CN105175670A - 一种氨基树脂改性水性聚氨酯及其制备方法与应用 - Google Patents
一种氨基树脂改性水性聚氨酯及其制备方法与应用 Download PDFInfo
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Abstract
本发明属于涂料技术领域，公开了一种氨基树脂改性水性聚氨酯及其制备方法与应用。所述氨基树脂改性水性聚氨酯由以下重量份的组分制备而成：二元醇34.6～39.2份，二异氰酸酯24.5～29.8份，二月桂酸二丁基锡0.03～0.09份，1,4-丁二醇1～4份，2，2-二羟甲基丙酸2～6份，氨基树脂2～8份，对甲苯磺酸0.5～1.25份，中和剂2～6份，小分子扩链剂1.2～1.9份。本发明使用预聚合的方法并改变氨基树脂的引入方式，所得产物具有热稳定性好、耐水、耐溶剂、硬度高、吸水率低和机械性能优良等优异性能，由其制备的漆膜烘烤温度低、工艺简单，符合绿色环保化工的概念。
Description
技术领域
本发明属于涂料技术领域，具体涉及一种氨基树脂改性水性聚氨酯及其制备方法与应用。
背景技术
聚氨酯是指分子链中含有氨酯基(-NHCOO-)的高分子聚合物，它由软链段和硬链段组成。软链段多为聚醚、聚酯多元醇，赋予树脂柔软性和韧性，硬链段多为二异氰酸酯与小分子二元醇或者二元胺的缩聚物。由于聚氨酯的软硬段可控可调性强，所以其拥有附着力好、硬度高、耐磨性好等众多优点，广泛应用于皮革、纺织、汽车、建材、医药等多个领域。但是，由于水性聚氨酯引入了较多的亲水性基团及其本身固有的交联度的不足，导致漆膜的硬度、耐水性、耐溶剂性和耐热性还不够好。因此，有必要对水性聚氨酯进行交联改性。
部分甲醚化高亚氨基三聚氰胺树脂是具有甲氧基甲基和亚氨基的氨基树脂，单纯由这种氨基树脂经高温自缩聚固化所制得的漆膜硬且脆，而且附着力差，但是用它对水性聚氨酯进行改性，可以提高体系的交联度，从而改善漆膜的硬度、耐水性、耐溶剂性、耐热性和降低吸水率等。一般的共混改性，由于两者相容性问题，效果并不是很理想且贮存稳定性不好，还有就是烘烤条件比较高，所以要对其进行化学改性。
专利CN104212330A公开了一种水性聚氨酯/氨基树脂复合乳液的制备方法，该法只是将自制的水性聚氨酯和氨基树脂进行简单的物理混合，所制得的漆膜虽然交联度和耐水耐腐蚀性均有所提高，但是这种复合乳液需要高达150℃的固化温度，且简单物理共混造成体系中水性聚氨酯和氨基树脂的形容性不是很好，造成乳液的稳定性不好。
发明内容
为了解决以上现有技术的缺点和不足之处，本发明的首要目的在于提供一种氨基树脂改性水性聚氨酯。
本发明的另一目的在于提供上述氨基树脂改性水性聚氨酯的制备方法。
本发明的再一目的在于提供上述氨基树脂改性水性聚氨酯在配漆中的应用。
本发明目的通过以下技术方案实现：
一种氨基树脂改性水性聚氨酯，由以下质量份的组分制备而成：
所述的二元醇优选聚己内酯二醇、聚丙二醇和聚己二酸乙二醇-1,4-丁二醇酯二醇中的一种或两种以上。
所述的二异氰酸酯优选甲苯二异氰酸酯(TDI)、二苯基甲烷-4，4-二异氰酸酯(MDI)、异佛尔酮二异氰酸酯(IPDI)和六亚甲基二异氰酸酯(HDI)中的一种或两种以上。
所述的氨基树脂优选具有式(1)所示分子结构式的部分甲醚化高亚氨基三聚氰胺树脂；部分甲醚化高亚氨基三聚氰胺树脂中的亚氨基(-NH-)在酸性催化剂对甲苯磺酸作用下与体系中的羧基(-COOH)发生多点反应从而达到交联改性的效果；
