CN111592807A - 一种玻璃涂料及其制备方法 - Google Patents

一种玻璃涂料及其制备方法 Download PDF

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CN111592807A
CN111592807A CN202010515966.4A CN202010515966A CN111592807A CN 111592807 A CN111592807 A CN 111592807A CN 202010515966 A CN202010515966 A CN 202010515966A CN 111592807 A CN111592807 A CN 111592807A
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stirring
parts
mixing
strontium carbonate
glass coating
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CN111592807B (zh
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马晓英
贾继霞
张晓菊
杨鉴政
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Anyang County Yongsheng Glass Paint&printing Co ltd
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Abstract

本发明公开一种玻璃涂料,由以下重量份数的原料制成:丙烯酸复合乳液65‑70份、填料4‑7份、玉米醇溶蛋白0.1‑0.2份、纳米陶瓷纤维0.3‑0.5份、硫酸钙晶须0.3‑0.5份、氨丙基三乙氧基硅烷0.6‑1份、偏硼酸钡0.2‑0.6份、纳米二氧化钛1‑2份、碳酸锶0.2‑0.5份、去离子水10‑15份、乙二醇1‑2份、消泡剂0.5‑1份、分散剂2‑3份;该涂料通过改进配方以及制备工艺,形成的涂膜与基材的附着力高,硬度高,且耐磨耐酸碱,性能优异。

Description

一种玻璃涂料及其制备方法
技术领域
本发明涉及玻璃涂料技术领域,尤其是涉及一种玻璃涂料及其制备方法。
背景技术
玻璃材料是装饰、装潢、包装等常用的材料,玻璃表面涂膜不仅能够保护玻璃制品,增加玻璃制品的强度、硬度、耐热性、耐腐蚀等性能,还能够美化玻璃制品,增加其美观性。日常常见的酒瓶一般是玻璃瓶,随着人们生活水平越来越高,对于酒瓶的外观就越来越重视,而对酒瓶表面的涂膜的要求也越来越高,比如不仅需要好的装饰性、耐候性、附着性以及耐高温性能等,还要低毒、环保、硬度高,使用寿命长;现有技术为了改进玻璃涂料的性能,会对其配方进行改进。
