CN104745070B - 一种聚氨酯外墙防腐阻燃涂料及其制备方法 - Google Patents
一种聚氨酯外墙防腐阻燃涂料及其制备方法 Download PDFInfo
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- CN104745070B CN104745070B CN201510143449.8A CN201510143449A CN104745070B CN 104745070 B CN104745070 B CN 104745070B CN 201510143449 A CN201510143449 A CN 201510143449A CN 104745070 B CN104745070 B CN 104745070B
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Abstract
一种聚氨酯外墙防腐阻燃涂料及其制备方法，该涂料是包括聚氨酯预聚体、N‑羟甲基丙烯酰胺、对苯二甲酸二辛酯、钛酸酯偶联剂TMC‑101、分散剂聚丙烯酸铵盐DA40、金红石型钛白粉、聚氧丙烯甘油醚、硅石灰粉、混合溶剂、阻燃材料和防腐剂；其制备方法：按重量每公斤N‑羟甲基丙烯酰胺加入1.8公斤的体积浓度70～85%的乙醇溶解，然后在反应釜中与聚氨酯预聚体混合，反应温度80～130℃，反应时间1.3～1.8小时后加入钛酸酯偶联剂TMC‑101和分散剂聚丙烯酸铵盐DA40；继续反应3.5～5.5小时；然后加入对苯二甲酸二辛酯、金红石型钛白粉、聚氧丙烯甘油醚、阻燃材料、硅石灰粉、混合溶剂和防腐剂，混合均匀即可得到聚氨酯外墙防腐阻燃涂料产品。
Description
技术领域
本发明涉及到一种防腐阻燃涂料，特别是涉及到一种聚氨酯外墙防腐阻燃涂料及其制备方法，属于化学组合物及其制备技术领域。
背景技术
随着建筑业的发展，涂料的需求量与日俱增。涂料是一种材料，这种材料可以用不同的施工工艺涂覆在物件表面，形成粘附牢固、具有一定强度、连续的固态薄膜，这样形成的膜通称涂膜，又称漆膜或涂层。物件暴露在大气之中，受到氧气、水分等的侵蚀，容易造成金属锈蚀、木材腐朽、水泥风化等破坏现象，在物件表面涂以涂料，形成一层保护膜，能够阻止或延迟这些破坏现象的发生和发展，能使各种材料的使用寿命延长寿命延长。
聚氨酯涂料是一种重要的建筑涂料，还可用作工业涂料，是在20世纪后半叶才发展起来的一种新型材料，因其涂膜外观优美，具有良好的装饰性，且因其良好的柔韧性、耐冲击性、耐腐蚀性、耐化学品性及优异的耐低温性和耐磨性、硬度大、高弹性等特点，已广泛地应用于车船、航空、电子、建筑、桥梁、机床、木器及室内装潢等领域的装饰和保护中，同时也大量用于石化设备、管道、海洋设施、重型机械等工业的防腐蚀保护和装饰。而外墙涂料是与外界大气环境直接接触的，需要经受气候、雨水、紫外线等的挑战，因此外墙涂料更需要具备耐酸雨、耐沾污、防腐性能高以及易清洗等性能。
目前在建筑防水领域，溶剂型聚氨酯涂料（WPU ）应用比较广泛，但随着环保的力度的加大，涂料势必要向无溶剂、水性化方向发展。溶剂型聚氨酯涂料由于引入亲水集团，涂料的耐水性不佳，无法满足建筑防水涂料的需求，所以可以通过改性来提高和改善相应性能。聚氨酯涂料的阻燃性能也很差，在发生火灾时，不能起到很好的阻燃作用，不能抑制火势的蔓延，而且聚氨基甲酸酯还有助燃的作用。因此，聚氨酯涂料在预防火灾方面存在很大的缺陷。而如果生产出来的聚氨酯涂料具有阻燃功能，在火灾发生时就能够有效地阻止、延缓或终止火焰的传播，达到阻燃的作用，有效减少消费者生命财产的损失。而对于提高聚氨酯涂料的耐水性、阻燃性等性能，目前公开文献报道了许多改性方法，例如
