聚二苯基二苯乙炔基硅烷树脂的制备与非等温热分解

doi:10.11868/j.issn.1001-4381.2015.000941

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摘要

以溴乙烷、二苯基二氯硅烷、苯乙炔为原料，通过格利雅反应合成二苯基二苯乙炔基硅烷单体（DPDPES），利用FTIR和¹H-NMR对单体分子结构进行表征。采用热聚合方法制备了聚二苯基二苯乙炔基硅烷树脂（PDPDPES），借助TG-DTG技术研究了PDPDPES的非等温热分解过程，运用模型法对热分解过程进行分析，建立动力学函数，推导出热分解机理，并应用非模型法对热分解机理函数进行验证。实验结果表明，6种分析方法得到的热分解活化能E_a= 245.37kJ/mol，指前因子lgA=13.78s^-1，机理函数式：。

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关键词 ：聚二苯基二苯乙炔基硅烷树脂, 模型法, 非模型法, 热分解机理

Abstract：

Diphenyldiphenylethynylsilane monomer (DPDPES) was synthesized with ethyl bromide, diphenyldichlorosilane and phenylacetylene by Grignard reaction. The molecular structure was characterized by FTIR and ¹H-NMR spectroscopy. The polymer of polydiphenyl(diphenylethynyl)silane (PDPDPES) was also prepared by thermal polymerization. Non-isothermal thermal decomposition process of PDPDPES was studied with TG-DTG technology via model method to get thermal decomposition function and the corresponding mechanism which was further verified by model-free method. Results show that the apparent activation energy and the pre-exponential factor are about E_a=245.37kJ/mol and lgA=13.78s^-1 obtained by six different kinetic methods, respectively. The mechanism of functions are .

Key words： polydiphenyl(diphenylethynyl)silane model method model-free method thermal decomposition mechanism

收稿日期: 2015-07-30 出版日期: 2017-07-21

中图分类号:

O631

基金资助:国家自然科学基金(51477002);国家自然科学基金(51303005);安徽省高校自然科学基金重点项目(KJ2013A087);安徽省高校自然科学基金重点项目(KJ2013A095)

通讯作者: 谭德新 E-mail: tdxin@163.com

作者简介: 谭德新(1977-), 男, 副教授, 硕士生导师, 博士, 功能高分子的合成与复合材料, 联系地址:广东省湛江市赤坎区寸金路29号岭南师范学院化学化工学院(524048), E-mail:tdxin@163.com

引用本文:

谭德新, 徐远, 王艳丽, 疏瑞文, 邢宏龙. 聚二苯基二苯乙炔基硅烷树脂的制备与非等温热分解[J]. 材料工程, 2017, 45(7): 77-83.
De-xin TAN, Yuan XU, Yan-li WANG, Rui-wen SHU, Hong-long XING. Synthesis and Non-isothermal Thermal Decomposition of Polydiphenyl(diphenylethynyl)Silane. Journal of Materials Engineering, 2017, 45(7): 77-83.

链接本文:

http://jme.biam.ac.cn/CN/10.11868/j.issn.1001-4381.2015.000941 或 http://jme.biam.ac.cn/CN/Y2017/V45/I7/77

Fig.1 单体DPDPES的合成示意图

Fig.2 单体DPDPES固化温度程序

Fig.3 单体DPDPES的FT-IR谱图

Fig.4 单体DPDPES的¹H-NMR谱图

Fig.5 PDPDPES在不同升温速率下的TG-DTG曲线

Table 1 不同升温速率下最大分解温度及残炭率

Fig.6 PDPDPES的Kissinger法ln(β/T_p²) -T_p^-1

Fig.7 PDPDPES的Ozawa法lgβ-T_p^-1

Table 2 Ozawa法得到的热分解动力学参数

Table 3 β为10℃/min由Coats-Redfern法和Achar法所得参数

Table 4 不同升温速率下44号机理函数计算所得参数

Fig.8 DPDPES的Vyazovkin-Wight法ln(β/T_p²)-T_p^-1

Fig.9 DPDPES的Tang法ln(β/T_p^1.894661)-T_p^-1

Table 5 由V-W法、Tang法计算所得到的动力学参数

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