Lipase-catalyzed polyester synthesis

The use of lipase as biocatalyst in polyesterification of aliphatic diacids or their derivatives, and diols in an organic solvent has been discussed. We have demonstrated that bis(2-chloroethyl) esters of succinic, fumaric, and maleic acid, and bis(2,2,2-trifluoroethyl) sebacate and -dodecanedioate can be polymerized by lipase-catalyzed polytransesterification. Maleate was isomerized to fumarate even under mild reaction conditions, resulting in poly(1,4-butyl fumarate). In order to obtain a high mass-average molar mass of the polyester, solid Mucor miehei lipase was found to be the best lipase and diphenyl ether the best solvent of several investigated. There was no clear relationship with the log P value of the solvent and the polyesterification activity of lipase. The highest degree of polymerization (DP = 184) of poly(1,4-butyl sebacate) with a mass-average molar mass of 46,600 g . mol(-1) was obtained in polytransesterification of bis(2,2,2-trifluoroethyl) sebacate and 1,4-butanediol using a programmed vacuum profile. However, a mass-average molar mass as high as about 42,000 g . mol(-1) (DP = 167) was also obtained with free sebacic acid when vacuum was employed to remove the water formed during esterification. The mass average molar mass of the polyester increased with an increase in the relative quantity of lipase up to 1 g per 1.5 mmol of diacid, with an increase in the molar mass of the aliphatic diol up to 1,5-pentanediol, and with an increase in the concentration of substrates up to 0.83 M.