CN104327234A - 一种高固含阳离子水性聚氨酯树脂的制备方法 - Google Patents
一种高固含阳离子水性聚氨酯树脂的制备方法 Download PDFInfo
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Abstract
本发明公开了一种高固含阳离子型水性聚氨酯树脂的制备方法。包括以下步骤:将聚酯二元醇,小分子二元醇,多元醇,双羟基聚环氧乙烷醚加入反应器内加热、真空度脱水;通氮气保护,在60~80℃下滴加二异氰酸酯;降温至45-55℃,加入催化剂后滴加亲水单体;保持反应温度45-50℃,直至检测异氰酸酯含量达到理论终点时停止加热;用丙酮调节黏度,在40℃用醋酸中和至pH6~7,然后加去离子水和扩链剂高速搅拌分散,减压脱除丙酮即得到。用作皮革涂饰剂由于其正电荷的优势,显示出与皮革黏着力更为牢固;涂覆在木器上时,通过电荷作用固定单宁酸以阻止其迁移,使木板平整光滑,有光泽,具有良好的封底作用。
Description
技术领域
本发明属于涂料领域,具体涉及一种高固含阳离子型水性聚氨酯树脂的制备方法。
背景技术
阳离子水性聚氨酯对疏水聚酯、植物纤维具有很好的浸润性,同时阳离子水性聚氨酯对水的硬度不敏感,并且可以在酸性条件下使用,因此其在纺织、皮革、造纸以及木器漆等领域有广泛的应用前景。性能优良的聚氨酯涂饰产品,能够遮盖皮革伤残,突出时尚特色,赋予成品革美观的外表、舒适的手感和良好的机械物理性能。水性聚氨酯树脂用作木器漆具有无毒,无味,无污染等特点,而且硬度,耐水性,耐腐蚀性也非常优异。高固含量聚氨酯方便运输,可以提高运输效率降低运输成本。
目前,聚氨酯皮革涂饰剂的研究存在明显不足:原料来源窄,多元醇主要用聚醚型,聚酯型次之,聚碳酸酯极少;异氰酸酯的品种更少,只有TDI的使用报道,HDI和IPDI较少报道。扩链剂多用醇类,胺类较少使用。从制备方法及种类来看,一般为自乳化、羧酸型阴离子体系;采用季胺盐型阳离子体系较少。在木器漆应用方面,市场上木器漆大多还是油性,存在污染和对有机溶剂需求量大等问题。
现今国外WPU涂饰剂尤其是阳离子型水性聚氨酯涂饰剂在我国市场中占有很大的份额,而国内产品起步较晚,规模较小,性能还有一定差距,在市场上占很小份额。所以需要加强开发高技术、多功能、高性价比的产品。阳离子型水性聚氨酯对木材的单宁酸封闭效果优异,是木器封闭底漆用的重要成膜物质。
发明内容
本发明目的在于提供一种性能优异的高固含阳离子水性聚氨酯树脂的制备方法。本发明制备的的阳离子水性聚氨酯具有固含量高,光泽好,耐水性优,耐溶剂性好等优良特性。为达到上述目的,采用的技术方案如下:
一种高固含阳离子水性聚氨酯树脂的制备方法,包括以下步骤:
1)将聚酯二元醇,小分子二元醇,多元醇,双羟基聚环氧乙烷醚加入反应器内加热、真空度脱水;
2)撤除真空,通氮气保护,在60~80℃下滴加二异氰酸酯,1h滴完;
3)降温至45-55℃,加入催化剂后滴加亲水单体,1h滴完;
4)保持反应温度45-50℃,直至检测异氰酸酯含量达到理论终点时停止加热;所述理论终点采用二正丁基胺法计算得来;
5)用丙酮调节黏度,在40℃用醋酸中和至pH6~7,然后加去离子水和扩链剂高速搅拌分散0.5h,减压脱除丙酮即得到阳离子水性聚氨酯树脂;
其中,上述原料按照重量份数计为:
按上述方案,所述的聚酯二元醇为脂肪族聚酯二醇、聚碳酸酯二醇、聚己内酯二醇中的一种;分子量为1000-2000。
按上述方案,所述的双羟基聚环氧乙烷醚为柏斯托公司产品YmerTMN120。
按上述方案,所述的小分子二元醇为1,4-丁二醇,1,6-己二醇或1,8-辛二醇中的一种。
按上述方案,所述的多元醇为三乙醇胺。
按上述方案,所述的二异氰酸酯为甲苯二异氰酸酯或异佛尔酮二异氰酸酯中的一种。
按上述方案,所述的亲水单体为N-甲基二乙醇胺。
按上述方案,所述的扩链剂为乙二胺。
