Page 33 - 201902
P. 33
第 36 卷第 2 期 精 细 化 工 Vol.36, No.2
201 9 年 2 月 FINE CHEMICALS Feb. 2019
功能材料
聚十二烷基三苯乙炔基硅烷树脂的制备与热性能
*
王艳丽,汪 猛,陈佰倍,叶丽红,苏 蕙,谭德新
(岭南师范学院 化学化工学院,广东 湛江 524048)
摘要:以镁条、溴乙烷、苯乙炔和十二烷基三氯硅烷为原料,通过 Grignard 反应制得十二烷基三苯乙炔基硅烷
13
1
29
单体(DTPES)。采用傅里叶变换红外光谱(FTIR)和核磁共振波谱( HNMR、 CNMR 和 SiNMR)对 DTPES
结构进行了表征;利用差示扫描量热法(DSC)确定了 DTPES 的最佳固化工艺。通过热聚合法制得聚十二烷基
三苯乙炔基硅烷树脂(PDTPES),利用 TG-DTG 分析了 PDTPES 树脂的热稳定性,并采用 6 种方法(Kissinger、
Ozawa、Achar、Cosat-Redfern、Friedman 和 Vyazonvkin-Weight 法)对树脂的热分解行为进行了探究。结果表明,
升温速率为 10 ℃/min 时,PDTPES 树脂质量损失 5%的温度(T d5 )为 440 ℃,800 ℃下残炭率为 48.1%。动力
学分析显示,不同分析方法下,PDTPES 树脂的热分解活化能(E a )分别为 182.76、181.53、179.48、179.45、
10
11
12
12
11
11
187.53 和 178.33 kJ/mol,指前因子(A)分别为 1.05×10 、3.40×10 、3.79×10 、1.88×10 、5.73×10 和 1.52×10
–1
s ,并求得热分解动力学方程。
关键词:十二烷基三苯乙炔基硅烷;固化工艺;热聚合;热分解;动力学;功能材料
中图分类号:O633. 2 文献标识码:A 文章编号:1003-5214 (2019) 02-0199-07
Preparation and Thermal Perperties of Polydodecyl-(triphenylethynyl) silane
*
WANG Yan-li, WANG Meng, CHEN Bai-bei, YE Li-hong, SU Hui, TAN De-xin
(School of Chemistry and Chemical Engineering, Lingnan Normal University, Zhanjiang 524048, Guangdong, China)
Abstract: Dodecyltris (2-phenylethynyl) silane (DTPES) was synthesized via Grignard reaction of dodecyl
trichlorosilane and phenyl acetylene in the presence of magnesium and ethyl bromide. Its chemical structure
was characterized by Fourier transform infrared spectroscopy (FTIR) and nuclear magnetic resonance
1
13
29
spectroscopy ( HNMR, CNMR, SiNMR). Its curing process was obtained by differential scanning
calorimetry (DSC). Subsequently, polydodecyl (triphenylethynyl) silane (PDTPES) was synthesized by
thermal polymerization of DTPES monomer. The thermal decomposition behavior was analyzed by TG and
DTG and the corresponding kinetics parameters and thermal decomposition characteristics were discussed
by six kinetics methods, i.e., Kissinger, Ozawa, Achar, Coast-Redfern, Friedman and Vyazonvkin-Weight
methods. The results showed that the decomposition temperature at 5% weight loss (T d5) of the resin was
440 ℃ and the char yield was 48.1% at 800 ℃ under a heating rate of 10 ℃/min. The activation energy
E a and the pre-exponential factor A were 182.76, 181.53, 179.48, 179.45, 187.53 and 178.33 kJ/mol, and
11
11
12
11 –1
10
12
1.05×10 , 3.40×10 , 3.79×10 ,1.88×10 , 5.73×10 and 1.52×10 s , respectively, by the above methods.
The thermal decomposition kinetics equation was also proposed.
Key words: dodecyltris(2-phenylethynyl)silane; curing process; thermal polymerization; thermal
decomposition; kinetics;functional materials
Foundation items: National Natural Science Foundation of China (51303005); Natural Science Foundation
of Guangdong Province (2017A030307028); Foundation of Lingnan Normal University (ZL1822, ZL1604)
近年来,用于合成树脂的含硅芳炔单体引起了 人们广泛关注 [1-3] ,此类芳炔单体可通过自身热聚合
收稿日期:2018-04-17; 定用日期:2018-08-03; DOI: 10.13550/j.jxhg.20180278
基金项目:国家自然科学基金(51303005);广东省自然科学基金(2017A030307028);岭南师范学院校级基金(ZL1822,ZL1604)
作者简介:王艳丽(1978—),女,博士,教授。联系人:谭德新(1977—),男,副教授,博士,E-mail:tdxin@163.com。