CN110746878B - 一种高硬度抗流挂聚氨酯水性功能涂料 - Google Patents
一种高硬度抗流挂聚氨酯水性功能涂料 Download PDFInfo
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Abstract
本发明涉及一种高硬度抗流挂聚氨酯水性功能涂料,按重量份计,其组成为:APAO改性聚氨酯水性树脂100.0~150.0份、硅改性水性聚氨酯树脂20.0~40.0份、成膜助剂5.0~10.0份、纳米玻璃微珠6.0~10.0份、白色石墨烯4.0~8.0份、硅烷偶联剂3.0~6.0份、流平剂0.3~0.8份、分散剂0.5~1.0份、消泡剂0.3~0.6份、润湿剂0.2~0.6份、增稠剂0.3~1.0份、去离子水15.0~40.0份;其中,所述的APAO改性聚氨酯水性树脂由二异氰酸酯、低聚物多元醇、丙烯酸羟乙酯接枝APAO、扩链剂、二羟甲基丙酸、丙烯酸羟丙酯、乙醇、乙二胺与中和剂通过反应制得;本发明制得的一种高硬度抗流挂聚氨酯水性功能涂料,具有硬度高、耐水性好、附着力好、抗流挂性好等性能;符合市场和用户需求,具有广阔的市场前景。
Description
技术领域
本发明涉及一种改性聚氨酯树脂水性涂料,尤其涉及到高硬度、耐水性好、附着力好、抗流挂性好的一种高硬度抗流挂聚氨酯水性功能涂料,属于水性特种涂料技术领域。
背景技术
溶剂型聚氨酯涂料是一种高档的涂料品种,九十年代产量提高很快;但常规的溶剂型聚氨酯涂料含有约40%的有机溶剂,因此涂料VOC(挥发性有机物)带给大气的污染非常巨大。21世纪涂料的发展方向之一是环保型涂料,即低污染或无污染涂料,主要包括高固体份涂料、水性涂料、粉末涂料和辐射固化涂料。其中,水性涂料是最重要的一类,聚氨酯涂膜中含有大量的脲键以及氨基甲酸酯键,由于氢键等的作用,涂膜具有优良的附着力、具有耐磨、耐油、耐酸碱、耐冲击性能,并且电绝缘性好。但现有技术中也存在如下问题:干燥速度太慢。常温下很多天内达不到最终硬度,产品叠放时很容易粘连,无法满足工业化高品质、高效率涂装的要求。并且特别容易出现泛白、开裂、光泽不均匀、易流挂等施工问题。
目前国内的一些大型工程,如大型体系场馆地下室墙面、高铁、地铁、隧道、人防等,需要在立面或斜坡面进行施工。但是通用型涂料涂刷在立面或斜坡面上时会流淌,造成上部薄、下部厚。上部挂不起厚度,且涂膜表面厚薄不均。因此开发一种能够应用在立面或斜坡面上的抗流挂的聚氨酯涂料将符合市场和用户需求,具有广阔的市场前景。目前,对于用于立面或斜坡面的防流挂聚氨酯涂料具有较大的需求。然而,市场上几乎没有适合用于立面或斜坡面上的防流挂聚氨酯涂料。
目前市面上推出的适合立面施工的抗流挂聚氨酯涂料,一般都是采用气相二氧化硅、有机膨润土、聚酰胺蜡粉等作为抗流挂剂(触变剂),这些传统的触变剂添加量大,生产时需要较高的剪切力才能分散均匀,对生产设备要求高,而且这些抗流挂助剂在使用前都需要单独进行脱水干燥处理,操作非常麻烦且造成粉尘污染问题。
中国专利CN109294428A公开了一种单组分抗流挂聚氨酯防水涂料,防水涂料的原料包括聚氨酯预聚体、触变剂、填料、溶剂和助剂,聚氨酯预聚体由聚醚多元醇与第一异氰酸酯反应制成,其特征在于,触变剂由改性纳米碳酸钙、聚脲和改性纳米气相二氧化硅复合而构成,其能够兼具优异的抗流挂性能以及物理力学性能和防水性能。
中国专利CN109321122A公开了一种快干型无溶剂抗流挂聚氨酯防水涂料,其原料包括聚氨酯预聚体、增塑剂、分散剂、填料、脱水剂、催化剂、消泡剂、噁唑烷活性稀释剂,其具有优异的成膜速度、抗流挂性能,且粘度低等优点。
