亲电缩聚反应合成芳香环状低聚醚酮砜及其开环聚合  

SYNTHESIS OF MACROCYCLIC ARYL ETHER KETONE SULFONE OLIGOMERS VIA ELECTROPHILIC REACTION AND THEIR THEIR RING-OPENING POLYMERIZATION

作　　者：郭庆中[1] 肖颖[1] 喻湘华[1] 程志毓[1] 陈天禄[2] 

机构地区：[1]武汉工程大学材料科学与工程学院,武汉430073 [2]中国科学院长春应用化学研究所,长春130022

出　　处：《高分子学报》2010年第5期536-541,共6页Acta Polymerica Sinica

基　　金：国家自然科学基金(基金号20904045);湖北省教育厅优秀中青年项目(项目号Q20081506);武汉市科学技术局青年晨光计划项目(项目号200750731257)资助

摘　　要："假高稀"条件下,以邻苯二酰氯为酰基化试剂,Lewis碱NMP存在下,通过亲电缩聚反应高产率地合成了2种芳香环状聚醚酮砜低聚物,利用MALDI-TOF-MS,NMR,GPC,FTIR,DSC等手段对环状结构进行了精确的表征.在负离子引发剂联苯双酚钾存在下,环状低聚物3a进行熔融开环聚合,得到了高分子量的线型聚合物,Tg为221.8℃.利用流变仪监测了环状低聚物3a开环聚合过程中的流变行为,结果表明,开环聚合初期的引发阶段,熔融体的黏度低于10Pa.s,随着时间的延长,黏度快速增长,而且低黏度的引发阶段随着引发剂浓度的增加而变短.Under pseudo-high dilution conditions,two kinds of macrocyclic aryl ether ketone sulfone oligomers have been synthesized in high yield from phthaloyl dichloride and electron-rich aromatic hydrocarbons in the presence of Lewis base via electrophilic reaction. The presence of Lewis base NMP in this reaction is demonstrated to be advantageous for forming macrocyclic oligomers. Detailed structural characterization of the oligomers confirmed the cyclic nature by a combination of MALDI-TOF-MS,GPC,IR and 1↑H-NMR analyses. The cyclic ether ketone sulfone oligomers 3a readily undergo anionic ring-opening polymerization in the melt by using potassium 4,4＇-biphenoxide as the initiator,producing linear,high molecular weight poly（ ether ketone sulfone） with Tg of 221. 8℃ and excellent thermal stability. Moreover,the isothermal chemorheology of the ringopening polymerization of cyclic oligomers 3a was also investigated. The results show that the shear viscosity of the molten reactive mixture increases slowly and is lower than 10 Pa.s at a constant shear rate of 0. 05 rad /s in the initial stage of ring-opening polymerization,and the length of the initial stage shortens as the content of initiator increases.

关 键 词：亲电反应 芳香环状低聚物 开环聚合 流变行为 

分 类 号：TQ326.5[化学工程—合成树脂塑料工业]