CN113045963B - 一种无溶剂酚醛环氧涂料 - Google Patents

一种无溶剂酚醛环氧涂料 Download PDF

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CN113045963B
CN113045963B CN201911380733.1A CN201911380733A CN113045963B CN 113045963 B CN113045963 B CN 113045963B CN 201911380733 A CN201911380733 A CN 201911380733A CN 113045963 B CN113045963 B CN 113045963B
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王菁
岳文华
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Avic Biam New Materials Technology Engineering Co ltd
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Abstract

本发明公开一种无溶剂酚醛环氧涂料,包括A组份和B组份,按重量份数计,所述A组分为:酚醛环氧树脂30%~50%,双酚A环氧树脂E51 15%~30%,填料30%~45%,助剂1~2%;所述B组分为:脂环胺固化剂60%~70%,反应型改性剂10%~20%,非活性增塑剂10%~20%,催化剂5%~10%;按质量比A组分:B组分=100:(18‑25)。本发明使用叔碳酸缩水甘油酯做改性剂对脂环胺固化剂进行改性,由于叔碳酸缩水甘油酯的位阻效应,减少了极性溶剂及化学物质对漆膜的渗透,使涂料具有更优异的耐化学性,可保证化纤酸碱储罐内壁长寿命使用。涂料既可以机械化喷涂,又可以手工涂覆,克服了以往采用衬胶硫化工艺复杂的缺点。

