取代烷基变化对芳炔单体及其聚合物性能影响

doi:10.16085/j.issn.1000-6613.2022-1032

摘要/Abstract

摘要：

含硅芳炔聚合物是一类新型热固性树脂，通常以芳炔单体或其预聚物为原料通过热聚合获得，具有潜在应用前景。本文以不同取代烷基（正辛基、癸基、十六烷基）三氯硅烷和苯乙炔为原料，通过格氏反应合成相应含硅芳炔单体，借助红外和核磁光谱对单体结构进行表征，研究了取代烷基变化对单体流变性能和固化行为的影响；并通过热聚合制备相应芳炔聚合物，系统讨论了取代烷基变化对聚合物热稳定性、介电性能的影响。实验结果表明，随着取代烷基碳链长度增加，单体出现凝胶点时间从519s增加到1222s，单体固化反应活化能从143.90kJ/mol增加到173.05kJ/mol。热重分析显示，聚合物热分解残炭率受芳炔单体取代基数量和取代基链段大小影响，对聚合物微分热重曲线进行分峰拟合显示，随着取代烷基碳链长度增加，分解峰1温度从464.4℃增加到499.3℃，对应固化产物中共轭烯结构的断链分解及取代基分解。在2~18GHz频率范围内，三种聚合物介电常数实部在2.0~2.9之间，虚部在0.3以下，介电损耗正切值tanδ在0~0.15之间，相比传统工程塑料，显示更为优良的透波性能。

关键词: 聚合物, 芳炔单体, 反应, 稳定性, 介电性能

Abstract:

Silicon-containing arylacetylenic polymers have potential applications as one kind of new thermosetting resin. They can be obtained using arylacetylenic monomer or arylacetylenic prepolymer as materials by thermal polymerization. A series of silicon-containing arylacetylenic monomers with different side alkyl groups on the silicon atom, including n-octyl (OTPES), decyl (DTPES) and hexadecyl (HTPES) were synthesized by Grignard reaction with phenylacetylene and different substituted trichlorosilane as raw materials. The chemical structure of monomers was characterized by Fourier transform infrared spectroscopy (FTIR) and nuclear magnetic resonance spectroscopy (NMR), and the effect of alkyl groups on the curing behavior and rheology was studied. The corresponding polymers were prepared by thermal polymerization and the influence of alkyl groups on the thermal stability and dielectric properties was also discussed. The results showed that the gel time increased from 519s to 1222s and the reaction activation energy also elevated from 143.90kJ/mol to 173.05kJ/mol with the increase of the carbon chain length of the substituent. Thermogravimetric analysis indicated that the thermal stability of polymers was affected by the quantity and size of the substituent and the peak Ⅰ decomposition temperature was increased from 464.4℃ to 499.3℃ by peak fitting with the increase of carbon chain length. In the frequency range of 2~18GHz, the real part was between 2.0~2.9 and the imaginary part of dielectric constant was less than 0.3, and the tangent value of dielectric loss was at 0~0.15 of three polymers, showing an excellent wave transmission performance compared with traditional engineering plastics.

Key words: polymer, arylacetylenic monomer, reaction, stability, dielectric propertity

中图分类号:

TQ221.24

谭德新, 曾佳欣, 梁莉敏, 申思慧, 曾子倩, 王艳丽. 取代烷基变化对芳炔单体及其聚合物性能影响[J]. 化工进展, 2023, 42(4): 2031-2037.

TAN Dexin, ZENG Jiaxin, LIANG Limin, SHEN Sihui, ZENG Ziqian, WANG Yanli. Effects of substituted alkyl on the properties of arylacetylenic monomers and their polymers[J]. Chemical Industry and Engineering Progress, 2023, 42(4): 2031-2037.

图/表 8

图1 三苯乙炔基硅烷的反应路线图

图2 三种单体的结构分析图

图3 三种单体的固化行为及其聚合物结构分析图

图4 DTPES的固化曲线及线性拟合曲线

图5 三种单体的原位红外光谱图

图6 三种聚合物的TG-DTG曲线

表1 固化后的聚合物的TGA分析数据

聚合物	峰	峰中心T_P/℃	峰高/g·℃^-1	峰面积比/%	Y/%
POTPES	1	464.4	0.27	59.8	62
POTPES	2	540.8	0.08	40.2	62
PDTPES	1	466.8	0.51	82.6	51
PDTPES	2	544.6	0.07	17.4	51
PHTPES	1	499.3	0.44	59.2	58
PHTPES	2	530.2	0.09	40.8	58

图7 聚合物在2~18GHz下的介电谱图

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