Solventless Enantioelective Ring-Opening Polymerization of Substituted ε-Caprolactones by Enzymatic Catalysis

Abstract

Highly (S)-enriched substituted poly(ε-caprolactone)s were synthesized from 4-methyl-ε-caprolactone (4-MeCL) and 4-ethyl-ε-caprolactone (4-EtCL) by lipase Novozym-435 (from Candida antarctica) catalyzed ring-opening polymerizations. The polymerizations were performed in bulk, thus eliminating the need for solvents in the polymerization process. Poly(4-EtCL) and poly(4-MeCL) having >95% enantiomeric purity (eep) have been prepared. Number-average molecular weights of the poly(4-EtCL) and poly(4-MeCL) were 4400 and 5400, respectively. The effect of reaction temperature on enzyme enantioselectivity, polymer molecular weight, and monomer conversion was also investigated at 45 and 60 °C. Contrary to many literature reports and conventional wisdom, the enantioselectivity of the lipase was greater at 60 °C, the higher reaction temperature. The solventless polymerization process appeared to be diffusion-controlled in which the monomer conversion and polymer molecular weight increased at higher reaction temperature.