石墨烯负载纳米粒子改性硅树脂热性能的研究

发布时间：2018-03-04 02:11

本文选题：复合纳米粒子　切入点：有机硅树脂　出处：《哈尔滨工业大学》2015年硕士论文　论文类型：学位论文

【摘要】：随着科学技术的快速发展,有机硅树脂作为一种新型材料广泛用于航空航天及电子等高端领域。大多数情况下有机硅树脂都采用高温固化,为了使有机硅树脂的机械性能和耐高温性能得到一定程度上的提升,一般采用提高有机硅树脂交联度和添加填料等手段。近年来紫外光固化由于其独特的优势得到了越来越广泛的关注,在体系中加入一定含量高分散性的纳米粒子更可以有效结合纳米粒子的性能以及紫外光快速固化和无溶剂的特点,从而得到性能优异的无机-有机纳米复合材料体系。本文主要研究的是不同的复合纳米粒子改性有机硅树脂在高温固化和UV光固化行为的研究,分析不同固化方式对有机硅树脂的热稳定性能的影响。首先采用两步法,在高温水热条件下合成Co3O4/rm GO,用X射线光电子能谱(XPS)、透射电镜(TEM)等表征手段对其结构和负载原理进行分析,发现在合成过程中加入氨水可以调节钴离子的水解和氧化以及对石墨烯的结构产生变化,得到N掺杂氧化石墨烯负载纳米粒子复合材料Co3O4/N-rm GO。对Co3O4/N-rm GO改性的甲基硅树脂进行热分解动力学研究,发现初始分解温度由原来的185℃提高到235℃,热分解活化能E1为87.95247 k J/mol,E2为248.7991 k J/mol,并求出在“回咬”和“重排”过程中甲基硅树脂的降解速率方程。为了使有机硅树脂可以在UV下进行固化,在合成甲基硅树脂的原料中加入γ-甲基丙烯酰氧基硅基丙基三甲氧基硅烷,在p H=4~5,60℃条件下水解缩聚得到带有双键的丙烯酰氧基有机硅树脂。通过核磁(NMR),气相凝胶色谱(GPC)等手段证实所合成树脂的结构端基为羟基,侧链带有酰氧官能团。之后在20 m W/cm2功率下,样品厚度也为10μm,紫外光引发剂量为1wt%条件下,得到丙烯酰氧基有机硅树脂每个自由基所连接的单元数为1153。无机-有机杂化材料在一定程度上结合了纳米粒子的高性能以及有机聚合物易加工和改性的特点。因为Ti O2/rm GO对紫外光有一定的吸收能力及催化能力,所以首先我们在水热条件下通过调节C2H5O H/H2O的比例得到不同粒径的Ti O2纳米粒子,发现10nm Ti O2/rm GO纳米粒子固化时间和最终转化率最高,复合纳米粒子的的加入量为5%时,转化率为85%,固化时间为15s。
[Abstract]:With the rapid development of science and technology, silicone resin as a new material widely used in aerospace and other high-end electronic fields. Most cases are silicone resin with high temperature curing, in order to make the mechanical properties of silicone resin and high temperature resistant performance has been improved to a certain extent, improve the use of general silicone resin crosslinking agent and adding filler etc. in recent years, the UV curing method. Because of its unique advantage has been more and more attention, adding some content in the system of nanoparticles with high dispersion can more effectively with nano particle properties and UV curing and non solvent characteristics, so as to obtain excellent properties of organic inorganic nanocomposite materials. This paper mainly studies the system the study of different composite nanoparticles modified silicone resin in high temperature curing and UV curing behavior, divided Effect of thermal stability analysis of different curing methods on silicone resin. The first two steps in high temperature hydrothermal synthesis conditions of Co3O4/rm GO, by X ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM) were characterized by means of the analysis of its structure and load principle, adding hydrolysis and oxidation of ammonia can regulate cobalt now the ions in the process of synthesis and structure on graphene changes, Co3O4/N-rm GO. composite nanoparticles were obtained on Co3O4/N-rm GO modified methyl silicone resin by thermal decomposition kinetics research supported N doped graphene oxide, it is found that the initial decomposition temperature increased from 185 C to 235 C, the activation energy of thermal decomposition of E1 87.95247 K J/mol E2 248.7991 K J/mol, and calculated in the degradation rate equation of methyl silicone resin bite back "and" rearrangement "in the process. In order to make the silicone resin can be cured under UV, Join gamma methacryloxy propyl trimethoxysilane silicon in the synthesis of methyl silicone resin raw materials, with double bond acryloxyl silicone resin in P H=4~5,60 C under the conditions of hydrolysis and condensation by NMR (NMR), gas chromatography gel (GPC) means that the terminal structure of synthetic resin the hydroxyl groups with acyl side chain oxygen functional groups. After 20 m W/cm2 power, the thickness of the sample is 10 m, the UV dose of 1wt% under the condition of the number of units are acryloxyl silicone resin each free radical connected 1153. inorganic organic hybrid materials to a certain extent with nanoparticles high performance organic polymer and easy processing and modification of Ti O2/rm GO. Because of absorptive capacity and catalytic ability of ultraviolet light, so first we under hydrothermal conditions were obtained by adjusting the C2H5O ratio of H/H2O Ti O2 nanoparticles with different particle sizes showed that the curing time and final conversion rate of 10nm Ti O2/rm GO nanoparticles were the highest. When the amount of composite nanoparticles was 5%, the conversion rate was 85%, and the curing time was 15s..

【学位授予单位】：哈尔滨工业大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：TB33

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