CN108299614A - 一种抗菌型阳离子水性聚氨酯树脂及其制备方法 - Google Patents

一种抗菌型阳离子水性聚氨酯树脂及其制备方法 Download PDF

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CN108299614A
CN108299614A CN201711482498.XA CN201711482498A CN108299614A CN 108299614 A CN108299614 A CN 108299614A CN 201711482498 A CN201711482498 A CN 201711482498A CN 108299614 A CN108299614 A CN 108299614A
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CN108299614B (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阳离子水性聚氨酯树脂及其制备方法，该制备方法包括以下步骤：将大分子多元醇和多异氰酸酯在80～95℃下反应2～4h；再加入小分子醇类扩链剂和绿原酸在75～85℃下反应1～3h；然后加入催化剂在55～65℃下反应2～4h；采用饥饿加料法加入亲水扩链剂，在35～45℃反应0.5～1.5h，降温至‑5～5℃加入中和剂进行中和，加入去离子乳化水分散均匀，然后减压蒸馏，获得阳离子水性聚氨酯树脂。本发明将绿原酸通过化学键合引入到阳离子水性聚氨酯分子链上，既可以避免功能添加剂对水性聚氨酯力学性能的影响，又可以实现良好的抗菌效果。

Description

一种抗菌型阳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阳离子水性聚氨酯树脂及其制备方法。
背景技术
水性聚氨酯是以聚氨酯为基料的水性材料，由于富含微生物生长的营养成分，因而只要环境温度等适合微生物生存的环境条件存在，微生物就会大量繁殖，使材料原有的性质遭到破坏，质量下降，甚至腐败变质而报废。因此，水性聚氨酯中必须加入防霉、杀菌剂。防霉、杀菌剂的作用方式有：1、抑制能量的产生；2、干扰病原菌的生物形成；、破坏细胞结构。常用的防霉、杀菌剂有取代芳烃类、杂环化合物、胺类化合物、有机金属化合物等几大类。其中有机汞类广谱防霉剂由于对人体的毒性大，已禁止使用。目前市场上水性聚氨酯防腐剂主要成分是异噻唑啉酮，异噻唑啉酮杀菌防腐剂主要成份为异噻唑啉酮类化合物是国际上公认的高效、低毒、广谱性的新型杀菌剂。但是这种防腐剂具有腐蚀性，对人体有较大的伤害。
发明内容
本发明的目的在于克服现有的缺陷，提供一种抗菌型阳离子水性聚氨酯树脂及其制备方法，本发明将绿原酸通过化学键合引入到阳离子水性聚氨酯分子链上，使得水性聚氨酯树脂具有良好的抗菌效果；并且绿原酸无毒环保，减少对环境的污染，减少对人体的伤害。
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，本发明提供一种抗菌型阳离子水性聚氨酯树脂的制备方法，包括以下步骤：将大分子多元醇和多异氰酸酯在80～95℃下反应2～4h；再加入小分子醇类扩链剂和绿原酸在75～85℃下反应1～3h；然后加入催化剂在55～65℃下反应2～4h；采用饥饿加料法加入亲水扩链剂，在35～45℃反应0.5～1.5h，降温至-5～5℃加入中和剂进行中和，加入去离子乳化水，分散均匀，然后减压蒸馏，获得阳离子水性聚氨酯树脂。
优选地，所述大分子多元醇、所述异氰酸酯、所述小分子醇类扩链剂、所述绿原酸、所述催化剂、所述亲水扩链剂、所述中和剂与所述去离子乳化水的重量比为(120～170)：(125～145)：(1.5～8)：(0.5-2)：(0.5～2)：(5～9)：(2～5)：(60～130)。
优选地，所述大分子多元醇包括聚四氢呋喃醚多元醇、聚碳酸酯多元醇、聚酯多元醇、聚己内酯多元醇、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，所述异氰酸酯包括甲苯二异氰酸酯和二苯基甲烷二异氰酸酯中的一种或两种。
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一种或多种。
优选地，所述亲水扩链剂包括二乙醇胺、三乙醇胺、N-甲基二乙醇胺、N-乙基二乙醇胺、N-丙基二乙醇胺和叔丁基二乙醇胺中的一种或多种。
优选地，所述催化剂选为有机铋催化剂。
优选地，所述中和剂包括乳酸、冰醋酸、乙醇酸和乙酸酐中的一种或多种。
第二方面，本发明提供一种由如上述所述的抗菌型阳离子水性聚氨酯树脂的制备方法获得的阳离子水性聚氨酯。
第三方面，本发明提供一种如上述所述的抗菌型阳离子水性聚氨酯树脂在制备木器漆的用途。
综上所述，本发明提供一种抗菌型阳离子水性聚氨酯树脂及其制备方法，本发明的有益效果：
本发明将绿原酸通过化学键合引入到阳离子水性聚氨酯分子链上，避免功能添加剂对水性聚氨酯力学性能的影响，本发明既提高了水性聚氨酯树脂的交联度，同时提高了水性聚氨酯的耐水性、耐化学性和机械强度。绿原酸能够更好的和多异氰酸酯进行反应，提高聚合反应稳定性。绿原酸是由金银花中提取，来源安全、环保，无污染。绿原酸具有抗菌和抗病毒的作用，本发明采用绿原酸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。
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120g分子量为2000的聚酯多元醇与128g的甲苯二异氰酸酯，升温至85℃保温反应2h，两小时测定NCO含量，达到理论值后降温至40℃，加入1.8g的1,4-丁二醇、1g的绿原酸和少量丙酮调整粘度，升温至80℃反应2h，达到时间后加入Coscat83催化剂和1mL丙酮，升温至60℃反应3h，然后测试NCO值，达到理论值后降温并加入2mL丙酮降低粘度，降温至40℃，然后采用滴加的方式在30min内缓慢加入6.2g的N-甲基二乙醇胺，在40℃下反应1h，然后降温至0-5℃，得到预聚体；将预聚体倒入梅花桶中，然后在800r/min的转速下加入3.13g的冰醋酸，分散10min后，将转速提高至1800r/min，加入213g去离子乳化水，然后分散30min，然后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。
