【作者】 张胜文；

【导师】 瞿雄伟；

【作者基本信息】 河北工业大学 ， 材料学， 2004， 硕士

【摘要】 本文通过原位聚合法制备了两种不同化学结构的聚甲亚胺／尼龙6(PAM／PA6)分子复合材料，PAM1为对苯二甲醛与1，6-己二胺反应制备的聚甲亚胺，PAM2为对苯二甲醛与4，4’-二氨基二苯醚合成的聚甲亚胺。研究中发现聚甲亚胺的端基对ε-己内酰胺的聚合有一定的阻聚作用。作者探讨和分析了聚甲亚胺端基类型对复合材料性能与结构的影响。 优化了复合材料的合成工艺条件，对聚甲亚胺的反应动力学、引发剂加入方式对尼龙聚合及尼龙微观形态的表征方法进行了研究。 通过实验对理论上得出的聚甲亚胺端基对尼龙阻聚影响的机理进行了初步验证，并利用红外光谱法对此进行了表征。结果表明，聚甲亚胺的醛端基与引发剂氢氧化钠发生了Cannizarro反应，从而对复合材料的制备产生阻聚影响。 改变聚甲亚胺合成所用醛／胺原始单体摩尔比的方法，可以减少醛端基在生成的聚甲亚胺分子中的含量。通过两个体系的PAM／PA-6复合材料的力学性能、SEM、XRD、DSC和TEM等测试方法研究复合材料的结构与性能间关系，表明聚甲亚胺端基对复合材料性能有一定的影响。 对于PAM1／AP-6体系，复合材料的拉伸强度随着醛／胺比值的减少呈现下降趋势，但是变化幅度不大，如在氢氧化钠加入量为0.09克的体系中，当醛／胺摩尔比由1.0减小到0.95时，复合材料的拉伸强度由64.6MPa减小到59.7MPa，变化率不到8％，而其冲击强度却由5.07 KJ／m~2增加到23.14KJ／m~2，增加了约3.56倍。 对于PAM2／PA-6体系，复合材料的拉伸强度与冲击强度随醛／胺摩尔比的变化趋势与引发剂用量有关，通过PAM2分子量、尼龙结晶度、球晶形态、SEM以及DSC等表征方法对这种变化趋势的研究表明，复合材料的力学性能与上述因素有密切的关系。 通过ε-己内酰胺单体先与引发剂氢氧化钠成盐的方法可以消除PAM分子链中醛端基对基体聚合的影响，为PAM／PA-6复合材料的工业化应用提供了一定的理论基础。更多还原

【Abstract】 In this paper, two kinds of Polyazomethine/nylon-6 (PAM/PA-6) composites with different chemical structures were prepared by means of in-situ polymerization. PAM1 and PAM2 were prepared from the reaction of Terephthalaldehyde with l,6-Hexanediamine(PAMl), and Terephthalaldehyde with 4,4’-Diamiediphenyl(PAM2). During the preparation, PAM chain ends played a retard role in the polymerization of s-caprolactam obviously. The effect of kind of PAM chain ends on the sub-micro morphologies and mechanical properties of PAM/PA-6 composites were characterized systematically.The preparation conditions of composite were optimized, including the initiator concentration (NaOH) and the molar ratio of aldehyde to amine. The polymerization kinetics of PAM, the feeding pattern of the initiator NaOH and a method used to characterize the spherulite morphology of monomer casting nylon were investigated.The mechanics of inhibition of PAM to the polymerization of nylon was certificated by means of a series of experiments. The results showed that the aldehyde end-group of PAM reacted with initiator NaOH of the polymerization of e-caprolactam through Cannizarro reaction by means of FT-IR technology.For the PAM1/nylon-6 composite, tensile strength reduced with the decreasing molar ratios of aldehyde to amine slightly. When the NaOH content was fixed 0.09g/100g e-caprolactam, and the aldehyde/amine was decreased from 1.0 to 0.95, the tensile strength of composite was changed from 63.6MPa to 59.7Mpa (<8%), while impact strength was increased from 5.07KJ/m2 to 23.14 KJ/m2 (increasing by 3.56 times). Through the characterization of the molecular weights of PAM, SEM and DSC of composite, the results clarified the change of mechanical properties of composites.The tensile strength and impact strength of PAM2/PA-6 composite showed that were related to the content of initiator NaOH for the polymerization of e-caprolactam. The intrinsic viscosity of PAM, SEM and the crystallinity of nylon phase carried out the results, which explained the change of mechanical properties of composites.Three methods of avoiding the effect of aldehyde end-group on the polymerization of e-caprolactam were compared. It was useful for the industrial application through the salting e-caprolactam monomer with the initiator NaOH firstly.更多还原