CN110982031A - 一种阳离子水性聚氨酯树脂、其制备方法和在涂料中的用途 - Google Patents

一种阳离子水性聚氨酯树脂、其制备方法和在涂料中的用途 Download PDF

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CN110982031A
CN110982031A CN201911203137.6A CN201911203137A CN110982031A CN 110982031 A CN110982031 A CN 110982031A CN 201911203137 A CN201911203137 A CN 201911203137A CN 110982031 A CN110982031 A CN 110982031A
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polyurethane resin
chain extender
polyol
cationic
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李维虎
汪飞
赵曦
朱保凌
戴家兵
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Lanzhou Scisky Aqueous Polymer Material Co ltd
Hefei Scisky Technology Co ltd
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Hefei Scisky Technology Co ltd
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Abstract

本发明提供一种涂料用阳离子水性聚氨酯树脂、其制备方法和在涂料中的用途。所述涂料用阳离子水性聚氨酯树脂为多个原料组分进行反应，并得到分子主链上包含式I结构的所述阳离子水性聚氨酯，其中，所述所述多个原料组分包括：包括至少由以下质量份的原料组分反应得到：多元醇70～100份；多异氰酸酯50～90份；第一扩链剂10～30份；第二扩链剂3～18份；包含式I结构的化合物8～20份；成盐剂1～12份。根据本发明提供的阳离子水性聚氨酯树脂用于涂料时，具有安全无毒，附着力高，且具有良好的驱蚊效果。

