水性涂料用含氟丙烯酸酯共聚物乳液的研究
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摘要
随着我国环保法规的日益完善和人们环保意识的不断增强，从保护环境、社会可持续性发展角度探索。既有良好性能和功能，又与环境协调较好的环境友好型涂料已受到世界各国的重视。我国从上世纪60年代开始研究水性涂料，90年代以后有了较快的发展，但是市场占有率并不是很高。这主要是由于水性涂料还存在着耐水性差，成膜时间较长，耐候性差，对金属材料有腐蚀等缺点，发展高性能水性涂料势在必行。
有机氟涂料含有C－F键，具有许多特殊优异的性能。从1965年发展到至今，氟碳涂料已有38年历史了,发展经历了热熔型→溶剂可溶型→常温/室温固化（交联）型→水性/高固含量几个阶段。80年代末氟涂料开始在亚洲经济发达区使用，90年代中期才进入中国市场。国内氟涂料研究起步很晚，而且有机氟涂料制作过程通常使用有毒含氟乙烯类单体与不含官能团的乙烯类单体通过乳液聚合制得含氟聚合物乳液。它们在常温下多为气体，给运输和储藏带来很大困难，而且有机氟涂料成膜温度高，需要高温烘烤。这些都限制了有机氟涂料的推广应用。
根据这种情况，论文结合水性涂料和含氟涂料的优点，解决了含氟丙烯酸乳液制备中的一些技术难题。本论文首先研究比较了各种乳液聚合工艺，并结合含氟乳液的合成特点，着重研究讨论了单体饥饿态半连续种子聚合的基本反应机理。为了获得含氟乳液最佳配方及其最佳的实验条件控制。实验着重对水用量的确定、单体配比的确定、聚四氟乙烯微粉用量的选择、引发剂的选择及其量的确定、乳化剂的选择及其量的确定、pH值的调节、温度的确定和搅拌
速度的选择等方面做了仔细的研究。然后对研制的含氟乳液综合性能进行检测，如外观及凝胶粒子或凝块、固含量、乳液的微观形貌、粘度、残余单体、最低成膜温度、机械稳定性和冻融稳定性、贮存稳定性和热稳定性以及稀释稳定性和钙离子稳定性等。为了进一步了解乳液的性能，还按照涂料标准，对含氟乳液涂膜各种性能进行检测，如涂膜颜色及外观、附着力、耐盐水性、化学稳定性、耐洗刷性、硬度、干燥时间、乳胶膜结构的红外光谱表征和乳胶膜结构的GPC表征等。最后，制备了该含氟乳液、PFA改性的丙烯酸酯乳液和纯丙烯酸酯乳液，并对乳液和涂膜性能做了比较。结果表明，该乳液的稳定性以及涂膜的耐水性、耐洗刷性等性能明显优于其它乳液。
以聚四氟乙烯微粉、丙烯酸丁酯、甲基丙烯酸甲酯、甲基丙烯酸、苯乙烯为主要原料合成了含氟丙烯酸酯共聚物乳液。试验证明，以其为基料制备的水性涂料不仅具有有机氟涂料的大部分优异性能，而且避免了使用有毒含氟乙烯类单体的种种不便，完全符合环保的要求。另外，该乳液的合成工艺简单实用，投资少，很容易投入生产。
With the improvement of environmental rule of law increasingly in our country and the enhancement of people’s environmental awareness continuously, the environmental amicable paint is attracting many countries of the world, which has excellent performance and harmony with the environment. The water-based paint in our country was researched firstly in the 1960s and developed rapidly in the 1990s, but it had low rate of market possession. The main reason is that the water-based paint has many disadvantages such as bad water-resisted property, long film forming time, weak resistance to atmosphere and corrosion to metallic material, so it is necessary to develop the water-based paint with high property.
The organic fluorine paint contains C－F bond and has many particularly excellent performance. The fluorocarbon paint has developed for 38 years since 1965, which experienced four phase: heat fusing type, solvent dissolved type, normal temperature/room temperature solidifying (crosslinking) type, water-based/high solid content type. The fluorine paint firstly was used in the developed area of Asia at the end of 1980s and entered into Chinese market in the middle of 1990s. The research of the domestic fluorine paint started late. Furthermore，in the producing course of the organic fluorine paint, poisonous fluorine monomer with vinyl and monomer with vinyl and without functional group are commonly used in synthesizing fluorine polymer emulsion through emulsion polymerization, which are gas in normal temperature and take great difficulty to
transportation and storage. What is more, the organic fluorine paint needs to be roasted in the high temperature, with high film forming temperature. All above limit the application and popularization of the organic fluorine paint.
