Polymer Journal (2015) 47, 771–778

& 2015 The Society of Polymer Science, Japan (SPSJ) All rights reserved 0032-3896/15
www.nature.com/pj

INVITED REVIEW

Synthesis and process development of polyether polyol

with high primary hydroxyl content using a new
propoxylation catalyst
Toru Miyajima1, Kenji Nishiyama2, Munekazu Satake3 and Takayuki Tsuji2

We have developed a novel class of propylene oxide-based polyether polyol (PPG) with up to 70% higher primary hydroxyl
content, which is produced through a Lewis acid-mediated propoxylation reaction using a specific borane catalyst. Conventional
PPGs produced via anionic ring-opening polymerization have secondary hydroxyls, resulting in poor reactivity in urethane
formation. To overcome the poor reactivity, ethylene oxide (EO) is often added to the terminal hydroxyls of conventional PPGs.
However, this modification decreases the humidity resistance of the resulting polymer. In contrast, our new PPG has enhanced
primary hydroxyl content with little or no added EO, thereby achieving a good balance between reactivity and hydrophobicity.
As a result, the new polyol has important advantages, such as enhanced durability, energy and resource conservation, and
environmental load reduction for a broad area of polyurethane applications. In addition, we developed an innovative continuous
process that uses tube reactors in combination with film evaporators for by-product removal. This review focuses on key
technological innovations in process development and examples of the practical applications of the new PPG.
Polymer Journal (2015) 47, 771–778; doi:10.1038/pj.2015.64; published online 26 August 2015

INTRODUCTION character of the EO block that is introduced. Consequently, achieving

Polyurethanes, which are traditionally and commonly formed by a good balance between reactivity and humidity resistance represents a
reacting polyisocyanates with polyols, are the most versatile polymer significant challenge in the polyurethane industry, and the develop-
materials and have excellent performance properties for a wide variety ment of a new class of polyols has emerged as an important subject to
of applications, such as in automobiles, furniture and bedding, polyol suppliers.
clothing materials, housing and building materials, and so on.1 The Recently, we successfully discovered a catalytic propoxylation
physical properties of polyurethanes depend on the chemical structure reaction for synthesizing an innovative PPG in which the primary
of the original reactants. In particular, the chemical characteristics of hydroxyl content was increased up to 70%. This finding presents a
the polyols used, namely, the number of hydroxyl groups per molecule solution to the long-standing problem described above. Since our
(functionality), molecular weight, hydrophilicity and steric character initial work, we have worked to develop an industrial production
of the terminal hydroxyls directly affect the chemical and physical process and to explore the market potential for this innovative PPG.
structure of the final polymers and the performance of the end In this review, we introduce this new PPG and its production
products. technology. Key technological innovations in process development
Propylene oxide (PO)-based polyether polyols (commonly referred and the superior performance of polyurethane products derived from
to as PPGs) are the most widely used polyols for polyurethane the new PPG are described in detail.
production because they are readily available and offer good structural
diversity. Over the past five decades, most PPGs have been SELECTIVE PROPOXYLATION REACTION USING A NEW
produced commercially through base-catalyzed, anionic ring-opening CATALYST
polymerization using strong bases (for example, KOH).2 With Structural optimization of the Lewis acid catalyst
the conventional KOH-initiated route, a serious problem is the Generally, the selectivity of PO ring cleavage, namely the ratio of
predominant formation of secondary hydroxyls, which exhibit poor primary to secondary hydroxyls in the product, strongly depends on
reactivity in urethane formation. To obtain more reactive primary the polymerization mechanism and the type of catalyst.3 As described
hydroxyls, ethylene oxide (EO) is often reacted in the final stage of the above, base catalysts such as KOH predominantly yield secondary
polymerization. However, this commonly used modification decreases hydroxyls with very high selectivity (495%). In base-catalyzed anionic
the humidity resistance of the resulting polymer due to the hydrophilic propoxylation, β-cleavage of the PO ring is strongly favored because it

