水性紫外光固化聚氨酯丙烯酸酯树脂的制备与研究
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摘要
水性紫外光固化涂料以固化速度快、涂膜性能优良、环境友好、节约能源、可涂装各种基材和费用较低等优异性能在近20多年来得到了高速发展,是面向二十一世纪的绿色环保产品。
本实验合成了四种不同的水性光固化聚氨酯丙烯酸酯树脂,编号分别为：WPUA-1、WPUA-2、WPUA-3、WPUA-4;其中WPUA-1树脂是基于聚丙二醇(PPG)、甲苯二异氰酸酯(TDI)、2,2-二羟甲基丙酸(DMPA)、丙烯酸羟乙酯(HEA),采用分步法合成的；WPUA-2树脂用聚酯二元醇(PHA)代替聚醚二元醇(PPG),其它单体不变,采用分步法合成的；WPUA-3树脂用合成出来的亲水二元醇(M-T)代替DMPA,其它单体不变,采用分步法合成的；WPUA-4树脂以聚丙二醇(PPG)、甲苯二异氰酸酯(TDI)、2,2-二羟甲基丙酸(DMPA)、丙烯酸羟乙酯(HEA)为单体,采用一步法合成的。本文主要讨论WPUA-1树脂及其乳液的性能,并对四种树脂及其乳液的性能进行对比。
本文详细讨论了在WPUA-1体系中,亲水基团含量、中和剂种类和中和度对树脂亲水性、乳液外观和乳液稳定性的影响,以及预聚物分子结构设计、光引发剂种类、光引发剂用量、干燥条件、中和度和乳液固含量对涂膜光固化速度的影响；同时对WPUA-1固化膜的力学性能及耐化学试剂性能进行了测定,最后考察了高支化聚酯加入量对WPUA-1涂膜光固化速度和力学性能的影响。
结果表明：在WPUA-1体系中,n(-COOH)为0.61 mmol时,制备的乳液为蓝光半透明稳定,乳液平均粒径为40.7nm,此时涂膜的光固化速度最快,固化膜的力学性能和耐化学试剂性能最好；选用三乙胺作为中和剂时,中和度为90%,树脂的水分散效果最佳；阻聚剂选用对羟基苯甲醚,占树脂的质量分数为5‰,溶剂为丁酮,在树脂合成中加入10mL,催化剂选用二月桂酸二丁基锡,合成出的树脂及其乳液的稳定性较好；n(PPG):n(TDI)为1：3,光引发剂为819-DW,占乳液的质量分数为3%,中和度为90%,乳液固含量为40%,涂膜在80℃条件下干燥2min,涂膜的光固化速度最快；高支化聚酯加入量为10%时,WPUA-1涂膜光固化速度和涂膜力学性能都大副提高；在WPUA-1、WPUA-2、WPUA-3、WPUA-4四种不同体系中,WPUA-1体系的综合性能最好。
Water-borne UV-curable coating for fast curing speed, film with excellent performance, environment friendly and energy saving, low cost of base material of excellent performance has been high-speed development in the past 20 years, is oriented to green products of the 21st century.
This experiment has four different synthesis of UV-curable polyurethane acrylates resins, respectively numbers for WPUA-1, WPUA-2, WPUA-3, WPUA-4. WPUA-1 resin is synthesized by polypropylene glycol (PPG), toluene diisocyanate (TDI), dimethylol propionic acid (DMPA), hydroxyl ethyl acrylate (HEA) for monomer by stepwise way; WPUA-2 resin is synthesized by polyester glycol (PHA) instead of polyether glycol (PPG) by stepwise way, and other monomers is constant; WPUA-3 resin is synthesized by hydrophilic glycol (M-T) instead of DMPA by stepwise way, and other monomers is constant; WPUA-4 resin is synthesized by polypropylene glycol (PPG), toluene diisocyanate (TDI), dimethylol propionic acid (DMPA), hydroxyl ethyl acrylate (HEA) for the monomer by one-step way. This article mainly discusses properties of WPUA-1 resin and emulsion, and compares the properties of four kinds of resins and emulsions.
This paper discusses WPUA-1 system, the hydrophilic group content, neutralizer type and neutralizer content, the degree of neutralization on the hydrophilicity of the resin and the appearance and stability of the emulsion, as well as prepolymer molecular design, photoinitiator type, photoinitiator, dry condition, neutralization degree, and solid content of the emulsion on the curing speed of the coating; the same time, mechanical properties and resistance to chemical reagents of the cured film of WPUA-1 are determined, the final test inspects effect of the high-branched polyester volume on curing rate and mechanical properties of the film of WPUA-1.
The results show that:In WPUA-1 system, when the amount of-COOH is 0.61 mmol, emulsion is stable translucent blue, which latex average particle size is 42nm, curing speed of the coating is the fastest, mechanical properties of cured film properties and resistance to chemical reagents are the best; Using triethylamine as the neutralizer, the neutralization degree of 90%, Water dispersion of the resin is the best; Hydroxyanisole is used as the inhibitor, total mass fraction of resin 5‰, methyl ethyl ketone is used as the solvent, adding volume to 10mL in the resin process, dibutyltin dilaurate is used as the catalyst, the synthesized resin and emulsion stability is good; n(PPG):n(TDI) for 1:3, photoinitiator for the 819-DW, total mass fraction of emulsion 3%, the neutralization degree of 90%,40% solid content of the emulsion, coating film dried at 80℃for 2min, the coating curing speed is the fastest; Addition of high-branched polyester for 10%, coating film curing rate and coating mechanical properties of WPUA-1 are bother improved greatly; In the four different systems, WPUA-1, WPUA-2, WPUA-3, WPUA-4, WPUA-1 system has the best comprehensive properties.