1、中国专利，名称: 一种有机硅改性水性聚氨酯涂料及其制备方法，申请（专利）号:CN201310396330.2 申请（专利权）人:盐城市昶桦户外用品有限公司 ，摘要: 一种有机硅改性水性聚氨酯及其制备方法，特别涉及一种主链上含有有机硅的水性聚氨酯涂料及其制备方法。该涂料原料组分及含量为：多异氰酸酯30～40；聚醚多元醇30～40；亲水性扩链剂3～10；扩链剂2～10；交联剂1～3；中和剂3～10。制备方法包括预聚物合成、预聚物中和、扩链及乳化等步骤。本发明所得的有机硅改性水性聚氨酯涂料在其分子主链上引入了硅氧键（-Si-O-Si-），由于硅氧键相比碳碳键（-C-C-）的键长大的多，使得链的柔顺性大大提高；同时，所用的聚醚多元醇为柔性链段；能够很好的改善聚氨酯的柔顺性，大幅度的降低聚氨酯的模量；在纺织品、皮革、建筑以及某些特殊行业有巨大的应用前景。
2、中国专利，名称:水性阻燃聚氨酯树脂及制备方法 申请（专利）号:CN201110119112.5 申请（专利权）人: 丹东恒悦新材料有限公司 摘要：一种水性阻燃聚氨酯树脂及制备方法，其是一种含溴阻燃聚醚的水性聚氨酯树脂，固含量在20～40%。制备方法由制备含溴聚醚的聚氨酯预聚体A、制备含溴聚醚的封闭异氰酸酯的聚氨酯B，把上述的预聚体A和聚氨酯B进行乳化扩链反应，制得水性阻燃聚氨酯树脂。其具有很好的阻燃性能和水洗牢度，可直接作为织物等的阻燃涂层胶，阻燃涂料使用。
3、中国专利，名称: 环保型水性纳米防火阻燃涂料及制备方法申请（专利）号:CN200710027403.5 申请（专利权）人: 中山市孙大化工科技有限公司 摘要：本发明是一种环保型水性纳米防火阻燃涂料及制备方法，属化工防火阻燃涂料制造业。它通过来用两种阻燃剂与水性树脂、多聚磷酸铵、三聚氰胺、成碳剂、纳米颜、填料，微米颜、填料及其它助剂复配得到的阻燃涂料。它不合有机溶剂和卤素阻燃剂，VOC含量很低，防火性能优异，理化性能优良。它的组成如下：水性树脂10～90％，含磷、氮有机物插层的层状硅酸盐纳米阻燃剂l～50％，聚合物包覆的纳米氢氧化镁阻燃剂l～50％，多聚磷酸铵l～30％，三聚氰胺l～20％，成碳剂 l～30％，纳米颜、填料0.1～30％，微米填料0.1～60％，分散剂0.1～10％，稳定剂0.1～10％，水0.1～50％，微米颜料适量。它是先将水性树脂、纳米阻燃剂、多聚磷酸铵、三聚氰胺、成碳剂、纳米颜、填料，分散剂及稳定剂投入行星搅拌釜中搅拌分散均匀；出料后的混合物再加入微米颜、填料、水、分散剂和稳定剂在高速分散机内分散均匀获得成品。
但要制备一种具同时有阻燃、轻质、防水、防腐、环保、不易老化、长效性的的涂料，还没有很成熟的技术，因此目前人们还在水性涂料方面还在不断的研究试验。
发明内容
本发明的目的提供一种聚氨酯外墙防腐阻燃涂料及其制备方法，按照该制备方法制备得到的涂料具有良好的阻燃效果，而且防腐性能高、环保、不易老化。
本发明是这样实现的：
一种聚氨酯外墙防腐阻燃涂料，制成该涂料包括以下重量份数的原料：
聚氨酯预聚体 45～55份；
N-羟甲基丙烯酰胺 2-4份；
对苯二甲酸二辛酯 3～5份；