中国专利文献(申请号2015100677238)公开一种有机硅烷丙烯酸聚氨酯的制备方法,并且,利用该有机硅烷丙烯酸聚氨酯作为基体树脂,用于耐水煮紫外光固化玻璃漆。它先由二异氰酸酯与丙烯酸羟基酯进行反应制备含有碳碳双键单封端的预聚物,再将含有碳碳双键单封端的预聚物分二步与计量的聚醚二元醇和含氨基的硅烷偶联剂反应,制备得到有机硅烷丙烯酸聚氨酯。将该聚氨酯作为基体树脂,与附着力促进剂、稀释剂和光引发剂在紫外光作用下制成玻璃漆,具有相对较高的表面硬度,收缩率极低;经100℃沸水煮2小时,漆膜无起泡脱落,百格刀试验附着力表现为优良。该专利中的基体树脂是有机硅烷丙烯酸聚氨酯,具体的制备方法工艺比较复杂繁琐,且二异氰酸酯与丙烯酸羟基酯形成的碳碳预聚物,之后分二步与计量的聚醚二元醇和含氨基的硅烷偶联剂反应,形成的主要是线形聚合物,其形成的漆膜的机械性能会比网络聚合物形成的漆膜差。中国专利文献(申请号2016102733699)公开一种纳米铟改性透明隔热纳米玻璃涂料,由下列重量份的原料制成:纳米氧化锡锑20-21、分散剂SN-5040 0.2-0.3、水性聚氨酯树脂79-81、去离子水30-35、N,N’-二甲基甲酰胺40-50、20%的硫酸溶液20-22、全氟辛酸20-22、甲基丙烯酸甲酯3-4、过硫酸钾0.1-0.2、异氰酸酯3-3.5、纳米铟0.7-0.9、10-十一烯酸0.4-0.6、二茂铁甲醛0.4-0.6。该发明专利是通过对配方中的辅料纳米铟、10-十一烯酸、二茂铁甲醛进行混合改性,提高纳米铟与树脂的相容性,使得纳米铟分散更均匀,提高涂料的机械性能。但是单纯的改进配方中的辅料,对涂膜的附着力改善效果不明显,漆膜的附着力、硬度和耐热性等因素需要综合考虑。
发明内容
有鉴于此,本发明的目的是针对现有技术的不足,提供一种玻璃涂料,该涂料通过改进配方以及制备工艺,形成的涂膜与基材的附着力高,硬度高,且耐磨耐酸碱耐冲击,性能优异。
为达到上述目的,本发明采用以下技术方案:
一种玻璃涂料,由以下重量份数的原料制成:丙烯酸复合乳液65-70份、填料4-7份、玉米醇溶蛋白0.1-0.2份、纳米陶瓷纤维0.3-0.5份、硫酸钙晶须0.3-0.5份、氨丙基三乙氧基硅烷0.6-1份、偏硼酸钡0.2-0.6份、纳米二氧化钛1-2份、碳酸锶0.2-0.5份、去离子水10-15份、乙二醇1-2份、消泡剂0.5-1份、分散剂2-3份。
进一步的,所述分散剂为硬脂酸单甘油脂和十二烷基硫酸钠按重量比1-2:1混合而成。
进一步的,所述填料为有机膨润土与云母粉按重量比1-2:1混合后经改性而成;
具体的改性方法包括以下步骤:
1)将硬脂酸溶解在3-4倍体积分数为75%乙醇中,得到混合液;
2)有机膨润土与云母粉浸泡在2-3倍重量浓度为12%盐酸溶液中酸化1-2h,去离子洗涤至中性,然后与混合液混合球磨1-2h,50-60℃低温烘干得产品;所述有机膨润土与云母粉总量与硬脂酸的重量比为10:0.5-0.8。
进一步的,所述碳酸锶为包覆型碳酸锶,具体制备方法为:
将碳酸锶分散在7-8倍重量体积分数为75%乙醇中,然后加入氨水调节PH至8-9,加入正硅酸乙酯,搅拌反应3-4h,产物用去离子水洗涤后50℃干燥得产品;
所述碳酸锶与正硅酸乙酯的摩尔比为1:2。
进一步的,所述丙烯酸复合乳液的制备方法包括以下步骤:
(1)氮气环境下,将聚醚二醇、戊二醇和N,N-二甲基乙醇胺搅拌混合后,升温至80-85℃,然后加入二苯甲烷二异氰酸酯和2-3滴二月桂酸二丁基锡搅拌反应3-4h;
(2)然后加入氨丙基三乙氧基硅烷反应1h,之后再加入苯乙烯、丙烯酸丁酯和甲基丙烯酸羟乙酯搅拌反应1-2h,温度降至室温后加入醋酸搅拌0.5h,然后加入去离子水搅拌乳化1h,继续升温至80-85℃,然后加入偶氮引发剂反应2-3h,得到丙烯酸复合乳液;
