水性聚氨酯乳液的合成、化学改性及其在阻燃涂层中的应用
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摘要
论文研究了水性聚氨酯合成过程中反应条件对反应结果的影响,确定了合适的反应条件。用环氧树脂和丙烯酸树脂合成了环氧改性和丙烯酸改性水性聚氨酯乳液PUE和PUA。通过红外光谱对制得的水性聚氨酯产品进行表征,并考察了环氧改性和丙烯酸改性对水性聚氨酯乳液及其成膜性能的影响。
对反应条件的研究结果表明,优化的反应条件为:合成亲水性聚氨酯预聚体时,甲苯二异氰酸酯(TDI)与聚醚多元醇(PPG)的反应温度70℃,-NCO/-OH的摩尔比2.4～3.5;异佛尔酮二异氰酸酯(IPDI)与聚醚反应温度为79-80℃,-NCO/-OH的摩尔比2.6～4。当采用二乙烯三胺代替乙二胺扩链时,可以得到交联的水性聚氨酯分子,其成膜耐水性和力学性能均有明显的改善。在反应过程中,采用丁酮溶剂均相法代替传统的本体法反应,并加入适量的二月桂酸二丁基锡-三乙胺复合催化剂,可以减少溶剂效应的不利影响,反应过程受环境的影响小,反应平行性、重现性好。芳香族水性聚氨酯乳液的粒径及粒径分布明显大于脂肪族水性聚氨酯乳液;随着乳液固含量的增加,分散相的粒径增大。测试结果显示,芳香族水性聚氨酯乳液成膜后的力学性能优于脂肪族水性聚氨酯乳液。采用环氧树脂改性水性聚氨酯乳液,可以得到成膜拉伸强度和耐水性能更佳的水性聚氨酯乳液,但乳液稳定性不佳;采用丙烯酸改性的水性聚氨酯乳液成膜,耐水性能很好,但成膜性较差。
论文以水性聚氨酯乳液为基材,分别研究了添加无机填充型、化学膨胀型和物理膨胀型等三种阻燃体系的涂层性能。添加无机填充型阻燃体系所制得的涂层具有阻燃性能差、涂层耐水性和涂饰性不佳的缺点;添加化学膨胀型阻燃体系所制得的涂层具有阻燃性能和涂饰性能较好的优点,但耐水性能较差;而添加物理膨胀型阻燃体系所获得涂层的阻燃效果和耐水效果均较好,但涂饰性能稍差。
Some chemical reaction conditions on the physical and chemical properties of waterborae polyurethane were discussed, and the resulted waterborne polyurethane (WPU) was also modified chemically by epoxy and acrylic acid resins. The chemical and mechanical properties of waterborne polyurethane were characterized by infrared spectroscopy and other test methods.Results showed that the appropriate reaction temperature is 70℃, and the suitable molar ratio of -NCO to -OH is 2.4~3.5 when tolylene diisocyanate (TDI) reacted with polyoxypropylene glycol (PPG). While isophorone diisocyanate (IPDI) reacted with PPG, the appropriate temperature is 79~80℃, and the suitable molar ratio of -NCO to -OH is 2.6~4. WPU with excellent mechanical and water-resistant properties can be obtained by crosslinking when diethylene triamine substituted for ethylenediamine as chain extender. During the reactions between TDI and PPG, the solvent effectiveness can be overcome greatly when a suitable amount of dibutyl tin laurate (DBTDL) and triethylamine compound catalysts were added to the reactants. Furthermore, the environment has little influence on the reaction systems, and the reaction results obtained preserve better reappearance.The film of aromatic WPU preserves better mechanical properties than that of the film of aliphatic WPU. The film of WPU modified by epoxy resin preserves better mechanical and water-resistant properties, but worse latex stability. The film of WPU modified by acrylic acid has the best water-resistant property, but a flaw of crisp. The particle size of aromatic WPU latex is bigger, and the size distribution is wider than those of aliphatic WPU latex, especially in the high solid percentage of WPU latex.As for WPU flame retardant coatings, the inorganic flame retardant systems can't achieve the demand for excellent flame retardant, ornamental and water-resistant properties. The chemical intumescent flame retardant (CIFR) systems show little
improvement on the ornamental and water-resistant property, but its flame retardant property is excellent. The physical intumescent flame retardant (PIFR) systems have worse ornamental property, but its water-resistant property is excellent.
