【作者】 尚丽娟；

【导师】 张超灿；

【作者基本信息】 武汉理工大学 ， 材料学， 2005， 硕士

【摘要】 本论文以聚醚改性聚硅氧烷为原料,进行硫酸酯化反应,并进一步用碱中和,合成了聚醚改性聚硅氧烷硫酸酯钠乳化剂,该乳化剂属于非离子、阴离子复合型乳化剂。与未进行硫酸酯化的乳化剂相比,其浊点明显提高,适用于常规的乳液聚合。 利用甲基丙烯酸甲酯(MMA)和自制的γ-甲基丙烯酰氧丙基三(三甲硅氧基)硅烷(TRIS)为原料,以聚醚改性聚硅氧烷硫酸酯钠与十二烷基硫酸钠为复配乳化剂,采用单体乳液半连续滴加法,分别制备了有机硅均聚物(PTRIS)乳液、有机硅-甲基丙烯酸甲酯共聚物(P(MMA-co-TRIS))乳液和聚甲基丙烯酸甲酯(PMMA)乳液。并用IR,TEM,DMA,水滴接触角测试等方法对所制备的均聚物和共聚物膜进行了表征。结果表明:当乳化剂用量在6%～8%(相对单体量)、改性乳化剂与十二烷基硫酸钠复配比为2:1、引发剂用量在0.4～0.8%(相对单体量)、聚合温度为80℃、搅拌速度在200～250rpm时,得到的均聚物和共聚物乳液稳定,而且粒径分布均匀;对于共聚物乳液来说,随着单体中TRIS含量的增加,所得聚合物膜的水滴接触角增加,即其表面能增加:另外,随着共聚单体中TRIS含量的增加,共聚物的玻璃化转变温度从PMMA的Tg的高温区向PTRIS的Tg的低温区移动。 对聚合物乳液共混行为的研究表明:在PTRIS和PMMA均聚物乳液中,加入共聚物(P(MMA-co-TRIS))后,可改善PTRIS和PMMA的相容性;多组分乳液共混时,可以得到一面是聚甲基丙烯酸甲酯端,另一面是有机硅聚合物端的结构渐变的梯度膜。对该膜的DMA,DSC,UV测试结果表明:所得梯度膜的玻璃化转变范围比各组分材料的玻璃化转变范围宽;该梯度膜具有较好的热稳定性、良好的憎水性能和紫外吸收性能。更多还原

【Abstract】 In this paper, the emulsifier sodium polyether sulfovinate modified polysiloxane was synthesized by sulfuric acid esterification between chlorosulfonic acid and polyether modified polysiloxane, then alkali neutralization. It was a kind of nonionic and anionic composite emulsifier. Compared with emulsifier unesterified, it has higher cloud point, which could apply to conventional emulsion polymerization.With sodium polyether sulfovinate modified polysiloxane and sodium lauryl sulfate as composite emulsifier system, using methyl methacrylate(MMA) and self-made monomer γ-[tris(trimethylsiloxy)silyl]propyl methacrylate(TRIS) as raw materials, we prepared the homopolymer of TRIS, MMA, and the copolymers (P(MMA-co- TRIS)) by means of semi continuous dropwise method of monomer emulsion. Then, IR, TEM, DMA and water contact angle measurements were utilized to study these polymers and their films. The result indicated that we can get stable homopolymer and copolymer emulsion with uniform size distribution, when the ratio of sodium polyether sulfovinate modified polysiloxane to sodium lauryl sulfate was two, the quantity of the emulsifiers ranged from 6% to 8%(relative to monomer), the quantity of initiator ranged from 0.4% to 0.8%(relative to monomer), the stirring speed ranged from 200rpm to 250rpm, the polymerization temperature was 80 centigrade degree. As for the copolymer emulsion, the more the TRIS content in the monomers, the larger the water contact angle of their films became, namely, the surface energy of the copolymer films increased with the TRIS content in the monomers. In addition, the glass-transition temperature of the copolymers ranged from high temperature region to low temperature region with the increasing of TRIS content in the monomers.The study of blend manner of homopolymer and copolymer emulsion indicated that we can improve the miscibility between PMMA and PTRIS by adding P(MMA-co-TRIS) copolymer, and we can obtain organosilicon polymer-poly(methyl methacrylate) gradient films with poly(methyl methacrylate) at the top surface and organosilicon polymer at the bottom one. The analysis result of DMA, DSC, UV measurements showed that the glass-transition range of the gradient films was wider than the component ones, and the gradient films had good thermo-stability, hydrophobicperformance and absorption capacity to ultraviolet ray.更多还原