CN113549387A - 一种改性环氧树脂涂料及其制备方法 - Google Patents
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Abstract
本发明公开了一种改性环氧树脂涂料及其制备防腐,改性环氧树脂涂料包括以下重量份的组分:环氧树脂20‑100份,固化剂10‑100份,三元纳米复合填料1‑10份,溶剂10‑50份,分散剂0.2‑1份,流平剂0.1‑0.5份,消泡剂0.2‑1份,防沉剂0.1‑1份,硅烷偶联剂0.1‑1份。本发明是利用将氧化石墨烯特殊的片层结构和优异的导电性能,聚苯胺的缓释屏蔽作用,纳米二氧化钛粒子的填补作用结合的功能性纳米复合粒子来改性环氧树脂的防腐效率,其耐腐蚀性能优异,且其稳定性好、成本低、制备工艺简单易行。
Description
技术领域
本发明涉及一种改性环氧树脂涂料及其制备方法,属于环氧树脂防腐技术领域。
背景技术
金属腐蚀问题广泛存在于国民经济发展的各个领域,造成了重大的经济损失,严重浪费生产资源。目前比较成熟的防腐蚀技术如,防护涂层、缓蚀剂、牺牲阳极阴极保护法和外加电流阴极保护法。防护涂层保护法因为其最经济,方便,有效等优点,是目前应用最广泛的防腐蚀技术。
环氧树脂为成膜基体的防腐涂层具有附着力强、污染低、耐腐蚀性强、经济易制得等特点,但是当环氧树脂这类高聚物做防腐涂料时容易产生孔洞,造成一定的渗透性,容易使腐蚀介质(水,氧气,cl-)渗透到金属表面,从而加速金属的腐蚀速率。
发明内容
基于上述,本发明提供一种改性环氧树脂涂料及其制备方法,以解决现有环氧树脂作为防腐涂料时存在的易产生孔洞,从而使腐蚀介质易渗透到金属表面加速腐蚀速率的技术问题。
本发明的技术方案是:一种改性环氧树脂涂料,包括以下重量份的组分:
环氧树脂20-100份,固化剂10-100份,三元纳米复合填料1-10份,溶剂10-50份,分散剂0.2-1份,流平剂0.1-0.5份,消泡剂0.2-1份,防沉剂0.1-1份,硅烷偶联剂0.1-1份。
可选的,所述改性环氧树脂涂料,包括以下重量份的组分:
环氧树脂40份,固化剂30份,三元纳米复合填料4份,溶剂20份,分散剂0.3份,流平剂0.2份,消泡剂0.3份,防沉剂0.2份,硅烷偶联剂0.2份。
可选的,所述环氧树脂为双酚A型环氧树脂、双酚F型环氧树脂、多酚型缩水甘油醚环氧树脂中的一种或者多种混合。
可选的,所述固化剂为胺类固化剂、酚类固化剂、酚醛类固化剂中的一种或者多种混合。
可选的,所述三元纳米复合填料的制备方法是:以苯胺为单体,掺杂氧化石墨烯和二氧化钛,通过氧化聚合制备得到。
可选的,按重量份计,所述苯胺为1-3份,所述氧化石墨烯为0.1-0.6份,所述二氧化钛为1-6份。
可选的,所述溶剂为二甲苯、正丁醇、丙酮中的一种或多种混合。
本发明还提供一种所述的改性环氧树脂涂料的制备方法,所述制备方法包括以下步骤:
1)制备涂料A组分
按配方,称取溶剂、分散剂、流平剂、消泡剂、防沉剂、硅烷偶联剂于反应容器中,混合均匀;
称取环氧树脂加入上述混合体系中,并搅拌分散均匀;
称取三元复合纳米复合填料加入上述混合体系中,并搅拌使其分散均匀,即得涂料A组分;
2)制备改性环氧树脂涂料
将固化剂作为涂料B组分加入到涂料A组分中,混合均匀,即得改性环氧树脂涂料。
本发明的有益效果是:本涂料是利用将氧化石墨烯特殊的片层结构和优异的导电性能,聚苯胺的缓释屏蔽作用,纳米二氧化钛粒子的填补作用结合的功能性纳米复合粒子来改性环氧树脂的防腐效率,其耐腐蚀性能优异,且其稳定性好、成本低、制备工艺简单易行。
附图说明
图1为本发明涂层防腐效果图;
图2为无添加剂环氧树脂涂层防腐效果图。
具体实施方式
