CN113025101B - 一种防腐散热石墨烯涂料 - Google Patents

一种防腐散热石墨烯涂料 Download PDF

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CN113025101B
CN113025101B CN202110281842.9A CN202110281842A CN113025101B CN 113025101 B CN113025101 B CN 113025101B CN 202110281842 A CN202110281842 A CN 202110281842A CN 113025101 B CN113025101 B CN 113025101B
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graphene
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陈嵩
陈亮
刘向阳
李伟
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Jin Kun Magnet Co ltd
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Abstract

本发明涉及磁铁技术领域,具体涉及一种防腐散热石墨烯涂料,包括A组分和B组分,所述A组分包括以下重量份的原料:环氧树脂40‑50份、丙烯酸树脂6‑10份、锌粉15‑20份、石墨烯0.4‑2份、分散剂2‑5份、偶联剂0.5‑4份、流平剂1‑3份、填料6‑10份、增效助剂9‑14份,所述B组分包括以下重量份的原料:固化剂1‑4份、稀释剂3‑5份、溶剂11‑16份。该防腐散热石墨烯涂料涂覆于磁铁表面,可提升磁铁的耐腐蚀性,散热性能好,提升磁铁的使用寿命,并扩展其应用范围。

Description

一种防腐散热石墨烯涂料
技术领域
本发明涉及磁铁技术领域,具体涉及一种防腐散热石墨烯涂料及其制备方法。
背景技术
磁铁是现代工业生产和日常生活中常用的元件。磁铁的种类有许多种,如铝镍钴、钐钴、铁氧体和钕铁硼等。钕铁硼磁铁目前发现商品化性能最高的磁铁,拥有很高的磁性能,且机械加工性也比较好。随着经济的发展和社会的进步,目前钕铁硼永磁材料已广泛应用于机械、交通、能源、医疗、IT、家电等行业,然而现有的钕铁硼的传热性差,且钕铁硼磁铁容易生锈、氧化,防腐蚀性不够,使热量难以向外传导,有待于进一步改进。
发明内容
为了克服现有技术中存在的缺点和不足,本发明的目的在于提供一种防腐散热石墨烯涂料,该防腐散热石墨烯涂料涂覆于磁铁表面,可提升磁铁的耐腐蚀性,散热性能好,提升磁铁的使用寿命,并扩展其应用范围。
本发明的目的通过下述技术方案实现:一种防腐散热石墨烯涂料,包括A组分和B组分,所述A组分包括以下重量份的原料:环氧树脂40-50份、丙烯酸树脂6-10份、锌粉15-20份、石墨烯0.4-2份、分散剂2-5份、偶联剂0.5-4份、流平剂1-3份、填料6-10份、增效助剂9-14份、溶剂22-30份,所述B组分包括以下重量份的原料:固化剂1-4份、稀释剂3-5份。
本发明的防腐散热石墨烯涂料包括含有环氧树脂、分散剂等原料的A组分和含有固化剂的B组分,使用前A组分和B组分分开放置,便于运输和储存,使用时两者混合;通过将石墨烯添加于环氧树脂混合物中,并与丙烯酸树脂、偶联剂、锌粉以及其他原料相配合,制得防腐散热石墨烯涂料;该防腐散热石墨烯涂料可均匀涂覆于磁铁表面,与磁铁表面结合紧密,附着力强,可提升磁铁的耐腐蚀性,散热性能好,提升磁铁的使用寿命,并扩展其应用范围。
