液态聚碳硅烷的固化反应动力学研究  

Studies on Curing Reaction Kinetics of Liquid Polycarbosilane

作　　者：王林豪[1] 罗永明[2] 徐彩虹[2] 王西新[1] 

机构地区：[1]河北工业大学材料科学与工程学院,天津300130 [2]中国科学院化学研究所高技术材料实验室,北京100190

出　　处：《高分子通报》2016年第9期149-155,共7页Polymer Bulletin

摘　　要：选用过氧化二异丙苯(DCP)和偶氮二异丁腈(AIBN)分别引发含乙烯基液态聚碳硅烷(VHPCS)聚合。采用非等温差示扫描量热法(DSC)研究VHPCS/DCP、VHPCS/AIBN两种体系的固化反应动力学,通过Kissinger方程和Crane方程确定相关动力学参数,并由此得出体系的n级固化模型。同时通过β-T外推法确定体系的固化工艺温度,并对体系交联机理及产物热性能进行分析。研究结果表明:VHPCS/DCP、VHPCS/AIBN二体系的活化能分别为72.17kJ/mol、94.11kJ/mol,反应级数分别为0.92、0.93。β-T外推法确定:当升温速率为0℃/min时二体系的近似凝胶化温度均为55℃,峰值温度分别为110℃、107℃,终止温度分别为129.5℃、134℃。FTIR结果表明,VHPCS的交联固化主要是通过双键的自聚合实现,交联后样品的陶瓷产率有所提高。In this paper, dicumyl peroxide（DCP） and azobisisobutyronitrile（AIBN） were used to initiate polymerization of liquid vinylpolyearbosilane（VHPCS）. The curing reaction kinetics of VHPCS/AIBN, VHPCS/DCP systems were studied by non-isothermal differential scanning calorimetry（DSC）. The related kinetic parameters were analyzed by Kissinger equation and Crane equation, and the nth-order curing models of both systems were obtained based on these curing kinetic parameters. The curing process temperatures of two systems were determined by the fl-T extrapolation method. In addition, the cross-linking mechanism of VHPCS and the thermal property of cross-linked products were also studied. The results showed that the activation energy E of VHPCS/AIBN, VHPCS/DCP systems were 72. 17 KJ/mol, 94. 11 KJ/mol, and the reaction order n were 0.92, 0.93, respectively. The characteristic temperatures of VHPCS/AIBN, VHPCS/DCP systems were approximate gelling temperature of 55℃, peak temperature of 110℃, 107℃, termination temperature of 129.5℃, 134℃, respectively. FTIR result indicated that the cross-linking of VHPCS mainly by self-polymerization of vinyl group. The mass residue of cross-linked products were higher than that of VHPCS.

关 键 词：聚碳硅烷 引发剂 DSC 反应动力学 固化工艺 

分 类 号：TQ174.1[化学工程—陶瓷工业] O634.41[化学工程—硅酸盐工业]