CN107722187A - 一种丙烯酸酯改性聚氨酯水分散体的制备方法及其应用 - Google Patents

一种丙烯酸酯改性聚氨酯水分散体的制备方法及其应用 Download PDF

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CN107722187A
CN107722187A CN201710991524.5A CN201710991524A CN107722187A CN 107722187 A CN107722187 A CN 107722187A CN 201710991524 A CN201710991524 A CN 201710991524A CN 107722187 A CN107722187 A CN 107722187A
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郭逍遥
陈之善
赵果
汤汉良
杨惠娟
李树伟
刘其平
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Guangdong Hualan Automobile Material Research Institute
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Abstract

本发明涉及一种丙烯酸酯改性聚氨酯水分散体的制备方法及应用，属汽车涂料系列。它公开了一种聚氨酯水分散体及丙烯酸酯改性聚氨酯水分散体的制备方法。本发明充分结合丙烯酸酯类和聚氨酯类的优势，在耐水、耐溶剂、硬度及附着力等方面性能优异，且漆膜外观金属质感、随角异性强，环保节能，VOC总排放可降低2/5，可操作性强，便于推广应用，市场前景广阔。

Description

一种丙烯酸酯改性聚氨酯水分散体的制备方法及其应用
技术领域
本发明涉及一种水性汽车金属闪光涂料；尤其涉及一种丙烯酸酯改性聚氨酯水分散体的制备方法。
背景技术
随着汽车工业的高速发展，汽车涂料的用量急剧增长，但是目前国内汽车涂料以溶剂型体系为主，含有大量的挥发性有机物，对环境造成的污染日趋严重，人们对环保型涂料的呼声日渐高涨，从环境保护和可持续发展的角度出发，研究开发环境友好型涂料已是势在必行。因此，开发高性能的水性汽车涂层材料不仅具有环保特性外，也减少了生产和施工过程中有害有机溶剂对人体的危害和安全隐患，意义重大，是汽车涂料发展的必然趋势。
目前水性汽车涂料成膜物主要包括水性聚氨酯分散体和聚丙烯酸酯水分散体。水性聚氨酯其结构是由软段和硬段交替组成，在强度、弹性及粘结性等方面性能突出，但耐水性、耐磨性、机械性能都比较差；而聚丙烯酸酯水分散体具有机械性能高、耐水性好、耐光耐候性好、耐老化、抗黄变性能好等优点，但其耐溶剂性差、柔韧性差、热粘冷脆。可见，两者具有很强的互补性，因此，充分的将聚氨酯树脂的韧性及弹性与丙烯酸树脂良好的保色性，光稳定性、硬度及低成本进行有机结合，制备出可操作性较强的高性能水性汽车涂料，既可用于对设备改造不大的修补行业，又可用于汽车原厂，为推动国内原厂修补汽车涂料水性化具有重大的意义。
发明内容
本发明的目的是提供一种丙烯酸酯改性聚氨酯水分散体的制备方法及其应用，本发明在于解决现有技术上的不足，代替现有的溶剂型汽车金属闪光涂料，合成出一种丙烯酸酯改性聚氨酯水分散体，并由其制备出一种高性能水性汽车金属闪光涂料，大大降低了VOC排放，性能优异，可操作性强，便于推广及应用。
本发明提供了一种丙烯酸酯改性聚氨酯水分散体的制备方法：
1)先将180-230份聚酯二元醇(聚碳酸酯二元醇、聚己二酸丁二醇酯二元醇)与N-甲基吡咯烷酮在80℃下，加入10-20份亲水扩链剂(二羟甲基丙酸、二羟甲基丁酸、二羧基半酯)，升温至105℃分散状态下保持0.5h后，降温至60℃，加入0.1-0.3份有机锡类催化剂(二月桂酸二丁基锡、辛酸亚锡)，在30min内加入60-80份多异氰酸酯(异佛尔酮二异氰酸酯或六亚甲基二异氰酸酯)，温度保持75℃以下，保持反应2-3h，冷却至55℃，加入8-12份中和剂(氨水或三乙胺或二甲基乙醇胺)进行中和，反应至pH值达到8-9；在分散条件下缓慢加入450-650份去离子水，保持30min分散均匀，最后加入4-8份乙二胺，保持反应2-4h，得到聚氨酯水分散体。
2)向1步中加入15-25份甲基丙烯酸甲酯、丙烯酸丁酯5-10份，40-60份去离子水，分散均匀后，升温至85℃，缓慢滴加0.1％-0.5％引发剂(过硫酸铵或过硫酸钾)，2h滴完，保持1.5h后得到丙烯酸酯改性聚氨酯水分散体。
本发明所述的用途是提供一种应用于水性汽车金属闪光漆的涂料，它包括：
