition 510 and UV 10 carboxylate) (PCCD). Hard coat layer 620 is added to
blocking layer 530. provide a scratch and mar resistance to the sheet or film, and
In a specific embodiment, the multilayer article 500 of can be applied to one or both sides. In an exemplary
FIG. 5, is opaque. For the opaque sheet, pigments and embodiment, suitable hard coats include AS4000 or AS4007
colorants can be added to either the thermosetting compo silicone hard coats, both available from GE Silicones.
sition or the UV blocking layer, or both. In addition, fillers 15 In another specific embodiment, a multilayer article 600
Such as, for example, glass and/or mica can be added to one is a scratch and mar resistant opaque article with Substan
or more of these layers. Addition of such fillers can also tially the same properties as the above opaque article 500,
increase Young's modulus of the sheet layer comprising the except that the article comprises a hard coat. The hard coat
thermoplastic composition 510 and thereby can increase layer 620, can be applied to one or both exposed sides of the
Young's modulus of the article, whereas addition of fillers to sheet layer 610 comprising the thermoplastic composition,
the UV blocking layer can decrease the gloss of sheet. and desirably does not significantly adversely affect the
In another specific embodiment, the multilayer article 500 properties of the sheet layer 610 comprising the thermoplas
is a transparent article having a high transparency by having tic composition. In another specific embodiment, a multi
either a high percent transmittance or a low haze, or both. layer article 600 is an opaque article having a hard coat 620,
For the transparent sheet, low levels of pigments and colo 25 wherein the hard coat is thermoformable.
rants can be added to either the thermosetting composition In another specific embodiment, the multilayer sheet 600
or the UV blocking layer, or both. is a scratch and marresistant, transparent article comprising
In another embodiment, the multilayer article 500 is a a thermally cured hard coat. In applications in which UV is
thermoformable, light-diffusive article having a high degree expected from both sides of the article, the UV absorbing
hiding power in combination with good luminance. For the 30 layer 630 can be applied to both sides of the article. This is
diffusive article, low levels pigments and colorants can be also useful to prevent the installation of the incorrect side of
added to either the sheet layer comprising the thermoplastic the sheet layer 610 comprising the thermoplastic composi
composition 510, the UV blocking layer 530 or both. To tion, towards the UV light. In another specific embodiment,
obtain the diffusive optical requirements the appropriate a multilayer article 600 is a scratch and mar resistant
about of a diffusive agent can be added to sheet layer 35 formable transparent article comprising a thermoformable
comprising the thermoplastic composition 510 or the UV hard coat layer 620.
blocking layer 530. In another embodiment, a multilayer article 600 is a
In another embodiment, a multilayer article 600 shown in scratch and marresistant, diffusive article comprising a hard
FIG. 6, comprises a sheet layer comprising the thermoplastic coat layer 620 that is thermally curable. In another specific
composition 610 (which meets at least the heat release 40 embodiment, a multilayer sheet comprises a scratch and mar
criteria disclosed herein), a UV blocking layer 630 disposed resistant formable, diffusive sheet comprising a hard coat
on a Surface of the sheet layer comprising the thermoplastic layer 620 that is thermoformable.
composition 610, and a hard coat layer 620 disposed on a The multilayer article 600 can be prepared by coextru
surface of the UV blocking layer 630 opposite the sheet Sion, laminating, calendaring, or injection molding, or other
layer comprising the thermoplastic composition 610. The 45 method suitable for preparing a multilayer article. In a
hard coat layer 620 can further comprise a primer layer (640, specific embodiment, the multilayer article is prepared by
not shown) disposed between the hard coat 620 and the UV coextrusion. Further, the hard coat layer 620 as disposed on
blocking layer 630. The UV blocking layer 630 is UV stable the UV blocking layer 630 can also be coextruded, spray
Such that it does not substantially shift in color on exposure coated, dip coated, curtain coated, and the like, or otherwise
to UV light of a wavelength of 275 to 410 nm. In addition, 50 coating using a suitable coating method for providing a hard
the UV blocking layer 630 is of a sufficient thickness to coat. The hard coat layer, when applied using an application
provide the desired UV protection to substantially prevent method such as spray coating dip coating, curtain coating, or
incident light from causing a photo degradation in the sheet the like, can be subsequently dried by air drying, oven
layer comprising the thermoplastic composition 610, but is drying, vacuum drying, or a combination of these to form a
present in a film thickness that does not cause the multilayer 55 pre-cured layer. The pre-cured layer is then cured to form the
article 600 to fail the heat release or smoke testing require hard coat layer using thermal cure, radiation cure, or a
ments described herein. The UV blocking layer 630 can, in combination comprising at least one of these, to affect the
an embodiment, comprise the thermoplastic compositions, a cure of the hard coat layer 620. The multilayer article 600
polycarbonate homopolymer, polycarbonate copolymer, can be thermoformed. In an embodiment, the hard coat layer
branched polycarbonate, or a blend comprising at least one 60 620 is partially cured prior to thermoforming the sheet or
of the foregoing polycarbonates. Optionally, the UV block film, and the hard coat layer is fully cured during or after
ing layer 630 can contain an effective amount of a UV thermoforming. In another embodiment, the hard coat layer
absorber for example, as a cap layer. The UV absorber levels 620, is applied to a partial sheet or film comprising sheet
for cap layers can be present at 0.5 to 15 wt % and preferable layer comprising the thermoplastic composition 610 and UV
4.0 to 8.0 wt %. The UV absorbers can be selected from the 65 blocking layer 630. In another embodiment, the multilayer
class of benzotriazoles, benzophenones, triazines, benzox article 600 can optionally comprise an additional layer 670
aZinones and cyanoacrylates. Some nonlimiting examples on a side of sheet layer 610 comprising the thermoplastic
 US 9,453,128 B2
47 48
composition, opposite UV blocking layer 630. In an embodi above. Examples of light-diffusive railway vehicle compo
ment, the additional layer 670 is a UV blocking layer (e.g., nents include partitions (which includes dividers), including
630). In another embodiment, the multilayer article can bulkhead partitions, and light covers (which includes light
further optionally comprise a second additional layer 680. In domes).
another embodiment, the second additional layer 680 is a Examples of medium clarity railway vehicle components
hard coat (e.g. 620). include trolley sidewalls, access doors, and access panels.
In another embodiment as show in FIG. 7, a plastic mirror Examples of high clarity railway vehicle components
comprising the thermoplastic composition is also provided. include window panes, window dust covers, partitions
The mirror 700 comprises a sheet layer 710 comprising the (which included dividers), light covers (which includes light
thermoplastic composition, a hard coat 720 disposed on a 10 domes), and glass replacements, for example electronics
Surface of the sheet, and an opacifying layer 750, e.g., a screens (e.g., a screen for an in-flight entertainment device)
metal layer disposed on a surface of the sheet layer 710 and covers for display panels, gauges and plastic mirrors,
comprising the thermoplastic composition, opposite the hard i.e., transparent sheets that have been rendered opaque on
coat layer 720. The hard coat layer 720 can further comprise one side, for example by metallization.
a primer layer (740, not shown) disposed between the hard 15 The railway vehicle components can be high impact or
coat layer 720 and the sheet layer 710 comprising the medium impact as defined above. In either embodiment the
thermoplastic composition. Optionally, a UV layer (730, not articles can be of good colorability. Examples of high
shown) is disposed between the hard coat layer 720 and the impact railway vehicle components include panels for
sheet layer 710 comprising the thermoplastic composition. access doors and components of trolley carts.
In an embodiment, the opacifying layer 750 is a metal layer, Examples of high-impact railway vehicle components
comprising aluminum, wherein the aluminum is applied to where good colorability is desired include interior cabin
the sheet layer 710 comprising the thermoplastic composi parts such as Stow bin components, magazine racks, seat
tion, using a method designed to provide a high optical back components, components of trolley carts, and access
quality Such as sputtering or vapor deposition under high door panels.
vacuum. The opacifying layer 750, for example, the metal 25 Examples of medium-impact railway vehicle components
layer, can have a thickness of 2 to 50 nm. A protective layer where good colorability is desired include call buttons, light
760 can optionally be applied a surface of the opacifying bezels, door pulls, door handles, arm rests, seat components,
layer 750 opposite the sheet layer 710 comprising the and foot rests.
thermoplastic composition, to protect the opacifying, e.g., In some applications, it can be desirable to have a
metal layer 750 from abrasion. 30 transparent flame retardant article, such as a sheet. With
Illustrative articles include access panels, access doors, air regard to the transparency of the sheet, end user specifica
flow regulators air gaspers, air grilles, arm rests, baggage tions (e.g., commercial airline specifications) generally
storage doors, balcony components, cabinet walls, ceiling specify that the component satisfy a particular predeter
panels, door pulls, door handles, duct housing, enclosures mined threshold. Haze values, as measured using the color
for electronic devices, equipment housings, equipment pan 35 space CIE 1931 (Illuminant C and a 2° observer), or by
els, floor panels, food carts, food trays, galley Surfaces, ANSI/ASTM D1003-00, Procedure A, illuminant C, can be
grilles, handles, housings for TVs and displays, light panels, a useful determination of the optical properties of the
magazine racks, telephone housings, partitions, parts for transparent flame retardant polycarbonate articles such as a
trolley carts, seat backs, seat components, railing compo sheet. The lower the haze levels, the better the transparency
nents, seat housings, shelves, side walls, speaker housings, 40 of the finished article.
storage compartments, storage housings, toilet seats, tray The transparent poly(siloxane) copolymer compositions
tables, trays, trim panel, window moldings, window slides, have special utility in applications requiring clarity, for
windows, and the like. The poly(siloxane) copolymer com example any of the above articles or components can be
positions are particularly useful in rail applications, specifi manufactured using the transparent thermoplastic composi
cally a variety of interior applications for a railway vehicle. 45 tions disclosed herein. In an embodiment, the transparent
The articles manufactured from the compositions described thermoplastic compositions are used for the manufacture of
herein can thus be a component of a train, such as a balcony components, balusters for stairs and balconies,
passenger train. Railway vehicle applications can be, for ceiling panels, covers for life Vests, covers for storage bins,
example exterior or interior component for a railway vehicle dust covers for windows, layers of an electrochromic device,
or item of railway vehicle equipment, including hulls, trim, 50 lenses for televisions, electronic displays, gauges, or instru
an enclosure, or housing: a motor housing; instrument ment panels, light covers, light diffusers, light tubes and
housing, step; Step covering, and the like. In a specific light pipes, mirrors, partitions, railings, refrigerator doors,
embodiment the articles are interior components for railway shower doors, sink bowls, trolley cart containers, trolley cart
vehicles, including access panels, access doors, air flow side panels, windows, or the like, particularly in railway
regulators baggage storage doors, display panels, display 55 vehicles.
units, door handles, door pulls, enclosures for electronic Any of the foregoing articles, but in particular the trans
devices, food carts, food trays, grilles, handles, magazine parent articles, can further have a hardcoat disposed on a
racks, seat components, partitions, refrigerator doors, seat Surface of the article to enhance abrasion and scratch resis
backs, side walls, tray tables, trim panels, and the like. The tance, chemical resistance, and the like. Hardcoats are
poly(siloxane) copolymer compositions can be formed (e.g., 60 known in the art, and include, for example, various poly
molded) into sheets that can be used for any of the above acrylates Such as hyperbranched polyacrylates, silicones,
mentioned components. It is generally noted that the overall polyfluoroacrylates, urethane-acrylates, phenolics, perfluo
size, shape, thickness, optical properties, and the like of the rpolyethers, and the like.
polycarbonate sheet can vary depending upon the desired The light transmissive polycarbonate and impact thermo
application. 65 plastic compositions are particularly useful for the manu
The railway vehicle components can be hard coated, facture of specific railway vehicle components having spe
light-diffusive, medium clarity, or high clarity as defined cific properties, including light diffusivity, high clarity,
 US 9,453,128 B2
49 50
medium clarity, transparency, high impact, high impact with ane block length from 35 to 55. In a specific embodiment,
good colorability, medium impact, and medium impact with the siloxane-containing copolymer contains carbonate units
good colorability. As described above, such thermoplastic derived from bisphenol A and poly(siloxane) block units
compositions comprise an amount of bromine-containing derived from a polysiloxane bisphenol of formula (15), (16),
polymer effective to provide 9 to 13 wt % of bromine, based 5 or a combination thereof.
on the total weight of the polymers in the thermoplastic In another embodiment, the siloxane-containing copoly
composition. Specifically, these thermoplastic compositions mer comprises a first siloxane-containing copolymer having
comprise 35 to 50 wt % of the bromine-containing polymer an average siloxane block length from 20 to 200, and a
based on the total weight of polymers in the thermoplastic siloxane content of 0.5 to 10 wt % based on the weight of
composition; and 10 to 65 wt %, 20 to 65 wt %, 30 to 65 wt 10 the siloxane-containing copolymer, wherein the first silox
%, 40 to 65 wt %, or 50 to 65 wt % of the siloxane ane-containing copolymer contributes 0.2 to 6.5 wt.% of the
containing copolymer based on the total weight of the total siloxane units, and an optional second siloxane-con
polymers in the thermoplastic composition, wherein the taining copolymer having an average siloxane block length
siloxane-containing copolymer comprises siloxane blocks from 5 to 20, and a siloxane content of 0.5 to 2 wt % based
having from 5 to 200 siloxane units per block. In some 15 on the weight of the siloxane-containing copolymer, wherein
embodiments a third, optional polymer is present, such that the optional second siloxane-containing copolymer contrib
the weight percents of the bromine-containing polymer, the utes 0 to 1.5 wt.% of the total siloxane units. For example,
siloxane-containing polymer, and the optional third polymer based on the total weight of the polymers in the thermo
totals 100 wt %. plastic polymer composition, the thermoplastic composition
A light-diffusive railway vehicle component selected comprises 10 to 65 wt.% of the first siloxane-containing
from a partition and a light cover, wherein the railway copolymer, wherein the first siloxane-containing copolymer
vehicle component can be molded or formed from a ther has an average siloxane block length of 35 to 55; and 0 to
moplastic polymer composition comprises a siloxane-con 55 wt % of the optional second siloxane-containing copo
taining copolymer in an amount effective to provide a total lymer, wherein the second siloxane-containing copolymer
of 0.2 to 6.5 wt % of siloxane units based on the total weight 25 has an average siloxane block length from 5 to 15. In a
of the polymers in the thermoplastic polymer composition, specific embodiment, the siloxane-containing copolymer
a bromine-containing polymer in an amount effective to contains carbonate units derived from bisphenol A and
provide 9 to 13 wt % of bromine, based on the total weight poly(siloxane) block units derived from a polysiloxane
of the polymers in the thermoplastic polymer composition; bisphenol of formula (15), (16), or a combination thereof.
and 0.05 to 10 wt % of a plurality of light diffuser additives, 30 In still another embodiment, a railway vehicle component
based on the total weight of polymers in the thermoplastic selected from a window, window dust cover, partition, light
polymer composition, wherein a molded or formed sample cover, electronics screen, display cover, or plastic mirror,
of the thermoplastic polymer composition has a transmission wherein the railway vehicle component is molded or formed
of 20% to 90% or a haze of 70% to 99.9%, each measured from a thermoplastic polymer composition comprising a
using the color space CIE 1931 (Illuminant C and a 2 35 siloxane-containing copolymer in an amount effective to
observer) at a thickness of 3.2 mm, an OSU integrated 2 provide a total of 0.2 to 1.5 wt % of siloxane units based on
minute heat release test value of less than 65 kW-min/m and the total weight of polymers in the thermoplastic polymer
a peak heat release rate of less than 65 kW/m, each composition, wherein a molded plaque of the siloxane
measured using the method of FAR F25.4, in accordance containing copolymer has a % haze value of 3% or less
with Federal Aviation Regulation FAR 25.853 (d), and an 40 measured using the color space CIE 1931 (Illuminant C and
E662 smoke test DsMax value of less than 200 when a 2° observer) at a thickness of 3.2 mm, a bromine-contain
measured at a thickness of 1.6 mm. In a specific embodi ing polymer in an amount effective to provide 9 to 13 wt %
ment, the siloxane-containing copolymer contains carbonate of bromine, based on the total weight of the polymers in the
units derived from bisphenol A and poly(siloxane) block thermoplastic polymer composition, and an optional third
units derived from a polysiloxane bisphenol of formula (15), 45 polymer, Such that the total weight percent of the polymers
(16), or a combination thereof wherein E has an average is 100 wt %; wherein a molded or formed sample of the
value of 5 to 200; specifically, E has an average value of 5 thermoplastic polymer composition has a transmission of
to 150, 5 to 65, or 5 to 20; or E has an average value of 25 87% or more or a haze of 2% or less, each measured using
to 200, 25 to 150, 25 to 65, or 35 to 55. the color space CIE 1931 (Illuminant C and a 2° observer)
In an embodiment the siloxane-containing copolymer 50 at a thickness of 3.2 mm, an OSU integrated 2 minute heat
comprises a first siloxane-containing copolymer having an release test value of less than 65 kW-min/m2 and a peak heat
average siloxane block length from 5 to 20, and a siloxane release rate of less than 65 kW/m2, each measured using the
content of 0.5 to 2 wt % based on the weight of the method of FAR F25.4, in accordance with Federal Aviation
siloxane-containing copolymer, wherein the first siloxane Regulation FAR 25.853 (d), and an E662 smoke test DsMax
containing copolymer contributes 0.2 to 6.5 wt.% of the 55 value of less than 200 when measured at a thickness of 1.6
total siloxane units, and an optional second siloxane-con mm. In an embodiment the siloxane-containing copolymer
taining copolymer having an average siloxane block length is a poly(carbonate-siloxane) copolymer having an average
from 25 to 65, and a siloxane content of 0.5 to 10 wt % based E value of 2 to 200; or 25 to 200, 25 to 150, or 25 to 65, for
on the weight of the siloxane-containing copolymer, wherein example 30 or 45; or 5 to 150, 5 to 65, or 5 to 20, for example
the optional second siloxane-containing copolymer contrib 60 10. The foregoing poly(carbonate-siloxane) copolymers can
utes 0 to 6.3 wt.% of the total siloxane units. In particular have carbonate units derived from bisphenol A and poly
the thermoplastic polymer composition comprise 10 to 65 (siloxane) block units derived from a polysiloxane bisphenol
wt.% of the first siloxane-containing copolymer, wherein of formula (15), (16), or a combination thereof.
the first siloxane-containing copolymer has an average silox In any of the embodiments of the foregoing light-diffusive
ane block length from 5 to 15; and 0 to 55 wt % of the 65 railway vehicle components, the light diffuser additive can
optional second siloxane-containing copolymer, wherein the comprise silicone, polymethylsilsesquioxane, crosslinked
second siloxane-containing copolymer has an average silox poly(methyl methacrylate), methyl methacrylate/ethyl
 US 9,453,128 B2
51 52
eneglycol dimethacrylate copolymer, TiO, or a combination based on the weight of the siloxane-containing copolymer,
comprising at least one of the foregoing. Further in any of wherein the optional second siloxane-containing copolymer
the embodiments of the foregoing light-diffusive railway contributes 0 to 0.4 wt.% of the total siloxane units. For
vehicle components, the siloxane-containing copolymer is a example, based on the total weight of the polymers in the
poly(carbonate-siloxane) comprising carbonate units thermoplastic polymer composition, 5 to 65 wt.% of the first
derived from bisphenol A; and poly(siloxane) block units siloxane-containing copolymer, wherein the first siloxane
derived from a polysiloxane bisphenol (15), (16), or a containing copolymer has an average siloxane block length
combination thereof, wherein E is the average number of of 35 to 55; and 0 to 60 wt % of the optional second
units in the poly(siloxane) blocks. Still further in any of the siloxane-containing copolymer, wherein the second silox
embodiments 0.00002 to 5.0 wt % of a colorant based on the 10 ane-containing copolymer has an average siloxane block
total weight of the polymers in the thermoplastic polymer length from 5 to 15 are present.
composition can be present. In any of the foregoing embodiments of the medium
A medium-clarity railway vehicle component selected clarity railway vehicle components the siloxane-containing
from a trolley sidewall, an access door, and an access panel copolymer is a poly(carbonate-siloxane) comprises carbon
wherein the railway vehicle component can molded or 15 ate units derived from bisphenol A; and poly(siloxane) block
formed from a thermoplastic polymer composition compris units derived from a polysiloxane bisphenol (15), (16), or a
ing a siloxane-containing copolymer in an amount effective combination thereof, wherein E is the average number of
to provide a total of 0.2 to 6.5 wt % of siloxane units based units in the poly(siloxane) blocks. Further, the thermoplastic
on the total weight of polymers in the thermoplastic polymer composition can comprise 0.00002 to 5.0 wt % of a colorant
composition, and a bromine-containing polymer in an based on the total weight of the polymers in the thermo
amount effective to provide 9 to 13 wt % of bromine based plastic polymer composition.
on the total weight of the polymers in the thermoplastic A light-diffusive railway vehicle component selected
polymer composition; wherein a molded or formed sample from a partition and a light cover, wherein the railway
of the thermoplastic polymer composition has a transmission vehicle component is molded or formed from the medium
of 70% to 87% or a haze of 2% to 10%, each measured using 25 clarity thermoplastic polymer composition as described
the color space CIE 1931 (Illuminant C and a 2° observer) above, further comprises 0.2 to 3.0 wt % of light diffuser
at a thickness of 3.2 mm, an OSU integrated 2 minute heat additives based on the total weight of the polymers in the
release test value of less than 65 kW-min/m and a peak heat thermoplastic composition. The light diffuser additive can be
release rate of less than 65 kW/m, each measured using the selected from silicone, polymethylsilsesquioxane, cross
method of FAR F25.4, in accordance with Federal Aviation 30 linked poly(methyl methacrylate), methyl methacrylate/eth
Regulation FAR 25.853 (d), and an E662 smoke test DsMax yleneglycol dimethacrylate copolymer, TiO, and a combi
value of less than 200 when measured at a thickness of 1.6 nation comprising at least one of the foregoing. In an
mm. In an embodiment the siloxane-containing copolymer embodiment, the light-diffusive thermoplastic composition
is a poly(carbonate-siloxane) copolymer having an average comprises 0.2 to 3.0, specifically 0.2 to 2.0, wt % of the
E value of 2 to 200; or 25 to 200, 25 to 150, or 25 to 65, for 35 polymethylsilsesquioxanes light diffuser additives; in
example 30 or 45; or 5 to 150, 5 to 65, or 5 to 20, for example another embodiment, 0.4 to 1.5 wt % of the crosslinked
10. poly(methyl methacrylate) light diffuser additives, 0.4 to 1.5
In the medium-clarity railway vehicle component, the wt % of the polymethylsilsesquioxanes light diffuser addi
siloxane-containing copolymer comprises a first siloxane tives, or a combination thereof.
containing copolymer having an average siloxane block 40 In still another embodiment, a high-clarity railway vehicle
length from 5 to 20, and a siloxane content of 0.5 to 2 wt % component selected from a window, window dust cover,
based on the weight of the siloxane-containing copolymer, partition, light cover, electronics screen, display cover, or
wherein the first siloxane-containing copolymer contributes plastic mirror, wherein the railway vehicle component can
0.2 to 6.5 wt.% of the total siloxane units, and an optional be molded or formed from a thermoplastic polymer com
second siloxane-containing copolymer having an average 45 position comprising a siloxane-containing copolymer in an
siloxane block length from 25 to 65, and a siloxane content amount effective to provide a total of 0.2 to 1.5 wt % of
of 0.5 to 10 wt % based on the weight of the siloxane siloxane units based on the total weight of polymers in the
containing copolymer, wherein the optional second silox thermoplastic polymer composition, and a bromine-contain
ane-containing copolymer contributes 0 to 6.2 wt.% of the ing polymer in an amount effective to provide 9 to 13 wt %
total siloxane units. For example, based on the total weight 50 of bromine, based on the total weight of the polymers in the
of the polymers in the thermoplastic polymer composition, thermoplastic polymer composition; wherein a molded or
5 to 65 wt.% of the first siloxane-containing copolymer, formed sample of the thermoplastic polymer composition
wherein the first siloxane-containing copolymer has an has a transmission of 87% or more or a haze of 2% or less,
average siloxane block length from 5 to 15; and 0 to 60 wt each measured using the color space CIE 1931 (Illuminant
% of the optional second siloxane-containing copolymer, 55 C and a 2° observer) at a thickness of 3.2 mm, an OSU
wherein the second siloxane-containing copolymer has an integrated 2 minute heat release test value of less than 65
average siloxane block length from 35 to 55 is present. kW-min/m and a peak heat release rate of less than 65
In another embodiment of the medium-clarity railway kW/m, each measured using the method of FAR F25.4, in
vehicle component the siloxane-containing copolymer com accordance with Federal Aviation Regulation FAR 25.853
prises a first siloxane-containing copolymer comprising an 60 (d), and an E662 smoke test DsMax value of less than 200
average siloxane block length from 25 to 65, and a siloxane when measured at a thickness of 1.6 mm. In an embodiment
content of 2 to 10 wt % based on the weight of the the siloxane-containing copolymer is a poly(carbonate-si
siloxane-containing copolymer, wherein the first siloxane loxane) copolymer having an average E value of 2 to 200;
containing copolymer contributes 0.3 to 4.0 wt.% of the or 25 to 200, 25 to 150, or 25 to 65, for example 30 or 45;
total siloxane units, and an optional second siloxane-con 65 or 5 to 150, 5 to 65, or 5 to 20, for example 10.
taining copolymer comprising an average siloxane block In the high-clarity railway vehicle component, the silox
length from 5 to 20, and a siloxane content of 0.5 to 2 wt %, ane-containing copolymer comprises a first siloxane-con
 US 9,453,128 B2
53 54
taining copolymer comprising an average siloxane block of the sheet, and a second ultraviolet light-blocking layer can
length from 5 to 20, and a siloxane content of 0.5 to 2 wt % be disposed between the second hard coat layer and the
based on the weight of the siloxane-containing copolymer, second side of the sheet. For example, the component is a
wherein the first siloxane-containing copolymer contributes dust cover for a window, the window comprising an outer
0.2 to 1.5 wt.% of the total siloxane units, and an optional window and an inner window separated by a space; the dust
second siloxane-containing copolymer comprising an aver cover separated from the inner window by a space, and a
age siloxane block length from 25 to 65, and a siloxane frame, wherein the outer window, inner window, and dust
content of 0.5 to 10 wt %, based on the weight of the cover are secured in the frame such that the inner window is
siloxane-containing copolymer, wherein the optional second disposed between and is substantially coplanar with each of
siloxane-containing copolymer contributes 0 to 1.3 wt.% of 10
the dust cover and the outer window.
the total siloxane units. For example, based on the total The high-clarity thermoplastic compositions can be used
weight of the polymers in the thermoplastic polymer com
position, 20 to 65 wt.% of the first siloxane-containing in the manufacture of railway vehicle component wherein
copolymer, wherein the first siloxane-containing copolymer the component is a is a mirror, comprising: a layer molded
has an average siloxane block length from 5 to 20; and 0 to 15 or formed from the thermoplastic polymer composition, a
30 wt % of the optional second siloxane-containing copo hard coat disposed on a surface of a first side of the layer,
lymer, wherein the second siloxane-containing copolymer and an opacifying layer disposed on a Surface of a second
has an average siloxane block length from 20 to 40 can be side of the layer opposite the first side. The opacifying layer
present. can be a metal layer. A protective coat can be disposed on a
In any of the foregoing embodiments of the high-clarity Surface of the opacifying layer opposite the layer molded or
railway vehicle component the siloxane-containing copoly formed from the thermoplastic polymer composition.
mer is a poly(carbonate-siloxane) comprising carbonate In another embodiment, a high-impact railway vehicle
units derived from bisphenol A; and poly(siloxane) block component selected from an access door panel, a seat back
units derived from a polysiloxane bisphenol (15), (16), or a component and a component of a trolley cart, wherein the
combination thereof, wherein E is the average number of 25 railway vehicle component is molded or formed from a
units in the poly(siloxane) blocks and is 5-80. Also in any of thermoplastic polymer composition comprising a siloxane
the foregoing embodiment, 0.00002 to 5.0 wt % of a containing copolymer in an amount effective to provide a
colorant, based on the total weight of the polymers in the total of 2.5 to 6.0 wt % of siloxane units based on the total
thermoplastic polymer composition, is present. For example, weight of polymers in the thermoplastic polymer composi
the thermoplastic composition can comprise 0.0001 to 0.001 30 tion, and a bromine-containing polymer in an amount effec
wt % of a blue colorant and 0.0001 to 0.001 wt % of violet tive to provide 9 to 13 wt % of bromine, based on the total
colorant; a phosphite heat stabilizer; and a UV absorber. The weight of the polymers in the thermoplastic polymer com
blue colorant can be Pigment Blue 60 and the violet colorant position; and wherein a molded or formed sample of the
can be Solvent Violet 36. The UV absorber can be 2,2'-(1, thermoplastic polymer composition has a notched Izod
4-phenylene)bis-2,2'-(1,4-phenylene)bis(4H-3,1-benzox 35 impact of 480 J/m or greater, measured according to ASTM
azin-4-one): 2-(2"hydroxy-5-t-octylphenyl)-benzotriazole; D 256-10 at a 3.2 mm thickness at 0°C., an OSU integrated
2-(2H-benzotriazol-2-yl)-4,6-bis(1-ethyl-1-phenylethylphe 2 minute heat release test value of less than 65 kW-min/m
nol; or a combination comprising at least one of the forgo and a peak heat release rate of less than 65 kW/m, each
1ng. measured using the method of FAR F25.4, in accordance
Light-diffusive railway vehicle component selected from 40 with Federal Aviation Regulation FAR 25.853 (d), and an
a partition and a light cover, wherein the railway vehicle E662 smoke test DsMax value of less than 200 when
component is molded or formed from the high-clarity ther measured at a thickness of 1.6 mm
moplastic polymer composition further comprise 0.2 to 3.0, In the high-impact railway vehicle component the silox
specifically 0.2 to 2.0, wt % of light diffuser additives based ane-containing copolymer comprises a first siloxane-con
on the total weight of the polymers in the thermoplastic 45 taining copolymer having an average siloxane block length
polymer composition. The light diffuser additive can com from 25 to 65, and a siloxane content of 15 to 25 wt % based
prise silicone, polymethylsilsesquioxane, crosslinked poly on the weight of the siloxane-containing copolymer, wherein
(methyl methacrylate) particles, methyl methacrylate/ethyl the optional second siloxane-containing copolymer contrib
eneglycol dimethacrylate copolymer, TiO, or a combination utes 2.5 to 6.0 wt.% of the total siloxane units; and a second,
comprising at least one of the foregoing , for example, 0.2 50 optional siloxane-containing copolymer having an average
to 3.0, specifically 0.2 to 2.0, wt % of the polymethylsils siloxane block length from 25 to 65, and a siloxane content
esquioxanes light diffuser additives; or 0.4 to 1.5 wt % of the of 4 to 10 wt % based on the weight of the siloxane
crosslinked poly(methyl methacrylate) light diffuser addi containing copolymer, wherein the first siloxane-containing
tives, 0.4 to 1.5 wt % of the polymethylsilsesquioxanes light copolymer contributes 0 to 3.0 wt.% of the total siloxane
diffuser additives, or a combination thereof, provided that 55 units. For example, based in the total weight of the polymers
the total amount of light diffuser additives is 3.0 wt % or less in the composition, 13 to 50 wt.% of the first siloxane
can be used. containing copolymer, wherein the first siloxane-containing
The high-clarity thermoplastic compositions can be used copolymer has an average siloxane block length from 40 to
in the manufacture of railway vehicle component wherein 50; and 0 to 37 wt % of the optional second siloxane
the component is a window article comprising a sheet 60 containing copolymer, wherein the second siloxane-contain
supported by a frame, wherein the sheet is molded or formed ing copolymer has an average siloxane block length from 40
from the thermoplastic polymer composition. The sheet can to 50 can be present.
have a first side and a second opposite side, and the window In any of the foregoing embodiments of the high-impact
article can further comprises a first hard coat layer disposed railway vehicle component the siloxane-containing copoly
on the first side and a second hard coat layer disposed on the 65 mer can be a poly(carbonate-siloxane) comprising carbonate
second side. A first ultraviolet light-blocking layer can be units derived from bisphenol A; and poly(siloxane) block
disposed between the first hard coat layer and the first side units derived from a polysiloxane bisphenol (15), (16), or a
 US 9,453,128 B2
55 56
combination thereof, wherein E is the average number of thermoplastic polymer composition; and 0.00002 to 5.0 wt
units in the poly(siloxane) blocks. % of a colorant based on the total weight of polymers in the
In still another embodiment, a high impact, colored rail thermoplastic polymer composition, wherein a molded or
way vehicle component selected from a stow bin compo formed sample of the thermoplastic polymer composition
nent, a magazine rack, a seat back component, a component has a notched IZod impact greater than or equal to 400 J/m,
of a trolley cart, and an access door panel, wherein the measured at 23° C. according to ASTM D 256-10 at a 3.2
railway vehicle component is molded or formed from a mm thickness, an OSU integrated 2 minute heat release test
thermoplastic polymer composition comprising a siloxane value of less than 65 kW-min/m and a peak heat release rate
containing copolymer in an amount effective to provide a of less than 65 kW/m, each measured using the method of
total of 2.5 to 5.3 wt % of siloxane units based on the total 10
weight of polymers in the thermoplastic polymer composi FARF25.4, in accordance with Federal Aviation Regulation
tion; a bromine-containing polymer in an amount effective FAR 25.853 (d), and an E662 smoke test DsMax value of
less than 200 when measured at a thickness of 1.6 mm.
to provide 9 to 13 wt % of bromine, based on the total weight In the medium-impact, colored railway vehicle compo
of the polymers in the thermoplastic polymer composition; nents, the siloxane-containing copolymer can comprise an
and 0.00002 to 5.0 wt % of a colorant based on the total 15
weight of the polymers in the thermoplastic polymer com optional first siloxane-containing copolymer comprising an
position, wherein a molded or formed sample of the ther average siloxane block length from 25 to 65, and a siloxane
moplastic polymer composition has a notched IZod impact content of 15 to 25 wt % based on the weight of the
of 400 J/m or greater, measured at 10° C. according to siloxane-containing copolymer, wherein the first siloxane
containing copolymer contributes 0.0 to 0.9 wt.% of the
ASTM D256-10 at a 3.2 mm thickness, an OSU integrated total siloxane units, and a second siloxane-containing copo
2 minute heat release test value of less than 65 kW-min/m lymer having an average siloxane block length from 25 to
and a peak heat release rate of less than 65 kW/m, each 65, and a siloxane content of 4 to 10 wt % based on the
measured using the method of FAR F25.4, in accordance weight of the siloxane-containing copolymer, wherein the
with Federal Aviation Regulation FAR 25.853 (d), and an second siloxane-containing copolymer contributes 2.4 to 5.5
E662 smoke test DsMax value of less than 200 when 25 wt.% of the total siloxane units. For example based on the
measured at a thickness of 1.6 mm. total weight of the polymers in the thermoplastic polymer
In the high impact, colored railway vehicle component the composition, 0 to 5 wt.% of the optional first siloxane
siloxane-containing copolymer can comprise a first silox containing copolymer, wherein first siloxane-containing
ane-containing copolymer comprising an average siloxane copolymer has an average siloxane block length from 35 to
block length from 25 to 65, and a siloxane content of 15 to 30 55; and 45 to 65 wt % of the second siloxane-containing
25 wt % based on the weight of the siloxane-containing copolymer, wherein the second siloxane-containing copoly
copolymer, wherein the first siloxane-containing copolymer mer has an average siloxane block length from 35 to 55 can
be present.
contributes 1.0 to 2.5 wt.% of the total siloxane units, and In any of the foregoing embodiments of the medium
a second siloxane-containing copolymer comprising an impact, colored railway vehicle component, the siloxane
average siloxane block length from 25 to 65, and a siloxane 35
containing copolymer can be a poly(carbonate-siloxane)
content of 4 to 10 wt %, based on the weight of the comprising carbonate units derived from bisphenol A, and
siloxane-containing copolymer, wherein the second silox poly(siloxane) block units derived from a polysiloxane
ane-containing copolymer contributes 0.3 to 3 wt.% of the bisphenol (15), (16), or a combination thereof, wherein E is
total siloxane units with the proviso that the composition the average number of units in the poly(siloxane) blocks.
comprises a total of 2.5 to 5.3 wt % of siloxane units, based 40
Further in any of the foregoing embodiments of the medium
on the total weight of polymers in the thermoplastic polymer impact, colored railway vehicle components, 0.025 to 5 wt
composition. For example, based on the total weight of the % TiO, based on the total weight of the polymers in the
polymers in the thermoplastic polymer composition, 5 to 12 composition can be present. Or, 0.00002 wt % to 0.02 wt %
wt.% of the first siloxane-containing copolymer, wherein of a red dye selected from Solvent Red 135 or Solvent Red
the first siloxane-containing copolymer has an average silox 45
52 and 0.00002 to 0.02% of a blue colorant Selected from
ane block length from 35 to 55; and 38 to 55 wt % of the Pigment Blue 28 or Pigment Blue 29:77007 can be present.
optional second siloxane-containing copolymer, wherein the Or, 0.0001 to 0.1 wt % of carbon black can be present.
second siloxane-containing copolymer has an average silox In another embodiment, a railway vehicle component
ane block length from 35 to 55 can be present. selected from an access door panel, a seat component, a
In any of the foregoing high-impact, colored railway 50 component of a stow bin component, a magazine rack, a seat
vehicle components the siloxane-containing copolymer is a component, a component of a trolley cart, an access door
poly(carbonate-siloxane) can comprising carbonate units panel call button, a light bezel, a door pull, a door handle, an
derived from bisphenol A; and poly(siloxane) block units arm rest, a foot rest and a trolley cart, wherein the railway
derived from a polysiloxane bisphenol (15), (16), or a vehicle component is molded or formed from a thermoplas
combination thereof, wherein E is the average number of 55 tic polymer composition comprises a siloxane-containing
units in the poly(siloxane) blocks. copolymer in an amount effective to provide a total of 2.5 to
In still another embodiment, a medium-impact, colored 6.0 wt % of siloxane units based on the total weight of
railway vehicle component selected from a call button, a polymers in the thermoplastic polymer composition, and
light bezel, a door pull, a door handles, an arm rest, a seat wherein the siloxane-containing copolymer comprises silox
component, and a foot rest, wherein the railway vehicle 60 ane blocks having 10-200 siloxane units per block; and a
component is molded or formed from a thermoplastic poly bromine-containing polymer in an amount effective to pro
mer composition comprises a siloxane-containing copoly vide 9 to 13 wt % of bromine, based on the total weight of
the polymers in the thermoplastic polymer composition; and
mer in an amount effective to provide a total of 2.4 to 5.5 wt wherein a molded or formed sample of the thermoplastic
% of siloxane units based on the total weight of polymers in polymer composition has a Notched Izod impact of 2.0
the thermoplastic polymer composition; a bromine-contain 65 ft-lb/in or greater, measured according to ASTM D 256-10
ing polymer in an amount effective to provide 9 to 13 wt % at a 3.2 mm thickness at room temperature (e.g., 23 C), an
of bromine, based on the total weight of the polymers in the OSU integrated 2 minute heat release test value of less than
 US 9,453,128 B2
57 58
65 kW-min/m and a peak heat release rate of less than 65 (102 g, 0.48 mole), triethylamine (75 g, 0.74 mole) and
kW/m, each measured using the method of FAR F25.4, in Sodium gluconate (10 g). The mixture was transferred to the
accordance with Federal Aviation Regulation FAR 25.853 batch reactor. The reactor agitator was started and circula
(d), and an E662 smoke test DSMax value of less than 200 tion flow was set at 80 L/min. Phosgene flow to the reactor
when measured at a thickness of 1.6 mm.
Still further, in any of the high impact, or high impact was initiated (80 g/min rate). A pH target of 10.0 was
colorable, medium impact, or medium impact colorable maintained throughout the batch by the addition of 33%
components, at least a portion of a Surface of the component aqueous Sodium hydroxide. The total phosgene addition
is painted. amount was 2500 g (25.3 moles). After the phosgene addi
The disclosure is further illustrated by the following 10
tion was complete, a sample from the reactor was obtained
Examples. It should be understood that the non-limiting and verified to be substantially free of unreacted monomers
examples are merely given for the purpose of illustration. and chloroformates. Mw of the reaction sample was deter
Unless otherwise indicated, parts and percentages are by mined by GPC (Mw =23660, PDI-2.6). The reactor was
weight based upon the total weight of the poly(siloxane) purged with nitrogen then the batch was transferred to the
copolymer, brominated polymer, and optional one or more 15 centrifuge feed tank. To the batch in the feed tank was added
third polymers in the poly(siloxane) copolymer composi dilution dichloromethane (10 L) then the mixture was puri
tions. The amount of additives is thus given in parts by fied using a railway vehicle of liquid-liquid centrifuges.
weight per hundred parts by weight of the resins (PHR). Centrifuge one removed the brine phase. Centrifuge two
removed the catalyst by extracting the polymer Solution with
EXAMPLES aqueous hydrochloric acid (pH 1). Centrifuges three through
eight Substantially removed residual ions by extracting the
Materials polymer solution with DI water. A sample of the polymer
The descriptions of the polycarbonates and polycarbonate solution was tested and verified less than 5 ppm each of ionic
copolymers used in the Examples are described in Table 1. chloride and residual triethylamine.
Methods for preparing the brominated polycarbonates and 25
The polymer solution was transferred to the precipitation
the poly(siloxane-carbonate) copolymers are described after feed tank. The polymer was isolated as a white powder by
Table 1. steam precipitation followed by drying in a cone shaped
In Table 1, a reference to D10, D30, or D45 means a dryer using heated nitrogen (210°F). Mw-23532. A pressed
dimethylsiloxane block having an average length of 10.5+/- film of a sample of the polymer was transparent and tough.
2.5, with two additional terminal silicon group (with silicon 30
SiPC 1 (1D10 Copolymer): A representative reaction
hydride levels of less than 20 ppm, volatiles of less than description for a 1% siloxane D10 poly(siloxane-carbonate)
0.4%), 30+/-4 with two additional terminal silicon groups is as follows. To the formulation tank was added dichlo
(with silicon hydride levels of less than 20 ppm, volatiles of romethane (15 L), DI water (12 L), bisphenol A (4410 g,
less than 0.4%, and D3 and D4 levels of less than 10 and 19.3 moles), D10 eugenol-capped siloxane (90 g, 0.07
1000 ppm respectively), or 45+/-5 with two additional 35
moles), p-cumylphenol (174g. 0.82 mole), triethylamine (30
terminal silicon groups (with silicon hydride levels of less g, 0.30 mole) and Sodium gluconate (10 g). The mixture was
than 20 ppm, volatiles of less than 0.4%, and D3 and D4 transferred to the batch reactor. The reactor agitator was
levels of less than 10 and 1000 ppm respectively.). The started and circulation flow was set at 80 L/min. Phosgene
values of D and wt % siloxane for the copolymers in Table flow to the reactor was initiated (80 g/min rate). A pH target
1 were as charged to the reactor. 40 of 10.0 was maintained throughout the batch by the addition
The weight average molecular weights (Mw) of the of 33% aqueous sodium hydroxide. The total phosgene
polymers and copolymers in Table 1 were measured by gel addition amount was 2300 g (23.3 moles). After the phos
permeation chromatography using polycarbonate standards. gene addition was complete, a sample from the reactor was
The endcap was PCP (p-cumyl phenol) or phenol. The obtained and verified to be substantially free of unreacted
percent of siloxane and bromine is weight percent based on BPA and chloroformates. Mw of the reaction sample was
the weight of the copolymer. determined by GPC (Mw-22370 Daltons, PDI-2.4). The
TABLE 1.
Wt 96 Avg. Siloxane Wt %
Acronym Description Mw PDI Endcap Siloxane Length Br
TBBPA-BPA TetrabromoBPA/BPA Copolymer 23,660 2.6 PCP 26
BCS2 Tetrabromo BPA Oligomer 2,638 1.7 Phenol 52
SPC 1 D10 siloxane block co-polycarbonate 30,000 PCP 1 10
SPC 1B D10 siloxane block co-polycarbonate 22,200 PCP 1 10
SPC 2 D10 siloxane block co-polycarbonate 23,600 3.0 PCP 5 10
SPC3 D30 siloxane block co-polycarbonate 23,472 2.2 PCP 6 30
SPC 4 D45 siloxane block co-polycarbonate 23,013 2.2 PCP 6 45
SPC 5 D45 siloxane block co-polycarbonate 29,852 2.6 PCP 2O 45
PC 1 PCP Capped BPA Polycarbonate 21,900 2.5 PCP
PC 2 PCP Capped BPA Polycarbonate 29,830 2.5 PCP

