有机—无机杂化涂料的制备与性能表征
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摘要
由于具有良好的成膜性、柔韧性、基材附着力及较低的成本,有机树脂一直是涂料的主要成膜物;无机材料具有高强度、性能稳定等特点,但同时存在脆性较大、成本高等的缺点。为了获得性能优异或功能独特的涂层,本论文研究有机-无机杂化涂料。将有机树脂与无机材料通过不同的手段进行复合,发挥二者的优势,以达到性能互补、提高涂层总体性能或引入新功能的目的。本论文研究利用不同相之间的化学键与物理作用力相结合的方式,使得涂料中的这种复合有机相和无机相的互分散性更高,且有机相和无机相之间的相互作用能力更强。有机-无机杂化涂料是两种性能迥异的组分之间的复合产物,不仅综合无机材料和有机聚合物的性能,而且是制备、开发新型涂料的有效途径。
本文实验选择正硅酸乙酯(TEOS)为无机相前驱体,分别以γ-缩水甘油醚氧丙基三甲氧基硅烷(KH560)、γ-氨丙基三乙氧基硅烷(KH550)、γ-甲基丙烯酰氧基丙基三甲氧基硅烷(KH570)为偶联剂,采用溶胶-凝胶法制备出硅烷偶联剂改性的硅溶胶,分别配制有机-无机杂化水性涂料、有机-无机杂化环氧热固化涂料及有机-无机杂化光固化涂料。采用红外、热重、接触角、极化曲线以及交流阻抗等手段对不同涂料的性能进行了研究。
通过研究发现,正硅酸乙酯为原料在盐酸的催化作用下,控制加入乙醇、水、反应体系的pH值及各类硅烷偶联剂的量及反应温度,可制备出优良的改性SiO2溶胶。其配制涂料并固化后的各项性能分析表明涂层的无机相与有机相之间形成了网络互穿结构,无明显相界面。两相之间存在化学键和氢键作用。涂层机械性能测试表明,其附着力、硬度、抗冲击性能、柔韧度性等都达到实际应用水平。接触角测试及热重分析表明,涂层的疏水性强、耐热性高。涂层的耐酸、耐碱、耐汽油、耐蒸馏水、耐盐水效果达到实际使用水平。极化曲线及交流阻抗测试表明,涂层具有高的耐腐蚀性能。
Due to the good film forming, flexibility, adhesion and lower cost of the substrate, organic resins have been major film-forming coating materials. Inorganic materials have features of high strength, stable performance, but shortcomings of fragile, higher cost also existed. In order to obtain high performance or special functional coating, different means were used to combine organic resin with inorganic materials, so as to integrate both advantages and complement each other for acheving the purpose of improving overall performance and introducing new features, and organic-inorganic hybrid paint were studied in this paper. The mutual dispersivity in paint is higher between organic phase and inorganic phase through the use of particular style of combining chemical bonds between the different phases with physical forces. The capability of mutual force becomes stronger. Organic-inorganic hybrid paint is special products which possess the function of two different characterial components. Their performances integrate the character of inorganic materials and organic polymers. Organic-inorganic hybrid paint is the direction of preparing and developing of new paint.
In this paper, sol-gel method was applied to prepare silica sol modified with coupling agents, simultaneously to prepare organic-inorganic hybrid water paint、organic-inorganic epoxy thermal curing paint and organic-inorganic hybrid photocurable paint, using tetraethyl orthosilicate (TEOS) as inorganic phase precursor,γ-glycidoxyproyltrimethoxysilane (KH560),γ-aminopropyltriethoxysilane (KH550),γ-methacryloyloxypropyltrimethoxysilane (KH570) as coupling agents respectively. All kinds of means, such as FT-IR、TG、wrapping angle、polarization curve and AC impedance and so on , were adopted to study the performance of different prepared paint.
Through research found that under the catalysis of hydrochloric acid, use tetraethyl orthosilicate as raw materials, excellent modified silicon dioxide sol was prepared in the control of pH value of reactional system, the amount of ethanol, water and various coupling agents and temperature. After the prepared paint cured, all performance analysises showed that interpenetrating network structure was formed, obvious phase interface was not exist, chemical bond and hydrogen bond were existed between inorganic phase and organic phase. The mechanical properties tests showed that the mechanical properties of coating, such as adhesion, hardness, impact resistance, flexibility and so on, are in line with the level of practical application. Wrapping angle test and thermogravimetric analysis showed that coatings have the ability of higher water repellence and heat resistance. The chemical solvent resistant tests showed that the anticorrosion of coatings, such as acid, alkali, gasoline, distilled water and 3.5% NaCl solution achieved the level of actual use. The polarization curve and AC impedance tests showed that the anticorrosion of coatings was good.