按上述方案,所述的催化剂为二月桂酸二丁基锡或辛酸亚锡。
本发明使用三乙醇胺,降低了水性单体用量,而且通过与二异氰酸酯反应,所制备的水性聚氨酯树脂具有分支结构,赋予涂层良好的柔软性和耐曲挠性。
除了常规的聚酯二元醇,本发明使用了YmerTMN120,由于其具有低黏度,对低PH值和电解质的不敏感型及出色的低温稳定性,在合成树脂时可避免使用大量溶剂。在进行水分散过程中,相反转变化时黏度适中,可制备出黏度小,固含高的阳离子水性聚氨酯。同时,使用黏度低的非离子型聚酯二元醇,可以降低亲水单体的使用量,使得制备工艺更加环保。
本发明的有益效果为:
本发明的高固含阳离子水性聚氨酯用作皮革涂饰剂在保持阴离子水性聚氨酯优点的同时,由于其正电荷的优势,显示出与皮革黏着力更为牢固,在皮革上吸收缓慢,并能在浅表面胶原纤维中形成一层薄薄的膜,起到封底的作用,阻止后期涂饰剂的过量渗透,能防止皮革因吸浆过多而失去弹性,同时能减少涂饰剂用量,涂层也具有较好的耐湿擦性能;赋予皮革柔软自然丰满的外观,又能有效地遮盖像针孔、伤痕等缺陷,提高皮革的等级。
由于阳离子水性聚氨酯的特殊优势,使之涂覆在木器上时,也具有良好的封底作用,遮盖木材表面的空隙,通过电荷作用固定单宁酸以阻止其迁移,使木板平整光滑,有光泽,且使木材具备耐水、耐有机溶剂、耐磨等特点,无浅色漆漆膜发花病态,是良好的水性木器封闭底漆。
具体实施方式
为了更好地理解本发明,下面结合实施例进一步阐明本发明的内容,但本发明的内容不仅仅局限于下面的实施例。
本发明高固含阳离子水性聚氨酯树脂的制备过程如下:
1)将聚酯二元醇,小分子二元醇,三乙醇胺,双羟基聚环氧乙烷醚加入反应器内加热、真空度脱水。聚酯二元醇为脂肪族聚酯二醇、聚碳酸酯二醇、聚己内酯二醇中的一种;分子量为1000-2000。小分子二元醇为1,4-丁二醇,1,6-己二醇或1,8-辛二醇中的一种。双羟基聚环氧乙烷醚为柏斯托公司产品YmerTMN120。
2)撤除真空,通氮气保护,在60~80℃下滴加二异氰酸酯,1h滴完;二异氰酸酯为甲苯二异氰酸酯或异佛尔酮二异氰酸酯中的一种。
3)降温至45-55℃,加入催化剂后滴加亲水单体,1h滴完;所述亲水单体为N-甲基二乙醇胺。
4)保持反应温度45-50℃,直至检测异氰酸酯含量达到理论终点时停止加热;所述理论终点采用二正丁基胺法计算得来。
5)用丙酮调节黏度,在40℃用醋酸中和至pH6~7,然后加去离子水和乙二胺高速搅拌分散0.5h,减压脱除丙酮即得到阳离子水性聚氨酯树脂。
其中,所用原料按照重量份数计为:
实施例1
1)将聚酯(Mn=1000)、YmerTMN120、1,8-辛二醇、三乙醇胺加入反应器内混合,并在0.05MPa,107℃真空脱水1h;
2)撤除真空,通入氮气保护,在60℃下开始滴加甲苯二异氰酸酯,1h滴完并保温1h;
3)加入二月桂酸二丁基锡,降温至50℃,开始滴加N-甲基二乙醇胺,1h滴加完后保温反应,测定NCO的含量,直至异氰酸酯含量达到理论终点4.7%;
4)在40℃时用冰醋酸中和至pH为6~7;
5)在40℃时加去离子水高速搅拌分散,加乙二胺扩链30min,减压脱除丙酮即得淡黄色较清透的阳离子水性聚氨酯树脂。
其中所用各种原料的原料为(按重量份数计)
经检测:本实验所得产品为淡黄色较清透的液体,固含为41.1%,PH值为7~8。
将本实例合成所得产品涂于基材表面,晾干后进行检测。硬度为0.63;光泽度(60度角)90;涂膜外观平整光滑;耐水性(24h)无变化;耐醇性(50%乙醇溶液)1h无变化。由测量结果可知,由本实验所得的阳离子水性聚氨酯固含量高,光泽度好,硬度高,耐水,耐醇性能优异。若加入0.5%的消泡剂(BYK-028,BYK公司)、0.7%的润湿剂(BL-240,罗地亚公司)、1.2%的增稠剂(RM2020,罗门哈斯公司)用作水性木器漆封闭底漆,可使木器外观光亮,耐磨,耐刮擦性好,而且有较强的防水性及良好的耐化学品性,尤其克服了白漆发花现象,是最新一代水性木器封闭漆。
