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CN107936814A - 一种poss 改性的高硬度聚氨酯净味木器漆 - Google Patents

一种poss 改性的高硬度聚氨酯净味木器漆 Download PDF

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CN107936814A
CN107936814A CN201711064341.5A CN201711064341A CN107936814A CN 107936814 A CN107936814 A CN 107936814A CN 201711064341 A CN201711064341 A CN 201711064341A CN 107936814 A CN107936814 A CN 107936814A
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谢义鹏
许钧强
康伦国
姚东生
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Shaoguan Union Chemical Co Ltd
Union Foshan Chemical Co Ltd
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Abstract

本发明涉及一种POSS改性的高硬度聚氨酯净味木器漆，由A、B两组分构成，A、B组分的重量配比为1.4～1.8:1；A组分为含羟基净味树脂、各种助剂和溶剂组成；B组分为POSS改性的低游离单体聚氨酯固化剂；本发明还提供POSS改性的低游离单体聚氨酯固化剂的制备方法。本发明制得的一种POSS改性的高硬度聚氨酯净味木器漆，涂膜具有优异的附着力、丰满度、高硬度、耐水性、柔韧性、透明性、耐磨性、耐热性、耐污染性和阻燃性；不含芳酮、不含重金属，涂装成膜48h后净味效果，为一种环保型的聚氨酯净味木器漆。

Description

一种POSS改性的高硬度聚氨酯净味木器漆
技术领域
本发明涉及一种聚氨酯木器漆，尤其涉及一种POSS改性的高硬度聚氨酯净味木器漆，属于木器涂料技术领域。
背景技术
随着人们物质文化生活水平的提高，消费者对家具的涂装效果要求亦越来越高，从而带动了国内木器涂料的快速增长。在家具涂料市场上美式涂装家具占据较大的市场份额，国内家具行业大多都用色精(一种金属络合染料，此类染料存在诸如重金属严重超标、含有致病物质、耐温性、耐晒性、耐迁移性差，俗称格丽斯)进行木纹擦色和罩光着色料，擦色用的树脂大多为普通的醇酸树脂和亚麻油，涂装后很长时间内家具仍有异味；当今庞大的木器漆市场对油漆产品的要求越来越高，龙其是木器聚氨酯(PU)漆综合性能优异，消费者使用广泛，但产品存在诸多不足之处，如发白、起泡、脱层、不抗划伤、鬼影、手印不易消失等。
中国专利CN104099000A公开了一种无苯净味型抗划伤PU哑光清漆，由甲组分树脂漆和乙组分固化剂组成，甲乙组分的重量配比为1:0.5；甲组分树脂漆由不含植物油(脂肪酸)的无苯净味抗划伤醇酸树脂、醛酮树脂、消光粉、助剂和溶剂组成；乙组分由固化剂和溶剂组成。该发明制得的无苯净味型抗划伤PU哑光清漆不含芳烃、不含酮、不含重金属，不含植物油(脂肪酸)，涂装成膜48小时后不残留不舒适性气味，为一种环保型净味PU木器漆。
但是现有聚氨酯木器漆存在树脂与固化剂之间交联密度差、疏水性差、耐热性差、阻燃性能低等缺陷。
发明内容
本发明旨在提供一种POSS改性的高硬度聚氨酯净味木器漆。
