Preparation and curing reaction kinetics of liquid vinyl silicone resin

doi:10.3969/j.issn.0438-1157.2014.04.048

CIESC Journal ›› 2014, Vol. 65 ›› Issue (4): 1509-1516.DOI: 10.3969/j.issn.0438-1157.2014.04.048

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Preparation and curing reaction kinetics of liquid vinyl silicone resin

LIU Huijuan¹, ZHAN Xibing¹, ZHU Wenqin¹, LIN Xin², CHENG Jue¹, ZHANG Junying^1,2

1 Key Laboratory of Carbon Fiber and Functional Polymers, Ministry of Education, Beijing University of Chemical Technology, Beijing 100029, China;
2 Changzhou Institute of Advanced Materials, Beijing University of Chemical Technology, Changzhou 213164, Jiangsu, China

Received:2013-07-26 Revised:2013-10-17 Online:2013-11-27 Published:2014-04-05
Supported by:
supported by the National High Technology Research and Development Program of China (2011AA03A109) and the International Science & Technology Cooperation Program of China (2012DFR40640).

液体乙烯基硅树脂的制备及固化反应动力学

刘慧娟¹, 展喜兵¹, 祝文亲¹, 林欣², 程珏¹, 张军营^1,2

1 北京化工大学教育部碳纤维及功能高分子教育部重点实验室, 北京 100029;
2 北京化工大学常州先进材料研究院, 江苏常州 213164

通讯作者: 张军营
作者简介:刘慧娟（1989—），女，硕士研究生。
基金资助:
国家高技术研究发展计划项目（2011AA03A109）；国家国际科技合作专项项目（2012DFR40640）；常州市应用基础研究计划项目（CJ20120011）。

Abstract

Abstract: A liquid vinyl silicone resin was prepared. Its structure was confirmed by FT-IR, GPC, ¹H NMR, ²⁹Si NMR. The curing kinetics of vinyl silicone resin/ phenyl hydrogen silicone oil system was studied by isothermal DSC. The activation energy of this system was obtained by the Kissinger method and advanced iso-conversional method proposed by Vyazovkin. The non-isothermal reaction kinetics was investigated based on the model-fitting Málek method. The curing parameters were obtained by the T-b extrapolation method. The results showed that the apparent activation energies of the curing reaction were 85.3 kJ·mol^-1 and 84.0 kJ·mol^-1 calculated by Kissinger method and Vyazovkin method, respectively. The Šesták-Berggren(m,n) model was found to be appropriate to describe the curing kinetics of the studied silicone resin system and the theoretically calculated curve agreed well with the experimental data. The characteristic temperatures of the resin system were approximate gelling temperature of 89.1℃, curing temperature of 127.8℃, and post-processing temperature of 157.6℃.

Key words: vinyl silicone resin, reaction kinetics, autocatalysis, kinetic modeling, Vyzaovkin method, Málek method

摘要： 合成了一种液体乙烯基硅树脂，并用FT-IR、GPC、¹H NMR和²⁹Si NMR等手段对其结构进行表征。采用非等温差示扫描量热法（DSC）研究了乙烯基硅树脂/苯基含氢硅油体系的固化反应动力学，用Kissinger方程和高级等转化率法（Vyazovkin方法）分别计算了该体系的表观活化能E_a，用Málek法进行模型拟合动力学分析，通过T-β外推法确定该体系的固化工艺参数。结果表明：Kissinger法和Vyazovkin法得到的活化能分别为85.3 kJ·mol^-1和84.0 kJ·mol^-1，二者所得结果的差别较小；乙烯基硅树脂体系固化动力学符合Šesták-Berggren（m，n）模型，m和n分别为0.092、1.440，拟合曲线与实验的DSC曲线吻合；该树脂体系的近似凝胶化温度为89.1℃，固化温度为127.8℃，后处理温度157.6℃。

关键词: 乙烯基硅树脂, 反应动力学, 自催化, 动力学模型, Vyazovkin法, Málek方法

CLC Number:

TQ320.1

LIU Huijuan, ZHAN Xibing, ZHU Wenqin, LIN Xin, CHENG Jue, ZHANG Junying. Preparation and curing reaction kinetics of liquid vinyl silicone resin[J]. CIESC Journal, 2014, 65(4): 1509-1516.

刘慧娟, 展喜兵, 祝文亲, 林欣, 程珏, 张军营. 液体乙烯基硅树脂的制备及固化反应动力学[J]. 化工学报, 2014, 65(4): 1509-1516.

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Preparation and curing reaction kinetics of liquid vinyl silicone resin

液体乙烯基硅树脂的制备及固化反应动力学

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