Halogen-Free Epoxy with Enhanced Corrosion Resistance for Microelectronics Packaging via γ SN2 Nucleophilic Substitution

Bisphenol A diglycidyl ether (DGEBA) is an essential epoxy resin in the microelectronics industry. However, circuit corrosion caused by hydrolyzable chlorinea persistent issue associated with DGEBAposes significant challenges in this field. In this study, we present a novel strategy for producing halogen-free DGEBA with high purity (up to 99%) and isolated yield (up to 94%) by utilizing glycidyl sulfonates as the starting material. A distinctive γ SN2 nucleophilic substitution pathway between glycidyl sulfonates and phenolic compounds effectively suppresses the formation of ring-opening byproducts and oligomers, as demonstrated through model reactions and kinetic studies. The scalability and versatility of our method are validated by its straightforward synthesis process and expanded substrate scope. Finally, the halogen-free DGEBA exhibits noncorrosive properties when employed as a matrix resin for prepreg and underfill applications. Our research underscores the potential of glycidyl sulfonate as a viable alternative to epichlorohydrin in large-scale epoxy production for electronics.双酚A二缩水甘油醚（Bisphenol A diglycidyl ether, DGEBA）是微电子工业中不可或缺的环氧树脂。然而，由可水解氯引发的线路腐蚀问题——这一与DGEBA密切相关的长期行业痛点——给该领域带来了严峻挑战。本研究提出了一种制备高纯度（最高可达99%）、分离产率（最高可达94%）无卤DGEBA的新型策略，该策略以缩水甘油磺酸酯（glycidyl sulfonates）为起始原料。通过模型反应与动力学研究证实，缩水甘油磺酸酯与酚类化合物之间独特的γ位SN2亲核取代路径，可有效抑制开环副产物与低聚物的生成。该方法合成流程简便、底物适用范围更广，验证了其可放大性与通用性。最后，该无卤DGEBA作为预浸料（prepreg）与底部填充材料（underfill）的基体树脂时，表现出无腐蚀性。本研究凸显了缩水甘油磺酸酯作为环氧氯丙烷（epichlorohydrin）的可行替代品，在规模化电子用环氧树脂生产中的应用潜力。