CN105482677A - 一种防污性聚氨酯涂料 - Google Patents

一种防污性聚氨酯涂料 Download PDF

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CN105482677A
CN105482677A CN201511016670.3A CN201511016670A CN105482677A CN 105482677 A CN105482677 A CN 105482677A CN 201511016670 A CN201511016670 A CN 201511016670A CN 105482677 A CN105482677 A CN 105482677A
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许戈文
熊潜生
霍俊丽
戴震
何纪慧
杨立春
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ANHUI ANDA-HUATAI NEW MATERIAL Co Ltd
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Abstract

本发明公开了一种防污性聚氨酯涂料，其原料包括：全氟烷基乙基醇、聚四氢呋喃醚二醇、聚碳酸酯二醇、二苯基甲烷二异氰酸酯、异佛尔酮二异氰酸酯、1，4-丁二醇、辛酸亚锡、油酸亚锡、氨基硅烷、纳米二氧化钛、纳米氧化锌、纳米碳酸钙、纳米氧化铁、滑石粉、改性抗污剂、分散剂、乙基纤维素、流平剂、丙二醇、成膜助剂、去离子水。本发明提出的防污性聚氨酯涂料，其与底材的附着力强，抗污性能优异，耐热性、耐候性和耐水性好。

Description

一种防污性聚氨酯涂料
技术领域
本发明涉及聚氨酯涂料技术领域，尤其涉及一种防污性聚氨酯涂料。
背景技术
聚氨酯全称为聚氨基甲酸酯，是主链上含有重复氨基甲酸酯基团的大分子化合物的统称，它是由有机二异氰酸酯或多异氰酸酯与二羟基或多羟基化合物加聚而成的，具有许多优良特性，如高弹性、耐磨性、耐低温性、耐溶剂性以及良好的电绝缘性等，因而用途非常广。聚氨酯涂料是目前较常见的一类涂料，其品种很多，主要应用方向有木器涂料、汽车修补涂料、防腐涂料、地坪漆、电子涂料、特种涂料、聚氨酯防水涂料等。虽然聚氨酯涂料具有某些优异的综合性能，但是其仍存在防污性、耐候性和耐水性不是很理想的缺点，限制了其使用范围。
发明内容
基于背景技术存在的技术问题，本发明提出了一种防污性聚氨酯涂料，其与底材的附着力强，抗污性能优异，耐热性、耐候性和耐水性好。
本发明提出的一种防污性聚氨酯涂料，其原料按重量份包括以下组分：全氟烷基乙基醇100-150份、聚四氢呋喃醚二醇130-200份、聚碳酸酯二醇50-85份、二苯基甲烷二异氰酸酯200-350份、异佛尔酮二异氰酸酯50-70份、1，4-丁二醇3-5份、辛酸亚锡0.5-2份、油酸亚锡0.5-1.3份、氨基硅烷5-15份、纳米二氧化钛2-5份、纳米氧化锌2-5份、纳米碳酸钙5-12份、纳米氧化铁3-15份、滑石粉2-10份、改性抗污剂6-20份、分散剂0.5-2份、乙基纤维素0.5-2份、流平剂0.5-2份、丙二醇3-15份、成膜助剂5-15份、去离子水20-40份。
