CN104804169B - 一种石墨烯改性聚氨酯导电性涂料的制备方法 - Google Patents
一种石墨烯改性聚氨酯导电性涂料的制备方法 Download PDFInfo
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Abstract
本发明公开了一种石墨烯改性聚氨酯导电性涂料的制备方法,其步骤为部分还原氧化石墨烯,使其保留部分羟基;并通过羟基与异氰酸根反应改性异氰酸酯,将其作为制备水性聚氨酯的原料与低聚物二元醇、亲水剂、扩链剂合成导电型水性聚氨酯,由于部分还原的氧化石墨烯有良好的导电性和分散性,可以提高涂料的导电性能、力学性能、老化性能和耐水性能,该涂料可用于皮革,纺织,木材,金属材料及电子器件表面,以提高表面的抗静电、散热、耐水、耐老化、电磁屏蔽等性能。
Description
技术领域
本发明涉及一种涂料的制备方法,特别涉及一种导电性涂料的制备方法。
技术背景
自从2004年英国曼彻斯顿大学的Geim和他的同事成功确认了石墨烯的存在,这种二维片层结构的纳米材料就获得了科学家的广泛关注。因其兼具石墨和碳纳米管的很多优异的性能,尤其是具有良好的导电性能、机械性能、热传导性、量子霍尔效应且无明显的生物毒性等众多独特性能,因此在金属材料、高分子材料和无机非金属材料领域有很好的应用前景。
导电涂料是近年来兴起并发展的一种新型特种涂料,它因为具有优越的抗静电和电磁屏蔽性能而被广泛应用于橡胶,塑料和电子产品等领域。而在一些特殊场合,如寒冷地区等,对导电涂料的导电、老化、强度和洗刷等性能要求比较高,而在涂料中加入纳米材料可有效地提高导电涂料的导电、老化、强度和洗刷等性能,从而延长涂料的使用寿命,提高涂料的档次。目前,采用纳米材料改性涂料的研究已经有了很大的发展,但报道的文献中大多采用机械共混或化学改性的方法 (比如:一种氧化石墨烯/水性聚氨酯纳米复合材料的制备方法,CN103254400A),其缺点是由于氧化石墨烯自身的导电性不高,按照这类方法制备的导电涂料的导电性也不能令人满意。
发明内容
本发明所要解决的技术问题是,提供一种石墨烯改性聚氨酯导电性涂料的制备方法,通过对氧化石墨烯改性,提高水性聚氨酯涂料的导电性,用以解决氧化石墨烯/水性聚氨酯材料导电性不高的问题。
本发明采用了以下技术方案:
一种石墨烯改性聚氨酯导电性涂料的制备方法,其特征在于按照以下步骤进行:
(1)、制备部分还原的氧化石墨烯(RGO):首先将0.5-2g氧化石墨烯置于去离子水中,在超声清洗器中超声1-5h,超声功率200W,超声频率400KHz,超声温度20-50℃,制得氧化石墨烯水分散液;然后在温度为40-100℃的条件下加入5-40g还原剂,反应0.5-8h,得到均匀稳定的RGO分散液;最后经反复离心过滤至上清液呈中性,取固体物干燥并研磨成粉;
(2)、制备改性异氰酸酯:取第一步产物0.01-0.5g加入到100ml脱水处理后的DMF中,超声分散后,在20-100℃温度下,加入异氰酸酯5-50g,通氮气保护下搅拌反应2h,离心过滤,取固体物于真空干燥箱60℃干燥48h;
(3)、制备石墨烯改性聚氨酯导电涂料:取第(2)步产物0.05-5g,分散在N,N-二甲基甲酰胺中,超声分散后,加入10-50g低聚物二元醇、0.5-3g二羟甲基丙酸,在通氮气保护下升温至70-90℃,反应1h,加入5-25g的异氰酸酯继续反应1h,滴加质量比为1:2的二月桂酸二丁基锡和三亚乙基二胺复合催化剂0.03-0.5g,反应2h后,降温至40℃,加入1-4g三乙胺,中和反应0.5h,加去离子水调节pH成中性,降温后加入0.1-2g乙二胺,扩链反应0.5h,减压蒸馏得到石墨烯改性聚氨酯导电涂料。
所述的还原剂为柠檬酸,柠檬酸钠,硼氢化钠,抗坏血酸中的一种或两种以上任意比例的混合物。
所述的异氰酸酯为甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、1,6-己二异氰酸酯、异佛尔酮二异氰酸酯中的一种或两种以上任意比例的混合物。
