Modified Rosin Ester Preparation

US Patent for Modified rosin ester preparation Patent (Patent # 4,643,8... https://patents.justia.
com/patent/4643848
Modified rosin ester preparation

Feb 21, 1986 - Westvaco Corporation
Phosphinic acid (also called hypophosphorous acid),

when used in very small quantities, is disclosed to
act as a catalyst to accelerate the reaction of rosin
with an unsaturated dibasic acid to form a modified
rosin for subsequent esterification with a polyhydric
alcohol. According to the process of the invention, a
rosin is reacted with an unsaturated dibasic acid
such as maleic anhydride or fumaric acid in the
presence of phosphinic acid at a temperature of from
about 180.degree. C. to about 220.degree. C. When
the modified rosin is subsequently esterified, the
1 of 17 07/06/2021, 14:37
US Patent for Modified rosin ester preparation Patent (Patent # 4,643,8... https://patents.justia.com/patent/4643848
rosin ester exhibits improved color, softening point,

and viscosity in a specified solution.
Latest Westvaco Corporation Patents:

CONTAINER HAVING MEANS FOR HOLDING LITERATURE THEREIN
CONTAINER
DISPENSER
CONTAINER WITH DISPENSER
PHOTOCURABLE MATERIALS with MICROFLUIDIC ENDOSKELETON
Skip to: Description · Claims · References Cited · Patent History · Patent History
Description
BACKGROUND OF THE INVENTION

1. Field of the Invention
This invention relates to a novel method of producing various types of modified rosin
resin esters of polyhydric alcohols. These modifications include the addition of maleic
anhydride or other unsaturated dibasic acids to rosin. In particular, this invention
relates to reacting rosin and the unsaturated dibasic acid in the presence of very low
quantities of phosphinic acid, as a catalyst. The modified rosin is subsequently reacted
with one or more various polyhydric alcohols to form modified rosin resins having
improved properties such as color, softening point and viscosity in a specified solution.
2. Description of the Prior Art
Rosin is mainly a mixture of C.sub.20, fused-ring, monocarboxylic acids, typified by

levopimaric and abietic acids, both of which are susceptible to numerous chemical
transformations. The rosins to which this invention relates include gum rosin, wood
rosin and tall oil rosin.
The natural separation and gradual conversion of some of the hydrophilic components
of sap and related plant fluids from the cambium layer of a tree into increasingly
hydrophobic solids are the generic process of forming diverse gums, resins and waxes.
The oleoresin intermediate in this process is typified in pine gum, which flows from
hacks on the trunks of southern yellow pine primarily in Portugal, Brazil and China, as
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well as and in other countries. Pine gum contains about 80% (gum) rosin and about
20% turpentine.
Resinification from oleoresin can result from either natural evaporation of oil from an
extrudate or slow collection in ducts in sapwood and heartwood. Pinus stumps are
valuable enough to be harvested, chipped, and extracted with hexane or higher-boiling
paraffins to yield wood rosin, wood turpentine, and other terpene-related compounds by
fractional distillation. In the kraft, i.e., sulfate, pulping process for making paper,
pinewood is digested with alkali producing crude tall oil and crude sulfate turpentine as
by-products. Fractionation of the crude tall oil yields tall oil rosin and fatty acids.
Prior to this invention dibasic modified rosin esters of polyhydric alcohols were
produced by adducting as much as 30% (based on the weight of the rosin) fumaric acid
or maleic anhydride to the rosin by thermally driving the reaction to completion.
Reaction times as long as four (4) hours could be expected when performing this
addition at 180.degree. C. to 210.degree. C. Fumaric acid additions take a longer time to
complete than maleinized adducts; however, maleic anhydride adducts yield a darker
colored product. High levels of unsaturated dibasic acids are used to give the resin the
basis for the high molecular weights needed to meet certain performance criteria such
as hardness, or softening point, viscosity, and rub resistence, as well as other specific
end use demands.
Also incorporated into some resins is the addition to the rosin of a phenolic-
formaldehyde condensate. Prior to this invention it has been difficult to form an adduct
of most common grades of rosin by reacting the rosin with a smaller level of a phenolic-
formaldehyde, followed by a higher level of fumaric acid. The nature of this problem is
not definitely known, but it is theorized that the rosin-phenolic condensation product
somehow blocks the fumaric addition reactions.
This problem is not evident when the phenolic is followed by a maleic anhydride
addition, but again the maleic adduct gives darker colors which are unacceptable for use
in the application for which the resin is intended. The phenolicformaldehyde
condensate addition product contributes better drying speed to the resin.
The above mentioned modified rosins upon completion are then esterified with one or
more polyhydric alcohols such as pentaerythritol, glycerine, sorbitol, or
trimethylolpropane. The esterification reaction is carried out at temperatures of
215.degree. C. to 280.degree. C. depending upon the polyalcohol used. The esterification
reaction may be carried out to an acid number of 220 to 15, depending upon the level of
modification of the rosin and the end use for which the resin is intended. This
esterification step can be carried out at atmospheric or reduced pressure typically with
the use of a calcium hydroxide catalyst.
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The beneficial product characteristics provided by rosin esterification for various