钛酸酯偶联剂TMC-101 0.5～1.0份；
分散剂 0.3～0.6份
钛白粉 15～20份；
消泡剂 0.2～0.5份；
硅石灰粉 6～10份；
混合溶剂 12～15份；
阻燃材料 5-10份；
防腐剂 3～7份；
所述的聚氨酯预聚体是带有NCO端基的预聚体，分子量在10000-4000之间；
所述的混合溶剂是木质素+丙二醇甲醚+水，重量比例为2：1：9；
所述的阻燃材料是季戊四醇、磷酸二甲苯酯、三聚氰酰胺中的两种或两种以上。
所述的分散剂是聚丙烯酸铵盐DA40；
所述的消泡剂是聚氧丙烯甘油醚；
所述的防腐剂为2-甲基-4-异噻唑啉-3-酮或5-氯-2-甲基-4-异噻唑啉-3-酮。
所述的钛白粉为金红石型二氧化钛，由于金红石型二氧化钛其折射率为2.71，通过加入二氧化钛（金红石型）材料，能增强光线的折射与散射。因此，具有较优的反射和隔热性能，还具有很好的光线遮盖效果，从而反射太阳近红外波段，提高太阳热辐射反射，降低太阳热吸收，不让太阳在物体表面累计升温。
本发明所述的一种聚氨酯外墙防腐阻燃涂料，其制备方法包括以下步骤：
按重量每公斤N-羟甲基丙烯酰胺加入1.8公斤的体积浓度70～85%的乙醇溶解，然后在反应釜中与聚氨酯预聚体混合，反应温度80～130℃，反应时间1.3～1.8小时后加入钛酸酯偶联剂TMC-101和分散剂聚丙烯酸铵盐DA40；继续反应3.5～5.5小时；然后加入对苯二甲酸二辛酯、金红石型钛白粉、聚氧丙烯甘油醚、阻燃材料、硅石灰粉、混合溶剂和防腐剂，混合均匀即可得到水溶性聚氨酯防腐阻燃涂料产品。
本发明所述的聚氨酯外墙防腐阻燃涂料，其原料还包括：流平剂、抗冻剂和防沉剂中的一种或多种，重量份数为2～5；所述的流平剂是丙烯酸酯；所述的抗冻剂是苯甲醇；所述的防沉剂是有机膨润土。
本发明所述的聚氨酯外墙防腐阻燃涂料，还可以进一步加入色料，提供外墙色彩缤纷的涂料。
本发明所述的聚氨酯预聚体是以异氰酸酯、聚醚为主要原料，进行聚合而成，带有NCO端基的预聚体，分子量在10000-4000之间，它具有良好的物理性能，粘结力强，常温湿固化。
本发明所述的N-羟甲基丙烯酰胺，为白色结晶粉末，熔点74～75℃， 易溶于水、乙醇，溶于脂肪酸酯类，不溶于烃、卤代烃等疏水性溶剂。当水溶液中有酸存在时，加热会迅速聚合成不溶的树脂。由于分子结构中含有聚合性能的乙烯基和缩合性能的羟甲基，因此使线型聚合物交联最为有效。如果与丙烯酸酯类单体共聚合，羟甲基被引入，仅加热即可交联。
本发明所述的对苯二甲酸二辛酯为淡黄透明油状液体 无色透明油状液体，不含邻苯二甲酸盐，是一种优良的环保型增塑剂，与目前常用的邻苯二甲酸二异辛酯（DOP）相比，具有耐热、耐寒、难挥发、抗抽出、柔软性和电绝缘性能好等优点，其增塑效率高，挥发性小，苯二甲酸二辛酯 用于涂料时，能提高涂料粘度、减少流动。
本发明所述的钛酸酯偶联剂TMC-101用于涂料中，可降低体系粘度，提高固体填充量； 可处理碳酸钙、滑石粉、等无机填料，以增加填料的疏水性、分散性；在涂料中加入钛酸酯偶联剂TMC-101可增大颜料填料量，使填料分散性能提高，具有防沉效果，可防发花，漆膜强度得到提高，色泽鲜艳，还具有催干特性，对烘漆还可以降低烘烤温度和缩短烘烤时间。
本发明所述的混合溶剂是木质素、丙二醇甲醚和水的混合物，木质素的官能团有酚式和羟基，在涂料中有良好的扩散性。丙二醇甲醚由于其分子结构中既有醚基又有羟基，因而它的溶解性能十分优异，作为溶剂、分散剂或稀释剂用于涂料、油墨、印染、农药、纤维素、丙烯酸酯等工业。也可用作燃料抗冻剂、清洗剂、萃取剂、有色金属选矿剂等。丙二醇甲醚在涂料制作过程中加入可以起到成膜助剂的作用。
