磷酸三丁酯对钼催化体系聚合丁二烯的影响  

Effect of tributyl phosphate on molybdenum-based catalyst system catalyzed polymerization of butadiene

作　　者：田维[1] 田健[1] 耿洁婷[1] 华静[1] 徐玲[1] 

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：《合成橡胶工业》2009年第3期196-200,共5页China Synthetic Rubber Industry

基　　金：国家自然科学基金资助项目(50603009)。

摘　　要：以磷酸三丁酯（TBP）改性MoCl5（简称MoTBP）为主催化剂，Al（OPhCH3）（i-Bu）2（简称Al）为助催化剂催化聚合丁二烯（Bd），通过紫外可见光谱对MoTBP的催化行为进行了表征，探讨了TBP用量对Bd聚合反应的影响，研究了适宜的聚合条件，并与辛醇取代MoCl5[MoCl3（OC8H17）2]催化体系进行了比较。结果表明，经TBP改性MoCl5，催化活性明显提高，TBP与MoCl5最佳摩尔比为2．0；最佳聚合条件：Al／MoTBP（摩尔比）为20，MoTBP／Bd（摩尔比）为（1．0—3．0）×10^-4，Bd质量浓度为0．14g／mL，聚合温度为60℃，聚合时间为6h；与MoCl3（OC8H17）2体系相比，MoTBP体系催化聚合所得1，2-聚丁二烯的相对分子质量减小，相对分子质量分布加宽，1，2-结构摩尔分数为85．7％左右，其中以全同立构体（摩尔分数为53．25％）为主，且含有质量分数小于0．32％的凝胶。Butadiene was polymerized with main catalyst Morse [ MoCl5 modified by tributyl phosphate （TBP） ] , promoter Al（ OPhCH3 ） （ i-Bu）2 （ simplified as Al）. The catalytic theory of MoTBP was characterized by ultraviolet visible spectrum. The effects of TBP amounts on polymerization of butadiene were investigated, the optimum polymerization conditions were studied, and compared with the catalyst system MoCl3（OC8H17）2. The results showed that the activity of MoTBP in hydrogenated gasoline was improved, and the optimum mole ratio of TBP to MoCl5 was 2. 0. The optimum polymerization conditions were Al/MoTBP （mole ratio ） 20, MoTBP/Bd （mole ratio）（1.0-3.0） ×10^-4,[Bd] 0. 14 g/mL at 60℃ for 6 h. Compared with MoCl3 （ OC8H17） 2, the relative molecular mass of 1,2-polybutadiene based MoTBP catalyst system was reduced, the relative molecular mass distribution was widened, and the mole fraction of 1,2-unit and isotactic isomer were 85.7% , 53.25% ,respectively.

关 键 词：磷酸三丁酯 五氯化钼 催化 丁二烯 聚合 

分 类 号：TQ333.2[化学工程—橡胶工业]