优选地，其原料中，全氟烷基乙基醇、聚四氢呋喃醚二醇、聚碳酸酯二醇、二苯基甲烷二异氰酸酯、异佛尔酮二异氰酸酯的重量比为120-140：160-185：60-75：260-320：60-68。
优选地，其原料按重量份包括以下组分：全氟烷基乙基醇132-138份、聚四氢呋喃醚二醇168-173份、聚碳酸酯二醇66-70份、二苯基甲烷二异氰酸酯280-300份、异佛尔酮二异氰酸酯65-67份、1，4-丁二醇3.9-4.3份、辛酸亚锡1-1.6份、油酸亚锡0.7-1.2份、氨基硅烷8-11份、纳米二氧化钛3.2-4份、纳米氧化锌3.6-4份、纳米碳酸钙7-10份、纳米氧化铁8-9份、滑石粉7-8.8份、改性抗污剂13-17份、分散剂1-1.6份、乙基纤维素1-1.8份、流平剂0.9-1.6份、丙二醇9-11份、成膜助剂9-14份、去离子水32-36份。
优选地，其原料按重量份包括以下组分：全氟烷基乙基醇135份、聚四氢呋喃醚二醇170份、聚碳酸酯二醇68份、二苯基甲烷二异氰酸酯285份、异佛尔酮二异氰酸酯66份、1，4-丁二醇4份、辛酸亚锡1.5份、油酸亚锡1份、氨基硅烷10份、纳米二氧化钛3.5份、纳米氧化锌4份、纳米碳酸钙8份、纳米氧化铁8.6份、滑石粉8.5份、改性抗污剂16份、分散剂1.5份、乙基纤维素1.3份、流平剂1份、丙二醇10份、成膜助剂12份、去离子水35份。
优选地，所述改性抗污剂按照以下工艺进行制备：按重量份将20-35份去离子水和0.2-0.5份烯丙基辛基酚聚氧乙烯醚混合均匀，然后加入10-15份质量分数为45-55wt％的环氧甲萘醌丙酮溶液，搅拌均匀后通入氮气，升温至65-75℃后加入5-12份混合单体，然后加入3-10份质量分数为1-3％的偶氮二异丁腈水溶液，搅拌反应1.5-3h后冷却至室温，加入氨水调节体系为中性后得到所述改性抗污剂；其中，所述混合单体由甲基丙烯酸、丙烯酸、苯乙烯、乙烯基三乙氧基硅烷、六氟丙烯按重量比为1-5:2-6：3-6：2-7：2-10混合而成。
优选地，所述改性抗污剂按照以下工艺进行制备：按重量份将30份去离子水和0.4份烯丙基辛基酚聚氧乙烯醚混合均匀，然后加入12份质量分数为50wt％的环氧甲萘醌丙酮溶液，搅拌均匀后通入氮气，升温至70℃后加入10份混合单体，然后加入8份质量分数为2％的偶氮二异丁腈水溶液，搅拌反应2.5h后冷却至室温，加入氨水调节体系为中性后得到所述改性抗污剂；其中，所述混合单体由甲基丙烯酸、丙烯酸、苯乙烯、乙烯基三乙氧基硅烷、六氟丙烯按重量比为3:4：5：6：5混合而成。
优选地，所述成膜助剂为醇酯十二、乙二醇丁醚、丙二醇单丁醚中的一种或者多种的混合物。
