CN106243919B - 一种防腐性能优异的聚苯胺导静电涂料及其制备方法 - Google Patents
一种防腐性能优异的聚苯胺导静电涂料及其制备方法 Download PDFInfo
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Abstract
本发明涉及化工涂料技术领域,特别是指一种防腐性能优异的聚苯胺导静电涂料及其制备方法。该涂料由甲、乙两组分构成,其中甲组分由以下重量份配比的原料制得:双酚A环氧树脂19~30份,润湿分散剂0.2~0.8份,消泡剂0.2~0.5份,偶联剂0.5~2份,导静电聚苯胺4~10份,填料35~50份,溶剂15~30份;乙组分为异氰酸酯固化剂,占甲组分总质量的10%~20%。本发明通过添加高效润湿分散剂与环氧树脂以制备聚苯胺预分散体,采用异氰酸酯作为固化剂取代常规使用的环氧固化剂,从而使涂层具有优良的防腐性和持久的导静电性。
Description
技术领域
本发明实施例涉及化学工业领域中的涂料行业,特别涉及一种防腐性能优异的聚苯胺导静电涂料及其制备方法。
背景技术
导静电涂料是伴随现代科技而迅速发展起来的具有传导静电流和消除积累电荷能力的功能性涂料,应用于电子、电器、航空、石化等众多领域,特别是在石油化工行业。传统的导静电涂料均为添加型,将导静电介质添加到主要成膜物质中,均匀分散形成连续的导静电网,电荷在导静电网中游走,发挥消除静电的作用。导静电介质有如炭黑、金属颗粒、导静电云母粉等。炭黑价格低廉,但其制备的涂料色泽深,易渗出而污染油品;金属颗粒易氧化而逐渐失去导静电性能;导静电云母粉虽具有色泽浅的优点,但是也会存在渗出污染油品的缺点。
聚苯胺是有机导静电聚合物,具有优良的导静电性能,其掺杂态电导率更是可与金属媲美;掺杂态聚苯胺不仅具有优异的导静电性能,而且兼具防腐性能,正符合石油储罐涂料的使用需求,但是聚苯胺的溶解性能一直是一个攻而未破的技术难点,目前国内外的聚苯胺导静电涂料多为掺杂态聚苯胺,聚苯胺防腐涂料多为不导静电本征态聚苯胺,都是以填料形式加入到主要成膜物质中,分散性的优异是考验涂层导静电、防腐性能的关键。
文献报道:聚苯胺防腐蚀涂料的研制及其性能[J].材料保护,2009,(第2期),介绍添加5%本征态聚苯胺时,制备的聚苯胺防腐涂层防腐性能最佳。聚苯胺涂料耐盐雾研究[J].涂料工业,2008,(第9期)介绍了聚苯胺涂料在耐腐蚀方面的特性,讨论了聚苯胺添加量、添加工艺、涂层厚度、配套涂层等对其防腐蚀性的影响。以上报道所采用导静电材料是以不导静电本征态聚苯胺为主。
国内对于聚苯胺涂料的研究多数以环氧树脂为主要成膜物质,固化剂为各种胺类。文献报道:掺杂型聚苯胺导静电涂料的研究[J].电镀与精饰,2010,(第3期),介绍了环氧树脂为成膜物质,掺杂型聚苯胺为导静电填料,固化剂采用聚酰胺类固化剂。专利(申请号:CN201210480052.4)研发无溶剂防静电抗菌环氧自流平地坪涂料,导静电填料选用氧化锌晶须或掺杂聚苯胺,而固化剂采用改性脂环族胺化物。专利(申请号:CN201110199612.4,CN201210261084.5)制备无溶剂聚苯胺导静电涂料,环氧树脂为主要成膜物质,固化剂均为改性酚醛胺类。