POSS又称笼型聚倍半硅氧烷，是由Si-O交替连接的硅氧骨架组成的无机内核，其形状如同一个“笼子”，属于纳米化合物。POSS基团的多样性、高活性以及较好的聚合物相容性使之既可以通过物理共混又可以通过化学共聚的方法将其引入到聚合物材料中。
本发明采用固化剂为POSS改性的低游离单体聚氨酯固化剂，与含羟基的树脂发生高度交联固化，漆膜具有高丰满度、高耐磨性、耐热性、耐水性和耐污染性。
为克服现有技术的缺点和不足，本发明采取以下技术方案，本发明所述的一种POSS改性的高硬度聚氨酯净味木器漆，由A、B两组分构成，A、B组分的重量配比为1.4～1.8:1；所述的A组分，按重量百分比计，其组成为：含羟基净味树脂50.0～85.0％、润湿分散剂0.2～2.0％、流平剂0.1～1.0％、流变助剂0.3～5.0％、消泡剂0.1～0.5％、功能助剂0～6.0％、溶剂12.0～40.0％；所述的B组分为POSS改性的低游离单体聚氨酯固化剂。
所述的POSS改性的低游离单体聚氨酯固化剂，以笼型聚倍半硅氧烷为中心，含有16个异氰酸酯基，其分子结构式如下所示：
所述的POSS改性的低游离单体聚氨酯固化剂，其制备步骤如下：
a)、异氰酸酯三聚体合成：在N2保护下，向反应釜中加入100.0份异氰酸酯单体、0.05～0.1份催化剂、30.0～60.0份溶剂，开启搅拌将物料搅拌均匀，加热至50～80℃反应2～4h后，逐滴滴加5.0份含有催化剂、促进剂和溶剂的混合液，在0.5h滴加完毕，然后保持在50～80℃继续反应，每隔0.5h检测一次NCO值，当检测的NCO值在10％～7％后立即加入占异氰酸酯单体质量0.1～0.5％的阻聚剂并降温至20℃，得所述的异氰酸酯三聚体；
b)、POSS改性的低游离单体聚氨酯固化剂的合成：在常温下，向所述的异氰酸酯三聚体中，逐滴滴加15.0～40.0份八氨基苯基POSS和30.0份溶剂的混合液，在0.5～1h滴加完毕，继续反应2～3h，得所述的POSS改性的低游离单体聚氨酯固化剂。
其中，所述的异氰酸酯单体为TDI、MDI、NDI、TODI、HDI、TMDI、XDI、IPDI、HMDI、HTDI中的至少一种。
所述的含有催化剂、促进剂和溶剂的混合液，其组成为：催化剂2.0％～10.0％、促进剂2.0％～10.0％、溶剂80.0％～96.0％。
所述的催化剂为二月桂酸二丁基锡、醋酸锂、三正丁基磷、辛酸亚锡、环烷酸锡、环烷酸铅、环烷酸钴、马来酸二丁基锡、二乙酸二丁基锡、三乙胺、K-1000、苯甲基缩水甘油醚中的至少一种。
所述的促进剂为N,N-二甲基对甲苯胺、N-甲基吡咯、三乙醇胺、N,N二甲基对甲苯磺酰氯中的至少一种。
所述的含羟基净味树脂为净味醇酸树脂、净味聚酯树脂或羟基丙烯酸树脂。
所述的润湿分散剂为含胺基衍生物聚羧酸高分子聚合物、含颜料亲和基团的高分子聚醚化合物、聚羧酸酰胺盐、聚羟酸有机胺电中性盐中的至少一种。
所述的流平剂为钛酸酯改性有机硅流平剂、钛酸酯改性聚丙烯酸酯流平剂、有机硅改性丙烯酸流平剂、氟改性丙烯酸流平剂、硅氧聚合物流平剂中的至少一种。
所述的流变助剂为纳米级气相法白炭黑、改性脲聚合物、聚酰胺蜡中的至少一种。
所述的溶剂为醋酸乙酯、醋酸丁酯、乙酸仲丁酯、120白油、D40脱芳溶剂、二乙二醇丁醚、丙二醇甲醚、丙二醇丁醚、二丙二醇丁醚、3-甲氧基丙酸甲酯中的至少一种。
所述的功能助剂为消光剂、增硬剂、抗划伤剂、抗粘连剂、耐磨剂、紫外线吸收剂。
所述的消泡剂为改性硅氧烷消泡剂、聚丙烯酸酯消泡剂的至少一种。
相对于本领域的其它技术，本发明所述的一种POSS改性的高硬度聚氨酯净味木器漆具有以下优点：(1)由于采用的固化剂单个分子含有16个异氰酸酯基，与树脂分子中的-OH固化时交联密度高，涂膜给获得高附着力、高丰满度、高硬度、高耐水性；(2)因固化剂中含有POSS基团，使涂膜能获得优异的疏水性、柔韧性、透明性、耐磨性、耐热性、耐污染性和阻燃性。(2)采用了净味树脂和低游离单体聚氨酯固化剂，不含芳酮、不含重金属，涂装成膜48h后净味效果，为一种环保型的聚氨酯净味木器漆。