本发明所述的一种聚氨酯外墙防腐阻燃涂料，该涂料可以在普通墙体、水工设备、气罐、石油精制设备、油管、油罐、输变电设备上的应用。
本发明的有益效果是：
1、本发明生产出来的一种聚氨酯外墙防腐阻燃涂料成膜物由于在聚氨酯预聚体中加入N-羟甲基丙烯酰胺、对苯二甲酸二辛酯、钛酸酯偶联剂TMC—101、分散剂聚丙烯酸铵盐DA40、金红石型二氧化钛和混合溶剂等材料以后，能够起到很好的化学交联作用，对聚氨酯涂料具有很好的改性作用， 使成膜物在常温下具有耐水、耐化学品、耐磨、收缩率小、粘接强度高的特点，而且延长涂料寿命。
2、加入的阻燃材料阻燃效果好，能够提高涂料的阻燃性能，使其在发生火灾时有效的抑制火势的蔓延，而且能使涂料膜的硬度、光泽和耐久性得以改善。加入的防腐剂2-甲基-4-异噻唑啉-3-酮或5-氯-2-甲基-4-异噻唑啉-3-酮，它们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。
3、本发明的聚氨酯外墙防腐阻燃涂料适用于普通墙体、水工设备、气罐、石油精制设备、油管、油罐、输变电设备上应用，而且涂料可根据装饰要求，进行色彩的挑选；用水作为溶剂，成本低，经济适用，施工简单。
具体实施方式
实施例1
首先按重量份数将聚氨酯预聚体45份、 N-羟甲基丙烯酰胺2份、对苯二甲酸二辛酯3份、钛酸酯偶联剂TMC-101 0.5份、分散剂聚丙烯酸铵盐DA40 0.3份、金红石型钛白粉15份、消泡剂聚氧丙烯甘油醚0.2份、硅石灰粉6份、混合溶剂（木质素+丙二醇甲醚+水，重量比例为2:1:9）12份、阻燃材料（季戊四醇和磷酸二甲苯酯按重量比例1:1配制）5份、防腐剂（2-甲基-4-异噻唑啉-3-酮 ） 3份、着色颜料钼铬红一份、流平剂丙烯酸酯2份，进行备料。
生产方法，按重量每公斤N-羟甲基丙烯酰胺加入1.8公斤的体积浓度70～85%的乙醇溶解，然后在反应釜中与聚氨酯预聚体混合，反应温度80℃，反应时间1.8小时后加入钛酸酯偶联剂TMC-101和分散剂聚丙烯酸铵盐DA40；继续反应3.5小时；然后加入对苯二甲酸二辛酯、金红石型钛白粉、聚氧丙烯甘油醚、阻燃材料、硅石灰粉、着色颜料钼铬红、流平剂丙烯酸酯、混合溶剂和防腐剂混合均匀即可得到红色聚氨酯外墙防腐阻燃涂料产品。
实施例2
首先按重量份数将聚氨酯预聚体50 份、 N-羟甲基丙烯酰胺3 份、对苯二甲酸二辛酯4 份、钛酸酯偶联剂TMC-101 0.7 份、分散剂聚丙烯酸铵盐DA40 0.5 份、金红石型钛白粉17 份、消泡剂聚氧丙烯甘油醚0.3 份、硅石灰粉8 份、混合溶剂（木质素+丙二醇甲醚+水，重量比例为2:1:9）14 份、阻燃材料（季戊四醇和三聚氰酰胺按重量比例1:1配制）8 份、防腐剂（5-氯-2-甲基-4-异噻唑啉-3-酮） 5 份、着色颜料甲苯胺红2份 、抗冻剂苯甲醇3份，进行备料。
生产方法，按重量每公斤N-羟甲基丙烯酰胺加入1.8公斤的体积浓度70～85%的乙醇溶解，然后在反应釜中与聚氨酯预聚体混合，反应温度120℃，反应时间1.5小时后加入钛酸酯偶联剂TMC-101和分散剂聚丙烯酸铵盐DA40；继续反应4.5小时；然后加入对苯二甲酸二辛酯、金红石型钛白粉、聚氧丙烯甘油醚、阻燃材料、硅石灰粉、着色颜料甲苯胺红 、抗冻剂苯甲醇 、混合溶剂和防腐剂，混合均匀即可得到红色聚氨酯外墙防腐阻燃涂料产品。