applications have led to the development of many esterification procedures, particularly
treatments with polyhydric alcohols. U.S. Pat. Nos. 2,369,125, 2,590,910 and 2,572,086
teach rosin esterification with glycerol and pentaerythritol, among other polyhydric
alcohols, usually preceded by a rosin disproportionation step.
It is generally known in the art that a significant disadvantage of pentaerythritol

esterification of tall oil rosin is the deterioration of rosin color in the ester product. For a
tall oil rosin with a starting color of 8 on the Gardner scale, a pentaerythritol ester would
have a color of 13-18 while a glycerol ester would have a color of 8-9. Also, extremely
long reaction times are required to make the tall oil rosin-pentaerythritol esters (up to
30-48 hours) as compared to making tall oil rosin-glycerol esters under identical
conditions (10-12 hours).
U.S. Pat. Nos. 3,780,012 and 3,780,013 acknowledge that tall oil rosin darkens
significantly upon pentaerythritol esterification and propose alternative solutions. U.S.
Pat. No. 3,780,012 teaches pretreating the rosin with catalytic amounts of
paraformaldehyde followed by distillation prior to the esterification reaction. U.S. Pat.
No. 3,780,013 teaches the incremental addition of a phenol sulfide compound during
the esterification. The color of the product of these procedures was claimed to be an M
on the U.S.D.A. scale. Also, the patents' examples employed a 20% equivalent excess of
pentaerythritol.
U.S. Pat. No. 2,729,660 also acknowledges the darkening effect which common
esterification catalysts such as strong acids cause on the product during esterification.
The patent teaches the use of 0.5 to 5% of either the aliphatic or aromatic esters of
phosphorous acid as a catalyst for the esterification of higher fatty acids or rosin acids,
or mixtures thereof. In addition to avoiding appreciable color formation during the
esterification, a reduction in reaction time is noted. A distinct disadvantage of the
process is the dissociation, during esterification, of the alcohol used to make the
phosphite ester catalyst resulting in a disagreeable odor.
Also, U.S. Pat. No. 4,172,070 teaches employing arylsulfonic acid in place of the
traditional basic esterification catalysts, such as calcium oxide, to reduce the time for
tall oil rosin-pentaerythritol esterification to obtain a rosin ester of improved oxygen
stability, color and softening point. This work is confounded, however, by the unusually
large amount of pentaerythritol used (35% equivalent excess) which by itself would
markedly increase the rate of acid number drop. Products with Ring and Ball softening
points of 77.degree. C. to 86.5.degree. C. were obtained. Normal commercial
pentaerythritol esters of rosins soften between 95.degree. C. and 105.degree. C.
The primary object of this invention is to provide a novel method of preparing the above
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mentioned phenolic dibasic modified rosin resins that yields products with lighter
colors without adversely affecting viscosities and softening points and facilitates the
addition of a phenolic-formaldehyde condensate prior to a fumaric acid addition to the
rosin.
SUMMARY OF THE INVENTION