所述聚醚二醇、二苯甲烷二异氰酸酯、戊二醇、N,N-二甲基乙醇胺、苯乙烯、丙烯酸丁酯、甲基丙烯酸羟乙酯、氨丙基三乙氧基硅烷、偶氮引发剂和醋酸的重量比为:5.2-5.36:7.2-7.3:0.15:1.65:5.01:10:0.27:0.2:0.15:0.8。
一种玻璃涂料的制备方法,包括以下步骤:
(1)将丙烯酸复合乳液、去离子水和乙二醇混合后加入分散釜中,高速搅拌5-8min;
(2)加入消泡剂和分散剂继续搅拌5-8min,然后加入剩余成分搅拌20-30min,形成混合液,放入研磨机中研磨至细度小于18μm,得产品。
进一步的,所述步骤(2)中纳米陶瓷纤维、硫酸钙晶须和氨丙基三乙氧基硅烷充分搅拌混合后再与其他成分进行混合搅拌。
本发明的有益效果是:
1、本发明公开一种玻璃涂料,通过改良配方,对涂料的基体树脂和添加组分均进行改良,充分考量涂膜的附着力、耐热性、硬度以及机械性能等各方面的因素,最终制备的玻璃涂料涂膜的与基材的附着力高,硬度高,且耐磨耐酸碱,性能优异。
2、本申请中采用的基体树脂是丙烯酸复合乳液,即丙烯酸/聚氨酯/有机硅的复合乳液,由于丙烯酸树脂具有防腐、耐酸碱、耐水、成膜性好、无污染等特点,但是耐热性不足,硬度低,机械强度偏低,耐溶剂性能等比较差,而聚氨酯与基底粘结力强,耐磨、耐溶剂,将丙烯酸树脂和聚氨酯共聚制备复合乳液,能够大大改善涂膜的耐磨、耐热和耐溶剂等性能;且在聚合物链上引入硅氧烷,能够提高涂层对玻璃表面的附着力,提高图层的耐水性以及与其他的无机材料的互溶性能,从而增加涂料的综合性能。
因此本申请中的丙烯酸复合乳液具体制备方法是:首先是二苯甲烷二异氰酸酯的-NCO与醇中的羟基反应成-NCO封端的预聚体,之后与氨丙基三乙氧基硅烷和甲基丙烯酸羟乙酯反应,一端与氨丙基三乙氧基硅烷反应成硅氧键,另一端与甲基丙烯酸羟乙酯反应形成有碳碳双键,在引发剂的作用下,引发丙烯酸丁酯、甲基丙烯酸羟乙酯单体与碳碳双键进行自由基聚合反应,从而形成互穿网络型的高分子复合乳液,该制备方法整个工艺简单,制备的复合乳液是通过双重的改性而成,具有优异的机械性能、耐热性和耐磨性,与玻璃基底附着力高。
3、本申请的涂料中还添加有填料,其中填料主要成分是有机膨润土和云母粉,再经过改性而成;其中有机膨润土粘性比较大,可塑性强,成膜性好,而云母粉则弹性、韧性比较好,将其混合添加在涂料中,能调节涂料的粘性,增加涂料的稳定性以及与玻璃基底的结合力,还能增加涂层的韧性和耐高温性能。另外为改善有机膨润土和云母粉与高分子树脂的结合力,还采用硬脂酸对其进行表面包覆,硬脂酸同时具有亲水端和亲油端,能极大改善填料与基材的结合力,从而提高涂料的机械性能和热力学性能。
4、涂料中还添加有纳米陶瓷纤维和硫酸钙晶须,陶瓷纤维重量轻、耐高温、热稳定性好、导热率低、比热小及耐机械震动等优点,而硫酸钙晶须强度高、韧性高、耐磨耐腐蚀;将这两种成分添加在涂料中,一方面可以综合其优点,另一方面两种不同的材料在高分子基体中的分散性不同,能够减少聚集沉降,且陶瓷纤维和硫酸钙晶须在高分子网络结构的均匀分散,能够作为有机材料和无机材料的结构粘结剂,从而在整体上增强涂层的力学性能;而为了增加其在树脂中的分散性,在制备涂料的时候可将其与氨丙基三乙氧基硅烷先行混合,进而提高其与树脂的结合力。
