CN106700823A - 一种2‑巯基苯并噻唑改性氧化石墨烯防腐涂料及其制备方法 - Google Patents

一种2‑巯基苯并噻唑改性氧化石墨烯防腐涂料及其制备方法 Download PDF

Info

Publication number
CN106700823A
CN106700823A CN201611036205.0A CN201611036205A CN106700823A CN 106700823 A CN106700823 A CN 106700823A CN 201611036205 A CN201611036205 A CN 201611036205A CN 106700823 A CN106700823 A CN 106700823A
Authority
CN
China
Prior art keywords
graphene oxide
mercaptobenzothiazole
modified graphene
anticorrosive paint
resin
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201611036205.0A
Other languages
English (en)
Other versions
CN106700823B (zh
Inventor
戴李宗
王世成
邵志恒
陈婷
袁丛辉
曾碧榕
许婷
许一婷
罗伟昂
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Xiamen University
Original Assignee
Xiamen University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Xiamen University filed Critical Xiamen University
Priority to CN201611036205.0A priority Critical patent/CN106700823B/zh
Publication of CN106700823A publication Critical patent/CN106700823A/zh
Priority to US16/463,771 priority patent/US10843926B2/en
Priority to PCT/CN2017/112586 priority patent/WO2018095364A1/zh
Application granted granted Critical
Publication of CN106700823B publication Critical patent/CN106700823B/zh
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/194—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/198—Graphene oxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/32—Epoxy compounds containing three or more epoxy groups
    • C08G59/3254—Epoxy compounds containing three or more epoxy groups containing atoms other than carbon, hydrogen, oxygen or nitrogen
    • C08G59/3263—Epoxy compounds containing three or more epoxy groups containing atoms other than carbon, hydrogen, oxygen or nitrogen containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/37—Thiols
    • C08K5/375—Thiols containing six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/37—Thiols
    • C08K5/378—Thiols containing heterocyclic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
    • C09D161/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D167/08—Polyesters modified with higher fatty oils or their acids, or with natural resins or resin acids
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C09D5/082—Anti-corrosive paints characterised by the anti-corrosive pigment
    • C09D5/086—Organic or non-macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/20—Two-dimensional structures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/042—Graphene or derivatives, e.g. graphene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/45—Heterocyclic compounds having sulfur in the ring
    • C08K5/46—Heterocyclic compounds having sulfur in the ring with oxygen or nitrogen in the ring
    • C08K5/47—Thiazoles

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Nanotechnology (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Paints Or Removers (AREA)

Abstract

本发明公开了一种2‑巯基苯并噻唑改性氧化石墨烯防腐涂料及其制备方法，按其质量比，其原料包括：2‑巯基苯并噻唑改性氧化石墨烯5‑20；基体树脂30‑70；流平剂0.5‑1.0；消泡剂0.5‑1.0；分散剂0.5‑1.0；成膜助剂0.5‑1.0；稀释剂20‑35。本发明在分子设计的基础上，利用氧化石墨烯表面官能团，将2‑巯基苯并噻唑接枝到氧化石墨烯表面。合成的材料既具备氧化石墨烯的物理阻隔性，又具备2‑巯基苯并噻唑的缓蚀性。同时氧化石墨烯表面的含氧官能团够使其与环氧树脂等一些有机树脂之间具有优异的相容性和接合面结构。以此作为填料，能够提高在环氧树脂中的分散性，并且防腐蚀性能明显增强。同时氧化石墨烯的加入能有效提高防腐涂料的机械性能。

