CN104789100A - 一种水性聚氨酯防潮防腐涂料及其制备方法 - Google Patents
一种水性聚氨酯防潮防腐涂料及其制备方法 Download PDFInfo
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Abstract
一种水性聚氨酯防潮防腐涂料及其制备方法，该涂料包括改性聚氨酯复合乳液、填料、羟乙基纤维素、防腐剂、甲基硅油、邻苯二甲酸二丁酯、锆-铝酸酯类偶联剂、颜料、变定剂、丙烯酸酯溶液、分散剂、助剂和水，其制备方法：将水、分散剂、颜料、填料、锆-铝酸酯类偶联剂、甲基硅油搅拌均匀后用砂磨机分散61-70min，制得颜填料浆；在容器中加入改性聚氨酯复合乳液，搅拌下加入颜填料浆、防腐剂、聚丙烯酸酯溶液、助剂，搅拌速度为410-450r／min，搅拌时间为21-30min，其中在5-10min时，加入羟乙基纤维素；最后，用160目的绢布滤网过滤得到的滤液与5-7份变定剂混合搅拌，即得本发明产品。本发明具有耐化学性强、耐水、防潮效果好、光泽度高、涂膜寿命长等特点。
Description
技术领域
本发明涉及一种涂料的制备方法，特别是一种水性聚氨酯防潮防腐涂料，属于化学组合物及其制备技术领域。
背景技术
为了研究挥发性有机化合物（VOC）在规定允许以下的涂料，迄今为止，涂料科学家们创造出一系列全新的涂料和涂装技术体系：粉末涂料、辐射固化涂料（UV/EB系统）、水性涂料、高固体分涂料和无溶剂型涂料，其中粉末涂料和辐射固化涂料在施工方面要用专门设备；高固体分涂料虽然在性能上很接近普通溶剂型涂料，但在施工方面仍有其不方便之处，如，施工设备很难清洗和热流挂现象等；而无溶剂型涂料一般多指无溶剂型环氧地坪涂料，其使用范围较窄；因此，水性涂料是最具发展前景的涂料品种之一，尤其是大部分水性涂料施工时，不需要特殊的施工设备，不必烘烤加温固化，适用范围广、应用场合多，因此备受瞩目。目前水性涂料已取得了长足的进步，涂料用4大合成树脂：醇酸树脂、丙烯酸树脂、环氧树脂和聚氨酯树脂都已实现了一定程度的水性化。
其中，应用最广的要属水性聚氨酯涂料。水性聚氨酯涂料是以水性聚氨酯树脂为基料并以水为分散介质的一类涂料，不仅具有无毒无臭味、无污染、不易燃烧、成本低、不易损伤被涂饰表面、施工容易、易于清理等优点，还具有溶剂型聚氨酯涂料所固有的高硬度、耐磨损等优异性能，因而在木器涂料、汽车涂料、建筑涂料、塑料涂料、纸张涂层以及织物和皮革涂饰等许多领域得到了广泛的应用。但是存在缺点是没有防腐性，当回南天气的时候，使用聚氨酯涂料的墙体受到一定的腐蚀性。
现有用于涂饰于材料表面的涂料有无机防腐耐磨涂料和有机防腐耐磨涂料。无机防腐耐磨涂料一般都是以无机结合剂为基体的水溶性涂料，其耐水性及耐冲蚀能力较差，不适合于潮湿环境工作的工况；而一般的有机防腐耐磨涂料则是以环氧树脂为结合剂，加入一定的大颗粒陶瓷骨料和固化剂制得。虽然环氧树脂具有优良的结合力和机械强度，但缺乏韧性，性脆。本发明旨在提供一种防腐、防蚀、耐磨性好的水性聚氨酯涂料，从而减轻施工难度，也扩大了水性涂料的使用范围。
发明内容
本发明的目的提供一种水性聚氨酯防潮防腐涂料及其制备方法，该涂料具有隔热、吸收声能，降低噪声，消除杂音、高耐候、环保、不易老化、长效的效果。
本发明是这样实现的：
水性聚氨酯防潮防腐涂料，制成该涂料包括以下重量份数的原料：
