基于双锂法的炔基功能化热塑性弹性体的合成  

Synthesis ofα,ω⁃End Alkynyl-functionalized Styrene-isoprene-styrene Polymer Based on Di-lithium Method

作　　者：杨琳燦 冷雪菲[1] 韩丽[1] 李超[1] 张松波 雷岚 马红卫[1] 李杨[1] YANG Lincan;LENG Xuefei;HAN Li;LI Chao;ZHANG Songbo;LEI Lan;MA Hongwei;LI Yang(State Key Laboratory of Fine Chemicals,Department of Polymer Science and Engineering,School of Chemical Engineering,Dalian University of Technology,Dalian 116024,China)

机构地区：[1]大连理工大学化工学院高分子材料系,精细化工国家重点实验室,大连116024

出　　处：《高等学校化学学报》2021年第3期866-874,共9页Chemical Journal of Chinese Universities

基　　金：国家重点研发计划项目(批准号:2017YFB0307101)资助.

摘　　要：苯乙烯-异戊二烯-苯乙烯三嵌段聚合物(SIS)是目前广泛使用的一种热塑性弹性体(TPE)材料,建立高效、精准、普适的SIS功能化方法一直是提高TPE材料性能的关键.首先,利用双烯单体与单官能度引发剂的反应合成了双官能度的双锂引发剂;然后采用双锂引发法,以炔基功能化单体封端,高效合成了α,ω-端炔基官能化SIS聚合物.采用叔丁醇锂作为异戊二烯聚合段的调节剂,叔丁醇钾作为苯乙烯聚合段的调节剂,合成了低乙烯基结构含量(5.8%)、窄分子量分布(<1.17)的SIS三嵌段聚合物;再向SIS三嵌段聚合物中一步加入炔基官能化的1,1-二苯基乙烯(DPE)衍生物进行封端,以高于90%的收率高效合成了α,ω-端炔基官能化SIS三嵌段模块聚合物,借助炔基的高效点击反应,实现了功能化及拓扑化TPE材料的制备.Styrene-isoprene-styrene(SIS)triblock polymer is widely used thermoplastic elastomer(TPE)ma⁃terial.Establishing an efficient,precise and universal method for SIS functionalization has always been the key to improve the properties of TPE materials.Herein,theα,ω-end alkynyl-functionalized SIS polymer was syn⁃thesized efficiently by using the di-lithium initiation method and capped with alkynyl-functionalized monomer.First,the bi-functional di-lithium initiator was synthesized by the reaction of diene monomer with monofunctional initiator.Then,using lithium t-butoxide as the additive of the isoprene polymerization and potassi⁃um t-butoxide as the additive of the styrene polymerization,SIS triblock polymer with low vinyl content(5.8%)and narrow polydispersity index(<1.17)was synthesized.Whereafter,using di-lithium compound as initiator,adding alkynyl-functionalized 1,1-diphenylethylene(DPE)derivative for end-capping in one step,theα,ω-end alkynyl-functionalized SIS triblock"brick"polymer was synthesized with efficiency higher than 90%.Com⁃bined with the study of“click”reaction of alkynyl group,the preparation of thermoplastic elastomer materials with functional groups and topology could be realized.

关 键 词：活性阴离子聚合 双锂引发剂 炔基功能化 热塑性弹性体 

分 类 号：O632.1[理学—高分子化学]