氟取代聚芳醚酮低温合成及其结构研究  

Synthesis of Fluorine-substituted Poly(aryl ether ketone)s under Low Temperature and Its Structure

作　　者：董大林 宾月珍[1] 蹇锡高[1,2] Da-lin Dong;Yue-zhen Bin;Xi-gao Jian(Department of Polymer Materials,Dalian University of Technology,Dalian 116024;Liaoning Province Engineering Technology Center of High Performance Resins,Dalian 116024)

机构地区：[1]大连理工大学高分子材料系,大连116024 [2]辽宁省高性能树脂工程技术研究中心,大连116024

出　　处：《高分子学报》2022年第3期261-272,共12页Acta Polymerica Sinica

基　　金：国家自然科学基金(基金号21374014,U1663226)资助项目。

摘　　要：通过傅克酰基化反应合成4,4’-二(4-氟苯甲酰基)二苯醚、4,4’-二(五氟苯甲酰基)二苯醚、4,4’-二(4-氟苯甲酰基)二苯硫醚以及4,4’-二(五氟苯甲酰基)二苯醚4种长链双卤单体,并进一步制备了含二氮杂萘酮聚芳醚酮聚合物.通过多氟取代双卤单体在含二氮杂萘酮聚芳醚酮聚合物主链中引入氟原子.多氟取代双卤单体具有多个反应位点,低温反应以及两步投料的聚合路线保证了溶液缩聚反应在多氟取代双卤单体的指定位点进行,保证了氟取代含二氮杂萘酮聚芳醚酮聚合物的线形结构并具有一定的分子量.讨论了氟原子的引入对于含二氮杂萘酮聚芳醚酮聚合物合成路线、分子结构、数均分子量、热性能以及序列结构的影响.Poly(aryl ether ketone)s are high performance engineering plastics with excellent comprehensive performance.They are usually prepared by solution polycondensation at high temperature with bisphenol monomers and dihalogen monomer.Polycondensation at high temperature makes it difficult to prepare and raises production costs.As a result,preparation of poly(aryl ether ketone)s at low temperature is significant in scientific research and industrial production.On the other hand,introduction of fluorine atoms into poly(aryl ether ketone)s with phthalazinone can optimize comprehensive properties.Here,fluorine atoms are introduced in dihalogen monomers to prepare fluorine substituted poly(aryl ether ketone)s at low temperature.Long-chain dihalogenated monomers are obtained by Friedel-Crafts acylation reaction with pentafluorobenzoic acid instead of p-fluorobenzoic acid.Fluorine substituted long-chain dihalogenated monomers are used in preparation of poly(aryl ether ketone)s with phthalazinone at low temperature.Fluorine atoms were introduced into main chain of poly(aryl ether ketone)s containing phthalazinone.Polyfluorosubstituted dihalogenated monomers have multiple reaction sites.Low temperature reaction and two-step feeding polymerization route ensure that solution polycondensation reaction is carried out at certain position of polyfluorosubstituted dihalogenated monomers and that fluorine substituted poly(aryl ether ketone)s with phthalazinone are linear polymers.The introduction of fluorine atoms has an impact on synthetic route,molecular structure,number average molecular weight,thermal properties and sequence structure of poly(aryl ether ketone)s with phthalazinone.Two kinds of fluorine substituted poly(aryl ether ketone)s with phthalazinone synthesised with long-chain dihalogenated monomers are amorphous polymers.With the introduction of fluorine atoms,glass transition temperatures of the corresponding poly(aryl ether ketone)s with phthalazinone are improved;while number-average molecule weight and thermal decompo

关 键 词：二氮杂萘酮 聚芳醚酮 氟取代 序列结构 

分 类 号：TQ316[化学工程—高聚物工业]