作者:Zhongbao Jian、Stefan Mecking
DOI:10.1021/acs.macromol.6b00983
日期:2016.6.28
six-membered (cis-/trans-1,3-dioxane) cyclic acetal units in the main chain, and also in the initiating ends of this functionalized polyethylene. Comprehensive NMR analysis of the microstructure of these copolymers revealed that under pressure reactor conditions consecutive 2,1–1,2-insertion of divinyl formal into a Pd–H bond is preferred, but consecutive 1,2–1,2-insertion of divinyl formal into more bulky Pd–alkyls
乙烯和二乙烯基缩甲醛的共聚由[κ 2 - P,O-(2-MeOC 6 H ^ 4)2 PC 6 H ^ 4 SO 3 } PDME(DMSO)](1)通过配位-插入机构,得到高度线性聚乙烯具有高(12.5mol%)二乙烯基甲醛的掺入。这大大超过了迄今为止插入聚合中相对较低的掺入量(6.9mol%)和与乙烯基醚单体的活性。所得的乙烯-二乙烯基正式共聚物(> 98%)仅包含五元(反式-1,3-二氧戊环)和六元(顺-/反式)在主链中以及在该官能化聚乙烯的起始端具有-1,3-二恶烷环缩醛单元。对这些共聚物的微观结构进行的全面NMR分析表明,在压力反应器条件下,连续2,1–1,2-插入二乙烯基甲醛成Pd-H键是优选的,但是连续1,2-1,2-插入二乙烯基正式使用更大体积的Pd-烷基(增长的聚合物链)。此外,二乙烯基缩甲醛的均聚得到的非交联聚(二乙烯基缩甲醛)与度DP的聚合Ñ ≈26。