向丙烯酸酯改性聚氨酯水分散体中添加润湿剂、消泡剂、乙二醇丁醚、水性铝银浆、纤维素酯分散体、增稠剂、流平剂、去离子水，分散均匀得到水性汽车金属闪光涂料。其中各组分的添加量如下：
丙烯酸酯改性聚氨酯水分散体：60-70份
润湿剂(天津赛菲化学公司DS-960)0.4-0.8份
流平剂(毕克公司的BYK346)：0.5-1份
纤维素酯分散体(合力工贸有限公司)1-5份
消泡剂(毕克公司BYK024)：0.2-0.6份
增稠剂(德国Borchers公司的Borchi Gel PW-25)：0.1-0.5份
助溶剂(乙二醇丁醚、丙二醇甲醚醋酸酯)3-8份
水性铝银浆(德国爱卡公司)：8-15份
去离子水：5-20份
本发明的积极效果在于：
1)制备出一种丙烯酸酯改性聚氨酯分散体，及其调配的成品水性汽车金属闪光涂料；
2)上述的丙烯酸酯改性聚氨酯分散体透明度好，有效减少对涂料湿膜状态颜色的干扰，适宜快速调色性；具有低剪切假稠态，高剪切优异流动性的特性，易于喷涂施工，在漆膜干燥过程中能够较大程度的收缩，从而对铝粉的定向排列产生良好的效果，漆膜光滑平整，具有优异的铝粉定向和随角异性效果；
3)上述的丙烯酸改性聚氨酯分散体具有良好的颜料润湿性，使丙烯酸酯类在耐水、耐溶剂、耐候及保光性等方面的优势和聚氨酯类在强度、弹性及粘结性等方面的优势充分的结合了起来，制备出的水性汽车金属闪光涂料不论在金属感、随角异性等外观特征，还是在现场可操作方面，综合性能指标优异；
4)对环境极其友好，大大减少VOC排放，总排放可降低2/5，不仅有效的提高了生产效率，而且实现了汽车涂装的节能减排，市场前景广阔。
具体实施方式：
实施例1：
1)先将200份聚碳酸酯二元醇与N-甲基吡咯烷酮在80℃下，加入15份二羟甲基丙酸，升温至105℃分散状态下保持0.5h后，降温至60℃，加入0.15份二月桂酸二丁基锡，在30min内加入70份脂肪族异佛尔酮二异氰酸酯，温度保持75℃以下，保持反应2-3h，冷却至55℃，加入9份三乙胺进行中和，反应至pH值达到8-9；在分散条件下缓慢加入520份去离子水，保持30min分散均匀，最后加入5份乙二胺，保持反应3h，得到聚氨酯水分散体。
2)向1步中加入20份甲基丙烯酸甲酯、丙烯酸丁酯8份，52份去离子水，分散均匀后，升温至85℃，缓慢滴加0.6份10％的过硫酸铵，2h滴完，保持1.5h后得到丙烯酸酯改性聚氨酯水分散体。
实施例2：
1)先将180份聚碳酸酯二元醇与N-甲基吡咯烷酮在80℃下，加入10份二羟甲基丁酸，升温至105℃分散状态下保持0.5h后，降温至60℃，加入0.1份辛酸亚锡催化剂，在30min内加入60份异佛尔酮二异氰酸酯，温度保持75℃以下，保持反应2-3h，冷却至55℃，加入8份三乙胺进行中和，反应至pH值达到8-9；在分散条件下缓慢加入450份去离子水，保持30min分散均匀，最后加入4份乙二胺，保持反应2h，得到聚氨酯水分散体；
2)向1步中加入15份甲基丙烯酸甲酯、丙烯酸丁酯5份，40份去离子水，分散均匀后，升温至85℃，缓慢滴加0.1份10％的过硫酸铵，2h滴完，保持1.5h后得到丙烯酸酯改性聚氨酯水分散体。
实施例3：
1)先将230份聚己二酸丁二醇酯二元醇与N-甲基吡咯烷酮在80℃下，加入20份二羟甲基丁酸，升温至105℃分散状态下保持0.5h后，降温至60℃，加入0.3份辛酸亚锡催化剂，在30min内加入80份六亚甲基二异氰酸酯，温度保持75℃以下，保持反应2-3h，冷却至55℃，加入12份二甲基乙醇胺进行中和，反应至pH值达到8-9；在分散条件下缓慢加入650份去离子水，保持30min分散均匀，最后加入8份乙二胺，保持反应4h，得到聚氨酯水分散体；
2)向1步中加入25份甲基丙烯酸甲酯、丙烯酸丁酯10份，60份去离子水，分散均匀后，升温至85℃，缓慢滴加0.5份的硫酸钾，2h滴完，保持1.5h后得到丙烯酸酯改性聚氨酯水分散体。
本发明应用于水性汽车金属闪光涂料的制备及性能指标
丙烯酸酯改性聚氨酯水分散体：68(份)
润湿剂(天津赛菲化学公司DS-960)0.5(份)
流平剂(毕克公司的BYK346)：0.65(份)
纤维素酯分散体(合力工贸有限公司)3.5(份)
消泡剂(毕克公司的BYK024)：0.3(份)
增稠剂(德国Borchers公司的Borchi Gel PW-25)：0.2(份)
助溶剂(乙二醇丁醚、丙二醇甲醚醋酸酯)6(份)
水性铝银浆(德国爱卡公司)：11(份)
去离子水：13(份)
性能指标
项目 性能指标 检测方法
外观 银色、平整光滑 目测
硬度 H GB/T 1730-1993
耐冲击/cm 50 GB/T 1732-1993
柔韧性/mm 1 GB/T 9754-1998
附着力/级 0 GB/T 9286-1998
耐酸碱性(24h) 无变化 GB/T 9274-1988
耐水性(40℃，240h) 无气泡、无变色 GB/T 1733-1993

