本文關鍵詞： 丙烯酸酯 有機硅 改性 硅氫加成 組分分析 實驗優(yōu)化　出處：《浙江大學》2017年碩士論文　論文類型：學位論文

【摘要】：有機硅改性丙烯酸酯是一類碳官能有機硅烷,它們在聚合物改性,紫外光固化涂料,防污涂料和接觸式眼鏡等領域具有廣闊的發(fā)展前景。而含硅氫鍵的硅氧烷與含不飽和鍵的丙烯酸酯進行硅氫加成反應,其反應條件溫和,實際應用廣泛,是合成有機硅改性丙烯酸酯的有效方法。因此對有機硅改性丙烯酸酯的硅氫加成反應進行研究是具有重要意義的。本論文主要研究了端氫硅氧烷與甲基丙烯酸烯丙酯的硅氫加成反應,其主要研究內容和結論如下：(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為原料,硅氫加成得到含苯基硅氧烷的丙烯酸酯單體。采用紅外光譜和核磁共振氫譜初步表征了單體的結構和封端基團,凝膠滲透色譜測定了相對分子質量和分子量分布。根據(jù)凝膠滲透色譜的實驗結果,單體的高、中和低分子質量的組分結構分別采取電噴霧三重串聯(lián)飛行時間質譜、超高效液相色譜三重串聯(lián)飛行時間質譜和氣相色譜-質譜聯(lián)用的分析方法進行表征。鑒定出產(chǎn)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,具體是二聚體大分子、加成產(chǎn)物和歧化小分子的三類組分。其中二聚體大分子的相對分子質量為998,加成產(chǎn)物的相對分子質量為577,歧化小分子的相對分子質量為329。實驗中對投料方式、反應溫度和投料比三方面因素進行合成優(yōu)化研究。確定反應投料方式優(yōu)選：將甲基丙烯酸烯丙酯、阻聚劑和催化劑進行混合,加熱攪拌,并緩慢滴加1,1,5,5-四甲基-3,3-二苯基三硅氧烷進行反應。反應溫度則優(yōu)選50～70℃。反應最優(yōu)投料比為：Si-H基與CH2=CHCH2-基的物質的量比等于1：2。按照優(yōu)選合成方法,并以氯鉑酸/四氫呋喃溶液為催化劑,2,6-二叔丁基對甲基苯酚為阻聚劑,反應3h,硅氧烷中的硅氫鍵完全反應,產(chǎn)品顏色呈現(xiàn)無色透明。通過核磁共振氫譜表征確定：含苯基硅氧烷的丙烯酸酯單體中甲基丙烯酰氧丙基、甲基丙烯酰氧基、丙基封端基團的比例為100：12：5。通過凝膠滲透色譜分析得到：二聚體大分子、加成產(chǎn)物和歧化小分子的含量分別為12.6%、84.3%、3.1%。(2)以含苯基硅氧烷的丙烯酸酯單體的合成及分析結論為指導,選取甲基丙烯酸烯丙酯和氫封端聚二甲基硅氧烷為原料,制備得到甲基丙烯酰氧丙基封端的聚二甲基硅氧烷。采用紅外光譜初步表征產(chǎn)物結構,核磁共振氫譜和電噴霧三重串聯(lián)飛行時間質譜分析確認產(chǎn)物結構。聚二甲基硅氧烷中的硅氫鍵完全反應,產(chǎn)物中不僅含有甲基丙烯酰氧丙基雙封端的聚二甲基硅氧烷結構,而且還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。初步研究證明,含苯基硅氧烷的丙烯酸酯單體的硅氫加成反應研究結論基本適用于甲基丙烯酰氧丙基封端的聚二甲基硅氧烷。本文的創(chuàng)新點：(1)以含苯基硅氧烷的丙烯酸酯單體為研究對象,采用多種表征方法對組分進行全面分析,確定了主成分和副產(chǎn)物的類型、端基結構,解決了有機硅改性丙烯酸酯組分分析難的問題,建立了有機硅改性丙烯酸酯類功能材料的分析方法。(2)對含苯基硅氧烷的丙烯酸酯單體、甲基丙烯酰氧丙基封端的聚二甲基硅氧烷進行合成優(yōu)化,得出最優(yōu)反應條件,為其工業(yè)化生產(chǎn)奠定了良好的基礎。
[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.

【學位授予單位】：浙江大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：O621.256.7

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