多元胺类固化剂是生产和科研中环氧涂料最常见的固化剂,但是胺类显碱性,而掺杂态聚苯胺显酸性,两组分混合后发生中和作用,使聚苯胺脱杂,从而涂层的导静电性能随着固化过程逐渐消失。因此选择一种合适的固化剂对于保持聚苯胺持久的导静电性能和良好的防腐性能至关重要。另外,导静电聚苯胺由于具有较大的比表面积,在加工搅拌过程中很难分散均匀,且易重新团聚。
发明内容
为解决以上问题,本发明提供一种防腐性能优异的聚苯胺导静电涂料及其制备方法,反腐性能好,导静电能力强。
本发明提供一种防腐性能优异的聚苯胺导静电涂料,包括甲组分和乙组分,其中甲组分主要由以下重量份配比的原料制得:
乙组分为异氰酸酯固化剂,占甲组分总质量的10%~20%。
进一步地,甲组分由以下按照重量份的原料组成:双酚A环氧树脂19~24份,润湿分散剂0.5~0.8份,消泡剂0.4~0.5份,偶联剂0.5~1.5份,导静电聚苯胺4~7份,填料47~48.5份,溶剂21~27份。
具体地,所述甲乙组分在使用时质量比为8:1。
优选地,所述的双酚A环氧树脂为E12型和E20型中的一种或两种混合,环氧当量为455~1110。
优选地,所述的润湿分散剂选自高分子有机共聚物磷酸酯盐、丙烯酸嵌段共聚物和聚酯改性共聚物中的至少一种。
进一步地,所述的偶联剂选自γ-氨丙基三乙氧基硅烷、γ-(2,3-环氧丙氧基)丙基三甲氧基硅烷和γ-甲基丙烯酸丙酯基三甲氧基硅烷中的至少一种。
进一步地,所述的消泡剂为破泡聚合物溶液,含有机硅;所述的溶剂包括二甲苯、醋酸丁酯、丙二醇甲醚醋酸酯,三者之间的质量份比例为2:1:1;所述填料包括钛白粉、硫酸钡粉、滑石粉,三者之间的质量份比例为1:2:3。
进一步地,所述的导静电聚苯胺为有机酸掺杂聚苯胺。
进一步地,所述氰酸酯类固化剂,其NCO含量为16.5%~19.6%,当量为215~250,采用该异氰酸酯类固化剂与环氧树脂进行固化,固化剂中的NCO与环氧树脂中含有的OH基团发生交联反应,形成互穿聚合网络,有利于漆膜的耐候性能。
本发明还提供一种防腐性能优异的聚苯胺导静电涂料的制备方法,聚苯胺导静电涂料包括甲组分和乙组分,乙组分为异氰酸酯固化剂,其中甲组分制备方法包括:
将导静电聚苯胺、部分溶剂和部分双酚A环氧树脂混合加入润湿分散剂,以1500rpm转速分散45min,形成均匀的预分散体;
将剩余的双酚A环氧树脂、消泡剂和偶联剂混合,以1500rpm转速分散搅拌10min,形成混合物;
将填料和预分散体加入到混合物中,以2000rpm转速分散2h;
加入剩余的溶剂,以1000rpm转速分散5~10min,用100目的滤网过滤即得到甲组分。
由于导静电聚苯胺是纳米结构,由于具有较大的比表面积,在常规的加工搅拌过程中很难分散均匀,且易重新团聚。而上述甲组分的制备方法通过将多级搅拌,使得搅拌的更充分,且通过添加高效润湿分散剂与环氧树脂制备聚苯胺预分散体,再与环氧树脂混合物搅拌,借助高速剪切力,使其在树脂基体中均匀分散,减少了聚苯胺重新团聚的现象,这有利于导静电聚苯胺形成连续的导静电网。
湿润分散剂可有效降低粘度,改进流平,有助于通过空间位阻效应帮助填料解絮凝。可选自DISPERBYK-110、DISPERBYK-161、BYK-220S、DISPERBYK-145、DISPERBYK-2050、BYK-3550、EFKA-4310、EFKA-5010、EFKA-5044、EFKA-5065中的一种或多种。
具体在使用本发明涂料时,甲乙组分按照质量比8:1进行配比,混合均匀后即可涂装使用。
