【作者】 许芸芸；

【导师】 钦维民；

【作者基本信息】 东华大学 ， 应用化学， 2007， 硕士

【摘要】 随着高新技术与产业的迅猛发展，性能优异的聚酰亚胺材料成为先进材料发展的一个重要方向，其应用涉及到航空、航天、微电子、光电信息和膜分离等领域。聚酰亚胺是一类以酰亚胺环为结构特征的高分子聚合物。通常的芳香聚酰亚胺难熔、也不溶于常规有机溶剂，加工成型困难。所以，人们通常将聚酰胺酸加工成型(涂覆成薄膜或拉成纤维等)，然后加热脱水环化制成各种聚酰亚胺制品。在聚酰亚胺主链中引入柔性基团是提高其溶解性能的一种常用方法。本论文工作对柔性基团进行选择，设计合成含有脂环、酯键、醚键的芳香二胺，通过改变主链上柔性基团的种类与数量，从而对聚酰亚胺进行改性，期望在聚酰亚胺大分子主链中引入柔性基团后可以改善其溶解性能，同时又保持其优异的热性能和力学性能。本论文以1，4-环己烷二甲醇(CHDM)为原料，分别与对硝基苯甲酰氯、对氯硝基苯通过酯化反应和Williamsion反应合成了1，4-双(4-硝基苯甲酰氧亚甲基)环己烷和1，4-双(4-硝基苯氧亚甲基)环己烷，再经水合肼还原得到目标产物：1，4-双(4-氨基苯甲酰氧亚甲基)环己烷和1，4-双(4-氨基苯氧亚甲基)环己烷。通过红外(FT-IR)，核磁共振(~1UNMg)及元素分析(EA)对其结构进行了验证，结果表明符合预期的结构式。将合成的两种二胺单体分别与芳香族二酐：3，3’，4，4’—二苯醚四羧酸二酐(ODPA)和均苯四甲酸酐(PMDA)在非质子极性溶剂中溶液缩聚，再经化学酰亚胺化法制备出一系列主链含有脂环结构的改性聚酰亚胺；对其结构进行表征，同时探讨结构与性能的关系。溶解性试验表明大分子链中同时含有酯基和醚键的聚酰亚胺具有良好的溶解性，脂环族改性聚酰亚胺的溶解性能随着柔性基团增加而提高；热性能分析结果显示脂环型改性聚酰亚胺的玻璃化温度和热分解温度都稍有降低，但仍然保持了较好的热性能；X—ray射线测试表明，该类聚酰亚胺有一定的结晶度，分子呈有序性排列。更多还原

【Abstract】 With the rapid development of high technology and industry,polyimide has become an important direction of advanced materials. Theyhave been extensively used in many fields such as avigation,photoelectricity and micro-electronics. Polyimide is a kind of polymerswhich contains imide rings. However, aromatic polyimide is traditionallydifficult to be processed because of its insolubility in organic solvents andhigh processing temperature. It was usually processed in form of itspoly(amicacid) prepolymer, then the prepolymer was imidized topolyimide.Introducing flexible groups into polyimide’s main chain is aconventional method to improve the solubility, and by choosing flexiblegroups also can get some special functions. The study of modified andfunctional polyimide has become popular recently. Following thistendency, we designed a novel diamine monomer containing alicyclicstructure in this article. We hoped that by introducing flexible group intopolyimide’s main chain can improve polyimide’s solubility and maintainits high themal stability. We synthesized two flexible diamine monomers1,4-bis(4-aminobenzoyloxymethylene)cyclohexane and 1,4-bis(4-aminoph-enzoyoxymethylene)cyclohexane which with alicyclic ring, ester-bond,ether-bond. They were synthesized from 1,4-cyclohexane dimethanol. Thestructure of the diamines was verified by Fourier Transform Infraredspectroscopy (FT-IR), Proton Nuclear Magnetic Resonance (~1HNMR) andElementary Analysis (EA).The prepared diamine monomers were condensed with two aromaticdianhydride monomers 3,3’,4,4’-oxydiphthalic dianhydride(ODPA) andpyromellitic dianhydride(PMDA) respectively and then chemicallyimidized to prepare polyimides. The structures of these alicyclicpolyimides were characterized, meanwhile we explore the relationshipbetween its structure and properties. The solubility test indicated thatalicyclic polyimide, containing both ester-bond and ether-bond, has goodsolubility. The research also indicated that modified alicyclic polyimide’ssolubility would improve while flexible groups increase. The thermalproperties of the alicyclic polyimides were characterized by means ofDifferential Scanning Calorimetry (DSC) and Thermogravimetric Analysis(TGA). All the modified polyimides indicated good thermal propertieswith initial thermal decomposition temperature. The X-ray diffractioncurves of these alicyclic polyimides showed that some crystallinemorphologies are related to rigidity and planar structure of the polymer chains.Xu Yunyun (Applied Chemistry)Supervised by Qin Weimin更多还原