通过共水解缩聚方法制备得到由单官能度Si-O链节(M 链节)、三官能度Si-O链节(T链节)和四官能度Si-O链节(Q链节)构成且有不同M∶T∶Q链节比值、不同分子量及不同苯基含量的改性有机硅树脂。随苯基含量增加,树脂折射率增大,当苯基含量为0.39时,树脂折射率达到1.5117。利用红外光谱(FT-IR)、核磁共振(1H-NMR)和凝胶渗透色谱(GPC)对树脂进行了表征,计算得到M∶T∶Q比值;采用热重分析(TGA)、X 射线衍射(XRD)及热重红外联用仪(TGA-IR)对惰性气氛中硅树脂的热稳定性、热降解过程及热降解产物结构进行了研究,MTQ硅树脂降解过程分为3个阶段,随苯基含量增加,热稳定性提高;经高温处理后,MTQ硅树脂完全转变为无定型的SiO2。
Phenyl modified MTQ silicone resins structurally consisted of momofunctional siloxyl group (M segment), trifunctional siloxyl group (T segment) and tetrafunctional siloxyl group (Q segment) with different molecular weight, different phenyl group contents and different segment ratios (M∶T∶Q) were synthesized by cohydrolysis-condensation method initiating from hexamethyldisiloxane, 1,1,3,3-tetramethyl-1,3-divinyl disiloxane, phenyltrimethoxysilane and tetraethoxysilane. The efractive index (RI) of MTQ increased with the increase of Ph/R value and it reached up 1.5117 when Ph/R value was 0.39. MTQ silicone resins were characterized by FT IR, 1H-NMR and GPC spectra, and M∶T∶Q ratio was calculated based on the quantitative analysis of 1H-NMR spectra. Thermal stabilities of MTQ resins in inert atmosphere were studied by TGA, DTG and TGA-IR spectra. The structure of the remnants collected after high temperature treatment was analyzed by XRD and FT-IR. The results indicate that the degradation of MTQ is consisted of three stages, and their thermal stabilities enhance with the increase of phenyl content. After calcinated under higher temperature, MTQ resins are completely transformed into amorphous SiO2.
张宝华,伍 川,董 红,程大海,杨科芳.苯基MTQ 硅树脂的制备及性能[J].高分子材料科学与工程,2013,29(3):137-142.复制