Description

一种2-巯基苯并噻唑改性氧化石墨烯防腐涂料及其制备方法
技术领域
本发明涉及一种防腐涂料，特别是涉及一种2-巯基苯并噻唑改性氧化石墨烯复合防腐涂料及其制备方法。
背景技术
金属腐蚀现象十分普遍，给国民经济造成了严重损失。现阶段防止金属腐蚀的方法很多，表面涂层保护作为防腐烛的常用手段之一，以其施工简单，维护方便，适应性广，成本低廉，成为当前防腐烛最主要的选择。
石墨烯是一种新型二维材料，其诸多优异的理化性质引起广泛关注。氧化石墨烯与石墨烯相比，表面带有较多的含氧有机官能团，这些含氧有机官能团能够使其与环氧树脂等一些有机树脂之间具有优异的相容性和接合面结构，可充分发挥氧化石墨烯作为增强相在连续相树脂中的作用，同时这些含氧官能团表现出来的强亲水性可使氧化石墨烯在一些溶剂中稳定分散。2-巯基苯并噻唑是一种特殊的缓蚀剂，研究发现氮、氧、硫等电负性较大的原子可以很好的满足金属空轨道缺电子的需求，含这些原子的化合物大多数都是碳钢防腐蚀的高效缓蚀剂。这些特点可以使氧化石墨烯和2-巯基苯并噻唑应用在涂料中。
为了改善防腐涂料工艺，减少污染，需要一种新型掺杂型涂料。专利(CN1011108947A，CN1221768A)先后介绍了以无机填料作为填料的涂料，这些涂料需要添加大量无机导电填料，而无机填料与树脂相容性差，使得漆膜力学性能下降。专利(CN102604533A)介绍了聚苯胺与石墨烯复合材料的防腐蚀涂料，发明认为石墨烯有利于提高漆膜的物理防腐蚀性能，但其在分散过程中容易团聚，分散不稳定。专利(CN102978625A)介绍了一种2-巯基苯并噻唑防腐保护剂，但其是简单的物理混合，分散程度难以保证。
发明内容
本文旨在结合2-巯基苯并噻唑和氧化石墨烯的特点，提供一种同时具备缓蚀性和物理阻隔性的2-巯基苯并噻唑改性氧化石墨烯防腐涂料及制备方法。
所述改性氧化石墨烯的防腐蚀涂料，按质量比组成包括：
所述2-巯基苯并噻唑改性氧化石墨烯由氧化石墨烯、三聚氯氰与2-巯基苯并噻唑合成。
所述基体树脂可选自环氧树脂、氟碳树脂、氨基树脂、丙烯酸树脂、聚氨酯树脂、醇酸树脂、聚酯树脂等中的一种。
所述流平剂可选自有机硅、丙烯酸类、单丁醚类中的一种。
所述消泡剂可选自有机硅类消泡剂、无机硅类消泡剂、非有机硅消泡剂中的一种，如德国毕克公司生产的BYK302、BYK065、BYK20、BYK011、BYK053或埃夫卡公司生产的Efka2018中的一种。
所述分散剂可选自熔性分散剂或润湿分散剂，如德国毕克公司生产的BYK101，BYK161，BYK163，或埃夫卡公司生产的Efka5044。
所述成膜助剂可选自丁基卞醇乙酸酯、乙二醇丁醚醇酸脂、乙二醇苯醚、二元酸二甲酯类、丙二醇丙醚、二元酸二乙酯类等中的一种。
所述稀释剂可选自1,4-丁二醇二缩水甘油醚、乙二醇二缩水甘油醚、丙酮、二甲苯、正丁醇、甲基异丁基酮、无水乙醇、醋酸乙酯、醋酸丁酯等中的至少一种。
所述2-巯基苯并噻唑改性氧化石墨烯，其结构如(Ⅰ)
所述2-巯基苯并噻唑改性氧化石墨烯的制备方法，具体如下：
步骤1、取一定量的氧化石墨烯、三聚氯氰、碳酸氢钠于烧瓶中，取一定体积N，N-二甲基甲酰胺将其分散，室温下搅拌0.5～4h小时，升温至50℃搅拌10～24h，冷却并过滤得到沉淀物。其中氧化石墨烯、三聚氯氰、碳酸氢钠按照投料比为氧化石墨烯：三聚氯氰：碳酸氢钠＝1～30g：1～8mol：1～20mol，N，N-二甲基甲酰胺体积为100～2000ml。
步骤2、取步骤1中沉淀物、2-巯基苯并噻唑、氢氧化钾于烧瓶中，取一定量丙酮将其分散，反应6～10小时，冷却并过滤。其中沉淀物、2-巯基苯并噻唑、氢氧化钾的投料比为沉淀物：2-巯基苯并噻唑：氢氧化钾＝1～30g：1～8mol:1～8mol，丙酮体积为100～2000ml。