进一步的,所述填料为云母粉、碳酸钙和滑石粉中的至少一种。所述填料的粒径为50-100nm。更进一步的,所述填料由云母粉、碳酸钙和滑石粉按重量比1-2:0.8-1.2:1组成。本发明通过采用上述填料,有助于降低生产成本,并增强防通过采用上述填料,有助于提升涂料的机械性、耐候性和耐腐蚀性。腐散热石墨烯涂料的机械性能、耐候性和耐腐蚀性,提高制品尺寸稳定及表面光洁性;采用纳米填料是可增加比表面积及表面吸附能力,提高分散效果。
进一步的,所述环氧树脂为双酚A型环氧树脂。采用上述环氧树脂与石墨烯等原料相配合,可使涂料具有良好的机械性能、耐腐蚀,与磁铁的结合性好。所述双酚A型环氧树脂优选但不限于为双酚A型环氧树脂E44。所述溶剂由丁醇、二甲苯和1,4-丁二醇缩水甘油醚按照重量比3-5:0.8-1.4:1组成。所述丙烯酸树脂优选但不限于为丙烯酸树脂DS8030-TB。
进一步的,所述偶联剂为硅烷偶联剂,所述硅烷偶联剂为γ-氨丙基三乙氧基硅烷、乙烯基三乙氧基硅烷和乙烯基三(β-甲氧乙氧基)硅烷中的至少一种。本发明采用上述硅烷偶联剂,提高了漆膜的交联密度和致密度,有助于提升涂料的机械性能、储存稳定性和附着力。
进一步的,所述分散剂为聚丙烯酸盐、聚羧酸钠盐和羧酸钠盐中的至少一种。通过采用上述分散剂,有助于使组分A中的石墨烯、填料等在涂料体系中分布均匀,石墨烯不易聚集,提升涂料在磁铁表面的涂覆性能。
进一步的,所述流平剂为聚二基硅氧烷和醋酸-丁酸纤维素中的至少一种。更进一步的,所述流平剂由聚二基硅氧烷和醋酸-丁酸纤维素按照重量比0.8-2:1组成。本发明通过采用上述流平剂,使防腐散热石墨烯涂料具有优异的基材润湿能力,与环氧树脂等原料的相容性好,防腐散热石墨烯涂料表面具有较佳的流平效果,涂层不容易产生流平异常,缩孔等缺陷,与磁铁表面的结合力好。
进一步的,每份所述增效助剂的制备方法包括如下步骤:按重量份计,将纳米氧化铝9-12份、PVDF树脂7-10份、马来酸酐接技乙烯-辛烯共聚物5-7份、γ-缩水甘油醚氧丙基三甲氧基硅烷4-7份加入聚乙二醇20-30份中,搅拌混合均匀后,制得混合物A;将混合物A在80-95℃搅拌,保温60-90min,进行超声分散,然后离心洗涤,烘干,制得增效助剂。所述马来酸酐接技乙烯-辛烯共聚物优选但不限于为南京塑泰马来酸酐接枝乙烯-辛烯共聚物ST-8。所述PVDF树脂优选但不限于Kynar 761。本发明通过将纳米氧化铝、PVDF树脂、马来酸酐接技乙烯-辛烯共聚物等相配合,所述增效助剂与原料中的环氧树脂等相容性好,有助于提升涂料的散热性能、耐腐蚀性和耐候性,涂覆时涂料分散均匀,与磁铁分散性好。石墨烯的导热率为4400-5780W/mK,与纳米氧化铝等相配合,在涂料中分布均匀,提升了涂料的散热性,使得涂层涂覆的磁铁用于电机转子等场合时,性能更为稳定。
进一步的,所述固化剂为二乙烯三胺、三乙烯四胺、二乙氨基丙胺和2,4,6—三(二甲胺基甲基)苯酚中的至少一种。本发明采用上述固化剂,可与环氧树脂发生化学反应,形成网状立体聚合物,提升涂料的机械性能、耐腐蚀性以及与磁铁表面的附着力。
进一步的,所述稀释剂为二甲苯、乙醇、癸酸缩水甘油醚和1-4丁二醇缩水甘油醚中的至少一种。更进一步的,所述稀释剂由二甲苯、乙醇和癸酸缩水甘油醚按照重量比0.4-0.8:1.5-2:1组成。通过采用上述稀释剂,可提高各原料的相容性,使防腐散热石墨烯涂料分散均匀,涂覆性好。
上述防腐散热石墨烯涂料的制备方法,包括以下步骤:
A组分的制备:
A1、按比例将石墨烯、偶联剂、分散剂混合,搅拌均匀,搅拌速度为1000-1600r/min,搅拌时间为10-20min;然后加入环氧树脂和丙烯酸树脂,在65-70℃温度下搅拌20-40min,得到树脂石墨烯浆料;
A2、往树脂石墨烯浆料加入锌粉、石墨烯、分散剂、流平剂、填料、增效助剂,在65-70℃温度下搅拌20-40min,搅拌速度为1000-1600r/min,得到混合浆料;将混合浆料研磨,出料细度控制为10-30μm,过滤后制得A组分,待用。
B组分的制备:
将固化剂、稀释剂混合,搅拌均匀,搅拌速度为1000-1600r/min,搅拌时间为10-20min,待用。
本发明的制备方法工艺简单,控制方便,生产效率高,利于工业化生产,有利于防止石墨烯以及填料等的团聚,涂覆性能好,在磁铁表面形成均一、附着力强的涂层。
本发明的有益效果在于:本发明的防腐散热石墨烯涂料包括含有环氧树脂、分散剂等原料的A组分和含有固化剂的B组分,使用前A组分和B组分分开放置,便于运输和储存,使用时两者混合;通过将石墨烯添加于环氧树脂混合物中,并与丙烯酸树脂、偶联剂、锌粉以及其他原料相配合,制得防腐散热石墨烯涂料;该防腐散热石墨烯涂料可均匀涂覆于磁铁表面,与磁铁表面结合紧密,附着力强,可提升磁铁的耐腐蚀性,散热性能好,提升磁铁的使用寿命,并扩展其应用范围。
附图说明
图1为实施例1的防腐散热石墨烯涂料部分涂覆于镀铬未充磁的钕铁硼磁铁的效果图。
图2为实施例1的防腐散热石墨烯涂料部分涂覆于未镀铬未充磁的钕铁硼磁铁的效果图。
具体实施方式
为了便于本领域技术人员的理解,下面结合实施例对本发明作进一步的说明,实施方式提及的内容并非对本发明的限定。
实施例1
一种防腐散热石墨烯涂料,包括A组分和B组分,所述A组分包括以下重量份的原料:环氧树脂45份、丙烯酸树脂8份、锌粉17份、石墨烯1份、分散剂3份、偶联剂2份、流平剂2份、填料7份、增效助剂12份、溶剂25份,所述B组分包括以下重量份的原料:固化剂2份、稀释剂4份。
进一步的,所述填料由云母粉、碳酸钙和滑石粉按重量比1,5:1:1组成。所述填料的粒径为50-100nm。所述双酚A型环氧树脂为双酚A型环氧树脂E44。所述溶剂由丁醇、二甲苯和1,4-丁二醇缩水甘油醚按照重量比4:1:1组成.所述丙烯酸树脂为丙烯酸树脂DS8030-TB。
进一步的,所述偶联剂为硅烷偶联剂,所述硅烷偶联剂为γ-氨丙基三乙氧基硅烷和乙烯基三(β-甲氧乙氧基)硅烷按照重量比1:1组成。
进一步的,所述分散剂为聚羧酸钠盐型分散剂SN-5040或聚丙烯酸钠分散剂Dispersant-9100。所述流平剂由聚二基硅氧烷和醋酸-丁酸纤维素按照重量比1.2:1组成。
进一步的,每份所述增效助剂的制备方法包括如下步骤:按重量份计,将纳米氧化铝11份、PVDF树脂8份、马来酸酐接技乙烯-辛烯共聚物6份、γ-缩水甘油醚氧丙基三甲氧基硅烷5份加入聚乙二醇25份中,搅拌混合均匀后,制得混合物A;将混合物A在85℃搅拌,保温75min,进行超声分散,然后离心洗涤,烘干,制得增效助剂。所述马来酸酐接技乙烯-辛烯共聚物为南京塑泰马来酸酐接枝乙烯-辛烯共聚物ST-8。所述PVDF树脂为Kynar 761。
进一步的,所述固化剂为二乙烯三胺和2,4,6—三(二甲胺基甲基)按照重量比2:1组成。
进一步的,所述稀释剂由二甲苯、乙醇和癸酸缩水甘油醚按照重量比0.6:1.8:1组成。
上述防腐散热石墨烯涂料的制备方法,包括以下步骤:
A组分的制备:
A1、按比例将石墨烯、偶联剂、分散剂混合,搅拌均匀,搅拌速度为1400r/min,搅拌时间为15min;然后加入环氧树脂和丙烯酸树脂,在68℃温度下搅拌30min,得到树脂石墨烯浆料;
A2、往树脂石墨烯浆料加入锌粉、石墨烯、分散剂、流平剂、填料、增效助剂,在68℃温度下搅拌30min,搅拌速度为1400r/min,得到混合浆料;将混合浆料研磨,出料细度控制为10-30μm,过滤后制得A组分,待用。
B组分的制备:
将固化剂、稀释剂混合,搅拌均匀,搅拌速度为1400r/min,搅拌时间为15min,待用。
图1为本实施例的防腐散热石墨烯涂料部分涂覆于镀铬未充磁的钕铁硼的效果图,图1中涂层表面形貌均匀,石墨烯分布均匀。图2为实施例1的防腐散热石墨烯涂料部分涂覆于未镀铬未充磁的钕铁硼的效果图。图2中涂层表面形貌均匀,石墨烯分布均匀,表面结合力均较强。
实施例2
一种防腐散热石墨烯涂料,包括A组分和B组分,所述A组分包括以下重量份的原料:环氧树脂40份、丙烯酸树脂6份、锌粉15份、石墨烯0.4份、分散剂2份、偶联剂0.5份、流平剂1份、填料6份、增效助剂9份、溶剂22份,所述B组分包括以下重量份的原料:固化剂1份、稀释剂3份。
进一步的,所述填料由云母粉、碳酸钙和滑石粉按重量比1:0.8:1组成。所述溶剂由丁醇、二甲苯和1,4-丁二醇缩水甘油醚按照重量比3:0.8:1组成。
进一步的,所述偶联剂为硅烷偶联剂,所述硅烷偶联剂为γ-氨丙基三乙氧基硅烷和乙烯基三乙氧基硅烷按照质量比2:1组成。
进一步的,所述分散剂为聚丙烯酸钠分散剂Dispersant-9100。所述流平剂由聚二基硅氧烷和醋酸-丁酸纤维素按照重量比0.8:1组成。
进一步的,每份所述增效助剂的制备方法包括如下步骤:按重量份计,将纳米氧化铝9份、PVDF树脂7份、马来酸酐接技乙烯-辛烯共聚物5份、γ-缩水甘油醚氧丙基三甲氧基硅烷4份加入聚乙二醇20份中,搅拌混合均匀后,制得混合物A;将混合物A在80℃搅拌,保温90min,进行超声分散,然后离心洗涤,烘干,制得增效助剂。
进一步的,所述固化剂为由二乙烯三胺和2,4,6—三(二甲胺基甲基)苯酚按照重量比1:1.5组成。所述稀释剂由二甲苯、乙醇和癸酸缩水甘油醚按照重量比0.4:1.5:1组成。
上述防腐散热石墨烯涂料的制备方法,包括以下步骤:
A组分的制备:
A1、按比例将石墨烯、偶联剂、分散剂混合,搅拌均匀,搅拌速度为1000r/min,搅拌时间为20min;然后加入环氧树脂和丙烯酸树脂,在65℃温度下搅拌35min,得到树脂石墨烯浆料;
A2、往树脂石墨烯浆料加入锌粉、石墨烯、分散剂、流平剂、填料、增效助剂,在65℃温度下搅拌40min,搅拌速度为1000r/min,得到混合浆料;将混合浆料研磨,出料细度控制为10-30μm,过滤后制得A组分,待用。
B组分的制备:
将固化剂、稀释剂混合,搅拌均匀,搅拌速度为1000r/min,搅拌时间为20min,待用。
实施例3
一种防腐散热石墨烯涂料,包括A组分和B组分,所述A组分包括以下重量份的原料:环氧树脂50份、丙烯酸树脂10份、锌粉20份、石墨烯2份、分散剂5份、偶联剂4份、流平剂3份、填料10份、增效助剂14份、溶剂30份,所述B组分包括以下重量份的原料:固化剂4份、稀释剂5份。
进一步的,所述填料由云母粉、碳酸钙和滑石粉按重量比2:1.2:1组成。所述溶剂由丁醇、二甲苯和1,4-丁二醇缩水甘油醚按照重量比5:1.4:1组成。
进一步的,所述硅烷偶联剂为γ-氨丙基三乙氧基硅烷、乙烯基三乙氧基硅烷和乙烯基三(β-甲氧乙氧基)硅烷按照重量比1:1:2组成。
进一步的,所述分散剂为聚羧酸钠盐型分散剂SN-5040。所述流平剂由聚二基硅氧烷和醋酸-丁酸纤维素按照重量比2:1组成。
