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以钪的膦酸酯盐Sc(P204)3和烷基铝组成催化体系催化降冰片烯(NBE)聚合,考察了聚合反应条件对单体转化率、产物分子量以及微观结构的影响.当以三乙基铝为助催化剂时,[NBE]/[Sc]=50(摩尔比),[Al]/[Sc]=30(摩尔比),40℃陈化5 min,在甲苯中于60℃聚合7 h,单体转化率为98%,所得聚合物可部分溶于有机溶剂;NBE以开环聚合方式为主,开环产物含量为81%~88%,其中顺式双键含量为48%~58%,分子量2.4×103~3.0×103,分子量分布1.9~2.2.当以三异丁基铝为助催化剂时,[NBE]/[Sc]=50(摩尔比),[Al]/[Sc]=5(摩尔比),50℃陈化2 h,80℃下于甲苯中聚合4 h,单体转化率为39%,所得白色聚合产物很难溶于有机溶剂,以开环聚合方式为主,产物中反式双键含量90%.
The effect of polymerization conditions on the monomer conversion, product molecular weight and microstructure was investigated by the catalytic system of norbornene (NBE) catalyzed by scandium phosphonate Sc (P204) 3 and aluminum alkyl. Ethylaluminum as a co-catalyst, [NBE] / [Sc] = 50 (molar ratio), [Al] / [Sc] = 30 (molar ratio), aging at 40 ° C for 5 min and polymerizing in toluene at 60 ° C 7 h, the monomer conversion rate was 98%, the resulting polymer can be partially dissolved in organic solvents; NBE mainly ring-opening polymerization, the open-loop product content of 81% to 88%, wherein the cis double bond content of 48% ~ 58%, molecular weight 2.4 × 103 ~ 3.0 × 103, and molecular weight distribution 1.9 ~ 2.2. [NBE] / [Sc] = 50 (molar ratio), [Al] / [ Sc] = 5 (molar ratio), aging at 50 ℃ for 2 h and polymerizing in toluene at 80 ℃ for 4 h, the monomer conversion was 39%. The obtained white polymerized product was hardly soluble in organic solvent, Mainly, the product contains 90% of the double bond content.