According to these conditions, the advantage of water-based paint and fluorine paint are combined to solve some difficult technical problem in the preparation of fluorine-containing acrylic ester copolymer. Firstly, all kinds of polymer technology are compared and the basic reaction mechanism of monomer starving semi-continuous seed polymerization is mainly discussed in this article. In order to gain optimal recipe of fluorine-containing paint and optimal experimental condition, we have mainly determined the volumes of water, the proportion of monomers, the dosage of PTFE micro-powder, the variety of initiating agent and its dosage, the variety of emulsifying agent and its dosage, the value of pH, the temperature and the velocity of stirring etc. Then, the synthetical property of fluorine-containing paint synthesized is examined, such as appearance and gel particle or gel block, solid content, micrograph of emulsion, viscidity, the remainder of monomer, minimum film forming temperature, mechanical stability, freeze-thaw stability, bin stability, thermal stability, dilution stability, calcium ion’s stability and so on. To comprehend the emulsion property further, we examine various properties of fluorine-containing emulsion film according to the standard of paint, such as the color and appearance of film, the clunging, the resistance to salt water, the chemical stability, the
washing fastness, the hardness, the drying time, the character of emulsion film structure through infrared spectrum and GPC and so forth. Finally, this fluorine-containing emulsion, property modified acrylic ester emulsion and pure acrylic ester emulsion are prepared, compared with the property of three kinds of emulsion and their film one another. The result proves that the fluorine-containing emulsion is better than other kinds of emulsion in the following properties: the water-resisted property, the oil-resisted property, the anti-corrosion property and so on.
The fluorine-containing acrylic ester polymer emulsion is synthesized, whose main raw materials are PTFE micro-powder, BA, MMA, MAA and ST. Experiments show that the water-based paint prepared with this emulsion not only has mostly excellent properties of organic fluorine paint, avoiding all sorts of i
有机氟涂料含有C－F键，具有许多特殊优异的性能。从1965年发展到至今，氟碳涂料已有38年历史了,发展经历了热熔型→溶剂可溶型→常温/室温固化（交联）型→水性/高固含量几个阶段。80年代末氟涂料开始在亚洲经济发达区使用，90年代中期才进入中国市场。国内氟涂料研究起步很晚，而且有机氟涂料制作过程通常使用有毒含氟乙烯类单体与不含官能团的乙烯类单体通过乳液聚合制得含氟聚合物乳液。它们在常温下多为气体，给运输和储藏带来很大困难，而且有机氟涂料成膜温度高，需要高温烘烤。这些都限制了有机氟涂料的推广应用。
根据这种情况，论文结合水性涂料和含氟涂料的优点，解决了含氟丙烯酸乳液制备中的一些技术难题。本论文首先研究比较了各种乳液聚合工艺，并结合含氟乳液的合成特点，着重研究讨论了单体饥饿态半连续种子聚合的基本反应机理。为了获得含氟乳液最佳配方及其最佳的实验条件控制。实验着重对水用量的确定、单体配比的确定、聚四氟乙烯微粉用量的选择、引发剂的选择及其量的确定、乳化剂的选择及其量的确定、pH值的调节、温度的确定和搅拌
速度的选择等方面做了仔细的研究。然后对研制的含氟乳液综合性能进行检测，如外观及凝胶粒子或凝块、固含量、乳液的微观形貌、粘度、残余单体、最低成膜温度、机械稳定性和冻融稳定性、贮存稳定性和热稳定性以及稀释稳定性和钙离子稳定性等。为了进一步了解乳液的性能，还按照涂料标准，对含氟乳液涂膜各种性能进行检测，如涂膜颜色及外观、附着力、耐盐水性、化学稳定性、耐洗刷性、硬度、干燥时间、乳胶膜结构的红外光谱表征和乳胶膜结构的GPC表征等。最后，制备了该含氟乳液、PFA改性的丙烯酸酯乳液和纯丙烯酸酯乳液，并对乳液和涂膜性能做了比较。结果表明，该乳液的稳定性以及涂膜的耐水性、耐洗刷性等性能明显优于其它乳液。
以聚四氟乙烯微粉、丙烯酸丁酯、甲基丙烯酸甲酯、甲基丙烯酸、苯乙烯为主要原料合成了含氟丙烯酸酯共聚物乳液。试验证明，以其为基料制备的水性涂料不仅具有有机氟涂料的大部分优异性能，而且避免了使用有毒含氟乙烯类单体的种种不便，完全符合环保的要求。另外，该乳液的合成工艺简单实用，投资少，很容易投入生产。
With the improvement of environmental rule of law increasingly in our country and the enhancement of people’s environmental awareness continuously, the environmental amicable paint is attracting many countries of the world, which has excellent performance and harmony with the environment. The water-based paint in our country was researched firstly in the 1960s and developed rapidly in the 1990s, but it had low rate of market possession. The main reason is that the water-based paint has many disadvantages such as bad water-resisted property, long film forming time, weak resistance to atmosphere and corrosion to metallic material, so it is necessary to develop the water-based paint with high property.