5、另外涂料中还添加有偏硼酸钡和纳米二氧化钛,一方面能作为补强剂,另一方面能增强涂料的抗菌作用;而少量的碳酸锶能够改善乳液的稳定性以及漆膜的稳定性、硬度和耐溶剂性能,而为了增加碳酸锶与树脂的相容性,还对碳酸锶进行表面处理。另外涂料还添加有玉米醇溶蛋白,其少量分散在基材中能改善树脂的成膜性能。
6、另外在制备涂料的过程中还可以根据需要添加比如透明的红色颜料、黄色颜料、黑色颜料等,制备出不同颜色的玻璃涂料。
具体实施方式
下面结合具体的实施方式对本发明作进一步的描述。
实施例1
一种玻璃涂料,由以下重量份数的原料制成:丙烯酸复合乳液65份、填料4份、玉米醇溶蛋白0.1份、纳米陶瓷纤维0.3份、硫酸钙晶须0.3份、氨丙基三乙氧基硅烷0.6份、偏硼酸钡0.2份、纳米二氧化钛1份、碳酸锶0.5份、去离子水10份、乙二醇1份、聚硅氧烷消泡剂0.5份、分散剂2份。
其中分散剂为硬脂酸单甘油脂和十二烷基硫酸钠按重量比1:1混合而成;硫酸钙晶须的平均直径1-2μm,平均长度10-20μm。
填料为有机膨润土与云母粉按重量比1:1混合后经改性而成;
具体的改性方法包括以下步骤:
1)将硬脂酸溶解在3倍体积分数为75%乙醇中,得到混合液;
2)有机膨润土与云母粉浸泡在2倍重量浓度为12%盐酸溶液中酸化1h,去离子洗涤至中性,然后与混合液混合球磨1h,50-60℃低温烘干得产品;其中有机膨润土与云母粉总量与硬脂酸的重量比为10:0.5。
碳酸锶为包覆型碳酸锶,具体制备方法为:
将碳酸锶分散在7倍重量体积分数为75%乙醇中,然后加入氨水调节PH至8,加入正硅酸乙酯,搅拌反应3h,产物用去离子水洗涤后50℃干燥得产品;碳酸锶与正硅酸乙酯的摩尔比为1:2。
丙烯酸复合乳液的制备方法包括以下步骤:
(1)氮气环境下,将聚醚二醇(聚四氢呋喃醚二醇1000)、戊二醇和N,N-二甲基乙醇胺搅拌混合后,升温至80℃,然后加入二苯甲烷二异氰酸酯和2-3滴二月桂酸二丁基锡搅拌反应3h;
(2)然后加入氨丙基三乙氧基硅烷反应1h,之后再加入苯乙烯、丙烯酸丁酯和甲基丙烯酸羟乙酯搅拌反应1h,温度降至室温后加入醋酸搅拌0.5h,并加入反应液等量的去离子水搅拌乳化1h,继续升温至80℃,然后加入偶氮引发剂(偶氮二异丁脒盐酸盐)反应2h,得到丙烯酸复合乳液;
其中聚醚二醇、二苯甲烷二异氰酸酯、戊二醇、N,N-二甲基乙醇胺、苯乙烯、丙烯酸丁酯、甲基丙烯酸羟乙酯、氨丙基三乙氧基硅烷、偶氮引发剂和醋酸的重量比为:5.2:7.3:0.15:1.65:5.01:10:0.27:0.2:0.15:0.8。
上述玻璃涂料的制备方法,包括以下步骤:
(1)将丙烯酸复合乳液、去离子水和乙二醇混合后加入分散釜中,800r/min高速搅拌8min;
(2)加入聚硅氧烷消泡剂和分散剂继续搅拌5min,纳米陶瓷纤维、硫酸钙晶须和氨丙基三乙氧基硅烷充分搅拌混合后,再与其他成分混合加入分散釜中搅拌20min,形成混合液,放入研磨机中研磨至细度小于18μm,得产品。
实施例2
一种玻璃涂料,由以下重量份数的原料制成:丙烯酸复合乳液66份、填料5份、玉米醇溶蛋白0.12份、纳米陶瓷纤维0.35份、硫酸钙晶须0.35份、氨丙基三乙氧基硅烷0.7份、偏硼酸钡0.3份、纳米二氧化钛1.2份、碳酸锶0.4份、去离子水11份、乙二醇1.2份、聚硅氧烷消泡剂0.6份、分散剂2.2份。