Description

一种阳离子水性聚氨酯树脂、其制备方法和在涂料中的用途
技术领域
本发明涉及高分子聚合物领域，具体公开了一种阳离子水性聚氨酯、其制备方法和在水性涂料中的用途。
背景技术
包含阳离子水性聚氨酯树脂的涂料由于安全无毒、附着力高、水性环保的特点，广泛适用于家具装饰，以及建筑墙体等。目前，蚊虫等害虫给人类生活带来了很多困扰，被叮咬后不仅会对人体出现瘙痒的症状，更大的危害是吸血时可将疟原虫、丝状蚴、乙脑等病毒注入人体内，使人感染发病。因此，蚊子不但叮人吸血影响睡眠，还会传播乙型脑炎、疟疾、登革热、血丝虫病等，给人类带来了极大的危害。目前市场上的驱蚊涂料，都是混合防蚊花草等植物粉末、N,N-二乙基间甲苯酰胺(DEET)等化学化学试剂的方式，没有关于将无毒的驱蚊材料合成涂料用的阳离子水性聚氨酯中的报道。因此，研究开发出一种阳离子水性聚氨酯树脂，其不但能够驱赶蚊虫防止叮咬，而且对人体无害，极大方便人们的生活，这具有十分重要的意义。
发明内容
鉴于以上所述现有技术的缺点，本发明的目的在于提供一种涂料用阳离子水性聚氨酯树脂，当将所述阳离子水性聚氨酯树脂用于涂料时，具有安全无毒，附着力高，且具有良好的驱蚊效果。
本发明的另一个目的在于提供了一种如上所述阳离子水性聚氨酯的制备方法。
本发明的另一个目的在于提供了一种涂料，所述涂料包含如上所述的阳离子水性聚氨酯。
为实现上述目的及相关目的，本发明通过包含以下的技术方案实现：一种涂料用阳离子水性聚氨酯树脂，所述阳离子水性聚氨酯为多个原料组分进行反应，并得到分子主链上包含式I结构的所述阳离子水性聚氨酯，
Figure BDA0002296359640000021
其中，所述所述多个原料组分包括：多元醇70～100份；多异氰酸酯50～90份；第一扩链剂10～30份；第二扩链剂3～18份；包含式I结构的化合物8～20份；成盐剂1～12份。
在本发明的一些实施方式中，所述多元醇选自聚己内酯多元醇、聚碳酸酯多元醇、聚四氢呋喃醚多元醇、聚环氧乙烷多元醇、聚环氧丙烷多元醇和端羟基聚丁二烯和聚硅氧烷多元醇和聚酯醚多元醇中的一种或上述任意其组合。
在本发明的一些实施方式中，所述多异氰酸酯选自甲苯二异氰酸酯、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一种或上述任意其组合。
在本发明的一些实施方式中，所述第一扩链剂选自乙二醇、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上述任意其组合。
在本发明的一些实施方式中，所述第二扩链剂选自二乙醇胺、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上述任意其组合。
在本发明的一些实施方式中，所述包含式I结构的化合物为：
Figure BDA0002296359640000022
其中，R1和R2独立的选自所述羟基、酰胺基、酯基，以及羧基中的任意一种。
本发明也提供如上所述的涂料用阳离子水性聚氨酯树脂的制备方法，所述方法包括：提供多个原料组分：多元醇70～100份；多异氰酸酯50～90份；第一扩链剂10～30份；第二扩链剂3～18份；式I结构的化合物8～20份；成盐剂1～12份。
所述原料组分进行反应得到分子主链上包含式I结构的所述阳离子水性聚氨酯；
Figure BDA0002296359640000031
在本发明的一些实施方式中，至少包括以下步骤：将所述多元醇和所述多异氰酸酯在85～95℃下反应2～3h；再加入所述第一扩链剂、所述包含式I结构的化合物在75～85℃下反应1～3h；接着加入所述第二扩链剂在30～50℃下反应1～2h；反应结束加入所述成盐剂中和，加水乳化，所得的产物经后处理步骤，获得所述涂料用阳离子水性聚氨酯树脂。9、如权利要求7所述的涂料用阳离子水性聚氨酯树脂的制备方法，其特征在于，加入所述第一扩链剂、所述包含式I结构的化合物和所述第二扩链剂的同时分别加入丙酮。
本发明还提供了一种涂料，所述涂料包含如上所述的涂料用阳离子水性聚氨酯树脂。
如上所述，本发明提供了一种阳离子水性聚氨酯树脂、其制备方法和在涂料中的用途。利用通过在阳离子水性聚氨酯的分子链上引入包含式I结构的化合物方式实现。本发明原料组分及产品中均不含有甲醛、苯类或其他易挥发有机物，因此，无毒环保；本发明用于内墙封闭底漆时，具有较小的表面张力，对底材的渗透性极强，碱性物质和温度都可促进阳离子乳液的交联反应，所以强碱性的墙壁会使之有更好的成膜效果，起到更好的封闭效果；本发明用于木器底漆时，可以封闭单宁酸，使面漆不泛黄；此外，使用本发明的树脂制成的内墙封闭底漆或木器底漆均可以达到驱蚊的效果，利于工业运用。
附图说明
图1显示为本发明的涂料用阳离子水性聚氨酯制备方法的一具体实施方式的流程图。
具体实施方式
以下通过特定的具体实例说明本发明的实施方式，本领域技术人员可由本说明书所揭露的内容轻易地了解本发明的其他优点与功效。本发明还可以通过另外不同的具体实施方式加以实施或应用，本说明书中的各项细节也可以基于不同观点与应用，在没有背离本发明的精神下进行各种修饰或改变。
需要说明的是，本实施例中所提供的图示仅以示意方式说明本发明的基本构想，遂图式中仅显示与本发明中有关的组件而非按照实际实施时的组件数目、形状及尺寸绘制，其实际实施时各组件的型态、数量及比例可为一种随意的改变，且其组件布局型态也可能更为复杂。
本发明提供了一种阳离子水性聚氨酯树脂、其制备方法和在涂料中的用途。所述阳离子水性聚氨酯的制备方法包括至少由以下质量份的原料组分反应过程：多元醇70～100份；多异氰酸酯50～90份；第一扩链剂10～30份；第二扩链剂3～18份；包含式I结构的化合物8～20份；成盐剂 1～12份。
请参阅图1，在本发明公开的一具体实施方式中，制备方法包括但不限于以下步骤。
请接着参阅图1，所述本发明的阳离子水性聚氨酯的制备方法包括步骤S1，将所述多元醇和所述多异氰酸酯在85～95℃下反应2～3h。
在步骤S1中，所述多元醇为脱水处理后的多元醇。具体地，例如可以将所述多元醇加热至90℃～120℃脱水例如一小时，然后降温至50℃，得到脱水处理后多元醇，接着与多异氰酸酯进行反应。基于提高所述水性聚氨酯保湿性能的角度，所述反应温度为88～90℃，进一步地，搅拌时间为2.5h。