所述的低聚物二元醇为聚丙二醇、聚己内酯二醇、聚四氢呋喃醚二醇、聚碳酸酯二醇中的一种或两种以上任意比例的混合物。
所述的低聚物二元醇的数均分子量为600-2000g/mol。
所述的方法制备的导电性涂料应用于皮革,纺织,木材,金属材料表面,以及用于抗静电、散热、耐水、耐老化、电磁屏蔽及电子器件领域。
本发明的积极效果在于:
(1)、本发明利用还原剂将氧化石墨烯上的部分含氧官能团还原,保留羟基,利用异氰酸根与羟基的反应,改性部分还原的氧化石墨烯,提高了水性聚氨酯涂料的导电性,解决了氧化石墨烯/水性聚氨酯材料导电性不高的问题。所制备的涂料具有良好的导电性、机械性能和耐老化性能。
(2)本发明在传统的水性聚氨酯聚合的基础上,利用改性后的异氰酸酯进行反应,不改变传统的乳液聚合的操作方式,可靠易行。
具体实施方式
下面结合实施例进一步说明本发明。
实施例一
(1)、制备部分还原的氧化石墨烯(RGO):取氧化石墨烯0.5g置于200ml去离子水中,在超声清洗器中超声1h,其超声功率200W,超声频率400KHz,超声温度20℃,制得氧化石墨烯水分散液,在温度为40℃的条件下加入5g柠檬酸钠,反应0.5h,得到均匀稳定的RGO分散液。在8000转/分钟的条件下反复离心过滤至上清液呈中性,取固体物于50℃真空干燥箱中干燥48h,取出研磨成粉;
(2)、制备改性异氰酸酯:取上述0.01gRGO加入到100ml脱水处理后的DMF中,超声分散0.5h后,在20℃温度下,加入异氟尔酮二异氰酸酯5g(用甲苯溶解),通氮气保护,搅拌反应2h,在8000转/分钟的条件下反复离心过滤,取固体物于真空干燥箱60℃干燥8h,得到改性异氟尔酮二异氰酸酯;
(3)、制备RGO/WPU导电性涂料:在装有冷凝管、温度计、搅拌器的四口烧瓶中,取上述0.05g改性异氟尔酮二异氰酸酯分散在N,N-二甲基甲酰胺中,超声0.5h,加入10g聚丙二醇、0.5g二羟甲基丙酸,通氮气保护,升温至70℃,反应1h,加入5g的异氟尔酮二异氰酸酯继续反应1h,滴加质量比为1:2的二月桂酸二丁基锡和三亚乙基二胺复合催化剂0.03g,反应2h后,降温至40℃,加入1g三乙胺中和0.5h,加去离子水调节pH成中性,降至室温,后加0.1g乙二胺扩链0.5h,减压蒸馏后,得到石墨烯改性聚氨酯导电涂料,所述聚丙二醇的数均分子量为2000g/mol。
实施例二
(1)制备部分还原的氧化石墨烯(RGO):取氧化石墨烯2g置于200ml去离子水中,在超声清洗器中超声5h,其超声功率200W,超声频率400KHz,超声温度50℃,制得氧化石墨烯水分散液,在温度为100℃的条件下加入40g硼氢化钠,反应8h,得到均匀稳定的RGO分散液。在8000转/分钟的条件下反复离心过滤至上清液呈中性,取固体物于50℃真空干燥箱中干燥48h,取出研磨成粉;
(2)制备改性异氰酸酯:取上述0.1gRGO加入到100ml脱水处理后的DMF中,超声分散0.5h后,在100℃温度下,加入用既然苯溶解的1,6-己二异氰酸酯50g,通氮气保护,搅拌反应2h,在8000转/分钟的条件下反复离心过滤,取固体物于真空干燥箱60℃干燥48h;
(3)制备RGO/WPU导电性涂料:在装有冷凝管、温度计、搅拌器的四口烧瓶中,取上述5g改性1,6-己二异氰酸酯分散在N,N-二甲基甲酰胺中,超声0.5h,加入50g聚己内酯二醇、3g二羟甲基丙酸,通氮气保护,升温至70-90℃,反应1h,加入25g的异氰酸酯继续反应1h,滴加质量比为1:2的二月桂酸二丁基锡和三亚乙基二胺复合催化剂0.5g,反应2h后,降温至40℃,加入4g三乙胺中和0.5h,加去离子水调节pH成中性,降至室温,后加2g乙二胺扩链0.5h,减压蒸馏后,得到石墨烯改性聚氨酯导电涂料,所述聚己内酯二醇的数均分子量为2000g/mol。
实施例三
