Precision enzymatic polymerization to polyesters with lipase catalysts

• Published in: Macromolecular Symposia
• Main Authors: Kobayashi, Shiro, Uyama, Hiroshi
• Format: Article in Journal/Newspaper
• Language: English
• Published: Wiley 1999
• Subjects: Antarc*; Antarctica
• Online Access: http://dx.doi.org/10.1002/masy.19991440121; https://api.wiley.com/onlinelibrary/tdm/v1/articles/10.1002%2Fmasy.19991440121; https://onlinelibrary.wiley.com/doi/pdf/10.1002/masy.19991440121

Abstract Ring‐opening polymerization of lactones with different ring‐size has been achieved via lipase catalysis. Small‐size (4‐membered) and medium‐size lactones (6‐ and 7‐membered) as well as macrolides (12‐, 13‐, 16‐, and 17‐membered) were subjected to the lipase‐catalyzed polymerization. The polymerization behaviors strongly depended on the lipase origin and the ring‐size of the lactones. In using Pseudomonas family lipases as catalyst, the polymerization of macrolides showing much lower anionic polymerizability proceeded much faster than that of ϵ‐caprolactone. The enzymatic polymerizability of the lactones was evaluated by Michaelis‐Menten kinetics. V max increased as a function of the ring‐size, whereas K m values were not so different with each other. The granular immobilized lipase derived from Candida antarctica . showed the extremely efficient catalysis in the polymerization of ϵ‐caprolactone. Single‐step synthesis of methacryl‐ and ω‐alkenyl‐type polyester macromonomers was achieved by the lipase‐catalyzed polymerization of 13‐membered lactone in the presence of vinyl esters acting as terminator. Lipase also catalyzed a polycondensation of dicarboxylic acid and glycol in the aqueous medium, in which the dehydration took place in water.