Description

一种无溶剂酚醛环氧涂料
技术领域
本发明涉及涂料领域,更具体地说,涉及一种应用于化纤酸碱储罐内防腐的无溶剂酚醛环氧涂料。
背景技术
化纤行业在粘胶、碱、工艺用水的贮存和输送系统及脱气罐中均为强碱强酸介质,目前多采用橡胶防腐衬里做内防腐。橡胶防腐衬里是在金属或其它材料工作表面,选用天然橡胶、氯丁橡胶和丁基橡胶等作为防腐材料,通过一系列工艺使之形成连续的隔离性的覆盖层。该技术广泛用于化纤厂的酸碱箱罐、管道等。具体施工工艺包括配制胶浆、涂刷胶浆、粘贴胶板和硫化。硫化工序可使胶料从塑性到高弹性,在硫化的过程中,胶料的定伸应力,弹性、硬度、抗溶胀性和化学稳定性会有明显的变化。
对于任何橡胶来说,橡胶分子链的交联和断链贯穿于整个硫化过程的始终,到了过硫阶段,如果交联仍占优势,则橡胶变硬,如果断链超过交联,则橡胶变软,影响粘结层的强度,导致衬胶层的脱开。若继续硫化达到过硫阶段,衬胶层往往发生“返原”现象,机械强度明显下降。因此,衬胶设备必须严格控制硫化条件,为了获得最佳的衬胶层质量,硫化条件需考虑到胶料种类,工作壁厚,衬贴方法、硫化方式及现场条件等因素,整个硫化工艺具有工艺复杂,效率低,合格率低的特点。
另外,在使用过程中衬里出现问题时,返修很困难,修补处的硫化也很困难。修补处的硫化只能采用局部烘烤硫化,在实际的操作中硫化温度和硫化时间都难以掌握,硫化温度过低或者硫化时间过短,会使胶板欠硫;如果硫化温度过高,或者硫化时间过长,都会导致胶板过硫,甚至导致胶板焦糊,这两种情况都会使衬里层耐腐蚀、耐老化和抗渗漏性能大大降低。此外,在配制胶浆时会使用到各类溶剂,不但危害工人的身体健康,而且不符合国家节能环保政策。
中国专利申请CN 109423167 A公开了一种无溶剂酚醛环氧涂料,包括酚醛环氧树脂、环氧活性稀释剂、固化剂、附着力促进剂、环氧促进剂、颜填料、助剂和溶剂,该涂料配方中仍然含有少量溶剂(4%-12%),不符合国家日益严格的环保要求。
发明内容
针对现有技术存在的不足,本发明的目的在于提供一种在较高的温度下具有优异的耐酸碱性能,既能采用双组份高压无气喷涂机械化施工,又可后期手工修补的无溶剂酚醛环氧涂料。
为实现上述第一个目的,本发明提供了如下技术方案:一种无溶剂酚醛环氧涂料,包括A组份和B组份,按重量份数计,
所述A组分为:酚醛环氧树脂30%~50%,双酚A环氧树脂E51 15%~30%,填料30%~45%,助剂1~2%;
所述B组分为:脂环胺固化剂60%~70%,反应型改性剂10%~20%,非活性增塑剂10%~20%,催化剂5%~10%;
按质量比A组分:B组分=100:(18-25);
所述助剂为防沉剂、消泡剂和流平剂中的一种或多种;
所述脂环胺固化剂为异佛尔酮二胺和4,4-二氨基二环己基甲烷中的一种或多种;
所述反应型改性剂为叔碳酸缩水甘油酯;
所述非活性增塑剂为邻苯二甲酸二丁酯和邻苯二甲酸二辛酯的一种或多种;
所述催化剂为水杨酸和叔胺促进剂中的一种或多种。
作为一个优选方案,所述酚醛环氧树脂包括F-44、F-48和F-51中的一种或多种。
作为一个优选方案,所述填料包括沉淀硫酸钡、滑石粉、石英粉和云母氧化铁中的一种或多种。
作为一个优选方案,所述消泡剂包括有机硅乳液消泡剂和矿物油消泡剂中的一种或多种。
作为一个优选方案,所述防沉剂包括有机膨润土类防沉剂、气相二氧化硅类防沉剂和聚酰胺蜡类防沉剂中的一种或多种。
作为一个优选方案,所述流平剂包括改性聚硅氧烷类流平剂和丙烯酸酯类流平剂中的一种或多种。
作为一个优选方案,所述B组分为异佛尔酮二胺60%~65%,叔碳酸缩水甘油酯10%~15%,邻苯二甲酸二丁酯和/或邻苯二甲酸二辛酯10%~20%,水杨酸5%~10%。
作为一个优选方案,所述B组分为4,4-二氨基二环己基甲烷65%~70%,叔碳酸缩水甘油酯10%~15%,邻苯二甲酸二丁酯和/或邻苯二甲酸二辛酯10%~20%,叔胺促进剂5%~10%。
酚醛环氧树脂(phenolic epoxy resin),又称F型环氧树脂,在酸性介质中苯酚与甲醛进行缩聚反应得到线型酚醛树脂,再与过量环氧丙烷在氢氧化钠存在下缩聚反应制得。其环氧基含量高,黏度较大,固化后产物交联密度高,其纤维增强塑料具有良好的物理机械性能。常用的有F-51,F-53,F-48,F-44,F-44-50,F-44-80,SMPN-638,SMPN-638S,本发明优选F-44、F-48和F-51中的一种或多种。
填料是一类在介质中以“填充”为主要作用的微细颗粒状物质,不溶于分散介质中,也称体质颜料。在涂料中使用的体质颜料主要品种有天然的碳酸钙、重晶石粉、石英粉、滑石粉、高岭土、云母粉、硅灰石、白云石、凹凸棒土(含水硅酸镁铝)以及人工合成的轻质碳酸钙、沉淀硫酸钡、合成硅酸钙、硅铝酸钠等品种。本发明优选沉淀硫酸钡、滑石粉、石英粉和云母氧化铁中的一种或多种。