(1)制备部分还原的氧化石墨烯(RGO):取氧化石墨烯0.501g置于200ml去离子水中,在超声清洗器中超声1h,其超声功率200W,超声频率400KHz,超声温度20℃,制得氧化石墨烯水分散液,在温度为60℃的条件下加入5.002g柠檬酸钠,反应0.5h,得到均匀稳定的RGO分散液。在8000转/分钟的条件下反复离心过滤至上清液呈中性,取固体物于50℃真空干燥箱中干燥48h,取出研磨成粉;
(2)制备改性异氰酸酯:取上述0.014gRGO加入到100ml脱水处理后的DMF中,超声分散0.5h后,在80℃温度下,加入用苯溶解的甲苯二异氰酸酯5.005g,通氮气保护,搅拌反应2h,在8000转/分钟的条件下反复离心过滤,取固体物于真空干燥箱60℃干燥48h;
(3)制备RGO/WPU导电性涂料:在装有冷凝管、温度计、搅拌器的四口烧瓶中,取上述0.05g改性甲苯二异氰酸酯分散在N,N-二甲基甲酰胺中,超声0.5h,加入13.45g聚四氢呋喃醚二醇,1.48g二羟甲基丙酸,通氮气保护,升温至70℃,反应1h,加入7.45g的甲苯二异氰酸酯继续反应1h,滴加质量比为1:2的二月桂酸二丁基锡和三亚乙基二胺复合催化剂0.05g,反应2h后,降温至40℃,加入1.005g三乙胺中和0.5h,加去离子水调节pH成中性,降至室温,后加0.365g乙二胺扩链0.5h,减压蒸馏后,得到石墨烯改性聚氨酯导电性涂料,所述聚四氢呋喃醚二醇的数均分子量为1000g/mol。
实施例四
(1)制备部分还原的氧化石墨烯(RGO):取氧化石墨烯1.547g置于200ml去离子水中,在超声清洗器中超声3h,其超声功率200W,超声频率400KHz,超声温度40℃,制得氧化石墨烯水分散液,在温度为80℃的条件下加入11.495g硼氢化钠,反应4h,得到均匀稳定的RGO分散液。在8000转/分钟的条件下反复离心过滤至上清液呈中性,取固体物于50℃真空干燥箱中干燥48h,取出研磨成粉;
(2)制备改性异氰酸酯:取上述0.058gRGO加入到100ml脱水处理后的DMF中,超声分散0.5h后,在60℃温度下,加入用二甲苯溶解的二苯基甲烷二异氰酸酯17.4g,通氮气保护,搅拌反应2h,在8000转/分钟的条件下反复离心过滤,取固体物于真空干燥箱60℃干燥48h;
(3)制备RGO/WPU导电性涂料:在装有冷凝管、温度计、搅拌器的四口烧瓶中,取上述0.135g改性二苯基甲烷二异氰酸酯分散在N,N-二甲基甲酰胺中,超声0.5h,加入10.095g聚四氢呋喃醚二醇,1.055g亲水扩链剂2,2-二羟甲基丙酸,通氮气保护,升温至70℃,反应1h,加入5.048g的二苯基甲烷二异氰酸酯继续反应1h,滴加质量比为1:2的二月桂酸二丁基锡和三亚乙基二胺复合催化剂0.2g,反应2h后,降温至40℃,加入0.717g三乙胺中和0.5h,加去离子水调节pH成中性,降至室温,后加0.12g乙二胺扩链0.5h,减压蒸馏后,得到石墨烯改性聚氨酯导电涂料,聚四氢呋喃醚二醇的数均分子量为1000g/mol
实施例五
(1)制备部分还原的氧化石墨烯(RGO):取氧化石墨烯1.985g置于200ml去离子水中,在超声清洗器中超声5h,其超声功率200W,超声频率400KHz,超声温度50℃,制得氧化石墨烯水分散液,在温度为80℃的条件下加入38.585g硼氢化钠,反应8h,得到均匀稳定的RGO分散液。在8000转/分钟的条件下反复离心过滤至上清液呈中性,取固体物于50℃真空干燥箱中干燥48h,取出研磨成粉;
(2)制备改性异氰酸酯:取上述0.084gRGO加入到100ml脱水处理后的DMF中,超声分散0.5h后,在50℃温度下,加入用二甲苯溶解的异佛尔酮二异氰酸酯27.008g,通氮气保护,搅拌反应2h,在8000转/分钟的条件下反复离心过滤,取固体物于真空干燥箱60℃干燥48h;
