文献类型：期刊文献

英文题名：A novel efficient flame-retardant curing agent for epoxy resin based on P-N synergistic effect: Bio-based benzoxazine phosphate ester

作者：Zhou, Xuan[1,2] Li, Rongzhi[1,2] Fu, Fei[3] Shen, Minggui[1] Li, Qiaoguang[4] Liu, He[1] Xu, Xu[2] Song, Zhanqian[1]

第一作者：Zhou, Xuan

通信作者：Shen, MG[1];Li, QG[2]

机构：[1]Chinese Acad Forestry, Inst Chem Ind Forestry Prod, Nanjing 210042, Jiangsu, Peoples R China;[2]Nanjing Forestry Univ, Coll Chem Engn, Jiangsu Coinnovat Ctr Efficient Proc & Utilizat Fo, Nanjing 210037, Peoples R China;[3]Henan Univ Technol, Coll Adv Interdisciplinary Sci & Technol, 100 Lianhua St, Zhengzhou 450001, Peoples R China;[4]Zhongkai Univ Agr & Engn, Coll Chem & Chem Engn, Guangzhou 510225, Guangdong, Peoples R China

年份：2024

卷号：499

外文期刊名：CHEMICAL ENGINEERING JOURNAL

收录：;EI(收录号：20244117172466);Scopus(收录号：2-s2.0-85205930405);WOS:【SCI-EXPANDED(收录号:WOS:001332066100001)】；

基金：This work was supported by the National Key R & D Program of China (2022YFD22007022) , the National Natural Science Foundation of China (Grant No. 32271816) and the National Natural Science Foundation of China (Grant No. 32101475) .

语种：英文

外文关键词：Epoxy resin; Polybenzoxazine; Bio-based; Flame-retardant; Degradation

摘要：Most epoxy resins on the market have low thermal stability and flammable defects. As a potential curing agent for epoxy resin, polybenzoxazine (PBz) can effectively improve the thermal properties of the resin due to its low heat release capacity (HRC) and rigid aromatic ring support, and its raw materials can be derived from renewable resources. Here, we have successfully developed a molecular design strategy to obtain a trifunctional benzoxazine monomer with phosphate ester. Firstly, guaiacol-ethanolamine benzoxazine monomer (GE) was synthesized by Mannich condensation using guaiacol and ethanolamine as raw materials. Then trifunctional benzoxazine phosphate ester (TBP) was synthesized by the nucleophilic reaction of GE with phosphorus oxychloride. Finally, the epoxy resin DGEBA was cured by TBP to obtain a PBz modified epoxy resin (EP-TBP polymer) with Tg of 113.7 degrees C and char yield of 37.4 %. Due to the introduction of TBP rich in phosphorus and nitrogen, it releases phosphorus radicals and nitrogen-containing inert gases during combustion, which leads to quenching effect and dilution effect. In addition, TBP can also promote the dehydration and dehydrogenation of the polymer and accelerate the formation of the aromatic hybrid char layer. Therefore, the THR of TBP modified epoxy resin is 49.3 % lower than that of epoxy resin without TBP, and the char yield is 47 times higher. And when the phosphorus content is 1.76 %, the flame-retardant grade can reach V-0. In addition, the introduction of TBP also enhanced the mechanical properties, adhesion properties and hydrophobicity properties of the polymer. It is worth mentioning that under alkaline conditions, the phosphate ester in the structure of EP-TBP polymer will undergo ammonolysis reaction with ethanolamine, and the resulting oligomers will be dissolved in it, thereby achieving rapid degradation of EP-TBP polymer. This work is to develop a high-performance multifunctional epoxy resin flame retardant curing agent based on renewable raw materials, and provide important insights for the subsequent development of halogen-free bio-based PBz flame retardant materials.