CN109280149B - 高耐候性红色水性聚氨酯乳液的合成方法 - Google Patents

高耐候性红色水性聚氨酯乳液的合成方法 Download PDF

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CN109280149B
CN109280149B CN201810988256.6A CN201810988256A CN109280149B CN 109280149 B CN109280149 B CN 109280149B CN 201810988256 A CN201810988256 A CN 201810988256A CN 109280149 B CN109280149 B CN 109280149B
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attapulgite
polyurethane emulsion
diisocyanate
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CN109280149A (zh
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倪伶俐
毛宇
韦坤炎
刘晓丹
高晓燕
蔡鹏�
姜孝武
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Huaiyin Institute of Technology
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Abstract

本发明涉及化工领域，公开了一种高耐候性红色水性聚氨酯乳液的合成方法，使用低聚二元醇、脂肪族二异氰酸酯、富铁红色凹土、亲水扩链剂进行逐步聚合反应，合成红色凹土改性的亲水性聚氨酯预聚体，然后自乳化分散在计量水中，再加入小分子二元胺扩链剂进行扩链后，制得红色凹土改性的红色水性聚氨酯乳液。本发明的制备方法操作方便，节能环保，制备的红色水性聚氨酯乳液，固含量>30wt.%，PH在6.0‑7.0之间，其涂层产品具有耐水性好、耐候性高、色彩艳丽等优点，具有广阔的市场前景。

