Lipase from Candida sp.99-125 catalyzed ring-opening polymerization of e-caprolactone in the presence of 6-mercapto-1-hexanol was presented as a new metal-free approach for direct synthesis of welldefined thiol-termin...Lipase from Candida sp.99-125 catalyzed ring-opening polymerization of e-caprolactone in the presence of 6-mercapto-1-hexanol was presented as a new metal-free approach for direct synthesis of welldefined thiol-terminated poly(e-caprolactone).Remarkably,high chemoselectivity of lipase from Candida sp.99-125 toward hydroxyl and thiol was exhibited and quantitative thiol fidelity over 90% was achieved.The tedious protecting/deprotecting steps for thiol and metal residue were avoided.The polymerizations with around 70% monomer conversion were conducted in bulk and toluene at relative low temperature of 40 ℃.Number–average molecular weight of resulted polymers ranged from 3000 to4700 Da by changing the feed ratio between monomer and initiator.The structures of obtained thiolterminated poly(e-caprolactone) were demonstrated by combining NMR and SEC analyses.展开更多
基金supported by a grant from the National Basic Research Program of China (Nos.2012CB725204 and 2011CB710803)the National High Technology Research and Development Program of China (No.2014AA021201)+1 种基金Natural Science Foundation of China (No.81302632)the Priority Academic Program Development of Jiangsu Higher Education Institutions and China Postdoctoral Science Foundation (No.2014M551574)
文摘Lipase from Candida sp.99-125 catalyzed ring-opening polymerization of e-caprolactone in the presence of 6-mercapto-1-hexanol was presented as a new metal-free approach for direct synthesis of welldefined thiol-terminated poly(e-caprolactone).Remarkably,high chemoselectivity of lipase from Candida sp.99-125 toward hydroxyl and thiol was exhibited and quantitative thiol fidelity over 90% was achieved.The tedious protecting/deprotecting steps for thiol and metal residue were avoided.The polymerizations with around 70% monomer conversion were conducted in bulk and toluene at relative low temperature of 40 ℃.Number–average molecular weight of resulted polymers ranged from 3000 to4700 Da by changing the feed ratio between monomer and initiator.The structures of obtained thiolterminated poly(e-caprolactone) were demonstrated by combining NMR and SEC analyses.