1
Research Division, SDP Global Co., Ltd., Kyoto, Japan; 2Urethane Raw Materials Research Department, Sanyo Chemical Industries, Ltd., Kyoto, Japan and 3Intellectual
Properties Department, Sanyo Chemical Industries, Ltd., Kyoto, Japan
Correspondence: T Miyajima, Research Division, SDP Global Co., Ltd., 11-1, Ikkyo Nomoto-cho, Higashiyama-ku, Kyoto 605-0995, Japan.
E-mail: [email protected]
Received 19 May 2015; revised 6 July 2015; accepted 9 July 2015; published online 26 August 2015
 Primary hydroxyl polyether polyol
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offers smaller steric hindrance. On the other hand, commonly used borane should favor α-cleavage because it has very strong acidity
Lewis acid catalysts such as boron trifluoride (BF3) are known to due to the electron-withdrawing character of the pentafluorophenyl
produce primary and secondary hydroxyls in almost equal propor- groups. A different hypothesis concerning the selectivity can be
tions. In the field of selective organic synthesis, catalysts with designed proposed from a steric viewpoint. As depicted in Figure 1, β-cleavage
ligands and sterically regulated spaces have received much attention in should be energetically unfavorable because its transition state has
recent years. Considering these points, structurally well-designed Lewis large steric hindrance between the methyl group of PO and the
acids are promising candidates as catalysts to promote α-cleavage of fluorine atom in the ortho position of the ligand. We believe that the
the PO ring with higher selectivity. We focused on boron compounds electronic and steric effects of the new catalyst work synergistically to
because they are easy to handle and have good structural diversity. promote α-cleavage in the propoxylation reaction.
A detailed study on catalyst optimization in terms of electronic and
steric effects revealed that tris(pentafluorophenyl)borane4 promotes Features of propoxylation reactions using the new catalyst
α-cleavage with a high selectivity of 70% in propoxylation reactions. The new catalyst affords not only high α-cleavage selectivity in
Scheme 1 shows the basic method for synthesizing an innovative propoxylation reactions but also demonstrates additional advantages
PPG with an increased proportion of primary hydroxyls that we over conventional propoxylation catalysts such as KOH, double metal
established.5 cyanide (DMC) complexes6 and BF3. A comparison of the properties
of these catalysts is summarized in Table 1. There are two notable
Reaction mechanism and origin of selectivity advantages of using the new catalyst:
Acid-mediated epoxide opening reactions are thought to proceed via a
borderline SN2 process (that is, bimolecular substitution having (1) Extremely high catalytic activity (2000 times as active as KOH).
considerable SN1 character in the transition state).3 The transition This property can dramatically reduce catalyst usage to approxi-
state geometry resembles that of a standard SN2 reaction, but C–O mately 30 p.p.m., making catalyst removal from the product
bond breaking is relatively more advanced compared with carbon– unnecessary.
nucleophile bond formation, resulting in a buildup of considerable (2) Immediate initiation of the reaction without any pretreatments.
positive charge on the carbons. In the presence of strong acids, this Unlike many of the other catalysts, catalyst activation before use is
positive charge buildup is enhanced. Thus, the transition state that has unnecessary and no induction period is observed.
a buildup of positive charge on the carbon that would be the more
stable carbocation is favored. Therefore, tris(pentafluorophenyl) Notably, these advantages play an important role in designing an
industrial production process, which is covered in detail in the
following section.

INDUSTRIAL PPG PRODUCTION PROCESS USING A NEW

CATALYST
Scheme 1 Selective propoxylation reaction mediated by tris General problems involved in using Lewis acid catalysts
(pentafluorophenyl)borane. A full color version of this scheme is available at Lewis acid catalysts have rarely been used in PPG synthesis, despite
Polymer Journal online. their unique reaction characteristics. Their infrequent use is probably

Figure 1 Plausible transition states for propoxylation mediated by tris(pentafluorophenyl)borane.