具体实施方式
下面结合实施例对本发明的一种POSS改性的高硬度聚氨酯净味木器漆做进一步的描述。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POSS改性的低游离单体聚氨酯固化剂A，其制备步骤如下：
a)、异氰酸酯三聚体合成：在N2保护下，向反应釜中加入100.0份IPDI单体、0.1份三正丁基磷、30.0份乙酸乙酯，开启搅拌将物料搅拌均匀，加热至80℃反应2h后，逐滴滴加5.0份含有2％三正丁基磷和2％N-甲基吡咯的乙酸乙酯溶液，在0.5h滴加完毕，然后保持在80℃继续反应，每隔0.5h检测一次NCO值，当检测的NCO值在9.0±0.5％后立即加入占异氰酸酯单体质量0.5％的阻聚剂并降温至20℃，得所述的异氰酸酯三聚体；
b)、POSS改性的低游离单体聚氨酯固化剂的合成：在常温下，向所述的异氰酸酯三聚体中，逐滴滴加19.2份八氨基苯基POSS与30.0份乙酸乙酯溶液，在1h滴加完毕，继续反应2h，得所述的POSS改性的低游离单体聚氨酯固化剂A。
实施例2
一种POSS改性的低游离单体聚氨酯固化剂B，其制备步骤如下：
a)、异氰酸酯三聚体合成：在N2保护下，向反应釜中加入100.0份HDI单体、0.1份K-1000、60.0份乙酸异丙酯，开启搅拌将物料搅拌均匀，加热至80℃反应4h后，逐滴滴加5.0份含有10％K-1000和6％三乙醇胺的乙酸异丙酯溶液，在0.5h滴加完毕，然后保持在80℃继续反应，每隔0.5h检测一次NCO值，当检测的NCO值在8.0±0.5％后立即加入占异氰酸酯单体质量0.3％的阻聚剂并降温至20℃，得所述的异氰酸酯三聚体；
b)、POSS改性的低游离单体聚氨酯固化剂的合成：在常温下，向所述的异氰酸酯三聚体中，逐滴滴加21.6份八氨基苯基POSS与30.0份乙酸异丙酯溶液，在1h滴加完毕，继续反应3h，得所述的POSS改性的低游离单体聚氨酯固化剂B。
实施例3
一种POSS改性的高硬度聚氨酯净味木器漆，由A、B两组分构成，A、B组分重量比为1.8:1；A组分组成为：饱和聚酯树脂75.0份、胺基衍生物聚羧酸聚合物分散剂0.5份、有机硅改性丙烯酸流平剂0.3份、纳米级气相法白炭黑3.0份、醋酸乙酯21.0份、改性硅氧烷消泡剂0.2份；所述B组分为：55.0份POSS改性的低游离单体聚氨酯固化剂A。
实施例4
一种POSS改性的高硬度聚氨酯净味木器漆，由A、B两组分构成，A、B组分重量比为1.67:1；A组分组成为：净味醇酸树脂70.0份、高分子润湿分散剂1.0份、氟改性丙烯酸流平剂型0.4份、改性脲聚合物型流变助剂3.0份、醋酸乙酯18.0份、丙二醇丁醚5.0份、消光剂2.5份、改性硅氧烷消泡剂0.1份；所述B组分为60.0份POSS改性的低游离单体聚氨酯固化剂B。
实施例5
一种POSS改性的高硬度聚氨酯净味木器漆，由A、B两组分构成，A、B组分重量比为1.75:1；A组分组成为：羟基丙烯酸树脂80.0份、高分子润湿分散剂0.5份、硅氧聚合物流平剂0.3份、聚酰胺蜡1.5份、乙酸丁酯14.0份、3-甲氧基丙酸甲酯3.6份、聚丙烯酸酯消泡剂0.1份；所述B组分为：57.0份POSS改性的低游离单体聚氨酯固化剂B。
将实施例3、4、5中的双组分聚氨酯木器涂料和市面上的净味双组分聚氨酯木器涂料(对比例)，按施工要求喷涂于木器表面，干燥24h后按照相关标准进行检测，其测试数据如表1所示：
表1聚氨酯木器涂料性能技术指标
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 (9)

