CN116120764A - 一种氨基改性石墨烯及其制备方法和应用 - Google Patents
一种氨基改性石墨烯及其制备方法和应用 Download PDFInfo
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Abstract
本发明公开了一种氨基改性石墨烯及其制备方法和应用,本发明利用光气对石墨烯进行氨基化改性,能够促进氨基在石墨烯表面生长,氨基化改性效果显著,有利益改性后的石墨烯与含有反应性基团的树脂等有机化合物结合。本发明中将氨基改性石墨烯与含羟基的氟树脂进行结合,得到有机氟‑石墨烯杂化树脂,该树脂同时具有石墨烯特殊结构和氟树脂优异的疏水性能的优点,是一种优良的疏水防腐涂料制备原料。本发明中的疏水防腐涂料中的面漆以有机氟‑石墨烯杂化树脂为主要成分,涂料的防腐性能和疏水性能均得到显著提升。
Description
技术领域
本发明属于涂料技术领域,具体涉及一种氨基改性石墨烯及其制备方法和应用。
背景技术
超疏水材料是指与水滴接触角大于150°,滚动角小于10°的材料,由于其超疏水性展示出很多独特有益的性能,比如自清洁性,防腐防污,防雾,防水,自清洁的功能,因此在日常生活领域和工业领域具有非常广阔的应用前景。比如在织物,建筑物,电器,玻璃制品,天线等领域具有重大的应用潜力。
超疏水材料在业界被广泛关注,报道的各种材料、制备方法很多,但对于最终的工业应用还有三个关键问题困扰。一是产品复杂的微纳材料的制备过程限制了其生产放大;二是构筑表面与基材的结合性和一定的耐用性;三是制备成本高昂限制了实际应用。把超疏水材料引入日常生活领域更是一个巨大的难题。
石墨烯具有优异的理化性能,其片层结构层层叠加、交错排列,在涂层中可形成“迷宫式”屏蔽结构,能够有效抑制腐蚀介质的浸润、渗透和扩散,提高涂层的物理阻隔性。同时,由于其小尺寸效应,石墨烯可以填充到涂层的缺陷当中,减少涂层孔隙率,增强涂层致密性,进一步延缓或阻止腐蚀因子浸入到基体表面。所以,使用石墨烯来制备高与超高性能重防腐涂料是工业界的发展趋势。
当今主流的制备石墨烯防腐涂料的方法,重点在研究石墨烯粉末在涂料体系与树脂、颜填料的分散工艺。涂料用树脂、颜料、填料等基本沿用原有的经典体系,如环氧树脂、聚氨酯树脂、氟碳树脂。有研究人员将石墨烯用硅氧烷修饰后获得了与环氧树脂良好的相容性;还有研究人员将改性石墨烯加入聚氨酯树脂制备了石墨烯聚氨酯防腐涂料。以上方法通过石墨烯的表面改性,优化分散工艺,制备性能良好的石墨烯防腐涂料。
但是以上制备方法仍然存在较大的局限性,对于更加严苛的环境不能胜任,如山区复杂多变的潮湿和易结露环境、海洋微生物对港口设施以及船舶的腐蚀、寒潮天气下涂层的冰冻破坏、严重酸雨的侵蚀等,在此环境下的钢结构工程、车辆等的保护年限被大大缩短。
发明内容
针对上述现有技术,本发明提供一种氨基改性石墨烯及其制备方法和应用,以解决现有技术中涂料的疏水性能和防腐性能差的问题。
为了达到上述目的,本发明所采用的技术方案是,提供一种氨基改性石墨烯,该氨基改性石墨烯经过以下步骤制得:
S1:将石墨烯和胺类化合物的混合物分散于有机溶剂中,以60~80m/min的研磨速度研磨30~45min,得浆料;
S2:将浆料导入3~5MPa的光气氛围中,于30~50℃的条件下反应20~25h,再过滤、洗涤、干燥,即得氨基改性石墨烯;光气的通入速率为2~5L/min。
本发明采取上述技术方案的有益效果是:本发明对石墨烯进行氨基化改性,可以在石墨烯的片层之间引入氨基,使改性后的石墨烯能够与含有反应性基团的树脂等有机化合物进行反应,在分子层面实现键合,可以将石墨烯牢固的结合到树脂等有机物中,石墨烯自身优良的物理和化学特性也被引入到树脂等有机材料中,从而改善树脂等有机材料的性能。