水性聚氨酯树脂乳液样品1的固含量为34.2％。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96.2％(检测标准为ASTM E2315-03)，说明本发明乳液抗菌性能优异。水性聚氨酯树脂乳液样品1的断裂强度为30.9Mpa，断裂伸长率(20℃)为170％，剥离强度72.12N/cm。
将乳液铺膜，凝固，得到水性聚氨酯涂膜，按照国家标准GB/T 23999-2009《室内装饰装修用水性木器涂料》对水性聚氨酯涂膜进行硬度、耐醇性和耐水性测试，测试结果：涂膜的硬度可达2H，将质量分数为50％的乙醇溶液滴在涂膜上2小时无异常，将自来是滴至涂膜上48小时无异常。将该水性聚氨酯树脂应用于制备木器漆的配方中，可得到具有良好抗菌性的木器漆。
实施例2
将165g分子量为1000的聚氧化丙烯二元醇与136g的甲苯二异氰酸酯，升温至85℃保温反应4h，两小时测定一次NCO含量，达到理论值后降温至40℃，加入6.2g的1,6-己二醇、1.5g的绿原酸和少量丙酮调整粘度，升温至80℃反应2h，达到时间后加入有机铋2010催化剂和1mL丙酮，升温至60℃反应3h，然后测试NCO值，达到理论值后降温并加入1mL丙酮进行降低粘度，然后采用滴加的方式在30min内缓慢加入5.3g的N-甲基二乙醇胺，在40℃下反应1h，然后降温至0-5℃，得到预聚体；将预聚体倒入梅花桶中，然后在800r/min的转速下加入2.67g的冰醋酸，分散10min后，将转速提高至2000r/min，加入254g去离子乳化水，然后分散30min，然后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2。
水性聚氨酯树脂乳液样品1的固含量为36.2％。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97.1％(检测标准为ASTM E2315-03)，说明本发明乳液抗菌性能优异。水性聚氨酯树脂乳液样品1的断裂强度为32.5Mpa，断裂伸长率(20℃)为240％，剥离强度65.12N/cm。
将乳液铺膜，凝固，得到水性聚氨酯膜，按照国家标准GB/T 23999-2009《室内装饰装修用水性木器涂料》进行硬度、耐醇性和耐水性测试，测试结果：涂膜的硬度可达3H，将质量分数为50％的乙醇溶液滴在涂膜上2小时无异常，将自来是滴至涂膜上48小时无异常。将该水性聚氨酯树脂应用于制备木器漆的配方中，可得到具有良好抗菌性的木器漆。
实施例3
将132g分子量为2000的聚四氢呋喃二元醇与129.5g的甲苯二异氰酸酯，升温至85℃保温反应4h，两小时测定一次NCO含量，达到理论值后降温至40℃，加入3g的一缩二乙二醇、0.8g的绿原酸和少量丙酮调整粘度，升温至80℃反应2h，达到时间后加入Coscat83催化剂和1mL丙酮，升温至60℃反应3h，然后测试NCO值，达到理论值后降温并加入1mL丙酮进行降低粘度，然后采用滴加的方式在30min内缓慢加入5.8g的N-甲基二乙醇胺，在40℃下反应1h，然后降温至0-5℃，得到预聚体；将预聚体倒入梅花桶中，然后在800r/min的转速下加入2.92g的冰醋酸，分散10min后，将转速提高至2000r/min，加入236g去离子乳化水，然后分散30min，然后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3。
水性聚氨酯树脂乳液样品1的固含量为35.2％。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96.7％(检测标准为ASTM E2315-03)，说明本发明乳液抗菌性能优异。水性聚氨酯树脂乳液样品1的断裂强度为33.2Mpa，断裂伸长率(20℃)为340％，剥离强度59.24N/cm。
将乳液铺膜，凝固，得到水性聚氨酯膜，按照国家标准GB/T 23999-2009《室内装饰装修用水性木器涂料》进行硬度、耐醇性和耐水性测试，测试结果：涂膜的硬度可达3H，将质量分数为50％的乙醇溶液滴在涂膜上2小时无异常，将自来是滴至涂膜上48小时无异常。将该水性聚氨酯树脂应用于制备木器漆的配方中，可得到具有良好抗菌性的木器漆。
实施例4
将120g分子量为1000的聚碳酸酯多元醇与144g的甲苯二异氰酸酯在85℃保温反应2h，两小时测定NCO含量，达到理论值后降温至40℃，加入2g的乙二醇和1.8g的绿原酸和少量丙酮调整粘度，升温至80℃反应2h，达到时间后加入有机铋2010催化剂和1mL丙酮，升温至60℃反应3h，然后测试NCO值，达到理论值后降温并加入2mL丙酮进行降低粘度，然后采用滴加的方式在30min内缓慢加入7g的N-甲基二乙醇胺，在40℃下反应1h，然后降温至0-5℃，得到预聚体；将预聚体倒入梅花桶中，然后在800r/min的转速下加入3.53g的冰醋酸，分散10min后，将转速提高至2000r/min，加入230g去离子乳化水，然后分散30min。然后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4。
水性聚氨酯树脂乳液样品4的固含量为38.2％。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93.5％(检测标准为ASTM E2315-03)，说明本发明乳液抗菌性能优异。水性聚氨酯树脂乳液样品1的断裂强度为36.2Mpa，断裂伸长率(20℃)为280％，剥离强度64.27N/cm。
将乳液铺膜，凝固，得到水性聚氨酯膜，按照国家标准GB/T 23999-2009《室内装饰装修用水性木器涂料》进行硬度、耐醇性和耐水性测试，测试结果：涂膜的硬度可达3H，将质量分数为50％的乙醇溶液滴在涂膜上2小时无异常，将自来是滴至涂膜上48小时无异常。将该水性聚氨酯树脂应用于制备木器漆的配方中，可得到具有良好抗菌性的木器漆。
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)

