水性紫外光固化树脂的合成以及结构与性能研究
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摘要
水性光固化涂料结合了传统光固化技术和水性涂料技术的优点,对环境无污染、对人体健康无影响,不易燃烧、安全性好,已成为涂料行业的研究热点。因此,本文先合成了改性环氧丙烯酸酯树脂和水性聚氨酯树脂,然后配制了水性光固化涂料,并添加有机蒙脱土制备了水性光固化抗菌涂料,研究了树脂及涂料的制备及表征。
首先合成了马来酸酐和丁二酸酐改性环氧丙烯酸酯树脂,研究反应速率、树脂水溶性和颜色的影响因素,优化了反应条件,用红外光谱(FTIR)表征了产物结构；由合成树脂配制了水性紫外光固化涂料,研究了固化工艺和涂膜性能。研究结果表明：丁二酸酐改性环氧丙烯酸酯树脂的水溶性好、颜色浅；丁二酸酐与双酚A型环氧丙烯酸酯反应的最佳条件为环氧丙烯酸酯与丁二酸酐的摩尔比为1：2,丙酮为溶剂,反应温度75℃,三乙胺催化剂用量1.0 mass%;由丁二酸酐改性环氧丙烯酸酯树脂配成的水性光固化涂料,其固化膜的光泽度好和柔韧性优良,将具有广阔的应用前景。
其次,用异佛尔酮二异氰酸酯(IPDI)、2,2-二羟甲基丙酸(DMPA).丙烯酸羟乙酯(HEA)和聚醚型聚乙二醇(PEG)、聚酯型聚己二酸丁二醇酯二醇(PBA)合成了水性聚氨酯丙烯酸酯树脂,研究了反应条件对反应速率、树脂水溶性的影响,优化了反应的工艺条件；然后由该树脂配制了水性紫外光固化涂料,研究了固化工艺和涂膜性能。得到了如下研究结果：水性聚氨酯树脂的耐黄变性能良好；优化的反应的工艺条件为：水性光固化聚氨酯反应的最佳条件为2,2-二羟甲基丙酸(DMPA)与聚乙二醇(PEG)摩尔比为2：1,溶剂为10%,反应温度80℃,催化剂二丁基二月桂酸二正丁锡用量0.6 mass%;由水性聚氨酯丙烯酸酯树脂配成的水性光固化涂料,其固化膜的光泽度好、柔韧性优良的优点,有望获得广泛应用。
最后,将有机蒙脱土加入水性紫外光固化环氧丙烯酸酯涂料中制备了抗菌涂料,研究了抗菌涂层的理化性能、抗菌防霉性能和耐水性。研究发现：抗菌水性光固化涂料具有优异的抗菌防霉性能；当有机蒙脱土的添加量为2.0 mass%时,抗菌涂层对E.coli和S.aureus的抑菌圈大小分别为7.0和9.0 mm,防霉等级为0级,耐水性良好,理化性能指标都达到国家或行业标准。
Waterborne UV-curing coatings combined with the traditional uv-curable technology and water-borne coatings advantages, no pollution to environment, no effect on human health, burning-free and high security, have become the hotspot of coating industry. Therefore, this paper first synthesized epoxy acrylates modified resin and water-borne polyurethane resin, and confected waterborne UV-curing coatings. Then waterborne UV-curing antibacterial coatings were prepared by adding organic montmorillonite into waterborne UV-curing coatings, and the preparation and characterization of these coatings were studied.
First, maleic anhydride and succinic anhydride modified epoxy acrylates resins were synthesized. From the reaction rate, water-solubility and colors of the resin, the optimum conditions to synthesize resins was explored, and the result coating was analyzed by FTIR. Then, waterborne UV-curing coatings were prepared from these resins, and the curing process and coating properties were studied. The results showed that succinic anhydride modified epoxy acrylates resins have good water-solubility and lighter color. The optimum reaction conditions for succinic anhydride and bisphenol A type epoxy resin were determined as molar ratio of 1:1 of succinic anhydride and bisphenol A type epoxy resin, catalyst amount of 1%-2% of triethylamine, reaction temperature of 60-65℃, solvent of acetone. The cured film of succinic anhydride modified epoxy acrylates resins has shining and excellent flexibility, and has wide application in future.
