含芳基均三嗪环耐高温低聚酰亚胺的合成与性能  

HEAT-RESISTANT OLIGO(PHTHALAZINONE IMIDE)S CONTAINING ARYL-s-TRIAZINE IN THE MAIN CHAIN

作　　者：刘程[1,2] 蔺恩成[1] 王锦艳[1,2] 宗立率[1] 蹇锡高[1,2] 

机构地区：[1]大连理工大学化工学院高分子材料研究所,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》2011年第5期560-566,共7页Acta Polymerica Sinica

基　　金：中央高校基本科研业务费专项资金(项目号DUT10LK15)资助

摘　　要：通过调控聚合单体的摩尔配比,合成了一系列新型的不同分子链长度的邻苯二甲腈封端含二氮杂萘酮联苯结构低聚酰亚胺,通过FTIR1、H-NMR、WAXD和元素分析对其结构进行表征.以4,4'-二氨基二苯砜为催化剂,低聚物经常压下固化交联后,得到含芳基均三嗪环结构的热固性聚酰亚胺.低聚物表现了良好的溶解性能,可溶于N-甲基-2-吡咯烷酮、间甲酚和吡啶中,而固化产物则不溶于任何溶剂.采用DSC、TGA和DTG对低聚物和固化产物进行了热性能分析,并考察了分子量对固化产物热性能的影响.结果表明低聚物具有较好的热稳定性和较高的玻璃化转变温度(Tg=200～249℃),而固化产物由于在交联过程中生成了含芳基均三嗪环的网状结构,使其展现了更优异的热稳定性,在100～400℃无玻璃化转变温度,5%热失重温度为522～532℃,10%热失重温度为556～567℃,800℃残碳率为69%～74%.A novel series of soluble and curable phthalonitrile-terminated oligo（phthalazinone imide）s with well controlled molecular weights were prepared by varying the molar ratio of dianhydrides to diamines.FTIR,1H-NMR and elemental analysis were applied to confirm the structures of the oligomers whose molecular weights were determined by 1H-NMR analysis.The crosslinking reactions of the phthalonitrile-terminated oligomers were performed under normal pressure in the presence of 4,4′-diaminodiphenylsulfone as catalyst at elevated temperatures to form the s-triazine rings-containing thermosetting oligo（phthalazinone imide）s.The oligomers possess good solubility in common aprotic solvents such as chloroform,pyridine,m-cresol and N-methyl-2-pyrrolidone due to the incorporation of crank,twisted and non-coplanar phthalazinone moiety into the polymer main chain,which disorders the close packing of the intermolecular chain.However,the cured samples are insoluble in all solvents because of the formation of the heterocyclic s-triazine networks during the crosslinking reaction of the cyano groups.The thermal properties of both the oligomers and the cured oligoimides were characterized by DSC,TGA and DTG.The oligomers have high glass transition temperatures（Tgs） in the range of 200～249℃.The cured samples show no Tg from 100～400℃ for the heterocyclic s-triazine networks decrease the flexibility of polymer backbone.And they exhibit excellent thermal stability with 5% weight loss temperature up to 522～532℃,10% weight loss temperature ranging from 556℃ to 567℃ and the carbonized residue values at 800℃ in the range of 69%～74%.For the excellent thermal stability of the cured oligoimides,they can be used as high performance polymeric materials in the aerospace and base materials for high temperature composite matrix.

关 键 词：聚酰亚胺 二氮杂萘酮联苯 邻苯二甲腈 芳基均三嗪环 热稳定性 

分 类 号：O633.22[理学—高分子化学]