【作者】 朱祖威； 张自豪； 司徒粤； 黄洪；

【Author】 Zuwei Zhu;Zihao Zhang;Yue Situ;Hong Huang;School of Chemistry and Chemical Engineering,South China University of Technology;Hansgrohe Sanitary Products (Shanghai) CO.LTD.;

【机构】 华南理工大学化学与化工学院； 汉斯格雅卫浴产品(上海)有限公司；

【摘要】 聚苯并噁嗪(PBZ)较酚醛树脂、环氧树脂等传统热固性树脂的交联密度更低,其优异的耐热性与机械强度主要是通过分子间氢键来实现,以环氧树脂(EP)对苯并噁嗪(BZ)共聚改性能够进一步强化产物的交联网络,进而优化热机械性能。BZ/EP共聚过程首先是热诱导BZ开环自聚,聚合生成的羟基与EP环氧键之间亲电加成而共聚,酚羟基反应活性低,且共聚反应因开环聚合网络扩散控制而抑制,因而共聚固化温度较噁嗪开环温度更高。本论文制备了含有氨基的苯并噁嗪(NH2-BZ),NH2-BZ与EP的共聚反应温度较苯并噁嗪单体显著降低,所得聚合物具有优异的耐热性与机械性能,分别对单体和聚合产物的分子结构与热行为进行表征,探讨了NH2-BZ与EP的共聚机理。研究表明,NH2-BZ与EP共聚为两阶段过程,由于氨基对环氧键的强亲核作用,NH2-BZ在远低于开环温度下与EP加成获得流动性好的苯并噁嗪封端环氧树脂(BZ-EP),并促进噁嗪在相对温和的条件下开环共聚而构成体型结构NH2-BZ/EP共聚物。更多还原

【Abstract】 Polybenzoxazine resins have attracted significant attention due to their outstanding thermal and mechanical properties. Taking into account their relatively lower cross-linking density comparing to other traditional thermosetting resins, strengthening crosslinking structure was a promising strategy for further enhancing their thermal mechanical properties. Copolymerization of benzoxazines and epoxy resins has been demonstrated to be a feasible method for increasing crosslinking density, but unfortunately, this binary system always require higher curing temperature than the pure benzoxazine. In this study, amine functional benzoxazine was adopted in the copolymerization with epoxy resin, in which the curing temperature was significantly lower than that of pure benzoxazine. Thermal curing behaviors of binary mixture was investigated to deduce mechanistic pathway, the two-step successive reactions including the addition reaction of amino with epoxy in a relatively low temperature region and the ring-opening of oxazine at higher temperature to obtain a crosslinking copolymer.更多还原