酞菁改性马来酰亚胺树脂体系的研究
摘要
高性能复合材料在能源、交通、航空及航天领域获得了广泛的应用。发展加工性能好、耐高温、力学性能优异的树脂始终是复合材料研究工作者追求的目标。马来酰亚胺是高性能先进复合材料基体树脂的重要品种，既有类似聚酰亚胺的耐高温、耐辐射、耐湿热等多种优良特性，又有类似环氧树脂的易加工性能，在多方面满足了先进树脂基复合材料的要求。因此，其作为一种高性能树脂基体受到了越来越多的关注。但是由于固化交联密度高，固化后所得材料表现出较大的脆性。改性马来酰亚胺树脂的研究主要集中在如何有效保持材料优良的耐热性、电学性能和高模量的同时改善材料的韧性。不管是物理共混改性或化学反应改性，往往会不同程度地降低马来酰亚胺树脂的耐热性能。
近年来，Keller等人对基于邻苯二甲腈单体的热固性酞菁树脂做了大量的研究工作。研究结果表明酞菁树脂具有优异的耐热性和热氧稳定性，通过控制固化催化剂用量和后固化条件可在较大范围内控制所得材料的热性能和机械性能。用酞菁树脂改性马来酰亚胺树脂引起了我们极大的兴趣，到目前为止，还未见文献报道。
我们合成了两种含有氰基的马来酰亚胺，并证明了结构。利用热分析手段研究该类化合物的固化反应机理和固化产物的热性能，证明了邻苯二甲腈基导入马来酰亚胺分子结构中，可以有效地提高马来酰亚胺树脂的热交联产物的高温热性能，提高残碳量。
我们利用常见的二元胺改性马来酰亚胺的方法，在含有氰基的马来酰亚胺化合物中引入胺类物质做为酞菁固化交联的催化剂，并证明了结构。利用热分析手段研究该固化体系的固化反应机理和固化产物的热性能。我们对前述的含有氰基的马来酰亚胺化合物做溶液中的自由基聚合反应，研究了反应条件对该反应的影响。对其均聚物的分子量，溶解性能和热行为做了一个初步的研究。
The high performance composite materials have been applied in the fields of energy, transportation, aviation and aerospace extensively. Developing the resin which has the excellent processability, heat resisting and mechanical properties is the target that researchers who dedicated to the composite material always pursues.
The maleimide is the important species of the advanced high performance polymeric composition. It has not only the heat, radiation and damp resisting property of maleimide, which are similar with the polyimide, but also the similar processability of epoxy resins; it can satisfy the requirement of the advanced resin in much aspect. Therefore, it is a kind of high performance resin to be subjected to more and more concerns. But due to the high crosslinking density after cured, the cured product become more brittleness. So the study on modification of maleimide resin is focused on how to improve the tenacity of the material, at the same time, keep the excellent heat resisting property、the electricity and the high modulus of the material, effectively. But both physical and chemical modifications usually reduce the heat resisting property of maleimide.
In recent years, Keller et al. has done a great deal of work on phthalocyanine resins based on bisphthalonitrile compounds. The results showed that phthalocyanine resins had the excellent heat resisting property and stability, the thermal and mechanical properties could be controlled by controlling the level of solidified agent used and post-curing condition. So it is interest that modifying the maleimide resins by phthalocyanine resins. And so far, we have seen no articles on this method of modifying maleimde were reported.
Two kinds of N-substituted phenyl maleimide which contain cyano-group were synthesized and the structure of them was characterized. The mechanism of curing reactions and the thermal property of cured product were studied by thermal analysis. It was proved that the thermal property of the cured product could be improved effectively by introducing phthalocyanine into maleimide.
We introduced amine operating as curing agent into the maleimide containing cyano-group. The structure of them was confirmed. The mechanism of curing reactions and the thermal property of cured product were studied by thermal analysis.
We made the free radicals reaction for the maleimde above, and the factors of the reaction condition affecting the reaction were studied .The molecular weight, solubility and thermal property of the homopolymers were also studied.
近年来，Keller等人对基于邻苯二甲腈单体的热固性酞菁树脂做了大量的研究工作。研究结果表明酞菁树脂具有优异的耐热性和热氧稳定性，通过控制固化催化剂用量和后固化条件可在较大范围内控制所得材料的热性能和机械性能。用酞菁树脂改性马来酰亚胺树脂引起了我们极大的兴趣，到目前为止，还未见文献报道。
我们合成了两种含有氰基的马来酰亚胺，并证明了结构。利用热分析手段研究该类化合物的固化反应机理和固化产物的热性能，证明了邻苯二甲腈基导入马来酰亚胺分子结构中，可以有效地提高马来酰亚胺树脂的热交联产物的高温热性能，提高残碳量。
我们利用常见的二元胺改性马来酰亚胺的方法，在含有氰基的马来酰亚胺化合物中引入胺类物质做为酞菁固化交联的催化剂，并证明了结构。利用热分析手段研究该固化体系的固化反应机理和固化产物的热性能。我们对前述的含有氰基的马来酰亚胺化合物做溶液中的自由基聚合反应，研究了反应条件对该反应的影响。对其均聚物的分子量，溶解性能和热行为做了一个初步的研究。
The high performance composite materials have been applied in the fields of energy, transportation, aviation and aerospace extensively. Developing the resin which has the excellent processability, heat resisting and mechanical properties is the target that researchers who dedicated to the composite material always pursues.
The maleimide is the important species of the advanced high performance polymeric composition. It has not only the heat, radiation and damp resisting property of maleimide, which are similar with the polyimide, but also the similar processability of epoxy resins; it can satisfy the requirement of the advanced resin in much aspect. Therefore, it is a kind of high performance resin to be subjected to more and more concerns. But due to the high crosslinking density after cured, the cured product become more brittleness. So the study on modification of maleimide resin is focused on how to improve the tenacity of the material, at the same time, keep the excellent heat resisting property、the electricity and the high modulus of the material, effectively. But both physical and chemical modifications usually reduce the heat resisting property of maleimide.
In recent years, Keller et al. has done a great deal of work on phthalocyanine resins based on bisphthalonitrile compounds. The results showed that phthalocyanine resins had the excellent heat resisting property and stability, the thermal and mechanical properties could be controlled by controlling the level of solidified agent used and post-curing condition. So it is interest that modifying the maleimide resins by phthalocyanine resins. And so far, we have seen no articles on this method of modifying maleimde were reported.
Two kinds of N-substituted phenyl maleimide which contain cyano-group were synthesized and the structure of them was characterized. The mechanism of curing reactions and the thermal property of cured product were studied by thermal analysis. It was proved that the thermal property of the cured product could be improved effectively by introducing phthalocyanine into maleimide.
We introduced amine operating as curing agent into the maleimide containing cyano-group. The structure of them was confirmed. The mechanism of curing reactions and the thermal property of cured product were studied by thermal analysis.
We made the free radicals reaction for the maleimde above, and the factors of the reaction condition affecting the reaction were studied .The molecular weight, solubility and thermal property of the homopolymers were also studied.
引文
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