The above objectives are met in the discovery that phosphinic acid (also known as
hypophosphorous acid), when used in small quantities, acts as a catalyst to accelerate
the unsaturated dibasic acid additions as well as enables the addition of high levels
fumaric acid to a rosin that has been previously adducted with small levels of a
phenolic-formaldehyde condensate. The phosphinic acid also accelerates the
subsequent esterification reaction, while maintaining excellent color in the final resin.
DESCRIPTION OF THE PREFERRED EMBODIMENT

Phosphinic acid is a strong, reducing acid, useful for its antioxidant or color-reducing
properties in the preparation of light colored fatty acid taurates (U.S. Pat. No.
3,232,968), carboxylic acid esters with poly(oxyalkylene) compounds (British Pat. No.
979,673 and U.S. Pat. No. 3,071,604), acrylic and methacrylic esters of glycols (Japanese
Pat. No. 73 11084), or in light colored alkyd resins (Japanese Pat. No. 12997). Also,
phosphinic acid has been used as a tall oil treatment agent to convert the impurities and
color bodies contained therein to a non-distillable form and to promote decarboxylation
of rosin acids present (U.S. Pat. No. 2,441,197).
A novel method of producing modified rosin resin esters of polyhydric alcohols is now
provided involving the use of very small quantities of phosphinic acid as the catalyst for
the rosin modification step and subsequent esterification.
As polyhydric alcohols, ethylene glycol, propylene glycol, diethylene glycol, triethylene

