含硅氧烷结构聚酰亚胺树脂的耐热稳定性及高温结构演变

doi:10.7503/cjcu20180342

摘要/Abstract

摘要：

基于含硅芳香二胺双(4-氨基苯氧基)二甲基硅烷(APDS)设计制备了系列苯乙炔基封端的含硅氧烷结构聚酰亚胺树脂预聚物(PEPA-PIS), 考察了硅氧烷含量对树脂固化物耐热稳定性的影响规律. 利用非反应性苯酐基团封端的模型预聚物(PA-PIS)证明了温度对于硅氧烷结构演变的影响. 通过对树脂固化物高温固化处理后耐热稳定性与微观结构和表面形貌的关系进行深入研究, 发现在高温下硅氧烷结构发生氧化交联反应, 并在树脂表面形成具有无机特性的二氧化硅结构, 这种有机/无机杂化特性可显著提高聚酰亚胺树脂的耐热稳定性.

关键词: 聚酰亚胺树脂, 硅氧烷, 耐热稳定性, 微观结构, 有机/无机杂化

Abstract:

A series of phenylethynyl-terminated imide oligomers(PEPA-PIS) based on siloxane-containing aromatic diamine, i.e., bis(p-aminophenoxy)dimethyl silane(APDS), was synthesized. The effect of siloxane content on the thermal stability of cured polyimides resins was investigated. The influence of temperature on the evolution of siloxane structure was confirmed by the non-reactive phthalic-terminated model imide oligomers(PA-PIS). The thermal stability of polyimide resins after post-curing at elevated temperature and the correlation with the microstructure and surface morphology were discussed. The results indicated that the oxidative crosslinking reaction of siloxane was occurred at elevated temperature, and even resulting in the formation of inorganic silica on the resin surface. The significant enhancement in thermal stability of polyimide containing siloxane structure is attributed to their organic/inorganic hybrid characteristics.

Key words: Polyimide resin, Siloxane, Thermal stability, Microstructure, Organic/inorganic hybrid

中图分类号:

O631

TrendMD:

刘仪, 许晓洲, 莫松, 翟磊, 何民辉, 范琳. 含硅氧烷结构聚酰亚胺树脂的耐热稳定性及高温结构演变. 高等学校化学学报, 2019, 40(1): 187.

LIU Yi, XU Xiaozhou, MO Song, ZHAI Lei, HE Minhui, FAN Lin. Thermal Stability of Polyimide Resins Containing Siloxane Structure and Their High Temperature Structural Evolution. Chem. J. Chinese Universities, 2019, 40(1): 187.

图/表 11

Fig.1 Chemical structures of PEPA-terminated and PA-terminated oligoimides

Table 1 Chemical composition of PEPA-terminated and PA-terminated oligoimides

Sample	n(TFDB):n(APDS)	Mass fraction of siloxane(%)	n	M_n(Theoretical)
PEPA-PIS-0	10:0	0	1.23	1500
PEPA-PIS-1	9:1	1.29	1.25	1500
PEPA-PIS-2	8:2	2.59	1.26	1500
PEPA-PIS-3	7:3	3.92	1.28	1500
PA-PIS-1	9:1	1.47	1.60	1500
PA-PIS-10	0:10	15.81	1.76	1500

Fig.2 Effect of siloxane content on the thermal stability of cured polyimide resins

Fig.3 DMA curves of polyimide resins after curing at 370 ℃(A) and post-curing at 450 ℃(B)

Fig.4 Isothermal melt viscosities of PA-PIS-1 at different temperatures for 2 h

Fig.5 29Si NMR spectra of PA-PIS-10 exposed at 370 ℃(a) and 500 ℃(b) for 1 h

Fig.6 Si2p XPS spectra of PEPA-PIS-1 cured at 370 ℃(A), as well as after post-curing at 420 ℃(B) and 450 ℃(C), respectively

Table 2 Curve fitting results of Si2p XPS spectra for cured and postcured PEPA-PIS-1

Structure	370 ℃		420 ℃		450 ℃
Structure	E_b/eV	Molar fraction of Si(%)	E_b/eV	Molar fraction of Si(%)	E_b/eV	Molar fraction of Si(%)
D[(CH₃)₂SiO_2/2]	102.01	90.19	102.06	14.76	101.96	6.90
T[CH₃SiO_3/2]	102.97	9.81	102.90	48.34	102.93	23.61
Q[SiO_4/2]	——	——	103.53	36.90	103.51	69.49

Fig.7 Si2p XPS spectra measured for different depths of PEPA-PIS-1 after post-curing at 450 ℃Depth/mm: (A) 0.02; (B) 0.10; (C) 0.15; (D) 0.20; (E) 0.40; (F) 0.80.

Fig.8 TEM image of PEPA-PIS-1 after post-curing at 450 ℃

Scheme 1 Schematic diagram of microstructural changes at elevated temperature for polyimide containing siloxane structure

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