(3)制备RGO/WPU导电性涂料:在装有冷凝管、温度计、搅拌器的四口烧瓶中,取上述0.2g改性异佛尔酮二异氰酸酯分散在N,N-二甲基甲酰胺中,超声0.5h,加入12.89g聚碳酸酯二醇,1.345g二羟甲基丙酸,通氮气保护,升温至70℃,反应1h,加入6.03g的异佛尔酮二异氰酸酯继续反应1h,滴加质量比为1:2的二月桂酸二丁基锡和三亚乙基二胺复合催化剂0.24g,反应2h后,降温至40℃,加入0.834g三乙胺中和0.5h,加去离子水调节pH成中性,降至室温,后加0.148g乙二胺扩链0.5h,减压蒸馏后,得到石墨烯改性聚氨酯导电涂料,聚碳酸酯二醇的数均分子量为2000g/mol。
表1是本发明实施例3所制备的导电性涂料与未添加部分还原的氧化石墨烯的导电性涂料的测试数据对比表。其中涂料1未添加部分还原的氧化石墨烯;涂料2是实施例3工艺制备的
涂料。 表2是不同添加物下涂料的老化性能变化对比表。
表1、不同添加物下涂料的性能变化变化
时间/h | 体积电阻系数/Ω·cm | 抗拉强度/MPa | 吸水率/﹪ |
涂料1 | 3.32×1011 | 29.60 | 106.43 |
涂料2 | 1.88×107 | 38.23 | 60.07 |
表2、不同添加物下涂料的老化性能变化
耐湿热老化 | 耐紫外老化 | |||||
老化前抗拉强度/MPa | 老化后抗拉强度/MPa | 保持率/% | 老化前抗拉强度/MPa | 老化后抗拉强度/MPa | 保持率/% | |
涂料1 | 29.60 | 11.97 | 40.44 | 29.60 | 13.18 | 44.52 |
涂料2 | 38.23 | 31.47 | 82.32 | 38.23 | 28.38 | 74.23 |
其中各项指标的检测分别依据如下标准:抗拉强度按GB/T528-1998进行测定,负荷50N,拉伸速率100mm/min,耐湿热老化性能按GB/T12000-2003进行测试,紫外老化性能按GB/T16422.2-1999进行测试。
从表1和表2中可以发现,涂料2明显比未添加部分还原的氧化石墨烯的涂料1的导电性能好,同时在力学性能,耐老化性方面都有明显的提高。
Claims (3)
1.一种石墨烯改性聚氨酯导电性涂料的制备方法,其特征在于按照以下步骤进行:
(1)、制备部分还原的氧化石墨烯 (RGO):首先将 0.5-2g 氧化石墨烯置于去离子水中,在超声清洗器中超声1-5h,超声功率200W,超声频率400KHz,超声温度20-50℃,制得氧化石墨烯水分散液;然后在温度为40-100℃的条件下加入5-40g还原剂,反应0.5-8h,得到均匀稳定的 RGO 分散液;最后经反复离心过滤至上清液呈中性,取固体物干燥并研磨成粉;
(2)、制备改性异氰酸酯:取第一步产物0.01-0.5g加入到100ml脱水处理后的DMF中,超声分散后,在 20-100℃温度下,加入异氰酸酯 5-50g,通氮气保护下搅拌反应2h,离心过滤,取固体物于真空干燥箱 60℃干燥 48h;
(3)、制备石墨烯改性聚氨酯导电涂料:取第(2)步产物0.05-5g,分散在N,N-二甲基甲酰胺中,超声分散后,加入 10-50g 低聚物二元醇、0.5-3g 二羟甲基丙酸,在通氮气保护下升温至 70-90℃,反应 1h,加入 5-25g 的异氰酸酯继续反应 1h,滴加质量比为 1:2 的二月桂酸二丁基锡和三亚乙基二胺复合催化剂 0.03-0.5g,反应 2h 后,降温至 40℃,加入1-4g 三乙胺,中和反应 0.5h,加去离子水调节 pH 成中性,降温后加入 0.1-2g 乙二胺,扩链反应 0.5h,减压蒸馏得到石墨烯改性聚氨酯导电涂料;
所述的还原剂为柠檬酸钠;所述的异氰酸酯为甲苯二异氰酸酯;所述的低聚物二元醇为聚四氢呋喃醚二醇。
2.根据权利要求 1 所述的石墨烯改性聚氨酯导电性涂料的制备方法,其特征在于:所述的低聚物二元醇的数均分子量为 600-2000g/mol。
3.权利要求1或2所述的方法制备的导电性涂料应用于皮革,纺织,木材,金属材料表面,以及用于抗静电、散热、耐水、耐老化、电磁屏蔽及电子器件领域。
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