glycol, tetraethylene glycol, trimethylene glycol, glycerol, pentaerythritol,
dipentaerythritol, tripentaerythritol, trimethylolethane, trimethylolpropane, mannitol,
sorbitol, as well as combinations of the aforementioned and other similar polyhydric
alcohols may be used. The amount of the alcohol used in the esterification may be varied
widely but generally no more than an approximate 20% excess over the equivalent
combining proportion will be necessary.
When glycerol is used for the esterification of the modified rosin, an esterification
catalyst is usually not required; and the residual phosphinic acid from the rosin
modification step may be preferably neutralized with sodium hydroxide,
monoethanolamine, or other basic compound.
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When a polyhydric alcohol other than glycerol is reacted with the modified rosin in the
presence of phosphinic acid, low acid numbers may be facilitated by following the
reaction with addition of up to 10% glycerol when the acid value is reduced to 50 or
below.
In general, the rosin is heated under an inert environment to 180.degree. C. At this time,
from 0.05%, but less than 0.5% phosphinic acid, based on the weight of the rosin, is
added to the molten rosin and allowed to mix well. A greater amount of phosphinic acid
may be used, but no benefit is derived from amounts of 0.5% or greater. To this blend
are added the desired resin components such as maleic anhydride, fumaric acid, or a
substituted phenol-formaldehyde blend. The dibasic acid addition is carried out at
temperatures of from about 180.degree. C. to about 220.degree. C. When a phenol-
formaldehyde blend is employed, the condensation is carried out at 125.degree.
C.-140.degree. C. to minimize loss of formaldehyde. After the phenolic-condensation is
complete, the temperature is increased to from about 180.degree. C. to about
200.degree. C.; and the dibasic acid is added. After the dibasic acid has reacted, the
molten product is heated to the appropriate esterification temperature and reacted with
the desired polyhydric alcohol at a temperature of 180.degree.-300.degree. C. until the
desired acid value is obtained.
The following examples serve to illustrate the modified rosin-polyhydric alcohol esters
made by the invention process. Unless otherwise specified, the parts are by weight.
EXAMPLE 1
To a suitable reaction vessel equipped with an overhead stirrer, condenser and
thermometer was added 1,000 parts tall oil rosin. The rosin was heated under an inert
gas blanket until molten. As the temperature reached 180.degree. C., 1.0 part of 50%
active aqueous solution of phosphinic acid was added. To this mixture were added 62.0
parts of maleic anhydride. The inert gas was stopped. The maleic anhydride was allowed
to react with the rosin for one hour at 250.degree. C.
After this time period, 163 parts pentaerythritol was added. The temperature was
increased to 285.degree. C. and held until the acid value was less than 25.
The same procedure was carried out without using phosphinic acid. The results are
shown in Table I. (In this and the following examples, viscosity is measured as a
Gardner-Holt type; and color measurements are expressed using the Gardner scale.)
TABLE I
______________________________________
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MODIFIED ROSIN ESTER PROPERTIES
Reaction Conditions
Without With
Property Phosphinic Phosphinic
______________________________________
Acid Value 23.2 24.3
Softening Point 119.degree. C.
125.degree. C.
Viscosity, 50% in Aliphatic Oil
Y Z4+
Color, 50% in Aliphatic Oil
11 8
Reaction Time 8 hours 7 hours
______________________________________
EXAMPLE 2
To a suitable reaction flask, equipped as in Example 1, were added 750 parts gum rosin
and 250 parts tall oil rosin. The blend was melted under an inert gas blanket until
molten. As the temperature reached 180.degree. C., 1.2 parts 50% active phosphinic acid
was added and allowed to mix well. To this mixture was added 285 parts fumaric acid.
The fumaric was allowed to react until clarity at 205.degree. C. After which, the
phosphinic acid was neutralized with 1.5 parts monoethanolamine.
To this molten product 62 parts glycerine and 37 parts sorbitol were added. The product
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was heated to 215.degree. C. and held until the acid value was less than 215.
A similar resin was prepared without using the phosphinic acid. The results were as
shown in Table II.
TABLE II
______________________________________
Reaction Conditions
Without With
Property Phosphinic
Phosphinic
______________________________________
Acid Value 210 212
155.degree. C.
Fumaric Reaction Time
2.1 hours 1.0 hour
Total Reaction Time 4.0 hours 3.5 hours
Viscosity, 60% in Ethanol
H-I J
Color, 60% in Ethanol
8-9 7+
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Color in a 5% Ammonium Solution
5-6 5+
(15% solids)
______________________________________
EXAMPLE 3
To a suitable reaction vessel equipped as in Example 1 1,000 parts tall oil rosin was
added. The rosin was heated under an inert gas blanket until molten. As the
temperature reached 180.degree. C., 1.2 parts 50% active aqueous solution of
phosphinic acid was added and allowed to mix thoroughly. The temperature of the
mixture was increased to 205.degree. C., and 283 parts fumaric acid was added. The
inert blanket was discontinued. The fumaric-rosin mixture was allowed to react at
205.degree. C. until complete.
After formation of the adduct, 109 parts pentaerythritol was added, and the temperature
increased to 220.degree. C. This mixture was held until the acid value was below 200.
A similar reaction also was carried out without using the phosphinic acid. A comparison
of the products made with and made without phosphinic acid as catalyst is given in
Table III.
TABLE III
______________________________________
Reaction Conditions
Without With
______________________________________
Acid Value 200 197
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155.degree. C.
Viscosity, 60% in Ethanol
L-M 0
Color, 60% in Ethanol
10+ 7+
Reaction Time for Adduct
4 hours 3 hours
Total Reaction Time
7 hours 5 hours
______________________________________
EXAMPLE 4
To a suitable reaction vessel, equipped as in Example 1, was added 100 parts gum rosin.
The rosin was heated under an insert gas blanket to 180.degree. C. at which time 0.1
part of 50% active phosphinic acid was added and stirred in well. Maleic anhydride (6.2
parts) was then added and the mixture stirred for one hour at 180.degree. C. The
temperature was then raised to 200.degree. C., and 16.3 parts pentaerythritol was
added. The temperature was increased to 280.degree. C. and held until the acid value
was less than 30.
shown in Table IV.
TABLE IV
______________________________________
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Reaction Conditions
Without With
______________________________________
Acid Value 18 29
138.degree. C.
Viscosity, 33% in Linseed Oil
Z W+
Color, 33% in Linseed Oil
13+ 10+
______________________________________
EXAMPLE 5
To a suitable reaction vessel, equipped as in Example 1, was added 100 parts tall oil
rosin. The rosin was heated under an inert gas blanket to 150.degree. C. at which time
0.05 part magnesium oxide and 10 parts of cresol were added. The mixture was then
allowed to cool to 130.degree. C., whereupon, 5.58 parts of paraformaldehyde were
added. The temperature of this mixture was held at 130.degree. C. for one hour, then
increased to 180.degree. C. At this time, 0.10 part of 50% active phosphinic acid was
added and stirred in well, after which 12.12 parts pentaerythritol was added. The
temperature was increased to 280.degree. C. and held until the acid value was less than
2.5.
The same procedure was carried out except replacing the phosphinic acid with 0.05
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parts of lime. The results are shown in Table V.
TABLE V
______________________________________
Reaction Conditions
Without With
______________________________________
Acid Value 19 20
110.degree. C.
Viscosity, 33% in Linseed Oil
S- R+
Color, 33% in Linseed Oil
11 9+
______________________________________
EXAMPLE 6
To a suitable reaction vessel, equipped as in Example 1, was added 100 parts tall oil
rosin. The rosin was heated under an inert gas blanket to 150.degree. C. at which time
0.05 parts magnesium oxide and 15 parts nonylphenol were added. The mixture was
then allowed to cool to 125.degree. C., whereupon, 5.1 parts of paraformaldehyde were
added. The temperature of this mixture was held at 125.degree. C. for one hour, then
12 of 17 07/06/2021, 14:37
increased to 180.degree. C. At this time, 0.10 part of 50% active phosphinic acid was
added and stirred in well, after which 3.0 parts of maleic anhydride were added. The
mixture was stirred at 180.degree. C. for 1 hour; then the temperature was increased to
200.degree. C. and 13.9 parts of pentaerythritol were added. The temperature was
increased to 250.degree. C., held for 0.5 hours, then raised to 280.degree. C. and held
for an acid value less than 25.
shown in Table VI.
TABLE VI
______________________________________
Reaction Conditions
Without With
______________________________________
Acid Value 18.4 19.7
131.degree. C.
Viscosity, 35% Aliphatic Oil
E-F C
Color, 35% Aliphatic Oil
9-10 8+
______________________________________
While the invention has been described and illustrated herein by references to various
specific materials, procedures and examples, it is understood that the invention is not
13 of 17 07/06/2021, 14:37
restricted to the particular materials, combinations of materials, and procedures

