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

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.