所述的中和剂优选为三乙胺、N，N-二甲基乙醇胺和氨水中的一种或两种以上。
所述的小分子扩链剂优选为二乙基甲苯二胺、3，5-二甲硫基甲苯二胺和乙二胺中的一种或两种以上。
上述氨基树脂改性水性聚氨酯的制备方法，包括以下制备步骤：
(1)聚氨酯预聚体制备：在60～80℃下，将二元醇、二异氰酸酯和二月桂酸二丁基锡加入到反应器中，反应1～3小时；
(2)扩链：在60～80℃下，将溶于丙酮的1，4-丁二醇滴加到反应器中，反应30～60分钟，然后加入溶于N-甲基吡咯烷酮的2,2-二羟甲基丙酸，反应2～4小时；
(3)中和成盐：在50～60℃下，加入丙酮降低粘度，再加入中和剂，搅拌保温10～30分钟；
(4)氨基树脂改性：在50～60℃下，将溶于蒸馏水的氨基树脂和对甲苯磺酸加入到反应器中，反应0.5～1小时，得到稠状的氨基树脂改性聚氨酯；
(5)乳化及后扩链：在搅拌条件下，向稠状的氨基树脂改性聚氨酯中加入去离子水，分散5～10分钟，再加入小分子扩链剂，分散20～30分钟，得到氨基树脂改性水性聚氨酯。
优选地，步骤(2)中所述的N-甲基吡咯烷酮和2,2-二羟甲基丙酸的质量比为(2～2.5):1。
优选地，步骤(4)中所述的氨基树脂和对甲苯磺酸溶于水后通过超声振动处理30分钟使其分散均匀。
优选地，步骤(5)中所述搅拌条件的搅拌速度为6000～7000r/min。
上述氨基树脂改性水性聚氨酯在配漆中的应用，所述配漆的组分按重量百分比配比如下：
优选地，所述的消泡剂优选为EVONIK的Foamex805；所述的润湿剂优选为Disperbyk-181。
本发明的制备方法及所得到的产物具有如下优点及有益效果：
(1)本发明使用预聚合的方法，使部分甲醚化高亚氨基三聚氰胺树脂中的亚氨基与水性聚氨酯中的羧基反应，成功地将部分甲醚化高亚氨基三聚氰胺树脂接入到水性聚氨酯中，增加体系的交联度，使得树脂漆膜硬度提高，耐水性、耐溶剂性、耐热性均增强，吸水率降低，拉伸强度及断裂伸长率增加；
(2)本发明引入氨基树脂的方法相比于共混法，所得树脂的粒径更加均一，稳定性更好，所得产物在热稳定性、硬度和附着力等性能上都较共混法好。
具体实施方式
下面结合实施例对本发明作进一步详细的描述，但本发明的实施方式不限于此。
实施例1
(1)聚氨酯预聚体制备：在75℃下，加入39.2g聚己内酯二醇、29.8g异佛尔酮二异氰酸酯(IPDI)和0.08g二月桂酸二丁基锡，反应2小时，采用二正丁胺-丙酮法对NCO残余量进行滴定，当NCO残余量接近或少于理论值达到反应终点；
(2)扩链：在75℃下，称取2.5g1，4-丁二醇溶于3g丙酮滴加到反应器中，反应30分钟，称取5.4g二羟甲基丙酸溶于7gN-甲基吡咯烷酮，加入到反应器中，反应2小时，采用二正丁胺-丙酮法对NCO残余量进行滴定，当NCO残余量接近或少于理论值达到反应终点；
(3)中和成盐：降温至50℃～60℃下，加入10g丙酮降低粘度，再加入3.8g三乙胺中和成盐，保温10分钟，降温至室温，得到透明粘稠状的聚氨酯；
(4)氨基树脂改性：在50～60℃下，将4g部分甲醚化高亚氨基三聚氰胺树脂和0.6g对甲苯磺酸溶于10g蒸馏水经超声振动30分钟后加入到反应器中，反应30分钟，得到稠状的氨基树脂改性聚氨酯；
(5)乳化及后扩链：在搅拌速度为7000r/min的条件下，向粘稠状的氨基树脂改性聚氨酯加入145g去离子水，先分散5分钟，再加入1.5g溶于5g去离子水中的乙二胺，分散25分钟，得到氨基树脂改性水性聚氨酯。