改性聚氨酯复合乳液 40～50份；
填料 3～10份；
羟乙基纤维素 0.1～0.3份；
甲基硅油 0.1～0.3份
邻苯二甲酸二丁酯 0.1～0.3份；
锆-铝酸酯类偶联剂 0.5～1份；
颜料 3～5份；
变定剂 5～7份；
聚丙烯酸酯溶液 0.1～0.3份；
分散剂 3～5份；
助剂 0.1～0.3份；
水 5～10份；
防腐剂 5～7份。
所述的改性聚氨酯复合乳液以二苯基甲烷二异氰酸酯、低聚物二元醇为主要原料，三羟甲基丙烷为助剂，环氧树脂-二乙醇胺加成物为内交联剂，环氧树脂为改性剂，进行聚合而成，制得固含量为35%以上、粒径低至 20～30 nm、分子量为6000-8000的复合乳液，它具有良好的物理性能，抗冲击性及耐磨性优异。该乳液具体的制备方法是：将二苯基甲烷二异氰酸酯和低聚物二元醇进行反应，制备线型聚氨酯预聚体，加入三羟甲基丙烷反应产生支化结构，通过化学反应引入羧基，得到含有 COOH 的聚氨酯预聚体，加入环氧树脂-二乙醇胺加成物作为内交联剂，制备微凝胶结构的预聚体。向预聚体中加入环氧树脂，使环氧树脂中的环氧基和仲羟基与的异氰酸酯基反应，然后中和成盐，加入去离子水分散乳化，制得本发明的改性聚氨酯微凝胶复合纳米乳液。在该过程中，通过加入内交联剂使水性聚氨酯具有疏水性的支化结构，这种结构在相转过程中会形成疏水微区，环氧树脂渗入到这种结构中，有助于体系的共混相容，可进一步对预聚体扩链和交联，形成交联密度较高的结构，同时，可使水性聚氨酯的疏水区具有环氧树脂骨架链，更有利于提高相容性，从而将环氧树脂的加入量提高。
所述的填料是粒径为10-300μm的云母粉末、钛白粉和滑石粉中的一种或一种以上。
所述的羟乙基纤维素是一种白色或淡黄色，无味、无毒的纤维状或粉末状固体，具有增稠、悬浮、粘合、乳化、分散、保持水分及保护胶体等性能，在本发明中作增稠剂、乳化稳定剂应用在涂料中。
所述的邻苯二甲酸二丁酯是一种增塑剂，可使制品具有良好的柔软性，稳定性、耐挠曲性、黏结性和防水性均优于其他增塑剂。
所述的甲基硅油是一种消泡剂，其具有优良的物理特性，可直接用于防潮绝缘，阻尼，减震，消泡，润滑，抛光等方面。
所述的锆-铝酸酯类偶联剂是一种两性物质，具有特殊功能“分子桥”的作用，其一端可与填料发生化学反应，形成强有力的化学键和，另一端可与纤维表面的电荷形成静电结合，从而使两种性质差异很大的材料牢固地结合起来。该类偶联剂与填料的反应主要是通过锆-铝之间的螯合实现的，对无机材料界面改性是不可逆的，不但可以改善其分散性及降低体系粘度，而且由于产生有机官能团的作用，还可提高填料与基材的结合力。通过添加锆-铝酸酯类偶联剂，可显著降低本发明的无机填充体系的粘度，改善其流动性，应用于本发明的涂料可降低粘度，提高产品质量。
所述的颜料为钛白粉、碳黑和铁红中的一种或一种以上。
所述的变定剂为乙二胺、己二胺和二乙烯三胺中的一种或一种以上，这三种的变定剂的活性都很大，能在室温使环氧树脂交联固化；伯胺和仲胺对环氧树脂的固化作用是由氮原子上的活泼氢打开环氧基团，而使之交联固化。
所述的聚丙烯酸酯溶液是一种流平剂，能形成光泽好而耐水的膜，粘合牢固，不易剥落，在室温下柔韧而有弹性，耐候性好，可应用在装饰涂料中。
所述的分散剂为聚乙二醇200或聚乙二醇400。这两种物质作为分散剂、增溶剂、润湿剂和溶剂存在于水溶性分散体系中。