TBBPA-BPA Copolymer. reactor was purged with nitrogen then the batch was trans
A representative reaction description for a 26 wt % ferred to the centrifuge feed tank.
bromine copolycarbonate batch is as follows. To the batch in the feed tank was added dilution dichlo
To the formulation tank was added dichloromethane (16 65 romethane (10 L) then the mixture was purified using a
L), DI water (12 L), bisphenol A (2250 g, 9.9 moles), railway vehicle of liquid-liquid centrifuges. Centrifuge one
tetrabromobisphenol A (2250 g, 4.1 moles), p-cumylphenol removed the brine phase. Centrifuge two removed the cata
 US 9,453,128 B2
59 60
lyst by extracting the polymer Solution with aqueous hydro SiPC 3 (6D30 Copolymer).
chloric acid (pH 1). Centrifuges three through eight sub The 6D30 copolymer (6 wt % siloxane D30 poly(silox
stantially removed residual ions by extracting the polymer ane-carbonate)) was made in similar fashion to Examples 14
solution with DI water. A sample of the polymer solution and 15 in U.S. Pat. No. 6,870,013 using a D30 eugenol
was tested and verified less than 5 ppm each of ionic capped siloxane fluid. The polymer contains about 6 wt %
chloride and residual triethylamine. siloxane. The Mw is about 23,500 Daltons.
The polymer solution was transferred to the precipitation SiPC 4 (6D45 Copolymer).
feed tank. The polymer was isolated as a white powder by
steam precipitation followed by drying in a cone shaped 10 The 6D45 polymer (6 wt % siloxane D45 poly(siloxane
dryer using heated nitrogen (99° C. (210°F.)). carbonate)) was made in similar fashion to Examples 14 and
SiPC 2 (5D10 Copolymer). 15 in U.S. Pat. No. 6,870.013 using D45 eugenol-capped
A representative reaction description for a 5 wt % silox siloxane fluid. The polymer contains about 6% siloxane. The
ane D10 poly(siloxane-carbonate) batch is as follows. Mw is about 23,000 Daltons.
To the formulation tank was added dichloromethane (15 15 SiPC 5 (20D45 Copolymer):
L), DI water (12 L), bisphenol A (4125 g, 18.1 moles), D10 The 20D45 polymer (20 wt % siloxane D45 poly(silox
eugenol capped siloxane (375 g, 0.30 moles), p-cumylphe
ane-carbonate)) was made in a like manner to the 5D10
nol (166 g., 0.78 mole), triethylamine (30 g, 0.30 mole) and poly(siloxane-carbonate)
Sodium gluconate (10 g). The mixture was transferred to the except that a D45 eugenol-capped
batch reactor. The reactor agitator was started and circula siloxane fluid was used. The polymer contains about 20%
tion flow was set at 80 L/min. Phosgene flow to the reactor 20 siloxane. The Mw is about 30,000 Daltons.
was initiated (80 g/min rate). A pH target of 10.0 was The additive types and details that were used in the
maintained throughout the batch by the addition of 33% compositions of the Examples are shown in Table 2.
TABLE 2
Component Chemical Name Supplier Grade
Phosphite Tris (2,4-di-tert-butylphenyl) phosphite various
DF1040 Methylhydrogen siloxane fluid Momentive DF 1040
Performance Materials
OPTS Octaphenylcyclotetrasiloxane Shin-Etsu Chemical Co. —
D4 Octamethyltetrasiloxane Aldrich Chemical Co.
KSS Potassium diphenylsulfone sulfonato Arichem LLC KSS
Rimar salt Potassium perfluorobutane sulfonato Lanxess Bayowet C4
STB Sodium trichlorobenzene sulfonato Arichem LLC STB
sesquihydrate
TSAN SAN encapsulated PTFE Sabic Innovative TSAN
Plastics
TiO2 Type 1 Titanium dioxide, (organic coating) Kronos Kronos 2233
TiO Type 2 Titanium dioxide, (organic coating) Kronos KRONOS 24SO
Phosphorus acid Phosphorus acid solution (0.15%)
Tinuwin 1577 2-(4,6-Diphenyl-1,3,5-triazin-2-yl)-5- Ciba Specialty Twin 1577 FF
hexyloxyphenol Company Corp.
UVA 234 2-(2-hydroxy-3,5-di-cumyl)benzotriazole Ciba Specialty Tinuvin 234
Company Corp.
Cyasorb 3638 2,2'-(1,4-Phenylene)bis(4H-3,1- CYTEC Industries CYASORBUV-3638
benzoxazin-4-one

