Regioselectivity Control in Lipase-Catalyzed Polymerization of Divinyl Sebacate and Triols

Lipase-catalyzed regioselective polymerization of divinyl sebacate and triols has been performed in bulk. NMR analysis of the product obtained by the polymerization of divinyl sebacate and glycerol using Candida antarctica lipase at 60°C showed that 1,3-diglyceride was a main unit and a small amount of the branching unit (triglyceride) was contained. The polymerization of divinyl sebacate with 1,2,4-butanetriol or 1,2,6-hexanetriol at 60°C produced a branched polymer. In polymerization at a lower temperature, the regioselectivity was perfectly controlled to give a linear polymer consisting of the α,ω-disubstituted unit exclusively. The lipase origin and feed ratio of monomers greatly affected the microstructure of the polymer; under selected conditions, regiospecific polymerization was achieved.