乙烯与1-癸烯共聚及其共聚物微观结构

采用合成的2种限制几何茂金属催化剂A(2 四甲基环戊二烯基 6 叔丁基苯氧基二氯化钛)、B(2-四甲基环戊二烯基-4,6-二叔丁基苯氧基二氯化钛)分别和助剂Al(iBu)3/［Ph3C］+［B (C6F5)4］-组成体系催化乙烯与1-癸烯共聚反应，并对共聚物微观结构的序列分布和链增长基元反应概率统计进行分析，探讨了该体系下的共聚机理和共聚物结构。结果表明：(1)共聚物主链上共聚单体1-癸烯质量分数在14.3%~67.2%之间；(2)共聚物链增长机理符合一级Markovian模型链增长机理；(3)所得共聚物结构更趋向于聚乙烯共聚物，1-癸烯更容易配位或插入到{共聚物主链-1-癸烯-1癸烯-催化剂}序列，乙烯更容易配位或插入到{共聚物主链-乙烯-乙烯-催化剂}序列；(4)随着1-癸-烯浓度的增加，乙烯与1-癸烯共聚物更趋向嵌段结构；(5)1-癸烯更容易插入到催化剂B上。

Copolymerization of Ethylene With 1-Decene and Its Microstructure

The copolymerization of ethylene and 1 decene catalyzed by synthetic restricted geometric metallocene catalysts A and B with additives of Al(iBu)3/［Ph3C］+［B (C6F5)4］- was studied. The sequence distribution of copolymer microstructures and the probability statistics of chain growth elementary reactions were analyzed. The copolymerization mechanism and the structure of copolymers were discussed. The results show that: (1) the content of copolymer 1-decene in the main chain of copolymer is between 14.% and 67.% (mass fraction); (2) the growth mechanism of copolymer chain conforms to the first-order Markovian model chain growth mechanism; (3) the copolymer structure tends to polyethylene copolymer. 1-decene is easier to be coordinated or inserted into {copolymer main chain-1-decene-1 decene catalyst} sequence, and ethylene is easier to be coordinated or inserted into {copolymer main chain-ethylene-ethylene-catalyst} sequence; (4) with the increase of 1-decene concentration, copolymers(ethylene/1-decene) tend to block structure; (5) 1-decene is easier to be inserted into catalyst B.