本发明石墨烯的氨基化改性过程中鼓泡通入光气,光气为活泼性很高的亲电试剂,而胺类化合物的N上含有孤对电子,在光气的进攻下,N从胺类化合物上脱落并形成具有较高反应活性的游离基团;同时,光气可以进攻石墨烯表面的碳碳双键,从而改变石墨烯的表面性能,使石墨烯具有更高的活性,游离的氨基更容易接枝到石墨烯表面,石墨烯的氨基化改性更加彻底。
在上述技术方案的基础上,本发明还可以做如下改进。
进一步,石墨烯与胺类化合物的质量之比为1:2~5;两者的混合物与有机溶剂的料液比为1g:6~10mL。
进一步,胺类化合物为芳香胺或脂肪胺;有机溶剂为甲苯或二甲苯。
进一步,芳香胺为N,N-二甲基苯胺、对苯二胺或二氨基二苯基甲烷;脂肪胺为十二胺、十六胺或十八胺。
进一步,S2中反应在4MPa、40℃的条件下进行,反应时间为24h。
本发明还提供了氨基改性石墨烯在制备有机氟-石墨烯杂化树脂中的应用。
有机氟-石墨烯杂化树脂的制备方法具体包括以下步骤:
将氨基改性石墨烯、含羟基的氟树脂、异氰酸酯和金属催化剂按1~3:2~4:3~6:0.05~0.2的质量比共溶于有机溶剂中,于60~80℃下反应2~5h,即得。
其中,含羟基的氟树脂为FEVE氟树脂;有机溶剂为甲苯或二甲苯;金属催化剂为二月桂酸二丁基锡或辛酸亚锡;异氰酸酯为甲苯二异氰酸酯(TDI)、异佛尔酮二异氰酸酯(IPDI)、二苯基甲烷二异氰酸酯(MDI)、二环己基甲烷二异氰酸酯(HMDI)、六亚甲基二异氰酸酯(HDI)和赖氨酸二异氰酸酯(LDI)中的至少一种。
本发明还提供了一种疏水防腐涂料,该疏水涂料包括包括底漆和面漆;底漆包括丙烯酸树脂40~60份,疏水填料25~35份,分散剂2~5份,消泡剂2~5份,流平剂1~3份,颜料1~5份和稀释剂50~60份;面漆包括权利要求7的有机氟-石墨烯杂化树脂15~30份,疏水填料5~10份和稀释剂30~40份;
其中,疏水填料为白炭黑、二氧化钛和硅藻土中的至少一种;稀释剂为乙酸乙酯。
本发明采取上述技术方案的有益效果是:本发明在面漆中加入有机氟-石墨烯杂化树脂,由于石墨烯和氟树脂均具有优良的疏水性能,两者结合后所形成的有机氟-石墨烯杂化树脂同样表现出优异的疏水特性,以该杂化树脂为面漆的主要成分,可以显著提升面漆的疏水能力。另外,石墨烯具有层层叠加、交错排列的二维片层结构,比表面积较高,可以在涂层中层层叠加,形成致密的物理隔绝层,能够有效抑制腐蚀介质的浸润、渗透和扩散,提高涂层的物理阻隔性。同时,由于其小尺寸效应,石墨烯可以填充到涂层的缺陷当中,减少涂层孔隙率,增强涂层致密性,进一步延缓或阻止腐蚀因子浸入到基体表面。石墨烯层与层之间有良好的润滑作用,石墨烯的片层结构可以将涂层分割成许多小区间,能够有效地降低涂层内部应力,消耗断裂能量,进而提高涂层的柔韧性、抗冲击性和耐磨性。另外,石墨烯的共轭结构使其具有很高的电子迁移率,表现出良好的导电性,同时,其片层结构亦能够保证涂层间有较好的电化学接触,形成导电网络,提供更佳的电化学保护。
本发明的有益效果是:
1.本发明利用光气对石墨烯进行氨基化改性,能够促进氨基在石墨烯表面生长,氨基化改性效果显著,有利益改性后的石墨烯与含有反应性基团的树脂等有机化合物结合。
2.本发明中将氨基改性石墨烯与含羟基的氟树脂进行结合,得到有机氟-石墨烯杂化树脂,该树脂同时具有石墨烯特殊结构和氟树脂优异的疏水性能的优点,是一种优良的疏水防腐涂料制备原料。
3.本发明中的疏水防腐涂料中的面漆以有机氟-石墨烯杂化树脂为主要成分,涂料的防腐性能和疏水性能均得到显著提升。
具体实施方式
下面结合实施例对本发明的具体实施方式做详细的说明。
实施例1
一种疏水防腐涂料,包括底漆和面漆;其中,