selected for that purpose. Numerous variations of such details can be employed, as will
be appreciated by those skilled in the art.
Claims
1. A process for esterifying modified rosin comprising the steps of
(a) reacting rosin in its molten state with an unsaturated dibasic acid in the
presence of a catalytic amount of phosphinic acid to prepare the modified rosin,
and
(b) reacting the modified rosin with a polyhydric alcohol to form a modified rosin
ester.
2. The process of claim 1 wherein step (a) is preceded by reacting the molten rosin with
a phenol-formaldehyde blend in the presence of the phosphinic acid.
3. The process of claim 2 wherein the catalytic amount of phosphinic acid is from 0.05%
to less than 0.5%, based on the weight of the rosin.
4. The process of claim 1 wherein the rosin is selected from the group consisting of tall
oil rosin, gum rosin, and wood rosin.
5. The process of claim 1 wherein the unsaturated dibasic acid is selected from the group
consisting of maleic anhydride and fumaric acid.
6. The process of claim 1, 2, 3, 4, or 5 wherein the polyhydric alcohol is selected from the
group consisting of ethylene glycol, propylene glycol, diethylene glycol, triethylene
glycol, tetraethylene glycol, trimethylene glycol, pentaerythritol, dipentaerythritol,
tripentaerythritol, trimethylolethane, trimethylolpropane, mannitol, sorbitol, and
mixtures thereof.
7. The process of claim 6 comprising an additional step (c) of adding up to 10% glycerol
to the esterification reaction when the acid value is reduced to 50 or below.
8. The process of claim 1, 2, 3, 4, or 5 wherein the polyhydric alcohol is glycerol and step
(b) is preceded by neutralization of the phosphinic acid catalyst by addition of a basic
compound to the modified rosin.
9. The process of claim 8 wherein the basic compound is monoethanolamine.
10. The process of claim 1 wherein step (a) is conducted in an inert environment at a
temperature of from about 180.degree. C. to about 220.degree. C. and step (b) is
14 of 17 07/06/2021, 14:37
conducted in an inert environment at a temperature of from about 180.degree. C. to