本发明的涂料以全氟烷基乙基醇、聚四氢呋喃醚二醇、聚碳酸酯二醇、二苯基甲烷二异氰酸酯和异佛尔酮二异氰酸酯为主要物质，并添加了1，4-丁二醇为扩链剂，从而在分子中引入了氟基团，使其极性提高，增加了聚氨酯的分子间内聚能，大大提高了涂料的弹性模量和抗张强度，同时使涂料表面的键能提高，并且阻止了磨损向涂层深处的进一步扩展，改善了涂料的抗污性、耐水性、耐候性、耐热性和抗冲蚀性能；以纳米二氧化钛、纳米氧化锌、纳米碳酸钙、纳米氧化铁、滑石粉为无机填料，在氨基硅烷的作用下，在体系中分散均匀，极大地增加了涂料表面的粗糙度，表现出了卓越的超疏水性，改善了涂料的耐水性和耐污性，同时无机填料在体系中与体系的结合牢固，很难被水浸泡冲洗掉，延长了涂料的使用寿命；在优选方式的改性抗污剂中，以环氧甲萘醌为主料，并以甲基丙烯酸、丙烯酸、苯乙烯、乙烯基三乙氧基硅烷、六氟丙烯为混合单体对环氧甲萘醌进行微胶囊化，通过控制制备过程中的工艺参数，使环氧甲萘醌完全被微胶囊化，加入体系中，在体系中分散均匀，随着囊壁的降解，囊芯环氧甲萘醌被释放出来，从而控制了环氧甲萘醌的释放速度，达到使环氧甲萘醌缓释的目的，有效防止了涂料中抗污剂渗出不可控的现象，在体系中，一方面与纳米二氧化钛和纳米氧化锌具有协同作用，改善了涂料的抗污性，起到了更好和更长久的防污效果，另一方面，因其表面引入了乙烯基三乙氧基硅烷和六氟丙烯，从而在体系中引入了硅和氟原子，与纳米氧化铁、纳米碳酸钙和滑石粉配合改善了涂料的耐热性、耐水性和耐候性。
具体实施方式
下面，通过具体实施例对本发明的技术方案进行详细说明。
实施例1
本发明提出的一种防污性聚氨酯涂料，其原料按重量份包括以下组分：全氟烷基乙基醇150份、聚四氢呋喃醚二醇130份、聚碳酸酯二醇85份、二苯基甲烷二异氰酸酯200份、异佛尔酮二异氰酸酯70份、1，4-丁二醇3份、辛酸亚锡2份、油酸亚锡0.5份、氨基硅烷15份、纳米二氧化钛2份、纳米氧化锌5份、纳米碳酸钙5份、纳米氧化铁15份、滑石粉2份、改性抗污剂20份、分散剂0.5份、乙基纤维素2份、流平剂0.5份、丙二醇15份、成膜助剂5份、去离子水40份。
实施例2
本发明提出的一种防污性聚氨酯涂料，其原料按重量份包括以下组分：全氟烷基乙基醇100份、聚四氢呋喃醚二醇200份、聚碳酸酯二醇50份、二苯基甲烷二异氰酸酯350份、异佛尔酮二异氰酸酯50份、1，4-丁二醇5份、辛酸亚锡0.5份、油酸亚锡1.3份、氨基硅烷5份、纳米二氧化钛5份、纳米氧化锌2份、纳米碳酸钙12份、纳米氧化铁3份、滑石粉10份、改性抗污剂6份、分散剂2份、乙基纤维素0.5份、流平剂2份、丙二醇3份、成膜助剂15份、去离子水20份。
实施例3
本发明提出的一种防污性聚氨酯涂料，其原料按重量份包括以下组分：全氟烷基乙基醇138份、聚四氢呋喃醚二醇168份、聚碳酸酯二醇70份、二苯基甲烷二异氰酸酯280份、异佛尔酮二异氰酸酯67份、1，4-丁二醇3.9份、辛酸亚锡1.6份、油酸亚锡0.7份、氨基硅烷11份、纳米二氧化钛3.2份、纳米氧化锌4份、纳米碳酸钙7份、纳米氧化铁9份、滑石粉7份、改性抗污剂17份、分散剂1份、乙基纤维素1.8份、流平剂0.9份、丙二醇11份、醇酯十二9份、去离子水36份；
其中，所述改性抗污剂按照以下工艺进行制备：按重量份将20份去离子水和0.5份烯丙基辛基酚聚氧乙烯醚混合均匀，然后加入10份质量分数为55wt％的环氧甲萘醌丙酮溶液，搅拌均匀后通入氮气，升温至65℃后加入5份混合单体，然后加入10份质量分数为1％的偶氮二异丁腈水溶液，搅拌反应3h后冷却至室温，加入氨水调节体系为中性后得到所述改性抗污剂；其中，所述混合单体由甲基丙烯酸、丙烯酸、苯乙烯、乙烯基三乙氧基硅烷、六氟丙烯按重量比为1:6：3：7：2混合而成。