进一步的,每份所述增效助剂的制备方法包括如下步骤:按重量份计,将纳米氧化铝12份、PVDF树脂10份、马来酸酐接技乙烯-辛烯共聚物7份、γ-缩水甘油醚氧丙基三甲氧基硅烷7份加入聚乙二醇30份中,搅拌混合均匀后,制得混合物A;将混合物A在95℃搅拌,保温60min,进行超声分散,然后离心洗涤,烘干,制得增效助剂。
进一步的,所述固化剂为二乙氨基丙胺和2,4,6—三(二甲胺基甲基)苯酚按照重量比2:1组成。
进一步的,进一步的,所述稀释剂由二甲苯、乙醇和癸酸缩水甘油醚按照重量比0.8:2:1组成。
上述防腐散热石墨烯涂料的制备方法,包括以下步骤:
A组分的制备:
A1、按比例将石墨烯、偶联剂、分散剂混合,搅拌均匀,搅拌速度为1600r/min,搅拌时间为10min;然后加入环氧树脂和丙烯酸树脂,在70℃温度下搅拌20min,得到树脂石墨烯浆料;
A2、往树脂石墨烯浆料加入锌粉、石墨烯、分散剂、流平剂、填料、增效助剂,在70℃温度下搅拌20min,搅拌速度为1600r/min,得到混合浆料;将混合浆料研磨,出料细度控制为10-30μm,过滤后制得A组分,待用。
B组分的制备:
将固化剂、稀释剂混合,搅拌均匀,搅拌速度为1600r/min,搅拌时间为10min,待用。
实施例4
一种防腐散热石墨烯涂料,包括A组分和B组分,所述A组分包括以下重量份的原料:环氧树脂46份、丙烯酸树脂7份、锌粉16份、石墨烯1.5份、分散剂3份、偶联剂3份、流平剂1.5份、填料7份、增效助剂11份、溶剂28份,所述B组分包括以下重量份的原料:固化剂3份、稀释剂5份。
进一步的,所述填料由云母粉、碳酸钙和滑石粉按重量比1.5:1:1组成。进一步的,所述溶剂由丁醇、二甲苯和1,4-丁二醇缩水甘油醚按照重量比3.5:1.2:1组成。所述流平剂由聚二基硅氧烷和醋酸-丁酸纤维素按照重量比0.8-2:1组成。所述分散剂为聚羧酸钠盐型分散剂SN-5040和聚丙烯酸钠分散剂Dispersant-9100按照重量比1.5:1组成。
进一步的,每份所述增效助剂的制备方法包括如下步骤:按重量份计,将纳米氧化铝11份、PVDF树脂8份、马来酸酐接技乙烯-辛烯共聚物5.5份、γ-缩水甘油醚氧丙基三甲氧基硅烷5份加入聚乙二醇24份中,搅拌混合均匀后,制得混合物A;将混合物A在85℃搅拌,保温80min,进行超声分散,然后离心洗涤,烘干,制得增效助剂。
上述防腐散热石墨烯涂料的制备方法,包括以下步骤:
A组分的制备:
A1、按比例将石墨烯、偶联剂、分散剂混合,搅拌均匀,搅拌速度为1500r/min,搅拌时间为15min;然后加入环氧树脂和丙烯酸树脂,在68℃温度下搅拌25min,得到树脂石墨烯浆料;
A2、往树脂石墨烯浆料加入锌粉、石墨烯、分散剂、流平剂、填料、增效助剂,在65℃温度下搅拌360min,搅拌速度为1300r/min,得到混合浆料;将混合浆料研磨,出料细度控制为10-30μm,过滤后制得A组分,待用。
B组分的制备:
将固化剂、稀释剂混合,搅拌均匀,搅拌速度为1300r/min,搅拌时间为20min,待用。
本实施例的其余内容与实施例1相似,此处不再赘述。
对比例1
本对比例与实施例1的不同之处在:本对比例中不含有增效助剂,由等量的环氧树脂和丙烯酸树脂代替,本对比例中环氧树脂和丙烯酸树脂的重量比与实施例1相同。