上述发明的抗流挂性能需外加抗流挂剂,而抗流挂剂生产时需要较高的剪切力才能分散均匀,对生产设备要求高,且易造成粉尘污染问题,在涂料中容易发生聚沉等现象,因此开发一种无需外加抗流挂剂聚氨酯涂料将符合市场和用户需求,具有广阔的市场前景。
发明内容
目前,单一性质的树脂已经不能满足涂料市场的要求,为了解决上述所述的技术问题,本发明采用具有良好附着力、耐水性以及抗流挂性能佳的APAO改性聚氨酯水性树脂为主要成膜物质,无需外加附着力促进剂与防流挂助剂,且APAO通过化学键与水性聚氨酯树脂相连,稳定性能好。
为提高涂层的硬度,本发明加入白色石墨烯氮化硼、纳米玻璃微珠与硅烷偶联剂。
本发明的目的提供一种高硬度抗流挂聚氨酯水性功能涂料。
为了解决上面所述的技术问题,本发明采取以下技术方案:本发明涉及一种高硬度抗流挂聚氨酯水性功能涂料,按重量份计,其组成为:APAO改性聚氨酯水性树脂100.0~150.0份、硅改性水性聚氨酯树脂20.0~40.0份、成膜助剂5.0~10.0份、纳米玻璃微珠6.0~10.0份、白色石墨烯4.0~8.0份、硅烷偶联剂3.0~6.0份、流平剂0.3~0.8份、分散剂0.5~1.0份、消泡剂0.3~0.6份、润湿剂0.2~0.6份、增稠剂0.3~1.0份、去离子水15.0~40.0份。
所述的成膜助剂为丙二醇丁醚、丙二醇甲醚醋酸酯和醇酯十二中的一种或几种的组合。
所述的硅改性水性聚氨酯树脂,主要由二异氰酸酯、多元醇、乙二胺、低聚物多元醇、二羟甲基丙酸、有机硅、中和剂和去离子水组成。
所述的APAO改性聚氨酯水性树脂,其特征在于:按重量份计,其组成为:二异氰酸酯25.0~60.0份、低聚物多元醇20.0~45.0份、丙烯酸羟乙酯接枝APAO 4.0~10.0份、扩链剂6.0~15.0份、二羟甲基丙酸2.5~5.0份、丙烯酸羟丙酯0.5~1.2份、二月桂酸二丁基锡0.03~0.1份、乙醇2.5~10.0份、乙二胺3.0~6.0份、中和剂2.5~10.0份、去离子水120.0~180.0份。
所述的丙烯酸羟乙酯接枝APAO采用溶剂法制得。
所述的二异氰酸酯为甲苯二异氰酸酯、异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯、苯二亚甲基二异氰酸酯、四甲基苯二亚甲基二异氰酸酯中的一种或几种的组合。
所述的低聚物多元醇为聚四氢呋喃二元醇、聚碳酸酯二元醇、聚己内酯二元醇、聚环氧乙烷多元醇、聚醚二元醇、聚环氧丙烷多元醇中的一种或几种的组合;所述的低聚物多元醇分子量为1000~3000。
所述的扩链剂为丙二醇、丁二醇、己二醇、新戊二醇、二缩二乙二醇、一缩二丙二醇、2-丁基-2-乙基-1,3-丙二醇、2,4-二乙基-1,5-戊二醇、三羟甲基丙烷中的一种或几种的组合。
所述的中和剂为三乙胺、氨水、二甲基乙醇胺中的至少一种。
本发明提供一种APAO改性聚氨酯水性树脂的制备方法,其制备工艺如下:
a)、在多功能反应器中,按配方重量份,依次加入低聚物多元醇、扩链剂、二羟甲基丙酸,升温至105~110℃,真空下脱水1.5~2.0h;
b)、降温至60~70℃,加入二异氰酸酯后通入N2,滴加配方量的二月桂酸二丁基锡,然后升温到80~82℃反应2.0~2.5h,得到亲水性聚氨酯预聚物;加入适量溶剂调节粘度,升温至84~85℃,加入丙烯酸羟丙酯,继续搅拌反应1.0h,然后升温至88~90℃,加入丙烯酸羟乙酯接枝APAO,保温反应1.5~2.0h,检测,当NCO值与设计值一致为止;
c)、继续搅拌将温度降至45℃以下,缓慢滴加中和剂,继续搅拌反应,加入计算量去离子水,高速分散均匀,然后加入乙二胺搅拌反应,最后加入乙醇,脱溶剂,过滤,即得APAO改性聚氨酯水性树脂。
