丙烯酸酯类聚合物乳液的制备及其相关应用的研究
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摘要
丙烯酸酯类共聚物乳液是丙烯酸酯类或甲基丙烯酸酯类与其它乙烯基酯类单体进行乳液聚合的产物。目前，应用最多的是(甲基)丙烯酸酯类共聚物、醋酸乙烯／(甲基)丙烯酸酯类共聚物和苯乙烯／(甲基)丙烯酸酯类共聚物乳液。由于丙烯酸酯类聚合物乳液具有优良的耐光性、耐酸碱性和耐腐蚀性，而广泛应用于涂料、胶粘剂等。但当丙烯酸酯聚合物乳液作为聚合物水泥防水涂料的液料时，存在耐水性差、弹性差、耐候性差等缺点，影响聚合物防水涂料的防水功能。乳胶涂料低挥发有机化合物(Volatile organic compounds，简称VOC)化的关键在于改进聚合物乳液的性能，由于聚合物乳液的成膜性与最终涂膜的力学性能存在着矛盾，而当丙烯酸酯聚合物乳液作为乳胶涂料的基料时，为了兼顾聚合物乳液的成膜性和最终涂膜的力学性能，需要在乳胶涂料中加入挥发性的有机溶剂，导致乳胶涂料中VOC含量偏高。通过对乳液的粒子和性能进行预先设计，并通过丙烯酸酯类乳液的少量功能单体的引入、乳化体系和引发体系的选择以及聚合工艺三方面的手段，制备出两种分别应用于聚合物水泥防水涂料和建筑乳胶涂料的丙烯酸酯类聚合物乳液，对于提高聚合物水泥防水涂料的性价比和降低乳胶涂料中VOC的含量，具有非常重要的理论意义和现实意义。
采用预乳化半连续种子乳液聚合工艺，制备用于聚合物水泥防水液料的丙烯酸酯乳液，并在乳液聚合过程中，加入功能性单体、活性交联单体和在乳液中加入耐水性单体。研究结果表明，加入的功能性单体和采用的聚合工艺极大的提高了聚合过程的稳定性；加入的活性交联单体和耐水性单体，提高了聚合物乳液的耐候性和耐水性。对聚合物乳液流变性的研究表明，聚合物乳液属非牛顿性流体，具有假塑性流体的流变性质。
以自制的聚合物乳液为液料，普通硅酸盐水泥为粉料，研究了液粉比和助剂对聚合物水泥防水涂料的拉伸性能、耐水性、低温柔性等的影响规律。研究结果表明：成膜助剂、分散剂、增塑剂等助剂提高了聚合物水泥防水涂料的弹性和低温柔性，但成膜助剂会降低防水涂料的耐水性，分散剂对防水涂料耐水性的影响存在着一个最佳值。探讨和分析聚合物水泥防水涂料的成膜机理和防水机理，结果表明：聚合物水泥防水涂料的成膜具有挥发固化和反应固化双重特点；防水机理是通过防水涂膜本身的憎水性来进行的。
采用半连续种子乳液聚合工艺，在聚合过程中加入功能性单体和反应性交联单体—甲基丙烯酸羟丙酯(HPMA)，并采用氧化还原引发体系，制备出超低VOC乳胶涂料用丙烯酸酯乳液。研究了软硬单体配比、pH、HPMA和搅拌器转速等对乳液聚合过程以及乳液性能的影响。研究结果表明：当m(丙烯酸丁酯)／m(甲基丙烯酸甲酯)=80／120时，加入HPMA后，HPMA作为潜交联剂，在聚合过程中与其它单体进行共聚，由分子链间官能基反应而提高聚合物乳液的交联度，制备出的是一种自交联型乳液，在室温条件下成膜过程中自交联，提高聚合物乳液的成膜稳定性。采用材质为不锈钢的间歇反应釜和注入式循环油加热系统进行放大实验
Acrylate copolymer emulsions are the products of acrylate or methacrylate which reacts with other vinyl esters through emulsion polymerization. At present, copolymer emulsions of (meth)acrylate, vinyl acetate/(meth)acrylate and styrene/(meth)acrylate are the most to be uesd. Acrylate polymer emulsions are widely uesd in coatings, adhesives and so on because of their good lightfastness, acid-alkali resistance and corrosion resistance. However, there exist many drawbacks such as poor water resistance, flexibility and durability when acrylate polymer emulsions are used as liquid of polymer-cement waterproof coatings, which has a great influence on the waterproof performance of polymer-cement waterproof coatings. Improvement of polymer emulsion properties is vital to emulsion paints with ultra-low VOC content. There is contradiction between film-forming stability of polymer emulsion and mechanical property of the formed film. In order to coordinate film-forming stability of polymer emulsion and mechanical property of film, a volatile organic solvent has to be added into emulsion paints, which leads to higher VOC content, when acrylate polymer emulsions are applied as a binder of emulsion paints. Two types of acrylate polymer emulsions were prepared, which was used in the polymer-cement waterproof coating and architectural emulsion paints resptctively. They are obtained through the way of pre-designing particle and property of polymer, introducing a small quantity of functional monomer, selecting emulsification systems and initiation systems and emulsion polymerization technology. They can raise the ratio of permormance to price of polymer-cement waterproof coatings and decrease VOC content in emulsion paint. Therefore, there are great meanings in theory and practice.
