橡胶技术网

合成橡胶工业
CHINA SYNTHETIC RUBBER INDUSTRY
2009 Vol.32 No.6 P.466-470

 橡胶技术网

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

宋顺玺　 张春庆　 李杨　 张雪涛　 郭欢欢　 王玉荣　

摘　要：以二乙二醇单乙醚基钡(简称Ba)/三异丁基铝(简称Al)/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(T_g)和熔点(T_m)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T_g上升5～10 ℃,而T_m升高幅度可达30 ℃;随着聚合温度的升高,HTPB的T_g和T_m均下降.
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 　文献标识码：A
文章编号：1000-1255(2009)06-0466-05

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

Song Shunxi（State Key Laboratory of Fine Chemicals, School of Chemical Engineering,Dalian University of Technology, Dalian 116012, China）　 Zhang Chunqing（State Key Laboratory of Fine Chemicals, School of Chemical Engineering,Dalian University of Technology, Dalian 116012, China）　 Li Yang（State Key Laboratory of Fine Chemicals, School of Chemical Engineering,Dalian University of Technology, Dalian 116012, China）　 Zhang Xuetao（State Key Laboratory of Fine Chemicals, School of Chemical Engineering,Dalian University of Technology, Dalian 116012, China）　 Guo Huanhuan（State Key Laboratory of Fine Chemicals, School of Chemical Engineering,Dalian University of Technology, Dalian 116012, China）　 Wang Yurong（State Key Laboratory of Fine Chemicals, School of Chemical Engineering,Dalian University of Technology, Dalian 116012, China）　

Abstract：High trans-1,4-polybutadiene(HTPB) was prepared with barium salt of di(ethyleneglycol) ethyl ether(simplified as Ba)/triisobutylaluminum(simplified as Al)/ multilithium(simplified as MLi) initiating system. Effect of component ratio of initiating system and polymerization temperature on trans-1,4-unit content, glass transition temperature(T_g) and melting point(T_m) 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′-tetramethylethylenediamine as polar additive. The mole fraction of trans-1,4-unit of HTPB reached the maximum of about 90% when Ba/Al/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 T_m was 30 ℃ with the increase of trans-1,4-content from 69.28% to 89.90%, while T_g increased by 5-10 ℃. T_m and T_g decreased with increasing polymerization temperature.
Keywords：barium salt of di(ethyleneglycol) ethyl ether; triisobutylaluminum; multilithium initiator;high trans-1,4-polybutadiene;anionic polymerization;microstructure;glass transition temperature;melting point

基金项目：中国石油天然气集团公司中青年创新基金资助项目(05 E 7006).
作者简介：宋顺玺(1983-),男,硕士研究生.已发表论文3篇.
作者单位：宋顺玺（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）　
　　　　　张春庆（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）　
　　　　　李杨（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）　
　　　　　张雪涛（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）　
　　　　　郭欢欢（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）　
　　　　　王玉荣（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）　

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收稿日期：2008年12月17日

修稿日期：2009年8月17日

出版日期：2009年11月15日