钼系催化体系制备高乙烯基含量丁苯共聚物的研究  

Study on Preparation of Bd-St Copolymer with High Vinyl Content by Molybdenum Catalytic System

作　　者：焦胜成[1] 华静[2] 李培培 JIAO Shengcheng;HUA Jing;LI Peipei(Rubber Plant,Sinopec Qilu Petrochemical Company,Zibo 255400,China;Qingdao University of Science and Technology,Qingdao 266042,China)

机构地区：[1]中国石化齐鲁分公司橡胶厂,山东淄博255400 [2]青岛科技大学橡塑材料与工程教育部重点实验室,山东青岛266042

出　　处：《橡胶工业》2021年第1期31-37,共7页China Rubber Industry

基　　金：山东省自然科学基金资助项目(ZR2017MEM021)。

摘　　要：以磷酸三丁酯(TBP)为配体改性的五氯化钼(MoCl5)为主催化剂、二丁基镁[Mg(Bu)2]为助催化剂组成二元催化体系,在丁二烯(Bd)物质的量浓度为2.6×103 mol·L-1和Bd/苯乙烯(St)质量比为3的条件下进行丁苯共聚物的配位聚合,研究催化体系和聚合条件对聚合反应的影响,并采用凝胶渗透色谱、傅里叶变换红外光谱、核磁共振氢谱、差示扫描量热法等对共聚物的微观结构进行分析。试验得出的最佳反应条件为:TBP/MoCl5物质的量比2,MoCl5/单体物质的量比1×10-3,Mg(Bu)2/MoCl5物质的量比3,聚合温度70℃,聚合时间12 h。在该条件下,Bd和St聚合活性较高,共聚物的数均相对分子质量为1.24×105,相对分子质量分布较宽,Bd单元中1,2-结构物质的量分数大于0.85,聚合产物为高乙烯基含量无规丁苯共聚物。The coordination polymerization of butadiene(Bd)and styrene(St)was carried out with binary molybdenum catalytic system which consisted of the main catalyst of molybdenum pentachloride(MoCl5)modified by tributyl phosphate(TBP)ligands and co-catalyst dibutyl magnesium[Mg(Bu)2]under the condition that the mole concentration of Bd was 2.6×103 mol·mL-1 and the mass ratio of Bd/St was 3.The effects of the catalytic system and polymerization conditions on the polymerization reaction were investigated,and the microstructure of the copolymer was analyzed by GPC,FTIR,1 H MNR and DSC.The results showed that,the optimum reaction conditions were as follows:the mole ratio of TBP/MoCl5 was 2,the mole ratio of MoCl5/monomer was 1×10-3,the mole ratio of Mg(Bu)2/MoCl5 was 3,the polymerization temperature was 70℃,and the polymerization time was 12 h.Under these conditions,the copolymerization activity of Bd and St was relatively high,the number average molecular weight of the copolymer was up to 1.24×105,the relative molecular weight distribution was wide,and Bd unit was mainly 1,2-structure with mole fraction over 0.85.The polymerization product was random Bd-St copolymer with high vinyl content.

关 键 词：钼系催化剂 丁苯共聚物 乙烯基含量 配位聚合 聚合活性 特性粘数 相对分子质量 

分 类 号：TQ330.53[化学工程—橡胶工业]