Claims (8)

1.一种丙烯酸酯改性聚氨酯水分散体的制备方法：其特征是：
1)先将180-230份聚酯二元醇与N-甲基吡咯烷酮在80℃下，加入10-20份亲水扩链剂，升温至105℃分散状态下保持0.5h后，降温至60℃，加入0.1-0.3份有机锡类催化剂，在30min内加入60-80份多异氰酸酯，温度保持75℃以下，保持反应2-3h，冷却至55℃，加入8-12份中和剂进行中和，反应至pH值达到8-9；在分散条件下缓慢加入450-650份去离子水，保持30min分散均匀，最后加入4-8份乙二胺，保持反应2-4h，得到聚氨酯水分散体；
2)向1步中加入15-25份甲基丙烯酸甲酯、丙烯酸丁酯5-10份，40-60份去离子水，分散均匀后，升温至85℃，缓慢滴加0.1％-0.5％引发剂，2h滴完，保持1.5h后得到丙烯酸酯改性聚氨酯水分散体。
2.根据权利要求1所述的一种丙烯酸酯改性聚氨酯水分散体的制备方法，其特征是：
1)先将200份聚酯二元醇与N-甲基吡咯烷酮在80℃下，加入15份亲水扩链剂，升温至105℃分散状态下保持0.5h后，降温至60℃，加入0.15份有机锡类催化剂，在30min内加入70份多异氰酸酯，温度保持75℃以下，保持反应2-3h，冷却至55℃，加入9份中和剂进行中和，反应至pH值达到8-9；在分散条件下缓慢加入520份去离子水，保持30min分散均匀，最后加入5份乙二胺，保持反应2-4h，得到聚氨酯水分散体；
2)向1步中加入20份甲基丙烯酸甲酯、丙烯酸丁酯8份，52份去离子水，分散均匀后，升温至85℃，缓慢滴加0.3％引发剂，2h滴完，保持1.5h后得到丙烯酸酯改性聚氨酯水分散体。
3.根据权利要求1所述的一种丙烯酸酯改性聚氨酯水分散体的制备方法，其特征是亲水扩链剂选为二羟甲基丙酸、二羟甲基丁酸、二羧基半酯。
4.根据权利要求1所述的一种丙烯酸酯改性聚氨酯水分散体的制备方法，其特征是有机锡类催化剂为二月桂酸二丁基锡、辛酸亚锡。
5.根据权利要求1所述的一种丙烯酸酯改性聚氨酯水分散体的制备方法，其特征是多异氰酸酯为异佛尔酮二异氰酸酯或六亚甲基二异氰酸酯。
6.根据权利要求1所述的一种丙烯酸酯改性聚氨酯水分散体的制备方法，其特征是中和剂为氨水或三乙胺或二甲基乙醇胺。
7.根据权利要求1所述的一种丙烯酸酯改性聚氨酯水分散体的制备方法，其特征是引发剂为过硫酸铵或过硫酸钾。
8.一种丙烯酸酯改性聚氨酯水分散体的应用。
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