实施例2
1)将聚碳酸酯二醇(Mn=2000)、YmerTMN120、1,4-丁二醇、三乙醇胺加入反应器内混合,并在0.05MPa,107℃真空脱水1h;
2)撤除真空,通入氮气保护,在60℃下开始滴加甲苯二异氰酸酯,1h滴完并保温1h;
3)加入二月桂酸二丁基锡,降温至50℃,开始滴加N-甲基二乙醇胺,1h滴加完后保温反应,测定NCO的含量,直至异氰酸酯含量达到理论终点6.57%;
4)在40℃时用冰醋酸中和至PH为6~7;
5)在40℃时加去离子水高速搅拌分散,加乙二胺扩链30min,减压脱除丙酮即得淡黄色清透的高含阳离子水性聚氨酯树脂。
其中所用各种原料的原料为(按重量份数计)
经检测:本实验所得产品为白色淡黄色透明液体,固含为41.8%,PH值为7~8。
将本实例合成所得产品涂于基材表面,晾干后进行检测。硬度为0.65;光泽度(60度角)90;涂膜外观平整光滑;耐水性(24h)无变化;耐醇性(50%乙醇溶液)1h无变化。由测量结果可知,由本实验所得的阳离子水性聚氨酯固含量高,光泽度好,硬度高,耐水,耐醇性能优异。若加入0.5%的消泡剂(BYK-028,BYK公司)、0.7%的润湿剂(BL-240,罗地亚公司)、1.2%的增稠剂(RM2020,罗门哈斯公司)用作水性木器漆封闭底漆,可使木器外观光亮,耐磨,耐刮擦性好,而且有较强的防水性及良好的耐化学品性,尤其克服了白漆发花现象,是最新一代水性木器封闭漆。
实施例3
1)将聚酯(Mn=1000)、YmerTMN120、1,4-丁二醇、三乙醇胺加入反应器内混合,并在0.05MPa,107℃真空脱水1h;
2)撤除真空,通入氮气保护,在65℃下开始滴加甲苯二异氰酸酯,1h滴完并保温1h;
3)加入二月桂酸二丁基锡,降温至50℃,开始滴加N-甲基二乙醇胺,1h滴加完后保温反应,测定NCO的含量,直至异氰酸酯含量达到理论终点6.492%;
4)在40℃时用醋酸中和至PH为6~7;
5)在40℃时加去离子水高速搅拌分散,加乙二胺扩链30min,减压脱除丙酮即得淡黄色较清透的阳离子水性聚氨酯树脂。
其中所用各种原料的原料为(按重量份数计)
经检测:本实验所得产品为淡黄色较清透的液体,固含为42.8%,PH值为7~8。
将本实例合成所得产品涂于基材表面,晾干后进行检测。硬度为0.63;光泽度(60度角)90;涂膜外观平整光滑;耐水性(24h)无变化;耐醇性(50%乙醇溶液)1h无变化。由测量结果可知,由本实验所得的阳离子水性聚氨酯固含量高,光泽度好,硬度高,耐水,耐醇性能优异。若加入0.5%的消泡剂(BYK-028,BYK公司)、0.7%的润湿剂(BL-240,罗地亚公司)、1.2%的增稠剂(RM2020,罗门哈斯公司)用作水性木器漆封闭底漆,可使木器外观光亮,耐磨,耐刮擦性好,而且有较强的防水性及良好的耐化学品性,尤其克服了白漆发花现象,是最新一代水性木器封闭漆。
实施例4
1)将聚己内酯二醇(Mn=1000)、YmerTMN120、1,8-辛二醇、三乙醇胺加入反应器内混合,并在0.05MPa,107℃真空脱水1h;
2)撤除真空,通入氮气保护,在80℃下开始滴加异佛尔酮二异氰酸酯,1h滴完并保温1h;
3)加入辛酸亚锡,降温至50℃,开始滴加N-甲基二乙醇胺,1h滴加完后保温反应,测定NCO的含量,直至异氰酸酯含量达到理论终点3.54%;
4)在40℃时用醋酸中和至PH为6~7;
5)在40℃时加去离子水高速搅拌分散,加乙二胺扩链30min,减压脱除丙酮即得白色不透明的阳离子水性聚氨酯树脂。
其中所用各种原料的原料为(按重量份数计)
经检测:本实验所得产品为白色不透明泛蓝光液体,固含为42.5%,PH值为7~8。
