AlEt_(1.5)Cl_(1.5)与Al(OPhCH_3)(i-Bu)_2复配对钼系催化丁二烯聚合和产物微观结构的影响  

Effect of Compounding of AlEt_(1.5)Cl_(1.5) and Al(OPhCH_3)(i-Bu)_2 on Polymerization Reactivity of Butadiene Catalyzed by Mo-Based Catalyst and Microstructure of Products

作　　者：张彬彬 李培培 赵煊 华静[1] Binbin Zhang;Peipei Li;Xuan Zhao;Jing Hua(Key Laboratory of Rubber-Plastics of Ministry of Education,Qingdao University of Science & Technology, Qingdao 266042, China)

机构地区：[1]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：《高分子材料科学与工程》2019年第3期8-13,共6页Polymer Materials Science & Engineering

基　　金：山东省自然科学基金资助项目(ZR 2016EMM03)

摘　　要：采用MoCl_5·磷酸三丁酯(TBP)/Al(OPhCH_3)(i-Bu)_2和MoCl_5·TBP/AlEt_(1.5)Cl_(1.5)钼系催化体系催化丁二烯(Bd)配位聚合可分别制备高1,2含量的聚丁二烯橡胶(HVPB)和含反式(trans)-1,4-结构的部分结晶的聚丁二烯橡胶。在同一反应器中先加入Al(i-Bu)_2(OPhCH_3)/MoCl_5·TBP催化丁二烯聚合,然后单独加入AlEt_(1.5)Cl_(1.5)或同时加入AlEt_(1.5)Cl_(1.5)/MoCl_5·TBP,制备1,2-结构和trans-1,4结构在一定范围内可调的聚丁二烯的立构共混物。文中研究了催化剂的加入方式、第二组分加入时间和聚合温度等对聚合活性和产物结构的影响。实验结果表明,通过2种Al加入量的调节和反应条件的改变可实现1,2-结构含量和trans-1,4-结构含量分别在30%～80%和15%～60%范围内的调节,从而制得含一定结晶微区的无定形1,2-PB,有望提高1,2-PB的力学强度。Polybutadiene rubbers with high 1,2-structure contents (HVBR) and partially crystallized trans-1,4 structures were prepared by the coordination polymerization of butadiene (Bd) catalyzed by two types of catalyst systems of MoCl5·tributyl phosphate (TBP)/ Al(OPhCH3)(i-Bu)2 and MoCl5·TBP/ AlEt1.5Cl1.5, respectively. The Al(i-Bu)2(OPhCH3)/MoCl5·TBP catalyst system was firstly added into the reactor to initiate the polymerization of butadiene, and then AlEt1.5Cl1.5 was added alone or AlEt1.5Cl1.5/MoCl5·TBP was joined at the same time to prepare the polymerization blends, of which 1,2-struceres and trans-1,4 structures could be adjusted at a certain range. The effects of the adding way of catalyst, adding time of second components and reaction temperature on the polymerization reactivity and microstructures were investigated. The experimental results show that the contents of 1,2-structure and trans-1,4-structure could be adjusted from 30% to 80% and from 15% to 60% through control of the adding amounts of two kinds of Al and reaction conditions, which is beneficial to prepare amorphous 1,2-polybutadiene (1,2-PB) with a certain crystalline region and is expected to improve the tensile strength of 1,2-PB.

关 键 词：钼系催化剂 1 2-聚丁二烯 反式-1 4-聚丁二烯 结晶 

分 类 号：TQ333.2[化学工程—橡胶工业]