实施例4
本发明提出的一种防污性聚氨酯涂料，其原料按重量份包括以下组分：全氟烷基乙基醇132份、聚四氢呋喃醚二醇173份、聚碳酸酯二醇66份、二苯基甲烷二异氰酸酯300份、异佛尔酮二异氰酸酯65份、1，4-丁二醇4.3份、辛酸亚锡1份、油酸亚锡1.2份、氨基硅烷8份、纳米二氧化钛4份、纳米氧化锌3.6份、纳米碳酸钙10份、纳米氧化铁8份、滑石粉8.8份、改性抗污剂13份、分散剂1.6份、乙基纤维素1份、流平剂1.6份、丙二醇9份、乙二醇丁醚8份、丙二醇单丁醚6份、去离子水32份；
其中，所述改性抗污剂按照以下工艺进行制备：按重量份将35份去离子水和0.2份烯丙基辛基酚聚氧乙烯醚混合均匀，然后加入15份质量分数为45wt％的环氧甲萘醌丙酮溶液，搅拌均匀后通入氮气，升温至75℃后加入12份混合单体，然后加入3份质量分数为3％的偶氮二异丁腈水溶液，搅拌反应1.5h后冷却至室温，加入氨水调节体系为中性后得到所述改性抗污剂；其中，所述混合单体由甲基丙烯酸、丙烯酸、苯乙烯、乙烯基三乙氧基硅烷、六氟丙烯按重量比为5:2：6：2：10混合而成。
实施例5
本发明提出的一种防污性聚氨酯涂料，其原料按重量份包括以下组分：全氟烷基乙基醇135份、聚四氢呋喃醚二醇170份、聚碳酸酯二醇68份、二苯基甲烷二异氰酸酯285份、异佛尔酮二异氰酸酯66份、1，4-丁二醇4份、辛酸亚锡1.5份、油酸亚锡1份、氨基硅烷10份、纳米二氧化钛3.5份、纳米氧化锌4份、纳米碳酸钙8份、纳米氧化铁8.6份、滑石粉8.5份、改性抗污剂16份、分散剂1.5份、乙基纤维素1.3份、流平剂1份、丙二醇10份、醇酯十二3份、乙二醇丁醚5份、丙二醇单丁醚4份、去离子水35份；
其中，所述改性抗污剂按照以下工艺进行制备：按重量份将30份去离子水和0.4份烯丙基辛基酚聚氧乙烯醚混合均匀，然后加入12份质量分数为50wt％的环氧甲萘醌丙酮溶液，搅拌均匀后通入氮气，升温至70℃后加入10份混合单体，然后加入8份质量分数为2％的偶氮二异丁腈水溶液，搅拌反应2.5h后冷却至室温，加入氨水调节体系为中性后得到所述改性抗污剂；其中，所述混合单体由甲基丙烯酸、丙烯酸、苯乙烯、乙烯基三乙氧基硅烷、六氟丙烯按重量比为3:4：5：6：5混合而成。
以上所述，仅为本发明较佳的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，根据本发明的技术方案及其发明构思加以等同替换或改变，都应涵盖在本发明的保护范围之内。

Claims (7)

1.一种防污性聚氨酯涂料，其特征在于，其原料按重量份包括以下组分：全氟烷基乙基醇100-150份、聚四氢呋喃醚二醇130-200份、聚碳酸酯二醇50-85份、二苯基甲烷二异氰酸酯200-350份、异佛尔酮二异氰酸酯50-70份、1，4-丁二醇3-5份、辛酸亚锡0.5-2份、油酸亚锡0.5-1.3份、氨基硅烷5-15份、纳米二氧化钛2-5份、纳米氧化锌2-5份、纳米碳酸钙5-12份、纳米氧化铁3-15份、滑石粉2-10份、改性抗污剂6-20份、分散剂0.5-2份、乙基纤维素0.5-2份、流平剂0.5-2份、丙二醇3-15份、成膜助剂5-15份、去离子水20-40份。
