环氧系纳米水性重防腐涂料的研究
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摘要
据统计,我国每年因腐蚀造成的损失高达约1.2万亿～2万亿元,远远高于自然灾害和各类事故损失的总和。同时,调查表明涂料涂层防腐蚀是最有效、最经济、应用最普遍的方法。重防腐涂料作为恶劣腐蚀环境下应用并具有长效使用寿命的特种涂料,它的研究改进具有重要意义。当前涂料发展呈现低污染,高性能的总体发展趋势。围绕涂料组分改进和新技术在涂料中的应用研究成为热点。
本实验主要包括三部分内容：(1)纳米二氧化硅的制备、表征和分散稳定性研究；(2)水溶性环氧树脂乳液的制备和性能检测；(3)纳米水性重防腐涂料的配制和性能检测以及涂料配方优化。
纳米二氧化硅的常用制备方法主要分为干法和湿法。湿法有沉淀法、溶胶-凝胶法等。本文分别采取沉淀法和溶胶-凝胶法制备纳米二氧化硅,结果显示沉淀法反应快速,但产品粒径偏大；溶胶-凝胶法产品纯度高,粒径较小,且匀度好。实验研究得出溶胶-凝胶法制备纳米二氧化硅最佳反应条件为：V_(止硅酸乙酯):V_(无水己醇)：V_(去离子水)=2：1：1,45°C,搅拌回流2h,100°C烘干1h,500°C焙烧1.5h；最佳分散条件为：六偏磷酸钠质量分数=2.7%,超声波分散3.5h。
水性环氧树脂乳液的制备方法主要分为外加乳化剂法和自乳化法。本文实验合成新型水性环氧乳化剂,然后采取相反转法制备水性环氧树脂乳液。结果表明,该法制备的水性环氧树脂乳液粒径小,不存在破乳现象。实验得出了新型环氧树脂乳化剂的最佳合成条件为：环氧基／羟基(摩尔比)=1：1,反应时间=7h,反应温度=180°C。新型水性环氧树脂乳化剂的最佳用量为14%(质量百分比)
通过自制环氧固化剂,参考相关涂料标准配方,初配出涂料,并对涂膜性能进行检验。在此配方基础上,选择主要组分含量为考查因素,开展正交试验,得出了较优配方,涂料涂膜性能也达到纳米水性重防腐涂料的要求。
According to statistics, the loss caused by corrosion in our country is about up to 1.2 trillion-2 trillion yuan in each year,which is much higher than the loss caused by the sum of the natural disasters and various types of the incident.In the same time. Survey shows that using coating is the most effective，economical and the common method of corrosion protection.As a special coating,Heavy-duty corrosion coatings have a long-term service life of the application in the harsh environment. The trends of current development of paint are low-polluting and overall performance.The improvement about the components of paint and the study about new technologies applied in coatings are becoming hot spot.
There are three contents in this paper:(1)The preparation, characterization and dispersion stability studies of nano-silica;(2)The preparation and performance testing of water-soluble epoxy resin emulsion;(3)The preparation, performance testing and formula optimize of Heavy-duty water-based nano-coatings.
The commonly methods used in preparation of nano-silica are divided into dry and wet. The wet method includs precipitation method,sol-gel method and so on.In this paper,we have used the precipitation method and the sol-gel method.The results showed that the precipitation method is rapid,but the particle size of product is larger than that of sol-gel method whose product is high purity and better evenness.The best recation conditions which were worked out by experimental studies of sol-gel method are:V_(TEOS):V_(Ethanol):V_(Deionized water)=2:1:1,45℃, stiring and refluxing for 2 hours, drying under 100℃for 1 hour, roasting under 500℃for 1.5 hours.The best dispersion conditions are as follows:the mass fraction of sodium hexametaphosphate=2.7%, ultrasonic dispersion 3.5 hours.
The method in preparation of Waterborne Epoxy Resin Emulsion is divided into plus and self-emulsifying method. In this paper, a new water-based epoxy emulsifier was prepared by the experimental synthesis,then Waterborne Epoxy Resin Emulsion was prepared by Self-emulsifying method.Results showed that waterborne epoxy resin emulsion prepared by this method was small particle size and demulsification situation did not exist. The best conditions for synthesis of the new type of epoxy resin emulsifier were worked out by experimental studies are:epoxy group/hydroxyl group=1:1,reaction time=7 hour,reaction temperature=180℃,the best dosage of water-based epoxy emulsifier is 21%(mass percentage).