底漆包括丙烯酸树脂50份,白炭黑30份,分散剂默克MOK5623 4份,消泡剂德丰DF-8205 4份,流平剂聚二甲基硅氧烷2份,颜料4份和乙酸乙酯55份;
面漆包括有机氟-石墨烯杂化树脂25份,白炭黑8份和乙酸乙酯35份。
有机氟-石墨烯杂化树脂经过以下步骤制得:
(1)制备氨基改性石墨烯
S1:将石墨烯和十二胺按1:3的质量比混合,并将混合物按1g:8mL的料液比分散于甲苯中,以70m/min的研磨速度研磨30min,得浆料;
S2:以4L/min的通气速率向浆料中鼓泡通入光气,并在4MPa、40℃的条件下反应24h,再过滤、洗涤、干燥,制得氨基改性石墨烯。
(2)制备有机氟-石墨烯杂化树脂
将氨基改性石墨烯、FEVE氟树脂、MDI和辛酸亚锡按2:3:5:0.1的质量比共溶于甲苯中,于70℃下搅拌反应4h,即得。
实施例2
一种疏水防腐涂料,包括底漆和面漆;其中,
底漆包括丙烯酸树脂40份,二氧化钛25份,分散剂默克MOK5623 2份,消泡剂德丰DF-8205 2份,流平剂聚二甲基硅氧烷1份,颜料1份和乙酸乙酯50份;
面漆包括有机氟-石墨烯杂化树脂15份,二氧化钛5份和乙酸乙酯30份。
有机氟-石墨烯杂化树脂经过以下步骤制得:
(1)制备氨基改性石墨烯
S1:将石墨烯和N,N-二甲基苯胺按1:2的质量比混合,并将混合物按1g:6mL的料液比分散于二甲苯中,以60m/min的研磨速度研磨45min,得浆料;
S2:以2L/min的通气速率向浆料中鼓泡通入光气,并在3MPa、30℃的条件下反应25h,再过滤、洗涤、干燥,制得氨基改性石墨烯。
(2)制备有机氟-石墨烯杂化树脂
将氨基改性石墨烯、FEVE氟树脂、TDI和辛酸亚锡按1:2:3:0.05的质量比共溶于二甲苯中,于60℃下搅拌反应5h,即得。
实施例3
一种疏水防腐涂料,包括底漆和面漆;其中,
底漆包括丙烯酸树脂60份,硅藻土35份,分散剂默克MOK5623 5份,消泡剂德丰DF-8205 5份,流平剂聚二甲基硅氧烷5份,颜料5份和乙酸乙酯60份;
面漆包括有机氟-石墨烯杂化树脂30份,硅藻土10份和乙酸乙酯40份。
有机氟-石墨烯杂化树脂经过以下步骤制得:
(1)制备氨基改性石墨烯
S1:将石墨烯和二氨基二苯基甲烷按1:5的质量比混合,并将混合物按1g:10mL的料液比分散于二甲苯中,以80m/min的研磨速度研磨45min,得浆料;
S2:以5L/min的通气速率向浆料中鼓泡通入光气,并在5MPa、50℃的条件下反应20h,再过滤、洗涤、干燥,制得氨基改性石墨烯。
(2)制备有机氟-石墨烯杂化树脂
将氨基改性石墨烯、FEVE氟树脂、HDI和二月桂酸二丁基锡按1:2:3:0.2的质量比共溶于二甲苯中,于80℃下搅拌反应2h,即得。
对比例1
一种疏水防腐涂料,包括底漆和面漆,底漆的组分与实施例1完全相同;面漆包括有机氟-石墨烯杂化树脂25份,白炭黑8份和乙酸乙酯35份。
有机氟-石墨烯杂化树脂经过以下步骤制得:
(1)制备氨基改性石墨烯
S1:将石墨烯和十二胺按1:3的质量比混合,并将混合物按1g:8mL的料液比分散于甲苯中,以70m/min的研磨速度研磨30min,得浆料;
S2:以4L/min的通气速率向浆料中鼓泡通入氯气,并在4MPa、40℃的条件下反应24h,再过滤、洗涤、干燥,制得氨基改性石墨烯。
(2)制备有机氟-石墨烯杂化树脂
将氨基改性石墨烯、FEVE氟树脂、MDI和辛酸亚锡按2:3:5:0.1的质量比共溶于甲苯中,于70℃下搅拌反应4h,即得。
对比例2
一种疏水防腐涂料,包括底漆和面漆,底漆的组分与实施例1完全相同;面漆包括有机氟-石墨烯杂化树脂25份,白炭黑8份和乙酸乙酯35份。
有机氟-石墨烯杂化树脂经过以下步骤制得:
(1)制备氨基改性石墨烯