2.根据权利要求1所述防污性聚氨酯涂料，其特征在于，其原料中，全氟烷基乙基醇、聚四氢呋喃醚二醇、聚碳酸酯二醇、二苯基甲烷二异氰酸酯、异佛尔酮二异氰酸酯的重量比为120-140：160-185：60-75：260-320：60-68。
3.根据权利要求1或2所述防污性聚氨酯涂料，其特征在于，其原料按重量份包括以下组分：全氟烷基乙基醇132-138份、聚四氢呋喃醚二醇168-173份、聚碳酸酯二醇66-70份、二苯基甲烷二异氰酸酯280-300份、异佛尔酮二异氰酸酯65-67份、1，4-丁二醇3.9-4.3份、辛酸亚锡1-1.6份、油酸亚锡0.7-1.2份、氨基硅烷8-11份、纳米二氧化钛3.2-4份、纳米氧化锌3.6-4份、纳米碳酸钙7-10份、纳米氧化铁8-9份、滑石粉7-8.8份、改性抗污剂13-17份、分散剂1-1.6份、乙基纤维素1-1.8份、流平剂0.9-1.6份、丙二醇9-11份、成膜助剂9-14份、去离子水32-36份。
4.根据权利要求1-3中任一项所述防污性聚氨酯涂料，其特征在于，其原料按重量份包括以下组分：全氟烷基乙基醇135份、聚四氢呋喃醚二醇170份、聚碳酸酯二醇68份、二苯基甲烷二异氰酸酯285份、异佛尔酮二异氰酸酯66份、1，4-丁二醇4份、辛酸亚锡1.5份、油酸亚锡1份、氨基硅烷10份、纳米二氧化钛3.5份、纳米氧化锌4份、纳米碳酸钙8份、纳米氧化铁8.6份、滑石粉8.5份、改性抗污剂16份、分散剂1.5份、乙基纤维素1.3份、流平剂1份、丙二醇10份、成膜助剂12份、去离子水35份。
5.根据权利要求1-4中任一项所述防污性聚氨酯涂料，其特征在于，所述改性抗污剂按照以下工艺进行制备：按重量份将20-35份去离子水和0.2-0.5份烯丙基辛基酚聚氧乙烯醚混合均匀，然后加入10-15份质量分数为45-55wt％的环氧甲萘醌丙酮溶液，搅拌均匀后通入氮气，升温至65-75℃后加入5-12份混合单体，然后加入3-10份质量分数为1-3％的偶氮二异丁腈水溶液，搅拌反应1.5-3h后冷却至室温，加入氨水调节体系为中性后得到所述改性抗污剂；其中，所述混合单体由甲基丙烯酸、丙烯酸、苯乙烯、乙烯基三乙氧基硅烷、六氟丙烯按重量比为1-5:2-6：3-6：2-7：2-10混合而成。
6.根据权利要求1-5中任一项所述防污性聚氨酯涂料，其特征在于，所述改性抗污剂按照以下工艺进行制备：按重量份将30份去离子水和0.4份烯丙基辛基酚聚氧乙烯醚混合均匀，然后加入12份质量分数为50wt％的环氧甲萘醌丙酮溶液，搅拌均匀后通入氮气，升温至70℃后加入10份混合单体，然后加入8份质量分数为2％的偶氮二异丁腈水溶液，搅拌反应2.5h后冷却至室温，加入氨水调节体系为中性后得到所述改性抗污剂；其中，所述混合单体由甲基丙烯酸、丙烯酸、苯乙烯、乙烯基三乙氧基硅烷、六氟丙烯按重量比为3:4：5：6：5混合而成。
7.根据权利要求1-6中任一项所述防污性聚氨酯涂料，其特征在于，所述成膜助剂为醇酯十二、乙二醇丁醚、丙二醇单丁醚中的一种或者多种的混合物。
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