DOPO基反应型阻燃剂的制备及其阻燃热塑性聚氨酯  

Preparation of DOPO-based reactive flame retardants and their flame-retardant thermoplastic polyurethanes

作　　者：齐鸣 张文佳 单德鹏 王金龙 彭正 杨承刚 陈泳齐 宋佳音[4] 刘鲁斌 QI Ming;ZHANG Wenjia;SHAN Depeng;WANG Jinlong;PENG Zheng;YANG Chenggang;CHEN Yongqi;SONG Jiayin;LIU Lubin(State Grid Heilongjiang Electric Power Company Limited,Harbin 150040,China;Heilongjiang Key Laboratory of Molecular Design and Preparation of Flame Retarded Materials,Harbin 150040,China;State Grid Sichuan Electric Power Transmission and Transformation Construction Company Limited,Chengdu 610000,China;College of Computer and Control Engineering,Northeast Forestry University,Harbin 150040,China)

机构地区：[1]国网黑龙江省电力有限公司,哈尔滨150040 [2]黑龙江省阻燃材料分子设计与制备重点实验室,哈尔滨150040 [3]国网四川电力送变电建设有限公司,成都610000 [4]东北林业大学计算机与控制工程学院,哈尔滨150040

出　　处：《工程塑料应用》2024年第2期142-147,共6页Engineering Plastics Application

基　　金：国家自然科学基金项目(52203082);中央高校基本科研业务费项目(2572022BU02);国网黑龙江省电力有限公司科技项目(522401220002);黑龙江省重点研发计划项目(GZ20220056);东北林业大学大学生创新训练计划项目(S202210225155)。

摘　　要：以10-(2,5-二羟基苯基)-10-氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO-HQ)和甲苯二异氰酸酯(TDI)为原料,通过加成反应成功制备了含端异氰酸酯基的DOPO基反应型阻燃剂(DRFR),并将其引入到热塑性聚氨酯(TPU)基体中,从而制备阻燃TPU复合材料,并对TPU/DRFR复合材料的阻燃性能、燃烧行为、热降解性能和力学性能进行研究。结果表明,当DRFR的质量分数为26%时,TPU/DRFR复合材料的阻燃等级达到UL 94 V-0级,极限氧指数达27.6%,且熔滴得到了明显的抑制。DRFR的引入促进了TPU基体的提前降解炭化,从而使TPU/DRFR复合材料表面形成了致密、均一且坚硬的炭层,其有效地在固相中发挥了“挡板”作用,使得TPU/DRFR复合材料的热释放速率峰值和总热释放量与纯TPU相比分别降低了49.64%和34.65%。与此同时,DRFR在分解过程中,产生的含磷自由基和惰性气体有效地在气相中发挥了抑制作用,从而使得TPU/DRFR复合材料获得了优异的火安全性能。此外,DRFR的引入对TPU分子链段起到了交联作用,显著增强了TPU复合材料的拉伸强度。10-(2,5-dihydroxyphenyl)-10-hydro-9-oxa-10-phospha-phenanthrene-10-oxide(DOPO-HQ)and toluene diisocyanate(TDI)were used as raw materials,and a DOPO-based reactive flame retardant(DRFR)containing terminal isocyanate groups was successfully prepared by addition reaction.DRFR was introduced into the thermoplastic polyurethane(TPU)matrix for preparing flame-retardant TPU composites.The flame retardancy,combustion behaviors,thermal degradation properties,and mechanical properties of TPU/DRFR composites were studied.The results show that,when the addition amount of DRFR is 26 wt%,the flame retardant rating of the TPU/DRFR composite successfully reaches UL 94 V-0 rating with limited oxygen index of 27.6%.The melting drops of TPU composites are significantly suppressed.The introduction of DRFR promotes the early degradation and charring of TPU matrix and leads to the formation of a dense,homogeneous and compact char layer on the surface of TPU/DRFR composites.It effectively exerts the shielding effect in condensed phase and the peak heat release rate and total heat release of TPU/DRFR composites are reduced by 49.64%and 34.65%compared with that of pure TPU.Meanwhile,the phosphorus-containing radicals and inert gases generated from the decomposition of DRFR effectively play the inhibition effect in gas phase.Therefore,the TPU/DRFR composites obtain excellent fire safety performance.In addition,the introduction of DRFR plays a cross-linking role on the TPU molecular chain segments,which significantly enhances the tensile strength of the TPU composites.

关 键 词：热塑性聚氨酯 DOPO基反应型阻燃剂 阻燃性能 力学性能 

分 类 号：TQ327[化学工程—合成树脂塑料工业]