Table 1 Comparison with commonly used catalytic propoxylation technologies

Conventional catalysts New catalyst

KOH Zn3[Co(CN)6]2 ·ZnX ·L BF3 B(C6F5)3

Mechanism of propoxylation Anionic Coordination Acid mediated Acid mediated

Primary hydroxyl content 2% 5% 50% 70%
Relative rate of propoxylation 1 300 200 2000
Typical catalyst loading 2000 p.p.m. 100 p.p.m. 300 p.p.m. 30 p.p.m.
Reaction temperature 100–110 °C 130–150 °C 80 °C or lower 80 °C or lower
Pretreatment Alkoxide formation by water removal Activation with heat (ligand exchange) Unnecessary Unnecessary
Catalyst removal (after treatment) Neutralization/ adsorption Unnecessary (difficult to remove) Removal of free acid (HF) Unnecessary

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Side reaction CH3

H+
H2 C CH CH3CH2CHO
Isomerization
O

Subsequent reactions
1 1 2
R OH H+ R O O R
CH3CH2CHO + 2 CH + H2 O
R OH Condensation
CH2 CH3
CH3 CH3
H+ PO Propylene glycol
H2 O + H2 C CH HO CH2 CHOH
Propoxylation Propoxylation propoxylates
O

Scheme 2 Acid-promoted isomerization of propylene oxide and subsequent undesirable reactions.

attributed to them being difficult to handle as well as the possibility

PO
of side reactions. As shown in Scheme 2, PO readily isomerizes to KOH
propionaldehyde in acidic conditions.7 In addition, acids promote Catalyst
Starter Product
subsequent reactions in which the aldehyde reacts with 2 mol of removal
alcohol species to produce acetal derivatives. The water formed also Aftertreatment
Reaction vessel equipment
reacts with PO to yield short chain diol derivatives. These by-products
are undesirable because they negatively affect basic qualities of the Figure 2 General batch-type process for conventional polyether polyol
PPG, such as functionality and molecular weight distribution. For production. A full color version of this figure is available at Polymer Journal
example, acetal by-products in PPG, which have higher functionality, online.
can cause the viscosity of the PPG to increase and lead to abnormal
reaction progress when reacted with polyisocyanates. Furthermore, These findings suggest that it is inherently difficult to suppress the
acetal derivatives in PPGs can be gradually hydrolyzed in humid formation of propionaldehyde itself and that it would be effective to
conditions to release propionaldehyde, which has a strong odor. prevent the subsequent reactions by controlling the concentration of
aldehyde that accumulates in the reaction system.
Short chain diol by-products can degrade the mechanical properties of
the resulting polyurethane by forming structural defects in the
General batch-type process for conventional PPG production
polyurethane network. These problems constitute a serious obstacle
Currently, industrial PPG production using traditional KOH catalysis
to industrial process development in terms of product quality control.
almost always employs a batch-type process. As shown in Figure 2, this
process consists of three basic steps. First, a starter (polyols are most
Basic information on temperature limitations and side reactions
often used) is treated with KOH in a reaction vessel and is converted
with the new catalyst
to the corresponding alkoxide, the actual active species, after removing
Unlike many of the other Lewis acids, the new catalyst tris
the water that is formed. Next, PO is slowly charged into the reaction
(pentafluorophenyl)borane is known to be an air-stable, water-
vessel and propoxylation is carried out. In this step, the reaction
tolerant and thermally robust compound.4 However, our stability
system is typically maintained at a temperature between 100 and
studies revealed that it reacts with trace moisture in the reaction
110 °C during the addition of PO. Heat removal and control over the
mixture during propoxylation at temperatures exceeding 90 °C to PO feed rate is of technical importance in this step because
form pentafluorobenzene and boric acid. Therefore, the reaction propoxylation is highly exothermic. In the last step, the catalyst is
temperature during propoxylation needs to be kept at ~ 80 °C or removed from the mixture after complete consumption of the PO. In
lower to reduce its decomposition to a tolerable level. This require- most cases, this step cannot be skipped because alkaline residue in
ment means that the preferred reaction temperature for the new PPG often causes abnormal reaction progress in practical use.
catalyst is ~ 30 °C lower than the typical temperatures used with KOH
as the catalyst. Newly developed continuous process for primary hydroxyl PPG
Like other Lewis acids, the new catalyst is prone to the side reactions production
shown in Scheme 2. Fundamental kinetics analysis made the following As discussed above, propoxylation with the new catalyst involves
points clear. A detailed description is omitted here for simplicity. a reduction in the reaction temperature by ~ 30 °C compared with
the conventional process using KOH. To use the new catalyst in the
(1) Approximately 3–10% of the total amount of PO consumed conventional batch process, the PO feed rate, and consequently the
is converted to propionaldehyde under the typical reaction production rate, is considerably restricted because of the limited
conditions used for PPG synthesis. surface area-to-volume ratio of the reaction vessel and the small
(2) The ratio of the amount of propionaldehyde produced to PO temperature difference between the reactants and the cooling medium.
consumption depends on the hydroxyl concentration of To solve this problem, we focused on developing a continuous flow
the reaction system but not on the concentration of other process using tube reactors, which are superior in terms of heat
components, including the catalyst. Aldehyde formation is removal efficiency. Continuous flow processes have rarely been
promoted in preparing high molecular weight PPG in which the applied to PPG production with conventional catalysts that require
hydroxyl concentration is low. pretreatment and catalyst removal steps. In contrast, it is suitable for
(3) The amount of propionaldehyde produced is nearly independent propoxylation with the new catalyst that requires neither. Thus, a
of reaction temperature because the difference in activation energy continuous flow process successfully enhances the strengths and
between propoxylation and aldehyde formation is small. eliminates the weaknesses of the new catalyst