所述的助剂为聚二甲基硅氧烷、聚苯基甲基硅氧烷和聚醚改性聚二甲基硅氧烷中的一种或一种以上。这三种化学助剂能提高涂膜平滑性能。
所述的防腐剂为2-甲基-4-异噻唑啉-3-酮，其是一种高活性的杀菌剂，对许多微生物的最低抑制浓度都在10mg/l以下，对细菌、霉菌、酵母菌、藻类都有极强的杀灭和抑制作用，且低浓度就与效。该品安全性好，毒性分级属低毒，可生物降解，无致畸致突变反应，在酸性和氧化性环境下比较稳定；加入到涂料中可以提高涂料的抗菌、防腐性能。
本发明所述的水性聚氨酯防潮防腐涂料，其制备方法包括以下步骤：
1）按下述配方准备重量份数的原料：
40-50份改性聚氨酯复合乳液,3-10份填料,0.1-0.3份羟乙基纤维素,0.1-0.3份甲基硅油,颜料3-5份,5-7份变定剂,5-7份防腐剂，0.1-0.3份邻苯二甲酸二丁酯,0.5-1份锆-铝酸酯类偶联剂,0.1-0.3份聚丙烯酸酯溶液,3-5份分散剂，0.1-0.3份助剂和5-10份水；
2）按配方量将水、分散剂、颜料、填料、锆-铝酸酯类偶联剂和甲基硅油搅拌均匀后用砂磨机分散，分散时间为61-70min，制得颜填料浆；在容器中加入配方量的改性聚氨酯复合乳液，在搅拌条件下加入上述制得的颜填料浆、防腐剂、聚丙烯酸酯溶液和助剂，搅拌速度为410-450r／min，搅拌时间为21-30min，其中在5-10min的时候，加入配方量的羟乙基纤维素；反应完成后，用160目的绢布滤网过滤，得到滤液，加入5-7份变定剂与滤液混合搅拌，即得水性聚氨酯防潮防腐涂料产品。
本发明的积极效果是：
1、水性聚氨酯涂料具有优良耐磨性、耐化学品性，良好的韧性、弹性和基材的粘接性，能在室温或低温固化，因此在各领域得到了广泛应用。
2、通过添加锆-铝酸酯类偶联剂，可显著降低本发明的无机填充体系的粘度，改善其流动性，应用于本发明的涂料可降低粘度，提高产品质量。
3、本发明的改性聚氨酯复合乳液中的聚氨酯预聚体中的羧基是亲水性的，而环氧树脂是油性乳液，聚氨酯预聚体将环氧树脂包覆形成核-壳的乳胶粒，提供了很好的成膜性，无需加入成膜助剂即可成膜，大大降低了涂料中的VOC合量，使得涂料更符合环保要求。加入固含量较高及具备耐水性耐化学性的改性聚氨酯复合乳液，使涂膜的硬度和拉伸强度增加，将其加入到涂料中能够提高涂料的防潮性能，使涂料在比较潮湿、特殊的环境下发挥防潮作用，在基体表面能形成连续的膜，使基材表面与水隔绝，起到防水和防潮作用。以该复合乳液为基料制备水性聚氨酯防潮防腐涂料，获得耐盐雾性好 （＞800 h）、光泽度高 、耐水、耐磨，普通墙体、屋面、钢架结构、塔架、船体、石油化工储罐、环保工程，并可做各种防腐涂料的配套底漆。
4、加入防腐剂2-甲基-4-异噻唑啉-3-酮或5-氯-2-甲基-4-异噻唑啉-3-酮，不仅能防止涂料的腐败变质,提高涂料的防腐性能，还可以使涂膜具有抵御霉菌侵袭的能力。
5、本发明的涂料，低温或室温固化，可刷涂或喷涂，具有良好的抗拉强度、延伸率、抗撕裂强度和耐候性，能在金属基体表面能形成连续的膜，使基材表面与水隔绝，起到防水和防潮作用，除此之外，还具有耐盐雾性好的性能，起到防腐作用。
具体实施方式
实施例1
首先按重量份数将改性聚氨酯复合乳液40份,粒径为100μm的云母粉末3份,羟乙基纤维素0.1份,甲基硅油0.1份,颜料钛白粉3份,变定剂乙二胺5份,防腐剂5份，邻苯二甲酸二丁酯0.1份,锆-铝酸酯类偶联剂0.5份,聚丙烯酸酯溶液0.1份,3份分散剂聚乙二醇200，助剂聚二甲基硅氧烷0.1份和水5份，进行备料；
