含芴基的羧酸酯类内给电子体化合物及其应用  

Carboxylate compound containing fluorene group as internal electron donor and application thereof

作　　者：刘海涛[1] 胡建军[1] 高明智[1] 蔡晓霞[1] 马吉星[1] 马晶[1] Liu Haitao;Hu Jianjun;Gao Mingzhi;Cai Xiaoxia;Ma Jixing;Ma Jing(Sinopec Beijing Research Institute of Chemical Industry,Beijing 100013,China)

机构地区：[1]中国石化北京化工研究院,北京100013

出　　处：《石油化工》2018年第4期327-331,共5页Petrochemical Technology

摘　　要：以9H-芴-9-羧酸甲酯为原料,通过与不同的溴代羧酸酯反应得到了三种含芴基的羧酸酯类化合物,将化合物作为内给电子体用于烯烃聚合固体催化剂的制备,利用~1H NMR,GPC等方法分析了化合物的结构,并考察了催化剂的丙烯聚合行为。实验结果表明,由于芴基团的9-位具有高反应活性,合成含芴基的羧酸酯类化合物的制备方法简单,有利于工业化推广。采用含芴基的羧酸酯类内给电子体化合物的催化剂进行丙烯聚合时,催化活性较高,其中,9-(1-乙氧基-3-甲基-1-氧代丁烷-2-基)-9H-芴-9-羧酸乙酯为内给电子体时,催化活性高于对比给电子体;催化剂的氢调敏感性好,所得聚合物的等规指数较高,相对分子质量分布较宽。Three carboxylate compounds containing fluorene group were synthesized by using methyl 9H-fluorene-9-carboxylate as the raw material to react with differentα-bromocarboxylates.The compounds were used as internal electron donors for the preparation of olefin polymerization solid catalyst.The structure of the compound was analyzed by 1H NMR and GPC,and the polymerization behavior of the catalyst was investigated.The experimental results showed that the synthesis method of the fluorenyl-containing carboxylic acid ester compound was simple since the 9-position of the fluorene group had high reactivity,thus easy for industrialization promotion.When the catalyst-contained fluorene carboxylic acid ester-type electron donor compound was used for propylene polymerization,the catalytic activity is high.In which,when 9-(1-ethoxy-3-methyl-1-oxobutane-2-yl)-9H-fluorene-9-carboxylic acid ethyl ester was an internal electron donor,the catalytic activity is higher than that of the ref.electron donor;the hydrogen sensitivity of the catalyst was desirable;the obtained polymer had a high isotactic index;and the relative molecular weight had a wider distribution.

关 键 词：内给电子体 羧酸酯 芴 烯烃聚合 ZIEGLER-NATTA催化剂 

分 类 号：TQ325.1[化学工程—合成树脂塑料工业]