对反应条件的研究结果表明,优化的反应条件为:合成亲水性聚氨酯预聚体时,甲苯二异氰酸酯(TDI)与聚醚多元醇(PPG)的反应温度70℃,-NCO/-OH的摩尔比2.4～3.5;异佛尔酮二异氰酸酯(IPDI)与聚醚反应温度为79-80℃,-NCO/-OH的摩尔比2.6～4。当采用二乙烯三胺代替乙二胺扩链时,可以得到交联的水性聚氨酯分子,其成膜耐水性和力学性能均有明显的改善。在反应过程中,采用丁酮溶剂均相法代替传统的本体法反应,并加入适量的二月桂酸二丁基锡-三乙胺复合催化剂,可以减少溶剂效应的不利影响,反应过程受环境的影响小,反应平行性、重现性好。芳香族水性聚氨酯乳液的粒径及粒径分布明显大于脂肪族水性聚氨酯乳液;随着乳液固含量的增加,分散相的粒径增大。测试结果显示,芳香族水性聚氨酯乳液成膜后的力学性能优于脂肪族水性聚氨酯乳液。采用环氧树脂改性水性聚氨酯乳液,可以得到成膜拉伸强度和耐水性能更佳的水性聚氨酯乳液,但乳液稳定性不佳;采用丙烯酸改性的水性聚氨酯乳液成膜,耐水性能很好,但成膜性较差。
论文以水性聚氨酯乳液为基材,分别研究了添加无机填充型、化学膨胀型和物理膨胀型等三种阻燃体系的涂层性能。添加无机填充型阻燃体系所制得的涂层具有阻燃性能差、涂层耐水性和涂饰性不佳的缺点;添加化学膨胀型阻燃体系所制得的涂层具有阻燃性能和涂饰性能较好的优点,但耐水性能较差;而添加物理膨胀型阻燃体系所获得涂层的阻燃效果和耐水效果均较好,但涂饰性能稍差。
Some chemical reaction conditions on the physical and chemical properties of waterborae polyurethane were discussed, and the resulted waterborne polyurethane (WPU) was also modified chemically by epoxy and acrylic acid resins. The chemical and mechanical properties of waterborne polyurethane were characterized by infrared spectroscopy and other test methods.Results showed that the appropriate reaction temperature is 70℃, and the suitable molar ratio of -NCO to -OH is 2.4~3.5 when tolylene diisocyanate (TDI) reacted with polyoxypropylene glycol (PPG). While isophorone diisocyanate (IPDI) reacted with PPG, the appropriate temperature is 79~80℃, and the suitable molar ratio of -NCO to -OH is 2.6~4. WPU with excellent mechanical and water-resistant properties can be obtained by crosslinking when diethylene triamine substituted for ethylenediamine as chain extender. During the reactions between TDI and PPG, the solvent effectiveness can be overcome greatly when a suitable amount of dibutyl tin laurate (DBTDL) and triethylamine compound catalysts were added to the reactants. Furthermore, the environment has little influence on the reaction systems, and the reaction results obtained preserve better reappearance.The film of aromatic WPU preserves better mechanical properties than that of the film of aliphatic WPU. The film of WPU modified by epoxy resin preserves better mechanical and water-resistant properties, but worse latex stability. The film of WPU modified by acrylic acid has the best water-resistant property, but a flaw of crisp. The particle size of aromatic WPU latex is bigger, and the size distribution is wider than those of aliphatic WPU latex, especially in the high solid percentage of WPU latex.As for WPU flame retardant coatings, the inorganic flame retardant systems can't achieve the demand for excellent flame retardant, ornamental and water-resistant properties. The chemical intumescent flame retardant (CIFR) systems show little
improvement on the ornamental and water-resistant property, but its flame retardant property is excellent. The physical intumescent flame retardant (PIFR) systems have worse ornamental property, but its water-resistant property is excellent.
引文
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