CN108299613A - 一种抗菌型阴离子水性聚氨酯树脂及其制备方法 - Google Patents

一种抗菌型阴离子水性聚氨酯树脂及其制备方法 Download PDF

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CN108299613A
CN108299613A CN201711478254.4A CN201711478254A CN108299613A CN 108299613 A CN108299613 A CN 108299613A CN 201711478254 A CN201711478254 A CN 201711478254A CN 108299613 A CN108299613 A CN 108299613A
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aqueous polyurethane
polyurethane resin
chain extender
antimicrobial form
form anion
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CN108299613B (zh
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戴家兵
汪飞
李维虎
王浩志
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Lnzhou Ketian Aqueous Polymer Material Co Ltd
Hefei Scisky Technology Co Ltd
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Hefei Scisky Technology Co Ltd
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Abstract

本发明提供一种抗菌型阴离子水性聚氨酯树脂及其制备方法，该水性聚氨酯包括以下原料组分及重量份：大分子多元醇70～85份；多异氰酸酯10～20份；亲水扩链剂4.5～12.5份；小分子醇类扩链剂0.5～2份；胺类扩链剂1～10份；催化剂0.01～0.5份；成盐剂2～5份；其中，所述亲水扩链剂为绿原酸。本发明采用绿原酸代替羧酸型亲水扩链剂，大大提高所制得的水性聚氨酯的耐水性、耐化学性和机械强度，绿原酸来源安全、环保，无污染，绿原酸作为亲水扩链剂使用，其易溶于丙酮，能够更好的和多异氰酸酯进行反应，提高聚合反应稳定性；绿原酸具有抗菌抗病毒的作用，使得获得水性聚氨酯无需外加杀菌剂即可达到防腐杀菌的效果。