45
aqueous sodium hydroxide. The total phosgene addition Extrusion and Molding Conditions.
amount was 2300 g (23.3 moles). After the phosgene addi Extrusions were performed either on a single screw
tion was complete, a sample of the reactor was obtained and extruder or a twin-screw extruder. Typically the D10 poly
verified to be substantially free of unreacted BPA and (siloxane-carbonate)-containing compositions and corre
chloroformates. Mw of the reaction sample was determined 50 sponding controls were performed on a single or a twin
by GPC (Mw-21991 Daltons, PDI-2.6). The reactor was screw extruder. The D30 and D40 poly(siloxane-carbonate)-
purged with nitrogen then the batch was transferred to the containing compositions and corresponding controls were
centrifuge feed tank. performed on a twin screw extruder.
To the batch in the feed tank was added dilution dichlo The compositions prepared with a single screw extruder
romethane (10 L) then the mixture was purified using a 55
were made as follows. All ingredients were dry blended for
railway vehicle of liquid-liquid centrifuges. Centrifuge one about 4 minutes using a paint shaker. The single screw
extruder was a Sterling 13/4 inch (44.5 mm) extruder
removed the brine phase. Centrifuge two removed the cata (Length/Diameter (L/D) ratio=24/1, with a vacuum port
lyst by extracting the polymer Solution with aqueous hydro located near die face, with barrel and die temperature set
chloric acid (pH 1). Centrifuges three through eight sub points of 270, 275,288, 288° C.).
stantially removed residual ions by extracting the polymer 60 The compositions prepared on the 30 mm WP twin screw
solution with DI water. A sample of the polymer solution extruder were made as follows. All ingredients were dry
was tested and verified less than 5 ppm each of ionic blended for about 4 minutes using a paint shaker or a drum
chloride and residual triethylamine. tumbler. The twin screw extruder contained a vacuum port
The polymer solution was transferred to the precipitation located near die face. Typically the compositions were
feed tank. The polymer was isolated as a white powder by 65 compounded with an applied vacuum of 20+inches of Hg.
steam precipitation followed by drying in a cone shaped The compositions prepared on a W&P 50 mm Mega twin
dryer using heated nitrogen (210°F). Mw-21589 Daltons. screw were made as follows. All additives (stabilizers and/or
 US 9,453,128 B2
61 62
colorants) were dry blended off-line as concentrates using Low Heat Release and Low Smoke Density Composi
one of the primary polymer powders as a carrier and tions.
starve-fed via gravimetric feeder(s) into the feed throat of 1. 1D10 (SiPC 1) Blends with TBBPA-BPA Copolymer.
the extruder. The remaining polymer(s) were starve-fed via Table 3 illustrates that a combination of a poly(siloxane
gravimetric feeder(s) into the feed throat of the extruder as carbonate) having an average siloxane block length (D) of
well. The compositions were compounded with an applied about 10 units and 1 wt % siloxane in the copolymer and a
bromine-containing copolycarbonate can produce a blend
vacuum of 20+inches of Hg. The extruder was a nine-barrel composition with excellent flame and Smoke performance
machine (approx. Length/Diameter (L/D) ratio=36:1) with a (EX 1-4) compared with compositions having only the
vacuum port located in barrel 7. 10
brominated copolycarbonate (CEX 2-6), only the poly(si
The compositions were molded after drying at 121°C. for loxane-carbonate) (CEX 1) or only a polycarbonate without
4 hours on a 260-ton (236 metric ton) Van Dorn or an 85 Ton either the poly(siloxane-carbonate) or the brominated poly
Van Dorn molding machine operating at about 300 to 320° carbonate present (CEX 2).
C. with a mold temperature of about 80° C. It will be Specifically a composition having poly(siloxane-carbon
recognized by one skilled in the art that the method is not 15
ate) in combination with a polycarbonate (CEX 1) passes the
limited to these temperatures or processing equipment. smoke testing (DsMax) target of less than 200 with a value
Testing Methods. of 109 but fails the 2-minute OSU test target of less than 65
Standard ASTM testing was performed at 50% relative kW-min/m with a value of 68 and also fails the peak OSU
test target of less than 65 with a value of 98. As brominated
humidity (RH) and unless otherwise indicated at room copolycarbonate is added to the composition the 2-minute
temperature (RT). OSU performance and the peak OSU performance improves
Notched Izod (NI-125) testing was conducted according (EX 1-EX 4) and both the target values for the 2-minute and
to ASTM D256-10 on a molded sample having a 0.125 inch peak OSU target values are achieved (values below 65)
(3.2 mm) thickness. while the smoke performance (DSMax) is maintained at
Multiaxial impact (MAI) was measured at a speed of 3.3 passing levels (values less than 200). This improvement in
m/s on a 3.2x102 mm disc using a plunger with a hemi 25 flame test performance was achieved with as little as 5.2 wt
spherical end and a diameter 12.70 mm in accordance with % bromine in the composition (EX 1). In addition EX 1-EX
ASTM D3763. 4 all have densities below the targeted maximum density of
Heat deflection temperature was measured on an annealed 1.320 for certain rail applications. A thermoplastic compo
3.2 mm sample in accordance with ASTM D 648 using a sition without the poly(siloxane-carbonate)or the bromi
Stress of 0.455 or 1.82 MPa. 30 nated copolycarbonate(CEX 2) also fails both the 2-minute
The tensile properties were measured in accordance with and peak OSU performance tests with values of 73 and 139
ASTM D638 at 50 mm/min. although it too passes the smoke test (DSMax) with a value
of 137.
The flexural properties were measured in accordance with The benefit of the presence of siloxane in the composition
ASTM D 790 at 1.27 mm/min. 35 is illustrated by compositions that only contain the bromi
In most cases melt volume ratio (MVR) was run at 300° nated copolycarbonate only (CEX 3-6). They pass the OSU
C./1.2 Kg at 360 second dwell. flame testing with 2-minute values of less than 65 and the
Molecular weight was measured via GPC using polycar OSU peak testing with values of less than 65 but perform
bonate standards. very poorly in the Smoke test exceeding the target of less
The reported transmission data (%T) was measured at the 40 than 200 with values of 561, 382 and 457.
indicated thickness on a Gretagmacbeth Color-Eye 7000A Furthermore the clarity as measured by % transmission
(Propalette Optiview Gold version 5.2.1.7) using the color and % haze is excellent for the poly(siloxane-carbonate)
space CIE 1931 (Illuminant C and a 2° observer) and is compositions with the brominated copolycarbonate(EX 1-4)
equivalent to the “Y” tristimulus value. with transmission values of 88% or greater and haze values
The reported the yellowness Index (YI) data was mea 45 of 1.2% or less. These values are as good or better than the
Sured at the indicated thickness on a Gretagmacbeth Color polycarbonate control (CEX 2) with a % transmission of 89
Eye 7000A (Propalette Optiview Gold version 5.2.1.7) in and a % haze of 2.4. The yellowness index value, a measure
accordance with ASTM E313-73 (D1925) using Illuminant of how yellow the part appears, for EX 1 and EX 2 at 2.7 and
C and a 2° observer. 2.9 is also very close to the value for the polycarbonate
Heat release testing was performed on 15.2x15.2 cm 50 control 2.4. As the brominated copolycarbonate content
plaques 1.5 mm thick using the Ohio State University (OSU) increases the yellowness index increases significantly from
rate-of-heat release apparatus, in accordance with the 2.5 (EX 1) at 5.2% bromine content to 5.2 at 13% bromine
method shown in FAR 25.853 (d), and in Appendix F. content (EX 4). High clarity, low yellowness, and low
section IV (FARF25.4). Total heat release was measured at density values in combination with excellent flame and
the two-minute mark in kW-min/m2 (kilowatt minutes per 55 Smoke performance are critical for use of these compositions
square meter). Peak heat release was measured as kW/m2 in airplane window applications and so higher bromine
(kilowatts per square meter). The heat release test method is content compositions are expected to have limited utility in
also described in the "Aircraft Materials Fire Test Hand window applications.
book” DOT/FAA/AR-00/12, Chapter 5 “Heat Release Test Notched Izod impact values at or near 2 ft-lbs/in (1.00
for Cabin Materials. 60 J/cm) or greater can also provide sufficient ductility for
Smoke density testing (ASTM E-662-83, ASTM F-8,4- preparation of polycarbonate sheet for use in window appli
83, Airbus ABD0031, Boeing BSS 7239) was performed on cations and EX 1-3 possess the targeted ductility perfor
7.5x7.5 cm plaques of 1.5 mm thickness according to the mance for window applications as well. As the bromine
method shown in FAR 25.853 (d), and in Appendix F. contents of the compositions increase the notched Izod
section V (FARF25.5). Smoke density was measured under 65 ductility decreases to values less than 2 (EX 4 and CEX 5-6)
flaming mode. Smoke density (Ds) at 4.0 min, and the max and so high bromine contents in the compositions at 11% or
level (DSMax) were reported. greater would likely not be useful in window applications.
 US 9,453,128 B2
63 64
TABLE 3
Components and Properties CEX 1 EX 1 EX 2 EX3 EX4 CEX 2 CEX3 CEX 4 CEX 5 CEX 6
TBBPA-BPA O 2O 30 40 50 O 2O 30 40 8O
SPC 1 40 40 40 40 40
PC 2 60 40 30 2O 10 100 8O 70 60 50
IRGAPHOS 1.68 O.O O.O O.O O.O O.O O.O O.O O.O O.O O.O
Formulated Total wt % Siloxane 0.4 0.4 0.4 0.4 0.4 O O O O O
Composition Total wt % Bromine O 5.2 7.8 10.4 13 O 5.2 7.8 10.4 13
-Siloxane D Length 10 10 10 10 10
MVR 6.5 6.O S.6 S.6 5.3 6.4 6.6 6.8 6.8 6.4
NI-125, RT Ductility 100 1OO O O O 100 1OO O O O
Jim 949 867 128 109 92 887 8SO 130 91 87
Ft-bStin 17.8 16.2 2.4 2.O 1.7 16.6 15.9 2.4 1.7 1.6
MAI-RT Ductility 1OOO 1OO.O 1OOO 1OO.O 1OOO 1OOO 1OO.O 1OOO 1OO.O 1OO.O
Energy to max load-Avg J 79 78 76 75 81 75 75 76 78 78
Energy to failure-Avg J 91 90 89 88 89 81 81 82 84 83