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CH3CH2CHO
Tube reactor
B(C6F5)3 Film evaporator
Starter Product

repeated to reach the

PO target molecular weight

Figure 3 Newly developed continuous process for primary hydroxyl polyether

polyol production. A full color version of this figure is available at Polymer
Journal online.

Next, we worked to find a solution for the by-products problem

and finally adopted the process depicted in Figure 3, in which
the propionaldehyde produced is continuously removed with film
evaporators that are directly attached to the tube reactors. We also
established a standard reaction condition in which the concentration
of propionaldehyde is controlled below a certain critical level by Figure 4 Relationship between primary hydroxyl content and the number of
ethylene oxide (EO) moles added per hydroxyl (Starter: Mw 3000 triol,
changing the PO feed concentration, depending on the molecular EO-capping catalyst: KOH). A full color version of this figure is available at
weight of the starter. On the basis of this standard condition, Polymer Journal online.
propoxylation and aldehyde removal are repeated alternately to reach
the target molecular weight. Thus, an innovative industrial process for
from a portion of raw material polyisocyanates that are not
the high-throughput production of high-quality primary hydroxyl
incorporated into the polymer networks during the foaming process.
PPG was developed.
Several voluntary certification systems such as CertiPUR10,11 and
Oeko-Tex,12 which are promoted by multiple international industrial
BASIC PROPERTIES OF PRIMARY HYDROXYL PPG
associations, set an upper limit on the amount of 2,4-TDA and other
The new PPG produced by propoxylation with the new catalyst is a
specific aromatic amines that can be contained in PU foams for
novel class of PPG that has an increased primary hydroxyl content of products to be certified as premium grade. For example, CertiPUR
up to 70% and, therefore, exhibits enhanced reactivity toward limits the amount of 2,4-TDA to no more than 5.0 p.p.m. (mg l− 1) in
polyisocyanates. For instance, it is several times more reactive than a foam. In addition, IKEA, the world’s largest furniture retailer sets a
conventional PPG propoxylated with KOH in urethane formation similar standard for its products. However, it is becoming increasingly
reactions at approximately room temperature. difficult for PU foam producers to meet the required residual amine
As shown in Figure 4, the primary hydroxyl content of the new PPG standards whereas also satisfying a series of foam physical property
is further enhanced by adding a small amount of EO. For certain specifications.
applications, such as highly resilient (HR)-molded polyurethane (PU) The most uncomplicated and effective approach in reducing
foam, reactivity-enhanced EO-modified PPG, which has a primary residual amines is to increase the conversion rate of NCO components
hydroxyl content ranging from 70 to 85%, is commonly used. In the to urethane bonds. Accordingly, highly reactive PPG, namely our
case of conventional PPG produced with KOH, the EO block required newly developed PPG, fits this purpose. To prove this advantage,
usually ranges from 4 to 8 mol (from 10 to 20% by weight of the we prepared foam samples according to typical TDI (toluene
polymer chain) per hydroxyl on average to reach a primary hydroxyl diisocyanate)-based free-foaming formulations with a low NCO index,
content in this range. On the other hand, the new PPG requires less in which a conventional PPG (2% primary hydroxyl) and the new
than half or no EO block. Thus, the new PPG can achieve an excellent PPG (70% primary hydroxyl) were used in different proportions.
and ideal balance between reactivity and humidity resistance.5 Then, the residual 2,4-TDA content of each sample was measured
according to the method defined by CertiPUR. The results are
PRACTICAL APPLICATIONS OF PRIMARY HYDROXYL PPG summarized in Figure 5. As expected, the amount of residual
The aforementioned features of our newly developed PPG 2,4-TDA in the foam is reduced dramatically as the proportion of
provide great opportunities to bring considerable benefits to a wide the new PPG is increased. Thus, the high reactivity of the new PPG
spectrum of PU applications. Advantages of using the new PPG in clearly has a positive impact on residual amine reduction, providing an
flexible PU foams, which have a huge global market, are primarily effective solution to the issue of satisfying certification requirements.
discussed here.8,9
Flexible PU foams for clothing materials with improved
Flexible PU foams with reduced residual aromatic amines for discoloration resistance
furniture and bedding One of the few drawbacks of PU materials is discoloration (yellowing)
Flexible PU foams have seen increased use in the furniture and over time. In the field of specialized PU foam applications, such as
bedding market in recent years. In this field, consumers are becoming bra-pads, there is a great need for anti-yellowing foams that remain
better informed and would like to understand the safety, health and bright and have a long-lasting clean look.
environment aspects of the materials inside the products that they buy It is well known that foam discoloration is primarily due to the
and use. formation of chromophores, such as azo compounds, which are
Among the chemical substances contained in PU foam products, derived from aromatic amine derivatives. In this regard, the use of a
specific aromatic amines that are suspected of being carcinogenic, such new PPG that is highly reactive toward NCO components would also
as 2,4-toluenediamine (TDA), are recognized as a serious concern in be effective in improving the anti-yellowing properties of foams. To
today’s furniture and bedding industry. Such amines are derived investigate this advantage of the new PPG, we evaluated yellowing

