【摘要】 使用3,3’,4,4’-联苯四酸二酐(s-BPDA),1,3,-双(4-氨基苯氧基)苯(TPER)和苯酐(PA)反应合成了一种半结晶型聚酰亚胺.根据DSC记录的不同速率下降温所得到的结晶放热曲线,分别采用Jeziorny、Ozawa及莫志深提出的方法对其非等温结晶行为进行了研究.发现由Jeziorny方法分析得到的曲线主要由两阶段构成,表观Avrami指数n由直线部分获得,由于二次结晶的出现,曲线后期偏离直线甚至出现波动;由Ozawa方法分析得到的曲线线性关系很差;而采用莫志深的方法分析时得到了一系列线性关系较好的直线,求得准确a、F(T)和m值;最后应用Kissinger方法求得从熔体降温过程的结晶活化能ΔE.实验结果表明该聚合物是一个很特殊的体系,具有非常快的结晶成核速率;当降温速率达到20 K/min之后,结晶成核机理或结晶生长方式发生了改变.更多还原

【Abstract】 A semicrystalline polyimide was synthesized from 3,3′,4,4′-biphenyltetracarboxylic dianhydride(s-BPDA)/1,3-bis-(4-aminophenoxy)benzene(TPER)/phthalic anhydride(PA).According to the crystallization exothermic peaks obtained from differential scanning calorimetry(DSC)when cooling from melt at 2,5,10,20 K/min,respectively,the method of Jeziorny,Ozawa and an approach proposed by MO Zhishen were applied to study the non-isothermal crystallization behaviour of this polyimide.The results suggested that s-BPDA/TPER/PA was a very special system,the onset crystallization temperatures were almost the same at different cooling rates.The apparent Avrami exponent n obtained by the Jeziorny method was 2.4 and then changed to 3.5 when cooling rate reached 20 K/min,indicating the mechanism of nucleation or the way of growth have changed.Besides,the kinetic parameter Zc increased with the increase of the cooling rate.Whereas deviations and fluctuations occurred in the later stage due to the secondary crystallization.The Ozawa method was also limited in obtaining the reliable kinetic parameters because of the substantial curvatures in the Ozawa plots.However,the approach proposed by Mo Zhishen appeared applicable due to the better linear relation,according to the new parameter a,the relationship between Ozawa exponent m and apparent Avrami exponent n was confirmed(n/m=1.3)and exact values of m were obtained.Finally,Kissinger method was used to get the value of the crystallization activation energy ΔE,about-936 kJ/mol,which meant a fast nucleation rate of this system.更多还原