Energy, Total-Avg J 91 90 89 88 89 81 81 84 84 83
Density, -Avg gfcc 1.194 1.239 1.268 1.288 1314 1.198 1242 1.265 1.289 1.315
Specific Gravity-Avg 1197 1242 1.271 1291 1.317 1.198 1243 1.266 1.290 1316
HDT 1.8 MPa. 128 132 137 137 142 132 137 139 142 143
OSU Test FAR 25.853 (d) Appendix F, Part IV
2 Min OSU Average 68 35 30 25 11 73 24 26 30 17
Standard deviation 14 7 1 4 10 19 4 5 3 2
Peak OSU Average 98 63 S4 48 43 139 70 57 66 56
Standard deviation 8 4 3 2 1 14 11 5 8 14
NBS Smoke Density (ASTM F814/E662, Flaming Mode)
DSMax Ave 109 139 68 97 59 137 561 382 457 3O4
Standard deviation 28 44 32 18 23 19 164 69 243 181
Optical Properties
Optical % T at 62 mil (1.58 mm) 89 89 89 88 88 89 89 89 88 88
Properties YI 2.7 2.7 2.9 S.1 5.2 2.4 3.3 4.1 S.O S.O
% Haze 1.O O.6 0.7 O.8 1.2 2.4 1.7 1.4 1.8 1.7

2.5D10Compositions (SiPC2) with TBBPA-BPA Copo- combination of polysiloxane block copolycarbonates and a
lymer 35 brominated copolycarbonate outperforms either polysilox
The results in Table 4 using a poly(siloxane-carbonate) ane block co thermoplastic compositions or the brominated
having an average siloxane block length of 10 units and 5 wt thermoplastic compositions in OSU flame and Smoke den
% siloxane in the copolycarbonate further illustrates that a sity testing.
TABLE 4

Components and Properties CEX 7 EX 5 EX 6 EX 7 EX 8 CEX 8

TBBPA-BPA O 50 70 8O 90 1OO
SPC 2 100 50 30 2O 10 O
IRGAPHOS 1.68 O.O6 O.O6 O.O6 O.O6 O.O6 O.O6
Formulated Total wt % Siloxane S.O 2.5 1.5 1.O O.S O.O
Composition Total wt % Bromine O.O 13.0 18.2 20.8 23.4 26.O
-Siloxane D Length 10 10 10 10 10 10
MVR-6 min Cc 10 min. 18.4 10.1 7.9 7.6 S.6 4.6
Tg o C. 141 161 168 170 178 182
NI-12S RT Ductility 100 O O O O O
Jim 721 127 78 68 57 50
ft-Ibsin 13.5 2.4 1.5 1.3 1.1 O.9
MAI-RT Ductility 100 1OO 100 1OO 100 60
Energy to max load-Avg J 65 66 76 76 77 77
Energy to failure-Avg J 73 72 82 82 82 83

Energy, Total-Avg 73 72 82 83 82 83
Modulus of Elasticity-Avg MPa. 2220 2410 2SOO 262O 2660
Stress at Yield-Avg MPa. 58 68 72 74 77
Stress at Break-Avg MPa. 50 60 61 61 65
Elongation at Yield-Avg % 6 7 7 7 7
Elongation at Break-Avg % 87 105 95 92 102
Flexural Modulus-Avg MPa. 2100 228O 248O 242O 2450
Flex Stress at 5% Strain-Avg MPa. 84 93 99 98 101
Flexural Stress at Yield-Avg MPa. 92 106 114 113 118
 US 9,453,128 B2
TABLE 4-continued
Components and Properties CEX 7 EX 5 EX 6 EX 7 EX 8 CEX 8
Density-Avg gfcc 1.183 1.307 1.363 1.385 1422 1.450
Specific Gravity-Avg 1186 1310 1.367 1.388 1.426 1.454
HDT 1.8 MPa. 117 134 136 146 150 1S6
HDT O455 MPa. 130 147 154 159 16S 171
OSU Test FAR 25.853 (d) Appendix F, Part IV
OSU 2 Min. Average 102 40 27 34 28 26
Standard deviation 11 3 6 3 6 5
OSU Peak Average 93 45 37 36 37 47
Standard deviation 13 2 3 3 3 12
NBS Smoke Density (ASTM F814/E662, Flaming Mode)
DSMax Ave 80.7 14.7 12.O 9.0 12.7 60.7
Standard deviation 33.6 O6 4.4 2.6 2.1 2O.S
Optical Properties
% T at 62 mil (1.58 mm) 88.6 85.8 86.0 86.5 88.2 89.0
YI 2.8 13.4 13.1 6.4 3.8 2.9
% Haze 12.2 5.5 4.1 2.4 O.9 1.1

CEX 7 contains no bromine and fails both the OSU 2 min mance and high flow properties can also be achieved by
total and peak heat release tests with values greater than 65. Some of the combinations of brominated polycarbonate
CEX 7 in this test passed the DsMax flame test. CEX 8 has copolymers and polysiloxane block copolycarbonates. For
no siloxane present and it passes the OSU flame and peak 25 Example EX 9, 12 and 22 in Table 5 passed the 2-min flame
heat release test with values below 65 but the DsMax values and heat release tests with flame and heat release values less
while passing with a value below 200. However, CEX 8 is than 65 and smoke values below 200 and showed excellent
extremely brittle which would make it difficult to machine room temperature ductility with 100% ductility and with
and form into parts, and has a high density, which would by impact energies of greater than 500 J/m at high melt flow
deleterious to weight savings needed to manufacture light 30 values (MVR values of 9.6-12 cc/10 min.). The results from
weight railway vehicles. By contrast compositions having Table 5 shows that compositions with polysiloxane content
poly(siloxane-carbonate) and brominated copolycarbonate greater than 1% achieve high room temperature impact (both
EX 14 and EX 15 have identical bromine content but EX 14
passed OSU flame and peak heat test with values below 65 has 1% polysiloxane content while EX 15 has 2 wt %
and exhibited DsMax Smoke results of less than 15 with polysiloxane content and EX 14 has no ductility and room
standard deviations below 4.4 units. 35
temperature while EX 15 shows partial room temperature
3. 6D30 (SiPC 2), 6D45 (SiPC 3) and 20D45 (SiPC 3) ductility). Furthermore it is also desirable for the composi
Compositions with TBBPA-BPA Copolymer tions to have less than 13 wt % brominated copolycarbonate
The flame and Smoke performances of a series of com content in order to achieve high ductility (EX 9 and EX 10
positions using a bromine copolycarbonate having 26 wt % both have 2 wt % polysiloxane in their compositions but EX
bromine atoms with siloxane block co-polycarbonates hav 40 9 has 10.4 wt % bromine content from the brominated
ing average siloxane chain lengths of 45 and 30 and siloxane copolymer while EX 10 has 13 wt % bromine content and
contents of 6 wt % in the copolymer and with a poly EX 9 has excellent room temperature impact while EX 10
(siloxane-carbonate) having an average of 45 polysiloxane has low room temperature impact). The examples show that
units and 20 wt % siloxane in the copolymer are shown in the polysiloxane block copolycarbonates that have 20 wt %
Table 5. 45 polysiloxane content are somewhat more efficient in pro
Examples EX 9-22 illustrate that the OSU flame and heat viding high ductility and room temperature impact strength
performance as well as Smoke performance is maintained in than the copolymers with 6 wt % content. EX 9 was made
compositions of polysiloxane block copolycarbonates and from a poly(siloxane-carbonate) having 20 wt % polysilox
brominated polycarbonate copolymers with siloxane change ane in the copolymer and EX 15 was made from a poly
lengths of 30 and 45 polysiloxane units and siloxane wt % 50 (siloxane-carbonate) having 6 wt % polysiloxane in the
as low as 5 wt % and as high as 20 wt % in the copolymers. copolymer, and both have identical bromine and polysilox
Comparative example CEX9 (Table 5) and CEX 5 (Table 3) ane contents, but EX9 has a higher impact and ductility
that have no poly(siloxane-carbonate) in the compositions value than EX 15. In addition the data in Table 5 show that
either fail the DsMax Smoke test with a value of 195 and 457 high impact values could be achieved using both the poly
or inconsistently pass as a result of high values and a high 55 siloxane block copolycarbonates having average siloxane
standard deviation of 78 and 243 units, respectively. This chain lengths of 45 and 30 repeating units. Furthermore the
result illustrates once again that the presence of siloxane in high ductility can be achieved with copolymers having
the blend is necessary to achieve consistent Smoke perfor either 20% polysiloxane content or 6% polysiloxane con
mance pass values. tent. In the case of the polysiloxane block copolycarbonates
EX 16 (without heat stabilizer), when compared with EX 60 that have 6% polysiloxane content, it is also possible to
17 (contain similar siloxane and bromine content as EX 16 achieve transparency. One particular benefit of the use of
but with heat stabilizer), demonstrates that the heat stabilizer long siloxane chain lengths (chain lengths greater than 10
IRGAPHOS 168 has no significant effect on the flame or repeating units) and with about 6 wt % siloxane in the
Smoke performance in the compositions. poly(siloxane-carbonate) copolymer is that a combination of
High Impact Compositions. 65 high impact and transparency can be achieved in addition to
Formulations passing both the OSU flame and smoke tests maintaining excellent OSU flame and Smoke performance in
and having excellent room temperature ductility perfor the compositions. Specifically EX 12 with 2 wt % siloxane
 US 9,453,128 B2
67 68
and 7.8 wt % bromine content and that is formulated from ing, excellent haze with a value of 3.3% and an excellent %
a poly(siloxane-carbonate)having an average chain length of transmission with of value of 88% while having an OSU
45 siloxane and about 6 wt % siloxane in the copolymer has flame value of 46, a peak heat release value of 55 and a
100% room temperature ductility during notched Izod test DSMax
TABLE 5
Components, Properties EX9 EX 10 EX 11 EX 12 EX 13 EX 14 EX 15 EX 16

TBBPA-BPA 40 50 60 30 40 40 40 40
2OD4S SPCS 10 10 10
6D4S SPC 4 34 9 17 34 34
6D30 SPC 3
PC1 50 40 30 36 51 43 26 26
PC 2
IRGAPHOS 1.68 O.O6 O.O6 O.O6 O.O6 O.O6 O.O6 O.O6 O.OO
Total Wt 96 Siloxane 2.0 2.0 2.O 2.0 O.S 1.O 2.0 2.O
Formulation Wt 96 Bromine 10.4 13.0 15.6 7.8 10.4 10.4 10.4 10.4
Siloxane D Length 45 45 45 45 45 45 45 45
MVR-6 min Cc 10 min. 11.1 9.7 7.5 13.6 15.8 13.7 11.4 11.4
Tg o C. 160 162 168 1S6 160 160 160 160
NI-12S RT Ductility 1OO O O 1OO O O 60 40
Jim 579.O 154.O 136.0 646 105 122 371 3O4
ft-lbs in 10.8 2.9 2.5 12.1 2.0 2.3 6.9 5.7
MAI-RT Ductility 1OO 100 100 1OO 100 1OO 100 100
Energy to max load-Avg J 71 74 76 75 73 77 75 75
Energy to failure-Avg J 75 77 81 82 77 82 83 81

Energy, Total-Avg J 75 77 81 82 77 82 83 81
Density-Avg gfcc 1.281 1.306 1.330 1.254 1284 1.281 1277 1.276
Specific Gravity-Avg 1.284 1309 1.333 1.257 1.287 1.284 128O 1.279
HDT 1.8 MPa. 139 141 144 128 134 133 132 132
2 Min OSU Average 32 23 19 46 39 41 45 35
Std. dew. 3.2 1.9 4.7 5.7 3.6 6.O 4.5 2.7
Peak OSU Average 50 42 41 55 49 48 55 46
Std. dew. 3.8 2.3 3.1 3.0 3.4 3.3 2.2 4.1
DSMax Ave 45 48 61 30 15 14 18 29
Std. dew. 13 9 35 8 6 7 10 12
% T at 62 mil (1.58 mm)
YI
% Haze
YI at 125 mill (3.2 mm) 39 43 47 12 6 9 15 14
% T at 125 mill (3.2 mm) 29.6 27.3 24.1 83.1 86.7 84.8 80.8 81.6
% Haze at 125 mill (3.2 mm) 99.2 99.2 99.9 3.3 1.6 2.2 4.9 3.9
Components, Properties EX 17 EX 18 EX19 EX 20 EX 21 EX 22 CEX 9

TBBPA-BPA 40 50 60 70 50 40 40
2OD4S SPCS
6D4S SPC 4 34 34 34 25
6D30 SPC 3 42 50
PC1 26 16 6
PC 2 5 8 10 60
IRGAPHOS 1.68 O.O6 O.O6 O.O60 OO60 OO6 O.O6 O.O6
Total Wt 96 Siloxane 2.0 2.O 2.0 1.5 2.5 3.0 O.O
Formulation Wt 96 Bromine 10.4 13.0 15.6 18.2 13.0 10.4 10.4
Siloxane D Length 45 45 45 45 30 30
MVR-6 min Cc 10 min. 1O.S 9.O 7.0 6.O 7.3 7.7 15.4
Tg o C. 159 163 167 171 164 161 158
NI-125 RT Ductility O O O O O 100 O
Jim 16O.O 129.0 102.0 83.8 139 S13.O 83.2
ft-Ibsin 3.0 2.4 1.9 1.6 2.6 9.6 1.6
MAI-RT Ductility 100 100 1OO 100 1OO 100 100
Energy to max load-Avg J 73 73 71 73 58 72 69
Energy to failure-Avg J 79 79 76 79 63 77 73

Energy, Total-Avg J 79 79 76 79 63 77 73
Density-Avg gfcc 1.281 1.307 1.329 1360 1.305 1277 1291
Specific Gravity-Avg 1.285 1311 1.333 1364 1.308 1.28O 1294
HDT 1.8 MPa. 136 140 142 143 136 131 139
2 Min OSU Average 27 23 2O 34 32 40 28
Std. dev. 6.7 3.1 O.6 2.3 2 2 10.1
Peak OSU Average 47 45 42 38 33 42 S4
Std. dev. 2.5 3.1 3.5 3.5 2 1 8.1
DSMax Ave 53 61 43 2O 76 58 195
Std. dev. 22 10 12 4 55 15 78
 US 9,453,128 B2
TABLE 5-continued
% T at 62 mil (1.58 mm) 75 79 87
YI 22.5 12.0 S.1
% Haze 14.6 12.1 6.6
YI at 125 mill (3.2 mm) 16 23 28 2
% T at 125 mill (3.2 mm) 79.9 72.9 63.9 89.3
% Haze at 125 mill (3.2 mm) 4.4 10.7 23.6 O6

smoke value of 30. EX 22 with 3.0 wt % siloxane and 10.4 10 than 10 polysiloxane chain lengths) and the '% polysiloxane
wt % bromine that is formulated from a poly(siloxane in the copolymer increases (20 wt % polysiloxane in the
carbonate)having an average chain length of 30 polysiloxane copolymer is much worse than 6 wt % polysiloxane) The
units and about 6 wt % siloxane in the copolymer also shows results further Suggest that the poly(siloxane-carbonate)
excellent impact performance, transparency, haZe and flame providing the best transparency, haZe and YI values and
and Smoke performance. 15 yellowness index values for use in window applications is
Transparent Compositions. the poly(siloxane-carbonate) having approximately 10 poly
Formulations that pass the OSU and smoke testing and siloxane repeating units and 1 wt % polysiloxane content in
that have very high percent transmission values (greater than the copolymer.
85%), very low haze values (less than 2.5%) and low Low OSU Heat Release, Low Smoke, TiO-Containing
yellowness values (less than 6) are also possible to obtain 20 Compositions.
using compositions of polysiloxane block copolycarbonates Titanium dioxide is a common additive used to increase
and brominated polycarbonate copolymers. Formulations the whiteness of polymer compositions. Compositions hav
with high transmission, low haZe and low yellowness index ing poly(siloxane-carbonate) and brominated copolycarbon
values that pass OSU flame and smoke tests are particularly ate were prepared that also contained various amounts of
useful in window articles, gauge and dashboard covers and 25 titanium dioxide in order to determine its effect on density
in window dust covers in railway vehicles. Formulations and stability of the thermoplastic compositions. The results
that meet the OSU flame and smoke and requirements and are shown in Table 6.
TABLE 6
Blend Composition Components EX 23 EX 24 EX 2S EX 26 EX 27 EX 28 EX 29
TBBPA-BPA 40.0 40.0 40.0 40.0 40.0 40.0 40.0
SPC 4 SO.OO SO.OO SO.OO SO.OO SO.OO SO.O SO.OO
PC 1 1O.O 1O.O 10.00 1O.OO 10.00 1O.O 1O.O
TiO2 O.O 1.O 2.0 3.0 4.0 S.O 7.0
IRGAPHOS 1.68 O.O6 O.O6 O.O6 O.O6 O.O6 O.O6 O.O6
Total Total wt % Siloxane 3.00 3.00 3.0 3.00 3.00 3.00 3.00
Formulation Total wt % Bromine 10.4 10.4 10.4 10.4 10.4 10.4 10.4
MVR-6 min 8.2 8.7 8.86 8.69 8.44 8.52 8.46
MVR-18 min 8.8 9.3 9.73 9.73 9.90 10.40 1O.OO
% MVR Change 6 min to 18 min 7.0 12.9 18.1 18.1 20.1 26.2 21.4
NI-125 RT Ductility 100 100 1OO 100 1OO 100 100
Jim 577 608 592 544 515 52O 487
ft-Ibsin 10.8 11.4 11.1 10.2 9.6 9.7 9.1
Density-Avg. g. cc 1.278 1.282 1.287 1.30S 1316 1.319 1.340
Specific Gravity-Avg 1.281 1.286 1290 1.308 1.319 1322 1343