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40 80 Flexible molded PU foams for automotive seats with low density

Residual 2,4-TDA
HR flexible molded PU foams are commonly used in automotive seats

Ave. primary hydroxyl (%)

Residual 2,4-TDA (ppm)

Ave. primary hydroxyl %

30 60
around the world. In this field, there is a strong and continuing
demand to reduce the product weight to improve fuel efficiency. For a
long time, reducing the weight of automotive seats has been achieved
20 40 by reducing the foam density. However, the density is getting close to
the limit of formulations using conventional raw materials.
10 20 The biggest problem with reducing the foam density is deteriorating
the durability of the foam. This problem is not simply because of a
reduction in the proportion of resin in the foam, but rather the
0 0
100/0 85/15 50/50 0/100
increased amount of urea groups in the resin due to the higher dose of
Conventional PPG / New PPG ratio water used as a blowing agent also has a role. Urea-rich foams often
have insufficient softness, resiliency and durability as a result of
Figure 5 Relationship between residual 2,4-toluenediamine and polyether aggregation of the highly hydrophilic and hydrogen-bonding urea
polyol (PPG) reactivity (PPG: Mw 3000 triol, NCO index: 85, foam density:
micro-domains. Moreover, the highly hydrophilic nature of the
24 ± 1 kg m −3). A full color version of this figure is available at Polymer
Journal online.
polyols typically used makes it difficult to maintain the humidity
resistance of the foams. In the manufacturing of HR-molded foam,
terminal EO-capped, highly reactive PPG with a primary hydroxyl
40 content of ~ 80% has been used as the main polyol to achieve good
Conventional PPG moldability with the ability to be de-molded in a short period.
New PPG This problem can be solved by using our new PPG, which can
30
provide a balance between high reactivity and humidity resistance. To
Yellow index

prove this, we prepared foam samples with three different densities

20 using a foaming machine, according to our basic formulation for an
automotive seat back. The relationship between wet compression set,
which is a generally accepted indicator of long-term foam durability
10 under hot and humid conditions, and foam density is illustrated in
Figure 7. As expected, the new PPG has a notable durability-enhancing
0 effect at all densities examine and shows a comparable wet compres-
initial 2 day 7 day sion set even at 15% reduced density. Other physical properties,
Sunlight-exposed time including ball rebound, tensile/tear strength and elongation, are
comparable to those of the conventional systems. These results
Figure 6 Color changes of foam samples under daylight (conventional demonstrate that the new PPG contributes to density reduction for
polyether polyol (PPG) vs new PPG).
HR-molded foam applications.

