水性聚氨酯革的制备与应用研究
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摘要
水性聚氨酯以水为溶剂,与溶剂型聚氨酯相比具有无毒、不燃、环保等特点,随着人们对环境保护意识的不断加强,水性聚氨酯取代溶剂型聚氨酯成为一种重要的发展方向。本文研究了水性聚氨酯革用聚酯二元醇的制备,探索了不同聚酯二元醇对水性聚氨酯性能的影响,并通过交联解决了水性聚氨酯耐水性差的缺点,制备了可用于水性聚氨酯革的树脂。
论文首先对聚氨酯的原料聚酯二元醇的合成进行了研究,实验以己二酸和一缩二乙二醇为原料考察了合成过程中催化剂种类及用量、醇过量比、反应时间、真空时间等因素对合成反应的影响,确定了合成相对分子质量为2000的聚酯二元醇的最佳工艺条件:反应温度180℃,催化剂甲烷磺酸用量占反应物质量的0.1%,常压反应时间3 h,真空时间3 h。
论文选用异佛尔酮二异氰酸酯(IPDI)、聚酯或聚醚二醇、二羟甲基丙酸(DMPA)等为原料,采用阴离子自乳化法合成了水性聚氨酯乳液。探讨了溶剂、DMPA用量、NCO/OH、中和度、扩链剂等对水性聚氨酯性能的影响,研究表明:溶剂用量占反应物用量的30%,DMPA含量在6%～8%,NCO/OH比值在1.1～1.5之间,中和度在80%～100%时,可以制得性能良好的乳液,同时考察了不同的聚酯多元醇聚己二酸丁二醇、聚己内酯多元醇、聚己二酸一缩二乙二醇和聚醚多元醇聚丙二醇、聚四氢呋喃二醇对水性聚氨酯革性能的影响,发现多元醇对水性聚氨酯的性能影响较大,聚丙二醇的引入可以提高涂膜的延伸率。
为提高水性聚氨酯涂膜的耐水性能实验采用了环氧树脂改性和交联改性,用环氧树脂(E-51)进行改性时,环氧树脂E-51用量在反应物总质量的20%以内时,耐水性能随着环氧树脂的增加逐渐增强。不同的交联剂对涂膜的力学性能和耐水性能影响不同,用三甲氧基亚甲基三聚氰胺树脂(TMMM)和六甲氧基亚甲基三聚氰胺树脂(HMMM)为交联剂时制备的水性聚氨酯,力学性能和耐水性能良好,用氮丙啶交联剂Sac-100,交联制备的水性聚氨酯,耐水性良好,但力学性能较差。
将制备的水性聚氨酯涂于皮革之上,与市售产品进行比较,发现性能与市售产品相近。
Waterborne polyurethane(WPU) is dispersibled in water. WPU don not contain organic solvent is a friendly environmental polymer material. As people’s awareness on environmental protection enhanced, WPU will replace solvent-based polyurethane and have a rapidly development. WPU leather as a new field of polyurethane has been caused gradually people's value.From reaction material,we searched the synthesis of polyesters and the effects to WPU,throuth crosslinking improved the water-resistence of WPU which could used to leather.
In this thesis,polyester was synthesised with adipic acid and diglycol,studied the effect of the reaction time, the percent excess of glycol,the kind and content of of catalyst,vacuum time et al on the reacion.Then the optimal condition of synthesis molecular weight is 2000 was as follows: reaction temperature was 180℃,the content of methanesulfonic acid(as catalyst) was 0.1%,reaction time 3 h,vacuum time 3 h.
In this thesis , waterborne polyurethane was prepared by isophorone diisocyanate (IPDI),polyster and dimethylol propinic acid(DMPA). Studied the effect of the conntent of solvent and DMPA,NCO/OH,degree of neutralization and chain-extender on waterborne polyurethane,the results showed that the emulsion is stable with the conntent of solvent is 30%,the content of DMPA between 6% and 8%,NCO/OH between 1.1 and 1.5,the degree of neutralization between 80% and 100%.At the same time ,we inspected the effect of polyesters and polyethers to WPU,found the kind of polylol have great influence to WPU.PPG could improve the elongation.
In order to improve the water-resistence ,we add crosslinging agent and epoxy resin .Waterborne polyurethane was modified by epoxy resin(E-51),when the content of E-51 under 20%,we could get stable emulsion and as the incresse of E-51,the water-resistence would improve.Different crosslinking agents had different influence,TMMM and HMMM not only improve the water-resistence but also improve the mechanical properties.Sac-100 could improve the water-resistence ,but would reduce the mechanical properties.