实施例2
(1)聚氨酯预聚体制备：在75℃下，加入34.6g聚丙二醇、24.5g甲苯二异氰酸酯(TDI)和0.08g二月桂酸二丁基锡，反应2小时，采用二正丁胺-丙酮法对NCO残余量进行滴定，当NCO残余量接近或少于理论值达到反应终点；
(2)扩链：在75℃下，称取2.5g1，4-丁二醇溶于4g丙酮滴加到反应器中，反应30分钟，称取5.8g二羟甲基丙酸溶于7gN-甲基吡咯烷酮，加入到反应器中，反应2小时，采用二正丁胺-丙酮法对NCO残余量进行滴定，当NCO残余量接近或少于理论值达到反应终点；
(3)中和成盐：降温至50℃以下，加入10g丙酮降低粘度，再加入3.9gN，N-二甲基乙醇胺中和成盐，保温10分钟，降温至室温，得到粘稠状的聚氨酯；
(4)氨基树脂改性：在50～60℃下，将2g部分甲醚化高亚氨基三聚氰胺树脂和0.25g对甲苯磺酸溶于10g蒸馏水经超声振动30分钟后，加入到反应器中，反应30分钟，得到稠状的氨基树脂改性聚氨酯；
(5)乳化及后扩链：在搅拌速度为7000r/min的条件下，向粘稠状的氨基树脂改性聚氨酯加入150g去离子水，先分散5分钟，再加入1.9g溶于5g去离子水中的二乙基甲苯二胺，分散25分钟，得到氨基树脂改性水性聚氨酯。
实施例3
(1)聚氨酯预聚体制备：在75℃下，加入37.2g聚丙二醇、29g甲苯二异氰酸酯(TDI)和0.08g二月桂酸二丁基锡，反应1.5小时，采用二正丁胺-丙酮法对NCO残余量进行滴定，当NCO残余量接近或少于理论值达到反应终点；
(2)扩链：在75℃下，称取1.8g1，4-丁二醇溶于3g丙酮滴加到反应器中，反应30分钟，称取4.3g二羟甲基丙酸溶于6gN-甲基吡咯烷酮，加入到反应器中，反应2小时，采用二正丁胺-丙酮法对NCO残余量进行滴定，当NCO残余量接近或少于理论值达到反应终点；
(3)中和成盐：降温至50℃以下，加入10g丙酮降低粘度，再加入2.8gN，N-二甲基乙醇胺中和成盐，保温10分钟，降温至室温，得到粘稠状的聚氨酯；
(4)氨基树脂改性：在50～60℃下，将8g部分甲醚化高亚氨基三聚氰胺树脂和1.25g对甲苯磺酸溶于20g蒸馏水经超声振动30分钟后，加入到反应器中，反应30分钟，得到稠状的氨基树脂改性聚氨酯；
(5)乳化及后扩链：在搅拌速度为7000r/min的条件下，向粘稠状的聚氨酯-部分甲醚化高亚氨基三聚氰胺树脂改性醇酸加入153g去离子水，先分散5分钟，再加入1.8g溶于5g去离子水中的乙二胺，分散25分钟，得到氨基树脂改性水性聚氨酯。
对比例1
(1)聚氨酯预聚体制备：在75℃下，加入39.2g聚己内酯二醇、29.8g异佛尔酮二异氰酸酯(IPDI)和0.08g二月桂酸二丁基锡，反应2小时，采用二正丁胺-丙酮法对NCO残余量进行滴定，当NCO残余量接近或少于理论值达到反应终点；
(2)扩链：在75℃下，称取2.5g1，4-丁二醇溶于3g丙酮滴加到反应器中，反应30分钟，称取5.4g二羟甲基丙酸溶于7gN-甲基吡咯烷酮，加入到反应器中，反应2小时，采用二正丁胺-丙酮法对NCO残余量进行滴定，当NCO残余量接近或少于理论值达到反应终点；
(3)中和成盐：降温至50℃～60℃下，加入10g丙酮降低粘度，再加入3.8g三乙胺中和成盐，保温10分钟，降温至室温，得到透明粘稠状的聚氨酯；
