Enzymatic Ring-Opening Polymerization and Copolymerization of 8-Octanolide by Lipase Catalyst

Kobayashi, Shiro; Uyama, Hiroshi; Namekawa, Shuhei; Hayakawa, Hiroshi

doi:10.1021/ma980396n

Cited by 110 publications

(95 citation statements)

References 31 publications

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“…[48,52] In contrast to lipase PF, Lipase CA exhibited higher catalytic activity for e-CL than for macrolides. The ROP of e-CL (1 mmol) with 10 mg of lipase CA in bulk at 60 8C for 4 h gave poly(e-CL) of M n 5 200 at 72% yields.…”

Section: Terminator Methodsmentioning

confidence: 99%

“…[52] Some enzyme screening data for ROP of PDL are also given in Table 1. Ring-opening copolymerization of PDL with four monomers, d-VL, e-CL, UDL, and DDL, by lipase PF and lipase PC at 60 8C in bulk was carried out to give copolymers with M n ranging from 1 200 to 6 300, not being statistically random (Scheme 4).…”

Section: Finding Of Lipase Catalyst and The Scope Of Reactionsmentioning

confidence: 99%

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Recent Developments in Lipase‐Catalyzed Synthesis of Polyesters

Kobayashi

2009

Macromol. Rapid Commun.

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258

205

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Polyester synthesis by lipase catalyst involves two major polymerization modes: i) ring-opening polymerization of lactones, and, ii) polycondensation. Ring-opening polymerization includes the finding of lipase catalyst; scope of reactions; polymerization mechanism; ring-opening polymerization reactivity of lactones; enantio-, chemo- and regio-selective polymerizations; and, chemoenzymatic polymerizations. Polycondensation includes polymerizations involving condensation reactions between carboxylic acid and alcohol functional groups to form an ester bond. In most cases, a carboxylic acid group is activated as an ester form, such as a vinyl ester. Many recently developed polymerizations demonstrate lipase catalysis specific to enzymatic polymerization and appear very useful. Also, since lipase-catalyzed polyester synthesis provides a good opportunity for conducting "green polymer chemistry", the importance of this is described.

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Section: Terminator Methodsmentioning

confidence: 99%

Section: Finding Of Lipase Catalyst and The Scope Of Reactionsmentioning

confidence: 99%

Recent Developments in Lipase‐Catalyzed Synthesis of Polyesters

Kobayashi

2009

Macromol. Rapid Commun.

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258

205

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“…When 2,2-dibutyl-2-stanna-1,3-dioxepane was used as catalyst, the copolymerization of TMC with b-butyrolactone produced A-B-A triblock copolymer, whereas the random copolymer was formed from d-valerolactone or e-CL 20) . We have already reported that the ring-opening copolymerization of lactones proceeded via the lipase catalysis 21,22) . Here, the copolymerization of cyclic dicarbonates with lactones using lipase CA as catalyst has been examined (Scheme 2).…”

Section: Enzymatic Copolymerization Of Cyclic Dicarbonates With Lactonesmentioning

confidence: 99%

Lipase-catalyzed ring-opening polymerization and copolymerization of cyclic dicarbonates

Namekawa

Uyama

Kobayashi³

et al. 2000

Macromol. Chem. Phys.

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“…Lots of investigations on different ring size of lactones, solvent effect, and an enzymatic activity of lipases immobilized on different matrix have been carried out. [2][3][4][5][6][7][8][9][10][11][12][13][14][15][16] In case of condensation of diol and diacid with aliphatic chain, the high molecular weight polyester can be obtained by removing a leaving group. Klibanov et al have explored the enzymatic catalyzed asymmetric polymerization of aliphatic diol and diacid.…”

Section: Introductionmentioning

confidence: 99%

Enzyme-Catalyzed Polymerization Mechanism of Aliphatic Polyester Investigated by 1H NMR and MALDI-TOF Mass Spectrum

Nakaoki

Danno

Kurokawa

2003

Polym J

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ABSTRACT:Enzyme-catalyzed polymerization mechanism of adipic acid and hexanediol was investigated by proton nuclear magnetic resonance ( 1 H NMR) and MALDI-TOF mass spectra. When the stoichiometric substrates were used for the reaction, 1 H NMR measurements showed that the hydroxyl terminated product was preferentially formed at the early stage, then with reaction time it changed to carboxyl terminated product. This process was also confirmed by MALDI-TOF mass spectra. First the chain propagation follows the step-growth mechanism accompanying the sequential addition of a diacid-diol unit. In this case, an enzyme-substrate complex is attacked by hydroxyl group of substrates, and as a result the hydroxyl terminated product was preferentially formed. And at the later stage of the reaction, the transesterification plays an important role to form the carboxyl terminated product. When an excess diacid was used, the end group structure showed the same behavior as the stoichiometric condition, i.e., the predominant end group is consisted of the hydroxyl group at the initial stage then it rapidly changed to the carboxyl group although the time to change to carboxyl terminated product became shorter. In case of the condition of an excess diol, the reaction was avoided at the early stage because no enzyme forms a complex with diacid.KEY WORDS Enzyme / Polycondensation / End Structure / Polyester / Nuclear Magnetic Resonance (NMR) / MALDI-TOF Mass Spectrum / Enzyme-catalyzed polymerization in organic media has been extensively investigated during the last decade. Generally lipases are known to catalyze esterification and transesterification. Enzymatic ring opening polymerization such as lactones has been wellestablished by many researches. In 1993, Kobayashi et al. succeeded to polymerize different lactones using some lipases. 1 The advantage of this polymerization is that a leaving group is not produced and high molecular weight product is obtained. Lots of investigations on different ring size of lactones, solvent effect, and an enzymatic activity of lipases immobilized on different matrix have been carried out. [2][3][4][5][6][7][8][9][10][11][12][13][14][15][16] In case of condensation of diol and diacid with aliphatic chain, the high molecular weight polyester can be obtained by removing a leaving group. Klibanov et al. have explored the enzymatic catalyzed asymmetric polymerization of aliphatic diol and diacid. 17 They observed the formation of hydroxyl terminated oligomers, as an excess diol was used. Morrow et al. recognized the importance of stoichiometry and studied polycondensation using equimolar quantities of diol and diacid. 18 They succeeded to prepare polyester with a several thousands of molecular weight. They also showed that the early stage of polymerization followed relatively rapid formation of hydroxyl terminated polyester and slower † To whom correspondence should be addressed.formation of carboxyl terminated one. Enzymatic synthesis of aliphatic polyester in solvent-free system was studied by Uyama e...

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Enzymatic Ring-Opening Polymerization and Copolymerization of 8-Octanolide by Lipase Catalyst

Cited by 110 publications

References 31 publications

Recent Developments in Lipase‐Catalyzed Synthesis of Polyesters

Recent Developments in Lipase‐Catalyzed Synthesis of Polyesters

Lipase-catalyzed ring-opening polymerization and copolymerization of cyclic dicarbonates

Enzyme-Catalyzed Polymerization Mechanism of Aliphatic Polyester Investigated by 1H NMR and MALDI-TOF Mass Spectrum

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