1.一种抗菌型阳离子水性聚氨酯树脂的制备方法，其特征在于：包括以下步骤：将大分子多元醇和多异氰酸酯在80～95℃下反应2～4h；再加入小分子醇类扩链剂和绿原酸在75～85℃下反应1～3h；然后加入催化剂在55～65℃下反应2～4h；采用饥饿加料法加入亲水扩链剂，在35～45℃反应0.5～1.5h，降温至-5～5℃加入中和剂进行中和，加入去离子乳化水分散均匀，然后减压蒸馏，获得阳离子水性聚氨酯树脂。
2.如权利要求1所述的抗菌型阳离子水性聚氨酯树脂，其特征在于：所述大分子多元醇、所述异氰酸酯、所述小分子醇类扩链剂、所述绿原酸、所述催化剂、所述亲水扩链剂、所述中和剂与所述去离子乳化水的重量比为(120～170)：(125～145)：(1.5～8)：(0.5-2)：(0.5～2)：(5～9)：(2～5)：(60～130)。
3.如权利要求1所述的抗菌型阳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四氢呋喃醚多元醇、聚碳酸酯多元醇、聚酯多元醇、聚己内酯多元醇、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。
4.如权利要求1所述的抗菌型阳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和二苯基甲烷二异氰酸酯中的一种或两种。
5.如权利要求1所述的抗菌型阳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一种或多种。
6.如权利要求1所述的抗菌型阳离子水性聚氨酯树脂，其特征在于：所述亲水扩链剂包括二乙醇胺、三乙醇胺、N-甲基二乙醇胺、N-乙基二乙醇胺、N-丙基二乙醇胺和叔丁基二乙醇胺中的一种或多种。
7.如权利要求1所述的抗菌型阳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。
8.如权利要求1所述的抗菌型阳离子水性聚氨酯树脂，其特征在于：所述中和剂包括乳酸、冰醋酸、乙醇酸和乙酸酐中的一种或多种。
9.一种由如权利要求1至8任一所述的抗菌型阳离子水性聚氨酯树脂的制备方法获得的阳离子水性聚氨酯。
10.一种如权利要求9所述的抗菌型阳离子水性聚氨酯树脂在制备木器漆的用途。
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