SYNTHE SIS AND APPLIED RE SEARCH OF POLYACTYLATE／NANO．S102 COMPOSITE LATEXA Thesis(or Dissertation) Submitted toShaanxi University of Science and Technologyin Partial Fulfillment of the Requirement for the Degree ofMaster of E堕gi卫星曼!i望gBy Li坚』坚望!iThesis(or Dissertation)Supervisor：Professor．M———————a—————J——ianzhongAssociate Professor Bao YanMarch，20 1 1聚丙烯酸酯／纳米Si02复合乳液的制备与应用研究摘要聚丙烯酸酯是皮革涂饰材料中应用广泛的一类成膜物质近年来，随着 人们环保意识的提高，制备性能优秀并且无毒、不燃、环境和谐的新一代绿 色环保涂饰剂越来越受到人们的青睐本研究正是以环境和谐为出发点，以 提高丙烯酸树脂涂饰剂的性能为目的，运用无机纳米材料的纳米效应，采用 反映性乳化剂替代常规乳化剂制备绿色、环保的聚丙烯酸酯／纳米Si02复合 涂饰剂，用于皮革涂饰，提高涂层的耐水性、耐溶剂性，使产品性价比极大 提高。
在课题组前期研究的基本上，同步采用常规乳液聚合法和溶胶．凝胶法， 以壬基酚聚氧乙烯醚一2一磺酸基琥珀酸单酯二钠盐(MS．1)和十二烷基苯磺酸 钠(SDBS)为乳化剂，制备聚甲基丙烯酸甲酯／丙烯酸丁酯／甲基丙烯酸十二酯 [P(MMA／BA／LMA)]／纳米Si02复合乳液考察了不同聚合工艺、LMA用量、 交联剂双丙酮丙烯酰胺(DAAM)用量对P(MMA／BA／LMA)／纳米Si02复合乳 液性能的影响采用红外光谱(FTIR)、差示扫描量热(DSC)和动态激光光散 射(DLS)等检测手段对P(MMA／BA／LMA)／纳米Si02复合乳液的构造进行了 表征并将所制备的复合乳液应用于皮革涂饰中，考察其应用性能P(MMA／BA／LMA)／纳米Si02复合乳液的优化制备工艺为：采用预乳化 半持续乳液聚合，LMA用量(以单体总质量计，下同)为3％，DAAM用量为 O．25％P(MMA／BA／LMA)／纳米Si02复合乳液的应用成果表白：与 P(MMA／BA)／纳米Si02乳液成膜相比，P(MMA／BA／LMA)／纳米Si02复合乳液 成膜的24h耐水性提高了5．7％，断裂伸长率、抗张强度分别提高了63．52％和 1 20．9‰但是采用P(MMA／BA／LMA)／纳米Si02复合乳液涂饰后革样的透水 汽性减少了6．79％，24h耐水性减少了28．60％。
同步采用无皂乳液聚合法和溶胶．凝胶法，制备了聚甲基丙烯酸甲酯／丙 烯酸丁酯[P(MMA／BA)]／纳米Si02复合乳液考察了反映性乳化剂种类及用 量、功能性单体甲基丙烯酸羟丙磺酸钠(HPMAS)jJN／N．方式及用量、单体配 比、正硅酸乙酉匕(TEOS)用量、硅烷偶联剂种类及用量对P(MMA／BA)／纳米 Si02复合乳液性能的影响采用差示扫描量热(DSC)、动态激光光散射 (DLS)、透射电镜(TEM)、原子力显微镜(AFM)等检测手段对P(MMA／BA)／ 纳米Si02复合乳液的构造进行表征并将所制备的复合乳液应用于皮革涂饰中，考察其应用性能P(MMNBA)/ 纳米Si02复合乳液的优化制备条件为:采用乳化剂 1-烯丙 氧基-3-(4-圭基苯盼)-2-丙醇聚氧乙烯隧硫酸钱 (DNS-86)制备P(MMAlBA)/纳 米Si02复合乳液且DNS-86用量为3% ，HPMAS采用半持续滴加法加入、用量 为 1%， n(MMA): n(BA)=5: 8，TEOS用量为 1.5%，硅炕偶联剂采用乙烯基 三乙氧基硅炕 (A-151)且用量为4% 应用成果表白:与采用常规乳化剂制 备的P(MMA/BA)/纳米Si02复合乳液相比，采用反映性乳化剂 DNS-86制备的P(MMA/BA)/纳米Si02复合乳液涂饰后革样的透气性提高了 40.82% ，透水汽性提高了3.07% ，24h吸水率减少了7.88% ，耐干擦达到4-5级，耐湿擦达到4 级， 100000次耐折测试后，涂层完好无损。
核心词:聚丙烯酸酶，纳米 Si02 ，乳液聚合，皮革涂饰剂，反映性乳化剂IISYNTHE SIS AND APPLIED RE SEARCH oF POLYACTYLATE／NANO-S102CoMPOSITE LATEXABSTRACTPolyacrylate is one of the most important film-foroming substances and has been widely used in 1eather finishing．As the awareness of environmental friendly protection is increasing，new generation leather finishing agent with outstanding performance，non—poisonous，non-flammable and environmentally friendly are of high scientific and technology interesting．The aim of thisresearch is protecting the environment and improving the performance ofpolyacrylate leather finishing agent．Inorganic nanomaterials and polymerizable surfactants were used to prepare the green and environmentalpolyacrylate／nano—Si02 composite leather finishing agent．Then it was used in leather finishing to improve water resistance and solvent resistance of the coating to obtain a good performance product．Poly(methyl methacrylate／butyl acrylate／lauryl methacrylate)[P(MMA／BA／ LMA)]／nano—Si02 composite latex was obtained via both conventional emulsion polymerization and sol-gel in one step method,disodium nonylphenyl polyoxye thylene ether surfosuccinate(MS一1) and sodium dodecyl benzene sulfonate(SDBS)were used as the emulsifier,basing on the previous studies in our group．Effects of different polymerization processes and the dosage of LMA， DAAM on the properties of P(MMA／BA／LMA)／nano—Si02 composite 1atex were investigated in detail．The structures of P(MMA／BA／LMA)／nano．SiO， composite latex were characterized by fourier transfoi'm infrared spectroscopy(FTIR)，differential scanning calorimetry(DSC)and dynamic light scattering(DLS)．At last，the above latex were applied in leather finish，and the applied properties of the finished leather were determined in detail．The optimum polymerization conditions were pre．emulsification semi．continual process，the dosage of LMA was 3％，DAAM was 0．25％． Results of the application showed that the water resistance，elongation at breakIIIand tensile strengths of P(MMA／BA／LMA)／nano—Si02 composite film were increased by 5．7％．63．52％and 1 20．9％respectively in contrast to that of P(MMA／BA)／nano．Si02 composite film．And water vapor permeability and water resistance of leather finished by P(MMA／BA／LMA)／nano-Si02 composite latex were decreased by 6．79％％and 28．60％。
Poly(methyl methacrylate／butyl acrylate)[P(MMA／BA)]／nano—Si02 composite 1atex was obtained via both emulsifier-free emulsion polymerization and s01．gel method in one step method．Ef．fects of different polymerizable surfactants，silane coupling agents，addition methods of propionic acid methyl methacrylate sodium(HPMAS)and the dosage of polymerizable surfactant，HPMAS，ratio of monomers，tetraethyl orthosilicate(TEOS)，silane coupling agent on the properties of P(MMA／BA／LMA)／nano—Si02 composite latex were investigated in detail．。