about 300.degree. C.
11. In a process of esterifying a modified rosin comprising the steps of reacting molten
rosin with an unsaturated dibasic acid to prepare the modified rosin and reacting the
modified rosin with a polyhydric alcohol to form a modified rosin ester, the
improvement of conducting the rosin modifying reaction in the presence of a catalytic
amount of phosphinic acid.
12. The process of claim 11 wherein the rosin modifying reaction is preceded by reacting
the molten rosin with a phenol-formaldehyde blend in the presence of the phosphinic
acid to form a rosin-phenol condensate.
13. The process of claim 12 wherein the catalytic amount of phosphinic acid is from
0.05% to less than 0.5%.
14. The process of claim 11 wherein the rosin is selected from the group consisting of tall
oil rosin, gum rosin, and wood rosin.
15. The process of claim 11 wherein the unsaturated dibasic acid is selected from the
group consisting of maleic anhydride and fumaric acid.
16. The process of claim 11, 12, 13, 14, or 15 wherein the polyhydric alcohol is selected
from the group consisting of ethylene glycol, propylene glycol, diethylene glycol,
triethylene glycol, tetraethylene glycol, trimethylene glycol, pentaerythritol,
dipentaerythritol, tripentaerythritol, trimethylolethane, trimethylolpropane, mannitol,
sorbitol, and mixtures thereof.
17. The process of claim 11, 12, 13, 14, or 15 wherein the polyhydric alcohol is glycerol
and the reaction with the modified rosin is preceded by neutralization of the phosphinic
acid catalyst by addition of a basic compound to the modified rosin.
18. The process of claim 17 wherein the basic compound is monoethanolamine.
19. The process of claim 11 wherein the rosin modifying reaction is conducted in an inert
environment at a temperature of from about 180.degree. C. to about 220.degree. C. and
the modified rosin ester is formed in an inert environment at a temperature of from
about 180.degree. C. to about 300.degree. C.
20. The process of claim 12 wherein the rosin-phenol condensate is formed in an inert
environment at a temperature of from about 125.degree. C. to about 140.degree. C.
Referenced Cited
15 of 17 07/06/2021, 14:37
U.S. Patent Documents
2369125 February 1945 Anderson
2572086 October 1951 Wittcoff et al.
2590910 April 1952 Wittcoff et al.
2729660 January 1956 Harrison
3071604 January 1963 Mohan et al.
3232968 February 1966 Schenck et al.
3317445 May 1967 Halbrook et al.
3780012 December 1973 Smith
3780013 December 1973 Smith
4172070 October 23, 1979 Scharrer
4548746 October 22, 1985 Duncan et al.
Foreign Patent Documents
979673 January 1965 GBX
Patent History
Patent number: 4643848
Type: Grant
Filed: Feb 21, 1986
Date of Patent: Feb 17, 1987
Assignee: Westvaco Corporation (New York, NY)
Inventors: John H. Thomas (Jacksonville, FL), Don P. Duncan (Mt. Pleasant, SC),
Michael A. Lake (Mt. Pleasant, SC), Gary B. Womack (Charleston, SC)
Primary Examiner: Herbert S. Cockeram
Attorneys: Terry B. McDaniel, Richard L. Schmalz
Application Number: 6/831,809
Classifications
Current U.S. Class: 260/104; With Phenolic Reactant (527/602); With
Polycarboxylic Acid Or Derivative And A Compound Having Two Or More Hydroxyl
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Groups As Reactants (527/604)