对本实例合成的产品进行检测。断裂伸长率33.2%;拉伸强度553MPa;涂膜外观平整光滑;耐水性24h无变化;耐醇性(50%乙醇溶液)1h无变化。由检测结果可知,本实验所得阳离子水性聚氨酯具有固含量高,光泽好,柔韧性强,耐水,耐溶剂性好,有较强的耐曲挠性,可用作皮革涂饰剂,使皮革具备良好的机械物理性能及良好的耐化学性能。
实施例5
1)将聚酯(Mn=1000)、YmerTMN120、丁二醇、三乙醇胺加入反应器内混合,并在0.05MPa,107℃真空脱水1h;
2)撤除真空,通入氮气保护,在65℃下开始滴加异佛尔酮二异氰酸酯,1h滴完并保温1h;
3)加入辛酸亚锡,降温至50℃,开始滴加N-甲基二乙醇胺,1h滴加完后保温反应,测定NCO的含量,直至异氰酸酯含量达到理论终点3.044%;
4)在40℃时用盐酸中和至PH为6~7;
5)在40℃时加去离子水高速搅拌分散,加乙二胺扩链30min,减压脱除丙酮即得白色不透明的阳离子水性聚氨酯树脂。
其中所用各种原料的原料为(按重量份数计)
经检测:经检测:本实验所得产品为白色不透明的液体,固含为43.8%,PH值为7~8。
对本实例合成的产品进行检测。断裂伸长率34.2%;拉伸强度545MPa;涂膜外观平整光滑;耐水性24h无变化;耐醇性(50%乙醇溶液)1h无变化。由检测结果可知,本实验所得阳离子水性聚氨酯具有固含量高,光泽好,柔韧性强,耐水,耐溶剂性好,有较强的耐曲挠性,可用作皮革涂饰剂,使皮革具备良好的机械物理性能及良好的耐化学性能。
实施例6
1)将聚碳酸酯二醇(Mn=2000)、YmerTMN120、1,6-己二醇、三乙醇胺加入反应器内混合,并在0.05MPa,107℃真空脱水1h;
2)撤除真空,通入氮气保护,在65℃下开始滴加异佛尔酮二异氰酸酯,1h滴完并保温1h;
3)加入辛酸亚锡,降温至50℃,开始滴加亲水单体N-甲基二乙醇胺,1h滴加完后保温反应,测定NCO的含量,直至异氰酸酯含量达到理论终点3.4%;
4)在20℃时用盐酸中和至PH为6~7;
5)在25℃时加去离子水高速搅拌分散,加乙二胺扩链30min,减压脱除丙酮即得白色不透明的阳离子水性聚氨酯树脂。
其中所用各种原料的原料为(按重量份数计)
经检测:本实验所得产品为白色不透明的液体,固含为43%,PH值为7~8。
对本实例合成的产品进行检测。断裂伸长率30.5%;拉伸强度558MPa;涂膜外观平整光滑;耐水性24h无变化;耐醇性(50%乙醇溶液)1h无变化。由检测结果可知,本实验所得阳离子水性聚氨酯具有固含量高,光泽好,柔韧性强,耐水,耐溶剂性好,有较强的耐曲挠性,可用作皮革涂饰剂,使皮革具备良好的机械物理性能及良好的耐化学性能。
Claims (9)
1.一种高固含阳离子水性聚氨酯树脂的制备方法,其特征在于包括以下步骤:
1)将聚酯二元醇,小分子二元醇,多元醇,双羟基聚环氧乙烷醚加入反应器内加热、真空度脱水;
2)撤除真空,通氮气保护,在60~80℃下滴加二异氰酸酯,1h滴完;
3)降温至45-55℃,加入催化剂后滴加亲水单体,1h滴完;
4)保持反应温度45-50℃,直至检测异氰酸酯含量达到理论终点时停止加热;所述理论终点采用二正丁基胺法计算得来;
5)用丙酮调节黏度,在40℃用醋酸中和至pH6~7,然后加去离子水和扩链剂高速搅拌分散0.5h,减压脱除丙酮即得到阳离子水性聚氨酯树脂;
其中,上述原料按照重量份数计为:
2.如权利要求1所述的高固含阳离子水性聚氨酯树脂的制备方法,其特征在于所述的聚酯二元醇为脂肪族聚酯二醇、聚碳酸酯二醇、聚己内酯二醇中的一种;分子量为1000-2000。
3.如权利要求1所述的高固含阳离子水性聚氨酯树脂的制备方法,其特征在于所述的双羟基聚环氧乙烷醚为柏斯托公司产品YmerTMN120。
4.如权利要求1所述的高固含阳离子水性聚氨酯树脂的制备方法,其特征在于所述的小分子二元醇为1,4-丁二醇,1,6-己二醇或1,8-辛二醇中的一种。
5.如权利要求1所述的高固含阳离子水性聚氨酯树脂的制备方法,其特征在于所述的多元醇为三乙醇胺。