其中分散剂为硬脂酸单甘油脂和十二烷基硫酸钠按重量比1.5:1混合而成;硫酸钙晶须的平均直径1-2μm,平均长度10-20μm。
填料为有机膨润土与云母粉按重量比1.5:1混合后经改性而成;
具体的改性方法包括以下步骤:
1)将硬脂酸溶解在3倍体积分数为75%乙醇中,得到混合液;
2)有机膨润土与云母粉浸泡在2.2倍重量浓度为12%盐酸溶液中酸化1h,去离子洗涤至中性,然后与混合液混合球磨1h,50-60℃低温烘干得产品;其中有机膨润土与云母粉总量与硬脂酸的重量比为10:0.6。
碳酸锶为包覆型碳酸锶,具体制备方法为:
将碳酸锶分散在7倍重量体积分数为75%乙醇中,然后加入氨水调节PH至8,加入正硅酸乙酯,搅拌反应3h,产物用去离子水洗涤后50℃干燥得产品;碳酸锶与正硅酸乙酯的摩尔比为1:2。
丙烯酸复合乳液的制备方法包括以下步骤:
(1)氮气环境下,将聚醚二醇(聚四氢呋喃醚二醇1000)、戊二醇和N,N-二甲基乙醇胺搅拌混合后,升温至80℃,然后加入二苯甲烷二异氰酸酯和2-3滴二月桂酸二丁基锡搅拌反应3h;
(2)然后加入氨丙基三乙氧基硅烷反应1h,之后再加入苯乙烯、丙烯酸丁酯和甲基丙烯酸羟乙酯搅拌反应1h,温度降至室温后加入醋酸搅拌0.5h,并加入反应液等量的去离子水搅拌乳化1h,继续升温至80℃,然后加入偶氮引发剂反应2h,得到丙烯酸复合乳液;
其中聚醚二醇、二苯甲烷二异氰酸酯、戊二醇、N,N-二甲基乙醇胺、苯乙烯、丙烯酸丁酯、甲基丙烯酸羟乙酯、氨丙基三乙氧基硅烷、偶氮引发剂和醋酸的重量比为:5.36:7.24:0.15:1.65:5.01:10:0.27:0.2:0.15:0.8。
上述玻璃涂料的制备方法,包括以下步骤:
(1)将丙烯酸复合乳液、去离子水和乙二醇混合后加入分散釜中,800r/min高速搅拌8min;
(2)加入聚硅氧烷消泡剂和分散剂继续搅拌5min,纳米陶瓷纤维、硫酸钙晶须和氨丙基三乙氧基硅烷充分搅拌混合后,再与其他成分混合加入分散釜中搅拌20min,形成混合液,放入研磨机中研磨至细度小于18μm,得产品。
实施例3
一种玻璃涂料,由以下重量份数的原料制成:丙烯酸复合乳液68份、填料6份、玉米醇溶蛋白0.15份、纳米陶瓷纤维0.4份、硫酸钙晶须0.4份、氨丙基三乙氧基硅烷0.9份、偏硼酸钡0.4份、纳米二氧化钛1.4份、碳酸锶0.3份、去离子水12份、乙二醇1.5份、聚硅氧烷消泡剂0.7份、分散剂2.5份。
其中分散剂为硬脂酸单甘油脂和十二烷基硫酸钠按重量比1.5:1混合而成;硫酸钙晶须的平均直径1-2μm,平均长度10-20μm。
填料为有机膨润土与云母粉按重量比1.5:1混合后经改性而成;
具体的改性方法包括以下步骤:
1)将硬脂酸溶解在3.5倍体积分数为75%乙醇中,得到混合液;
2)有机膨润土与云母粉浸泡在2.6倍重量浓度为12%盐酸溶液中酸化1.5h,去离子洗涤至中性,然后与混合液混合球磨1.5h,50-60℃低温烘干得产品;其中有机膨润土与云母粉总量与硬脂酸的重量比为10:0.7。
碳酸锶为包覆型碳酸锶,具体制备方法为:
将碳酸锶分散在7.5倍重量体积分数为75%乙醇中,然后加入氨水调节PH至8.5,加入正硅酸乙酯,搅拌反应3.5h,产物用去离子水洗涤后50℃干燥得产品;碳酸锶与正硅酸乙酯的摩尔比为1:2。
丙烯酸复合乳液的制备方法包括以下步骤:
(1)氮气环境下,将聚醚二醇(聚四氢呋喃醚二醇1000)、戊二醇和N,N-二甲基乙醇胺搅拌混合后,升温至85℃,然后加入二苯甲烷二异氰酸酯和2-3滴二月桂酸二丁基锡搅拌反应3.5h;
(2)然后加入氨丙基三乙氧基硅烷反应1h,之后再加入苯乙烯、丙烯酸丁酯和甲基丙烯酸羟乙酯搅拌反应1.5h,温度降至室温后加入醋酸搅拌0.5h,并加入反应液等量的去离子水搅拌乳化1h,继续升温至85℃,然后加入偶氮引发剂反应3h,得到丙烯酸复合乳液;
其中聚醚二醇、二苯甲烷二异氰酸酯、戊二醇、N,N-二甲基乙醇胺、苯乙烯、丙烯酸丁酯、甲基丙烯酸羟乙酯、氨丙基三乙氧基硅烷、偶氮引发剂和醋酸的重量比为5.3:7.3:0.15:1.65:5.01:10:0.27:0.2:0.15:0.8。
上述玻璃涂料的制备方法,包括以下步骤:
(1)将丙烯酸复合乳液、去离子水和乙二醇混合后加入分散釜中,900r/min高速搅拌7min;
(2)加入聚硅氧烷消泡剂和分散剂继续搅拌5min,纳米陶瓷纤维、硫酸钙晶须和氨丙基三乙氧基硅烷充分搅拌混合后,再与其他成分混合加入分散釜中搅拌20min,形成混合液,放入研磨机中研磨至细度小于18μm,得产品。
实施例4
一种玻璃涂料,由以下重量份数的原料制成:丙烯酸复合乳液70份、填料7份、玉米醇溶蛋白0.2份、纳米陶瓷纤维0.5份、硫酸钙晶须0.5份、氨丙基三乙氧基硅烷1份、偏硼酸钡0.5份、纳米二氧化钛1.8份、碳酸锶0.35份、去离子水14份、乙二醇1.8份、聚硅氧烷消泡剂0.8份、分散剂2.8份。
其中分散剂为硬脂酸单甘油脂和十二烷基硫酸钠按重量比2:1混合而成;硫酸钙晶须的平均直径1-2μm,平均长度10-20μm。
填料为有机膨润土与云母粉按重量比2:1混合后经改性而成;
具体的改性方法包括以下步骤:
1)将硬脂酸溶解在3.5倍体积分数为75%乙醇中,得到混合液;
2)有机膨润土与云母粉浸泡在2.8倍重量浓度为12%盐酸溶液中酸化1.5h,去离子洗涤至中性,然后与混合液混合球磨1.5h,50-60℃低温烘干得产品;其中有机膨润土与云母粉总量与硬脂酸的重量比为10:0.8。
碳酸锶为包覆型碳酸锶,具体制备方法为:
将碳酸锶分散在7.5倍重量体积分数为75%乙醇中,然后加入氨水调节PH至9,加入正硅酸乙酯,搅拌反应3.5h,产物用去离子水洗涤后50℃干燥得产品;碳酸锶与正硅酸乙酯的摩尔比为1:2。
丙烯酸复合乳液的制备方法包括以下步骤:
(1)氮气环境下,将聚醚二醇(聚四氢呋喃醚二醇1000)、戊二醇和N,N-二甲基乙醇胺搅拌混合后,升温至85℃,然后加入二苯甲烷二异氰酸酯和2-3滴二月桂酸二丁基锡搅拌反应3h;
(2)然后加入氨丙基三乙氧基硅烷反应1h,之后再加入苯乙烯、丙烯酸丁酯和甲基丙烯酸羟乙酯搅拌反应2h,温度降至室温后加入醋酸搅拌0.5h,并加入反应液等量的去离子水搅拌乳化1h,继续升温至85℃,然后加入偶氮引发剂反应3h,得到丙烯酸复合乳液;
其中聚醚二醇、二苯甲烷二异氰酸酯、戊二醇、N,N-二甲基乙醇胺、苯乙烯、丙烯酸丁酯、甲基丙烯酸羟乙酯、氨丙基三乙氧基硅烷、偶氮引发剂和醋酸的重量比为:5.27:7.33:0.15:1.65:5.01:10:0.27:0.2:0.15:0.8。
上述玻璃涂料的制备方法,包括以下步骤:
(1)将丙烯酸复合乳液、去离子水和乙二醇混合后加入分散釜中,1000r/min高速搅拌5min;
