六(γ-氨丙基硅烷三醇)环三磷腈的制备及其在膨胀阻燃聚丙烯中的应用  

Synthesis of hexakis(γ-aminopropylsilanetriol) cyclotriphosphazene and application in intumescent flame retardant polypropylene

作　　者：李雄杰[1] 何英杰[1] 邹国享[1] 屈鑫[1] 杨荣[1] 李锦春[1] 

机构地区：[1]常州大学材料科学与工程学院,江苏常州213164

出　　处：《复合材料学报》2017年第6期1221-1229,共9页Acta Materiae Compositae Sinica

基　　金：国家自然科学基金面上项目(51473024)

摘　　要：以六氯环三磷腈、对羟基苯甲醛及γ-氨丙基硅烷三醇(KH553)为反应原料,合成了具有席夫碱结构的有机硅型成炭剂六(γ-氨丙基硅烷三醇)环三磷腈(HKHPCP)。以HKHPCP与聚磷酸铵(APP)的复配物为抗熔滴剂,以N-烷氧基受阻胺(NOR116)为阻燃协效剂,通过熔融共混技术制备了膨胀阻燃聚丙烯(PP)基复合材料(APP-HKHPCP-NOR116/PP)。利用FTIR、核磁共振(1 H和31P NMR)对HKHPCP的化学结构进行了表征。采用热失重、极限氧指数、垂直燃烧、锥形量热、拉曼光谱和SEM研究了阻燃体系的热降解行为、阻燃性能及炭层的石墨化程度和致密性。HKHPCP的热失重结果表明,其在氧气氛围下的初始分解温度为300.2℃,1 000℃时残余率为34.8%。当添加总量为30wt%的阻燃剂时,APP-HKHPCP-NOR116/PP复合材料的极限氧指数(LOI)达到43%,且能通过UL-94V-0级,其热释放速率(HRR)、总热释放速率(THR)及烟释放速率(SPR)、总烟释放量(TSP)相比于纯PP分别降低了75.0%、50.5%和88.0%、80.8%,表现出显著的隔热、抑烟性能。APPHKHPCP-NOR116/PP复合材料燃烧后形成了高石墨化、致密的炭层。A novel charring agent named as hexakis （γ-aminopropylsilanetriol） cyclotriphosphazene （HKHPCP） was synthesized by using hexachlorocyclotriphosphazene （HCCP）, p-hydroxy benzaldehyde and γ-aminopropylsilan-etriol （KH553）. The intumescent flame retardant polypropylene （PP） matrix composites （APP-HKHPCP- NORl16/PP） was prepared using HKHPCP and ammonium polyphosphate （APP） as the anti-dripping agent and N-alkoxy hindered amine （NOR116） as the synergistic agent by the melt compounding method. The chemical structures of intermediate and HKHPCP were characterized by FTIR, 1 H nuclear magnetic resonance （1 H NMR） and 31 p NMR. The effects of the flame retardant APP-HKHPCP-NORll6/PP on the thermal degradation, flame retardancy and char layer structure were investigated by thermogravimetric analysis （TGA）, limiting oxygen index （LOI）, vertical burning test （UL-94）, cone calorimetric test, SEM and laser Raman spectroscopy, respectively. The TGA results show that the temperature of 5% mass loss of HKHPCP in oxygen is 300.2℃, and the residues at 1 000℃ of HKHPCP in oxygen is 34.8%. The results show that the LOI value of APP-HKHPCP-NOR116/PP is 43%, while the intumescent flame retardant loading is 30wt%. The APP-HKHPCP-NOR116/PP could reach a V-0 rating in the UL-94 tests. The cone calorimetry results indicate that heat release rate （HRR）, total heat release （THR）, smoke produce rate （SPR） and total smoke production （TSP） are reduced by 75.0%, 50.5M, 88.0% and 80.8%, respectively. In addition, the APP-HKHPCP-NOR116/PP can form a compact and more graphitic carbon char layer during combustion.

关 键 词：聚丙烯 受阻胺 有机硅 席夫碱 熔滴 膨胀阻燃体系 

分 类 号：TB332[一般工业技术—材料科学与工程] TQ323.8[化学工程—合成树脂塑料工业]