在步骤S1中，所述多元醇选自聚己内酯多元醇、聚碳酸酯多元醇、聚四氢呋喃醚多元醇、聚环氧乙烷多元醇、聚环氧丙烷多元醇和端羟基聚丁二烯和聚硅氧烷多元醇和聚酯醚多元醇中的一种或几种。进一步地，例如为聚四氢呋喃二元醇、聚碳酸酯二元醇、聚酯醚二元醇，所述多元醇的分子量为1000-2000。
在步骤S1中，所述多异氰酸酯选自甲苯二异氰酸酯、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一种或几种。进一步地，例如为甲苯二异氰酸酯、异佛尔酮二异氰酸酯。所述多异氰酸酯氰基当量对树脂软硬度有影响，是通过多元醇也多异氰酸酯的比例来控制。所述多元醇与所述多异氰酸酯的比例为(70～100)：(50～90)，进一步地，例如可以为(80～95)：(58～82)。在上述范围内时，获得的所述阳离子水性聚氨酯性能在运用到涂料上时，硬度和附着力理想。
请接着参阅图1，所述本发明的阳离子水性聚氨酯的制备方法包括步骤S2，接着加入所述第一扩链剂、所述包含式I结构的化合物在75～85℃下反应1～3h。
在步骤S2中，进一步地，可以依次添加第一扩链剂和包含式I结构的化合物。基于提高所述包含式I结构的化合物和所述多异氰酸酯反应性的角度，所述反应温度例如为75～80℃。进一步地，所述反应时间3h。
在步骤S2中，所述第一扩链剂选自乙二醇、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几种。进一步地，所述第一扩链剂为一缩二乙二醇、二甘醇、1，4-丁二醇、三羟甲基丙烷。在上述原料组分下，所述第一扩链剂的含量为10～20份。
在步骤S2中，将包含式I结构的化合物，引入阳离子水性聚氨酯的分子主链上时，获得包含式I结构的阳离子水性聚氨酯，其具有良好的驱蚊效果和保湿效果，运用在护肤液等化妆品时，符合市场运用标准，所述包含式I结构的化合物中：
Figure BDA0002296359640000051
R1、R2可以独立地选自于所述羟基、酰胺基、酯基，以及羧基中的任意一种，具体地例子例如可以列举2-乙-1,3-己二醇。所述2-乙-1,3-己二醇例如可以购自上海依赫生物科技有限公司。在本发明的包含式I结构的化合物与所述预聚物的异氰酸根基具有反应性。基于提高所述2-乙-1,3-己二醇和所述多异氰酸酯反应性的角度，2-乙-1,3-己二醇与所述多元醇、多异氰酸酯的比例为(70～100)：(50～90)：(8～20)，进一步地为(80～85)：(58～82)：(8～15)。例如为80:62:9；85:58:12；83：:70：15。
请接着参阅图1，所述本发明的阳离子水性聚氨酯的制备方法包括步骤S3，接着加入所述第二扩链剂在30～50℃下反应1～2h。
在步骤S3中，进一步地，反应温度为35℃，反应时间为1h。
在步骤S3中，所述第二扩链剂选自二乙醇胺、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几种。进一步地，所述成盐剂为二乙醇胺、N-甲基二乙醇胺。
在步骤S3中，所述成盐剂选自乳酸、冰醋酸、乙醇酸、乙酸酐中的一种或多种。进一步地，所述成盐剂为乳酸、乙酸酐。
请接着参阅图1，所述本发明的阳离子水性聚氨酯的制备方法包括步骤S4，反应结束加入所述成盐剂中和，加水乳化，所得的产物经后处理步骤，获得所述涂料用阳离子水性聚氨酯树脂。
具体地，在本发明的一个实施例中，将80g分子量为2000的聚四氢呋喃二元醇加入三口烧瓶中，加热至100℃～110℃脱水一小时，然后降温至50℃，加入62g的甲苯二异氰酸酯，升温至90℃保温反应2小时，两小时测定NCO含量，达到理论值后降温至50℃，加入16g的1，6-己二醇、7g的三羟甲基丙烷、9g的2-乙-1,3-己二醇和少量丙酮调整粘度，升温至80℃反应2小时，反应结束测定NCO含量，然后降温至50℃，加入丙酮调整粘度，缓慢加入3.75g的二乙醇胺。反应1小时后再加入丙酮进行乳化，将2.25g冰醋酸加入预聚体中，中和反应2分钟，然后高速搅拌下加入去离子水，减压蒸馏得到样品1.
具体地，在本发明的另一个实施例中，将92g分子量为1000的聚碳酸酯二元醇加入三口烧瓶中，加热至100℃～110℃脱水一小时，然后降温至50℃，加入58g的甲苯二异氰酸酯，升温至90℃保温反应2小时，两小时测定NCO含量，达到理论值后降温至50℃，加入8g的1，4-丁二醇、3g的三羟甲基丙烷、12g的2-乙-1,3-己二醇和少量丙酮调整粘度，升温至80℃反应2小时，反应结束测定NCO含量，然后降温至50℃，加入丙酮调整粘度，缓慢加入6g的N-甲基二乙醇胺。反应1小时后再加入丙酮进行乳化，将4.76g乳酸加入预聚体中，中和反应2分钟，然后高速搅拌下加入去离子水，减压蒸馏得到样品2.
具体地，在本发明的另一个实施例中，将40g分子量为1000的聚四氢呋喃二元醇和50g分子量为2000的聚己内酯二元醇加入三口烧瓶中，加热至100℃～110℃脱水一小时，然后降温至50℃，加入80g的甲苯二异氰酸酯，升温至90℃保温反应2小时，两小时测定NCO含量，达到理论值后降温至50℃，加入14g的一缩二乙二醇、4g的三羟甲基丙烷、15g的2-乙-1,3-己二醇和少量丙酮调整粘度，升温至80℃反应2小时，反应结束测定NCO含量，然后降温至50℃，加入丙酮调整粘度，缓慢加入8g的N-乙基二乙醇胺。反应1小时后再加入丙酮进行乳化，将6.4g乙酸酐加入预聚体中，中和反应2分钟，然后高速搅拌下加入去离子水，减压蒸馏得到样品3。
具体地，在本发明的另一个实施例中，将85g分子量为2000的聚酯醚二元醇加入三口烧瓶中，加热至100℃～110℃脱水一小时，然后降温至50℃，加入63g的甲苯二异氰酸酯，升温至90℃保温反应2小时，两小时测定NCO含量，达到理论值后降温至50℃，加入14.3g的新戊二醇、5g的三羟甲基丙烷、13g的2-乙-1,3-己二醇和少量丙酮调整粘度，升温至80℃反应2小时，反应结束测定NCO含量，然后降温至50℃，加入丙酮调整粘度，缓慢加入6.9g的N-甲基二乙醇胺。反应1小时后再加入丙酮进行乳化，将3.67g冰醋酸加入预聚体中，中和反应2分钟，然后高速搅拌下加入去离子水，减压蒸馏得到样品4。
上述实施例仅例示性说明本发明的原理及其功效，而非用于限制本发明。任何熟悉此技术的人士皆可在不违背本发明的精神及范畴下，对上述实施例进行修饰或改变。因此，举凡所属技术领域中具有通常知识者在未脱离本发明所揭示的精神与技术思想下所完成的一切等效修饰或改变，仍应由本发明的权利要求所涵盖。

