PJ 201564
PJ 201564
PJ 201564
& 2015 The Society of Polymer Science, Japan (SPSJ) All rights reserved 0032-3896/15
www.nature.com/pj
INVITED REVIEW
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
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
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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.
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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
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CH3CH2CHO
Tube reactor
B(C6F5)3 Film evaporator
Starter Product
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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
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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)
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4.5 2
Conventional PPG Conventional 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
• Reduction in harmful heavy metal catalysts Publishers, New York, NY, USA, 1962).
• Durability and strength enhancement of 2 Penczek, S., Cypryk, M., Duda, A., Kubisa, P. & Slomkowski, S. Living ring-opening
polymerizations of heterocyclic monomers. Prog. Polym. Sci. 32, 247–282 (2007).
resulting resin
3 Parker, R.E. & Isaacs, N.S. Mechanisms of epoxide reaction. Chem. Rev. 59,
737–799 (1959).
4 Erker, G. Tris(pentafluorophenyl)borane: a special boron Lewis acid for special
reactions. Dalton Trans. 1883–1890 (2005).
5 Nishiyama, K., Tsuji, T., Ohta, H., Tomosada, T., Kaku, M., Satake, M. & Takashima, Y.
CONCLUSIONS Newly Designed High Performance Raw Material System for Automotive Seat Foam.
The establishment of a Lewis acid-mediated selective propoxylation Proceedings of the Conference on Polyurethanes Expo. 2002; 13–16 October 2002;
(Salt Lake City, UT, USA, 89–95, 2002).
reaction using a specific borane catalyst enabled the synthesis of a 6 Herold, R.J. & Livigni, R.A. Hexacyanometalate salt complexes as catalysts for epoxide
novel class of PPG with an increased primary hydroxyl content of up polymerizations. Adv. Chem. 128, 208–229 (1973).
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/.
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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