含1,4-萘基氯化聚芳醚酮酮无规共聚物的合成与性能

Synthesis and Properties of Cholorinated Poly(aryl ether ketone ketone) Random Copolymers Containing 1,4-naphthylene Moieties

以无水AlCl3为催化剂、ClCH2 CH2 Cl和NMP(N ,N 二甲基吡咯烷酮 )为复合溶剂 ,由二苯醚 (DPE) ,2 ,5 二氯对苯二甲酰氯 (DCTPC)和 4 ,4′ 二 (α 萘氧基 )二苯酮 (DNBP)通过亲电缩聚反应合成了一系列新型主链含1,4 亚萘基结构的氯化聚芳醚酮酮无规共聚物。优化后的工艺条件为 :n(AlCl3)∶n(DCTPC)∶n(DNBP +DPE) =0 0 6∶0 0 1∶0 0 1,预聚合温度小于 - 10℃下反应 2h ,再逐渐升温至 2 5℃左右反应约 8h。研究了DNBP结构单元及含氯侧基对共聚物性能的影响 ,并用IR、DSC、TG、WAXD等方法对其进行了表征。结果表明 ,所得聚合物在 193～2 12℃的温度范围内均只出现一个玻璃化温度 (Tg)转变峰 ,且随着共聚物中DNBP结构单元含量的增加 ,其Tg 逐渐升高 ,而熔融温度 (Tm)和结晶度逐渐降低。同时由于芳环上氯取代基的影响 ,降低了共聚物的热分解温度(Td) ,但仍具有良好的耐热性并且明显提高了阻燃性能和溶解性能。当x(DNBP) <30 %时 ,共聚物仍为半结晶性 ,并选择n(DNBP)∶n(DPE)在 10∶90～ 30∶70范围内为理想的聚合物加工成型条件。共聚物的断裂伸长率随着DNBP结构单元的引入逐渐增加 ,而拉伸强度和拉伸模量却有所下降。该类共聚物的拉伸强度可达 78MPa以上 ,拉伸模量在 2 8GPa以上 。

A series of novel chlorinated PEKK random copolymers containing 1,4-naphthalene moieties in the main ring were prepared by electrophilic copolycondensation of DNBP with diphenylether(DPE) and 2,5-dichloroterephthaloyl chloride(DCTPC) using AlCl 3 as catalyst, ClCH 2CH 2Cl and NMP as complex solvent. The optimal synthetic conditions obtained are as follows:the material proportion n(AlCl 3)∶n(DCTPC)∶n(DNBPDPE)0.06∶0.01∶0.01. The prepolymerization is for 2h below -10℃, then the reaction temperature is raised increasingly to 25℃ to be copolycondensed for about 8h. The effects of DNBP unit and pendant group with chloride on properties of copolymers were studied. The copolymers obtained were characterized by IR, DSC, TG, WAXD et al. The results indicate that each polymer obtained appears only a glass temperature transition peak in the range of from 193℃ to 212℃, and the Tg of the copolymers increases however the Tm and the crystallinity of the copolymers decrease with the increasing of DNBP content. The Td of the copolymers compared with PEKK drops sharply due to pendant group with chloride in the aryl ring, but the copolymers still have good thermostabilities and the solubility and combustion-resistance of the copolymers are improved greatly. When the content of DNBP is below 30mol%, the copolymers are semi-crystalline and the material proportion n(DNBP)∶n(DPE) used as an optimal processing condition is in the range of from 10∶90 to 30∶70. The elongation at break of the copolymers is increased owing to introduce DNBP unit, much higher than that of PEKK. However the tensile modulus and tensile strength of the copolymers are lower than those of PEKK, but the tensile strength or tensile modulus of the obtained polymers is more than 78MPa or 2.8GPa respectively, along with good mechanical property.