Description

高耐候性红色水性聚氨酯乳液的合成方法
技术领域
本发明涉及化工技术领域，特别涉及一种高耐候性红色水性聚氨酯乳液的合成方法。
背景技术
水性聚氨酯由于其突出的环保优势和优良的综合性质，已广泛应用于涂料、皮革、粘合剂、油墨、建筑等行业。但是彩色水性聚氨酯产品的获得普遍使用小分子染料。由于一般小分子染料通常是通过离子键、氢键、范德华力等被固定在水性聚氨酯上，因此与聚氨酯结合力不强，在放置、水洗、干洗、使用等过程中，易迁移至材料表面，造成不断脱落和褪色。同时由于实现水性聚氨酯树脂在水中良好分散的需要，在合成水性聚氨酯乳液时在其链段上引入了亲水性基团，导致所得水性聚氨酯产品耐水、耐磨、耐热性较差，机械强度较低等缺点，严重阻碍了其应用。
发明内容
发明目的：针对现有技术中存在的问题，本发明提供一种高耐候性红色水性聚氨酯乳液的合成方法，通过简洁的有机合成步骤将富铁红色凹土作为颜料引入到水性聚氨脂的分子链上，改善所得水性聚氨酯革产品的机械性能和耐候性等。
技术方案：本发明提供了一种按重量百分比取用原料：红色凹土5%-20%、低聚二元醇5%-25%、二异氰酸酯20%-60%、亲水扩链剂0%-10%、小分子二元胺扩链剂0%-10%、有机铋催化剂0%-1%、丙酮10%-20%、余量为水；合成步骤如下：S1：红色凹土改性的亲水性聚氨酯预聚体的制备：将二异氰酸酯和低聚二元醇于80℃下搅拌反应0.5-2小时，加入红色凹土，搅拌反应1小时后，加入亲水扩链剂，搅拌反应0.5-1小时后，加入有机铋催化剂，继续搅拌反应1.5小时，加入丙酮，继续搅拌反应1.5小时，然后加水高速搅拌自乳化分散，得红色凹土改性的亲水性聚氨酯预聚体；S2：二次扩链：在亲水性聚氨酯预聚体中加入小分子二元胺扩链剂，然后升温至50℃扩链4-8小时；S3：脱丙酮：待体系成均一乳状液后，在50℃，0.1MPa下脱丙酮，得红色凹土改性的红色水性聚氨酯乳液。
优选地，所述红色凹土为天然富铁凹凸棒石黏土矿物经沸水活化除杂干燥后的活化红色凹土。经过活化的红色凹土表面具有更多的硅羟基，有利于凹土与异氰酸酯的反应，使凹土更好的与聚氨酯复合，获得更加优异的力学性能和色牢度。
进一步地，所述活化红色凹土的具体制备步骤如下：将≥200目的天然富铁红色凹凸棒石黏土加入到沸水中，活化处理12～24h，过滤，75~85℃烘干后粉碎，得表面有大量硅羟基的活化红色凹土。
优选地，所述天然富铁红色凹凸棒石黏土与所述沸水的质量体积比为100g：500～2000mL。
优选地，所述亲水扩链剂为含羧基的小分子二元醇亲水扩链剂。
优选地，所述低聚二元醇为以下任意一种或其组合：聚己二酸新戊二醇酯二醇、聚已二酸乙二醇-丙二醇酯二醇、聚已二酸乙二醇-1.4丁二醇酯二醇中。
优选地，所述二异氰酸酯为以下任意一种或其组合：异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯、4，4’-二环己基甲烷二异氰酸酯、甲基环己基二异氰酸酯中。
有益效果：与现有技术相比，本发明具有以下优点：
1、本发明提供的富铁红色凹土改性的红色水性聚氨酯乳液颜色鲜亮，具有很好的耐候性，其制备工艺简单，绿色环保，适合工业化生产。
2、通过异氰酸酯与红色凹土表面的硅羟基的扩链反应制备富铁凹土颜料改性的水性聚氨酯，可以使红色凹土颜料在聚氨酯链段上达到微纳米级别的分散，提高了其与聚氨酯树脂的相容性，有利于提升该乳液的稳定性，便于储藏和运输。
3、采用本发明水性聚氨酯制备的产品，无溶剂残留，色牢度好、耐候性强，耐水、耐热和耐磨等性能优异。
具体实施方式
下面结合具体实施方式对本发明进行详细的介绍。
实施方式1：
本实施方式提供了一种高耐候性红色水性聚氨酯乳液的合成方法，按重量百分比取用原料：活化红色凹土5%、聚己二酸新戊二醇酯二醇20%、异佛尔酮二异氰酸酯20%、二羟甲基丙酸10%、乙二胺10%、有机铋催化剂1%、丙酮10%，余量为水；
合成步骤如下：
S1：活化红色凹土的制备：
将≥200目的天然富铁红色凹凸棒石黏土100g加入到2000mL的沸水中，活化处理12h，过滤，冷冻干燥后粉碎，得表面有大量硅羟基的活化红色凹土；
S2：红色凹土改性亲水性聚氨酯预聚体的制备：
异佛尔酮二异氰酸酯和聚己二酸新戊二醇酯二醇于80℃下搅拌反应0.5小时，加入S1制备的活化红色凹土中，搅拌反应1小时后，加入二羟甲基丙酸，搅拌反应0.5小时后，加入有机铋催化剂，继续搅拌反应1.5小时，加入丙酮，继续搅拌反应1.5小时，然后加水高速搅拌自乳化分散，得红色凹土改性的亲水性聚氨酯预聚体；
S3：二次扩链：
在亲水性聚氨酯预聚体中加入乙二胺，然后升温至50℃，扩链4小时；
S4：脱丙酮：
待体系成均一乳状液后，在50℃，0.1MPa下脱丙酮，得红色凹土改性的红色水性聚氨酯乳液。
实施方式2：
本实施方式提供了一种高耐候性红色水性聚氨酯乳液的合成方法，活化红色凹土12%、聚已二酸乙二醇-丙二醇酯二醇和聚已二酸乙二醇-1.4丁二醇酯二醇20%、异佛尔酮二异氰酸酯和甲基环己基二异氰酸酯35%、二羟甲基丁酸20%、异佛尔酮二胺15%、有机铋催化剂1%、丙酮10%，余量为水；
合成步骤如下：
S1：红色凹土的制备：
将≥200目的天然富铁红色凹凸棒石黏土100g加入到1000mL的沸水中，活化处理18h，过滤，冷冻干燥后粉碎，得表面有大量硅羟基的活化红色凹土；
S2：红色凹土改性亲水性聚氨酯预聚体的制备：
异佛尔酮二异氰酸酯和甲基环己基二异氰酸酯以及聚已二酸乙二醇-丙二醇酯二醇和聚已二酸乙二醇-1.4丁二醇酯二醇于80℃下搅拌反应1小时，加入S1制备的活化红色凹土，搅拌反应1小时后，加入二羟甲基丁酸，搅拌反应1小时后，加入有机铋催化剂，继续搅拌反应1.5小时，加入丙酮，继续搅拌反应1.5小时，然后加水高速搅拌自乳化分散，得红色凹土改性的亲水性聚氨酯预聚体；
S3：二次扩链：
在亲水性聚氨酯预聚体中加入异佛尔酮二胺，然后升温至50℃扩链8小时；
S4：脱丙酮：
待体系成均一乳状液后，在50℃，0.1MPa下脱丙酮，得红色凹土改性的红色水性聚氨酯乳液。
实施方式3：
本实施方式提供了一种高耐候性红色水性聚氨酯乳液的合成方法，按重量百分比取用原料：活化红色凹土20%、聚己二酸新戊二醇酯二醇和聚已二酸乙二醇-丙二醇酯二醇10%、异佛尔酮二异氰酸酯和4，4-二环己基甲烷二异氰酸酯和甲基环己基二异氰酸酯30%、二羟甲基丁酸10%、乙二胺和异佛尔酮二胺10%、有机铋催化剂0.5%、丙酮10%和余量为水；
合成步骤如下：
S1：活化红色凹土的制备：
将≥200目的天然富铁红色凹凸棒石黏土100g加入到500mL的沸水中，活化处理24h，过滤，冷冻干燥后粉碎，得表面有大量硅羟基的活化红色凹土；
S2：红色凹土改性亲水性聚氨酯预聚体的制备：
异佛尔酮二异氰酸酯和4，4-二环己基甲烷二异氰酸酯和甲基环己基二异氰酸酯以及聚己二酸新戊二醇酯二醇和聚已二酸乙二醇-丙二醇酯二醇于80℃下搅拌反应2小时，加入S1制备的活化红色凹土，搅拌反应1小时后，加入二羟甲基丁酸，搅拌反应1小时后，加入有机铋催化剂，继续搅拌反应1.5小时，加入丙酮，继续搅拌反应1.5小时，然后加水高速搅拌自乳化分散，得红色凹土改性的亲水性聚氨酯预聚体；
S3：二次扩链：
在亲水性聚氨酯预聚体中加入乙二胺和异佛尔酮二胺，然后升温至50℃扩链6小时；
S4：脱丙酮：
待体系成均一乳状液后，在50℃，0.1MPa下脱丙酮，得红色凹土改性的红色水性聚氨酯乳液。
分别对采用上述各实施方式中的方法制备出的红色水性聚氨酯乳液的耐候性、耐水性、耐磨性进行测试，测试方法如下：
耐候性：根据GB/T 16422.2-2014，将红色水性聚氨酯乳液制成薄膜后，在UV氙灯（500W）照射下进行老化时间测试，即耐候性性能测试。
耐水性：将红色水性聚氨酯乳液在四氟乙烯板上制成厚度约为1mm 的薄膜，完全烘干后放入25℃的去离子水中浸泡24h，考察浸泡前后薄膜总量的变化。
耐磨性：将红色水性聚氨酯乳液制成薄膜后，在TABER 摩擦测试仪上用H22砂轮测试磨破的圈数。
将实施方式1、2、3得到的红色水性聚氨酯乳液进行耐候性、耐水性以及耐磨性测试，结果如下：
Figure DEST_PATH_IMAGE002AAAAA
上述各实施方式只为说明本发明的技术构思及特点，其目的在于让熟悉此项技术的人能够了解本发明的内容并据以实施，并不能以此限制本发明的保护范围。凡根据本发明精神实质所做的等效变换或修饰，都应涵盖在本发明的保护范围之内。