为使本发明的上述目的、特征和优点能够更加明显易懂,下面结合附图对本发明的具体实施方式做详细的说明。在下面的描述中阐述了很多具体细节以便于充分理解本发明。但是本发明能够以很多不同于在此描述的其它方式来实施,本领域技术人员可以在不违背本发明内涵的情况下做类似改进,因此本发明不受下面公开的具体实施的限制。
除非另有定义,本文所使用的所有的技术和科学术语与属于本发明的技术领域的技术人员通常理解的含义相同。本文中在本发明的说明书中所使用的术语只是为了描述具体的实施例的目的,不是旨在于限制本发明。本文所使用的术语“及/或”包括一个或多个相关的所列项目的任意的和所有的组合。
实施例1
1)制备三元纳米复合填料
以石墨为原料,通过改性Hummers法制备氧化石墨烯;以1g苯胺为单体,掺杂0.1g氧化石墨烯和1g二氧化钛,通过氧化聚合制备三元纳米复合填料。
2)制备涂料A组分
称取溶剂10g、分散剂0.2g、流平剂0.1g、消泡剂0.2g、防沉剂0.1g、硅烷偶联剂0.1g于反应容器中,混合均匀;
在上述混合体系中加入环氧树脂加入20g,搅拌30min,分散均匀;
在以中低速搅拌上述混合体系的同时,加入三元纳米复合填料1g,填料粒子加入完成后继续搅拌30min,使其分散均匀后制得涂料A组份。
2)制备改性环氧树脂涂料
将10g固化剂作为涂料B组分加入到涂料A组分中,混合均匀,即得改性环氧树脂涂料。
实施例2
1)制备三元纳米复合填料
以石墨为原料,通过改性Hummers法制备氧化石墨烯;以2g苯胺为单体,掺杂0.2g氧化石墨烯和3g二氧化钛,通过氧化聚合制备三元纳米复合填料。
2)制备涂料A组分
称取溶剂20g、分散剂0.3g、流平剂0.2g、消泡剂0.3g、防沉剂0.2g、硅烷偶联剂0.2g于反应容器中,混合均匀;
在上述混合体系中加入环氧树脂加入40g,搅拌40min,分散均匀;
在以中低速搅拌上述混合体系的同时,加入三元纳米复合填料4g,填料粒子加入完成后继续搅拌40min,使其分散均匀后制得涂料A组份。
2)制备改性环氧树脂涂料
将30g固化剂作为涂料B组分加入到涂料A组分中,混合均匀,即得改性环氧树脂涂料。
实施例3
1)制备三元纳米复合填料
以石墨为原料,通过改性Hummers法制备氧化石墨烯;以3g苯胺为单体,掺杂0.6g氧化石墨烯和6g二氧化钛,通过氧化聚合制备三元纳米复合填料。
2)制备涂料A组分
称取溶剂50g、分散剂1g、流平剂0.5g、消泡剂1g、防沉剂1g、硅烷偶联剂1g于反应容器中,混合均匀;
在上述混合体系中加入环氧树脂加入100g,搅拌60min,分散均匀;
在以中低速搅拌上述混合体系的同时,加入三元纳米复合填料10g,填料粒子加入完成后继续搅拌60min,使其分散均匀后制得涂料A组份。
2)制备改性环氧树脂涂料
将100g固化剂作为涂料B组分加入到涂料A组分中,混合均匀,即得改性环氧树脂涂料。
本发明实施例中,环氧树脂选用双酚A型环氧树脂,溶剂选用二甲苯,固化剂选用乙二胺,分散剂、流平剂选用、消泡剂、防沉剂和硅烷偶联剂均选用常规剂型。
本发明中三元纳米复合填料的制备方法为:先取氧化石墨烯与稀盐酸(浓度6mol/L)溶液混合,经分散处理后成均匀的氧化石墨烯分散液,再将其移入到容器中,0℃下搅拌;然后取二氧化钛,加入到上述反应体系中,0℃下搅拌,使其与氧化石墨烯分散液混合均匀;再取苯胺,加入到上述反应体系中,0℃下搅拌,使其与氧化石墨烯/二氧化钛分散液混合均匀;再将过硫酸铵溶解于稀盐酸(浓度6mol/L)中,使其充分溶解后缓慢滴加至上述溶液中,在0℃下反应;反应结束后,将产物用乙醇、水洗涤,最后经60℃干燥、研磨,制得三元纳米复合材料。
防腐性能测试:
在Q235A表面分别涂覆本发明实施例1至3的改性环氧树脂涂料,在Q235A表面涂覆纯EP(环氧树脂)作为对照,使用上海晨华公司的CHI760E电化学工作站对制得的样品的光电化学性能进行表征。电化学分析仪为三电极系统,将饱和甘汞用作参比电极,将铂片用作对电极,将自制的Q235碳钢电极用作工作电极,使用3.5%NaCl作为电解质。测试前把Q235碳钢电极放在3.5%NaCl溶液中浸泡2小时,使开路电压达到稳定后再开始测试。在10-2-105Hz范围内,以0.05V的振幅在开路电压下测试交流阻抗;在开路电压上下500mv的范围内,以10mv/s的扫描速度进行极化测试。
表1纯EP涂层与本发明复合涂层的电化学极化测试结果
表1表明,本发明制备的改性环氧树脂涂料涂层后腐蚀电位从-0.743V提升至-0.059V,腐蚀电流从3.542×10-5A/cm2减少至8.073×10-7A/cm2,表面电阻从956.8ohms/cm2升至44715.8ohms/cm2,使得防腐效能提高至97.86%。
在一段时间后,观察实施例1与涂覆环氧树脂的涂层效果,图1为本发明涂层防腐效果图,图2为无添加剂环氧树脂涂层防腐效果图,可见,图2中的涂层在一段时间后产生了大量的孔洞,导致防腐效果较差,而本申请的防腐涂层较为致密,未产生孔洞,可见本发明可以解决现有环氧树脂作为防腐涂料时存在的易产生孔洞,从而使腐蚀介质易渗透到金属表面加速腐蚀速率的技术问题。
以上所述实施例仅表达了本发明的几种实施方式,其描述较为具体和详细,但并不能因此而理解为对本发明专利范围的限制。应当指出的是,对于本领域的普通技术人员来说,在不脱离本发明构思的前提下,还可以做出若干变形和改进,这些都属于本发明的保护范围。因此,本发明专利的保护范围应以所附权利要求为准。
Claims (8)
1.一种改性环氧树脂涂料,其特征在于,包括以下重量份的组分:
环氧树脂20-100份,固化剂10-100份,三元纳米复合填料1-10份,溶剂10-50份,分散剂0.2-1份,流平剂0.1-0.5份,消泡剂0.2-1份,防沉剂0.1-1份,硅烷偶联剂0.1-1份。
2.根据权利要求1所述的改性环氧树脂涂料,其特征在于,包括以下重量份的组分:
环氧树脂40份,固化剂30份,三元纳米复合填料4份,溶剂20份,分散剂0.3份,流平剂0.2份,消泡剂0.3份,防沉剂0.2份,硅烷偶联剂0.2份。
3.根据权利要求1所述的改性环氧树脂涂料,其特征在于,所述环氧树脂为双酚A型环氧树脂、双酚F型环氧树脂、多酚型缩水甘油醚环氧树脂中的一种或者多种混合。
4.根据权利要求1所述的改性环氧树脂涂料,其特征在于,所述固化剂为胺类固化剂、酚类固化剂、酚醛类固化剂中的一种或者多种混合。
5.根据权利要求1所述的改性环氧树脂涂料,其特征在于,所述三元纳米复合填料的制备方法是:以苯胺为单体,掺杂氧化石墨烯和二氧化钛,通过氧化聚合制备得到。
6.根据权利要求5所述的改性环氧树脂涂料,其特征在于,按重量份计,所述苯胺为1-3份,所述氧化石墨烯为0.1-0.6份,所述二氧化钛为1-6份。
7.根据权利要求1所述的改性环氧树脂涂料,其特征在于,所述溶剂为二甲苯、正丁醇、丙酮中的一种或多种混合。
8.如权利要求1至7任一项所述的改性环氧树脂涂料的制备方法,其特征在于,所述制备方法包括以下步骤:
1)制备涂料A组分
按配方,称取溶剂、分散剂、流平剂、消泡剂、防沉剂、硅烷偶联剂于反应容器中,混合均匀;
称取环氧树脂加入上述混合体系中,并搅拌分散均匀;
称取三元复合纳米复合填料加入上述混合体系中,并搅拌使其分散均匀,即得涂料A组分;
2)制备改性环氧树脂涂料
将固化剂作为涂料B组分加入到涂料A组分中,混合均匀,即得改性环氧树脂涂料。
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