实施例3
首先按重量份数将聚氨酯预聚体55份、 N-羟甲基丙烯酰胺4份、对苯二甲酸二辛酯5份、钛酸酯偶联剂TMC-101 1.0份、分散剂聚丙烯酸铵盐DA400.6份、金红石型钛白粉 20份、消泡剂聚氧丙烯甘油醚0.5份、硅石灰粉 10份、混合溶剂（木质素+丙二醇甲醚+水，重量比例为2:1:9）15份、阻燃材料（磷酸二甲苯酯和三聚氰酰胺按重量比例1:1配制） 10份、防腐剂（5-氯-2-甲基-4-异噻唑啉-3-酮）7份、着色颜料 酞箐蓝B一份、 防沉剂有机膨润土5份，进行备料。
生产方法，按重量每公斤N-羟甲基丙烯酰胺加入1.8公斤的体积浓度70～85%的乙醇溶解，然后在反应釜中与聚氨酯预聚体混合，反应温度 130℃，反应时间1.3 小时后加入钛酸酯偶联剂TMC-101和分散剂聚丙烯酸铵盐DA40；继续反应 5.5小时；然后加入对苯二甲酸二辛酯、金红石型钛白粉、聚氧丙烯甘油醚、阻燃材料、硅石灰粉、着色颜料 酞箐蓝B、 防沉剂有机膨润土、混合溶剂和防腐剂，混合均匀即可得到蓝色聚氨酯外墙防腐阻燃涂料产品。
本发明的各项技术指标检测结果达到GB/T9757-2001和JG/T235-2008标准评定，为了便于参考，列于下表。
由上述检测结果可见，本发明各项指标均符合国家标准，适于工业大批量推广应用。
Claims (1)
1.一种聚氨酯外墙防腐阻燃涂料，其特征在于：制成该涂料包括以下重量份数的原料：
聚氨酯预聚体 45～55份；
N-羟甲基丙烯酰胺 2-4份；
对苯二甲酸二辛酯 3～5份；
钛酸酯偶联剂TMC-101 0.5～1.0份；
分散剂 0.3～0.6份；
钛白粉 15～20份；
消泡剂 0.2～0.5份；
硅石灰粉 6～10份；
混合溶剂 12～15份；
阻燃材料 5-10份；
防腐剂 3～7份；
所述的聚氨酯预聚体是带有NCO端基的预聚体，分子量在10000-4000之间；
所述的混合溶剂是木质素+丙二醇甲醚+水，重量比例为2:1:9；
所述的阻燃材料是季戊四醇、磷酸二甲苯酯、三聚氰酰胺中的两种或两种以上；
所述的分散剂是聚丙烯酸铵盐DA40；所述的消泡剂是聚氧丙烯甘油醚；所述的防腐剂为2-甲基-4-异噻唑啉-3-酮或5-氯-2-甲基-4-异噻唑啉-3-酮；所述的钛白粉为金红石型钛白粉；
所述的聚氨酯外墙防腐阻燃涂料，其制备方法包括以下步骤：
按重量每公斤N-羟甲基丙烯酰胺加入1.8公斤的体积浓度70～85%的乙醇溶解，然后在反应釜中与聚氨酯预聚体混合，反应温度80～130℃，反应时间1.3～1.8小时后加入钛酸酯偶联剂TMC-101和分散剂聚丙烯酸铵盐DA40；继续反应3.5～5.5小时；然后加入对苯二甲酸二辛酯、金红石型钛白粉、聚氧丙烯甘油醚、阻燃材料、硅石灰粉、混合溶剂和防腐剂，混合均匀即可得到聚氨酯外墙防腐阻燃涂料产品；
所述的聚氨酯外墙防腐阻燃涂料还包括：流平剂、抗冻剂和防沉剂中的一种或多种，重量份数为2～5；所述的流平剂是丙烯酸酯；所述的抗冻剂是苯甲醇；所述的防沉剂是有机膨润土；
所述的聚氨酯外墙防腐阻燃涂料，还进一步加入色料；
所述的聚氨酯外墙防腐阻燃涂料，该涂料在普通墙体、水工设备、气罐、石油精制设备、油管、油罐、输变电设备上的应用。
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