采用茂金属催化剂制备乙烯-1-辛烯共聚物及其性能研究  

Study on preparation and properties of ethylene-1-octene copolymer catalyzed by metallocene catalyst

作　　者：张玉良[1] 陈志康 蒋文军[1] 刘振宇 封水彬[1] 朱红平[2] ZHANG Yu-liang;CHEN Zhi-kang;JIANG Wen-jun;LIU Zhen-yu;FENG Shui-bin;ZHU Hong-ping(Research InstituTEof Maoming Petrochemical Branch Company,SINOPEC,Maoming 525011,China;StaTEKey Laboratory of Physical Chemistry of Solid Surfaces,Xiamen University,Xiamen 361005,China)

机构地区：[1]中国石化茂名石化分公司研究院,广东茂名525011 [2]厦门大学化学化工学院固体表面物理化学国家重点实验室,福建厦门361005

出　　处：《石化技术与应用》2019年第5期305-309,共5页Petrochemical Technology & Application

摘　　要：采用自制单茂金属催化剂MXC,经Al(i-Bu)3和[Ph3C]+[B(C6F5)4]-活化后对乙烯和1-辛烯进行了催化共聚,利用核磁共振碳谱(13C-NMR)、凝胶渗透色谱(GPC)、差示扫描量热法(DSC)考察了聚合条件对催化剂催化性能的影响,对比了共聚物样品以及进口韩国SK公司的聚烯烃弹性体(POE)产品。结果表明:共聚物样品与SK公司的POE产品在13C-NMR中有相似的吸收峰,组成及聚集态结构相近;随催化剂Al/Ti比(摩尔比,下同)减小,催化活性增加,共聚物的重均相对分子质量(Mw)先减小后增大;聚合温度从90℃升高至130℃,催化活性降低,共聚物的相对分子质量减小,相对分子质量分布指数(PDI)变宽;当Al/Ti比为300时,共聚物Mw由24.36×10^4降至9.87×10^4;当Al/Ti比为150,聚合温度为110℃时,催化活性达到11.77×10^6g/(mol·h),共聚物Mw,PDI,熔融温度、结晶度依次为10.05×10^4,3.14,76.95℃,2.27%,1-辛烯插入率达到13.2%。The self-made half-metallocene catalyst MXC was used to catalyze the copolymerization of ethylene and 1-octene after activation by Al(i-Bu)3 and[Ph 3C]+[B(C6F5)4]-,and the effect of polymerization conditions on the catalytic performance of the catalyst was investigated by nuclear magnetic resonance(13C-NMR),gel permeation chromatography(GPC)and differential scanning calorimetry(DSC).The properties of the samples were compared to that of POE products from SK company.Results showed that the obtained samples had similar absorption peaks with the POE products of SK Company in 13C-NMR,and the composition and aggregation structure of the copolymer were similar.As the Al/Ti ratio(mole ratio)decreased,the catalytic activity increased,and the molecular weight(Mw)of the copolymer decreased first and then increased.When the polymerization temperature increased from 90℃to 130℃,the catalytic activity and Mw both decreased,while the molecular weight distribution(PDI)became wider.When the Al/Ti ratio was 300,the Mw of the copolymer decreased from 24.36×10^4 to 9.87×10^4.When the Al/Ti ratio was 150 and temperature was 110℃,the catalytic activity reached 11.77×10^6 g/(mol·h).Mw,PDI,T m and X c were sequentially 10.05×10^4,3.14,76.95℃and 2.27%,and the 1-octene content was 13.2%.

关 键 词：单茂金属催化剂 Al/Ti摩尔比 乙烯-1-辛烯共聚物 烯烃聚合 催化活性 13C-NMR 

分 类 号：TQ325.12[化学工程—合成树脂塑料工业]