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含二氮杂荼酮结构新型聚芳醚系列高性能聚合物的合成与性能
引用本文:蹇锡高,陈平,廖功雄,朱秀玲,张守海,王锦艳.含二氮杂荼酮结构新型聚芳醚系列高性能聚合物的合成与性能[J].高分子学报,2003(4):469-475.
作者姓名:蹇锡高  陈平  廖功雄  朱秀玲  张守海  王锦艳
作者单位:大连理工大学高分子材料系,大连,116012
基金项目:国家自然科学基金 (基金号 5 9473 0 19),国家“九五”重点科技攻关 (项目号 97 5 64 0 1 0 6和 97 5 64 0 1 0 7),“十五”国家 863计划 (项目号 2 0 0 1AA3 3 40 2 0 3 )资助项目
摘    要:从分子结构设计出发 ,以价廉易得的苯酚、苯酐为原料 ,经温和的工艺合成了结构全新的 4 ( 4′ 羟基苯基 ) 2 ,3 二氮杂萘 1 酮 (DHPZ) ,对其合成反应路线、合成反应动力学、反应机理进行了深入研究 .在大量实验研究基础上 ,结合分子立体结构的计算机模拟 ,确认其具有非共平面扭曲结构特征 ,其N—H键和O—H键具有类似的反应活性 ,是一种类似双酚的新单体 .以DHPZ与多种市售双卤单体如二氟二苯酮 (DFK)、二氯二苯砜 (DCS)、二氯二苯双酮 (DCKK)、二氯二苯腈 (DCBN)等经溶液亲核取代逐步聚合反应制得一系列含二氮杂萘酮结构的新型高性能聚醚砜 (PPES)、聚醚酮 (PPEK)、聚醚砜酮 (PPESK)、聚醚酮酮 (PPEKK)、聚醚砜酮酮(PPESKK)、聚醚腈酮 (PPENK)、聚醚腈砜 (PPENS)、聚醚腈砜酮 (PPENSK)等 ,对其结构进行了谱学表征 ,对其性能进行了全面测试 ,研究了其结构与性能关系 .谱学数据证明皆为无定型高聚物 .其玻璃化温度Tg 在 2 5 0~370℃之间 ,可以通过取代基团结构或主链上砜 酮基团比例进行调控 .在大量实验研究基础上 ,创造性提出“引入全芳环非共平面扭曲分子链结构赋予高聚物既耐高温又可溶解的优异综合性能”的分子结构设计理论 .在此分子设计理论指导下 ,设计并合成了含联苯二氮杂萘酮结构的新型二

关 键 词:4(4羟基苯基)2  3二氮杂萘1酮  聚芳醚聚合物  结构  性能  分子结构设计理论
修稿时间:2002年11月26

SYNTHESES AND PROPERTIES OF NOVEL HIGH PERFORMANCE SERIES POLY(AROMATIC ETHERS) POLYMERS CONTAINING PHTHALAZINONE MOIETIES
JIAN Xigao,CHEN Ping,LIAO Gongxiong,ZHU Xuling,ZHANG Shouhai,WANG Jinyan.SYNTHESES AND PROPERTIES OF NOVEL HIGH PERFORMANCE SERIES POLY(AROMATIC ETHERS) POLYMERS CONTAINING PHTHALAZINONE MOIETIES[J].Acta Polymerica Sinica,2003(4):469-475.
Authors:JIAN Xigao  CHEN Ping  LIAO Gongxiong  ZHU Xuling  ZHANG Shouhai  WANG Jinyan
Abstract:Based on molecular design,a novel biphenonl like monomer 4 (4′ hydroxyphenyl) 2,3 phthalazin 1 one (DHPZ) was originally synthesized through simple reactions from phenol and phthalic anhydride which are common and easily available chemicals.The synthesizing processes,reaction dynamics and mechanism were studied in detail.According to a lot of experiments and computer aided molecular simulation,it has been confirmed that this new compound has non coplanar and twisted structure and the hydrogen atoms in N—H and O—H bonds show similar polycondensation reactivity,so it is proved to be a biphenol like monomer.By solvent nucleophilic substitution polycondensation,a series of polymers such as poly(ether ketone)(PPEK),poly(ether sulfone)(PPES),poly(ether ketone ketone)(PPEKK),poly(ether sulfone ketone)(PPESK),poly(ether sulfone ketone ketone)(PPESKK),poly(ether nitrile ketone)(PPENK),poly(ether nitrile sulfone)(PPENS) and poly(ether nitrile sulfone ketone)(PPENSK),were successfully prepared from DHPZ,and commercial bihalogen monomers such as difluorodiphenylketone(DFK),dichlorodiphenylsulfone(DCS),4 (chlorobenzoyl)phenyl] (4 chlorophenyl)methanone(DCKK) and 2,6 dichlorobenzonitrile(DCBN).The structures of these resultant polymers were characterized by spectroscopy,and the properties of these polymers were measured.Also the relationships between structures and properties were thoroughly studied.Spectroscopic data show that all these polymers are amorphous.The glass transition temperatures of all these polymers are in the range of 250℃ to 370℃,which can be controlled by the substituted groups or the proportion of the ketone and sulfone groups in the backbones of the polymers.Based on these results,a new molecular designing theory was put forward that introducing the non coplanar twisted aramatic structure into polymers' backbones contributes to improving polymers' solubility and outstanding thermal resistance at the same time.Directed by this theory,a series of novel diamine,diacid and dianhydride monomers containing phthalazinone moities were successfully synthesized from DHPZ.And the corresponding polymers which have good solubility and outstanding thermal properties such as PPEA,PPEI,PPEAI were prepared.These polymers exhibit excellent comprehensive properties such as good solubility and outstanding thermal properties,forming a polymer system of new structure and high performance.
Keywords:Hydroxyphenyl)  2  3  pthalazin  1  one  Poly(aryl ether)s  Structure  Property  Molecular designing theory
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