摘要
不饱和树脂(UPR)的易燃性和其苯乙烯稀释剂的毒性、挥发性给其带来严重的安全隐患.本文合成了三种不同含磷结构的非挥发性阻燃稀释交联剂(PBHA、POHA和PSHA),在完全取代苯乙烯的同时为UPR带来极好的阻燃性能.其结构通过FTIR和NMR(^(1)H,^(31)P)表征.通过挥发性、黏度、固化动力学和凝胶含量测试,评估其作为阻燃稀释交联剂的可能性.同时,比较不同磷结构对UPR阻燃性能的影响.当使用PBHA时, UP/PBHA在UL-94测试中达到V0级别,其LOI为28%.与苯乙烯稀释的UPR材料相比, UP/PBHA的热释放速率峰值(PHRR)和总热释放(THR)分别降低64.06%和61.54%.当PBHA稀释的UPR树脂用于玻纤增强复合材料时(GF/UP/PBHA),其同样达到V0级别,并且LOI高达38%.同时,通过热稳定性、热降解过程和燃烧过程研究发现PBHA阻燃稀释交联剂是以气相捕捉H·和HO·自由基为主,以固相促进致密炭层形成隔绝氧与热辐射为辅的阻燃机理.
The flammability of unsaturated polyester resins(UPR) and the volatility of their toxic styrene diluents pose serious safety risks. In this paper, three non-volatile flame retardant diluents(PBHA, POHA and PSHA) containing different phosphorus structures were synthesized, which can completely replace styrene and provide excellent flame retardant performance for UPR. Their structures were characterized by FTIR and NMR(^(1)H,^(31)P). The potential of synthesized reactive diluents as substitutes in UPR and their glass fabric reinforced composites was assessed through volatility, processability, curing kinetics and gel contents. Meanwhile, by comparing the effects of different phosphorous structures, PBHA diluent can bring best flame retardant efficiency. UP/PBHA reached V0 in UL-94 and 28% of LOI.The PHRR and THR of UP/PBHA were decreased by 64.06% and 61.54% compared with neat UP/St. For glass fabric/UPR composites, GF/UP/PBHA also reached V0 rating, and LOI was as high as 38%. Meanwhile, through the study of thermal stability, thermal degradation and combustion process, it was found that PBHA mainly worked in gas phase to capture H· and HO·, supplemented by promoting formation of dense carbon layer in condensed phase to isolate oxygen and thermal radiation.
作者
褚夫凯
张圣贺
周一帆
徐周美
朱雨露
周侠
宋磊
胡伟兆
胡源
Fukai Chu;Shenghe Zhang;Yifan Zhou;Zhoumei Xu;Yulu Zhu;Xia Zhou;Lei Song;Weizhao Hu;Yuan Hu(State Key Laboratory of Fire Science,University of Science and Technology of China,Hefei 230026,China)
出处
《中国科学：化学》
CAS
CSCD
北大核心
2021年第12期1646-1659,共14页
SCIENTIA SINICA Chimica
基金
国家自然科学基金(编号:51991352,51973203,51874266)
中央高校基本科研业务费专项资金(编号:WK2320000043,WK2320000044)资助项目。
关键词
不饱和聚酯树脂
阻燃稀释交联剂
非挥发性
可加工性能
阻燃性能
玻纤增强复合材料
unsaturated polyester resin
flame retardant crosslinking diluents
non-volatile
processibility
flame retardant
glass fiber reinforced composites