按配方量将水、分散剂聚乙二醇200、颜料钛白粉、粒径为100μm的云母粉末、锆-铝酸酯类偶联剂和甲基硅油搅拌均匀后用砂磨机分散，分散时间为61-70min，制得颜填料浆；在容器中加入配方量的改性聚氨酯复合乳液，在搅拌条件下加入上述制得的颜填料浆、防腐剂2-甲基-4-异噻唑啉-3-酮、聚丙烯酸酯溶液和助剂聚二甲基硅氧烷，搅拌速度为410-450r／min，搅拌时间为21-30min，其中在5-10min的时候，加入配方量的羟乙基纤维素；反应完成后，用160目的绢布滤网过滤，得到滤液，加入5份变定剂乙二胺与滤液混合搅拌，即得水性聚氨酯防潮防腐涂料产品。
实施例2
首先按重量份数将改性聚氨酯复合乳液45份,粒径为200μm的钛白粉6份,羟乙基纤维素0.2份,甲基硅油0.2份,颜料碳黑4份,变定剂己二胺6份,防腐剂6份、邻苯二甲酸二丁酯0.2份,锆-铝酸酯类偶联剂0.7份,聚丙烯酸酯溶液0.2份,4份分散剂聚乙二醇400、助剂聚苯基甲基硅氧烷0.2份和水8份，进行备料；
按配方量将水、分散剂聚乙二醇400、颜料碳黑、粒径为200μm的钛白粉、锆-铝酸酯类偶联剂和甲基硅油搅拌均匀后用砂磨机分散，分散时间为61—70min，制得颜填料浆；在容器中加入配方量的改性聚氨酯复合乳液，在搅拌条件下加入上述制得的颜填料浆、防腐剂2-甲基-4-异噻唑啉-3-酮、聚丙烯酸酯溶液和助剂聚苯基甲基硅氧烷，搅拌速度为410-450r／min，搅拌时间为21-30min，其中在5-10min的时候，加入配方量的羟乙基纤维素；反应完成后，用160目的绢布滤网过滤，得到滤液，加入6份变定剂己二胺与滤液混合搅拌，即得水性聚氨酯防潮防腐涂料产品。
实施例3
首先按重量份数将改性聚氨酯复合乳液50份,粒径为300μm的滑石粉10份,羟乙基纤维素0.3份,甲基硅油0.3份,颜料铁红5份,变定剂二乙烯三胺7份,防腐剂7份，邻苯二甲酸二丁酯0.3份,锆-铝酸酯类偶联剂1份,聚丙烯酸酯溶液0.3份,5份聚乙二醇200、助剂聚醚改性聚二甲基硅氧烷0.3份和水8份，进行备料；
按配方量将水、聚乙二醇200、颜料铁红、粒径为300μm的滑石粉、锆-铝酸酯类偶联剂和甲基硅油搅拌均匀后用砂磨机分散，分散时间为61—70min，制得颜填料浆；在容器中加入配方量的改性聚氨酯复合乳液，在搅拌条件下加入上述制得的颜填料浆、防腐剂2-甲基-4-异噻唑啉-3-酮、聚丙烯酸酯溶液和助剂聚醚改性聚二甲基硅氧烷，搅拌速度为410-450r／min，搅拌时间为21-30min，其中在5-10min的时候，加入配方量的羟乙基纤维素；反应完成后，用160目的绢布滤网过滤，得到滤液，加入7份变定剂二乙烯三胺与滤液混合搅拌，即得水性聚氨酯防潮防腐涂料产品。
耐候性的考察：涂膜在室温下不流淌、无气泡和脱落现象的性能，由实施例l—3所得。
本发明的水性聚氨酯防潮防腐涂料制备的漆膜：粘度(涂3杯，24℃)，s：50-60、附着力(级)：＜2、抗冲击强度≥60 kg·cm、遮盖力(g／m2)≤l02、硬度(双摆)：≥0.6、耐3％NaCl(常温)≥27h：涂层完好耐15％NaOH(常温)≥27h：涂层完好耐15％H2SO4(常温)≥27h：涂层完好耐水性(常温)≥54h：热传到系数w／m·k：≤0．055。