将实施例1-4和对比例1制备得到的防腐散热石墨烯涂料经过浸渍、提拉和固化,在未镀铬的钕铁硼环状磁铁表面形成防腐散热石墨烯涂层。涂覆方法包括如下步骤:将磁铁基体浸渍于配置好的防腐散热石墨烯涂料中;浸渍后向上提拉磁体基体,使磁体基体悬空于防腐散热石墨烯涂料的上方,使磁铁基体表面形成连续的胶膜,重复上述浸渍、提拉步骤,得到带有涂层初膜的磁铁基体;其中,每次浸渍时间为30s,每次提拉后磁铁基体悬空的时间为80s,重复次数为40次。每次提拉磁铁基体的速度为3cm/min;将磁体基体的涂层初膜进行固化,得到涂设有防腐散热石墨烯涂料的磁体,固化温度为90℃,固化时间为25min。按照HG/T 4759-2014进行测试,性能测定结果如下:
实施例1-4和对比例1的涂层外观均平整光滑无颗粒,闪锈抑制性均正常,对比例1中边缘弧度处涂层的相对较少。耐水性/500h:实施例1-4和对比例1均不起泡、不剥落、不生锈、不开裂。耐盐雾性/500h:实施例1-4均不起泡、不剥落、不生锈、不开裂;对比例1起泡、轻微剥落、生锈。耐碱性/240h(50g/L,NaOH):实施例1-4均不起泡、不剥落、不生锈、不开裂;对比例1轻微剥落、生锈。耐酸性/36h(50g/L,H2SO4):实施例1-4均不起泡、不剥落、不生锈、不开裂;对比例1起泡。
实施例1-4和对比例1的其余性能如下:
Figure BDA0002978845760000111
本发明实施例1-4的防腐散热石墨烯涂料形成的涂层厚度为20-25μm。耐冲击性测试以5cm为一个区间。本发明的防腐散热石墨烯涂料涂覆于磁铁表面,与磁铁的附着力好,可提升磁铁的耐腐蚀性,散热性能好,提升磁铁的使用寿命,并扩展其应用范围。
上述实施例为本发明较佳的实现方案,除此之外,本发明还可以其它方式实现,在不脱离本发明构思的前提下任何显而易见的替换均在本发明的保护范围之内。

Claims (6)

1.一种防腐散热石墨烯涂料,其特征在于:包括A组分和B组分,所述A组分包括以下重量份的原料:环氧树脂40-50份、丙烯酸树脂6-10份、锌粉15-20份、石墨烯0 .4-2份、分散剂2-5份、偶联剂0 .5-4份、流平剂1-3份、填料6-10份、增效助剂9-14份,溶剂22-30份,所述B组分包括以下重量份的原料:固化剂1-4份、稀释剂3-5份;
每份所述增效助剂的制备方法包括如下步骤:按重量份计,将纳米氧化铝9-12份、PVDF树脂7-10份、马来酸酐接技乙烯-辛烯共聚物5-7份、γ-缩水甘油醚氧丙基三甲氧基硅烷4-7份加入聚乙二醇20-30份中,搅拌混合均匀后,制得混合物A;将混合物A在80-95℃搅拌,保温60-90min,进行超声分散,然后离心洗涤,烘干,制得增效助剂;
所述稀释剂由二甲苯、乙醇和癸酸缩水甘油醚按照重量比0.4-0.8:1.5-2:1组成;
所述填料由云母粉、碳酸钙和滑石粉按重量比1-2:0.8-1.2:1组成;所述填料的粒径为50-100nm。
2.根据权利要求1所述的防腐散热石墨烯涂料,其特征在于:所述环氧树脂为双酚A型环氧树脂。
3.根据权利要求1所述的防腐散热石墨烯涂料,其特征在于:所述偶联剂为γ-氨丙基三乙氧基硅烷、乙烯基三乙氧基硅烷和乙烯基三(β-甲氧乙氧基)硅烷中的至少一种。
4.根据权利要求1所述的防腐散热石墨烯涂料,其特征在于:所述分散剂为聚丙烯酸盐、聚羧酸钠盐和羧酸钠盐中的至少一种。
5.根据权利要求1所述的防腐散热石墨烯涂料,其特征在于:所述流平剂为聚二基硅氧烷和醋酸-丁酸纤维素中的至少一种。
6.根据权利要求1所述的防腐散热石墨烯涂料,其特征在于:所述固化剂为二乙烯三胺、三乙烯四胺、二乙氨基丙胺和2,4,6- 三(二甲胺基甲基)苯酚中的至少一种。
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