低介电、高耐热的本征阻燃脂环族环氧树脂的设计合成及性能研究

Focusing on the high requirement on flame retardance, dielectric properties and heat resistance of epoxy resins (EP) for high-tech electronic devices, in this project, a new approach to prepare intrinsically flame-retardant cycloaliphatic EP by phosphorus-containing cycloaliphatic epoxides with different phosphorous oxidation states and steric hindrance will be proposed. The appropriate way to control gaseous/condensed flame-retardant effect of the resins and obtain highly flame-retardant cycloaliphatic EP will be suggested by a series of flame-retardant, dielectric and heat-resistant property test, thus the difficulty in flame-retarding cycloaliphatic EP for hardly char-forming and easily dripping will be overcome. Then, the relationships between structure of phosphorus-containing cycloaliphatic EP and flame retardancy, dielectric and heat-resistant properties of the cured resins will be further revealed; accordingly, the balance between flame retardancy, dielectric and heat-resistant properties will be achieved by incorporating phosphorus-containing aromatic cycloaliphatic epoxides, which can restrict the thermal and dielectric relaxation of the epoxy chains. The project will provide a novel idea and approach to effectively flame-retarding cycloaliphatic EP and preparing high-performance cycloaliphatic EP acclaimed in highly integrated electronic devices. Therefore, the project exhibits both scientific significance and application values.

针对新兴领域的电子封装对热固性环氧树脂的高阻燃性、低介电性、高耐热性的高要求，本项目提出以不同磷氧化态及空间位阻的含磷脂环族环氧树脂制备本征阻燃脂环族环氧树脂的新方法。通过对设计合成的不同磷氧化态和空间位阻的环氧树脂的固化行为、阻燃性和阻燃机理、介电性及耐热性等的系统研究，提出有效调控树脂固化物气相和凝聚相阻燃作用的途径和方法，解决脂环族环氧树脂因难成炭、易熔滴而阻燃困难的问题，实现脂环族环氧树脂的高效阻燃；构建含磷脂环族环氧树脂结构与树脂固化物阻燃、介电、耐热性能的构效关系，引入空间位阻“适当”的含磷芳香族脂环族环氧树脂，以之抑制树脂固化物分子链的热松弛及介电松弛，实现脂环族环氧树脂的高阻燃性与低介电性和高耐热性的协调平衡。本项目的开展可为高效阻燃脂环族环氧树脂提供一种新思路，为制备满足新兴领域电子封装所需的高阻燃性、低介电性、高耐热性的环氧树脂提供一种新途径，具备学术和应用价值。

针对5G等高频高速领域的电子封装对环氧树脂的阻燃、介电、耐热等性能的高要求，以解决脂环族环氧树脂因难成炭、易熔滴而存在的阻燃困难等问题为目标，本项目将9，10-二氢-9-氧杂-10-磷杂菲-10-氧化物衍生物和磷酰氯等与3-环己烯-1-甲醇反应制得磷系含烯基前驱物，而后再将之环氧化，合成了2种含磷脂环族环氧树脂。而后将之与异氰脲酸三缩水甘油酯共固化，制备一系列含磷、氮的环氧树脂，获得一种介电性能突出、耐热性能优良的阻燃环氧树脂固化物；系统研究了所合成环氧树脂的固化行为、阻燃性能、介电性能、耐热性能，探明了脂环族环氧树脂的结构与阻燃、介电及耐热等性能的构效关系，为设计制备满足高阻燃性、低介电性和高耐热性的电子封装材料奠定科学基础。此外，为进一步理解不同含磷化合物对树脂材料阻燃、耐热、力学等性能的影响规律，从含磷酸和1-乙烯基咪唑出发，通过简单的酸碱中和反应，合成一系列含磷酸1-乙烯基咪唑盐，将之作为阻燃交联剂，制备含磷阻燃乙烯基树脂；系统研究了含磷酸1-乙烯基咪唑盐对乙烯基树脂的固化行为、阻燃性能、燃烧行为、热稳定性、热机械性能、力学性能等的影响规律，着重分析了不同磷化学环境对乙烯基树脂阻燃效果及链间离子网络对乙烯基树脂各项性能的影响情况；相关研究成果丰富了阻燃理论体系，可为设计高效阻燃剂提供一种新思路，对高性能树脂材料的设计制备及阻燃机理分析具有借鉴意义。