(4)乳化及后扩链：在搅拌速度为7000r/min的条件下，向粘稠状的氨基树脂改性聚氨酯加入145g去离子水，先分散5分钟，再加入1.5g溶于5g去离子水中的乙二胺，分散25分钟，得到水性聚氨酯。
(5)共混改性：直接在上述制得的水性聚氨酯中加入4g部分甲醚化高亚氨基三聚氰胺树脂和0.6g对甲苯磺酸，并用玻璃棒搅拌均匀。
将实例1～3和对比例1所制得的氨基树脂改性水性聚氨酯进行配漆，配漆的组分按重量百分比如下：
消泡剂为EVONIK的Foamex805，润湿剂为Disperbyk-181。
实施例1～3的漆膜样品在80℃烘烤20分钟，对比例1的漆膜样品在130℃烘烤30分钟。
对乳液及漆膜的性能进行测试，结果如表1所示。其中粒径采用动态光散射激光粒度仪(DLS，Malvern，ZS-Nano-S)测定；吸水率通过将胶膜裁成25mmX25mm的正方形，称重(m1)，在室温下置于自来水中浸泡24小时，用吸水纸吸去胶膜表面水分，称量(m2)，按(m1-m2)/m1X100％公式计算；拉伸强度、断裂伸长率采用通用的拉力试验机(InstronCorporation，SeriesIX)测定；漆膜硬度按GB/T6739-2006测定；附着力按GB/T9286-1998测定；耐溶剂性通过将漆膜浸泡于二甲苯中24h，观察漆膜变化测定。
表1实施例1～3以及对比例1乳液及漆膜性能测试结果
由表1结果可以看出，本发明引入氨基树脂的方法相比于共混法，所得乳液及漆膜的各项性能均有所提高，主要体现为吸水率降低、拉升强度增大、断裂伸长率增大、硬度增高、附着力提高、耐溶剂性增强。随着氨基树脂用量的增多，体系交联度增大，因而漆膜表现为拉升强度提高、吸水率和断裂伸长率等性能有所下降。
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其它的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。
Claims (10)
1.一种氨基树脂改性水性聚氨酯，其特征在于，由以下质量份的组分制备而成：
2.根据权利要求1所述的一种氨基树脂改性水性聚氨酯，其特征在于：所述的二元醇是指聚己内酯二醇、聚丙二醇和聚己二酸乙二醇-1,4-丁二醇酯二醇中的一种或两种以上。
3.根据权利要求1所述的一种氨基树脂改性水性聚氨酯，其特征在于：所述的二异氰酸酯是指甲苯二异氰酸酯、二苯基甲烷-4，4-二异氰酸酯、异佛尔酮二异氰酸酯和六亚甲基二异氰酸酯中的一种或两种以上。
4.根据权利要求1所述的一种氨基树脂改性水性聚氨酯，其特征在于：所述的氨基树脂为具有式(1)所示分子结构式的部分甲醚化高亚氨基三聚氰胺树脂，
5.根据权利要求1所述的一种氨基树脂改性水性聚氨酯，其特征在于：所述的中和剂为三乙胺、N，N-二甲基乙醇胺和氨水中的一种或两种以上。
6.根据权利要求1所述的一种氨基树脂改性水性聚氨酯，其特征在于：所述的小分子扩链剂为二乙基甲苯二胺、3，5-二甲硫基甲苯二胺和乙二胺中的一种或两种以上。
7.权利要求1～6任一项所述的氨基树脂改性水性聚氨酯的制备方法，其特征在于，包括以下制备步骤：
(1)聚氨酯预聚体制备：在60～80℃下，将二元醇、二异氰酸酯和二月桂酸二丁基锡加入到反应器中，反应1～3小时；
(2)扩链：在60～80℃下，将溶于丙酮的1，4-丁二醇滴加到反应器中，反应30～60分钟，然后加入溶于N-甲基吡咯烷酮的2,2-二羟甲基丙酸，反应2～4小时；
