Thiol-functionalized copolymeric polyesters by lipase-catalyzed esterification and transesterification of 1,12-dodecanedioic acid and its diethyl ester, respectively, with 1-thioglycerol.
Copolymeric polyoxoesters containing branched-chain methylenethiol functions, i.e., poly(1,12-dodecanedioic acid-co-1-thioglycerol) and poly(diethyl 1,12-dodecanedioate-co-1-thioglycerol), were formed by lipase-catalyzed polyesterification and polytransesterification of 1,12-dodecanedioic acid and diethyl 1,12-dodecanedioate, respectively, with 1-thioglycerol (3-mercaptopropane-1,2-diol) using immobilized lipase B from Candida antarctica (Novozym 435) in vacuo without drying agent in the reaction mixture. After 360-480 h, both polyoxoesters were purified by extraction from the reaction mixtures followed by solvent fractionation. The precipitate of poly(1,12-dodecanedioic acid-co-1-thioglycerol) demonstrated a M(W) of ~170,000 Da, whereas a M(W) of ~7,100 Da only was found for poly(diethyl 1,12-dodecanedioate-co-1-thioglycerol). Both polycondensates were analyzed by GPC/SEC, alkali-catalyzed transmethylation, NMR- and FTIR-spectrometry.
Fehling
Eberhard
E
Max Rubner-Institute, Federal Research Institute for Nutrition and Food, Piusallee 68/76, 48147, Münster, Germany. eberhard.fehling@mri.bund.de
Bergander
Klaus
K
Klein
Erika
E
Weber
Nikolaus
N
Vosmann
Klaus
K
D002175:Candida / Q000201:enzymology*; D002850:Chromatography, Gel; D003998:Dicarboxylic Acids / Q000378:metabolism*; D004800:Enzymes, Immobilized / Q000378:metabolism; D004951:Esterification; D005656:Fungal Proteins; D008401:Gas Chromatography-Mass Spectrometry; D005990:Glycerol / Q000031:analogs & derivatives* / Q000378:metabolism; D008049:Lipase / Q000378:metabolism*; D009682:Magnetic Resonance Spectroscopy; D008970:Molecular Weight; D011091:Polyesters / Q000737:chemistry / Q000302:isolation & purification / Q000378:metabolism*; D017550:Spectroscopy, Fourier Transform Infrared
D003998:Dicarboxylic Acids; D004800:Enzymes, Immobilized; D005656:Fungal Proteins; D011091:Polyesters; C036836:dodecanedioic acid; C009465:thioglycerol; D008049:Lipase; C431349:lipase B, Candida antarctica; D005990:Glycerol