(2)加入聚硅氧烷消泡剂和分散剂继续搅拌5min,纳米陶瓷纤维、硫酸钙晶须和氨丙基三乙氧基硅烷充分搅拌混合后,再与其他成分混合后加入分散釜中搅拌20min,形成混合液,放入研磨机中研磨至细度小于18μm,得产品。
实施例5
一种玻璃涂料,由以下重量份数的原料制成:丙烯酸复合乳液67份、填料5份、玉米醇溶蛋白0.18份、纳米陶瓷纤维0.4份、硫酸钙晶须0.45份、氨丙基三乙氧基硅烷0.9份、偏硼酸钡0.6份、纳米二氧化钛2份、碳酸锶0.2份、去离子水15份、乙二醇2份、聚硅氧烷消泡剂1份、分散剂3份。
其中分散剂为硬脂酸单甘油脂和十二烷基硫酸钠按重量比1.5:1混合而成;硫酸钙晶须的平均直径1-2μm,平均长度10-20μm。
填料为有机膨润土与云母粉按重量比1.5:1混合后经改性而成;
具体的改性方法包括以下步骤:
1)将硬脂酸溶解在4倍体积分数为75%乙醇中,得到混合液;
2)有机膨润土与云母粉浸泡在3倍重量浓度为12%盐酸溶液中酸化2h,去离子洗涤至中性,然后与混合液混合球磨2h,50-60℃低温烘干得产品;其中有机膨润土与云母粉总量与硬脂酸的重量比为10:0.8。
碳酸锶为包覆型碳酸锶,具体制备方法为:
将碳酸锶分散在8倍重量体积分数为75%乙醇中,然后加入氨水调节PH至9,加入正硅酸乙酯,搅拌反应4h,产物用去离子水洗涤后50℃干燥得产品;碳酸锶与正硅酸乙酯的摩尔比为1:2。
丙烯酸复合乳液的制备方法包括以下步骤:
(1)氮气环境下,将聚醚二醇(聚四氢呋喃醚二醇1000)、戊二醇和N,N-二甲基乙醇胺搅拌混合后,升温至85℃,然后加入二苯甲烷二异氰酸酯和2-3滴二月桂酸二丁基锡搅拌反应3.5h;
(2)然后加入氨丙基三乙氧基硅烷反应1h,之后再加入苯乙烯、丙烯酸丁酯和甲基丙烯酸羟乙酯搅拌反应1.5h,温度降至室温后加入醋酸搅拌0.5h,并加入反应液等量的去离子水搅拌乳化1h,继续升温至85℃,然后加入偶氮引发剂反应2.5h,得到丙烯酸复合乳液;
其中聚醚二醇、二苯甲烷二异氰酸酯、戊二醇、N,N-二甲基乙醇胺、苯乙烯、丙烯酸丁酯、甲基丙烯酸羟乙酯、氨丙基三乙氧基硅烷、偶氮引发剂和醋酸的重量比为:5.25:7.35:0.15:1.65:5.01:10:0.27:0.2:0.15:0.8。
上述玻璃涂料的制备方法,包括以下步骤:
(1)将丙烯酸复合乳液、去离子水和乙二醇混合后加入分散釜中,1000r/min高速搅拌5min;
(2)加入聚硅氧烷消泡剂和分散剂继续搅拌5min,纳米陶瓷纤维、硫酸钙晶须和氨丙基三乙氧基硅烷充分搅拌混合后,再与其他成分混合加入分散釜中搅拌20min,形成混合液,放入研磨机中研磨至细度小于18μm,得产品。
性能检测:
将实施例1-5制备的产品喷涂在玻璃板表面,干膜厚度30μm,为并对其性能进行检测,光泽度(60°)参照GB/T1743-1979,耐磨性参照GB/T1768-2006,硬度参照GB/T6739,附着力参照GB/T9286-1998,抗冲击性能参照GB/T1732,结果见表1所示。
表1 性能检测数据
Figure 501599DEST_PATH_IMAGE002
将实施例1-5制备的漆膜分别浸泡在浓度为5%氢氧化钠和盐酸溶液中72h,无气泡和脱落现象,说明本申请制备的涂膜耐酸碱腐蚀。另外由表1可知,本申请涂料树脂交联度高,因此其涂膜的光泽高,硬度大,且涂膜与基材的附着力高,耐磨耐腐蚀耐冲击,综合性能优异,使用寿命长。