6.如权利要求1所述的高固含阳离子水性聚氨酯树脂的制备方法,其特征在于所述的二异氰酸酯为甲苯二异氰酸酯或异佛尔酮二异氰酸酯中的一种。
7.如权利要求1所述的高固含阳离子水性聚氨酯树脂的制备方法,其特征在于所述的亲水单体为N-甲基二乙醇胺。
8.如权利要求1所述的高固含阳离子水性聚氨酯树脂的制备方法,其特征在于所述的扩链剂为乙二胺。
9.如权利要求1所述的高固含阳离子水性聚氨酯树脂的制备方法,其特征在于所述的催化剂为二月桂酸二丁基锡或辛酸亚锡。
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CN105237727A (zh) * | 2015-09-17 | 2016-01-13 | 合肥思敬齐化工材料有限责任公司 | 一种高耐水性水溶性聚氨酯树脂及其制备方法 |
CN108559055A (zh) * | 2018-04-04 | 2018-09-21 | 吉林乾仁新材料有限公司 | 自组装自乳化粒径可控的阳离子水性聚氨酯型上浆剂/浸润剂/成膜剂的制备方法 |
CN109852129A (zh) * | 2018-12-29 | 2019-06-07 | 烟台大学 | 一种抑制单宁扩散的水性涂料助剂及其制备方法 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101440152A (zh) * | 2008-12-19 | 2009-05-27 | 天津科技大学 | 阳离子水性聚氨酯乳液的制备方法及其应用 |
CN102093533A (zh) * | 2010-12-31 | 2011-06-15 | 王奇 | 一种阳离子型水性聚氨酯及其制备方法 |
-
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Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101440152A (zh) * | 2008-12-19 | 2009-05-27 | 天津科技大学 | 阳离子水性聚氨酯乳液的制备方法及其应用 |
CN102093533A (zh) * | 2010-12-31 | 2011-06-15 | 王奇 | 一种阳离子型水性聚氨酯及其制备方法 |
Non-Patent Citations (2)
Title |
---|
丁彩凤 等: ""阳离子型水性聚氨酯乳液的合成"", 《过程工程学报》 * |
钟倪 等: ""阳离子水性聚氨酯的合成与性能"", 《过程工程学报》 * |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
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CN105237727A (zh) * | 2015-09-17 | 2016-01-13 | 合肥思敬齐化工材料有限责任公司 | 一种高耐水性水溶性聚氨酯树脂及其制备方法 |
CN108559055A (zh) * | 2018-04-04 | 2018-09-21 | 吉林乾仁新材料有限公司 | 自组装自乳化粒径可控的阳离子水性聚氨酯型上浆剂/浸润剂/成膜剂的制备方法 |
CN109852129A (zh) * | 2018-12-29 | 2019-06-07 | 烟台大学 | 一种抑制单宁扩散的水性涂料助剂及其制备方法 |
CN109852129B (zh) * | 2018-12-29 | 2021-07-20 | 烟台大学 | 一种抑制单宁扩散的水性涂料助剂及其制备方法 |
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