钼基开环移位催化剂催化双环戊二烯聚合研究

分别用对甲基苯酚、壬基酚、2,6-二叔丁基-4-甲基苯酚、2,4,6-三溴苯酚和2,4-二硝基苯酚与五氯化钼(MoCl5)反应,制备出系列用于双环戊二烯(DCPD)开环移位聚合的钼-酚催化剂。考察了不同结构催化剂的活性及其在不同条件下对催化DCPD开环聚合的影响。以红外光谱和示差扫描量热分析表征了聚合产物的结构和性能。结果表明,产物中钼-对甲基苯酚的活性最高,其催化DCPD聚合的单体转化率为98.07%,交联度为90.44%。同时发现钼-酚催化剂催化DCPD聚合的凝胶时间随着Mo、Et2AlCl物质的量的增加和温度的升高而减小,而单体转化率和交联度则先增大后减小。

Study on the polymerization of dicyclopentadiene with molybdenumbased ring-opening metathesis polymerization catalysts

The series Mo-phenol catalysts for ring-opening metathesis polymerization(ROMP) of dicyclopentadiene(DCPD)were prepared by the reaction of p-cresol,nonylphenol,2,6-di-tert-butyl-p-cresol,2,4,6-tribromophenol and 2,4-dinitrophenol with MoCl5.The activity of catalysts with different structures and the influences on the polymerization of DCPD under different conditions were investigated.The structure and properties of polymerization product were chatacterized by FT-IR and DSC.The results showed that MoCl5-p-cresol catalyst had the highest activity among the five catalysts and the monomer conversion was 98.07% and crosslinking degree was 90.44%.The gel time of DCPD polymerization catalyzed by MoCl5-p-cresol was shortened and the monomer conversion and crosslinking degree were increased first and then decreased with the incresing of temperature and the number of moles of Mo and Et2AlCl.