CN110684454B - 自催化快干型改性醇酸树脂、制备方法及涂料 - Google Patents

自催化快干型改性醇酸树脂、制备方法及涂料 Download PDF

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CN110684454B
CN110684454B CN201810736835.1A CN201810736835A CN110684454B CN 110684454 B CN110684454 B CN 110684454B CN 201810736835 A CN201810736835 A CN 201810736835A CN 110684454 B CN110684454 B CN 110684454B
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庄国波
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Bauhinia Paints Shanghai Co ltd
Yip's Chemical Research Development Shanghai Co ltd
HENGCHANG PAINT (HUIYANG) CO Ltd
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Yip's Chemical Research Development Shanghai Co ltd
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Abstract

自催化快干型改性醇酸树脂、制备方法及涂料，制备方法包括以下步骤：S1：制备中间体单体，将丙酮和异氰酸酯单体混合打底，边搅拌边依次滴加（甲基）丙烯酸羟乙酯单体或者（甲基）丙烯酸羟丙酯单体、DMP‑30、丁醇，在T1温度下进行反应，反应时间为t1；S2：制备醇酸树脂反应物，将醇酸树脂和顺丁烯二酸酐或者甲基丙烯酸缩水甘油酯，在温度T2下进行反应，反应时间为t2；S3：制备自催化快干型改性醇酸树脂，步骤S2后进行冷却，冷却到温度T3，加入步骤S1制备的中间体单体，反应时间t3后制备得到自催化快干型改性醇酸树脂。本发明的改性醇酸树脂具有自催化、干燥快的特点，尤其是低温干燥速率和硬度上升快、对产品可使用时间和防沉性影响小、残留气味低等优点。