本发明将掺杂态聚苯胺预分散成分散性能优良的浆料来制备防腐性能优异的聚苯胺导静电涂料。掺杂态聚苯胺不仅具有优异的导静电性能,而且兼具防腐性。
通过添加高效润湿分散剂与环氧树脂制备聚苯胺预分散体,再与环氧树脂混合物搅拌,借助高速剪切力,使其在树脂基体中均匀分散,减少了聚苯胺重新团聚的现象,这有利于导静电聚苯胺形成连续的导静电网,对于涂料导静电性能的持久性和防腐性有重大的意义。
采用该异氰酸酯类固化剂与双酚A环氧树脂进行反应固化,固化剂中NCO与环氧树脂中含有的OH基团交联反应,形成互穿聚合网络,有利于漆膜的耐候性能。
本发明提供的防腐性能优异的聚苯胺导静电涂料采用异氰酸酯固化剂,取代环氧涂料的传统固化剂,既保证了聚苯胺的防腐性能,又保证了其导静电性,涂层表面电阻率控制在108Ω~1011Ω,符合GB13348-2009《液体石油产品静电安全规程》。
具体实施方式
为使本发明实施例的目的、技术方案和优点更加清楚,下面将对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
本发明提供的实施例见表1:
表1
实施例1:
甲组分制备方法:将导静电聚苯胺4份、溶剂18份和双酚A环氧树脂9.5份混合加入润湿分散剂0.5份,以1500rpm转速分散45min,形成均匀的预分散体;将双酚A环氧树脂9.5份、消泡剂0.5份和偶联剂1份,以1500rpm转速分散搅拌10min,形成混合物;将填料48份和预分散体加入到混合物中,以2000rpm转速分散2h;加入溶剂9份,以1000rpm转速分散5~10min,用100目的滤网过滤即得到甲组分;
乙组分:异氰酸酯15份;
在使用本发明涂料时,甲乙组分按照质量比8:1进行配比,混合均匀后即可涂装使用。
实施例2:
甲组分制备方法:将导静电聚苯胺5份、溶剂14份和双酚A环氧树脂12份混合加入润湿分散剂0.8份,以1500rpm转速分散45min,形成均匀的预分散体;将双酚A环氧树脂12份、消泡剂0.5份和偶联剂1.5份,以1500rpm转速分散搅拌10min,形成混合物;将填料47份和预分散体加入到混合物中,以2000rpm转速分散2h;加入溶剂7份,以1000rpm转速分散5~10min,用100目的滤网过滤即得到甲组分;
乙组分:异氰酸酯12份;
在使用本发明涂料时,甲乙组分按照质量比8:1进行配比,混合均匀后即可涂装使用。
实施例3:
甲组分制备方法:将导静电聚苯胺7份、溶剂14份和双酚A环氧树脂11份混合加入润湿分散剂0.6份,以1500rpm转速分散45min,形成均匀的预分散体;将双酚A环氧树脂11份、消泡剂0.4份和偶联剂0.5份,以1500rpm转速分散搅拌10min,形成混合物;将填料48.5份和预分散体加入到混合物中,以2000rpm转速分散2h;加入溶剂7份,以1000rpm转速分散5~10min,用100目的滤网过滤即得到甲组分;
乙组分:异氰酸酯15份;
在使用本发明涂料时,甲乙组分按照质量比8:1进行配比,混合均匀后即可涂装使用。
申请人对上述三个实施例所制得的防腐性能优异的聚苯胺导静电涂料进行性能测试,表2是防腐性能优异的聚苯胺导静电涂料的主要性能检验指标。
表2
申请人对上述三个实施例所制得的防腐性能优异的聚苯胺导静电涂料、以及现有的导静电涂料的对比样本A(含有导静电云母粉)和对比样本B,按照表2的检验标准进行测试,测试对比结果如表3所示:
表3