Flexible molded PU foams for automotive seats with a

35
comfortable ride
poor

Wet compression set (%)

Conventional PPG Ride comfort improvement has recently become one of the most
30 New PPG important issues in automotive seat development. Vibration absorbing
characteristics, namely the frequency dependence of vibration trans-
Durability

mission in PU foams used for cushioning, are the most important

25 indicator of the ride comfort of seat pads. To achieve a comfortable
ride, a reduction in transmissibility at ~ 6 Hz is effective because the
human stomach is sensitive to vibrations at this frequency range.
20
good

As illustrated in Figure 8, there are two approaches to reducing

transmissibility at ~ 6 Hz. One is to shift the resonance frequency
15 (that is, the peak position in Figure 8a) to a lower direction. The other
26 28 30 32 34 36 is to lower the maximum transmissibility (that is, the peak height in
Core density (kg/m3) Figure 8a). The former approach is deeply related to enhancing the
Figure 7 Wet compression sets depending on foam densities (conventional elasticity of the resin. As shown in Figure 9, we found that reducing
polyether polyol (PPG) vs new PPG). A full color version of this figure is the tan δ of the resin in the foams has a positive impact on the
available at Polymer Journal online. resonance frequency shift in our fundamental studies. The latter
approach is related to enhancing the viscosity of the foam by reducing
resistance of the foams prepared for the residual 2,4-TDA study air permeability through the cell structure. Therefore, a combination
described above. The test pieces were placed by a window and exposed of these two approaches is effective for improving the vibration
to daylight for a week. The degree of discoloration of each test piece characteristics. In particular, the enhancement of elasticity is of great
was evaluated using a spectrophotometer to calculate the yellow index importance in the design of a desired resin composition. As shown in
of the pieces after predetermined time intervals. As shown in Figure 6, Figure 10, another fundamental study concerning the effect of PPG
foam prepared using the new PPG changes its color slowly compared compositions on the viscoelastic behavior of foams revealed that tan δ
to the conventional system. Hence, our new technology contributes to of the resin tends to decrease as the primary hydroxyl content of the
improving the anti-yellowing properties of PU foams. PPG is increased. We assume that high reactivity and fast viscosity

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Transmissibility

Elasticity: Viscosity:
1) depends on resin 1) depends on cell structure
0 Resonance 6 15 (PPG) structure (air permeability)
frequency 2) correlates with 2) correlates with maximum
resonance frequency transmissibility
Frequency (Hz)
Figure 8 Conceptual diagram for a comfortable ride based on the vibration characteristics of the foam. (a) Frequency dependence of vibration
transmissibility; (b) Voigt model for polyurethane foam. A full color version of this figure is available at Polymer Journal online.

7.0 buildup in the foaming process derived from a high primary hydroxyl
Resonance Frequency (Hz)

content contribute to the formation of fine and homogeneous phase-

6.0 separated structures of hard segments and enhance the elasticity of
the resin.
5.0
These findings indicate that the vibration characteristics of the foam
can be controlled by using our new PPG. To prove this advantage,
we prepared 100 mmt foam samples with a core density of 60 kg m − 3
4.0
according to our basic formulation. The foam vibration characteristics
are summarized in Table 2. As expected, the new PPG resulted in the
3.0
0 0.1 0.2 0.3 0.4 resonance frequency being down-shifted by 0.26 Hz as well as a slight
Tanδ at 25°C decrease in the maximum transmissibility compared with the con-
ventional PPG, resulting in an ~ 30% reduction in transmissibility at
Figure 9 Relationship between resonance frequency and tan δ. (core density:
52 ± 1 kg m− 3, 25% indentation load deflection (ILD): 180 ± 10 N per 6 Hz. These results show that the new PPG is effective for improving
314 cm2, air permeability: 17 ± 5 cc cm −2 s −1). the ride comfort of seat pads.

