中国胶粘剂

针对环氧树脂胶粘剂韧性不足、耐热性与介电性能难以协同提升的问题，本研究以4,4′-二氟二苯甲酮和3,3′-二烯丙基双酚S为原料，经亲核取代缩聚反应合成聚烯丙基芳砜醚酮(PAEK)。将其与双酚A型环氧树脂、酸酐固化体系复配，引入过氧化二苯甲酰引发烯丙基交联，制备了PAEK/环氧胶粘剂系列(E-1～E-5)。对其结构和性能进行表征，此外还基于Kissinger与Crane方程分析了其固化动力学。研究结果表明：(1)PAEK的收率在99%以上，玻璃化转变温度为162℃，具备优异的耐热性。(2)适量PAEK的引入实现了环氧胶粘剂体系的增强与增韧的协同提升。当PAEK添加量为10%(E-4)时，胶粘剂的综合力学性能相对最优：120℃高温下拉伸剪切强度仍保持12.2 MPa，冲击强度达22.3 kJ/m2，弯曲强度达106.4 MPa。(3)对典型配方E-3的固化动力学进行分析，计算得到活化能(E_a)为68.31 kJ/mol，反应级数(n)为0.9。(4)PAEK的引入有效降低了体系极性基团密度，使胶粘剂在100 kHz频率下介电损耗稳定在1.04%～1.12%区间，电容值为4.39～5.25 pF，表现出优异的介电稳定性。同时，致密的交联网络使各配方吸水率均低于0.4%，具备良好的疏水性与电绝缘性能。(5)该PAEK/环氧胶粘剂在保持环氧体系优异粘接性能的基础上，同步提升了耐热性、韧性与介电性能，在高频高速电子封装、航空航天绝缘结构粘接等领域具有重要的应用潜力。

To address the problems of insufficient toughness of epoxy adhesive and the difficulty in simultaneously improving heat resistance and dielectric properties,4, 4′-difluorobenzophenone and 3,3′-diallylbisphenol S were employed as raw materials,and polyallylarylsulfone ether ketone(PAEK) was synthesized via nucleophilic substitution polycondensation.It was then blended with bisphenol A epoxy resin and an anhydride curing system.Benzoyl peroxide was introduced to initiate allyl crosslinking,and PAEK/epoxy adhesive series(E1-E5) were finally prepared. Their structures and properties were characterized,in addition,the curing kinetics were analyzed based on the Kissinger and Crane equations.The research results showed that,(1) The yield of PAEK was over 99%,the glass transition temperature was 162 ℃,demonstrating it had excellent heat resistance.(2) The introduction of an appropriate amount of PAEK had achieved a synergistic improvement in the reinforcement and toughening of epoxy adhesive system.When the addition amount of PAEK was 10%(E-4),the comprehensive mechanical properties of the adhesive were relatively optimal:the tensile shear strength remained at 12.2 MPa at high temperature of 120 ℃,the impact strength reached 22.3 kJ/m2,and the flexural strength reached 106.4 MPa.(3) The curing kinetics of typical formula E-3 were analyzed,and the activation energy(E_a) was calculated to be 68.31 kJ/mol,with the reaction order(n) of 0.9.(4) The introduction of PAEK effectively reduced the density of polar groups in the system,stabilizing the dielectric loss of the adhesive in the range of 1.04%-1.12% at a frequency of 100 kHz,with the capacitance value of 4.39～5.25 pF,exhibiting excellent dielectric stability.At the same time,the dense cross-linked network resulted in the water absorption rate of less than 0.4% for all formulations,possessing good hydrophobicity and electrical insulation properties.(5) This PAEK/epoxy adhesive not only maintained excellent bonding performance of epoxy system,but also simultaneously improved heat resistance,toughness,and dielectric properties.It had important application potential in high-frequency and highspeed electronic packaging,aerospace insulation structure bonding,and other fields.