最后说明的是,以上实施例仅用以说明本发明的技术方案而非限制,本领域普通技术人员对本发明的技术方案所做的其他修改或者等同替换,只要不脱离本发明技术方案的精神和范围,均应涵盖在本发明的权利要求范围当中。

Claims (7)

1.一种玻璃涂料,其特征在于:由以下重量份数的原料制成:丙烯酸复合乳液65-70份、填料4-7份、玉米醇溶蛋白0.1-0.2份、纳米陶瓷纤维0.3-0.5份、硫酸钙晶须0.3-0.5份、氨丙基三乙氧基硅烷0.6-1份、偏硼酸钡0.2-0.6份、纳米二氧化钛1-2份、碳酸锶0.2-0.5份、去离子水10-15份、乙二醇1-2份、消泡剂0.5-1份、分散剂2-3份。
2.根据权利要求1所述的一种玻璃涂料,其特征在于:所述分散剂为硬脂酸单甘油脂和十二烷基硫酸钠按重量比1-2:1混合而成。
3.根据权利要求1所述的一种玻璃涂料,其特征在于:所述填料为有机膨润土与云母粉按重量比1-2:1混合后经改性而成;
具体的改性方法包括以下步骤:
1)将硬脂酸溶解在3-4倍体积分数为75%乙醇中,得到混合液;
2)有机膨润土与云母粉浸泡在2-3倍重量浓度为12%盐酸溶液中酸化1-2h,去离子洗涤至中性,然后与混合液混合球磨1-2h,50-60℃低温烘干得产品;所述有机膨润土与云母粉总量与硬脂酸的重量比为10:0.5-0.8。
4.根据权利要求1所述的一种玻璃涂料,其特征在于:所述碳酸锶为包覆型碳酸锶,具体制备方法为:
将碳酸锶分散在7-8倍重量体积分数为75%乙醇中,然后加入氨水调节PH至8-9,加入正硅酸乙酯,搅拌反应3-4h,产物用去离子水洗涤后50℃干燥得产品;
所述碳酸锶与正硅酸乙酯的摩尔比为1:2。
5.根据权利要求1所述的一种玻璃涂料,其特征在于:所述丙烯酸复合乳液的制备方法包括以下步骤:
(1)氮气环境下,将聚醚二醇、戊二醇和N,N-二甲基乙醇胺搅拌混合后,升温至80-85℃,然后加入二苯甲烷二异氰酸酯和2-3滴二月桂酸二丁基锡搅拌反应3-4h;
(2)然后加入氨丙基三乙氧基硅烷反应1h,之后再加入苯乙烯、丙烯酸丁酯和甲基丙烯酸羟乙酯搅拌反应1-2h,温度降至室温后加入醋酸搅拌0.5h,然后加入去离子水搅拌乳化1h,继续升温至80-85℃,然后加入偶氮引发剂反应2-3h,得到丙烯酸复合乳液;
所述聚醚二醇、二苯甲烷二异氰酸酯、戊二醇、N,N-二甲基乙醇胺、苯乙烯、丙烯酸丁酯、甲基丙烯酸羟乙酯、氨丙基三乙氧基硅烷、偶氮引发剂和醋酸的重量比为:5.2-5.36:7.2-7.3:0.15:1.65:5.01:10:0.27:0.2:0.15:0.8。
6.一种权利要求1所述的玻璃涂料的制备方法,其特征在于:包括以下步骤:
(1)将丙烯酸复合乳液、去离子水和乙二醇混合后加入分散釜中,高速搅拌5-8min;
(2)加入消泡剂和分散剂继续搅拌5-8min,然后加入剩余成分搅拌20-30min,形成混合液,放入研磨机中研磨至细度小于18μm,得产品。
7.根据权利要求6所述的一种玻璃涂料的制备方法,其特征在于:所述步骤(2)中纳米陶瓷纤维、硫酸钙晶须和氨丙基三乙氧基硅烷充分搅拌混合后再与其他成分进行混合搅拌。
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