新型含有苯并环丁烯单体的合成及其发展可溶性高耐热绝缘聚酰亚胺/聚醚醚酮的方法研究

Polyimides (PI)s and Poly(ether ether ketone)s (PEEK)s are important high-performance materials utilized in military and civil fields due to their excellent overall properties. However, their high melt viscosity and poor solubilty in organic solvents leads to their deficiencies in processability, which limits their applications in many fields, such as microelectronics, light-emitting diodes and so on. Therefore, a considerable amount of structural modifications of polymers have been carried out to improve their solubility. Some approcoachs were proved to be sucessful to improve the solubility of the polymers, but their thermal stabilities and mechanical properties were usually scraficed. The strategy of introducing the cross-linkable groups to the copolymers as pendants can improve the solubility of the polymers, meawhile it can endow them good thermal stabilities and mechnical properties by postpolymerzation to convert them to cross-linking networks. However, few of momomers containing cross-linkable groups for development of PIs and PEEKs have been reported, and some of them can not give the polymers ideal overall properties. It is known that benzocyclobutene (BCB) is a molecule with high reactivity. BCB-functionalized oligomers or polymers can be readily converted to cross-linking matrixs at heating, which have been recognized as a new generation of high performance materials for microelectronic applications due to their excellent thermal stability and dielectric properites. The characteristic of BCB inspired us to develop a series of new monomers, which can be utilized to synthesize novel thermosetting PIs and PEEKs with good processability and high heat resistance. In this project, we will explore the synthesis, properties and postpolymerzation of the PIs and PEEKs containing BCB pendant groups to obtain the polymers with ideal overall properties. This research will provide a novel approach to develop solution-processable PIs and PEEKs to obtain excellent processability, thermal stabilities and dielectric properties.

聚酰亚胺（PI）和聚醚醚酮（PEEK）是综合性能优越的高性能聚合物，也是重要的军用和民用材料。但其熔点高溶解性差，不易加工，限制了其应用范围。在其改性工作中，虽然许多方法能提高聚合物的溶解性，但往往以牺牲材料的耐热性为代价。也有研究将具有交联基团的共聚单体引入上述聚合物中，既提高了聚合物的溶解性，又能通过后聚合交联，使聚合物获得良好的热力学性能。然而，可交联的共聚单体的品种有限，并且有些改性效果不理想。鉴于苯并环丁烯的高反应活性，以其改性的聚合物具有良好的绝缘性和热稳定性的优点，本项目将利用我们最新发展的含有苯并环丁烯的双胺/双酚单体，将其引入PI和PEEK中，获得易加工高耐热的热固性聚合物。本项目将深入研究含有苯并环丁烯侧链的PI和PEEK的合成、性能和后聚合反应，进而发现性能优异的品种。开展本项目的研究，将为发展可溶性PI和PEEK提供新途径，并能获得加工性良好、高耐热绝缘的聚合物。

聚酰亚胺（PI）等高性能聚合物是重要的军用和民用材料，但其不溶不熔，不易加工，限制了其应用范围。在这类材料的改性工作，虽然可以提高聚合物的溶解性，但也降低了其耐热性。综合来看，引入可固化基团，通过固化交联使聚合物形成网状结构，是在不影响聚合物性能的前提下改善其溶解性及可加工性的有效方法。然而含有可固化基团的单体品种有限，有些改性效果不理想。鉴于苯并环丁烯（BCB）的高反应活性，且其改性的聚合物具有良好热稳定性等优点，我们将其引入到新的双酚、双胺等重要的化工原料中，设计了多种含有BCB的新型单体。利用其发展可溶性的PI、聚醚醚酮等的高性能材料。. 我们设计了含有BCB的双胺单体，并合成了PI。所得PI显示出良好的溶解性和成膜性。用溶液法可得到表面平整的薄膜。其还显示出良好的透光率、热稳定性和介电性能。新型双胺还可用作添加剂对传统PI的性能进行调节，只需少量添加即能有效地提高其储能模量、抗张强度、Tg以及降低其CTE等。我们将这一方法扩展，通过开发新型含有BCB单体，制备了一系列可固化的聚醚醚酮、聚碳酸酯、聚三嗪等高性能聚合物。其均可用溶液法制备成质地均匀的薄膜，其均展现了良好的耐热性、力学性能，疏水性等，拓宽了其应用范围。在研究过程中，我们发现BCB可以和大茴香脑在加热条件下发生反应。大茴香脑是我国特有的植物资源，含有苯环和不饱和的丙烯键，可作为合成高性能聚合物的前驱体。我们以生物制资源为原料，设计了几种含有BCB的单体，用于发展可热固化的高性能聚合物。这些单体加热后发生交联聚合，所得聚合物均展现出良好的热力学性能及介电性能，且加工性能优异，可用于发展高耐热低介电常数材料。. 本项目发展了多种简便高效获得含有BCB单体的合成方法，制备几类可热固化聚合物，建立了改善高性能聚合物加工性的有效策略。通过本项目的研究，获得高耐热低介电且加工性良好的高性能聚合物，其有望作为涂层材料，用于航空航天、电气，微电子及汽车等领域。