本发明的涂料防潮、防水、防腐蚀效果好，可广泛应用于普通墙体、屋面、钢架结构、塔架、船体、石油化工储罐、环保工程，并可做各种防腐涂料的配套底漆。本发明的防护涂料，对施工面的要求宽松，可直接刷涂在金属基体表面，同样可以起到很好的防护效果，施工难度低。
Claims (7)
1.一种水性聚氨酯防潮防腐涂料，其特征在于：制成该涂料包括以下重量份数的原料：
改性聚氨酯复合乳液 40～50份；
填料 3～10份；
羟乙基纤维素 0.1～0.3份；
甲基硅油 0.1～0.3份
邻苯二甲酸二丁酯 0.1～0.3份；
锆-铝酸酯类偶联剂 0.5～1份；
颜料 3～5份；
变定剂 5～7份；
聚丙烯酸酯溶液 0.1～0.3份；
分散剂 3～5份；
助剂 0.1～0.3份；
水 5～10份；
防腐剂 5～7份；
所述的改性聚氨酯复合乳液是固含量为35%以上、粒径为20-30nm和分子量在6000-8000之间的复合乳液；
所述的羟乙基纤维素是一种白色或淡黄色，无味、无毒的纤维状或粉末状固体；
所述的甲基硅油是一种消泡剂。
2.根据权利要求1所述的水性聚氨酯防潮防腐涂料，其特征在于：所述的填料是粒径为10-300μm的云母粉末、钛白粉和滑石粉中的任一种或一种以上。
3.根据权利要求1所述的水性聚氨酯防潮防腐涂料，其特征在于：所述的邻苯二甲酸二丁酯是一种增塑剂。
4.根据权利要求1所述的水性聚氨酯防潮防腐涂料，其特征在于：所述的锆-铝酸酯类偶联剂是一种两性物质，具有特殊功能“分子桥”的作用，其一端可与填料发生化学反应，形成强有力的化学键和，另一端可与纤维表面的电荷形成静电结合，从而使两种性质差异很大的材料牢固地结合起来。
5.根据权利要求1所述的水性聚氨酯防潮防腐涂料，其特征在于：所述的颜料为钛白粉、碳黑和铁红中的一种或一种以上；所述的变定剂为乙二胺、己二胺和二乙烯三胺中的一种或一种以上；所述的聚丙烯酸酯溶液是一种流平剂。
6.根据权利要求1所述的水性聚氨酯防潮防腐涂料，其特征在于：所述的分散剂为聚乙二醇200或聚乙二醇400；所述的助剂为聚二甲基硅氧烷、聚苯基甲基硅氧烷和聚醚改性聚二甲基硅氧烷中的一种或一种以上。
7.根据权利要求1所述的水性聚氨酯防潮防腐涂料，其特征在于：其制备方法包括以下步骤：
1）按下述配方准备重量份数的原料：
40-50份改性聚氨酯复合乳液,3-10份填料,0.1-0.3份羟乙基纤维素,0.1-0.3份甲基硅油,颜料3-5份,5-7份变定剂,5-7份防腐剂，0.1-0.3份邻苯二甲酸二丁酯,0.5-1份锆-铝酸酯类偶联剂,0.1-0.3份聚丙烯酸酯溶液,3-5份分散剂，0.1-0.3份助剂和5-10份水；
2）按配方量将水、分散剂、颜料、填料、锆-铝酸酯类偶联剂、甲基硅油
搅拌均匀后用砂磨机分散，分散时间为61-70min，制得颜填料浆；在容器中加入配方量的改性聚氨酯复合乳液，在搅拌条件下加入上述制得的颜填料浆、防腐剂、聚丙烯酸酯溶液、助剂，搅拌速度为410-450r／min，搅拌时间为21-30min，其中在5-10min的时候，加入配方量的羟乙基纤维素；反应完成后，用160目的绢布滤网过滤，得到滤液，加入5-7份变定剂与滤液混合搅拌，即得水性聚氨酯防潮防腐涂料产品。
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