含氰基和Cardo侧基马来酰亚胺封端聚醚酰亚胺的合成与性能  

Synthesis and Characterization of Maleimide-Capped Polyetherimides Containing Cyano and Cardo Side Groups

作　　者：熊需海[1] 刘东辉 任荣[1] 王静[1] 李桂阳 Xuhai Xiong;Donghui Liu;Rong Ren;Jing Wang;Guiyang Li(Liaoning Key Laboratory of Advanced Polymeric Composites,Shenyang Aerospace University,Shenyang 110136,China;Aerospace Research Institute of Materials&Processing Technology,Beijing 100076,China)

机构地区：[1]沈阳航空航天大学先进聚合物基复合材料辽宁省重点实验室,辽宁沈阳110136 [2]航天材料及工艺研究所,北京100076

出　　处：《高分子材料科学与工程》2023年第11期34-43,共10页Polymer Materials Science & Engineering

基　　金：国家自然科学基金资助项目(51873109);辽宁省科技重大专项(2019JH1/10100028)。

摘　　要：通过调整中间体二氨基化合物(CNMPDA)与双酚A二醚二酐(BPADA)的比例,设计并合成了3种不同相对分子质量的马来酰亚胺封端聚醚酰亚胺低聚物(CNMPEI)。采用傅里叶变换红外光谱和核磁共振氢谱对中间体和低聚物的化学结构进行了表征和分析;用凝胶渗透色谱法测定了低聚物的相对分子质量和分子量分布;对其堆积结构、溶解度、固化行为和机理、热稳定性及耐热性、复合材料的力学性能和耐溶剂性进行了系统研究。X射线衍射结果显示其衍射峰为弥散峰,为非晶态结构。这些低聚物在普通有机溶剂中具有良好的溶解性,其特性黏度在0.031~0.061 dL/g范围内。采用差示扫描量热仪测定了低聚物的热流曲线,在250℃以上出现了宽广的固化放热峰,马来酰亚胺和氰基分别在不同温度时参与了交联反应。CNMPEI聚合物具有较好的热稳定性,动态力学热分析结果显示,固化后的CNMPEI低聚物具有较高的耐热性。CNMPEI/CF复合材料具有优异的力学性能和耐溶剂腐蚀性。结果表明,在聚醚酰亚胺链中引入氰基和Cardo基团可以有效地改善其热性能。Three novel maleimide-capped polyetherimide oligomers containing cyano and Cardo side groups(CNMPEI)with different molecular weight were designed and synthesized by adjusting the ratio of intermediate diamino compound(CNMPDA)to bisphenol A diether dianhydride(BPADA).The chemical structures of the intermediates and as-prepared oligomers were characterized and analyzed by Fourier transform infrared(FT-IR)spectroscopy and hydrogen nuclear magnetic resonance(1H-NMR).The molecular weight and molecular weight distribution of the oligomers were determined by GPC.The stacking structure,solubility,curing behavior and mechanism,thermal stability,heat resistance,and mechanical properties and solvent resistance of the composites were also systematically studied.X-ray diffraction(XRD)results show a blunt diffraction peak,suggesting an amorphous structure.These oligomers have good solubility in common organic solvents,and the inherent viscosities are in the range of 0.031~0.061 dL/g.The heat flow curves of the oligomers measured by differential scanning calorimeter(DSC)display a broad curing exothermic peak above 250℃,maleimide and cyano groups participate in the crosslinking reaction at different temperatures.CNMPEI polymers have a good thermal stability,and the dynamic mechanical analysis(DMA)results show that the cured CNMPEI oligomers have a high heat resistance.CNMPEI/CF composites have excellent mechanical properties and solvent corrosion resistance.The results indicate that the introduction of cyano and Cardo moieties into polyetherimide chains can effectively improve their thermal properties.

关 键 词：聚醚酰亚胺 马来酰亚胺 氰基 Cardo基团 热性能 

分 类 号：TQ323.7[化学工程—合成树脂塑料工业]