(3)中和成盐：在50～60℃下，加入丙酮降低粘度，再加入中和剂，搅拌保温10～30分钟；
(4)氨基树脂改性：在50～60℃下，将溶于蒸馏水的氨基树脂和对甲苯磺酸加入到反应器中，反应0.5～1小时，得到稠状的氨基树脂改性聚氨酯；
(5)乳化及后扩链：在搅拌条件下，向稠状的氨基树脂改性聚氨酯中加入去离子水，分散5～10分钟，再加入小分子扩链剂，分散20～30分钟，得到氨基树脂改性水性聚氨酯。
8.根据权利要求7所述的一种氨基树脂改性水性聚氨酯的制备方法，其特征在于：步骤(2)中所述的N-甲基吡咯烷酮和2,2-二羟甲基丙酸的质量比为(2～2.5):1；步骤(4)中所述的氨基树脂和对甲苯磺酸溶于水后通过超声振动处理30分钟使其分散均匀；步骤(5)中所述搅拌条件的搅拌速度为6000～7000r/min。
9.权利要求1～6任一项所述的氨基树脂改性水性聚氨酯在配漆中的应用，其特征在于，所述配漆的组分按重量百分比配比如下：
10.根据权利要求9所述的一种氨基树脂改性水性聚氨酯在配漆中的应用，其特征在于，所述的消泡剂为Foamex805；所述的润湿剂为Disperbyk-181。
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| CN110591629A (zh) * | 2019-08-14 | 2019-12-20 | 萍乡高恒材料科技有限公司 | 一种单组份自排气中等剥离力聚氨酯压敏胶组合物 |
| CN111440479A (zh) * | 2020-05-15 | 2020-07-24 | 珠海乐通新材料科技有限公司 | 一种纯水型热收缩膜标签用凹印油墨及其制备方法 |
| CN111777982A (zh) * | 2020-07-30 | 2020-10-16 | 深圳市安伯斯科技有限公司 | 一种耐黄变无溶剂型聚氨酯复合胶及其制备方法 |
| CN113831725A (zh) * | 2021-11-12 | 2021-12-24 | 成都市红宝丽新材料科技发展有限公司 | 一种生产效率高的聚氨酯包覆式阻燃密封胶条及制备方法 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107090069A (zh) * | 2017-05-27 | 2017-08-25 | 杭州传化精细化工有限公司 | 一种二次后扩链的水性聚氨酯制备方法及其制备的分散液 |
| CN110591629A (zh) * | 2019-08-14 | 2019-12-20 | 萍乡高恒材料科技有限公司 | 一种单组份自排气中等剥离力聚氨酯压敏胶组合物 |
| CN111440479A (zh) * | 2020-05-15 | 2020-07-24 | 珠海乐通新材料科技有限公司 | 一种纯水型热收缩膜标签用凹印油墨及其制备方法 |
| CN111777982A (zh) * | 2020-07-30 | 2020-10-16 | 深圳市安伯斯科技有限公司 | 一种耐黄变无溶剂型聚氨酯复合胶及其制备方法 |
| CN113831725A (zh) * | 2021-11-12 | 2021-12-24 | 成都市红宝丽新材料科技发展有限公司 | 一种生产效率高的聚氨酯包覆式阻燃密封胶条及制备方法 |
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