Description

一种抗菌型阴离子水性聚氨酯树脂及其制备方法
技术领域
本发明涉及高分子聚合物技术领域，具体公开了一种抗菌型阴离子水性聚氨酯树脂及其制备方法。
背景技术
水性聚氨酯材料由于其具有环保、安全等性能被越来越多的人所熟悉，目前水性聚氨酯主要有阳离子型、阴离子型和非离子型，阴离子型包括磺酸型和羧酸型，羧酸型水性聚氨酯的制备方法主要依靠二羟甲基丙酸(DMPA)和二羟甲基丁酸(DMBA)等亲水性扩链剂来制备，但是这两种亲水性扩链剂生产过程中均产生较重的污染，DMPA目前使用最广泛，但是由于其很难溶于丙酮中，所以在水性聚氨酯合成过程中较难反应；DMBA在丙酮中溶解度较大，合成过程中粘度也较小，但是生产污染严重，合成技术复杂，难度高，目前国内很少有规模生产的厂商。
发明内容
本发明的目的在于克服现有的缺陷，提供一种抗菌型阴离子水性聚氨酯树脂及其制备方法，该水性聚氨酯树脂采用亲水扩链剂绿原酸，绿原酸从金银花中提取，来源安全、环保，并且该水性聚氨酯树脂在应用过程中，无需外加杀菌剂即可达到防腐杀菌的效果，进一步减少了污染环境。
为了实现以上目的，本发明通过包括以下技术方案实现的：
第一方面，一种抗菌型阴离子水性聚氨酯树脂，包括以下原料组分及重量份：
优选地，所述大分子多元醇为75～80份。
优选地，所述多异氰酸酯为13～17份。
优选地，所述亲水扩链剂为6～9份。
优选地，所述小分子醇类扩链剂为1～1.5份。
优选地，所述胺类扩链剂为2～8份。
优选地，所述催化剂为0.1～0.3份。
优选地，所述成盐剂为3～4份。
其中，所述亲水扩链剂为绿原酸。
优选地，所述大分子多元醇包括聚酯多元醇、聚己内酯多元醇、聚碳酸酯多元醇、聚四氢呋喃醚多元醇、聚环氧乙烷多元醇、聚环氧丙烷多元醇、聚酯醚多元醇和聚硅氧烷多元醇中的任意一种或多种。
优选地，所述大分子多元醇的分子量为1000-3000。
优选地，所述异氰酸酯包括甲苯二异氰酸酯、异佛尔酮二异氰酸酯、二苯基甲烷二异氰酸酯、1,6-己二异氰酸酯、苯二亚甲基二异氰酸酯、萘-1,5-二异氰酸酯多亚甲基多苯基异氰酸酯、四甲基苯二亚甲基二异氰酸酯、甲基环己基二异氰酸酯和二环己基甲烷二异氰酸酯中的任意一种或多种。
优选地，所述小分子醇类扩链剂包括乙二醇、2-甲基-1,3-丙二醇、一缩二乙二醇、1,4-丁二醇、2,3-丁二醇、1,6-己二醇、新戊二醇、二甘醇、甘油、山梨醇、三羟甲基丙烷和二羟甲基环己烷中的任意一种或多种。
优选地，所述胺类扩链剂为乙二胺、1,6-己二胺、异佛尔酮二胺和聚醚胺中的一种或多种。
优选地，所述催化剂选为有机铋催化剂。
更优选地，所述催化剂选自有机铋Coscat83、有机铋1610、有机铋2010、有机铋2810和有机铋2808中的任意一种或多种。
优选地，所述成盐剂包括三乙胺、氨水和氢氧化钠中的任意一种或者多种。
第二方面，本发明提供一种制备如上述所述的抗菌型阴离子水性聚氨酯树脂的方法，包括以下步骤：将所述多元醇和所述多异氰酸酯在85～95℃下反应2～3h；再加入所述亲水扩链剂和所述小分子醇类扩链剂在75～85℃下反应1.5～2.5h；然后加入所述催化剂，在65～75℃下反应2～3h，降温至-5～5℃加入所述成盐剂中和；加水后再加入所述胺类扩链剂，减压蒸馏，获得水性聚氨酯树脂。
优选地，加入所述催化剂的同时加入丙酮。
丙酮的作用为调整反应溶液的粘度。丙酮的添加量可根据反应需要酌情添加。所述丙酮在减压蒸馏阶段被蒸馏除去。
第三方面，本发明提供一种如上述所述的抗菌型阴离子水性聚氨酯树脂在制备皮革的用途。
综上所述，本发明提供一种抗菌型阴离子水性聚氨酯树脂及其制备方法，本发明的有益效果：
本发明采用绿原酸代替羧酸型亲水扩链剂，其分子结构中含有五个羟基和一个羧基，既可以作为扩链剂、亲水剂还可以作为交联剂，大大提高水性聚氨酯的耐水性、耐化学性和机械强度。绿原酸由金银花中提取，来源安全、环保，无污染。绿原酸作为亲水扩链剂使用，其易溶于丙酮，能够更好的和多异氰酸酯进行反应，提高聚合反应稳定性。另外，绿原酸具有抗菌抗病毒的作用，使得获得水性聚氨酯无需外加杀菌剂即可达到防腐杀菌的效果，有利于将该水性聚氨酯广泛应用于制备皮革领域。
具体实施方式
下面结合实施例进一步阐述本发明。应理解，实施例仅用于说明本发明，而非限制本发明的范围。
实施例1
将80g的聚四氢呋喃醚多元醇(分子量为3000)在105℃脱水1h，然后降温至50℃，加入15g的甲苯二异氰酸酯，升温至90℃保温反应3小时，两小时测定NCO含量，达到理论值后降温至50℃，然后加入6g绿原酸、1.5g乙二醇在80℃下反应2h，降温至50℃，然后加入0.2g有机铋Coscat83和2ml丙酮调整粘度，在70℃下反应2.5h，反应结束测定NCO含量，然后降温至0℃，加入2.32g的三乙胺进行中和，中和30min后，高速剪切下加入去离子水，分散2分钟，然后缓慢加入2g的乙二胺，减压蒸馏除去体系中的丙酮，即得到水性聚氨酯树脂乳液样品1，固含量为34％。
水性聚氨酯树脂乳液样品1对金黄色葡萄球菌的抑菌率为97.4％(检测标准为ASTM E2315-03)，说明本发明乳液抗菌性能优异。将乳液铺膜，凝固，得到水性聚氨酯膜，参照GB/T 1040-92《塑料拉伸性能试验方法》对得到水性聚氨酯膜进行拉伸强度、断裂伸长率测试，测试结果：拉伸强度为25.8MPa，断裂伸长率为509.5％。将该水性聚氨酯树脂应用于制备皮革的配方中，可得到具有良好抗菌性的皮革。
实施例2
将78g的聚环氧乙烷多元醇(分子量为3000)在105℃脱水1h，然后降温至50℃，加入15g的异佛尔酮二异氰酸酯，升温至90℃保温反应3小时，两小时测定NCO含量，达到理论值后降温至50℃，然后加入8g绿原酸、1.5g甘油在80℃下反应2h，降温至50℃，然后加入0.15g有机铋1610和2ml丙酮调整粘度，在70℃下反应2.5h，反应结束测定NCO含量，然后降温至0℃，加入2.12g的三乙胺进行中和，中和30min后，高速剪切下加入去离子水，分散2min，然后缓慢加入8g的聚醚胺，减压蒸馏除去体系中的丙酮，即得到水性聚氨酯树脂样品2，固含量为36％。