Description

自催化快干型改性醇酸树脂、制备方法及涂料
技术领域
本发明涉及一种自催化快干型改性醇酸树脂，尤其涉及到自催化快干型改性醇酸树脂、制备方法及涂料。
背景技术
木器双组份聚氨酯涂料一般由醇酸树脂搭配异氰酸酯类固化剂制成，该制成的双组份聚氨酯涂料因其漆膜强韧，光泽丰满，附着力强，耐水耐磨、耐腐蚀性等优点，在高级木器家具涂料中有较大的占比。但是，此类型的双组份聚氨酯涂料，操作配比繁琐导致配置时间长、效率较低，有遇潮易起泡，常温以及低温干燥慢等缺点，一直影响其进一步发展，特别在目前国内劳力成本上升的国情下，为了提高企业竞争力，对如何降低成本，提高交货效率有了进一步的要求。因此，如何开发一种在常温条件下，特别是低温条件下的具备高干燥速率的醇酸树脂成为非常必要的发展方向。
在醇酸树脂类双组份聚氨酯涂料中，催化剂是一种常见的助剂，常见的催化剂主要有叔胺类催化剂和有机金属化合物两大类，用量虽少，作用很大，聚氨酯催化剂可以缩短反应时间，提高生产效率，选择性促进正反应、抑制副反应。但是少量的外加催化剂，要么低温条件下容易失效（如二月桂酸二丁基锡），要么严重影响涂料气味和防沉性（如胺类催干剂），要么严重缩短涂料的可使用时间（如二月桂酸二丁基锡与胺类催干剂搭配），均无法满足当下涂料对低气味、易施工、高效率以及使用时间长的要求。
发明内容
本发明克服了现有技术中在常温或者低温条件下的醇酸树脂干燥速率慢、可使用时间短等问题，现提供一种自催化快干型改性醇酸树脂的制备方法，该树脂具有自催化、低温快干、残留气味小的特点，且不影响防沉性和可使用时间。
一种自催化快干型改性醇酸树脂，按重量百分比计，所采用的原料组成为：中间体单体5%~10%，醇酸树脂反应物90%~95；其中，中间体单体包括丙酮75%、丁醇1%、异氰酸酯单体6~8%、（甲基）丙烯酸羟乙酯单体或者（甲基）丙烯酸羟丙酯单体4~6%、DMP-30为8~10%；醇酸树脂反应物包括醇酸树脂99.5~97%，顺丁烯二酸酐1.5~3%或者甲基丙烯酸缩水甘油酯0.5~1.5%，。
优选的，一种自催化快干型改性醇酸树脂的制备方法，包括以下步骤：
S1：制备中间体单体，将丙酮和异氰酸酯单体混合打底，边搅拌边依次滴加（甲基）丙烯酸羟乙酯单体或者（甲基）丙烯酸羟丙酯单体、DMP-30、丁醇，在T1温度下进行反应，反应时间为t1；
S2：制备醇酸树脂反应物，将醇酸树脂和顺丁烯二酸酐或者甲基丙烯酸缩水甘油酯，在温度T2下进行反应，反应时间为t2；
S3：制备自催化快干型改性醇酸树脂，步骤S2后进行冷却，冷却到温度T3，加入步骤S1制备的中间体单体，反应时间t3后制备得到自催化快干型改性醇酸树脂。
优选的，所述的T1为40~60℃，t1为4~6h。
优选的，所述的T2为180~210℃，t2为8~12h。
优选的，所述的T3为100~150℃，t3为2~3h。
优选的，所述的丁醇为正丁醇或者异丁醇。
优选的，所述的异氰酸酯为甲苯二异氰酸酯（TDI）、异佛尔酮二异氰酸酯（IPDI）、六亚甲基二异氰酸酯（HDI）和二苯基甲烷二异氰酸酯（MDI）中的任意一种或几种。
优选的，所述的DMP-30为2、4、6-三（二甲氨基甲基）苯酚。
优选的，一种自催化快干型改性醇酸树脂涂料，由以下组分组成：权利要求1-8中任意一项所述的自催化快干型改性醇酸树脂、颜填料、助剂和溶剂。
优选的，所述的助剂为分散剂、消泡剂、流平剂、催干剂和润湿剂中的任意一种或者多种，所述的颜填料为钛白粉、色粉、滑石粉、锌粉、透明粉、重钙中的任意一种或者多种，所述的溶剂为醋酸丁酯、醋酸乙酯、甲苯、二甲苯、丙二醇甲醚醋酸酯、碳酸二甲酯中的任意一种或者多种。
本发明自制一种催化活性高的中间体单体，中间体单体含可共聚双键，能够通过双键聚合与醇酸树脂反应物进行化学接枝改性，制备得到自催化快干型改性醇酸树脂。本发明制备的自催化快干型改性醇酸树脂，具有自催化、低温干燥快的特点，同时具有对产品可使用时间和防沉性影响小、残留气味低的优点，制备方法工艺简单，效率高。由此自催化快干型改性醇酸树脂制备的涂料，在常温甚至低温条件下，具有硬度上升快、干燥效率高、防沉性和可使用时间可控、漆膜无不友好的胺类气味等优点，能有效的提高生产效率，降低成本，节能环保。
具体实施方式
下面结合实施例对本发明进行进一步的阐述。
一种自催化快干型改性醇酸树脂，按重量百分比计，所采用的原料组成为：中间体单体5%~10%，醇酸树脂反应物90%~95；其中，中间体单体包括丙酮75%、丁醇1%、异氰酸酯单体6~8%、（甲基）丙烯酸羟乙酯单体或者（甲基）丙烯酸羟丙酯单体4~6%、DMP-30为8~10%；醇酸树脂反应物包括醇酸树脂99.5~97%，顺丁烯二酸酐1.5~3%或者甲基丙烯酸缩水甘油酯0.5~1.5%），其中异氰酸酯为甲苯二异氰酸酯（TDI）、异佛尔酮二异氰酸酯（IPDI）、六亚甲基二异氰酸酯（HDI）和二苯基甲烷二异氰酸酯（MDI）中的任意一种或几种，DMP-30为2、4、6-三（二甲氨基甲基）苯酚，丁醇为正丁醇或者异丁醇，本发明的一种自催化快干型改性醇酸树脂，具有低温干燥速率高、对产品可使用时间和防沉性影响小、残留气味低的优点。