从表3可以看出,本发明提供的防腐性能优异的聚苯胺导静电涂料对比现有的产品,在防腐蚀性和导静电性能上均有很大的提高,尤其是在耐盐雾性方面,本发明提供的涂料在3000h测试时间内均达到不起泡,不脱落,无锈蚀的性能指标,而测试的对比样本只能实现在1000h测试时间内达到不起泡,不脱落,无锈蚀的性能指标,超过1000h后就会出现起泡,脱落,锈蚀等问题;而在耐酸性方面,本发明提供的涂料在720h内漆膜保持完好,而对比样本测试情况最好的也只有600h。
最后应说明的是:以上各实施例仅用以说明本发明的技术方案,而非对其限制;尽管参照前述各实施例对本发明进行了详细的说明,本领域的普通技术人员应当理解:其依然可以对前述各实施例所记载的技术方案进行修改,或者对其中部分或者全部技术特征进行等同替换;而这些修改或者替换,并不使相应技术方案的本质脱离本发明各实施例技术方案的范围。
Claims (8)
1.一种防腐性能优异的聚苯胺导静电涂料,其特征在于,包括甲组分和乙组分,其中甲组分由以下重量份配比的原料制得:
乙组分为异氰酸酯固化剂,占甲组分总质量的10%~20%;
所述的润湿分散剂选自高分子有机共聚物磷酸酯盐、丙烯酸嵌段共聚物和聚酯改性共聚物中的至少一种;
所述的导静电聚苯胺为有机酸掺杂聚苯胺。
2.根据权利要求1所述的一种防腐性能优异的聚苯胺导静电涂料,其特征在于,甲组分由以下按照重量份的原料组成:双酚A环氧树脂19~24份,润湿分散剂0.5~0.8份,消泡剂0.4~0.5份,偶联剂0.5~1.5份,导静电聚苯胺4~7份,填料47~48.5份,溶剂21~27份。
3.根据权利要求1或2中所述的一种防腐性能优异的聚苯胺导静电涂料,其特征在于:所述甲乙组分在使用时质量比为8:1。
4.根据权利要求1或2中所述的一种防腐性能优异的聚苯胺导静电涂料,其特征在于:所述的双酚A环氧树脂为E12型和E20型中的一种或两种混合。
5.根据权利要求1或2中所述的一种防腐性能优异的聚苯胺导静电涂料,其特征在于:所述的偶联剂选自γ-氨丙基三乙氧基硅烷、γ-(2,3-环氧丙氧基)丙基三甲氧基硅烷和γ-甲基丙烯酸丙酯基三甲氧基硅烷中的至少一种。
6.根据权利要求1或2中所述的一种防腐性能优异的聚苯胺导静电涂料,其特征在于:所述的消泡剂为破泡聚合物溶液,含有机硅;所述的溶剂包括二甲苯、醋酸丁酯、丙二醇甲醚醋酸酯,三者之间的质量份比例为2:1:1;所述填料包括钛白粉、硫酸钡粉、滑石粉,三者之间的质量份比例为1:2:3。
7.根据权利要求1或2中所述的一种防腐性能优异的聚苯胺导静电涂料,其特征在于:所述异氰酸酯固化剂的NCO含量为16.5%~19.6%。
8.一种如权利要求1所述的防腐性能优异的聚苯胺导静电涂料的制备
方法,其特征在于,聚苯胺导静电涂料包括甲组分和乙组分,乙组分为异氰酸酯固化剂,其中甲组分制备方法包括:
将导静电聚苯胺、部分溶剂和部分双酚A环氧树脂混合加入润湿分散剂,以1500rpm转速分散45min,形成均匀的预分散体;
将剩余的双酚A环氧树脂、消泡剂和偶联剂混合,以1500rpm转速分散搅拌10min,形成混合物;
将填料和预分散体加入到混合物中,以2000rpm转速分散2h;
加入剩余的溶剂,以1000rpm转速分散5~10min,用100目的滤网过滤即得到甲组分。
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