Then, polyurethane acrylate (PUA) UV-curable waterborne coating was synthesized by isophorone diisocyanate (IPDI),2,2-dimethylol propionic acid (DMPA), hydroxyethyl acrylate (HEA) and polyether polyethylene glycol (PEG). From the reaction rate, water-solubility and colors of the resin, the optimum conditions to synthesize resins was explored. Then, waterborne UV-curing coatings were prepared from these resins, and the curing process and coating properties were studied. The results showed that polyurethane acrylate UV-curable waterborne coating have excellent performance of yellowing resistance. The optimum reaction conditions for polyurethane acrylate UV-curable waterborne coating were determined as molar ratio of 1:1 of DMPA and PEG, solvent amount of 10%, reaction temperature of 60-65℃, catalyst amount of 1%-2% of dibutyltindilaurate. The cured film of polyurethane acrylate UV-curable waterborne coating has shining and excellent flexibility, and has wide application in future.
Finally, antimicrobial water-based UV-curing coating was prepared by means of composite organic montmorillonite antimicrobial agents with water-based UV-curing coating, and its physiochemical performance, antibacterial and anti-mildew performance as well as water resisting property were investigated. The results showed that antimicrobial water-based UV-curing coating has excellent antibacterial and anti-mildew performance, when the additive content of antibacterial agent is 2.0 mass%, the inhibition zone of the antimicrobial water-based UV-curing coating against E. coli and S. aureus is 7.0 and 9.0 mm, respectively, the fungicidal grade is 0. The antimicrobial water-based UV-curing coating has excellent water-proofing, physical and chemical property index reaches the national or trade standards.
首先合成了马来酸酐和丁二酸酐改性环氧丙烯酸酯树脂,研究反应速率、树脂水溶性和颜色的影响因素,优化了反应条件,用红外光谱(FTIR)表征了产物结构；由合成树脂配制了水性紫外光固化涂料,研究了固化工艺和涂膜性能。研究结果表明：丁二酸酐改性环氧丙烯酸酯树脂的水溶性好、颜色浅；丁二酸酐与双酚A型环氧丙烯酸酯反应的最佳条件为环氧丙烯酸酯与丁二酸酐的摩尔比为1：2,丙酮为溶剂,反应温度75℃,三乙胺催化剂用量1.0 mass%;由丁二酸酐改性环氧丙烯酸酯树脂配成的水性光固化涂料,其固化膜的光泽度好和柔韧性优良,将具有广阔的应用前景。
其次,用异佛尔酮二异氰酸酯(IPDI)、2,2-二羟甲基丙酸(DMPA).丙烯酸羟乙酯(HEA)和聚醚型聚乙二醇(PEG)、聚酯型聚己二酸丁二醇酯二醇(PBA)合成了水性聚氨酯丙烯酸酯树脂,研究了反应条件对反应速率、树脂水溶性的影响,优化了反应的工艺条件；然后由该树脂配制了水性紫外光固化涂料,研究了固化工艺和涂膜性能。得到了如下研究结果：水性聚氨酯树脂的耐黄变性能良好；优化的反应的工艺条件为：水性光固化聚氨酯反应的最佳条件为2,2-二羟甲基丙酸(DMPA)与聚乙二醇(PEG)摩尔比为2：1,溶剂为10%,反应温度80℃,催化剂二丁基二月桂酸二正丁锡用量0.6 mass%;由水性聚氨酯丙烯酸酯树脂配成的水性光固化涂料,其固化膜的光泽度好、柔韧性优良的优点,有望获得广泛应用。
最后,将有机蒙脱土加入水性紫外光固化环氧丙烯酸酯涂料中制备了抗菌涂料,研究了抗菌涂层的理化性能、抗菌防霉性能和耐水性。研究发现：抗菌水性光固化涂料具有优异的抗菌防霉性能；当有机蒙脱土的添加量为2.0 mass%时,抗菌涂层对E.coli和S.aureus的抑菌圈大小分别为7.0和9.0 mm,防霉等级为0级,耐水性良好,理化性能指标都达到国家或行业标准。
Waterborne UV-curing coatings combined with the traditional uv-curable technology and water-borne coatings advantages, no pollution to environment, no effect on human health, burning-free and high security, have become the hotspot of coating industry. Therefore, this paper first synthesized epoxy acrylates modified resin and water-borne polyurethane resin, and confected waterborne UV-curing coatings. Then waterborne UV-curing antibacterial coatings were prepared by adding organic montmorillonite into waterborne UV-curing coatings, and the preparation and characterization of these coatings were studied.
First, maleic anhydride and succinic anhydride modified epoxy acrylates resins were synthesized. From the reaction rate, water-solubility and colors of the resin, the optimum conditions to synthesize resins was explored, and the result coating was analyzed by FTIR. Then, waterborne UV-curing coatings were prepared from these resins, and the curing process and coating properties were studied. The results showed that succinic anhydride modified epoxy acrylates resins have good water-solubility and lighter color. The optimum reaction conditions for succinic anhydride and bisphenol A type epoxy resin were determined as molar ratio of 1:1 of succinic anhydride and bisphenol A type epoxy resin, catalyst amount of 1%-2% of triethylamine, reaction temperature of 60-65℃, solvent of acetone. The cured film of succinic anhydride modified epoxy acrylates resins has shining and excellent flexibility, and has wide application in future.