实施例1：
一种自催化快干型改性醇酸树脂的制备方法，其特征在于：包括以下步骤：
S1：制备中间体单体，将丙酮和异氰酸酯单体混合后，边搅拌边依次滴加（甲基）丙烯酸羟乙酯单体或者（甲基）丙烯酸羟丙酯单体、DMP-30、丁醇，在40温度下进行反应，反应时间为4h，其中丁醇为正丁醇或者异丁醇，DMP-30为2、4、6三(二甲氨基甲基)苯酚的简称，异氰酸酯为甲苯二异氰酸酯（TDI）、异佛尔酮二异氰酸酯（IPDI）、六亚甲基二异氰酸酯（HDI）和二苯基甲烷二异氰酸酯（MDI）中的任意一种或几种；
S2：制备醇酸树脂反应物，将醇酸树脂和顺丁烯二酸酐或者甲基丙烯酸缩水甘油酯，搅拌后在温度180℃下进行反应，反应时间为8h，其中甲基丙烯酸缩水甘油酯所占重量比为0.5%，顺丁烯二酸酐所占重量比为1.5%；
S3：制备自催化快干型改性醇酸树脂，步骤S2后进行冷却，冷却到温度100℃，加入步骤S1制备的中间体单体，反应时间2h后制备得到自催化快干型改性醇酸树脂，中间体单体所占重量比为5%。
实施例2：
一种自催化快干型改性醇酸树脂的制备方法，其特征在于：包括以下步骤：
S1：制备中间体单体，将丙酮和异氰酸酯单体混合后，边搅拌边依次滴加（甲基）丙烯酸羟乙酯单体或者（甲基）丙烯酸羟丙酯单体、DMP-30、丁醇在60℃温度下进行反应，反应时间为6h，其中丁醇为正丁醇或者异丁醇，DMP-30为2、4、6三(二甲氨基甲基)苯酚的简称，异氰酸酯为甲苯二异氰酸酯（TDI）、异佛尔酮二异氰酸酯（IPDI）、六亚甲基二异氰酸酯（HDI）和二苯基甲烷二异氰酸酯（MDI）中的任意一种或几种；
S2：制备醇酸树脂反应物，将醇酸树脂和顺丁烯二酸酐或者甲基丙烯酸缩水甘油酯，搅拌后在温度210℃下进行反应，反应时间为12h，甲基丙烯酸缩水甘油酯所占重量比为1.5%，顺丁烯二酸酐所占重量比为3%；
S3：制备自催化快干型改性醇酸树脂，步骤S2后进行冷却，冷却到温度150℃，加入步骤S1制备的中间体单体，反应时间3h后制备得到自催化快干型改性醇酸树脂，中间体单体所占重量比为10%。
实施例3：
一种自催化快干型改性醇酸树脂的制备方法，其特征在于：包括以下步骤：
S1：制备中间体单体，将丙酮和异氰酸酯单体混合后，边搅拌边依次滴加（甲基）丙烯酸羟乙酯单体或者（甲基）丙烯酸羟丙酯单体、DMP-30、丁醇，在50℃温度下进行反应，反应时间为5h，其中丁醇为正丁醇或者异丁醇，DMP-30为2、4、6三(二甲氨基甲基)苯酚的简称，异氰酸酯为甲苯二异氰酸酯（TDI）、异佛尔酮二异氰酸酯（IPDI）、六亚甲基二异氰酸酯（HDI）和二苯基甲烷二异氰酸酯（MDI）中的任意一种或几种；
S2：制备醇酸树脂反应物，将醇酸树脂和顺丁烯二酸酐或者甲基丙烯酸缩水甘油酯，搅拌后在温度200℃下进行反应，反应时间为10h，甲基丙烯酸缩水甘油酯所占重量比为1.0%，顺丁烯二酸酐所占重量比为2.0%；
S3：制备自催化快干型改性醇酸树脂，步骤S2后进行冷却，冷却到温度125℃，加入步骤S1制备的中间体单体，反应时间2.5h后制备得到自催化快干型改性醇酸树脂，中间体单体所占重量比为7%。
本发明制备的一种自催化快干型改性醇酸树脂，具有低温干燥速率高、对产品可使用时间和防沉性影响小、残留气味低的优点，制备方法较简单，效率高。
一种自催化快干型改性醇酸树脂涂料，由以下组分组成：权利要求1-8中任意一项所述的自催化快干型改性醇酸树脂、颜填料、助剂和溶剂。助剂为分散剂、消泡剂、流平剂、催干剂和润湿剂中的任意一种或者多种，颜填料为钛白粉、色粉、滑石粉、锌粉、透明粉、重钙中的任意一种或者多种，溶剂为醋酸丁酯、醋酸乙酯、甲苯、二甲苯、丙二醇甲醚醋酸酯、碳酸二甲酯中的任意一种或者多种。
由自催化快干型改性醇酸树脂制备的自催化快干型改性醇酸树脂涂料，在常温甚至低温条件下，具有硬度上升快、干燥效率高、可使用时间长、漆膜无不友好的胺类气味等优点，能有效的提高生产效率，降低成本，节能环保。
DMP-30（2、4、6三（二甲氨基甲基）苯酚）是一种催化活性非常高的叔胺类催化剂，但由于其颜色深、气味大、影响最终产品的可使用时间的缺陷，不适用于醇酸树脂制备的聚氨酯涂料中。本发明采用DMP-30、异氰酸酯单体、（甲基）丙烯酸羟乙酯单体或者（甲基）丙烯酸羟丙酯单体、丙酮和丁醇，自制一种催化活性高的中间体单体，中间体单体含可共聚双键；本发明的醇酸树脂先通过顺丁烯二酸酐引入可共聚双键或使用甲基丙烯酸缩水甘油酯对醇酸树脂末端羧基进行改性，得到的醇酸树脂反应物具备与中间体单体反应的能力，中间体单体能够通过双键聚合与醇酸树脂反应物进行化学接枝改性，由此制备自催化快干型的改性醇酸树脂。
以上所述仅为本发明的优选实施例而已，并不用于限制本发明，尽管参照前述实施例对本发明进行了详细的说明，对于本领域技术人员来说，其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分技术特征进行等同替换。凡在本实施的精神和原则之内，所作的任何修改、等同替换、改进等，均包含在本发明的保护范围内。