Flexible molded PU foams for automotive seats with reduced

thickness
0.4 In the field of automotive seats, a thinner seat design has become
increasingly important in terms of both weight reduction and
expanding the space in the car, especially with the popularization of
0.3
Tanδ at 25°C

hybrid cars. Accordingly, foam thickness reduction is one of the most

important themes in this industry. In general, foam thickness
0.2
reduction leads to a deterioration in vibration characteristics and ride
comfort. Indeed, as the thickness is reduced, resonance frequency
0.1 typically shifts in the positive direction and the transmissibility at
~ 6 Hz rises.
0.0 This problem can be overcome by using the new PPG. Encouraged
65 70 75 80 85
by the results described in the previous section, we prepared foam
Primary hydroxyl content (%)
samples in the same manner, except that foam thickness was reduced
Figure 10 Relationship between tan δ and primary hydroxyl content of the to 80 mmt using a height tunable mold. The vibration characteristics
PPG (core density: 52 ± 1 kg m − 3, 25% ILD: 180 ± 10 N per 314 cm2, air of the foams were measured, and the relationship between the
permeability: 17 ± 5 cc cm − 2 s − 1).
vibration characteristics and foam thickness is illustrated in
Figures 11a and b. As expected, 80 mmt foam prepared using the
new PPG shows a sufficiently low level of resonance frequency and
Table 2 Vibration characteristics of 100 mmt foam samples
(conventional PPG vs new PPG) transmissibility at 6 Hz, comparable to what is achieved with 100 mmt
conventional foam. These results demonstrate that thickness can be
Conventional PPG New PPG reduced by 20% by using our new PPG.

Resonance frequency (Hz) 3.62 3.36

Other application examples
Maximum transmissibility 3.50 3.25
Transmissibility at 6 Hz 1.02 0.71
The new PPG has many other technical advantages besides the ones
described above for both foam and non-foam (that is, elastomer and
Abbreviation: PPG, polyether polyol.
Core density: 60 ± 1 kg m − 3, 25% ILD: 270 ± 10 N per 314 cm2, air permeability: sealant) applications. The benefits of using the new PPG in each
10 ± 5 cc cm − 2 s − 1. application are summarized in Table 3.

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4.5 2
Conventional PPG Conventional PPG

Resonance Frequency (Hz)

New PPG New PPG

Transmissibility at 6Hz
1.5
4

3.5
0.5

3 0
80mm 100mm 80mm 100mm
Foam thickness Foam thickness
Figure 11 Vibration characteristics as a function of foam thickness (conventional polyether polyol (PPG) vs new PPG). (a) Resonance frequency;
(b) transmissibility at 6 Hz (core density: 60 ± 1 kg m − 3, 25% ILD: 270 ± 10 N per 314 cm2, air permeability: 10 ± 5 cc cm − 2 s − 1).

