有机硅改性丙烯酸酯的硅氢加成反应研究

发布时间：2018-02-27 21:10

本文关键词： 丙烯酸酯有机硅改性硅氢加成组分分析实验优化　出处：《浙江大学》2017年硕士论文　论文类型：学位论文

【摘要】：有机硅改性丙烯酸酯是一类碳官能有机硅烷,它们在聚合物改性,紫外光固化涂料,防污涂料和接触式眼镜等领域具有广阔的发展前景。而含硅氢键的硅氧烷与含不饱和键的丙烯酸酯进行硅氢加成反应,其反应条件温和,实际应用广泛,是合成有机硅改性丙烯酸酯的有效方法。因此对有机硅改性丙烯酸酯的硅氢加成反应进行研究是具有重要意义的。本论文主要研究了端氢硅氧烷与甲基丙烯酸烯丙酯的硅氢加成反应,其主要研究内容和结论如下：(1)以甲基丙烯酸烯丙酯和1,1,5,5-四甲基-3,3-二苯基三硅氧烷为原料,硅氢加成得到含苯基硅氧烷的丙烯酸酯单体。采用红外光谱和核磁共振氢谱初步表征了单体的结构和封端基团,凝胶渗透色谱测定了相对分子质量和分子量分布。根据凝胶渗透色谱的实验结果,单体的高、中和低分子质量的组分结构分别采取电喷雾三重串联飞行时间质谱、超高效液相色谱三重串联飞行时间质谱和气相色谱-质谱联用的分析方法进行表征。鉴定出产物中含有甲基丙烯酰氧丙基、甲基丙烯酰氧基和丙基封端的硅氧烷,具体是二聚体大分子、加成产物和歧化小分子的三类组分。其中二聚体大分子的相对分子质量为998,加成产物的相对分子质量为577,歧化小分子的相对分子质量为329。实验中对投料方式、反应温度和投料比三方面因素进行合成优化研究。确定反应投料方式优选：将甲基丙烯酸烯丙酯、阻聚剂和催化剂进行混合,加热搅拌,并缓慢滴加1,1,5,5-四甲基-3,3-二苯基三硅氧烷进行反应。反应温度则优选50～70℃。反应最优投料比为：Si-H基与CH2=CHCH2-基的物质的量比等于1：2。按照优选合成方法,并以氯铂酸/四氢呋喃溶液为催化剂,2,6-二叔丁基对甲基苯酚为阻聚剂,反应3h,硅氧烷中的硅氢键完全反应,产品颜色呈现无色透明。通过核磁共振氢谱表征确定：含苯基硅氧烷的丙烯酸酯单体中甲基丙烯酰氧丙基、甲基丙烯酰氧基、丙基封端基团的比例为100：12：5。通过凝胶渗透色谱分析得到：二聚体大分子、加成产物和歧化小分子的含量分别为12.6%、84.3%、3.1%。(2)以含苯基硅氧烷的丙烯酸酯单体的合成及分析结论为指导,选取甲基丙烯酸烯丙酯和氢封端聚二甲基硅氧烷为原料,制备得到甲基丙烯酰氧丙基封端的聚二甲基硅氧烷。采用红外光谱初步表征产物结构,核磁共振氢谱和电喷雾三重串联飞行时间质谱分析确认产物结构。聚二甲基硅氧烷中的硅氢键完全反应,产物中不仅含有甲基丙烯酰氧丙基双封端的聚二甲基硅氧烷结构,而且还含有少量的甲基丙烯酰氧基和丙基封端的聚二甲基硅氧烷。初步研究证明,含苯基硅氧烷的丙烯酸酯单体的硅氢加成反应研究结论基本适用于甲基丙烯酰氧丙基封端的聚二甲基硅氧烷。本文的创新点：(1)以含苯基硅氧烷的丙烯酸酯单体为研究对象,采用多种表征方法对组分进行全面分析,确定了主成分和副产物的类型、端基结构,解决了有机硅改性丙烯酸酯组分分析难的问题,建立了有机硅改性丙烯酸酯类功能材料的分析方法。(2)对含苯基硅氧烷的丙烯酸酯单体、甲基丙烯酰氧丙基封端的聚二甲基硅氧烷进行合成优化,得出最优反应条件,为其工业化生产奠定了良好的基础。
[Abstract]:Silicone modified acrylate is a kind of organic carbon functional silane, their modification in polymer, UV curable coatings, has broad prospects for the development of antifouling coatings and contact lenses and other fields. And silicon containing hydrogen silicone and acrylate containing unsaturated bonds hydrosilylation, its mild reaction conditions, a wide range of practical application that is an effective method for the synthesis of organosilicon modified acrylate. The silicon hydrogen silicone modified acrylate addition reaction of research is of great significance. This paper mainly studies the silicon hydrogen hydrogen terminated siloxane and methacrylic acid allyl addition reaction, the main research contents and conclusions are as follows: (1) to allyl methacrylate and methyl phenyl three 1,1,5,5- four -3,3- two silicone as raw material, hydrosilylation by acrylate monomer containing phenyl siloxane. By infrared spectroscopy and nuclear magnetic resonance The hydrogen spectrum were used to characterize the structure of monomer and end capping groups, molecular weight and molecular weight distribution were determined by gel permeation chromatography. According to the experimental results of gel permeation chromatography, monomer, and low molecular weight components of the structure to take three tandem electrospray ionization time of flight mass spectrometry analysis method respectively, three tandem time-of-flight mass spectrometry and gas chromatography-mass spectrometry by ultra high performance liquid chromatography was investigated. The identification of products containing methyl