International Classification: C09F 700; C09F 104; C09F 900;
17 of 17 07/06/2021, 14:37

Modified Rosin Ester Preparation

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US Patent for Modified rosin ester preparation Patent (Patent # 4,643,8... https://patents.justia.

Modified rosin ester preparation

Phosphinic acid (also called hypophosphorous acid),

rosin ester exhibits improved color, softening point,

Latest Westvaco Corporation Patents:

BACKGROUND OF THE INVENTION

2. Description of the Prior Art

Rosin is mainly a mixture of C.sub.20, fused-ring, monocarboxylic acids, typified by

The beneficial product characteristics provided by rosin esterification for various

It is generally known in the art that a significant disadvantage of pentaerythritol

SUMMARY OF THE INVENTION

DESCRIPTION OF THE PREFERRED EMBODIMENT

As polyhydric alcohols, ethylene glycol, propylene glycol, diethylene glycol, triethylene

MODIFIED ROSIN ESTER PROPERTIES

Property Phosphinic Phosphinic

Acid Value 23.2 24.3

Softening Point 119.degree. C.

Viscosity, 50% in Aliphatic Oil

Color, 50% in Aliphatic Oil

Reaction Time 8 hours 7 hours

MODIFIED ROSIN ESTER PROPERTIES

Acid Value 210 212

Softening Point 154.degree. C.

Fumaric Reaction Time

2.1 hours 1.0 hour

Total Reaction Time 4.0 hours 3.5 hours

Viscosity, 60% in Ethanol

Color, 60% in Ethanol

Color in a 5% Ammonium Solution

MODIFIED ROSIN ESTER PROPERTIES

Property Phosphinic Phosphinic

Acid Value 200 197

Softening Point 156.degree. C.

Viscosity, 60% in Ethanol

Color, 60% in Ethanol

Reaction Time for Adduct

Total Reaction Time

MODIFIED ROSIN ESTER PROPERTIES

Property Phosphinic Phosphinic

Softening Point 146.degree. C.

Viscosity, 33% in Linseed Oil

Color, 33% in Linseed Oil

parts of lime. The results are shown in Table V.

MODIFIED ROSIN ESTER PROPERTIES

Property Phosphinic Phosphinic

Softening Point 110.degree. C.

Viscosity, 33% in Linseed Oil

Color, 33% in Linseed Oil

Property Phosphinic Phosphinic

Acid Value 18.4 19.7

Softening Point 128.degree. C.

Viscosity, 35% Aliphatic Oil

Color, 35% Aliphatic Oil

restricted to the particular materials, combinations of materials, and procedures

9. The process of claim 8 wherein the basic compound is monoethanolamine.

conducted in an inert environment at a temperature of from about 180.degree. C. to

18. The process of claim 17 wherein the basic compound is monoethanolamine.

U.S. Patent Documents

2369125 February 1945 Anderson

2572086 October 1951 Wittcoff et al.

2590910 April 1952 Wittcoff et al.

2729660 January 1956 Harrison

3071604 January 1963 Mohan et al.