本文实验选择正硅酸乙酯(TEOS)为无机相前驱体,分别以γ-缩水甘油醚氧丙基三甲氧基硅烷(KH560)、γ-氨丙基三乙氧基硅烷(KH550)、γ-甲基丙烯酰氧基丙基三甲氧基硅烷(KH570)为偶联剂,采用溶胶-凝胶法制备出硅烷偶联剂改性的硅溶胶,分别配制有机-无机杂化水性涂料、有机-无机杂化环氧热固化涂料及有机-无机杂化光固化涂料。采用红外、热重、接触角、极化曲线以及交流阻抗等手段对不同涂料的性能进行了研究。
通过研究发现,正硅酸乙酯为原料在盐酸的催化作用下,控制加入乙醇、水、反应体系的pH值及各类硅烷偶联剂的量及反应温度,可制备出优良的改性SiO2溶胶。其配制涂料并固化后的各项性能分析表明涂层的无机相与有机相之间形成了网络互穿结构,无明显相界面。两相之间存在化学键和氢键作用。涂层机械性能测试表明,其附着力、硬度、抗冲击性能、柔韧度性等都达到实际应用水平。接触角测试及热重分析表明,涂层的疏水性强、耐热性高。涂层的耐酸、耐碱、耐汽油、耐蒸馏水、耐盐水效果达到实际使用水平。极化曲线及交流阻抗测试表明,涂层具有高的耐腐蚀性能。
Due to the good film forming, flexibility, adhesion and lower cost of the substrate, organic resins have been major film-forming coating materials. Inorganic materials have features of high strength, stable performance, but shortcomings of fragile, higher cost also existed. In order to obtain high performance or special functional coating, different means were used to combine organic resin with inorganic materials, so as to integrate both advantages and complement each other for acheving the purpose of improving overall performance and introducing new features, and organic-inorganic hybrid paint were studied in this paper. The mutual dispersivity in paint is higher between organic phase and inorganic phase through the use of particular style of combining chemical bonds between the different phases with physical forces. The capability of mutual force becomes stronger. Organic-inorganic hybrid paint is special products which possess the function of two different characterial components. Their performances integrate the character of inorganic materials and organic polymers. Organic-inorganic hybrid paint is the direction of preparing and developing of new paint.
In this paper, sol-gel method was applied to prepare silica sol modified with coupling agents, simultaneously to prepare organic-inorganic hybrid water paint、organic-inorganic epoxy thermal curing paint and organic-inorganic hybrid photocurable paint, using tetraethyl orthosilicate (TEOS) as inorganic phase precursor,γ-glycidoxyproyltrimethoxysilane (KH560),γ-aminopropyltriethoxysilane (KH550),γ-methacryloyloxypropyltrimethoxysilane (KH570) as coupling agents respectively. All kinds of means, such as FT-IR、TG、wrapping angle、polarization curve and AC impedance and so on , were adopted to study the performance of different prepared paint.
Through research found that under the catalysis of hydrochloric acid, use tetraethyl orthosilicate as raw materials, excellent modified silicon dioxide sol was prepared in the control of pH value of reactional system, the amount of ethanol, water and various coupling agents and temperature. After the prepared paint cured, all performance analysises showed that interpenetrating network structure was formed, obvious phase interface was not exist, chemical bond and hydrogen bond were existed between inorganic phase and organic phase. The mechanical properties tests showed that the mechanical properties of coating, such as adhesion, hardness, impact resistance, flexibility and so on, are in line with the level of practical application. Wrapping angle test and thermogravimetric analysis showed that coatings have the ability of higher water repellence and heat resistance. The chemical solvent resistant tests showed that the anticorrosion of coatings, such as acid, alkali, gasoline, distilled water and 3.5% NaCl solution achieved the level of actual use. The polarization curve and AC impedance tests showed that the anticorrosion of coatings was good.
引文
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