acryloyl oxygen propyl, methacryl and allyl terminated siloxane, particularly two polymer molecules, adduct and disproportionation of small molecules of three kinds of components two. The relative molecular mass of polymer molecules was 998, with relative molecular mass of the products is 577, the relative molecular mass of disproportionation of small molecules in the experiments, 329. feeding mode, reaction temperature and feed ratio of the three factors of synthesis Study on Optimization of reaction. Determine the feeding mode selection: allyl methacrylate, inhibitor and catalyst are mixed, heated and stirred, and slowly dropping four methyl two phenyl 1,1,5,5- -3,3- three siloxane reaction. Reaction temperature is 50~70 degrees Celsius. Preferably optimal reaction ratio: Si-H based and CH2=CHCH2- based materials the amount is equal to 1:2. according to the preferred synthesis method, and with chloroplatinic acid / THF solution as catalyst, 2,6- Di tert butyl phenol as inhibitor, 3h reaction, the reaction bonding of silicone products, color is colorless transparent. By 1HNMR: containing phenyl siloxane acrylate monomer in Methacryloyloxy propyl, methacryloxy propyl terminated groups, ratio of 100:12:5. by gel permeation chromatography analysis: two dimer molecules, adduct and disproportionation The content of small molecules were 12.6%, 84.3%, 3.1%. (2) to synthesis and analysis conclusion containing phenyl siloxane acrylate monomer as a guide, select the allyl methacrylate and hydrogen terminated poly two methyl siloxane as raw materials, preparation of methacryloyl terminated poly two methyl propyl siloxane. Using the structure IR characterization of products, 1H NMR and electrospray three tandem time-of-flight mass spectrometry analysis confirmed that the structure of the product. Poly two methyl siloxane bonding in the complete reaction product not only contains poly two methyl siloxane structure methacrylato propyl double terminated, but also contains a small amount of methacryloxypropyl and allyl terminated poly two methyl siloxane. Preliminary studies have shown that the phenyl siloxane acrylate monomer containing the hydrosilylation reaction of the conclusion of the study is basically applicable to methacrylato capped Poly two methyl siloxane. The innovation of this paper: (1) with phenyl siloxane acrylate monomer as the research object, using a variety of characterization methods were divided to group types, comprehensive analysis, principal component and by-products to determine the end group structure, solved the organosilicon modified acrylic ester group analysis of the difficult problem of building the analysis method of silicone modified acrylate functional materials. (2) acrylate monomer containing phenyl siloxane, synthesis optimization of methacryloyl capped poly two methyl siloxane, the optimal reaction conditions, which has laid a good foundation for industrial production.

【学位授予单位】：浙江大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O621.256.7

【参考文献】