四氢呋喃基胺-醚类调节剂对聚共轭二烯烃微观结构影响  

The Microstructure Influence of Tetrahydrofuranyl [N,O]-Chelated Polar-Additives on Anionic Polymerization of Conjugated Dienes

作　　者：谢锋历 杨帅 熊巧巧 古卓玮 彭承俊 肖哲 龚林林 袁煜艳 梁智英 佘振银 夏金魁 蔡江伟 李安 刘坤 XIE Feng-li;YANG Shuai;XIONG Qiao-qiao;GU Zhuo-wei;PENG Cheng-jun;XIAO Zhe;GONG Lin-lin;YUAN Yu-yan;LIANG Zhi-ying;SHE Zhen-yin;XIA Jin-kui;CAI Jiang-wei;LI An;LIU Kun(College of Chemistry and Chemical Engineering,Hunan Institute of Science and Technology,Yueyang 414000,China;China Petroleum and Chemical Corporation Baling Branch,Yueyang414000,China;Yueyang Xingyue Petroleum and Chemical Limited Liability Corporation,Yueyang 414000,China)

机构地区：[1]湖南理工学院化学化工学院,岳阳414000 [2]中石化巴陵石油化工有限公司,岳阳414000 [3]岳阳兴岳石油化工有限责任公司,岳阳414000

出　　处：《高分子通报》2023年第4期495-504,共10页Polymer Bulletin

基　　金：国家自然科学基金青年项目(21901070);湖南省自然科学基金青年项目(2019JJ50213);湖南省教育厅重点项目(20B263);中石化巴陵石油化工有限公司博士后项目;湖南省创新群体项目(2020JJ1004)资助。

摘　　要：聚共轭二烯烃微观结构直接影响产品弹性、结晶性、耐热性、加氢、阻尼等性能。为系统探索四氢呋喃基胺-醚类调节剂(PA)对共轭二烯烃阴离子聚合微观结构的影响,本文选取N,N-二甲基四氢糠胺(DMTHFA)、N-四氢糠基吗啉(THFM)、N-四氢糠基哌啶(THFHP)和N-四氢糠基吡咯(THFP)四种高效调节剂对正丁基锂(n-BuLi)引发丁二烯(BD)、异戊二烯(IP)和间戊二烯(PD)阴离子聚合的影响,同时与工业常用的四氢呋喃(THF)进行对比。通过核磁共振氢谱(1H-NMR)数据分析表明:(1)四氢呋喃基胺-醚类调节剂都具有微量高效调节作用,可用于生产中高支化度聚丁二烯橡胶(10%~88%)及聚异戊二烯橡胶(10%~89%),但聚间戊二烯1,2-结构含量仅能在20%~38%范围内调控摩尔比(PA/Li≤4.0);(2)在DMTHFA和THFM调节剂作用下,聚丁二烯和聚异戊二烯支化结构随着温度升高而降低,聚间戊二烯支化结构却略有增加,且DMTHFA调节剂对温度不敏感;(3)反应釜放大SEBS实验表明该类型调节剂能显著提升聚合速率,调节能力及加氢性能均优于现有工业装置醚类调节剂,具有工业化前景。The microstructure of polydienes directly affects the elasticity, crystallinity, heat resistance, hydrogenation, damping and other properties of the product. In order to explore the influence of tetrahydrofuranyl [N,O]-chelated polar-additives(PA) on microstructure of anionic polymerization of conjugated dienes, four high-efficient PAs including N,N-dimethyl-tetrahydrofurfuralamide(DMTHFA), N-tetrahydrofuromorpholine(THFM), N-tetrahydrofuropipine(THFHP) and N-tetrahy-drofurfuryl pyrrole(THFP) were selected to co-initiate butadiene(BD), isoprene(IP) and 1,3-pentadiene(PD) polymerization with n-BuLi. It is also compared with tetrahydrofuran(THF) commonly used in industry. The results based on ~1H-NMR data showed that:(1) all PAs had highly efficient regulation(molar ratio, PA/Li≤4.0), which can be used for the production of medium and high branched polybutadiene and polyisoprene rubber. However, the 1,2-polypentadiene can only be regulated in the range of 20%~38% due to its special molecular conformation;(2) under the effect of DMTHFA and THFM, the branched structure of polybutadiene and polyisoprene decreased with increasing temperature, but the 1,2-polypentadiene increased slightly. Interestingly, the DMTHFA is not sensitive to temperature;(3) the amplification experiment showed that PA can significantly increase the polymerization rate and the regulation ability is better than that of the ether regulator used in industry equipment. Moreover, the PA had positive effect on the hydrogenation degree of the SBS, which has the prospect of industrialization.

关 键 词：胺-醚类调节剂 共轭二烯烃 阴离子聚合 微观结构 支化结构 

分 类 号：TQ317[化学工程—高聚物工业]