The organic fluorine paint contains C－F bond and has many particularly excellent performance. The fluorocarbon paint has developed for 38 years since 1965, which experienced four phase: heat fusing type, solvent dissolved type, normal temperature/room temperature solidifying (crosslinking) type, water-based/high solid content type. The fluorine paint firstly was used in the developed area of Asia at the end of 1980s and entered into Chinese market in the middle of 1990s. The research of the domestic fluorine paint started late. Furthermore，in the producing course of the organic fluorine paint, poisonous fluorine monomer with vinyl and monomer with vinyl and without functional group are commonly used in synthesizing fluorine polymer emulsion through emulsion polymerization, which are gas in normal temperature and take great difficulty to
transportation and storage. What is more, the organic fluorine paint needs to be roasted in the high temperature, with high film forming temperature. All above limit the application and popularization of the organic fluorine paint.
According to these conditions, the advantage of water-based paint and fluorine paint are combined to solve some difficult technical problem in the preparation of fluorine-containing acrylic ester copolymer. Firstly, all kinds of polymer technology are compared and the basic reaction mechanism of monomer starving semi-continuous seed polymerization is mainly discussed in this article. In order to gain optimal recipe of fluorine-containing paint and optimal experimental condition, we have mainly determined the volumes of water, the proportion of monomers, the dosage of PTFE micro-powder, the variety of initiating agent and its dosage, the variety of emulsifying agent and its dosage, the value of pH, the temperature and the velocity of stirring etc. Then, the synthetical property of fluorine-containing paint synthesized is examined, such as appearance and gel particle or gel block, solid content, micrograph of emulsion, viscidity, the remainder of monomer, minimum film forming temperature, mechanical stability, freeze-thaw stability, bin stability, thermal stability, dilution stability, calcium ion’s stability and so on. To comprehend the emulsion property further, we examine various properties of fluorine-containing emulsion film according to the standard of paint, such as the color and appearance of film, the clunging, the resistance to salt water, the chemical stability, the
washing fastness, the hardness, the drying time, the character of emulsion film structure through infrared spectrum and GPC and so forth. Finally, this fluorine-containing emulsion, property modified acrylic ester emulsion and pure acrylic ester emulsion are prepared, compared with the property of three kinds of emulsion and their film one another. The result proves that the fluorine-containing emulsion is better than other kinds of emulsion in the following properties: the water-resisted property, the oil-resisted property, the anti-corrosion property and so on.
The fluorine-containing acrylic ester polymer emulsion is synthesized, whose main raw materials are PTFE micro-powder, BA, MMA, MAA and ST. Experiments show that the water-based paint prepared with this emulsion not only has mostly excellent properties of organic fluorine paint, avoiding all sorts of i
引文
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[2]FP 2569703
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[2]FP 2569703
[3]李薇雅等，脂肪醇对聚硅氧烷乳液稳定性的影响，功能高分子学报，2003，3：42－43
[4]芮涛，建筑用氟涂料与喷涂技术，涂料工业，200，7：19－21
[5] 管从胜，王威强，氟树脂涂料及应用，化学工业出版社，2004: 17－19
[6]贾正峰，武超等，含氟不粘性涂料，涂料工业，2003，11:41－43
[7]邓海球，常温固化型氟树脂涂料，涂料工业，1999，10：
32－35
[8]US 6326437 B1
[9]H.Mouaziz,A.Larsson,One-Step batch synthesis of high solids monodisperse styrene/glycidyl methacrylate and styrene/methacrylic acid emulsion copolymers,Macromolecules 2004,37,1319-1323
[10]CN 1276399A, CN 1244556A, CN 1145386A
[11]邓海球，涂料工业，2000，（7）:28
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