Hayashi Hiroto, Yanagishita Yoshio, Matsumura Shuichi
Department of Applied Chemistry, Faculty of Science and Technology, Keio University, 3-14-1 Hiyoshi, Kohoku-ku, Yokohama 223-8522, Japan.
Int J Mol Sci. 2011;12(9):5490-507. doi: 10.3390/ijms12095490. Epub 2011 Aug 29.
Novel poly(ester-urethane)s were prepared by a synthetic route using a lipase that avoids the use of hazardous diisocyanate. The urethane linkage was formed by the reaction of phenyl carbonate with amino acids and amino alcohols that produced urethane-containing diacids and hydroxy acids, respectively. The urethane diacid underwent polymerization with polyethylene glycol and α,ω-alkanediols and also the urethane-containing hydroxy acid monomer was polymerized by the lipase to produce high-molecular-weight poly(ester-urethane)s. The periodic introduction of ester linkages into the polyurethane chain by the lipase-catalyzed polymerization afforded chemically recyclable points. They were readily depolymerized in the presence of lipase into cyclic oligomers, which were readily repolymerized in the presence of the same enzyme. Due to the symmetrical structure of the polymers, poly(ester-urethane)s synthesized in this study showed higher T(m), Young's modulus and tensile strength values.
通过使用脂肪酶的合成路线制备了新型聚（酯 - 聚氨酯），该路线避免了使用危险的二异氰酸酯。碳酸苯酯与氨基酸和氨基醇反应分别生成含氨基甲酸酯的二酸和羟基酸，从而形成氨基甲酸酯键。含氨基甲酸酯的二酸与聚乙二醇和α,ω - 链烷二醇发生聚合反应，含氨基甲酸酯的羟基酸单体也通过脂肪酶进行聚合反应，以生产高分子量的聚（酯 - 聚氨酯）。脂肪酶催化聚合反应将酯键周期性引入聚氨酯链中，从而提供了化学可回收点。它们在脂肪酶存在下很容易解聚成环状低聚物，这些低聚物在相同酶存在下很容易再聚合。由于聚合物的对称结构，本研究中合成的聚（酯 - 聚氨酯）表现出更高的熔点、杨氏模量和拉伸强度值。
