[ONSO]AlCl配合物催化4-乙烯基环氧环己烷聚合制备聚醚及其功能化

Preparation and Functionalization of Polyether Prepared by 1,2-Epoxy-4-Vinycyclohexane Catalyzed by [ONSO] Al Complex

通过溶剂挥发法得到[ONSO]型配体L的晶体,对其单晶结构进行了解析;制备该配体的金属Al配合物1,以1为催化剂,研究了单体与催化剂摩尔比、邻苯二甲酸酐(PA)加入量对4-乙烯基环氧环己烷(4-VCHO)聚合反应的影响。在[VCHO]∶[PA]∶[1]=250∶50∶1,90℃时本体聚合反应30min,收率达到49%,催化活性(TOF值)为245h-1,相对分子质量为22000,相对分子质量分布为2.1。对所得的聚乙烯基环氧环己烷(PVCHO)进行功能化修饰,依次将聚合物侧链双键转变为环氧基团、环状碳酸酯、羟基(-OH)、巯基(-SH)。PVCHO侧链的环氧化和环状碳酸酯化使得其玻璃化转变温度分别提高了58℃和84℃。

The single crystal of L was obtained by solvent evaporation method,and its structure was analyzed by X-ray single crystal diffractometer.The Al complex 1 was formed from L and aluminum salt was prepared,and used as catalyst to be applied in the polymerization reaction of 1,2-epoxy-4-vinycyclohexane(4-VCHO).The effects of the mole ratio of monomer and catalyst and the amount of phathalic anhydride(PA)were studied.When the mole ratio of[VCHO]:[PA]:[1]is 250:50:1,and the bulk polymerization takes 30 min at 90℃,the yield reaches 49%,TOF value is 245 h 1,the molecular weight is 22000,the molecular weight distribution is 2.1.The functional modification of polyethylene-based epoxy cyclohexane(PVCHO)was performed,and the double bonds on polymer side chains were converted to epoxy group,cyclic carbonate,一OH and一SH.The epoxidation and cyclic carbonatation of PVCHO side chains can make the glass transition temperature of polymers increase 58℃and 84℃,respectively.