Then, polyurethane acrylate (PUA) UV-curable waterborne coating was synthesized by isophorone diisocyanate (IPDI),2,2-dimethylol propionic acid (DMPA), hydroxyethyl acrylate (HEA) and polyether polyethylene glycol (PEG). From the reaction rate, water-solubility and colors of the resin, the optimum conditions to synthesize resins was explored. Then, waterborne UV-curing coatings were prepared from these resins, and the curing process and coating properties were studied. The results showed that polyurethane acrylate UV-curable waterborne coating have excellent performance of yellowing resistance. The optimum reaction conditions for polyurethane acrylate UV-curable waterborne coating were determined as molar ratio of 1:1 of DMPA and PEG, solvent amount of 10%, reaction temperature of 60-65℃, catalyst amount of 1%-2% of dibutyltindilaurate. The cured film of polyurethane acrylate UV-curable waterborne coating has shining and excellent flexibility, and has wide application in future.
Finally, antimicrobial water-based UV-curing coating was prepared by means of composite organic montmorillonite antimicrobial agents with water-based UV-curing coating, and its physiochemical performance, antibacterial and anti-mildew performance as well as water resisting property were investigated. The results showed that antimicrobial water-based UV-curing coating has excellent antibacterial and anti-mildew performance, when the additive content of antibacterial agent is 2.0 mass%, the inhibition zone of the antimicrobial water-based UV-curing coating against E. coli and S. aureus is 7.0 and 9.0 mm, respectively, the fungicidal grade is 0. The antimicrobial water-based UV-curing coating has excellent water-proofing, physical and chemical property index reaches the national or trade standards.
引文
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2.3小结
1. 丁二酸酐改性环氧丙烯酸酯比马来酸酐改性环氧丙烯酸酯颜色更好,其它性能也符合实际应用要求。
2. 确定丁二酸酐与双酚A型环氧丙烯酸酯反应的最佳条件：环氧丙烯酸酯与丁二酸酐的摩尔比为1：2,丙酮为溶剂,反应温度75℃,三乙胺催化剂用量1.0mass%。
3.由丁二酸酐改性环氧丙烯酸酯配成的水性光固化涂料的固化膜光泽度好,柔韧性优良,将具有广阔的应用前景。
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择合适的大分子多元醇为原料。
3.3小结
1. 合成了水性紫外光固化聚氨酯,其耐黄变性能良好。
2. 确定了优化的反应的工艺条件：水性光固化聚氨酯反应的最佳条件为2,2-二羟甲基丙酸(DMPA)与聚乙二醇(PEG)摩尔比为2：1,溶剂为10mass%,反应温度80℃,催化剂二丁基二月桂酸二正丁锡用量0.6 mass%。
3. 由水性紫外光固化聚氨酯配成的水性光固化涂料的固化膜光泽度好、柔韧性优良、耐光性优异,有望获得广泛应用。
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2. 含2.0 mass%有机蒙脱土的抗菌涂层的耐水性良好,理化性能指标都达到国家或行业标准。
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2.3小结
1. 丁二酸酐改性环氧丙烯酸酯比马来酸酐改性环氧丙烯酸酯颜色更好,其它性能也符合实际应用要求。
2. 确定丁二酸酐与双酚A型环氧丙烯酸酯反应的最佳条件：环氧丙烯酸酯与丁二酸酐的摩尔比为1：2,丙酮为溶剂,反应温度75℃,三乙胺催化剂用量1.0mass%。
3.由丁二酸酐改性环氧丙烯酸酯配成的水性光固化涂料的固化膜光泽度好,柔韧性优良,将具有广阔的应用前景。
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择合适的大分子多元醇为原料。
3.3小结
1. 合成了水性紫外光固化聚氨酯,其耐黄变性能良好。
2. 确定了优化的反应的工艺条件：水性光固化聚氨酯反应的最佳条件为2,2-二羟甲基丙酸(DMPA)与聚乙二醇(PEG)摩尔比为2：1,溶剂为10mass%,反应温度80℃,催化剂二丁基二月桂酸二正丁锡用量0.6 mass%。
3. 由水性紫外光固化聚氨酯配成的水性光固化涂料的固化膜光泽度好、柔韧性优良、耐光性优异,有望获得广泛应用。
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