1.一种POSS改性的高硬度聚氨酯净味木器漆，其特征在于：所述的POSS改性的高硬度聚氨酯净味木器漆，由A、B两组分构成，A、B组分的重量配比为1.4～1.8:1；所述的A组分，按重量百分比计，其组成为：含羟基净味树脂50.0～85.0％、润湿分散剂0.2～2.0％、流平剂0.1～1.0％、流变助剂0.3～5.0％、消泡剂0.1～0.5％、功能助剂0～6.0％、溶剂12.0～40.0％；所述的B组分为POSS改性的低游离单体聚氨酯固化剂；
其中，所述的POSS改性的低游离单体聚氨酯固化剂，以笼型聚倍半硅氧烷为中心，含有16个异氰酸酯基，其分子结构式如下所示：
其制备步骤如下：
a)、异氰酸酯三聚体合成：在N2保护下，向反应釜中加入100.0份异氰酸酯单体、0.05～0.1份催化剂、30.0～60.0份溶剂，开启搅拌将物料搅拌均匀，加热至50～80℃反应2～4h后，逐滴滴加5.0份含有催化剂、促进剂和溶剂的混合液，在0.5h滴加完毕，然后保持在50～80℃继续反应，每隔0.5h检测一次NCO值，当检测的NCO值在10％～7％后立即加入占异氰酸酯单体质量0.1～0.5％的阻聚剂并降温至20℃，得所述的异氰酸酯三聚体；
b)、POSS改性的低游离单体聚氨酯固化剂的合成：在常温下，向所述的异氰酸酯三聚体中，逐滴滴加15.0～40.0份八氨基苯基POSS和30.0份溶剂的混合液，在0.5～1h滴加完毕，继续反应2～3h，得所述的POSS改性的低游离单体聚氨酯固化剂；
所述的POSS改性的低游离单体聚氨酯固化剂中的游离单体含量＜0.5％。
2.根据权利要求1所述的POSS改性的高硬度聚氨酯净味木器漆，其特征在于：所述的含羟基净味树脂为净味醇酸树脂、净味聚酯树脂或羟基丙烯酸树脂。
3.根据权利要求1所述的POSS改性的高硬度聚氨酯净味木器漆，其特征在于：所述的异氰酸酯单体为TDI、MDI、NDI、TODI、HDI、TMDI、XDI、IPDI、HMDI或HTDI中的至少一种。
4.根据权利要求1所述的POSS改性的高硬度聚氨酯净味木器漆，其特征在于：所述的含有催化剂、促进剂和溶剂的混合液，按质量百分比计，其组成为：催化剂2.0％～10.0％、促进剂2.0％～10.0％、溶剂80.0％～96.0％。
5.根据权利要求1所述的POSS改性的高硬度聚氨酯净味木器漆，其特征在于：所述的催化剂为二月桂酸二丁基锡、醋酸锂、三正丁基磷、辛酸亚锡、环烷酸锡、环烷酸铅、环烷酸钴、马来酸二丁基锡、二乙酸二丁基锡、三乙胺、K-1000或苯甲基缩水甘油醚中的至少一种。
6.根据权利要求1所述的POSS改性的高硬度聚氨酯净味木器漆，其特征在于：所述的促进剂为N,N-二甲基对甲苯胺、N-甲基吡咯、三乙醇胺或N,N二甲基对甲苯磺酰氯中的至少一种。
7.根据权利要求1所述的POSS改性的高硬度聚氨酯净味木器漆，其特征在于：所述的润湿分散剂为含胺基衍生物聚羧酸高分子聚合物、含颜料亲和基团的高分子聚醚化合物、聚羧酸酰胺盐或聚羟酸有机胺电中性盐中的至少一种；所述的流平剂为钛酸酯改性有机硅流平剂、钛酸酯改性聚丙烯酸酯流平剂、有机硅改性丙烯酸流平剂、氟改性丙烯酸流平剂或硅氧聚合物流平剂中的至少一种；所述的流变助剂为纳米级气相法白炭黑、改性脲聚合物或聚酰胺蜡中的至少一种；所述的消泡剂为改性硅氧烷消泡剂或聚丙烯酸酯消泡剂的至少一种。
8.根据权利要求1所述的POSS改性的高硬度聚氨酯净味木器漆，其特征在于：所述的功能助剂为消光剂、增硬剂、抗划伤剂、抗粘连剂、耐磨剂或紫外线吸收剂。
9.根据权利要求1或4所述的POSS改性的高硬度聚氨酯净味木器漆，其特征在于：所述的溶剂为醋酸乙酯、醋酸丁酯、乙酸仲丁酯、120白油、D40脱芳溶剂、二乙二醇丁醚、丙二醇甲醚、丙二醇丁醚、二丙二醇丁醚、3-甲氧基丙酸甲酯中的至少一种。
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