Claims (9)

1.一种自催化快干型改性醇酸树脂的制备方法，其特征在于：
按重量百分比计，所采用的原料组成为：中间体单体5％～10％，醇酸树脂反应物90％～95％；其中，中间体单体包括丙酮75％、丁醇1％、异氰酸酯单体6～8％、(甲基)丙烯酸羟乙酯单体或者(甲基)丙烯酸羟丙酯单体4～6％、DMP-30为8～10％；醇酸树脂反应物包括醇酸树脂99.5～97％，顺丁烯二酸酐1.5～3％或者甲基丙烯酸缩水甘油酯0.5～1.5％；
制备方法包括以下步骤：
S1：制备中间体单体，将丙酮和异氰酸酯单体混合打底，边搅拌边依次滴加(甲基)丙烯酸羟乙酯单体或者(甲基)丙烯酸羟丙酯单体、DMP-30、丁醇，在T1温度下进行反应，反应时间为t1；
S2：制备醇酸树脂反应物，将醇酸树脂和顺丁烯二酸酐或者甲基丙烯酸缩水甘油酯，在温度T2下进行反应，反应时间为t2；
S3：制备自催化快干型改性醇酸树脂，步骤S2后进行冷却，冷却到温度T3，加入步骤S1制备的中间体单体，反应时间t3后制备得到自催化快干型改性醇酸树脂。
2.根据权利要求1所述的一种自催化快干型改性醇酸树脂的制备方法，其特征在于：所述的T1为40～60℃，t1为4～6h。
3.根据权利要求1所述的一种自催化快干型改性醇酸树脂的制备方法，其特征在于：所述的T2为180～210℃，t2为8～12h。
4.根据权利要求1所述的一种自催化快干型改性醇酸树脂的制备方法，其特征在于：所述的T3为100～150℃，t3为2～3h。
5.根据权利要求1所述的一种自催化快干型改性醇酸树脂的制备方法，其特征在于：所述的丁醇为正丁醇或者异丁醇。
6.根据权利要求1所述的一种自催化快干型改性醇酸树脂的制备方法，其特征在于：所述的异氰酸酯为甲苯二异氰酸酯(TDI)、异佛尔酮二异氰酸酯(IPDI)、六亚甲基二异氰酸酯(HDI)和二苯基甲烷二异氰酸酯(MDI)中的任意一种或几种。
7.根据权利要求1所述的一种自催化快干型改性醇酸树脂的制备方法，其特征在于：所述的DMP-30为2、4、6-三(二甲氨基甲基)苯酚。
8.一种自催化快干型改性醇酸树脂涂料，其特征在于：由以下组分组成：权利要求1-7中任意一项所述的自催化快干型改性醇酸树脂、颜填料、助剂和溶剂。
9.根据权利要求8所述的一种自催化快干型改性醇酸树脂涂料，其特征在于：所述的助剂为分散剂、消泡剂、流平剂、催干剂和润湿剂中的任意一种或者多种，所述的颜填料为色粉、滑石粉、锌粉、透明粉、重钙中的任意一种或者多种，所述的溶剂为醋酸丁酯、醋酸乙酯、甲苯、二甲苯、丙二醇甲醚醋酸酯、碳酸二甲酯中的任意一种或者多种。
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