所述的溶剂为丙酮等,添加的溶剂仅起到调节预聚体粘度的作用,视粘度变化酌情添加。
本发明制得的一种高硬度抗流挂聚氨酯水性功能涂料,具有涂膜机械强度高、硬度高、耐水性好、附着力好、抗流挂性好等性能;符合市场和用户需求,具有广阔的市场前景。
具体实施方式
下面结合实施例对本发明的一种高硬度抗流挂聚氨酯水性功能涂料做进一步的描述。可以理解的是,此处所描述的具体实施例仅仅用于解释相关发明,而非对该发明的限定。
实施例1
一种APAO改性聚氨酯水性树脂X,按重量份计,由以下配方组成:异佛尔酮二异氰酸酯42.0份、聚四氢呋喃二元醇32.0份、丙烯酸羟乙酯接枝APAO 7.0份、丁二醇8.0份、三羟甲基丙烷2.5份、二羟甲基丙酸3.5份、丙烯酸羟丙酯0.8份、二月桂酸二丁基锡0.06份、乙醇5.0份、乙二胺4.5份、三乙胺6.8份、去离子水150.0份。
本实施例中一种APAO改性聚氨酯水性树脂X的制备方法,包括以下步骤:
a)、在多功能反应器中,按配方重量份,依次加入聚四氢呋喃二元醇、丁二醇、三羟甲基丙烷、二羟甲基丙酸,升温至110℃,真空下脱水1.5h;
b)、降温至65℃,加入异佛尔酮二异氰酸酯后通入N2,滴加配方量的二月桂酸二丁基锡,然后升温到82℃反应2.0h,得到亲水性聚氨酯预聚物;加入适量溶剂调节粘度,升温至84~85℃,加入丙烯酸羟丙酯,继续搅拌反应1.0h,然后升温至88~90℃,加入丙烯酸羟乙酯接枝APAO,保温反应2.0h,检测,当NCO值与设计值一致为止;
c)、继续搅拌将温度降至42℃,缓慢滴加三乙胺,继续搅拌反应,加入计算量去离子水,高速分散均匀,然后加入乙二胺搅拌反应,最后加入乙醇,脱溶剂,过滤,即得APAO改性聚氨酯水性树脂X。
实施例2
一种APAO改性聚氨酯水性树脂Y,按重量份计,由以下配方组成:甲苯二异氰酸酯35.0份、聚碳酸酯二元醇35.0份、丙烯酸羟乙酯接枝APAO 6.0份、新戊二醇7.0份、一缩二丙二醇4.0份、二羟甲基丙酸4.0份、丙烯酸羟丙酯0.7份、二月桂酸二丁基锡0.06份、乙醇6.8份、乙二胺4.5份、氨水5.0份、去离子水140.0份。
本实施例中一种APAO改性聚氨酯水性树脂Y的制备方法,包括以下步骤:
a)、在多功能反应器中,按配方重量份,依次加入聚碳酸酯二元醇、新戊二醇、一缩二丙二醇、二羟甲基丙酸,升温至105℃,真空下脱水2.0h;
b)、降温至70℃,加入甲苯二异氰酸酯后通入N2,滴加配方量的二月桂酸二丁基锡,然后升温到82℃反应2.0h,得到亲水性聚氨酯预聚物;加入适量溶剂调节粘度,升温至84~85℃,加入丙烯酸羟丙酯,继续搅拌反应1.0h,然后升温至88~90℃,加入丙烯酸羟乙酯接枝APAO,保温反应2.0h,检测,当NCO值与设计值一致为止;
c)、继续搅拌将温度降至42℃,缓慢滴加氨水,继续搅拌反应,加入计算量去离子水,高速分散均匀,然后加入乙二胺搅拌反应,最后加入乙醇,脱溶剂,过滤,即得APAO改性聚氨酯水性树脂Y。
实施例3
一种高硬度抗流挂聚氨酯水性功能涂料,按重量份计,其组成为:APAO改性聚氨酯水性树脂X 120.0份、硅改性水性聚氨酯树脂30.0份、丙二醇甲醚醋酸酯7.0份、纳米玻璃微珠8.0份、白色石墨烯6.0份、硅烷偶联剂5.0份、流平剂0.5份、分散剂0.8份、消泡剂0.5份、润湿剂0.4份、增稠剂0.5份、去离子水25.0份。
实施例4
一种高硬度抗流挂聚氨酯水性功能涂料,按重量份计,其组成为:APAO改性聚氨酯水性树脂Y 100.0份、硅改性水性聚氨酯树脂35.0份、醇酯十二6.0份、纳米玻璃微珠6.0份、白色石墨烯7.0份、硅烷偶联剂4.0份、流平剂0.4份、分散剂0.7份、消泡剂0.5份、润湿剂0.4份、增稠剂0.6份、去离子水20.0份。
