Lipases ring-opening copolymerizations

Matsumura, S. Tsukada, K. Toshima, K. Novel lipase-catalyzed ring-opening copolymerization of lactide and trimethylene carbonate forming poly(ester carbonate)s. Int. J. Biol. Macromol. 1999, 25 (1-3), 161-167. 

Scheme 4.23 Lipase-catalyzed ring-opening copolymerization of 3(S)-isopropylmorpholine-2,5-dione (IPDM) and D,L-lactide (DLLA).

Scheme 4.24 Ring-opening copolymerization of cyclic thioester and cyclic ester using Candida antarctica lipase.

Matsumura, S., Okamoto, T., Tsukada, K., and Toshima, K. (1998) Novel lipase-catalyzed ring-opening copolymerization of oxiranes and succinic anhydride forming polyesters bearing functional groups. Macromol. Rapid Commun., 19 (6), 295-298. 

In the lipase-catalyzed ring-opening copolymerization of cyclic monomers, the first example with lactones involved 5-VL and e-CL, using a lipase PF catalyst [98]. 

The higher activity of lipase Novozym-435 over PPL was also confirmed by Deng et a in the study of lipase-catalyzed ring-opening copolymerization of CL and TMC. An increase in the lipase concentration in CL and TMC polymerization led to higher initial rates of conversion. In contrast, the Ain decreased at the same level of conversion with increasing catalyst concentration. 

Poly(TMC-co-ethylene ethyl phosphate) was prepared by ring-opening copolymerization catalyzed by lipase enzymes (pancreas lipase, PPL and Candida rugosa lipase, CL) as catalysts in bulk at 100 °C with molecular weight (Mn) from 3200 to 10 200. Degradation experiments showed that introducing phosphate groups into the TMC chain increases the hydrolysis rate of the copolymer. 

Also, the novel enzymatic ring-opening copolymerization of ethyl ethylene phosphate (EEP) and TMC was performed in bulk at 100 °C using PPL or C. rugosa lipase to yield random copolymers having molecular weights ranging from 3200 to... 

Uyama H, Takeya K, Kobayashi S (1993) Synthesis of polyesters by enzymatic ring-opening copolymerization using lipase catalyst. Proc Jpn Acad B 69 203—207... 

Furthermore, the ring-opening co-polymerization of BTMC with 5,5-dimethyl-trimethylene carbonate (DTC) by immobilized porcine pancreatic lipase (0.1 wt%) catalyzed in bulk copolymerization at 150°C for 24h [117]. Under these conditions, the highest molecular weight of poly(BTMC-co-DTC) of M =26 400 was obtained, with 83% monomer conversion. 

This chapter provides numerous examples of significant advancements documented in the literature describing cell-free enzyme-catalyzed polymerizations, predominantly using lipases as catalysts. Polymerization reactions occurred by (i) condensations (ii) ring-opening homo- and copolymerizations and (iii) combination of condensation and ring-opening polymerization. 

Uyama, H., Kikuchi, H., Takeya, K., and Kobayashi, S. (1996) Lipase-catalyzed ring-opening polymerization and copolymerization of 15-pentadecanolide. Acta Polymerica, 47 (8), 357-360. 

Enzymatic ring-opening polymerization and copolymerization of 8-octanolide by lipase catalyst. Macromolecules, 31 (17), 5655-5659. 

For example Kumar, A., and Gross, R. A., 2000, Candida antarctica Lipase B-Catalyzed Transesterification New Synthetic Routes to Copolyesters. J. Am. Chem. Soc. 122 11767-11770 Kumar, A., and Gross, R. A., 2000, Candida antartica lipase B catalyzed polycaprolactone synthesis effects of organic media and temperature. Biomacromolecules 1 133-138 Kobayashi, S, Uyama, H., Namekawa, S., and Hayakawa, H., 1998, Enzymic Ring-Opening Polymerization and Copolymerization of 8-Octanolide by Lipase Catalyst. Macromolecules 31 5655. 

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