【作者】 高敬民；

【导师】 王云普；

【作者基本信息】 西北师范大学 ， 高分子化学与物理， 2007， 硕士

【摘要】 氟碳涂料由于氟碳键键能是化学键中之最,表面能低,分子链柔性大等特点而成为高耐候性、高耐沾污性建筑涂料的首选。但是由于近年来石化资源的价格上涨和人类生存环境状况的恶化,减少对不可再生资源的浪费,减少对人类生存环境的污染,大力开发环保涂料和高性能涂料已成为当今世界涂料行业的迫在眉睫的发展方向。溶剂型氟碳涂料虽然有着很好的性能,但同时也存在很多的缺陷,例如容易浮色发花、常温不易固化、在固化的过程中会释放出挥发性有机化合物对环境造成污染等从而限制了其在涂料工业中的应用。水性涂料是一种以水为溶剂或分散介质的环境友好型涂料,这种涂料具有污染少使用安全的优点,随着聚合技术的发展,水性涂料的性能可以和传统的溶剂型涂料相媲美,因此越来越多的注意力在关注水性涂料。含氟丙烯酸酯是一类被广泛使用的单体,利用该类单体和其他的丙烯酸酯类单体共聚而制备出性能和溶剂型氟碳涂料相当的涂料,已成为氟碳涂料发展的重要发展方向。纳米材料由于其独特的性能而引起更多学者的关注。在涂料中添加纳米材料可以获得优异的性能。水性涂料成为现代涂料的主流,其含有机溶剂很少,没有污染,并且如何将纳米材料分散均匀,发挥其优异的特性是研究的热点。本论文制备了四种用于建筑涂料用的乳液,研究了这些乳液在制备过程中含氟丙烯酸酯单体用量、叔碳酸乙烯酯用量、含氟丙烯酸酯单体的加入方式、纳米二氧化硅胶体的加入方式等对聚合反应的影响,利用红外、光电子能谱、透射电镜、紫外等进行了表征。全文研究工作分五部分:第一部分:国内外研究进展综述了水性氟碳涂料在国内外的发展过程、核壳乳液的概念、制备方法、原理、性能、应用;水性氟碳乳液的研究进展、水性氟碳乳液的制备方法、改性方法、性能及应用,最后对水性氟碳乳液的发展方向作了展望。第二部分:水分散体氟碳共聚乳液的研究以叔碳酸乙烯酯和丙烯酸六氟丁酯共聚制备了共聚乳液,并研究了反应温度、反应时间、乳化剂用量、乳化剂配比、引发剂用量、反应物料量等对聚合反应的影响、利用红外、紫外、高速离心、光电子能谱等进行了表征。研究了涂料固化过程中氟元素的迁移规律。第三部分:水性氟碳微乳液的合成及研究采用正戊醇为助乳化剂,利用叔碳酸乙烯酯和丙烯酸六氟丁酯、丙烯酸等共聚制备了共聚乳液,并研究了叔碳酸乙烯酯的用量对接触角的影响、叔碳酸乙烯酯的用量对聚合稳定性的影响、正戊醇用量对分子量的影响、正戊醇用量对分子量分布的影响、利用红外、GPC、KrussK12型动态表面能分析仪、。研究了微乳液形成的机理。第四部分:纳米SiO₂改性核-壳结构氟碳乳液的合成及研究以纳米SiO₂为核,利用叔碳酸乙烯酯和丙烯酸六氟丁酯、丙烯酸及其酯类单体等为壳,采用核壳聚合工艺制备了核壳结构的氟碳乳液,并研究了纳米SiO₂的用量、添加方式对聚合稳定性的影响;含氟丙烯酸酯的用量、添加方式对聚合稳定性的影响;乳化剂对聚合稳定性的影响,利用红外、JEM-100SX型JEOL电子显微镜等进行了表征。第五部分:水性绿色环保涂料的制备研究以纳米SiO₂改性核-壳结构氟碳乳液为成膜物质,颜、填料、助剂、去离子水等制备了建筑涂料并进行了全项检测,经甘肃省涂料质量监督检验站检测,涂料所有性能符合国家标准,部分检测指标远远高于国家标准,未检出挥发性有机化合物。采用本论文的制备方法制备的涂料均以水为分散介质,在涂料固化的过程中不会释放出对环境和人体有害的挥发性有机化合物,符合绿色环保涂料的标准,同时极大的保护了用户和施工人员的身体健康,减少了对有机溶剂的浪费,节约了能源。以纳米SiO₂为核,采用含氟丙烯酸酯类单体、叔碳酸乙烯酯和丙烯酸酯类单体为壳制备的核壳型氟碳乳液符合CEPC（欧洲涂料、油墨、颜料工业协会联合会）标准,目前尚未见国内外相同文献报道。更多还原