按照相关标准,对本发明的实施例与常规水性聚氨酯涂料(对比例)进行对比,检测的性能指标如表1所示。
其中,附着力:按照GB/T1720-1988的规定,使用划格法进行测试;
硬度:按照GB/T6739-2006色漆和清铅笔法测定漆膜硬度;
耐水性:按照GB/T1733-93的规定进行检测;
耐盐雾性:按照GB/T1771-1991的规定进行检测;
抗流挂性:按照GB/T9264-2012的规定进行检测。
表1:本发明的实施例与常规水性聚氨酯涂料性能对比
检测项目 | 实施例3 | 实施例4 | 常规水性聚氨酯涂料 |
耐水性 | 840h | 800h | 240h |
附着力 | 0级 | 0级 | 2级 |
硬度 | 2H | 2H | HB |
耐盐雾性 | 960h | 800h | 240h |
抗流挂性 | 良好 | 良好 | 差 |
由表1可以看出本发明的实施例3、实施例4样品的附着力、抗流挂性、耐盐雾性、耐水性等性能远远超过常规水性聚氨酯涂料。
尽管本发明已作了详细说明并引证了实施例,但对于本领域的普通技术人员,显然可以按照上述说明而做出的各种方案、修改和改动,都应该包括在权利要求的范围之内。
Claims (3)
1. 一种高硬度抗流挂聚氨酯水性功能涂料,其特征在于:按重量份计,其组成为:APAO改性聚氨酯水性树脂100.0~150.0份、硅改性水性聚氨酯树脂20.0~40.0份、成膜助剂5.0~10.0份、纳米玻璃微珠6.0~10.0份、白色石墨烯4.0~8.0份、硅烷偶联剂3.0~6.0份、流平剂0.3~0.8份、分散剂0.5~1.0份、消泡剂0.3~0.6份、润湿剂0.2~0.6份、增稠剂0.3~1.0份、去离子水15.0~40.0份;其中,所述的硅改性水性聚氨酯树脂主要由二异氰酸酯、多元醇、乙二胺、低聚物多元醇、二羟甲基丙酸、有机硅、中和剂和去离子水组成;所述的APAO改性聚氨酯水性树脂,按重量份计,其组成为:二异氰酸酯25.0~60.0份、低聚物多元醇20.0~45.0份、丙烯酸羟乙酯接枝APAO 4.0~10.0份、扩链剂6.0~15.0份、二羟甲基丙酸2.5~5.0份、丙烯酸羟丙酯0.5~1.2份、二月桂酸二丁基锡0.03~0.1份、乙醇2.5~10.0份、乙二胺3.0~6.0份、中和剂2.5~10.0份、去离子水120.0~180.0份;
所述的一种APAO改性聚氨酯水性树脂,其制备工艺如下:
a)、在多功能反应器中,按配方重量份,依次加入低聚物多元醇、扩链剂、二羟甲基丙酸,升温至105~110℃,真空下脱水1.5~2.0h;
b)、降温至60~70℃,加入二异氰酸酯后通入N2,滴加配方量的二月桂酸二丁基锡,然后升温到80~82℃反应2.0~2.5h,得所述的亲水性聚氨酯预聚物;加入适量溶剂调节粘度,升温至84~85℃,加入丙烯酸羟丙酯,继续搅拌反应1.0h,然后升温至88~90℃,加入丙烯酸羟乙酯接枝APAO,保温反应1.5~2.0h,检测,当NCO值与设计值一致为止;
c)、继续搅拌将温度降至45℃以下,缓慢滴加中和剂,继续搅拌反应,加入计算量去离子水,高速分散均匀,然后加入乙二胺搅拌反应,最后加入乙醇,脱溶剂,过滤,即得APAO改性聚氨酯水性树脂。
2.如权利要求1所述的一种高硬度抗流挂聚氨酯水性功能涂料,其特征在于:所述的成膜助剂为丙二醇丁醚、丙二醇甲醚醋酸酯和醇酯十二中的一种或几种的组合。
3.如权利要求1所述的一种高硬度抗流挂聚氨酯水性功能涂料,其特征在于:所述的溶剂为丙酮,添加的溶剂仅起到调节预聚体粘度的作用,视粘度变化酌情添加。
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