45

that have high percent transmissions, low haZe and low The data in Table 6 illustrate that melt stability decreases
yellowness index values can be obtained from a variety of as the TiO, content increases (EX 24-EX 29) compared to a
polysiloxane block copolycarbonates with the brominated control that has no TiO present (EX 23) as measured by the
polycarbonate copolymer. Examples include EX 1. EX 2. change in the MVR values after 6 and 18 minute heating at
50 300° C. To achieve 20% or less melt change, then 4 PHR or
EX 3 and EX 4 from Table 3 above prepared from a
poly(siloxane-carbonate) having 10 polysiloxane repeating less TiO2 can be used in the thermoplastic compositions (EX
units and 1 wt % polysiloxane content in the copolymer; EX 24-EX 26 vs. EX 27-EX 29).
5, EX6, EX 7, and EX 8 from Table 4 above prepared from The data in Table 7 shows the effect of TiO, on the smoke
a poly(siloxane-carbonate)have 10 polysiloxane repeating density performance of a composition with and without
55 poly(siloxane-carbonate) present.
units and 5 wt % polysiloxane content in the copolymer; EX
13 and EX 14 from Table 5 above prepared from a poly TABLE 7
(siloxane-carbonate) have 45 polysiloxane repeating units
and 6 wt % polysiloxane content in the copolymer and EX Component, Properties CEX 10 EX 30
22 from Table 5 above prepared from a poly(siloxane 60
TBBPA-BPA Copolymer 40.0 40.O
carbonate) have 30 polysiloxane repeating units and 6 wt % SPC 4 O.OO SO.OO
polysiloxane content in the copolymer. The yellowness PC 1 6O.O 1O.O
index generally increases as the wt % of brominated copo TiO2 2.0 2.0
IRGAPHOS 1.68 O.O60 OO60
lycarbonate in the compositions increases, the percent haZe Formulated Blend Composition Total wt % Siloxane O 3
generally increases as the wt % polysiloxane in the compo 65 Total wt % Bromine 10.4 10.4
sition increases and the chain length of the polysiloxane MVR-6 min 17.7 9.5
increases (30 and 45 polysiloxane chain lengths are worse
 US 9,453,128 B2
71 72
TABLE 7-continued is shown in Table 4 where the wt % bromine increases from
Component, Properties CEX 10 EX 30
0 to 26 wt % and the density increases from 1.183 to 1.450
g/cc. The results in Table 5 above also illustrate that increas
MVR-18 min 186 10.4 ing the amount of siloxane in the compositions does slightly
MVR, % Change S.1 9.6 5 decrease the density in the compositions. For example, the
Tg 160 161 wt % bromine is the same in CEX 10 and EX 13-EX 15 at
NI-125 RT putility s: S 10.4 wt %, but the wt % siloxane increases from 0 to 2.0 wt
ft-Ibsin 1.6 8.7 % and the density decreases from 1.291 to 1.277 g/cc. The
MAI-RT Ductility 100 1OO chain length of siloxane or the wt % siloxane in the
Energy to max load-Average J 72 70 10 poly(siloxane-carbonate)does not show a large influence in
E. tity. Arge g 2. 2. the density based on the results in Table 5. In order to obtain
Density.Avg gfcc 1.304 1293 a density below the targeted maximum density of 1.320 g/cc
Specific Gravity-Average 1.3O8 1296 for certain rail applications, it appears that less than 15 wt %
FAA Smoke Density Average 231.0 72.O bromine can be used.
Ds at 4 min Standard deviation 78.2 43.6 is The presence of titanium dioxide further increases the
density of the compositions as illustrated in Table 6. In Table
The results in Table 7 show that the ability of poly 6, compositions are shown having 3.0 wt % siloxane and
(siloxane-carbonate)s in the compositions to reduce Smoke 10.4 wt % bromine contents and increasing amounts of
is not diminished by the presence of TiO, in the composi- titanium dioxide. In EX 23-29 the wt % titanium dioxide
tions, even though it is known in the art that TiO2 can 20 increases from 0 wt % to 7 wt % and the density increases
improve polycarbonate flame performance. Even with 2 from 1.278 to 1.340 g/cc. Therefore in order to achieve a
PHR TiO present, without any poly(siloxane-carbonate), maximum density of less than 1.320, less than 5 wt %
CEX 10 does not pass the DsMax Smoke target of less than titanium dioxide can be used in the compositions shown in
200, having a value of 231. By contrast EX 30 (with Table 6.
poly(siloxane-carbonate) present) passes the DSMax test 25 Combining the results from the various Tables shows
target value of less than 200 with a value of only 72. achieving the targeted density maximum of 1.320 g/cc for
Furthermore the impact performance of molded parts certain rail applications can be accomplished by balancing
from compositions containing TiO is improved by the the amount of titanium dioxide with the amount of bromi
presence of a poly(siloxane-carbonate) as illustrated by EX nated copolycarbonate. Bromine contents of less than 13 wit
24-29 in Table 6 and EX 30 in Table 7 (which show 100%. 30 % and titanium contents of less than 5 wt % can be used to
ductility performance at room temperature) while CEX 10 meet the rail density targets for white product compositions
has 0% ductility performance at room temperature. (EX 24-EX 27 vs. EX 28-EX 29).
Density of Low OSU Heat Release, Low Smoke Thermo- Alternative Bromine Sources.
plastic Compositions. Property comparisons were made between thermoplastic
The density results in Tables 3-5 illustrate the factors that 35 compositions having similar wt % polysiloxane and similar
most strongly affect the density of the compositions that do wt % bromine in the compositions using three different
not contain titanium dioxide. The strongest influence on bromine-containing additives, in particular a brominated
density is the wt % of bromine in the thermoplastic com- epoxy oligomer (F3100 from ICL Industrial Products, EX
positions. For example in CEX 2, 3, 4, 5, and 6 in Table 3 30), a brominated polycarbonate oligomer (BC52, EX 31)
the wt % bromine increases from 0 to 13 wt % and the 40 and a brominated copolycarbonate(TBBPA-BPA copolymer,
density increases from 1.198 to 1.315 g/cc. A similar trend EX 32). The results are shown in Table 8.
TABLE 8
Components EX 31 EX 32 EX33
SPC 4 SO.O SO.O SO.O
PC 2 30.70 3O.OO 2O.OO
F-3100 19.300
BCS2 2O.O
TBBPA-BPA Copolymer 40.OOO
Phosphite O.O60 O.O60 O.O60
Mw of Br compound 15,000 2,665 22,500
Softening Temp C. 2OO 171 182
Total Formulation % Siloxane 3 3 2.7
% Bromine 10.4 10.4 9.5
D length 45.O 4S.O 45.O
Properties
MVR-6 15.7 11.8 8.3
% Change 17.5 4.9 11.9
Tg 146.5 1514 159.8
NI-125 RT Ductility 100.00 O.O 1OO.O
Jim 773.0 123.0 744.O
ft-Ibsin 14.5 2.3 13.9
MAI-RT Ductility 1OO.O 1OOO 1OO.O
Energy to max load-Avg J 68.1 75.1 78.4
Energy to failure-Avg J 72.6 79.8 85.O
Energy, Total-Avg J 72.6 79.8 85.1
Density-Avg gfcc 1.282 1.273 1.268
Specific Gravity-Avg 1.285 1.276 1.271
HDTASTM-G 1.8 MPa. 123.8 127.7 135.2
 US 9,453,128 B2
73 74
TABLE 8-continued
Components EX 31 EX 32 EX33
HDTASTM-G O455 MPa.
OSU 2 min. TTF 42.4 30.1 36.4
45.8 24.0 26.2
33.8 21.8 18.2
Average 40.7 25.3 26.9
Standard deviation 6.2 4.3 9.1
OSU Peak 50.5 50.5 60.3
SO.8 43.1 49.5
59.5 6O2 54.6
Average S3.6 51.3 54.8
Standard deviation S.1 8.6 5.4
FAA Smoke Density
Ds at 4 min 96.6 23.81 2O.S
66.3 35.3 18.2
88.6 16.6 42.7
Average 83.8 26.0 27.1
Standard deviation 15.7 13.2 13.5
DSMax 96.8 23.81 2O.S
66.3 35.3 18.2
88.6 16.6 42.7
Ave 83.9 26.0 27.1
Standard deviation 15.7 13.2 13.5
Optical Properties
% T at 125 mill (3.2 mm) 22.O 78.7 77.3
YI 62.7 19.1 19.8
% Haze 102.6 7.3 6.5

The results in Table 8 show that the targeted flame and Other Additives
Smoke properties (2-min total heat release and peak heat 30 The effect of additives often used as flame retardants in
values of less than 65 and a smoke DsMax value of less than polycarbonate, on the Smoke density properties of compo
200) were achieved in thermoplastic compositions contain sitions made from combinations of the poly(siloxane-car
bonate) and brominated copolycarbonate, were also inves
ing siloxane using the different sources of bromine as flame tigated and the results are shown in Table 9.
retardants. The high impact values in EX31 (100% ductility 35 When used at levels commonly employed to improve
in the notched Izod test) as compared to EX 32, illustrates flame performance, improve the color stability, or reduce
the importance of selecting a bromine composition with an haze in polycarbonates, the additives showed no effect on
Mr of at least approximately 15,000 when formulations of the flame retardant performance of the thermoplastic com
high toughness are needed. High transparency (greater than positions. EX 34 (with TiO) possessed a similar DSMax
value to EX 35-39 (with the flame retardant, color stabili
75%) and low haze (less than 10%) were also found with EX 40 zation, or haze reducing additives) (EX 34 had a DsMax of
32. In addition, all three of the compositions showed density 21, whereas the highest DSMax values measured for the
values below the 1.320 g/cc upper limit. compositions of Table 9 was 29).
TABLE 9
Name EX 34 EX35 EX36 EX37 EX 38 EX39

TBBPA-BPA 40.O 40.O 40.O 40.O 40.O 40.O

SPC 4 SO.OO SO.OO SO.OO SO.OO SO.OO SO.OO
PC 1 1O.O 1O.O 1O.O 1O.O 1O.O 1O.O
KSS O.30
KSS O.30
Rimar salt O.08 O.08
Octaphenylcyclotetrasiloxane O.10
STB 0.75
Phosphorus acid solution (0.15%) O.10
TiO2 2.OO 2.00 2.OO 2.00 2.OO 2.OO
Phosphite O.O6 O.O6 O.O6 O.O6 O.O6 O.O6
Total Formulation Wt 90 Siloxane 3.0 3.0 3.0 3.0 3.0 3.0
Wt 96 Bromine 10.4 10.4 10.4 10.4 10.4 10.4
Properties
MVR-6 Cc 10 min 9.6 1O.O 12.4 13.6 10.4 9.9
Tg o C. 159 157 160 159 160 160
NI-12S RT Ductility 100 1OO 100 1OO O 100
Jim S88.0 S44.0 S34.O 596.O 1430 498.O
ft-lbs in 11.O 10.2 1.O.O. 11.2 2.7 9.3
Density-Avg gfcc 1.287 1291 1291 1.288 1.293 1291
Specific Gravity-Avg 1.290 1294 1294 1291 1296 1294
HDTASTM-G 1.8 MPa. 134 134 134 134 134 135
 US 9,453,128 B2
75 76
Other Silicone-Containing Additives. TABLE 11
The impact of replacing the polysiloxane block copoly
Component EX 40 EX 41 EX 42 EX 43
carbonate with other silicone-containing additives was also
investigated and the results shown in Table 10. TBBPA-BPA 40.O 40.O 40.O 40.O
SPC 4 SO.OO SO.OO SO.OO SO.OO
PC 1 1O.O 1O.O 1O.O 1O.O
TABLE 10 Tinuwin 1577 O O.3
UVA 234 O.300
Components CEX 11 CEX 12 CEX 13 CEX 14
Cyasorb 3638 O.3
TBBPA-BPA 3O.OO 3O.OO 3O.OO 3 O.OO TiO2 2.0 2.0 2.0 2.0
PC 2 70.OO 69.50 69.SO 69.50 10 IRGAPHOS 1.68 O.O60 O.O60 OO60 O.O60
DF1040 OSO Total Formulation Total wt % 3.00 3.00 3.00 3.00
OPTS OSO Siloxane
D4 O.SOO Total wt % 10.4 10.4 10.4 10.4
Phosphite O.O60 OO60 OO60 OO60 Bromine
Total Formulation Wt 96 O O.S O.S O.S Properties
Siloxane 15
Wt 96 7.8 7.8 7.8 7.8 MVR-6 minutes 8.9 8.7 9.4 9.0
Bromine MVR-18 minutes 8.9 11.2 10.6 9.0
Properties NI-12S RT Ductility 100 1OO 100 100
Jim 566 S42 539 525
MVR-6 5.5 5.9 5.5 S.6 ft-lbs in 10.6 10.1 10.1 9.8
NI-125 RT Ductility O.O O.O O.O O.O OSU 2 min. TTF 26.0 21.3 23.0 18.3
Jim 139 148 132 135 60 mi 19.0 17.6 25.1 21.6
ft-Ibsin 2.6 2.8 2.5 2.5 21.0 23.8 25.7 23.4
Density-Avg gfcc 1.262 1.263 1.264 1.264 Average 22.0 20.9 24.6 21.1
Specific Gravity-Avg 1.265 1.267 1.267 1.267 Standard 3.6 3.1 1.4 2.6
HDTASTM-G 1.8 MPa. 136 135 136 135 Deviation
OSU TTF 44.0 44.7 45.1 38.4
OSU Test FAR 25.853 (d) Appendix F, Part IV 25 60 mi 43.2 4.1.8 47.3 49.4
2 Min OSU Average 17 59 19 28 445 43.0 44.3 48.3
Standard 9.7 2.6 2O2 15.9 Average 43.9 43.2 45.6 45.3
deviation Standard 0.7 1.5 1.5 6.O
Peak OSU Average 60 75 65 65 Deviation
Standard 4.5 4.0 3.8 8.7 FAA Smoke De TTF 11.5 16.4 21.1 2S.OO
deviation 30 Ds at 4 minutes 60 mi 10.7 16.8 22.0 22.5
NBS Smoke Density (ASTM F814/E662, Flaming Mode) 11.5 27.3 23.5 20.8
Ave 11.2 2O2 22.2 22.8
DS Max Ave 529 306 521 4O6 Standard 0.4 6.2 1.2 2.1
Standard 84 197 219 199 Deviation
deviation DSMax TTF 11.5 16.4 21.3 2SO
35 60 mi 10.7 16.8 22.0 22.5
11.5 27.3 23.5 20.8
The results in Table 10 show that none of the siloxane Ave 11.2 2O2 22.3 22.8
Standard 0.4 6.2 1.1 2.1
Sources performed as well as the poly(siloxane-carbonate) of Deviation
the invention. The results for EX 3 and EX 4 from Table 3
(with 0.4 wt % polysiloxane content and either 7.8 or 10 wt 40
All of the compositions were 100% ductile in notched
% bromine) show that both pass the OSU heat release and IZod testing, have a density requirement of less than 1.320
smoke tests, with values less than 65 for the OSU tests and
less than 200 for the smoke tests. In contrast CEX 12, 13, g/cc (data not shown), and all showed passing values in the
and 14 have slightly higher amounts of siloxane (0.5 wt %) OSU heat release and smoke testing, with OSU values below
65 and smoke DsMax values below 200.
and the same amount of bromine (7.8 wt %) and fail the 45
Bright white sample plaques were placed on a 45 degree
smoke tests with DSMax values of 300 or greater. These angle South facing rack exposed to an unobstructed Sunlight
other sources of silicone are therefore much less effective at
Suppressing Smoke in the Smoke tests than poly(siloxane light exposure for 466 hours and then tested for a color shift
carbonate) described herein. While not wishing to be bound by measuring the reflected light of the light-exposed plaques
by any specific theory, it is believed that providing the 50 using a spectrophotometer. The color stability/weathering
results are shown in Table 12.
siloxane in a less volatile, less mobile (higher Tg), high
molecular weight polymer could help to maintain the silox TABLE 12
ane in the composition longer and keep the siloxane better
dispersed during burning. 55
EX 41 EX 43
Color Stability and Weathering Performance. Outdoor Comparative (a) EX 40 Tinuvin EX 42 Cyasorb
Exposure, No UWA No UVA 1577 UVA234 3638
Materials used in the transportation industry, especially Hrs DE DE DE DE DE
those that pass the OSU and DsMax Smoke requirements,
O
often have poor stability when exposed to outdoors light. 110 5.9 O.3 O.3 O.S O.S
Thus manufactures must either paint the finished part or risk 60 466 7.9 0.7 O.6 0.4 O.3
the yellowing or other discoloration of the parts. In order to
demonstrate the improved color stability performance of the (a) White LEXAN* FST9705 plaque.
Trademark of SABIC Innovative Plastics IPBW
poly(siloxane-carbonate) and brominated cothermoplastic
compositions over those found in art, the compositions were All four of the samples (EX 40-43) of the present inven
formulated with and without UV stabilization additives in a 65 tion have better color stability than the existing commercial
bright white color package. These compositions and results OSU comparative resin. All three of the samples containing
are shown in Table 11. UV stabilizing additives showed even lower tendency to
 US 9,453,128 B2
77
yellow as determined by lower DE values than the sample or TABLE 14-continued
the sample with no UV stabilizers, even after 466 hours. The Component CEX 44 CEX 45
benefits in color stability of the compositions of the present
invention compared to a composition that has comparable Total Formulation Total wt % Siloxane 1 O.88
OSU smoke and flame performance but employs polyarylate Total wt % Bromine O 3.1
poly(siloxane-carbonate)s in the composition (LEXAN* NBS Smoke Density ASTM F814/E662
FST 9705 polymer) is also illustrated by comparing the DE Ds at 1.5 min 1 na
values of EX 40 with FST 9705 after 466 hours of weath Ds at 4.0 min 23 25
ering (neither sample contained UV stabilization additive). DSMax 23 25
The FST 9705 showed much higher DE values than CEX 15 10 DsMax time 3.98 4
(DE 7.9 vs. 0.7).
Materials used in the following examples of the poly The data shows that the addition of the bromine copoly
(siloxane-etherimide) compositions are listed Table 13. mer to the siloxane containing poly(ester-carbonate) does
Amounts in these Examples are in parts by weight per not yield improved Smoke performance, as in general, the
hundred parts by weight of the total amount of polymer 15
results are no better or worse than the siloxane-containing
otherwise noted. poly(ester-carbonate) without the brominated polymer.
TABLE 13
Further according to US 2007/0129492, high arylate ester
levels and low polycarbonate levels are needed to pass the
Component Description Source OSU test. In contrast, the data below shows that when using
the composition of this invention, no arylates are needed to
PC LEXAN 100 grade Sabic obtain good OSU heat release values.
Innovative
Plastics
PEI-Siloxane Arandom poly(etherimide- Sabic Examples 46-49
dimethylsiloxane) copolymer comprising Innovative
25
structural units derived from m-phenylene Plastics These Examples show the synergistic effect of siloxane
diamine, BPADA, and an aminopropyl from a poly(etherimide-siloxane) and a brominated polymer
terminated polydimethylsiloxane containing
on average 10 silicon atoms, with 37 it 2 wt.% on heat release and Smoke density in thermoplastic compo
siloxane content: Mw about 38,500 sitions. Results are shown in Table 15.
amu determined by GPC relative to PC
standards (SILTEM (R) D9000) 30
TABLE 1.5
TBBPA BPA and tetrabromo-BPA (50/50 wt %)
BPA was used, Mw = 23,100 Components EX 46 EX 47 EX 48 CEX 49
TBBPA-BPA 40.OO 40.00 40.OO 40.00
The examples were prepared on 30 mm Werner Pfleiderer SILTEM 7.OO S.OO 2.50 O.OO
twin extruders as follows. All components were dry blended 35 PC 53.0 55.0 57.5 60.0
for about 4 minutes using a paint shaker or a drum tumbler. Additive
Total Formulation Wt 96 Siloxane
O.O6
2.6
O.O6
1.9
O.O6
O.9
O.O
O.O
The twin screw extruder contained a vacuum port located Wt 96 Bromine 10.4 10.4 10.4 10.4
near die face. The compositions were compounded with an Properties
applied vacuum of 20+inches of Hg, and chopped into
pellets after cooling in a water bath. 40 MVR 6 minutes
NI-125, RT Ductility
5.5
O.O
S.6
O.O
5.7
O.O
6.8
O.O
The compositions are molded after drying at 121° C. for Jim 130 119 117 90.8
4 hrs on a 260-ton (236 metric ton) Van Dorn or an 85 Ton ft-lbs in 2.4 2.2 2.2 1.7
Van Dorn molding machine operating at 300 to 320°C. with MAI, RT Ductility 100 1OO 100 1OO
a mold temperature of 80° C. It will be recognized by one Energy to max J 75.0 75.8 78.2 78.1
skilled in the art that the method is not limited to these 45 Energy to failure J 81.6 81.8 83.6 84.3
Energy, Total-A J 81.7 81.9 83.7 84.3
temperatures or processing equipment. Density, average 1.285 1286 1.287 1.289
All the performance tests were conducted as described HDTASTM-G 1.8 MPa. 138.4 139.7 139.7 141.5
above. OSU Test FAR 25.853 (d) Appendix F, Part IV
2 Min OSU Average 17 21 25 30
Comparative Examples 44 and 45 50
Standard 9.74 6 7 3
deviation
Comparative examples 1 and 2 show that synergy Peak OSU Average, TTF 46 41 45 66
between siloxane containing-resins and bromine-containing Standard
deviation
11 6 3 8
resins to achieve low heat release and low Smoke density is NBS Smoke Density (ASTM F814/E662, Flaming Mode)
not known in the art. In accordance with U.S. Pat. No. 55
7,790,292, (from EX 2-15), a siloxane-containing poly(es DSMax Average, TTF 10 13 22 457
ter-carbonate) copolymer was compared to a commercial Standard 1 6 8 243
deviation
composition containing the siloxane-containing poly(ester Optical properties
carbonate) copolymer and 12 wt % of a bromine-containing
polycarbonate copolymer. Results are shown in Table 14. 60 YI 9.8 8.2 S.6 7.1
% T at 125 mil 67.6 70.6 79.7 86.5
% Haze 48.5 34.O 10.9 0.7
TABLE 1.4
Component CEX 44 CEX 45 A series of blends using a poly(etherimide-siloxane) block
Poly(ester-carbonate) copolymer 1OO 88 65 copolymer, a brominated polymer, and polycarbonate (EX
TBBPA-BPA Copolymer O 12.0 46-EX 48) were made and compared to the control with no
siloxane (CEX 49). Without the poly(etherimide-siloxane)
 US 9,453,128 B2
79 80
block copolymer, the smoke levels are above the FAA's Examples 50-54
acceptable limit of 200 for DSMax and have a high standard
deviation in the E662 test (Table 14). The peak heat release The target transparency or haze of the thermoplastic
compositions can be achieved by adjusting the total amount
rate in the OSU test is also above the FAA's acceptable limit of bromine and siloxane units in the thermoplastic compo
of 65. With the addition of the poly(etherimide-siloxane), sitions. Combinations of different poly(carbonate-siloxane)
the Smoke levels drop dramatically and are consistently copolymers can be used. The siloxane-containing copoly
below 25 with a low standard deviation (Table 14). Again mers can have first repeating units that are a carbonate unit,
an ester unit, an arylene ether unit, an arylene Sulfone unit,
with the addition of the poly(etherimide-siloxane), the peak an arylene ether Sulfone unit, an arylene ether ketone unit, or
OSU values drop and are consistently 20 points below the 10 a combination comprising at least one of the foregoing units.
FAA standard of 65. A poly(carbonate-siloxane) copolymer can be specifically
In addition, the compositions have improved toughness mentioned. The brominated polymer can be, for example,
TBBPA-BPA, BC-52, or a brominated epoxy. Prospective
over the control (CEX 49). The control has an impact values ranges and specific prospective examples are shown in Table
of less than 2 ft-lbs/in; whereas EX 46-EX 48 have impacts 15 16. Where the total amount of polymers shown is less than
over 2 ft-lbs/in. All compositions are 100% ductile in MAI 100 wt %, an optional third polymer is present, such that the
testing at room temperature. weight of the polymers totals 100 wt %.
TABLE 16
EX50-Light Diffusing EX51-Light Diffusing EX52-Med. Clarity
Components Range-1 Range-2 EX50A Range-1 Range-2 EX51A Range-1 Range-2 EX52A

