Mono-hydroxyl terminated polycaprolactone(PCL) was prepared by Novozyme 435 catalyzed ring-opening polymerization(ROP) of ε-caprolactone(ε-CL) initiated by methanol,and subsequently converted to bromine ended PCL by the esterification of the resulting macromolecules with α-bromopropionyl bromide.The macroinitiators containing α-bromoester group were employed in the atom transfer radical polymerization(ATRP) of glycidyl methacrylate(GMA) with CuCl/2,2-bipyridine(bpy) as the catalyst system to obtain amphiphilic diblock copolymer PCL-b-PGMA.
用酶促开环聚合与ATRP方法相结合,制备了聚甲基丙烯酸六氟丁酯-聚己内酯-聚乙二醇-聚己内酯-聚甲基丙烯酸六氟丁酯(PHFMA-b-PCL-b-PEG-b-PCL-b-PHFMA)五嵌段聚合物.首先用Novozym e 435作为催化剂合成了聚己内酯-聚乙二醇-聚己内酯三嵌段聚合物,然后通过端基官能化法合成了大分子引发剂,并用其引发甲基丙烯酸六氟丁酯(HFMA)的ATRP反应,合成了五嵌段聚合物.通过核磁和GPC证明了大分子引发剂和五嵌段共聚物的结构,五嵌段共聚物的GPC分析表明这种合成方法的可行.共聚物胶束的直径和大小通过动态光散射方法和原子力显微镜测试,五嵌段共聚物在水中的的自组装行为也被研究.结果证明胶束是球形,其平均直径为77 nm.聚合物在四氢呋喃中的浓度对聚合物的聚集形貌有很大的影响.
This work was directed to develop a novel method for the synthesis of hyperbranched polymers by combining enzymatic ring-opening polymerization(ROP) with self-condensing vinyl copolymerization(SCVCP). Functionalized PCL was prepared by ROP of ε-CL with HEMA as the initiator and catalyzed by Novozyme 435, and subsequently converted to AB* macroinimer by the esterification with 2-bromoisobutyryl bromide. The target polymer was obtained by SCVCP of AB* macroinimer with styrene via ATRP.