水性聚氨酯树脂乳液样品2对金黄色葡萄球菌的抑菌率为98.4％(检测标准为ASTM E2315-03)，说明本发明乳液抗菌性能优异。将乳液铺膜，凝固，得到水性聚氨酯膜，参照GB/T 1040-92《塑料拉伸性能试验方法》对得到水性聚氨酯膜进行拉伸强度、断裂伸长率测试，测试结果：拉伸强度为18MPa，断裂伸长率为460％。将该水性聚氨酯树脂应用于制备皮革的配方中，可得到具有良好抗菌性的皮革。
实施例3
将75g的聚酯醚多元醇(分子量为3000)在105℃脱水1h，然后降温至50℃，加入15g的1,6-己二异氰酸酯，升温至90℃保温反应3小时，两小时测定NCO含量，达到理论值后降温至50℃，然后加入7.2g绿原酸、1.5g乙二醇在80℃下反应2h，降温至50℃，然后加入0.2g有机铋2010和2ml丙酮调整粘度，在70℃下反应2.5h，反应结束测定NCO含量，然后降温至0℃，加入2.51g的三乙胺进行中和，中和30min后，高速剪切下加入去离子水，分散2min，然后缓慢加入5g的异佛尔酮二胺，减压蒸馏除去体系中的丙酮，即得到水性聚氨酯树脂样品3，固含量为34％。
水性聚氨酯树脂乳液样品3对金黄色葡萄球菌的抑菌率为97.1％(检测标准为ASTM E2315-03)，说明本发明乳液抗菌性能优异。将乳液铺膜，凝固，得到水性聚氨酯膜，参照GB/T 1040-92《塑料拉伸性能试验方法》对得到水性聚氨酯膜进行拉伸强度、断裂伸长率测试，测试结果：拉伸强度为32MPa，断裂伸长率为483％。将该水性聚氨酯树脂应用于制备皮革的配方中，可得到具有良好抗菌性的皮革。
实施例4
将80g的聚环氧丙烷多元醇(分子量为4000)在105℃脱水1h，然后降温至50℃，加入15g的苯二亚甲基二异氰酸酯，升温至90℃保温反应3小时，两小时测定NCO含量，达到理论值后降温至50℃，然后加入6.8g绿原酸、1.5g乙二醇在80℃下反应2h，降温至50℃，然后加入0.2g有机铋Coscat83和2ml丙酮调整粘度，在70℃下反应2.5h，反应结束测定NCO含量，然后降温至0℃，加入2.32g的三乙胺进行中和，中和30min后，高速剪切下加入去离子水，分散2min，然后缓慢加入6g的1,6-己二胺，减压蒸馏除去体系中的丙酮，即得到水性聚氨酯树脂样品4，固含量为35％。
水性聚氨酯树脂乳液样品4对金黄色葡萄球菌的抑菌率为96.2％(检测标准为ASTM E2315-03)，说明本发明乳液抗菌性能优异。将乳液铺膜，凝固，得到水性聚氨酯膜，参照GB/T 1040-92《塑料拉伸性能试验方法》对得到水性聚氨酯膜进行拉伸强度、断裂伸长率测试，测试结果：拉伸强度为16.5MPa，断裂伸长率为677％。将该水性聚氨酯树脂应用于制备皮革的配方中，可得到具有良好抗菌性的皮革。
实施例5
将83g的聚硅氧烷多元醇(分子量为3000)在105℃脱水1h，然后降温至50℃，加入15g的甲基环己基二异氰酸酯，升温至90℃保温反应3小时，两小时测定NCO含量，达到理论值后降温至50℃，然后加入7.6g绿原酸、1.6g丁二醇在80℃下反应2h，降温至50℃，然后加入0.2g有机铋Coscat83和3ml丙酮调整粘度，在70℃下反应3h，反应结束测定NCO含量，然后降温至0℃，加入2.32g的三乙胺进行中和，中和30min后，高速剪切下加入去离子水，分散2min，然后缓慢加入2.3g的乙二胺，减压蒸馏除去体系中的丙酮，即得到水性聚氨酯树脂样品5，固含量为36％。
水性聚氨酯树脂乳液样品5对金黄色葡萄球菌的抑菌率为97.2％(检测标准为ASTM E2315-03)，说明本发明乳液抗菌性能优异。将乳液铺膜，凝固，得到水性聚氨酯膜，参照GB/T 1040-92《塑料拉伸性能试验方法》对得到水性聚氨酯膜进行拉伸强度、断裂伸长率测试，测试结果：拉伸强度为18MPa，断裂伸长率为462％。将该水性聚氨酯树脂应用于制备皮革的配方中，可得到具有良好抗菌性的皮革。
对比例1
将80g的聚四氢呋喃醚多元醇(分子量为3000)在105℃脱水1h，然后降温至50℃，加入15g的甲苯二异氰酸酯，升温至90℃保温反应3小时，两小时测定NCO含量，达到理论值后降温至50℃，然后加入6g二羟甲基丙酸、1.5g乙二醇在80℃下反应2h，降温至50℃，然后加入0.2g有机铋Coscat83和2ml丙酮调整粘度，在70℃下反应2.5h，反应结束测定NCO含量，然后降温至0℃，加入2.32g的三乙胺进行中和，中和30min后，高速剪切下加入去离子水，分散2min，然后缓慢加入2g的乙二胺，减压蒸馏除去体系中的丙酮，即得到水性聚氨酯树脂样品6，固含量为34％。
水性聚氨酯树脂乳液样品6对金黄色葡萄球菌的抑菌率为31.4％(检测标准为ASTM E2315-03)。将乳液铺膜，凝固，得到水性聚氨酯膜，参照GB/T 1040-92《塑料拉伸性能试验方法》对得到水性聚氨酯膜进行拉伸强度、断裂伸长率测试，测试结果：拉伸强度为20.8MPa，断裂伸长率为471％。
以上，仅为本发明的较佳实施例，并非对本发明任何形式上和实质上的限制，应当指出，对于本技术领域的普通技术人员，在不脱离本发明方法的前提下，还将可以做出若干改进和补充，这些改进和补充也应视为本发明的保护范围。凡熟悉本专业的技术人员，在不脱离本发明的精神和范围的情况下，当可利用以上所揭示的技术内容而做出的些许更动、修饰与演变的等同变化，均为本发明的等效实施例；同时，凡依据本发明的实质技术对上述实施例所作的任何等同变化的更动、修饰与演变，均仍属于本发明的技术方案的范围内。

