有机铬催化剂用于气相聚合  

Gas phase polymerization with organic chromium catalyst

作　　者：崔楠楠[1] 王如恩[1] 傅捷 苟清强[1] 王洪涛[1] Cui Nannan;Wang Ruen;Fu Jie;Gou Qingqiang;Wang Hongtao(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》2021年第8期755-759,共5页Petrochemical Technology

基　　金：中国石油化工股份有限公司资助项目(4-11ZS0437)。

摘　　要：采用硅烷铬酸酯类有机铬催化剂进行乙烯气相聚合,利用GPC,DSC等方法考察了不同的助催化剂对催化剂乙烯聚合活性、聚合动力学及聚合物性能的影响。实验结果表明,与不加助催化剂相比,以三乙基铝(TEA)为助催化剂时,引发时间基本不变,聚合活性提高;以三乙基硼(TEB)为助催化剂时,引发时间显著缩短,聚合活性显著增大;以复配TEA/TEB为助催化剂时,引发时间显著缩短,聚合活性与以TEA为助催化剂相当。与不加助催化剂所得聚合物相比,加入TEB所得聚合物的分子量增加,高分子量部分出现肩峰,分子量分布变宽,熔点和结晶度降低;加入TEA所得聚合物的分子量减小,高分子量部分减少,分子量分布变窄,熔点和结晶度增大。采用TEA/TEB复配助催化剂时,所得聚合物性能的变化趋势与以TEB为助催化剂时的结果类似。Organic chromium based silane chromate catalyst was applied in the ethylene gas polymerization,and the effects of different cocatalysts on the activity,kinetics of polymerization and properties of the polymer were investigated by GPC and DSC.The results showed that the polymerization activity was enhanced,while the initiation time kept almost unchanged by using triethylaluminium(TEA)as cocatalyst,compared that without addition of cocatalyst.Using triethylboron(TEB)as cocatalyst,the initiation time was significantly shortened and the polymerization activity was greatly increased.Using TEA/TEB as the composite cocatalysts,the initiation time was also dramatically shortened,while the polymerization activity was almost equivalent to that of TEA.Compared with the polymer prepared without cocatalyst,the molecular weight of the polymer prepared with TEB increased,a shoulder peak appearing in the high molecular weight part,the molecular weight distribution becoming widen,the melting point and crystallinity decreased.On the contrary,the molecular weight of the polymer prepared with TEA decreased,the high molecular weight part decreased,the molecular weight distribution becoming narrow,the melting point and crystallinity increased.Using TEA/TEB composite as the cocatalyst,the change trend of polymer performance was quite similar to that of TEB.

关 键 词：硅烷铬酸酯有机铬催化剂 气相聚合 三乙基铝 三乙基硼 分子量分布 

分 类 号：TQ426.94[化学工程]