本实验合成了四种不同的水性光固化聚氨酯丙烯酸酯树脂,编号分别为：WPUA-1、WPUA-2、WPUA-3、WPUA-4;其中WPUA-1树脂是基于聚丙二醇(PPG)、甲苯二异氰酸酯(TDI)、2,2-二羟甲基丙酸(DMPA)、丙烯酸羟乙酯(HEA),采用分步法合成的；WPUA-2树脂用聚酯二元醇(PHA)代替聚醚二元醇(PPG),其它单体不变,采用分步法合成的；WPUA-3树脂用合成出来的亲水二元醇(M-T)代替DMPA,其它单体不变,采用分步法合成的；WPUA-4树脂以聚丙二醇(PPG)、甲苯二异氰酸酯(TDI)、2,2-二羟甲基丙酸(DMPA)、丙烯酸羟乙酯(HEA)为单体,采用一步法合成的。本文主要讨论WPUA-1树脂及其乳液的性能,并对四种树脂及其乳液的性能进行对比。
本文详细讨论了在WPUA-1体系中,亲水基团含量、中和剂种类和中和度对树脂亲水性、乳液外观和乳液稳定性的影响,以及预聚物分子结构设计、光引发剂种类、光引发剂用量、干燥条件、中和度和乳液固含量对涂膜光固化速度的影响；同时对WPUA-1固化膜的力学性能及耐化学试剂性能进行了测定,最后考察了高支化聚酯加入量对WPUA-1涂膜光固化速度和力学性能的影响。
结果表明：在WPUA-1体系中,n(-COOH)为0.61 mmol时,制备的乳液为蓝光半透明稳定,乳液平均粒径为40.7nm,此时涂膜的光固化速度最快,固化膜的力学性能和耐化学试剂性能最好；选用三乙胺作为中和剂时,中和度为90%,树脂的水分散效果最佳；阻聚剂选用对羟基苯甲醚,占树脂的质量分数为5‰,溶剂为丁酮,在树脂合成中加入10mL,催化剂选用二月桂酸二丁基锡,合成出的树脂及其乳液的稳定性较好；n(PPG):n(TDI)为1：3,光引发剂为819-DW,占乳液的质量分数为3%,中和度为90%,乳液固含量为40%,涂膜在80℃条件下干燥2min,涂膜的光固化速度最快；高支化聚酯加入量为10%时,WPUA-1涂膜光固化速度和涂膜力学性能都大副提高；在WPUA-1、WPUA-2、WPUA-3、WPUA-4四种不同体系中,WPUA-1体系的综合性能最好。
Water-borne UV-curable coating for fast curing speed, film with excellent performance, environment friendly and energy saving, low cost of base material of excellent performance has been high-speed development in the past 20 years, is oriented to green products of the 21st century.
This experiment has four different synthesis of UV-curable polyurethane acrylates resins, respectively numbers for WPUA-1, WPUA-2, WPUA-3, WPUA-4. WPUA-1 resin is synthesized by polypropylene glycol (PPG), toluene diisocyanate (TDI), dimethylol propionic acid (DMPA), hydroxyl ethyl acrylate (HEA) for monomer by stepwise way; WPUA-2 resin is synthesized by polyester glycol (PHA) instead of polyether glycol (PPG) by stepwise way, and other monomers is constant; WPUA-3 resin is synthesized by hydrophilic glycol (M-T) instead of DMPA by stepwise way, and other monomers is constant; WPUA-4 resin is synthesized by polypropylene glycol (PPG), toluene diisocyanate (TDI), dimethylol propionic acid (DMPA), hydroxyl ethyl acrylate (HEA) for the monomer by one-step way. This article mainly discusses properties of WPUA-1 resin and emulsion, and compares the properties of four kinds of resins and emulsions.
This paper discusses WPUA-1 system, the hydrophilic group content, neutralizer type and neutralizer content, the degree of neutralization on the hydrophilicity of the resin and the appearance and stability of the emulsion, as well as prepolymer molecular design, photoinitiator type, photoinitiator, dry condition, neutralization degree, and solid content of the emulsion on the curing speed of the coating; the same time, mechanical properties and resistance to chemical reagents of the cured film of WPUA-1 are determined, the final test inspects effect of the high-branched polyester volume on curing rate and mechanical properties of the film of WPUA-1.
The results show that:In WPUA-1 system, when the amount of-COOH is 0.61 mmol, emulsion is stable translucent blue, which latex average particle size is 42nm, curing speed of the coating is the fastest, mechanical properties of cured film properties and resistance to chemical reagents are the best; Using triethylamine as the neutralizer, the neutralization degree of 90%, Water dispersion of the resin is the best; Hydroxyanisole is used as the inhibitor, total mass fraction of resin 5‰, methyl ethyl ketone is used as the solvent, adding volume to 10mL in the resin process, dibutyltin dilaurate is used as the catalyst, the synthesized resin and emulsion stability is good; n(PPG):n(TDI) for 1:3, photoinitiator for the 819-DW, total mass fraction of emulsion 3%, the neutralization degree of 90%,40% solid content of the emulsion, coating film dried at 80℃for 2min, the coating curing speed is the fastest; Addition of high-branched polyester for 10%, coating film curing rate and coating mechanical properties of WPUA-1 are bother improved greatly; In the four different systems, WPUA-1, WPUA-2, WPUA-3, WPUA-4, WPUA-1 system has the best comprehensive properties.
引文
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