Claims (10)

1.一种抗菌型阴离子水性聚氨酯树脂，其特征在于：包括以下原料组分及重量份：
其中，所述亲水扩链剂为绿原酸。
2.如权利要求1所述的抗菌型阴离子水性聚氨酯树脂，其特征在于：所述大分子多元醇包括聚酯多元醇、聚己内酯多元醇、聚碳酸酯多元醇、聚四氢呋喃醚多元醇、聚环氧乙烷多元醇、聚环氧丙烷多元醇、聚酯醚多元醇和聚硅氧烷多元醇中的任意一种或多种。
3.如权利要求1所述的抗菌型阴离子水性聚氨酯树脂，其特征在于：所述异氰酸酯包括甲苯二异氰酸酯、异佛尔酮二异氰酸酯、二苯基甲烷二异氰酸酯、1,6-己二异氰酸酯、苯二亚甲基二异氰酸酯、萘-1,5-二异氰酸酯多亚甲基多苯基异氰酸酯、四甲基苯二亚甲基二异氰酸酯、甲基环己基二异氰酸酯和二环己基甲烷二异氰酸酯中的任意一种或多种。
4.如权利要求1所述的抗菌型阴离子水性聚氨酯树脂，其特征在于：所述小分子醇类扩链剂包括乙二醇、2-甲基-1,3-丙二醇、一缩二乙二醇、1,4-丁二醇、2,3-丁二醇、1,6-己二醇、新戊二醇、二甘醇、甘油、山梨醇、三羟甲基丙烷和二羟甲基环己烷中的任意一种或多种。
5.如权利要求1所述的抗菌型阴离子水性聚氨酯树脂，其特征在于：所述胺类扩链剂为乙二胺、1,6-己二胺、异佛尔酮二胺和聚醚胺中的一种或多种。
6.如权利要求1所述的抗菌型阴离子水性聚氨酯树脂，其特征在于：所述催化剂选为有机铋催化剂。
7.如权利要求1所述的抗菌型阴离子水性聚氨酯树脂，其特征在于：所述成盐剂包括三乙胺、氨水和氢氧化钠中的任意一种或者多种。
8.一种制备如权利要求1至7任一所述的抗菌型阴离子水性聚氨酯树脂的方法，其特征在于：包括以下步骤：
将所述多元醇和所述多异氰酸酯在85～95℃下反应2～3h；再加入所述亲水扩链剂和所述小分子醇类扩链剂在75～85℃下反应1.5～2.5h；然后加入所述催化剂，在65～75℃下反应2～3h，降温至-5～5℃加入所述成盐剂中和；加水后再加入所述胺类扩链剂，减压蒸馏，获得水性聚氨酯树脂。
9.如权利要求1所述的抗菌型阴离子水性聚氨酯树脂的制备方法，其特征在于：加入所述催化剂的同时加入丙酮。
10.一种如权利要求1至7任一所述的抗菌型阴离子水性聚氨酯树脂在制备皮革的用途。
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