Brominated polymer, wt %** 35-50 4S-SO 49.S 3S-SO 45-SO 49.S 3S-SO 45-SO 49.5
Siloxane Wt 9:8: O-65 20-6S SO O-55 O-40 SO O-6S 20-6S SO
copolymer- Block Length S-20 5-15 10 O-2O S-15 10 S-20 S-15 10
1 (D10) % Siloxane OS-2.O O.3-1.5 1.O 0.5-2.0 (0.3-1.5 1.O 0.5-2.0 O3-15 1.O
% Sloxane: O-15 0.1-1.0 O.S O-1.5 O. 1-1.O O.S O-15 0.1-10 O.S
Siloxane Wt % copolymer O-65 O-2O O.S 10-65 O-2O O.S O-65 1-2S O.S
copolymer- Block Length 20-65 35-55 45 35-55 35-55 45 20-6S 3S-5S 45
2 (D45) % Siloxane O5-10 4.0-8.0 6.O O.5-10 4.0-8.0 6 O.5-10 4.0-8.0 6
% Sloxane: O-6.5 O-3.5 O.S O-6.5 O-3S O.S O-15 0.1-10 O.S
Siloxane Wt 9%
copolymer- Block Length
3 (D30) % Siloxane
% Sloxane:
Light Diffuser Additive O.2-10 O.2-3.O. O.2-3.0 O2-1O O.2-3.0 (0.2-3.0
Total Wt 90 Bronine: 9-13 9-13 9-13
Formulation Wt 96 Siloxane'* 0.2-6.5 O.2-3.0 OS 0.2-6.5 O.2-3.0 OS 0.2-6.5 O.2-3.0 O.S
Properties

2 Min OSU FAR 25.853 (d) s65 kW/m2 s65 kW/m s65 kW/m
MAHRE FAR 25.853 (d) s65 kW/m2 s65 kW/m2 s65 kW/m2
DsMax ASTM E662) s2OO s2OO s2OO
% T at 3.2 mm CIE 1931) 20-90 20-90 70-87
% Haze 3.2 mm CIE 1931) 70-99 70-99 2.0-10

EX53-Med. Clarity EX54-High Clarity EX55-Transparent

Components Range-1 Range-2 EX53A Range-1 Range-2 EX54A Range-1 Range-2 EX55A

Brominated polymer, wt %** 35-50 45-50 49 35-50 45-50 50 35-50 45-50 49.5
Siloxane Wt 9:8: O-60 20-65 50 O-6S 1-SO 50
copolymer- Block Length S-20 5-15 10 S-20 5-15 10
1 (D10) % Siloxane OS-2.O O.3-1.5 1.O OS-2.O O.3-1.5 1.O
% Sloxane: O-15 0.1-1.0 O.S O.2-1.5 0.1-1.0 O.S
Siloxane Wt % copolymer 5-65 1-2S O.S
copolymer- Block Length 20-65 35-55 45
2 (D45) % Siloxane O5-10 4.0-8.0 6
% Sloxane: O-15 0.1-1.0 O.S
Siloxane Wt 9% O-6S
copolymer- Block Length 15-65 20-50 30
3 (D30) % Siloxane O5-10 4.0-8.0
% Sloxane: O-15 O-1.O
Light Diffuser Additive
Total Wt 90 Bronine: 9-13 9-13 9-13
Formulation Wt 96 Siloxane O.2-6.5 O.2-3.0 O.2-1.5 0.2-1.0 O.S O.2-1.5 0.2-1.0 O.S
 US 9,453,128 B2
TABLE 16-continued
Properties
2 Min OSU FAR 25.853 (d) s65 kW/m2 s65 kW/m2 s65 kW/m2
MAHRE FAR 25.853 (d) s65 kW/m2 s65 kW/m2 s65 kW/m2
DsMax ASTM E662) s2OO 23 200 s2OO
% T at 3.2 mm CIE 1931) 70-87 e87 e87
% Haze 3.2 mm CIE 1931) 2.0-10 <2.O <2.0
Based on the weight of the siloxane-containing copolymer
**Based on the total weight of the polymers in the composition

A series of blends using a siloxane-containing copolymer plurality of diffuser particles, sample formed of the compo
having first repeating units that are a carbonate unit, an ester sitions have the indicated properties, including low Smoke
unit, an arylene ether unit, an arylene Sulfone unit, an 15
density and maximum heat release rate are kept within limits
arylene ether Sulfone unit, an arylene ether ketone unit, or a required by FAR 25.853 (d).
combination comprising at least one of the foregoing units, As stated above, the transparent compositions, for
specifically a poly(carbonate-siloxane) block copolymer, example the transparent compositions of EX 55 can be
more specifically a derived from bisphenol A and poly obtained using a wide variety of different siloxane-contain
(siloxane) block units derived from a polysiloxane bisphenol ing copolymers and combinations thereof, provided that a
of formula (15), (16), or a combination thereof and a molded plaque of the siloxane-containing copolymer(s)
brominated polymer (TBBPA-BPA, BC-52, or a brominated have a % haze value of 3% or less measured using the color
epoxy) are made. Clarity measured as transmission and haZe space CIE 1931 (Illuminant C and a 2° observer) at a
are measured in accordance with CIE 1931. By controlling thickness of 3.2 mm. Examples of bromine-containing poly
the siloxane block size, the amount of siloxane in each 25
mers and siloxane-containing copolymers that can be used to
copolymer, and the total amount of siloxane in the final manufacture the transparent compositions are set forth in
formulation, combined optionally with the addition of a Table 17.
TABLE 17
Avg.
Wt 9% Siloxane 96 Haze
Acronym Description Mw PDI Endcap Siloxane Length (125 mil)
TBBPA-BPA TetrabromoBPA/BPA Copolymer 23,660 2.6 PCP <2
BCS2 Tetrabromo BPA Oligomer 2,638 1.7 Phenol
SPCA D10 siloxane block co-polycarbonate 30,000 — PCP 1 10 <2
SPC A1 D10 siloxane block co-polycarbonate 22,200 — PCP 1 10 <2
SPCB D10 siloxane block co-polycarbonate 23,600 3.0 PCP 5 10 5(1)
SPCC D30 siloxane block co-polycarbonate 23,472 2.2 PCP 6 30 <2.5
SPC D D45 siloxane block co-polycarbonate 23,013 2.2 PCP 6 45 <2.5
SPCE D45 siloxane block co-polycarbonate 29,852 2.6 PCP 2O 45 Opaque')
At 60 mil (1.5 mm).
Substantially opaque.

Examples 56-59
45 These Examples show the effect of various poly(carbon
ate-siloxane) copolymers and a brominated polymer or
oligomer on impact strength and colorability for high impact
and medium impact thermoplastic compositions. Results are
shown in Table 17.
TABLE 1.8
EX 56-High Impact EX 57-High Impact, Colorability
Components Range-1 Range-2 EX 56A Range-1 Range-2 EX57A

Brominated polymer, wt %** 35-50 45-50 50 35-50 5-50 50

Siloxane Wt 9** O.O-SO O.O-37 30 5.0-55 40
copolymer Block Length 25-50 40-50 45 25-50 45
4 (D45) % Siloxane 4.0-10 4.0-10 6.O 4.0-10 6.O
% Sloxane.** O.O-3.O. O.O-3.0 1.5 O.2-3.0 2.4
Siloxane Wt 96 13-2S 13-40 2O 5.0-12 10
copolymer Block Length 40-65 40-50 45 40-65 45
5 (D45) % Siloxane 15-25 15-25 2O 15-25 2O
% Sloxane: 2.55-6.O 2.5-6.O 4.0 1.0-25 2.0
Colorant wt % OOOO2-SO OOOOO6.-O.OO2
Total Wt 96 Bromine 9-13 9-13
Formulation Wt 96 Siloxane 2.55-6.0 4.O-6.O 5.5 2.5-5.3 3.9-5.1 4.4
 US 9,453,128 B2
TABLE 18-continued
Properties
2 Min OSU FAR 25.853 s65 kW/m2 s65 kW/m2
(d)
MAHRE FAR 25.853 (d) s65 kW/m2 s65 kW/m2
DsMax ASTM E662) s2OO s2OO
Notched Izod ASTM D 480 Jim 400 Jim
256-10
EX-58-Med. Impact, Good EX-59 High or medium
Colorability impact
Components Range-1 Range-2 EX58A Range-1 Range-2 EX59A
Brominated polymer, wt %** 35-50 45-50 50 35-50 45-50 50
Siloxane Wt 9** 10-65 50
copolymer Block Length 25-50 45
4 (D45) % Siloxane 4.0-10 6.O
% Sloxane ** 2.4-5.5 999
Siloxane Wt 96 O-S.O O
copolymer Block Length 20-65 45
5 (D45) % Siloxane 15-25 2O
% Sloxane: O-O.9 O
Colorant wt % OOOO2-5.0 OOOOO6.-O.OO2
Total Wt 96 Bromine 9-13 9-13
Formulation Wt 96 Siloxane 2.4-5.5 3.9-5.1 2.5-6. O*** 4.0-6.O 5.5
Properties
2 Min OSU FAR 25.853 s65 kW/m2 s65 kW/m
(d)
MAHRE FAR 25.853 (d) s65 kW/m2 s65 kW/m2
DsMax ASTM E662) s2OO s2OO
Notched Izod ASTM D 400 Jim e2.0 ft-lb.in
256-10
Based on the weight of the siloxane-containing copolymer
**Based on the total weight of the polymers in the composition
***10-200 siloxane units per block