异佛尔酮二胺CAS号:2855-13-2,分子式:C9H18N2O;4,4-二氨基二环己基甲烷CAS号:1761-71-3,分子式:C13H26N2;叔碳酸缩水甘油酯CAS号:26761-45-5,分子式:C13H24O3;水杨酸CAS号:69-72-7,分子式:C7H6O3;邻苯二甲酸二丁酯CAS号:84-74-2,分子式:C16H22O4;邻苯二甲酸二辛酯CAS号:117-81-7,分子式:C24H38O4。
叔胺促进剂能同时对环氧树脂和酸酐起双重的催化作用,一般包括三乙醇胺、二甲基苯胺、DMP-30等。
本发明具有以下有益效果:本发明A组分和B组分协同发生作用,使用叔碳酸缩水甘油酯做改性剂对脂环胺固化剂进行改性,由于叔碳酸缩水甘油酯的位阻效应,减少了极性溶剂及化学物质对漆膜的渗透,使涂料具有更优异的耐化学性,可保证化纤酸碱储罐内壁长寿命使用。涂料既可以机械化喷涂(双组份高压无气喷涂),又可以手工涂覆,克服了以往采用衬胶硫化工艺复杂的缺点。
具体实施方式
以下,结合具体实施方式对本发明的技术进行详细描述。应当知道的是,以下具体实施方式仅用于帮助本领域技术人员理解本发明,而非对本发明的限制。
A组份的制备方法为:将各组分加入不锈钢桶中,高速分散混合均匀,即得。
B组份的制备方法为:将各组分加入不锈钢桶中,搅拌加热至100℃保温2-4h,即得。
实施例1.
一种无溶剂酚醛环氧涂料,包括A组份和B组份,A组份按质量份数包括酚醛环氧树脂38份,双酚A环氧树脂E51 15份,云母氧化铁15份,滑石粉15份,石英粉15份,助剂2份,助剂为消泡剂和防沉剂。B组份为异佛尔酮二胺65份,叔碳酸缩水甘油酯12份,邻苯二甲酸二丁酯和邻苯二甲酸二辛酯各8份,水杨酸7份。A组份和B组份混合后即得所述的无溶剂酚醛环氧液体涂料。在施工时,A组份和B组份的用量比为质量比100:18。
实施例2.
一种无溶剂液体酚醛环氧涂料,包括A组份和B组份,A组份按质量份数包括酚醛环氧树脂30份,双酚A环氧树脂E51 30份,云母氧化铁10份,滑石粉18份,沉淀硫酸钡10份,助剂2份,助剂为消泡剂和防沉剂。B组份为异佛尔酮二胺60份,叔碳酸缩水甘油酯15份,邻苯二甲酸二丁酯15份,水杨酸10份。A组份和B组份混合后即得所述的无溶剂液体酚醛环氧涂料。在施工时,A组份和B组份的用量比为质量比为100:22。
实施例3.
一种无溶剂液体酚醛环氧涂料,包括A组份和B组份,A组份按质量份数包括酚醛环氧树脂50份,双酚A环氧树脂E51 18份,云母氧化铁15份,滑石粉10份,沉淀硫酸钡10份,助剂2份,助剂为消泡剂和流平剂。B组份为异佛尔酮二胺35份,4,4-二氨基二环己基甲烷35份,叔碳酸缩水甘油酯10份,邻苯二甲酸二丁酯15份,DMP30 5份,A组份和B组份混合后即得所述的无溶剂液体酚醛环氧涂料。在施工时,A组份和B组份的用量比为质量比100:25。
实施例4.
一种无溶剂液体酚醛环氧涂料,包括A组份和B组份,A组份按质量份数包括酚醛环氧树脂45份、双酚A环氧树脂E51 20份,沉淀硫酸钡14份,滑石粉10份,云母氧化铁10份,助剂1份,助剂为流平剂。B组份为4,4-二氨基二环己基甲烷68份,叔碳酸缩水甘油酯12份,邻苯二甲酸二辛酯15份,DMP30 5份。在施工时,A组份和B组份的用量比为质量比100:22。
对比例1:A组份同实施例1,B组份为嘉信115聚酰胺环氧固化剂。
对比例2:A组份同实施例2,B组份为庄维T-31环氧固化剂。
将实施例1-4的产品与对比例1-2进行性能测试,试验主要结果见下表:
Figure BDA0002342154750000041
Figure BDA0002342154750000051
从上表可以看出,本发明的无溶剂液体酚醛环氧涂料具有优异的耐温性能和耐介质性能。涂料不含溶剂,施工时不污染环境,不会引起中毒、火灾、爆炸等危险。涂层光亮致密无微孔,没有因溶剂挥发形成的腐蚀通道,所以防护性能好,使用寿命长,可应用于化纤厂酸碱储罐内壁防护。涂层表面光亮如镜,降低了粘胶在涂层表面的粘结现象,延长了刷洗周期,而且刷洗时比以前容易得多,大大减少了劳动强度,提高了工作效率。涂层耐酸碱性能优异,保护基材不被腐蚀,减少了由铁的硫化物而产生的胶体质点和由其引发的纤维素质点的缔合,提高了过滤性能。使用过程中需要对涂层修补时,只需对待修补处手工打磨除尘后,手工涂覆涂料,采用碘钨灯加温固化即可投入使用。与橡胶衬里相比,简化了维修流程,保证了维修质量。
以上所述仅是本发明的优选实施方式,应当指出,对于本技术领域的普通技术人员,在不脱离本发明原理的前提下,还可以做出若干改进和润饰,这些改进和润饰也应视为本发明的保护范围。