S1:将石墨烯和十二胺按1:3的质量比混合,并将混合物按1g:8mL的料液比分散于甲苯中,以70m/min的研磨速度研磨30min,得浆料;
S2:以4L/min的通气速率向浆料中鼓泡通入光气,并在4MPa、40℃的条件下反应24h,再过滤、洗涤、干燥,制得氨基改性石墨烯。
(2)制备石墨烯杂化树脂
将氨基改性石墨烯、聚醚多元醇MSDS、MDI和辛酸亚锡按2:3:5:0.1的质量比共溶于甲苯中,于70℃下搅拌反应4h,即得。
结果分析
将实施例和对比例所制得的疏水防腐涂料通过GB/T 30790.6-2014中记载的检测标准进行性能检测,结果列于表1中。
表1涂料性能测试
从表1可以看出,用本发明中的氨基改性石墨烯和有机氟-石墨烯杂化树脂制得的涂料具有优良的疏水性能和防腐性能。对比例1与实施例1相比,改性石墨烯的制备过程中通入的是氯气而不是光气,导致石墨烯的氨基化改性达不到预期效果,与氟树脂结合不彻底,所得有机氟-石墨烯杂化树脂性能较差,进而导致涂料性能变差。对比例2与实施例1相比,有机氟-石墨烯杂化树脂制备过程中将FEVE氟树脂替换为聚醚多元醇MSDS,MSDS偏亲水,导致所得石墨烯杂化树脂的疏水性能变差,进而对最终涂料的性能造成不利影响。
虽然结合实施例对本发明的具体实施方式进行了详细地描述,但不应理解为对本专利的保护范围的限定。在权利要求书所描述的范围内,本领域技术人员不经创造性劳动即可作出的各种修改和变形仍属本专利的保护范围。
Claims (10)
1.一种氨基改性石墨烯的制备方法,其特征在于,包括以下步骤:
S1:将石墨烯和胺类化合物的混合物分散于有机溶剂中,以60~80m/min的研磨速度研磨30~45min,得浆料;
S2:向浆料中鼓泡通入光气,并在3~5MPa、30~50℃的条件下反应20~25h,再过滤、洗涤、干燥,即得氨基改性石墨烯;光气的通入速率为2~5L/min。
2.根据权利要求1所述的氨基改性石墨烯的制备方法,其特征在于:所述石墨烯与胺类化合物的质量之比为1:2~5;两者的混合物与有机溶剂的料液比为1g:6~10mL。
3.根据权利要求2所述的氨基改性石墨烯的制备方法,其特征在于:所述胺类化合物为芳香胺或脂肪胺;所述有机溶剂为甲苯或二甲苯。
4.根据权利要求3所述的氨基改性石墨烯的制备方法,其特征在于:所述芳香胺为N,N-二甲基苯胺、对苯二胺或二氨基二苯基甲烷;所述脂肪胺为十二胺、十六胺或十八胺。
5.根据权利要求1所述的氨基改性石墨烯的制备方法,其特征在于:S2中反应在4MPa、40℃的条件下进行,反应时间为24h。
6.权利要求1~5任一项所述的制备方法制得的氨基改性石墨烯。
7.权利要求6所述的氨基改性石墨烯在制备有机氟-石墨烯杂化树脂中的应用。
8.根据权利要求7所述的应用,其特征在于,所述有机氟-石墨烯杂化树脂经过以下步骤制得:
将氨基改性石墨烯、含羟基的氟树脂、异氰酸酯和金属催化剂按1~3:2~4:3~6:0.05~0.2的质量比共溶于有机溶剂中,于60~80℃下反应2~5h,即得。
9.根据权利要求8所述的应用,其特征在于:所述含羟基的氟树脂为FEVE氟树脂;所述有机溶剂为甲苯或二甲苯;所述金属催化剂为二月桂酸二丁基锡或辛酸亚锡。
10.一种疏水防腐涂料,其特征在于:包括底漆和面漆;所述底漆包括丙烯酸树脂40~60份,疏水填料25~35份,分散剂2~5份,消泡剂2~5份,流平剂1~3份,颜料1~5份和稀释剂50~60份;所述面漆包括权利要求7所述的有机氟-石墨烯杂化树脂15~30份,疏水填料5~10份和稀释剂30~40份;
所述疏水填料为白炭黑、二氧化钛和硅藻土中的至少一种;所述稀释剂为乙酸乙酯。
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