磷氮协同环三磷腈阻燃剂的制备及其应用  

Preparation and Application of Phosphorus-Nitrogen Synergistic Cyclotriphosphazene Flame Retardant

作　　者：董淑玲[1] 娄帅 王红霞 王彦林[1] Dong Shuling;Lou Shuai;Wang Hongxia;Wang Yanlin(School of Chemistry and Life Sciences,Suzhou University of Science and Technology,Suzhou 215009,China)

机构地区：[1]苏州科技大学化学与生命科学学院,江苏苏州215009

出　　处：《工程塑料应用》2022年第10期131-135,共5页Engineering Plastics Application

摘　　要：为了提高饱和聚酯及不饱和聚酯材料的阻燃性能,以六氯环三磷腈(HCCP)、烯丙胺及苯胺为主要原料,二步反应制备了一种新型磷氮协同阻燃剂烯丙胺基五苯胺基环三磷腈(ANNCTP),磷氮总含量高达33.7%。探索合成工艺,得到最优反应条件:物料比n(HCCP)∶n(烯丙胺)∶n(苯胺)=1∶1∶5.1,在60℃下反应7 h,产率最高(为89.2%)。通过傅里叶变换红外光谱、核磁共振氢谱、热重分析表征了产物结构与目标产物一致,800℃时仍有22.5%的残余物,热稳定性良好。采用氧指数法及扫描电子显微镜测试其阻燃性能,结果表明,添加20%(质量分数,下同)ANNCTP的聚对苯二甲酸丁二酯(PBT)的氧指数(LOI)为29%,添加10%ANNCTP的191不饱和树脂LOI为27%,皆为难燃级别,ANNCTP中磷/氮两种阻燃元素协同作用,阻燃效能良好。材料燃烧后残炭形貌致密而有微孔,主要为气相阻燃机理。In order to improve the flame retardant properties of saturated polyester materials and unsaturated polyester materials,a novel phosphorus-nitrogen synergistic flame retardant,allylamine pentaphenylamine cyclotriphosphazene(ANNCTP) was prepared by two-step reaction using hexachlorocyclotriphosphazene(HCCP),allylamine and aniline as main materials.The total content of phosphorus and nitrogen of ANNCTP is as high as 33.7%.After exploring the synthesis process,the optimum reaction conditions were obtained:material ratio n(HCCP)∶n(allylamine)∶n(aniline)=1∶1∶5.1,and the reaction time is 7 hours at 60℃.Under this condition,the yield is the highest(89.2%).By Fourier transform infrared spectroscopy,nuclear magnetic resonance hydrogen spectrum and thermogravimetric characterization,it was proved that the product structure is consistent with the target product and has good thermal stability,there is still 22.5% residue at 800℃.The flame retardant properties of ANNCTP was tested by oxygen index method and scanning electron microscope.The oxygen index(LOI) of polybutylene terephthalate(PBT) added with 20%(mass fraction,the same below) ANNCTP is 29%,and the LOI of 191 unsaturated resin added with 10% ANNCTP is 27%,both of which belong to flame retardant grade.The two flame retardant elements phosphorus and nitrogen play a synergistic role,and ANNCTP has a good flame retardant effect on both PBT and 191 unsaturated resin.The microscopic morphology of the carbon residue is dense and microporous,which is mainly due to the gas phase flame retardant mechanism.

关 键 词：协同阻燃 烯丙胺基五苯胺基环三磷腈 聚对苯二甲酸丁二酯 191不饱和树脂 

分 类 号：TQ323.41[化学工程—合成树脂塑料工业]