A series of blends using a siloxane-containing copolymer 35 “an herein do not denote a limitation of quantity, but rather
having first repeating units that are a carbonate unit, an ester denote the presence of at least one of the referenced item.
unit, an arylene ether unit, an arylene Sulfone unit, an Reference throughout the specification to “an embodiment'.
arylene ether Sulfone unit, an arylene ether ketone unit, or a "another embodiment”, “an embodiment,” and so forth,
combination comprising at least one of the foregoing units, means that a particular element (e.g., feature, structure,
specifically a poly(carbonate-siloxane) block copolymer, 40 and/or characteristic) described in connection with the
more specifically a derived from bisphenol A and poly embodiment is included in at least an embodiment described
(siloxane) block units derived from a polysiloxane bisphenol herein, and can or cannot be present in other embodiments.
of formula (15), (16), or a combination thereof and a In addition, it is to be understood that the described elements
brominated polymer (TBBPA-BPA, BC-52, or a brominated can be combined in any suitable manner in the various
epoxy) are made. Impact strength is measured in accordance 45 embodiments. The suffix "(s)' as used herein is intended to
with ASTM D256-10. Good colorability is considered when include both the singular and the plural of the term that it
samples show no, or minimal flow lines, Swirls or gate blush modifies, thereby including at least one of that term (e.g., the
when injection molded. The color is visually uniform across colorant(s) includes at least one colorants).
the molded part. Additionally, the base color (color of the As used herein, a “railway vehicle' is inclusive of rolling
blend without colorants of the blend has a low YI, e.g., 50 stock, and includes but is not limited to a locomotive, coach,
below a YI of 12, specifically below 8, more specifically light rail vehicle, underground rail vehicle, tram, trolley,
below 5. By controlling the siloxane block size, the amount magnetic levitation vehicle, and a cable car.
of siloxane in each copolymer and the total amount of Compounds are described using standard nomenclature.
siloxane in the final formulation, optionally combined with For example, any position not substituted by any indicated
a colorant, samples formed of the compositions have con 55 group is understood to have its valency filled by a bond as
trollable impact strength. Likewise, low Smoke density and indicated, or a hydrogen atom. A dash ('-') that is not
maximum heat release rate are kept within limits required by between two letters or symbols is used to indicate a point of
FAR 25.853 (d). attachment for a substituent. For example, —CHO is
Ranges disclosed herein are inclusive and combinable attached through carbon of the carbonyl group. The term
(e.g., ranges of “up to 25 wt %, or, more specifically, 5 wt 60 “alkyl includes both Clso branched and straight chain,
% to 20 wt %, is inclusive of the endpoints and all unsaturated aliphatic hydrocarbon groups having the speci
intermediate values of the ranges of “5 wt % to 25 wt %.” fied number of carbon atoms. Examples of alkyl include, but
etc.). “Combination' is inclusive of compositions, blends, are not limited to, methyl, ethyl, n-propyl, i-propyl. n-butyl,
mixtures, alloys, reaction products, and the like. Further S-butyl, t-butyl, n-pentyl, S-pentyl, n- and S-hexyl, n- and
more, the terms “first,” “second,' and the like do not denote 65 S-heptyl, and, n- and S-octyl. The term “aryl' means an
any order, quantity, or importance, but rather are used to aromatic moiety containing the specified number of carbon
distinguish one element from another, and the terms 'a' and atoms, such as to phenyl, tropone, indanyl, or naphthyl. The
 US 9,453,128 B2
85 86
term "hydrocarbon group' encompasses groups containing 2. A railway vehicle component wherein the component is
the specified number of carbon atoms and having carbon, a partition or a light cover, and wherein the component is
hydrogen, and optionally one to three heteroatoms selected molded or formed from a thermoplastic polymer composi
from O, S. P. and N. Hydrocarbon groups can contain tion comprising:
saturated, unsaturated, or aromatic moieties, or a combina 5 35 to 50 wt % of a bromine-containing polymer based on
tion comprising any of the foregoing, e.g., an alkyl moiety the total weight of polymers in the thermoplastic poly
and an aromatic moiety. Hydrocarbon groups can be halo mer composition, wherein the bromine-containing
genated, specifically chlorinated, brominated, or fluorinated, polymer is effective to provide 9 to 13 wt % of bromine,
including perfluorinated. The term 'aromatic group' based on the total weight of the polymers in the
includes groups having an aromatic moiety, optionally 10
thermoplastic polymer composition; and
together with a saturated or unsaturated moiety. 20 to 65 wt % of a siloxane-containing copolymer based
All cited patents, patent applications, and other references on the total weight of the polymers in the thermoplastic
are incorporated herein by reference in their entirety. How polymer composition, wherein the siloxane-containing
ever, if a term in the present application contradicts or copolymer comprises a first repeating unit and a poly
conflicts with a term in the incorporated reference, the term 15
from the present application takes precedence over the (siloxane) unit having the formula:
conflicting term from the incorporated reference.
While the invention has been described with reference to
embodiments, it will be understood by those skilled in the art
that various changes can be made and equivalents can be SO
substituted for elements thereof without departing from the
Scope of the invention. In addition, many modifications can R
E.
be made to adapt a particular situation or material to the
teachings of the invention without departing from essential
scope thereof. Therefore, it is intended that the invention not 25 wherein R is each independently C-Co hydrocarbon
be limited to the particular embodiment disclosed as the best group, and E has an average value of 5 to 200, and
mode contemplated for carrying out this invention, but that wherein the siloxane-containing copolymer is effective
the invention will include all embodiments falling within the to provide a total of 0.2 to 6.5 wt % of siloxane units
Scope of the appended claims. based on the total weight of the polymers in the
What is claimed is: 30 thermoplastic polymer composition; and
1. A railway vehicle component wherein the component is wherein the first repeating unit of the siloxane-containing
a partition or a light cover, and wherein the component is copolymer comprises a carbonate unit, an ester unit, an
molded or formed from a thermoplastic polymer composi arylene Sulfone unit, an arylene ether Sulfone unit, an
tion comprising: arylene ether ketone unit, or a combination comprising
a siloxane-containing copolymer in an amount effective to 35 at least one of the foregoing units; and
provide a total of 0.2 to 6.5 wt % of siloxane units based optionally a third polymer, wherein the wt% of the
on the total weight of the polymers in the thermoplastic siloxane-containing copolymer, bromine-containing
polymer composition, polymer, and the optional third polymer, sum to 100 wt
a bromine-containing polymer in an amount effective to %, and
provide 9 to 13 wt % of bromine, based on the total 40 0.05 to 10 wt % of a light diffuser additive, based on the
weight of the polymers in the thermoplastic polymer total weight of polymers in the thermoplastic polymer
composition, and composition;
optionally a third polymer comprising carbonate units, wherein a molded or formed sample of the thermoplastic
imide units, etherimide units, arylene ether Sulfone polymer composition has
units, arylene ether units or a combination thereof, 45 a transmission of 20% to 90% or a haze of 70% to 99.9%,
wherein the wt % of the siloxane-containing copoly each measured using the color space CIE 1931 (Illu
mer, the bromine-containing polymer, and the optional minant C and a 2° observer) at a thickness of 3.2 mm,
third polymer, sum to 100 wt %, and an OSU integrated 2 minute heat release test value of less
0.05 to 10 wt % of a light diffuser additive, based on the than 65 kW-min/m and a peak heat release rate of less
total weight of polymers in the thermoplastic polymer 50 than 65 kW/m, each measured using the method of
composition; FARF25.4, in accordance with Federal Aviation Regu
wherein the thermoplastic polymer composition is free of lation FAR 25.853 (d), and
polyarylester-polycarbonate copolymers comprising an E662 smoke test DsMax value of less than 200 when
carbonate units and arylate ester units and the thermo measured at a thickness of 1.6mm.
plastic composition is free of polyalkylene esters; and 55 3. The railway vehicle component of claim 2, wherein the
wherein a molded or formed sample of the thermoplastic siloxane-containing copolymer comprises
polymer composition has a first siloxane-containing copolymer having an average
a transmission of 20% to 90% or a haze of 70% to 99.9%, siloxane block length from 5 to 20, and a siloxane
each measured using the color space CIE 1931 (Illu content of 0.5 to 2 wt % based on the weight of the
minant C and a 2° observer) at a thickness of 3.2 mm, 60 siloxane-containing copolymer, wherein the first silox
an OSU integrated 2 minute heat release test value of less ane-containing copolymer contributes 0.2 to 6.5 wt.%
than 65 kW-min/m and a peak heat release rate of less of siloxane units, based on the total weight of the
than 65 kW/m, each measured using the method of polymers in the thermoplastic polymer composition,
FARF25.4, in accordance with Federal Aviation Regu and
lation FAR 25.853 (d), and 65 an optional second siloxane-containing copolymer having
an E662 smoke test DsMax value of less than 200 when an average siloxane block length from 25 to 65, and a
measured at a thickness of 1.6 mm. siloxane content of 0.5 to 10 wt % based on the weight
 US 9,453,128 B2
87 88
of the siloxane-containing copolymer, wherein the 8. The railway vehicle component of claim 7, wherein
optional second siloxane-containing copolymer con the siloxane-containing copolymer is a poly(carbonate
tributes 0 to 6.3 wt.% of siloxane units, based on the siloxane) comprising carbonate units derived from bis
total weight of the polymers in the thermoplastic com phenol A and poly(siloxane) units derived from a
position. polysiloxane bisphenol of the formula
4. The railway vehicle component of claim 3, comprising,
based on the total weight of the polymers in the thermo
plastic polymer composition,
20 to 65 wt.% of the first siloxane-containing copolymer, $H | H.
wherein the first siloxane-containing copolymer has an 10 HO (CH2)3 s-o i-CH.) OH,
average siloxane block length from 5 to 15; and CH3 CH3
0 to 55 wt % of the optional second siloxane-containing H3CO E
OCH
copolymer, wherein the second siloxane-containing
copolymer has an average siloxane block length from CH CH
35 to 55.
5. The railway vehicle component of claim 2, wherein the
15
(CH2)3 —o -ch
siloxane-containing copolymer comprises: CH3
E
CH3
a first siloxane-containing copolymer having an average OH HO
siloxane block length from 25 to 65, and a siloxane
content of 0.5 to 10 wt % based on the weight of the or a combination thereof and wherein E is the average
siloxane-containing copolymer, wherein the first silox number of siloxane units in each block;
ane-containing copolymer contributes 0.2 to 6.5 wt.% the bromine-containing polymer is a brominated epoxy
of siloxane units, based on the total weight of the polymer, a polycarbonate copolymer comprising first
polymers in the thermoplastic polymer composition,
and carbonate repeating units derived from bisphenol-A
25 and second repeating brominated carbonate units
an optional second siloxane-containing copolymer having
an average siloxane block length from 5 to 20, and a derived from 2.2".6,6'-tetrabromo-4,4'-isopropylidene
siloxane content of 0.5 to 2 wt % based on the weight diphenol, a tetrabromo-bisphenol-A homopolymer, or a
of the siloxane-containing copolymer, wherein the combination comprising at least one of the foregoing;
optional second siloxane-containing copolymer con 30
and
tributes 0 to 1.5 wt.% of siloxane units, based on the the optional third polymer is a Bisphenol-A homopoly
total weight of the polymers in the thermoplastic com C.
position. 9. The railway vehicle component of claim 2, wherein the
6. The railway vehicle component of claim 5, comprising, light diffuser additive comprises silicone, polymethylsilses
based on the total weight of the polymers in the thermo 35 quioxane, crosslinked poly(methyl methacrylate), methyl
plastic polymer composition, methacrylate/ethyleneglycol dimethacrylate copolymer,
20 to 65 wt.% of the first siloxane-containing copolymer, TiO, or a combination comprising at least one of the
wherein the first siloxane-containing copolymer has an foregoing.
average siloxane block length of 35 to 55; and 10. The railway vehicle component of claim 2, further
0 to 55 wt % of the optional second siloxane-containing 40 comprising 0.00002 to 5.0 wt % of a colorant based on the
copolymer, wherein the second siloxane-containing total weight of the polymers in the thermoplastic polymer
copolymer has an average siloxane block length from 5 composition.
to 15. 11. A railway vehicle component, wherein the component
7. The railway vehicle component of claim 2, wherein the is a trolley sidewall, an access door, or an access panel, and
siloxane-containing copolymer is a poly(carbonate-silox 45 wherein the component is molded or formed from a ther
ane) derived from at least one dihydroxy aromatic contain moplastic polymer composition comprising:
ing polycarbonate unit, and at least one polysiloxane bis 35 to 50 wt % of a bromine-containing polymer based on
phenol of formula (1), formula (2), or a combination thereof: the total weight of polymers in the thermoplastic poly
mer composition, wherein the bromine-containing
(1)
50 polymer is effective to provide 9 to 13 wt % of bromine,
based on the total weight of the polymers in the
thermoplastic polymer composition; and
HO-Air-O o Air-OH 20 to 65 wt % of a siloxane-containing copolymer based
on the total weight of the polymers in the thermoplastic
R
E. 55 polymer composition, wherein the siloxane-containing
(2) copolymer comprises a first repeating unit, and a poly
(siloxane) unit having the formula:
HO-R2 o --on 60
R R
E
SO
wherein R
E.
R is each independently a C-C hydrocarbon group,
R is each independently a C7-Cso hydrocarbon group, 65
Ar is a C-Clso aromatic group and wherein R is each independently a C-Clso hydrocarbon
E is the average number of siloxane units in each block. group, and E has an average value of 5 to 200, and
 US 9,453,128 B2
89 90
wherein the siloxane-containing copolymer is effective the optional second siloxane-containing copolymer
to provide a total of 0.2 to 6.5 wt % of siloxane units contributes 0 to 0.4 wt.% of siloxane units, based on
based on the total weight of the polymers in the the total weight of the polymers in the thermoplastic
thermoplastic polymer composition; polymer composition.
wherein the first repeating unit of the siloxane-containing 5 15. The railway vehicle component of claim 14, compris
copolymer comprises a carbonate unit, an ester unit, an ing, based on the total weight of the polymers in the
arylene Sulfone unit, an arylene ether Sulfone unit, an thermoplastic polymer composition,
arylene ether ketone unit, or a combination comprising 20 to 65 wt.% of the first siloxane-containing copolymer,
at least one of the foregoing units; and wherein the first siloxane-containing copolymer has an
optionally a third polymer, wherein the wt % of the 10
average siloxane block length of 35 to 55; and
siloxane-containing copolymer, the bromine-contain 0 to 60 wt % of the optional second siloxane-containing
ing polymer, and the optional third polymer, Sum to 100 copolymer, wherein the second siloxane-containing
wt %: copolymer has an average siloxane block length from 5
wherein a molded or formed sample of the thermoplastic to 15.
polymer composition has 15
a transmission of 70 to 87% or a haze of 2% to 10%, each 16. The railway vehicle component of claim 11, wherein
measured using the color space CIE 1931 (Illuminant C the siloxane-containing copolymer is a poly(carbonanate
and a 2° observer) at a thickness of 3.2 mm, siloxane) derived from at least one dihydroxy aromatic
an OSU integrated 2 minute heat release test value of less containing polycarbonate unit, and at least one polysiloxane
than 65 kW-min/m and a peak heat release rate of less bisphenol of formula (1), formula (2), or a combination
than 65 kW/m2, each measured using the method of thereof
FARF25.4, in accordance with Federal Aviation Regu
lation FAR 25.853 (d), and
an E662 smoke test DsMax value of less than 200 when (1)
measured at a thickness of 1.6mm. 25
12. The railway vehicle component of claim 11, the HO-Air-O jo Air-OH
siloxane-containing copolymer comprises:
a first siloxane-containing copolymer having an average R
E.
siloxane block length from 5 to 20, and a siloxane (2)
content of 0.5 to 2 wt % based on the weight of the 30 R R
siloxane-containing copolymer, wherein the first silox
ane-containing copolymer contributes 0.2 to 6.5 wt.% HO-R so --oh
of siloxane units, based on the total weight of the R R
polymers in the thermoplastic polymer composition, E
and 35
an optional second siloxane-containing copolymer having wherein
an average siloxane block length from 25 to 65, and a R is each independently a C-C hydrocarbon group,
siloxane content of 0.5 to 10 wt % based on the weight R is each independently a C7-Cso hydrocarbon group,
of the siloxane-containing copolymer, wherein the Ar is a C-Clso aromatic group and
optional second siloxane-contammg copolymer con 40
E is the average number of siloxane units in each block.
tributes 0 to 6.2 wt.% of siloxane units, based on the 17. The railway vehicle component of claim 16, wherein
total weight of the polymers in the thermoplastic poly the first and second siloxane-containing copolymer is a
mer composition. poly(carbonate-siloxane) comprising
13. The railway vehicle component of claim 12 compris carbonate units derived from bisphenol A and poly(silox
ing, based on the total weight of the polymers in the 45
ane) units derived from a polysiloxane bisphenol of the
thermoplastic polymer composition, formula
20to 65 wt.% of the first siloxane-containing copolymer,
wherein the first siloxane-containing copolymer has an
average siloxane block length from 5 to 15; and CH3 CH3
0 to 60 wt % of the optional second siloxane-containing 50
copolymer, wherein the second siloxane-containing HO (CH2)3 i-o i-CH.) OH,
copolymer has an average siloxane block length from CH
E
CH
35 to 55. HCO OCH
14. The railway vehicle component of claim 11, wherein CH3 CH3
the siloxane-containing copolymer comprises, 55
a first siloxane-containing copolymer comprising an aver (CH2)3 —o -ch
age siloxane block length from 25 to 65, and a siloxane CH CH
content of 2 to 10 wt % based on the weight of the OH
E
HO
siloxane-containing copolymer, wherein the first silox
ane-containing copolymer contributes 0.3 to 4.0 wt.% 60
of siloxane units, based on the total weight of t e or a combination thereof and wherein E is the average
polymers in the thermoplastic polymer composition, number of siloxane units in each block;
and the bromine-containing polymer is a brominated epoxy
an optional second siloxane-containing copolymer com polymer, a polycarbonate copolymer comprising first
prising an average siloxane block length from 5 to 20, 65 carbonate repeating units derived from bisphenol-A
and a siloxane content of 0.5 to 2 wt %, based on the and second repeating brominated carbonate units
weight of the siloxane-containing copolymer, wherein derived from 2.2".6,6'-tetrabromo-4,4'-isopropylidene
 US 9,453,128 B2
91 92
diphenol, a tetrabromo-bisphenol-A homopolymer, or a wherein the component is molded or formed from a ther
combination comprising at least one of the foregoing; moplastic polymer composition, comprising
and 35 to 50 wt % of a bromine-containing polymer based on
the optional third polymer is a Bisphenol-A homopoly the total weight of polymers in the thermoplastic poly
C. 5 mer composition, wherein the bromine-containing
18. The railway vehicle component of claim 11, further polymer is effective to provide 9 to 13 wt % of bromine,
comprising 0.00002 to 5.0 wt % of a colorant based on the based on the total weight of the polymers in the
total weight of the polymers in the thermoplastic polymer thermoplastic polymer composition; and
composition. 20 to 65 wt % of a siloxane-containing copolymer based
19. A railway vehicle component that is a partition or a 10
on the total weight of the polymers in the thermoplastic
light cover, wherein the component is molded or formed polymer composition, wherein the siloxane-containing
from the thermoplastic polymer composition of claim 11, copolymer comprises a first repeating unit, and a poly
further comprising 0.2 to 3.0 wt % of a light diffuser additive (siloxane) unit having the formula
based on the total weight of the polymers in the thermo
plastic composition. 15
20. The railway vehicle component of claim 19, wherein
the diffuser additive is silicone, polymethylsilsesquioxane,
crosslinked poly(methyl methacrylate), methyl methacry SO
late/ethyleneglycol dimethacrylate copolymer, TiO, and a
combination comprising at least one of the foregoing. R
E.
21. The railway vehicle component of claim 20, compris
ing 0.2 to 3.0 wt % of the polymethylsilsesquioxane light
diffuser additive. wherein R is each independently a C-C hydrocarbon
22. The railway vehicle component of claim 21, compris group and E is the average number of siloxane units in
ing 0.4 to 1.5 wt % of the crosslinked poly(methyl meth 25 each block, and wherein the siloxane-containing copo
acrylate) light diffuser additive, 0.4 to 1.5 wt % of the lymer is effective to provide a total of 0.2 to 1.5 wt %
polymethylsilsesquioxane light diffuser additive, or a com of siloxane units based on the total weight of polymers
bination thereof, provided that the total amount of light in the thermoplastic polymer composition; and
diffuser additive is 3.0 wt % or less. wherein the first repeating unit of the siloxane-containing
23. A railway vehicle component, wherein the component 30 copolymer comprises a carbonate unit, an ester unit, an
is a window, window dust cover, partition, light cover, arylene Sulfone unit, an arylene ether Sulfone unit, an
electronics screen, display cover, or plastic mirror, and arylene ether ketone unit, or a combination comprising
wherein the component is molded or formed from a ther at least one of the foregoing units; and
moplastic polymer composition comprising: optionally, a third polymer, wherein the wt % of the
a siloxane-containing copolymer in an amount effective to 35
siloxane-containing copolymer, the bromine-contain
provide a total of 0.2 to 1.5 wt % of siloxane units based ing polymer, and the optional third polymer Sum to 100
on the total weight of polymers in the thermoplastic wt %:
polymer composition;
a bromine-containing polymer in an amount effective to wherein a molded or formed sample of the thermoplastic
provide 9 to 13 wt % of bromine, based on the total 40 polymer composition has
weight of the polymers in the thermoplastic polymer a transmission of 87% or more or a haze of 2% or less,
composition, and each measured using the color space CIE 1931 (Illu
optionally, a third polymer comprising carbonate units, minant C and a 2° observer) at a thickness of 3.2 mm,
imide units, etherimide units, arylene ether Sulfone an OSU integrated 2 minute heat release test value of less
units, arylene ether units, or a combination thereof, 45 than 65 kW-min/m and a peak heat release rate of less
wherein the wt % of the siloxane-containing copoly than 65 kW/m, each measured using the method of
mer, the bromine-containing polymer, and the optional FARF25.4, in accordance with Federal Aviation Regu
third polymer sum to 100 wt %; lation FAR 25.853 (d), and
wherein the thermoplastic polymer composition is free of an E662 smoke test DsMax value of less than 200 when
polyarylester-polycarbonate copolymers comprising 50 measured at a thickness of 1.6 mm.
carbonate units and arylate ester units and the thermo 25. The railway vehicle component of claim 24, wherein
plastic composition is free of polyalkylene esters; and the siloxane-containing copolymer comprises:
wherein a molded or formed sample of the thermoplastic a first siloxane-containing copolymer comprising an aver
polymer composition has age siloxane block length from 5 to 20, and a siloxane
a transmission of 87% or more or a haze of 2% or less, 55 content of 0.5 to 2 wt % based on the weight of the
each measured using the color space CIE 1931 (Illu siloxane-containing copolymer, wherein the first silox
minant C and a 2° observer) at a thickness of 3.2 mm, ane-containing copolymer contributes 0.2 to 1.5 wt.%
an OSU integrated 2 minute heat release test value of less of siloxane units, based on the total weight of the
than 65 kW-min/m and a peak heat release rate of less polymer in the thermoplastic polymer composition, and
than 65 kW/m, each measured using the method of 60 an optional second siloxane-containing copolymer com
FARF25.4, in accordance with Federal Aviation Regu prising an average siloxane block length from 25 to 65,
lation FAR 25.853 (d), and and a siloxane content of 0.5 to 10 wt %, based on the
an E662 smoke test DsMax value of less than 200 when weight of the siloxane-containing copolymer, wherein
measured at a thickness of 1.6mm. the optional second siloxane-containing copolymer
24. A railway vehicle component wherein the component 65 contributes 0 to 1.3 wt.% of the total siloxane units,
is a window, window dust cover, partition, light cover, based on the total weight of the polymer in the ther
electronics screen, display cover, or plastic mirror, and moplastic polymer composition.
 US 9,453,128 B2
93 94
26. The railway vehicle component of claim 25 compris 29. The railway vehicle component of claim 23, further
ing, based on the total weight of the polymers in the comprising 0.00002 to 5.0 wt % of a colorant based on the
thermoplastic polymer composition, total weight of the polymers in the thermoplastic polymer
20 to 65 wt.% of the first siloxane-containing copolymer, composition.
wherein the first siloxane-containing copolymer has an 5 30. The railway vehicle component of claim 29, compris
average siloxane block length from 5 to 20; and 1ng
0 to 30 wt % of the optional second siloxane-containing 0.00003 to 0.001 wt % of a blue colorant and 0.00003 to
copolymer, wherein the second siloxane-containing 0.001% of violet colorant;
copolymer has an average siloxane block length from 10
a phosphite heat stabilizer, and
20 to 40. a UV absorber.
27. The railway vehicle component of claim 24, wherein 31. The railway vehicle component of claim 30, wherein
the siloxane-containing copolymer is a poly(carbonate-si the blue colorant is Pigment Blue 60 and the violet colorant
loxane) derived from at least one dihydroxy aromatic con is Solvent Violet 36.
taining polycarbonate unit, and at least one polysiloxane 15 32. The railway vehicle component of claim 31, wherein
bisphenol of formula (1), formula (2), or a combination the UV absorber is 2,2'-(1,4-phenylene)bis-2,2'-(1,4-phe
thereof: nylene)bis(4H-3,1-benzoxazin-4-one): 2-(2"hydroxy-5-t-oc
tylphenyl)-benzotriazole: 2-(2H-benzotriazol-2-yl)-4,6-bis
(1-ethyl-1-phenylethylphenol; or a combination comprising
(1) at least one of the forgoing.
33. The railway vehicle component of claim 24, wherein
HO-Air - O o Air-OH the component is a partition or a light cover, and wherein the
thermoplastic polymer composition further comprises 0.2 to
R 2.0 wt % of a light diffuser additive based on the total weight
E.
(2) 25 of the polymers in the thermoplastic polymer composition.
34. The railway vehicle component of claim 33, wherein
the diffuser additive comprise silicone, poly tmethylsilses
HO-R2 o -R-O- quioxane, crosslinked poly(methyl methacrylate), methyl
methacrylate lethyleneglycol dimethacrylate copolymer,
R R
E 30 TiO, or a combination comprising at least one of the
foregoing.
wherein 35. The railway vehicle component of claim 34, compris
R is each independently a C-C hydrocarbon group, ing 0.2 to 2.0wt % of the polymethylsilsesquioxane light
R is each independently a C-Cso hydrocarbon group, diffuser additive.
Ar is a C-Clso aromatic group and 35 36. The railway vehicle component of claim 33, compris
E is the average number of siloxane units in each block. ing 0.4 to 1.5 wt % of the crosslinked poly(methyl meth
28. The railway vehicle component of claim 27, wherein acrylate) light diffuser additive 0.4 to 1.5 wt % of the
the siloxane-containing copolymer is a poly(carbonate polymethylsilsesquioxane light diffuser additive, or a com
siloxane) comprising carbonate units derived from bis bination thereof provided that the total amount of light
phenol A and poly(siloxane) units derived from a 40 diffuser additive is 3 wt % or less.
polysiloxane bisphenol of the formula 37. The railway vehicle component of claim 24, wherein
the component is a window article comprising a sheet
supported by a frame, wherein the sheet is molded or formed
CH3 CH3
from the thermoplastic polymer composition.
45 38. The railway vehicle component of claim 37, wherein
HO (CH2)3 5-0 Š-(CH), OH, the sheet has a first side and a second opposite side, and the
H, I E- h, window article further comprises a first hard coat layer
HCO OCH disposed on the first side and a second hard coat layer
CH disposed on the second side.
st || 50 39. The railway vehicle component of claim 38, further
comprising
(CH2)3 —o -ch a first ultraviolet light-blocking layer disposed between
CH CH
OH
E
HO the first hard coat layer and the first side of the sheet,
and
55 a second ultraviolet light-blocking layer disposed
or a combination thereof and wherein E is the average between the second hard coat layer and the second side
number of siloxane units in each block; of the sheet.
the bromine-containing polymer is a brominated epoxy 40. The railway vehicle component of claim 37, wherein
polymer, a polycarbonate copolymer comprising first the component is a dust cover for a window, the window
carbonate repeating units derived from bisphenol-A 60 comprising:
and second repeating brominated carbonate units an outer window and an inner window separated by a
derived from 2.2".6,6'-tetrabromo-4,4'-isopropylidene Space;
diphenol, a tetrabromo-bisphenol-A homopolymer, or a the dust cover separated from the inner window by a
combination comprising at least one of the foregoing; space, and
and 65 a frame,
the optional third polymer is a Bisphenol-A homopoly wherein the outer window, inner window, and dust cover
C. are secured in the frame such that the inner window is
 US 9,453,128 B2
95 96
disposed between and is substantially coplanar with 45. The railway vehicle component of claim 44, wherein
each of the dust cover and the outer window. the siloxane-containing copolymer comprises
41. The railway vehicle component of claim 24, wherein a first siloxane-containing copolymer having an average
the component is a mirror, comprising: siloxane block length from 25 to 65, and a siloxane
a layer molded or formed from the thermoplastic polymer content of 15 to 25 wt % based on the weight of the
composition, siloxane-containing copolymer, wherein the optional
a hard coat disposed on a Surface of a first side of the second siloxane-containing copolymer contributes 2.5
layer, and to 6.0 wt.% of the total siloxane units; and
an opacifying layer disposed on a Surface of a second side a second, optional siloxane-containing copolymer having
of the layer opposite the first side. an average siloxane block length from 25 to 65, and a
42. The mirror of claim 41, wherein the opacifying layer siloxane content of 4 to 10 wt % based on the weight
is a metal layer. of the siloxane-containing copolymer, wherein the Sec
43. The mirror of claim 41, further comprising a protec ond siloxane-containing copolymer contributes 0 to 3.0
tive coat disposed on a Surface of the opacifying layer 15
wt.% of the total siloxane units, based on the total
opposite the layer molded or formed from the thermoplastic wight of the polymers in the thermoplastic polymer
polymer composition. composition.
44. A railway vehicle component, wherein the component 46. The railway vehicle component of claim 45, compris
is an access door panel, a seat component and a component ing
of a trolley cart, wherein the component is molded or formed 20 to 40 wt.% of the first siloxane-containing copolymer,
from a thermoplastic polymer composition comprising wherein the first siloxane-containing copolymer has an
35 to 50 wt % of a bromine-containing polymer based on average siloxane block length from 40 to 50; and
the total weight of polymers in the thermoplastic poly 0 to 37 wt % of the optional second siloxane-containing
mer composition, wherein the bromine-containing copolymer, wherein the second siloxane-containing
polymer is effective to provide 9 to 13 wt % of bromine, 25 copolymer has an average siloxane block length from
based on the total weight of the polymers in the 40 to 50.
thermoplastic polymer composition; and
20 to 65 wt % of a siloxane-containing copolymer based 47. The railway vehicle component of claim 44, wherein
on the total weight of the polymers in the thermoplastic the first and second siloxane-containing copolymer is a
polymer composition, wherein the siloxane-containing 30
poly(carbonate-siloxane) derived from at least one dihy
copolymer comprises a first repeating unit, and a poly droxy aromatic containing polycarbonate unit, and at least
(siloxane) unit having the formula: one polysiloxane bisphenol of formula (1), formula (2), or a
combination thereof:

35
(1)
SO

R
E.
HO-Air - O jo Air-OH
R
40 E.
wherein R is each independently a C-Clso hydrocarbon (2)
group, and E has an average value of 5 to 200, and
wherein the siloxane-containing copolymer is effective
to provide a total of 2.5 to 6.0 wt % of siloxane units
based on the total weight of polymers in the thermo 45
HO-R2 jo -R-oil
R R
plastic polymer composition; E

wherein the first repeating unit of the siloxane-containing

copolymer comprises a carbonate unit, an ester unit, an wherein
arylene Sulfone unit, an arylene ether Sulfone unit, an
arylene ether ketone unit, or a combination comprising 50 R is each independently a C-C hydrocarbon group,
at least one of the foregoing units; and R is each independently a C7-Cso hydrocarbon group,
optionally, a third polymer wherein the wt % of the Ar is a C-Clso aromatic group and
siloxane-containing copolymer, the bromine-contain
ing polymer, and the optional third polymer, Sum to 100 E is the average number of siloxane units in each block.
wt %: 55 48. The railway vehicle component of claim 47, wherein
wherein a molded or formed sample of the thermoplastic the siloxane-containing copolymer is a poly(carbonate
polymer composition has siloxane) comprising carbonate units derived from bis
a notched IZod impact strength of 480 J/m or greater, phenol A and poly(siloxane) units derived from a
measured according to ASTM D 256-10 at a 3.2 mm polysiloxane bisphenol of the formula
thickness at 0°C., 60
an OSU integrated 2 minute heat release test value of less
than 65 kW-min/m and a peak heat release rate of less
than 65 kW/m, each measured using the method of $H | H.
FARF25.4, in accordance with Federal Aviation Regu HO (CH2)3 s-o i-CH.) OH,
lation FAR 25.853 (d), and 65 CH3 CH3
an E662 smoke test DsMax value of less than 200 when H3CO E- OCH
measured at a thickness of 1.6mm.
 US 9,453,128 B2
97 98
-continued an OSU integrated 2 minute heat release test value of less
than 65 kW-min/ and a peak heat release rate of less
it it than 65 kW/m, each measured using the method of
—o CH-ch
CH
5
FARF25.4, in accordance with Federal Aviation Regu
lation FAR 25.853 (d), and
OH
E
HO an E662 smoke test DsMax value of less than 200 when
measured at a thickness of 1.6mm.
or a combination thereof and wherein E is the average 50. The colored railway vehicle component of claim 49,
number of siloxane units in each block; 10
wherein the siloxane-containing copolymer comprises
the bromine-containing polymer is a brominated epoxy a first siloxane-containing copolymer comprising an aver
polymer, a polycarbonate copolymer comprising first age siloxane block length from 25 to 65, and a siloxane
carbonate repeating units derived from bisphenol-A content of 15 to 25 wt % based on the weight of the
and second repeating brominated carbonate units siloxane-containing copolymer, wherein the first silox
derived from 2.2".6,6'-tetrabromo-4,4'-isopropylidene 15 ane-containing copolymer contributes 1.0 to 2.5 wt.%
diphenol, a tetrabromo-bisphenol-A homopolymer, or a of siloxane units, based on the total weight of the
combination comprising at least one of the foregoing; polymers in the thermoplastic polymer composition,
and and
the optional third polymer is a Bisphenol-A homopoly a second siloxane-containing copolymer comprising an
C. average siloxane block length from 25 to 65, and a
49. A colored railway vehicle component, wherein the siloxane content of 4 to 10 wt %, based on the weight
component is a stow bin component, a magazine rack, a seat of the siloxane-containing copolymer, wherein the Sec
component, a component of a trolley cart, and an access door ond siloxane-containing copolymer contributes 0.3 to
panel, wherein the component is molded or formed from a 3wt.% of siloxane units, based on the total weight of
thermoplastic polymer composition comprising 25 the polymers in the thermoplastic composition,
35 to 50 wt % of a bromine-containing polymer based on with the proviso that the composition comprises a total of
the total weight of polymers in the thermoplastic poly 2.5 to 5.3 wt % of siloxane units, based on the total
mer composition, wherein the bromine-containing weight of polymers in the thermoplastic polymer com
polymer is effective to provide 9 to 13 wt % of bromine, position.
based on the total weight of the polymers in the 30
51. The colored railway vehicle component of claim 50,
thermoplastic polymer composition; and
20 to 65 wt % of a siloxane-containing copolymer based comprising, based on the total weight of the polymers in the
on the total weight of the polymers in the thermoplastic thermoplastic polymer composition,
polymer composition, wherein the siloxane-containing 5 to 12 wt.% of the first siloxane-containing copolymer,
copolymer comprises a first repeating unit, and a poly 35 wherein the first siloxane-containing copolymer has an
(siloxane) unit having the formula: average siloxane block length from 35 to 55; and
38 to 55 wt % of the optional second siloxane-containing
copolymer, wherein the second siloxane-containing
copolymer has an average siloxane block length from
40 35 to 55.
SO
52. The colored railway vehicle component of claim 49,
R
E.
wherein the first and second siloxane-containing copolymer
is a poly(carbonate-siloxane) derived from at least one
dihydroxy aromatic containing polycarbonate unit, and at
wherein R is each independently a C-Clso hydrocarbon 45 least one polysiloxane bisphenol of formula (1), formula (2),
group, and E has an average value of 5 to 200, wherein or a combination thereof:
the siloxane-containing copolymer is effective to pro
vide a total of 2.5 to 5.3 wt % of siloxane units based
on the total weight of polymers in the thermoplastic (1)
polymer composition; 50
wherein the first repeating unit of the siloxane-containing
copolymer comprises a carbonate unit, an ester unit, an HO-Air-O jo Air-OH
arylene Sulfone unit, an arylene ether Sulfone unit, an R
arylene ether ketone unit, or a combination comprising E.

at least one of the foregoing units; and 55 (2)

optionally, a third polymer wherein the wt% of the
siloxane-containing copolymer, the bromine-contain
ing polymer, and the optional third polymer, Sum to 100 HO-R2 io --oil
wt %; and R R
E
0.00002 to 5.0 wt % of a colorant based on the total 60
weight of the polymers in the thermoplastic polymer
composition, wherein
wherein a molded or formed sample of the thermoplastic R is each independently a C-C hydrocarbon group,
polymer composition has R is each independently a C7-Cso hydrocarbon group,
a notched iZod impact strength of 400 J/m or greater, 65
measured at 10° C. according to ASTM D256-10 at a Ar is a C-Clso aromatic group and
3.2 mm thickness, E is the average number of siloxane units in each block.
 US 9,453,128 B2
99 100
53. The colored railway vehicle component of claim 52, wherein the wt % of the siloxane-containing copoly
wherein mer, the bromine-containing polymer, and the optional
the siloxane-containing copolymer is a poly(carbonate third polymer, sum to 100 wt %;
siloxane) comprising carbonate units derived from bis wherein the thermoplastic polymer composition is free of
phenol A and poly(siloxane) units derived from a 5 polyarylester-polycarbonate copolymers comprising
polysiloxane bisphenol of the formula carbonate units and arylate ester units and the thermo
plastic composition is free of polyalkylene esters; and
wherein a molded or formed sample of the thermoplastic
CH3 CH3
10
polymer composition has
HO (CH2)3 -o Si-(CH2) OH, a notched Izod impact strength of 2.0 ft-lb/in or greater,
CH CH measured according to ASTM D 256-10 at a 3.2 mm
HCO E- OCH thickness at room temperature,
an OSU integrated 2 minute heat release test value of less
th CH3 15 than 65 kW-min/m and a peak heat release rate of less
(CH2)3 —o -ch than 65 kW/m, each measured using the method of
CH CH
FARF25.4, in accordance with Federal Aviation Regu
OH
E
HO
lation FAR 25.853 (d), and
an E662 smoke test DsMax value of less than 200 when
measured at a thickness of 1.6mm.
or a combination thereof and wherein E is the average 59. A railway vehicle component, wherein the component
number of siloxane units in each block; is an access door panel, a seat component, a component of
the bromine-containing polymer is a brominated epoxy a stow bin, a magazine rack, a seat component, a component
polymer, a polycarbonate copolymer comprising first of a trolley cart, an access door panel call button, a light
carbonate repeating units derived from bisphenol-A 25 bezel, a door pull, a door handle, an arm rest, a foot rest, or
and second repeating brominated carbonate units a trolley cart, wherein the component is molded or formed
derived from 2.2".6,6'-tetrabromo-4,4'-isopropylidene from a thermoplastic polymer composition comprising
diphenol, a tetrabromo-bisphenol-A homopolymer, or a 35 to 50 wt % of a bromine-containing polymer based on
combination comprising at least one of the foregoing; the total weight of polymers in the thermoplastic poly
and 30
mer composition, wherein bromine-containing polymer
the optional third polymer is a Bisphenol-A homopoly is effective to provide 9 to 13 wt % of bromine, based
e.
54. The railway vehicle component of claim 49, compris on the total weight of the polymers in the thermoplastic
ing 0.025 to 5 wt % TiO, based on the total weight of the polymer composition; and
polymers in the composition. 35 20 to 65 wt % of a siloxane-containing copolymer based
55. The railway vehicle component of claim 49, compris on the total weight of the polymers in the thermoplastic
1ng polymer composition, wherein the siloxane-containing
0.00002 wt % to 0.02 wt % of Solvent Red 135, Solvent copolymer comprises a first repeating unit, and a poly
Red 52, or a combination comprising at least one of the (siloxane) unit having the formula:
foregoing; and 40
0.00002 to 0.02% of a Pigment Blue 28, Pigment Blue
29:77007, or a combination comprising at least one of
the foregoing. SO
56. The railway vehicle component of claim 49, compris
ing 0.0001 to 0.1 wt % of carbon black. 45 R
E.
57. The railway vehicle component of claim 49, wherein
at least a portion of a Surface of the component is painted.
58. A railway vehicle component, wherein the component wherein R is each independently a C-Clso hydrocarbon
is an access door panel, a seat component, a component of group, and E has an average value of 5 to 200, wherein
a stow bin, a magazine rack, a seat component, a component 50 the siloxane-containing copolymer is effective to pro
of a trolley cart, an access door panel call button, a light vide a total of 2.5 to 6.0 wt % of siloxane units based
bezel, a door pull, a door handle, an arm rest, a foot rest, or on the total weight of polymers in the thermoplastic
a trolley cart, wherein the component is molded or formed polymer composition;
from a thermoplastic polymer composition comprising wherein the first repeating unit of the siloxane-containing
a first siloxane-containing copolymer in an amount effec 55 copolymer comprises a carbonate unit, an ester unit, an
tive to provide a total of 2.5 to 6.0 wt % of siloxane arylene Sulfone unit, an arylene ether Sulfone unit, an
units based on the total weight of polymers in the arylene ether ketone unit, or a combination comprising
thermoplastic polymer composition, and wherein the at least one of the foregoing units; and
siloxane-containing copolymer comprises siloxane optionally a third polymer, wherein the wt % of the
blocks having 10 to 200 siloxane units per block; 60 siloxane-containing copolymer, the bromine-contain
a bromine-containing polymer in an amount effective to ing polymer, and the optional third polymer, Sum to 100
provide 9 to 13 wt % of bromine, based on the total wt %:
weight of the polymers in the thermoplastic polymer wherein a molded or formed sample of the thermoplastic
composition, and polymer composition has
optionally a third polymer comprising carbonate units, 65 a notched Izod impact strength of 2.0 ft-lb/in or greater,
imide units, etherimide units, arylene ether Sulfone measured according to ASTM D 256-10 at a 3.2 mm
units, arylene ether units, or a combination thereof thickness at room temperature,
 US 9,453,128 B2
101 102
an OSU integrated 2 minute heat release test value of less 63. The railway vehicle component of claim 62, compris
than 65 kW-min/m and a peak heat release rate of less ing 0.025 to 5 wt % TiO, based on the total weight of the
than 65 kW/m, each measured using the method of polymers in the composition.
FARF25.4, in accordance with Federal Aviation Regu 64. The railway vehicle component of claim 62, compris
lation FAR 25.853 (d), and 1ng
an E662 smoke test DsMax value of less than 200 when
measured at a thickness of 1.6mm. 0.00002 wt % to 0.02 wt % of Solvent Red 135, Solvent
60. The railway vehicle component of claim 59, wherein Red 52, or a combination comprising at least one of the
the siloxane-containing copolymer is a poly(carbonate-si foregoing; and
loxane) derived from at least one dihydroxy aromatic con 10 0.00002 to 0.02% of Pigment Blue 28, Pigment Blue
taining polycarbonate unit, and at least one polysiloxane 29:77007, or a combination comprising at least one of
bisphenol of formula (1), formula (2), or a combination the foregoing.
thereof: 65. The railway vehicle component of claim 62, compris
ing 0.0001 to 0.1 wt % of carbon black.
(1)
15 66. The railway vehicle component of claim 62, wherein
at least a portion of a surface of the component is painted.
67. The railway vehicle component of claim 23,
HO-Air - O o Air-OH wherein a molded plaque of the siloxane-containing copo
R lymer has a percent haze value of 3% or less measured
E.
using the color space CIE 1931 (Illuminant C and a 2°
(2) observer) at a thickness of 3.2 mm.
68. The railway vehicle component of claim 24, wherein
a molded plaque of the siloxane-containing copolymer has a
HO-R2 o -R-O- 25 percent haze value of 3% or less measured using the color
R R
E space CIE 1931 (Illuminant C and a 2° observer) at a
thickness of 3.2 mm.
wherein 69. The railway vehicle component of claim 68, wherein
R is each independently a C-C hydrocarbon group, the siloxane-containing copolymer is a poly(carbonate-si
R is each independently a C7-Cohydrocarbon group, 30 loxane) derived from at least one dihydroxy aromatic con
Ar is a C-Clso aromatic group, and taining polycarbonate unit, and at least one polysiloxane
E is the number of siloxane units in each block. bisphenol of formula (1), formula (2), or a combination
thereof
61. The railway vehicle component of claim 60, wherein
the siloxane-containing copolymer is a poly(carbonate
35
siloxane) comprising carbonate units derived from bis (1)
phenol A and poly(siloxane) units derived from a
polysiloxane bisphenol of the formula
HO-Air-O jo Air-OH
40 R
CH3 CH3 E.

Si-(CH2) OH, (2)

HO (CH2)3 -o
CH CH
HCO
CH3
E-
CH3
OCH
45
HO-R2 jo --oil
R R
E

(CH2)3 –o -ch
CH E
CH wherein
OH HO
50 R is each independently a C-C hydrocarbon group,
Ris each independently a C7-Cso hydrocarbon group,
or a combination thereof and wherein E is the average Ar is a C-Clso aromatic group and
number of siloxane units in each block;
the bromine-containing polymer is a brominated epoxy E is the average number of siloxane units in each block.
polymer, a polycarbonate copolymer comprising first 55 70. The railway vehicle component of claim 69, wherein
carbonate repeating units derived from bisphenol-A the siloxane-containing copolymer is a poly(carbonate
and second repeating brominated carbonate units siloxane) comprising carbonate units derived from bis
derived from 2.2 '6,6'-tetra bromo-4.4"-isopropy phenol A and poly(siloxane) units derived from a
lidenediphenol, a tetrabromo-bisphenol-A homopoly polysiloxane bisphenol of the formula
mer, or a combination comprising at least one of the 60
foregoing; and
the optional third polymer is a Bisphenol-A homopoly
C. $H | H.
62. The railway vehicle component of claim 59, further HO (CH2)3 s-o i-CH.) OH,
comprising 0.00002 to 5.0 wt % of a colorant based on the 65 CH3 CH3
total weight of the polymers in the thermoplastic polymer H3CO E- OCH
composition.
 US 9,453,128 B2
103 104
-continued the optional third polymer is a Bisphenol-A homopoly
CH CH C.
71. The railway vehicle component of claim 67, further
(CH2)3 –0 – (CH)3 comprising 0.05 to 10 wt % of a light diffuser additive, based
CH CH on the total weight of polymers in the thermoplastic polymer
OH
E-1
HO composition.
72. The railway vehicle component of claim 71, wherein
the light diffuser additive comprises silicone, polymethyl
or a combination thereof and wherein E is the average sillsesquioxane, crosslinked poly(methyl methacrylate),
number of siloxane units in each block; 10
methyl methacrylate/ethyleneglycol ditnethacrylate copoly
the bromine-containing polymer is a brominated epoxy
polymer, a polycarbonate copolymer comprising first mer, TiO, or a combination comprising at least one of the
carbonate repeating units derived from bisphenol-A foregoing.
and second repeating brominated carbonate units 73. The railway vehicle component of claim 67, further
derived from 2.2".6,6'-tetrabromo-4,4'-isopropylidene 15 comprising 0.00002 to 5.0 wt % of a colorant based on the
diphenol, a tetrabromo-bisphenol-A homopolymer, or a total weight of the polymers in the thermoplastic polymer
combination comprising at least one of the fore composition.
going; and