Kinetics and mechanism studies on scandium calix[6]arene complex initiating ring-opening polymerization of 2,2-dimethyltrimethylene carbonate  

作　　者：GOU PengFei ZHU WeiPu SHEN ZhiQuan 

机构地区：[1]Key Laboratory of Macromolecule Synthesis and Functionalization, Ministry of Education, Institute of Polymer Science, Zhejiang University, Hangzhou 310027, China Key Laboratory of Macromolecule Synthesis and Functionalization, Ministry of Education, Institute of Polymer Science, Zhejiang University, Hangzhou 310027, China Key Laboratory of Macromolecule Synthesis and Functionalization, Ministry of Education, Institute of Polymer Science, Zhejiang University, Hangzhou 310027, China

出　　处：《Science China Chemistry》2007年第5期648-653,共6页中国科学（化学英文版）

基　　金：Supported by the National Natural Science Foundation of China (Grant no. 20434020);the Special Fund for Major State Basic Research Project (Grant No. G2005CB623802);the Committee of Science and Technology of Zhejiang Prov-ince

摘　　要：Scandium p-tert-butylcalix[6]arene complex has been synthesized from scandium isopropoxide and p-tert-butylcalix[6]arene and used as a single component initiator for the first time. The polymerization of 2,2-dimethyltrimethylene carbonate (DTC) using this complex can proceed under mild conditions. Poly (2,2-dimethyltrimethylene carbonate) (PolyDTC) with weight-average molecular weight of 33700 and molecular weight distribution of 1.21 can be prepared. Kinetics study indicates that the polymeri- zation rate is first order with respect to both monomer and initiator concentrations, and the apparent activation energy of the polymerization is 22.7 kJ/mol. 1H NMR spectrum of the polymer reveals that the monomer ring opens via acyl-oxygen bond cleavage leading to an active center of Sc-O.Scandium p-tert-butylcalix[6]arene complex has been synthesized from scandiumisopropoxide and p-tert-butylcalix[6]arene and used as a single component initiator for the firsttime.The polymerization of 2,2-dimethyltrimethylene carbonate (DTC) using this complex can proceedunder mild conditions.Poly (2,2-dimethyltrimethylene carbonate) (PolyDTC) with weight-averagemolecular weight of 33700 and molecular weight distribution of 1.21 can be prepared.Kinetics studyindicates that the polymerization rate is first order with respect to both monomer and initiatorconcentrations,and the apparent activation energy of the polymerization is 22.7 kJ/mol.1H NMRspectrum of the polymer reveals that the monomer ring opens via acyl-oxygen bond cleavage leading toan active center of Sc-O.

关 键 词：RING-OPENING polymerization  SCANDIUM CALIXARENE complex  2 2-dimethyltrimethylene carbonate (DTC)  POLYCARBONATES 

分 类 号：N[自然科学总论]