含烯丙基苯氧基环三磷腈改性不饱和聚酯树脂研究(Ⅰ):固化反应动力学及机理

Modification of Unsaturated Polyester Resins by Allylaryloxy-cyclotripolyphosphazene(Ⅰ):Curing Reaction Kinetics and Mechanism

分别以1,3,5-三(2-烯丙基苯氧基)-2,4,6-三苯氧基环三磷腈(TAPPCP)和六(2-烯丙基苯氧基)环三磷腈(HAPPCP)作为耐烧蚀填料,经复配、固化制备出改性UPR包覆层;通过红外光谱、X射线能谱和差示扫描量热法(DSC)分别研究了TAPPCP、HAPPCP与UPR的分散性、固化反应动力学和固化反应机理;通过研究非等温固化反应参数,建立了非等温固化反应动力学方程。结果表明,TAPPCP、HAPPCP与UPR具有良好的混溶性,可通过自由基共聚反应形成交联结构;TAPPCP、HAPPCP分子结构中的不饱和双键有助于降低与UPR发生共聚反应的活化能,TAPPCP/UPR体系的特征固化温度Tp和Tf随着TAPPCP添加量的提高(0→20phr)分别由88.37℃和109.58℃降至83.58℃和99.42℃,HAPPCP/UPR体系的特征固化温度Tp和Tf随着HAPPCP添加量的提高(0→20phr)分别由88.37℃和109.58℃降至79.28℃和96.15℃。

The modification of unsaturated polyester resins(UPR)inhibition formulas were prepared via compounding and curing reaction using 1,3,5-tri(2-allylaryloxy)-2,4,6-triaryloxycyclotriphazene(TAPPCP)and hexa(2-allylaryloxy)cyclotriphazene(HAPPCP)as ablative fillers.The dispersivity,curing reaction kinetics and curing reaction mechanism of TAPPCP and HAPPCP with UPR were studied by FT-IR,X-ray energy spectrum and DSC,respectively.The non-isothermal curing reaction kinetic parameters were determined.The non-isothermal curing reaction kinetic equation was found.The results show that TAPPCP and HAPPCP have good compatibility with UPR,and the crosslinking structure can be formed by free radical copolymerization.The unsaturated double bond of TAPPCP and HAPPCP could reduce the activation energy of copolymerization with UPR.The characteristic curing temperature(Tp/Tf)of TAPPCP/UPR decreases from 88.37℃and 109.58℃to 83.58℃and 99.42℃with increasing the content of TAPPCP(from 0 to 20phr).The characteristic curing temperature(Tp/Tf)of HAPPCP/UPR decrease from 88.37℃and 109.58℃to 79.28℃and 96.15℃with increasing the content of HAPPCP(from 0 to 20phr).