Through preparing the epoxy curing agent and refering to the relevant standard coating formulations,a initial paint was prepared and its formulation was tested. The content of the main components were selected to be factors and the orthogonal test was carried out, a better formula was worked out,paint film performance was also essential to achieve the nano-heavy-duty water-based paint requirements.
本实验主要包括三部分内容：(1)纳米二氧化硅的制备、表征和分散稳定性研究；(2)水溶性环氧树脂乳液的制备和性能检测；(3)纳米水性重防腐涂料的配制和性能检测以及涂料配方优化。
纳米二氧化硅的常用制备方法主要分为干法和湿法。湿法有沉淀法、溶胶-凝胶法等。本文分别采取沉淀法和溶胶-凝胶法制备纳米二氧化硅,结果显示沉淀法反应快速,但产品粒径偏大；溶胶-凝胶法产品纯度高,粒径较小,且匀度好。实验研究得出溶胶-凝胶法制备纳米二氧化硅最佳反应条件为：V_(止硅酸乙酯):V_(无水己醇)：V_(去离子水)=2：1：1,45°C,搅拌回流2h,100°C烘干1h,500°C焙烧1.5h；最佳分散条件为：六偏磷酸钠质量分数=2.7%,超声波分散3.5h。
水性环氧树脂乳液的制备方法主要分为外加乳化剂法和自乳化法。本文实验合成新型水性环氧乳化剂,然后采取相反转法制备水性环氧树脂乳液。结果表明,该法制备的水性环氧树脂乳液粒径小,不存在破乳现象。实验得出了新型环氧树脂乳化剂的最佳合成条件为：环氧基／羟基(摩尔比)=1：1,反应时间=7h,反应温度=180°C。新型水性环氧树脂乳化剂的最佳用量为14%(质量百分比)
通过自制环氧固化剂,参考相关涂料标准配方,初配出涂料,并对涂膜性能进行检验。在此配方基础上,选择主要组分含量为考查因素,开展正交试验,得出了较优配方,涂料涂膜性能也达到纳米水性重防腐涂料的要求。
According to statistics, the loss caused by corrosion in our country is about up to 1.2 trillion-2 trillion yuan in each year,which is much higher than the loss caused by the sum of the natural disasters and various types of the incident.In the same time. Survey shows that using coating is the most effective，economical and the common method of corrosion protection.As a special coating,Heavy-duty corrosion coatings have a long-term service life of the application in the harsh environment. The trends of current development of paint are low-polluting and overall performance.The improvement about the components of paint and the study about new technologies applied in coatings are becoming hot spot.
There are three contents in this paper:(1)The preparation, characterization and dispersion stability studies of nano-silica;(2)The preparation and performance testing of water-soluble epoxy resin emulsion;(3)The preparation, performance testing and formula optimize of Heavy-duty water-based nano-coatings.
The commonly methods used in preparation of nano-silica are divided into dry and wet. The wet method includs precipitation method,sol-gel method and so on.In this paper,we have used the precipitation method and the sol-gel method.The results showed that the precipitation method is rapid,but the particle size of product is larger than that of sol-gel method whose product is high purity and better evenness.The best recation conditions which were worked out by experimental studies of sol-gel method are:V_(TEOS):V_(Ethanol):V_(Deionized water)=2:1:1,45℃, stiring and refluxing for 2 hours, drying under 100℃for 1 hour, roasting under 500℃for 1.5 hours.The best dispersion conditions are as follows:the mass fraction of sodium hexametaphosphate=2.7%, ultrasonic dispersion 3.5 hours.
The method in preparation of Waterborne Epoxy Resin Emulsion is divided into plus and self-emulsifying method. In this paper, a new water-based epoxy emulsifier was prepared by the experimental synthesis,then Waterborne Epoxy Resin Emulsion was prepared by Self-emulsifying method.Results showed that waterborne epoxy resin emulsion prepared by this method was small particle size and demulsification situation did not exist. The best conditions for synthesis of the new type of epoxy resin emulsifier were worked out by experimental studies are:epoxy group/hydroxyl group=1:1,reaction time=7 hour,reaction temperature=180℃,the best dosage of water-based epoxy emulsifier is 21%(mass percentage).
Through preparing the epoxy curing agent and refering to the relevant standard coating formulations,a initial paint was prepared and its formulation was tested. The content of the main components were selected to be factors and the orthogonal test was carried out, a better formula was worked out,paint film performance was also essential to achieve the nano-heavy-duty water-based paint requirements.
引文
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[126]GB 1727-92
[127]GB/T1728-79(89)
[128]GB1730-93
[129]GB/T 1720-79(89)
[130]GB/T1733-93
[131]GB 1763-79(89)