Claims (7)

1.一种高耐候性红色水性聚氨酯乳液的合成方法，其特征在于：按重量百分比取用原料：红色凹土5%-20%、低聚二元醇5%-25%、二异氰酸酯20%-60%、亲水扩链剂0%-10%、小分子二元胺扩链剂0%-10%、有机铋催化剂0%-1%、丙酮10%-20%、余量为水；其中，所述亲水扩链剂、所述小分子二元胺扩链剂以及所述有机铋催化剂不为0；
合成步骤如下：
S1：红色凹土改性的亲水性聚氨酯预聚体的制备：
将二异氰酸酯和低聚二元醇于80℃下搅拌反应0.5-2小时，加入红色凹土，搅拌反应1小时后，加入亲水扩链剂，搅拌反应0.5-1小时后，加入有机铋催化剂，继续搅拌反应1.5小时，加入丙酮，继续搅拌反应1.5小时，然后加水高速搅拌自乳化分散，得红色凹土改性的亲水性聚氨酯预聚体；
S2：二次扩链：
在亲水性聚氨酯预聚体中加入小分子二元胺扩链剂，然后升温至50℃扩链4-8小时；
S3：脱丙酮：
待体系成均一乳状液后，在50℃，0.1MPa下脱丙酮，得红色凹土改性的红色水性聚氨酯乳液。
2.根据权利要求1所述的高耐候性红色水性聚氨酯乳液的合成方法，其特征在于，所述红色凹土为天然富铁凹凸棒石黏土矿物经沸水活化除杂干燥后的活化红色凹土。
3.根据权利要求2所述的高耐候性红色水性聚氨酯乳液的合成方法，其特征在于，所述活化红色凹土的具体制备步骤如下：将≥200目的天然富铁红色凹凸棒石黏土加入到沸水中，活化处理12～24h，过滤，75~85℃烘干后粉碎，得表面有大量硅羟基的活化红色凹土。
4.根据权利要求3所述的高耐候性红色水性聚氨酯乳液的合成方法，其特征在于，所述天然富铁红色凹凸棒石黏土与所述沸水的质量体积比为100g：500～2000mL。
5.根据权利要求1至4中任一项所述的高耐候性红色水性聚氨酯乳液的合成方法，其特征在于，所述亲水扩链剂为含羧基的小分子二元醇亲水扩链剂。
6.根据权利要求1至4中任一项所述的高耐候性红色水性聚氨酯乳液的合成方法，其特征在于，所述低聚二元醇为以下任意一种或其组合：
聚己二酸新戊二醇酯二醇、聚已二酸乙二醇-丙二醇酯二醇、聚已二酸乙二醇-1.4丁二醇酯二醇中。
7.根据权利要求1至4中任一项所述的高耐候性红色水性聚氨酯乳液的合成方法，其特征在于，所述二异氰酸酯为以下任意一种或其组合：
异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯、4，4’-二环己基甲烷二异氰酸酯、甲基环己基二异氰酸酯中。
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