Applied our products to the leather ,we found our products have the same capability as products sold in maket.
论文首先对聚氨酯的原料聚酯二元醇的合成进行了研究,实验以己二酸和一缩二乙二醇为原料考察了合成过程中催化剂种类及用量、醇过量比、反应时间、真空时间等因素对合成反应的影响,确定了合成相对分子质量为2000的聚酯二元醇的最佳工艺条件:反应温度180℃,催化剂甲烷磺酸用量占反应物质量的0.1%,常压反应时间3 h,真空时间3 h。
论文选用异佛尔酮二异氰酸酯(IPDI)、聚酯或聚醚二醇、二羟甲基丙酸(DMPA)等为原料,采用阴离子自乳化法合成了水性聚氨酯乳液。探讨了溶剂、DMPA用量、NCO/OH、中和度、扩链剂等对水性聚氨酯性能的影响,研究表明:溶剂用量占反应物用量的30%,DMPA含量在6%～8%,NCO/OH比值在1.1～1.5之间,中和度在80%～100%时,可以制得性能良好的乳液,同时考察了不同的聚酯多元醇聚己二酸丁二醇、聚己内酯多元醇、聚己二酸一缩二乙二醇和聚醚多元醇聚丙二醇、聚四氢呋喃二醇对水性聚氨酯革性能的影响,发现多元醇对水性聚氨酯的性能影响较大,聚丙二醇的引入可以提高涂膜的延伸率。
为提高水性聚氨酯涂膜的耐水性能实验采用了环氧树脂改性和交联改性,用环氧树脂(E-51)进行改性时,环氧树脂E-51用量在反应物总质量的20%以内时,耐水性能随着环氧树脂的增加逐渐增强。不同的交联剂对涂膜的力学性能和耐水性能影响不同,用三甲氧基亚甲基三聚氰胺树脂(TMMM)和六甲氧基亚甲基三聚氰胺树脂(HMMM)为交联剂时制备的水性聚氨酯,力学性能和耐水性能良好,用氮丙啶交联剂Sac-100,交联制备的水性聚氨酯,耐水性良好,但力学性能较差。
将制备的水性聚氨酯涂于皮革之上,与市售产品进行比较,发现性能与市售产品相近。
Waterborne polyurethane(WPU) is dispersibled in water. WPU don not contain organic solvent is a friendly environmental polymer material. As people’s awareness on environmental protection enhanced, WPU will replace solvent-based polyurethane and have a rapidly development. WPU leather as a new field of polyurethane has been caused gradually people's value.From reaction material,we searched the synthesis of polyesters and the effects to WPU,throuth crosslinking improved the water-resistence of WPU which could used to leather.
In this thesis,polyester was synthesised with adipic acid and diglycol,studied the effect of the reaction time, the percent excess of glycol,the kind and content of of catalyst,vacuum time et al on the reacion.Then the optimal condition of synthesis molecular weight is 2000 was as follows: reaction temperature was 180℃,the content of methanesulfonic acid(as catalyst) was 0.1%,reaction time 3 h,vacuum time 3 h.
In this thesis , waterborne polyurethane was prepared by isophorone diisocyanate (IPDI),polyster and dimethylol propinic acid(DMPA). Studied the effect of the conntent of solvent and DMPA,NCO/OH,degree of neutralization and chain-extender on waterborne polyurethane,the results showed that the emulsion is stable with the conntent of solvent is 30%,the content of DMPA between 6% and 8%,NCO/OH between 1.1 and 1.5,the degree of neutralization between 80% and 100%.At the same time ,we inspected the effect of polyesters and polyethers to WPU,found the kind of polylol have great influence to WPU.PPG could improve the elongation.
In order to improve the water-resistence ,we add crosslinging agent and epoxy resin .Waterborne polyurethane was modified by epoxy resin(E-51),when the content of E-51 under 20%,we could get stable emulsion and as the incresse of E-51,the water-resistence would improve.Different crosslinking agents had different influence,TMMM and HMMM not only improve the water-resistence but also improve the mechanical properties.Sac-100 could improve the water-resistence ,but would reduce the mechanical properties.
Applied our products to the leather ,we found our products have the same capability as products sold in maket.
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