氮杂环单体的分子结构对共聚芳醚酮酮性能的影响  

The Effects of Structure of N-heterocyclic Monomers on the Performance of Copoly(aryl ether ketone ketone)s

作　　者：刘乾 王昭琪 杨晓庆 武楷文 符少奎 王旭[1] 张守海[1] 蹇锡高[1] Qian Liu;Zhao-qi Wang;Xiao-qing Yang;Kai-wen Wu;Shao-kui Fu;Xu Wang;Shou-hai Zhang;Xi-gao Jian(School of Chemical Engineering,National Key Laboratory of Fine Chemical Engineering,Liaoning High Performance Polymer Engineering Research Center,Liaoning Key Laboratory of Polymer Science and Engineering,Dalian University of Technology,Dalian 116024)

机构地区：[1]大连理工大学化工学院,精细化工国家重点实验室,辽宁省高性能树脂工程技术研究中心,辽宁省高分子科学与工程重点实验室,大连116024

出　　处：《高分子学报》2021年第9期1184-1191,共8页Acta Polymerica Sinica

基　　金：国家重点研发计划项目(项目号2017YFB0307600);国家自然科学基金(基金号91860204);国家自然科学基金委创新研究群体项目(项目号22021005);辽宁省“兴辽英才计划”项目(项目号XLYC1802073);大连市高层次人才创新支持计划(项目号2019RD08)资助。

摘　　要：合成4,4’-二苯基-7,7’-双(2,2’,3,3’)二氮杂萘(1,1’)酮(7,7-DBD)与4,4’-二苯基-6,7’-双(2,2’,3,3’)二氮杂萘(1,1’)酮(6,7-DBD)2种杂环单体,探究2种单体和4-(4-羟基苯基)-2,3-二氮杂萘酮与1,4-二(4-氟苯甲酰基)苯的共聚行为,得到2种侧苯基位置不同的氮杂环聚芳醚酮酮P-CDs与P-TDs.两者的特性黏度介于0.5~1.1 dL/g,P-CDs的特性黏度更高,制备更容易.P-CDs的玻璃化转变温度介于254~296℃,250℃的储能模量保持率高达67%,均高于相同共聚组成的P-TDs.2种聚合物可溶于N-甲基吡咯烷酮与1,1,2,2-四氯乙烷等有机溶剂中;拉伸模量介于1.56~1.78 GPa,拉伸强度介于50.1~102.9 MPa,断裂伸长率介于11.0%~18.1%,绝缘性基本一致.P-CDs的耐热性、溶解性、机械性能均优于P-TDs.故调整主链上侧基分布方式可以明显改变聚合物的耐热性、机械性能、溶解性和可制备性,为制备耐热等级更高且可溶解的高性能聚合物提供参考.4,4′-Diphenyl-6,7′-biphthalazin-1,1′(2 H,2′H)-dione(6,7-DBD)and 4,4′-diphenyl-7,7′-biphthalazin 1,1′(2 H,2′H)-dione(7,7-DBD)were synthesized.The copolymerization behaviors of two DBDs and 4-(4-hydroxyphenyl)-2,3-phthalazin-1-one with 1,4-bis(4-fluorobenzoyl)benzene were investigated,separately.N-heterocyclic copoly(aryl ether ketone ketone)s with different locations of side-phenyl groups(P-CDs and P-TDs)were obtained.The intrinsic viscosities(ηint)of the copolymers are in the range of 0.5-1.1 dL/g.P-CDs perform the easier preparation process and higherηintthan P-TDs.The glass transition temperature of P-CDs ranges from 254℃to 296℃,and the retention rate of storage modulus is up to 67%at 250℃,which is higher than that of P-TDs with the similar polymerization composition.Both copolymers are soluble in commom solvent,such as N-methylpyrrolidone and1,1,2,2-tetrachloroethane.The tensile modulus is in the range of 1.56-1.78 GPa,the tensile strength is in the range of 50.1-102.9 MPa,the elongation at break is in the range of 11.0%-18.1%,and the insulation properties are little short of the same.In summary,P-CDs exhibit better heat resistance,solubility,and mechanical proteties than P-TDs.It can be found that adjusting the distribution of side phenyl in main chains can significantly affect the thermal stability,mechanical property,solubility,and preparability of the polymer,which provides an attempt direction for the preparation of high-performance polymers with high heat resistance and solubility.

关 键 词：分子结构 聚芳醚 双二氮杂萘酮 溶解性 耐热性 

分 类 号：TQ317[化学工程—高聚物工业]