Claims (8)

1.一种无溶剂酚醛环氧涂料,其特征在于,包括A组份和B组份,按重量份数计,
所述A组分为:酚醛环氧树脂30%~50%,双酚A环氧树脂E51 15%~30%,填料30%~45%,助剂1~2%;
所述B组分为:脂环胺固化剂60%~70%,反应型改性剂10%~20%,非活性增塑剂10%~20%,催化剂5%~10%;
按质量比A组分:B组分=100:(18-25);
所述助剂为防沉剂、消泡剂和流平剂中的一种或多种;
所述脂环胺固化剂为异佛尔酮二胺和4,4-二氨基二环己基甲烷中的一种或多种;
所述反应型改性剂为叔碳酸缩水甘油酯;
所述非活性增塑剂为邻苯二甲酸二丁酯和邻苯二甲酸二辛酯的一种或多种;
所述催化剂为水杨酸和叔胺促进剂中的一种或多种;
其中所述B组份的制备方法为:将各组分加入不锈钢桶中,搅拌加热至100℃保温2-4h,即得。
2.根据权利要求1所述一种无溶剂酚醛环氧涂料,其特征在于,所述酚醛环氧树脂包括F-44、F-48和F-51中的一种或多种。
3.根据权利要求1所述一种无溶剂酚醛环氧涂料,其特征在于,所述填料包括沉淀硫酸钡、滑石粉、石英粉和云母氧化铁中的一种或多种。
4.根据权利要求1所述一种无溶剂酚醛环氧涂料,其特征在于,所述消泡剂包括有机硅乳液消泡剂和矿物油消泡剂中的一种或多种。
5.根据权利要求1所述一种无溶剂酚醛环氧涂料,其特征在于,所述防沉剂包括有机膨润土类防沉剂、气相二氧化硅类防沉剂和聚酰胺蜡类防沉剂中的一种或多种。
6.根据权利要求1所述一种无溶剂酚醛环氧涂料,其特征在于,所述流平剂包括改性聚硅氧烷类流平剂和丙烯酸酯类流平剂中的一种或多种。
7.根据权利要求1所述一种无溶剂酚醛环氧涂料,其特征在于,所述B组分为异佛尔酮二胺60%~65%,叔碳酸缩水甘油酯10%~15%,邻苯二甲酸二丁酯和/或邻苯二甲酸二辛酯10%~20%,水杨酸5%~10%。
8.根据权利要求1所述一种无溶剂酚醛环氧涂料,其特征在于,所述B组分为4,4-二氨基二环己基甲烷65%~70%,叔碳酸缩水甘油酯10%~15%,邻苯二甲酸二丁酯和/或邻苯二甲酸二辛酯10%~20%,叔胺促进剂5%~10%。
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