羟基邻位三齿[OSO]双酚钛络合催化剂催化乙烯聚合性能的研究  

Study on the catalytic performance of hydroxy ortho-tridentate[OSO]bisphenol titanium complex catalyst for ethylene polymerization

作　　者：王静云 张丹[1] 于洪博 李君华[1] 钱建华[1] WANG Jing-yun;ZHANG Dan;YU Hong-bo;LI Jun-hua;QIAN Jian-hua(School of Petrochemical Engineering,Liaoning Petrochemical University,Fushun 113001,China;PetroChina Fushun Petrochemical Company,Fushun 113001,China)

机构地区：[1]辽宁石油化工大学石油化工学院,辽宁抚顺113001 [2]中国石油天然气股份有限公司抚顺石化分公司研究院,辽宁抚顺113001

出　　处：《应用化工》2024年第1期122-125,共4页Applied Chemical Industry

基　　金：辽宁省科技厅揭榜挂帅(科技攻关专项)(2021JH1/10400090);辽宁省教育厅项目(L2020004)。

摘　　要：以4-叔丁基苯酚为原料,通过改变羟基邻位取代基经过溴甲基化、亲核取代以及金属络合反应得到了4种三齿[OSO]双酚钛络合催化剂[S(2-CH_(2)-4-^(t)Bu-6-R-C_(6)H_(2)O)2]TiCl_(2)(R^(1)=CMe_(3),R^(2)=CPhMe_(2),R^(3)=CPh_(2)Me,R^(4)=CPh_(3))。在温度30,50,70℃,压力0.6 MPa的条件下探讨乙烯聚合反应性能,通过改变催化剂的Al/Ti比和反应时间,得到不同条件下的聚烯烃产物,并利用凝胶色谱(GPC)对产物进行表征分析。对不同反应条件下的这4种催化剂进行比较,由于R基团位阻效应的影响,位阻越大催化剂的活性越高,结合实验结果得出,在50℃条件下[S(2-CH_(2)-4-^(t)Bu-6-CMePh_(2)-C_(6)H_(2)O)_(2)]TiCl_(2)催化剂的活性最高,为6.7×10^(6)g PE/(mol Ti·h)以及得到的聚烯烃产品M W为1.68×10^(5),分子量分布为3.2。Four kinds of tridentate[OSO]bisphenol titanium complex catalysts[S(2-CH_(2)-4-^(t)Bu-6-R-C_(6)H_(2)O)_(2)]TiCl_(2)(R_(1)=CMe_(3),R_(2)=CPhMe_(2),R_(3)=CPh_(2)Me,R^(4)=CPh_(3))were prepared from 4-tert-butyl phenol through bromination,nucleophilic substitution and metal complexation reaction by changing the ortho-substituent of hydroxyl.The reaction performance of ethylene polymerization was investigated under the conditions of 30,50,70℃,and pressure of 0.6 MPa.Polyolefin products under different conditions were obtained by changing the Al/Ti ratio of the catalyst and the reaction time.The products were characterized and analyzed by gel chromatogram phy(GPC).The four catalysts under different reaction conditions were compared.Due to the effect of R group steric hindrance,the larger the steric hindrance,the higher the activity of the catalyst.Based on the experimental results,it was concluded that the activity of the[S(2-CH_(2)-4-^(t)Bu-6-CMePh_(2)-C_()6H_(2)O)_(2)]TiCl_(2)catalyst at 50℃was up to 6.7×10^(6)g PE/(mol Ti·h),and the obtained polyolefin product M W was 1.68×10^(5),with a molecular weight distribution of 3.2.

关 键 词：4-叔丁基苯酚 三齿[OSO]双酚钛络合催化剂 邻位取代基 乙烯聚合 凝胶色谱 

分 类 号：TQ016[化学工程] TQ025