Acrylate polymer emulsion, which was used to manufacture polymer-cement waterproof coating, was prepared with pre-emulsified semi-continuous seeded emulsion polymerization technology. A proper quantity of functional and active crosslinking monomer was added during the couse of emulsion polymerization, and water-resistant monomer was added into the acrylate emulsion. The experimental results show that added functional monomer and adopted polymerization technology improve polymerization stability greatly, and that added active crosslinking monomer and water-resistant monomer improve durability and water resiatance of polymer emulsion. Rheological property of acrylate emulsion was studied. The research results show that polymer emulsion belongs to non-Newtonian fluid, and has the rheological property of pseudoplasric fluid.
The weight ratio of self-made polymer emulsion to Portand cement and the different kind of assistant, which had an effect on the tensile property, water resistance and flexibility at low
采用预乳化半连续种子乳液聚合工艺，制备用于聚合物水泥防水液料的丙烯酸酯乳液，并在乳液聚合过程中，加入功能性单体、活性交联单体和在乳液中加入耐水性单体。研究结果表明，加入的功能性单体和采用的聚合工艺极大的提高了聚合过程的稳定性；加入的活性交联单体和耐水性单体，提高了聚合物乳液的耐候性和耐水性。对聚合物乳液流变性的研究表明，聚合物乳液属非牛顿性流体，具有假塑性流体的流变性质。
以自制的聚合物乳液为液料，普通硅酸盐水泥为粉料，研究了液粉比和助剂对聚合物水泥防水涂料的拉伸性能、耐水性、低温柔性等的影响规律。研究结果表明：成膜助剂、分散剂、增塑剂等助剂提高了聚合物水泥防水涂料的弹性和低温柔性，但成膜助剂会降低防水涂料的耐水性，分散剂对防水涂料耐水性的影响存在着一个最佳值。探讨和分析聚合物水泥防水涂料的成膜机理和防水机理，结果表明：聚合物水泥防水涂料的成膜具有挥发固化和反应固化双重特点；防水机理是通过防水涂膜本身的憎水性来进行的。
采用半连续种子乳液聚合工艺，在聚合过程中加入功能性单体和反应性交联单体—甲基丙烯酸羟丙酯(HPMA)，并采用氧化还原引发体系，制备出超低VOC乳胶涂料用丙烯酸酯乳液。研究了软硬单体配比、pH、HPMA和搅拌器转速等对乳液聚合过程以及乳液性能的影响。研究结果表明：当m(丙烯酸丁酯)／m(甲基丙烯酸甲酯)=80／120时，加入HPMA后，HPMA作为潜交联剂，在聚合过程中与其它单体进行共聚，由分子链间官能基反应而提高聚合物乳液的交联度，制备出的是一种自交联型乳液，在室温条件下成膜过程中自交联，提高聚合物乳液的成膜稳定性。采用材质为不锈钢的间歇反应釜和注入式循环油加热系统进行放大实验
Acrylate copolymer emulsions are the products of acrylate or methacrylate which reacts with other vinyl esters through emulsion polymerization. At present, copolymer emulsions of (meth)acrylate, vinyl acetate/(meth)acrylate and styrene/(meth)acrylate are the most to be uesd. Acrylate polymer emulsions are widely uesd in coatings, adhesives and so on because of their good lightfastness, acid-alkali resistance and corrosion resistance. However, there exist many drawbacks such as poor water resistance, flexibility and durability when acrylate polymer emulsions are used as liquid of polymer-cement waterproof coatings, which has a great influence on the waterproof performance of polymer-cement waterproof coatings. Improvement of polymer emulsion properties is vital to emulsion paints with ultra-low VOC content. There is contradiction between film-forming stability of polymer emulsion and mechanical property of the formed film. In order to coordinate film-forming stability of polymer emulsion and mechanical property of film, a volatile organic solvent has to be added into emulsion paints, which leads to higher VOC content, when acrylate polymer emulsions are applied as a binder of emulsion paints. Two types of acrylate polymer emulsions were prepared, which was used in the polymer-cement waterproof coating and architectural emulsion paints resptctively. They are obtained through the way of pre-designing particle and property of polymer, introducing a small quantity of functional monomer, selecting emulsification systems and initiation systems and emulsion polymerization technology. They can raise the ratio of permormance to price of polymer-cement waterproof coatings and decrease VOC content in emulsion paint. Therefore, there are great meanings in theory and practice.
Acrylate polymer emulsion, which was used to manufacture polymer-cement waterproof coating, was prepared with pre-emulsified semi-continuous seeded emulsion polymerization technology. A proper quantity of functional and active crosslinking monomer was added during the couse of emulsion polymerization, and water-resistant monomer was added into the acrylate emulsion. The experimental results show that added functional monomer and adopted polymerization technology improve polymerization stability greatly, and that added active crosslinking monomer and water-resistant monomer improve durability and water resiatance of polymer emulsion. Rheological property of acrylate emulsion was studied. The research results show that polymer emulsion belongs to non-Newtonian fluid, and has the rheological property of pseudoplasric fluid.
The weight ratio of self-made polymer emulsion to Portand cement and the different kind of assistant, which had an effect on the tensile property, water resistance and flexibility at low
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