Claims (10)

1.一种涂料用阳离子水性聚氨酯树脂，其特征在于，所述阳离子水性聚氨酯为多个原料组分进行反应，并得到分子主链上包含式I结构的所述阳离子水性聚氨酯，
Figure FDA0002296359630000011
其中，所述所述多个原料组分包括：多元醇 70～100份；多异氰酸酯 50～90份；第一扩链剂 10～30份；第二扩链剂 3～18份；包含式I结构的化合物 8～20份；成盐剂 1～12份。
2.如权利要求1所述的涂料用阳离子水性聚氨酯树脂，其特征在于，所述多元醇选自聚己内酯多元醇、聚碳酸酯多元醇、聚四氢呋喃醚多元醇、聚环氧乙烷多元醇、聚环氧丙烷多元醇和端羟基聚丁二烯和聚硅氧烷多元醇和聚酯醚多元醇中的一种或上述任意其组合。
3.如权利要求1所述的涂料用阳离子水性聚氨酯树脂，其特征在于，所述多异氰酸酯选自甲苯二异氰酸酯、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一种或上述任意其组合。
4.如权利要求1所述的涂料用阳离子水性聚氨酯树脂，其特征在于，所述第一扩链剂选自乙二醇、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上述任意其组合。
5.如权利要求1所述的涂料用阳离子水性聚氨酯树脂，其特征在于，所述第二扩链剂选自二乙醇胺、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上述任意其组合。
6.如权利要求1所述的涂料用阳离子水性聚氨酯树脂，其特征在于，所述包含式I结构的化合物为：
Figure FDA0002296359630000021
其中，R1和R2独立的选自所述羟基、酰胺基、酯基，以及羧基中的任意一种。
7.一种涂料用阳离子水性聚氨酯树脂的制备方法，其特征在于，所述方法包括：
提供多个原料组分：多元醇70～100份；多异氰酸酯50～90份；第一扩链剂10～30份；第二扩链剂3～18份；式I结构的化合物8～20份；成盐剂1～12份。
所述原料组分进行反应得到分子主链上包含式I结构的所述阳离子水性聚氨酯；
Figure FDA0002296359630000022
8.如权利要求7所述的涂料用阳离子水性聚氨酯树脂的制备方法，其特征在于，至少包括以下步骤：
将所述多元醇和所述多异氰酸酯在85～95℃下反应2～3h；
接着加入所述第一扩链剂、所述包含式I结构的化合物在75～85℃下反应1～3h；
接着加入所述第二扩链剂在30～50℃下反应1～2h；
反应结束加入所述成盐剂中和，加水乳化，所得的产物经后处理步骤，获得所述涂料用阳离子水性聚氨酯树脂。
9.如权利要求7所述的涂料用阳离子水性聚氨酯树脂的制备方法，其特征在于，加入所述第一扩链剂、所述包含式I结构的化合物和所述第二扩链剂的同时分别加入丙酮。
10.一种涂料，其特征在于，所述涂料包含权利要求1～6任意一项所述的涂料用阳离子水性聚氨酯树脂。
CN201911203137.6A 2019-11-29 2019-11-29 一种阳离子水性聚氨酯树脂、其制备方法和在涂料中的用途 Pending CN110982031A (zh)

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