【Abstract】 Fluorocarbon coatings has been preferred for it highly resistance to weather, highly stain resistance because of it’s has a strongest bond, lower surface energy, flexibility and etc. But with the raising price of the petrol chemical materials, the pollution to the environment become more seriously. Reduce the waste of the resource which not regenesis, lessen the hazard to the people’s resident environment, To empolder environment protection coatings and highly performance coatings with hard work is become very important mission. Although solvent-based fluorocarbon coatings has some good performance, but at the same time it also have some limitation, such as flooding, floating, it will not easely curing at the room temperature, at the curing process it will emit some volatile organic compounds that may pollute the environment and so on, that limited it application to the coatings industry.Water-borne coatings is an environment-friendly coatings with water served as solvent or dispersing medium. This kind of coatings has the virtue of little pollution and construction security. With the development of polymerization technology, the performance of water-borne coatings is close to or equal to the performance of traditional coatings using organic solvent as dispersing medium. So more and more attention are putting to water-borne coatings. Acrylic acid ester containing fluoro monomer is one kind of monomer which had been widely used, use this monomer and other acrylic acid and it’s ester to prepare copolymer will have a character as solvent fluorocarbon coatings, it was erected as the most important developing direction. This article prepared three kind of emulsion which use for the building coatings. This article also discussed the effect of feeding method of monomers, reaction temperature, initiator dosage, amount of nano-scale SiO₂ colloid, pH value, and polymerization process on the emulsion polymerization. The emulsion was characterized.Nanometer-materials attracted more and more scholars attention because of it’s particular nanometer effects. Adding the nanometer-materials into coatings can obtain excellent performances. The water-borne coatings are the mainstream of the modern coatings, which have the fewer organic solvents, no pollute and innocuity. Therefore, how to disperse and rectify the nanometer-materials well, exert its good performance is also a challenge to the scholar who study on the subject of coatings.All of the work contain five part:Part one: Study evolve in domestics and overseasThe general introduction were given about the progress of water-borne fluorocarbon coatings, the concept of Core-Shell emulsion, preparation, mechanism, property, application, the progress of water-borne fluorocarbon emulsion, the preparation of water-borne fluorocarbon, the methods of modify, property and application, at lastPart two: Study of the fluorocarbon copolymer emulsion,Prepared fluorocarbon copolymer emulsion with Veova-10 and , study the effect of the reaction temperature, time of the reaction, emulsifier dosage, the ratio of different emulsifier, initiator dosage, amount of the materials, character it structure by FT-IR, XPS, studied the law of the at the process of the coatings film forming.Part three: Synthesis and Study of the water-borne fluorocarbon micro emulsionUse n-Pentyl alcohol as assist emulsifier, prepared copolymer emulsion with Veova-10, 2,2,3,4,4,4-Hexafluorobutyl acrylate, acrylic acid etc, studied the impact of the amount of Veova-10 to the contact angle, the impact of the amount of Veova-10 to the stability of polymerization, the impact of theCharacter it structure by FT-IR, GPC, KrussK12 surface energy analytical apparatus, studied the forming mechanism of the micro emulsion.Part four: Synthesis and Study of nano scale SiO₂ collide modified core-shell structure water-borne fluorocarbon emulsionUse nano scale SiO₂ collide as core, Veova-10 and 2,2,3,4,4,4-Hexafluorobutyl acrylate, acrylic acid and it’s ester as shell, prepared core-shell structure fluorocarbon emulsion by core-shell technology, studied the amount of the nano scale SiO₂ collide, the influence of the adding style to the stability of polymerization, he dosage of the acrylic acid ester containing fluoro monomer, the effect of the emulsifier to the stability of polymerization, character it structure by FT-IR, the structure of the emulsion was observed with transmission electron microscopy（TEM） by the JEM-100SX. Part five: Preparation of the water-borne green environment protection coatingsUse nano scale SiO₂ collide modified Core-shell structure water-borne fluorocarbon emulsion as film forming material, prepared building coatings with paint, agent, DW etc, and then character all of the property, after the center of coatings quality supervisory and proof-test of Gansu province , all of the property content to the coatings standard of China, some of the property higher than the coatings standard of China, there is no VOC had been found.Prepare coatings use the methods provide from this article, use water as dispersing medium, at the process of film forming it will not give off hazard gas which harm to environment and human body, it’s character content to the standard of green environment protect coatings, at the same time, it protect the body health of the user and the builder, released the waste of the organic solvent. Saved the energy resource.Use nano scale SiO₂ collide as core, prepared Core-Shell structure water-borne fluorocarbon with acrylic acid ester containing fluoro monomer, Veova-10, acrylic acid and it’s ester as monomer, it’s character content to the standard of CEPC, at now ,there is no the same article published in domestics and overseas.更多还原