二乙二醇单乙醚基钡/三异丁基铝/多锂体系合成高反式-1,4-聚丁二烯  

Synthesis of high trans-1,4-polybutadiene with barium salt of di(ethyleneglycol) ethyl ether/triisobutylaluminum/multilithium system

作　　者：宋顺玺[1] 张春庆[1] 李杨[1] 张雪涛[1] 郭欢欢[1] 王玉荣[1] 

机构地区：[1]大连理工大学化工学院精细化工国家重点实验室,辽宁大连116012

出　　处：《合成橡胶工业》2009年第6期466-470,共5页China Synthetic Rubber Industry

基　　金：中国石油天然气集团公司中青年创新基金资助项目(05E7006)

摘　　要：以二乙二醇单乙醚基钡（简称Ba）／三异丁基铝（简称A1）／多锂（简称MLi）组成的三元引发体系制得了高反式-1，4-聚丁二烯（HTPB），考察了引发体系各组分配比及聚合温度对HTPB反式结构含量及其玻璃化转变温度（Tg）和熔点（Tm）的影响。结果表明，以MLi为引发剂，四甲基乙二胺为极性调节剂，可以得到最大臂数为3.64、平均臂数约为2.50的星形聚丁二烯；当聚合温度为50℃、Ba／Al／MLi（摩尔比）为1／4／4时，HTPB的反式结构摩尔分数最高，接近90％；升高聚合温度使聚丁二烯的反式结构摩尔分数下降；当HTPB的反式结构摩尔分数由69.28％增至89.90％时，其Tg上升5-10℃，而Tm升高幅度可达30℃；随着聚合温度的升高，HTPB的Tg和Tm均下降。High trans-1,4-polybutadiene （ HTPB ） was prepared with barium salt of di （ethyleneglycol） ethyl ether （ simplified as Ba）/triisobutylaluminum （simplified as A1）/ muhilithium（simplified as MLi） initiating system. Effect of component ratio of initiating system and polymerization temperature on trans-1,4-unit content, glass transition temperature （Tg） and melting point （Tm） of HTPB were investigated. The results showed that the star polybutadiene （PB） with the maximum arm number of 3.64 and average arm number of 2.50 were obtained with self-made MLi as initiator and N,N,N＇, N＇-tetramethylethylene-diamine as polar additive. The mole fraction of trans-1,4-unit of HTPB reached the maximum of about 90% when Ba/A1/MLi （mole ratio） was 1/4/4 at 50℃. The mole fraction of trans-1,4-unit of PB decreased with increasing polymerization temperature. The increase extent of Tm was 30℃ with the increase of trans-1,4-content from 69.28% to 89.90% , while Ts increased by 5-10℃. Tm and Tg decreased with increasing polymerization temperature.

关 键 词：二乙二醇单乙醚基钡 三异丁基铝 多锂引发剂 高反式-1 4-聚丁二烯 负离子聚合 微观结构 玻璃化转变温度 熔点 

分 类 号：TQ333.2[化学工程—橡胶工业]