Table 3 Summary of advantages by using the new PPG humidity resistance, which has been a long outstanding trade-off
problem with conventional PPGs. These unique features of our newly
Application Advantages
developed PPG translate to considerable benefits in terms of durability
Flexible foams for furniture and • Reduction in aromatic amines to satisfy enhancement, energy and resource conservation, and environmental
bedding certification systems load reduction for a wide spectrum of practical PU applications,
• Slow discoloration (yellowing) including flexible foams, elastomers and sealants. The technical
• Consistent physical property distribution in the advantages of the new PPG have been widely recognized by domestic
foam and overseas customers. We believe that the versatility of our new PPG
• Improvement of tensile/tear/elongation and will be further explored in the future.
durability
Flexible molded foams for • Density reduction while maintaining durability
automotive seats • Comfortable ride CONFLICT OF INTEREST
• Thickness reduction while maintaining vibration The authors declare no conflict of interest.
characteristics
Elastomers and sealants • Prevention of foaming while curing
• Productivity improvement derived from high
reactivity 1 Sanders, J.H. & Frisch, K.C. Polyurethanes: Chemistry and Technology, (Interscience
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CONCLUSIONS Newly Designed High Performance Raw Material System for Automotive Seat Foam.
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(Salt Lake City, UT, USA, 89–95, 2002).
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7 Smith, J.G. Synthetically useful reactions of epoxides. Synthesis 8, 629–656
to 70%. In addition, we developed a high yielding continuous process (1984).
for producing the new PPG with a low amount of by-products by 8 Miyajima, T., Hirano, T., Nobukuni, E. & Nishiyama, K. Newly-developed High
Performance Polyols with High Primary Hydroxyl Groups for Flexible Polyurethane
using tube reactors combined with film evaporators for by-product Foams. Proceedings of the Conference on 2012 polyurethanes Technical Conference;
removal. The pilot plant for this innovative process started running in 24–26 September 2012; (Atlanta, GA, USA, 2012).
2011 and expanded to regular commercial production in 2013. The 9 Nishiyama, K., Murata, K., Miyajima, T., Arai, I. & Yoshida, Y. Newly-developed High
Performance Polyols with High Primary Hydroxyl Groups for Flexible Molded Foams.
first step in expanding its production capacity is scheduled to be Proceedings of the Conference on 2013 polyurethanes Technical Conference; 23–25
completed in 2015 in response to increase in demand. September 2013; (Phoenix, AZ, USA, 2013).
10 CertiPUR program is run by EUROPUR, the association of European Flexible
Our newly developed PPG has a high primary hydroxyl content Polyurethane Foam Block Manufacturers. Available at http://www.europur.org/certipur.
with little or no added EO, resulting in high reactivity toward 11 CertiPUR-US is an extension of the European CertiPUR program and run by Alliance for
Flexible Polyurethane Foam, Inc. Available at http://certipur.us/.
polyisocyanates while maintaining hydrophobicity. As a result, the 12 Oeko-Tex Standard 100 is run by the International Association for Research and Testing
new PPG achieves an excellent balance between reactivity and in the Field of Textile Ecology. Available at https://www.oeko-tex.com/.

Polymer Journal
 Primary hydroxyl polyether polyol
T Miyajima et al
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Toru Miyajima received his MS degree in Molecular Engineering from Kyoto University in 2008. In the same year he joined Sanyo
Chemical Industries. He was engaged in the process innovation for PPG production and the development of raw materials for flexible
PU foam for furniture and bedding (2010–2013). He is currently a unit chief at SDP Global Co, a consolidated subsidiary of Sanyo
Chemical Industries. His current research interests focus on superabsorbent polymers. He received the Award of the Society of Polymer
Science, Japan (2014) for his work on Primary Hydroxyl Polyether Polyol.

Kenji Nishiyama received his MS degree in Applied Chemistry from the Ritsumeikan University in 1998. In the same year he joined
Sanyo Chemical Industries. Since then he has been mainly engaged in the development of raw materials for flexible PU foam for
automotive seats. He is currently a unit chief at Urethane Raw Materials Research Department. He received the Kinki Chemical Society
Award for Chemical Technology (2007) and the Award of the Society of Polymer Science, Japan (2014) for his work on Primary
Hydroxyl Polyether Polyol.

Munekazu Satake received his MS degree in Chemistry from Kyoto University in 1993. In the same year he joined Sanyo Chemical
Industries. He was engaged in the development of new catalytic reactions including propoxylation reaction and electronics chemicals. He
is currently a manager at Intellectual Properties Department. He received the Kinki Chemical Society Award for Chemical Technology
(2007) and the Award of the Society of Polymer Science, Japan (2014) for his work on Primary Hydroxyl Polyether Polyol.

Takayuki Tsuji received his MS degree in Applied Chemistry from Osaka University in 1989. In the same year he joined Sanyo Chemical
Industries. Since then he has been mainly engaged in the development of raw materials for flexible PU foams. He is currently a manager
at Urethane Raw Materials Research Department. He received the Award of the Society of Polymer Science, Japan (2014) for his work
on Primary Hydroxyl Polyether Polyol.

Polymer Journal