所述2-巯基苯并噻唑改性氧化石墨烯的合成路线，具体如下：
所述2-巯基苯并噻唑改性氧化石墨烯复合防腐涂料的制备方法：
将各组分分散混合后1～4h，过滤后既得2-巯基苯并噻唑改性氧化石墨烯复合防腐涂料。
本发明首先制备了一种2-巯基苯并噻唑改性氧化石墨烯，按防腐涂料组份配比取5～20份改性氧化石墨烯、30～70份基体树脂、0.5～1.0份流平剂、0.5～1.0份消泡剂、0.5～1.0份分散剂、0.5～1.0份成膜助剂、20～35份稀释剂。在分散机上均匀分散，过滤后即可得到防腐涂料。
本发明在分子设计的基础上，利用氧化石墨烯表面官能团，将2-巯基苯并噻唑接枝到氧化石墨烯表面。合成的材料既具备氧化石墨烯的物理阻隔性，又具备2-巯基苯并噻唑的缓蚀性。同时氧化石墨烯表面的含氧官能团够使其与环氧树脂等一些有机树脂之间具有优异的相容性和接合面结构。以此作为填料，能够提高在环氧树脂中的分散性，并且防腐蚀性能明显增强。同时氧化石墨烯的加入能有效提高防腐涂料的机械性能。
具体实施方式
下面通过实施例具体说明本发明的内容
实施例1
(1)制备2-巯基苯并噻唑改性氧化石墨烯
a、取10g氧化石墨烯、2mol三聚氯氰、6mol碳酸氢钠分散于1000ml N，N-二甲基甲酰胺中，充入氮气保护，室温下搅拌2h，升温至50℃，搅拌22h。待反应结束用N，N-二甲基甲酰胺洗涤5次，水洗2次，真空干燥24h，得到沉淀。
b、取a中沉淀10g、2mol 2-巯基苯并噻唑、2mol氢氧化钾分散于1000ml丙酮中，充入氮气保护，45℃下反应8h，待反应结束用丙酮洗涤5次，水洗2次，真空干燥24h，得到沉淀。
(2)制备2-巯基苯并噻唑改性氧化石墨烯复合防腐涂料
取5份改性氧化石墨烯、30份环氧树脂、0.5份有机硅、0.5份消泡剂BYK302、0.5份分散剂BYK101、0.5份乙二醇苯醚、20份1，4-丁二醇缩水甘油醚混合，在分散机上均匀分散4h，过滤后即可得到2-巯基苯并噻唑改性氧化石墨烯复合防腐涂料。其防腐性能如表1所示。
实施例2
(1)制备2-巯基苯并噻唑改性氧化石墨烯
a、取20g氧化石墨烯、4mol三聚氯氰、12mol碳酸氢钠分散于1500ml N，N-二甲基甲酰胺中，充入氮气保护，室温下搅拌3h，升温至50℃，搅拌24h。待反应结束用N，N-二甲基甲酰胺洗涤5次，水洗2次，真空干燥24h，得到沉淀。
b、取a中沉淀20g、4mol 2-巯基苯并噻唑、4mol氢氧化钾分散于1500ml丙酮中，充入氮气保护，45℃下反应10h，待反应结束用丙酮洗涤5次，水洗2次，真空干燥24h，得到沉淀。
(2)制备2-巯基苯并噻唑改性氧化石墨烯复合防腐涂料
取10份改性氧化石墨烯、50份环氧树脂、0.8份有机硅、0.6份消泡剂BYK302、0.6份分散剂BYK101、0.8份乙二醇苯醚、30份1，4-丁二醇缩水甘油醚混合，在分散机上均匀分散4h，过滤后即可得到2-巯基苯并噻唑改性氧化石墨烯复合防腐涂料。其防腐性能如表1所示。
实施例3
(1)制备2-巯基苯并噻唑改性氧化石墨烯
a、取30g氧化石墨烯、6mol三聚氯氰、18mol碳酸氢钠分散于2000ml N，N-二甲基甲酰胺中，充入氮气保护，室温下搅拌4h，升温至50℃，搅拌24h。待反应结束用N，N-二甲基甲酰胺洗涤5次，水洗2次，真空干燥24h，得到沉淀。
b、取a中沉淀30g、6mol 2-巯基苯并噻唑、6mol氢氧化钾分散于2000ml丙酮中，充入氮气保护，50℃下反应10h，待反应结束用丙酮洗涤5次，水洗2次，真空干燥24h，得到沉淀。
(2)制备2-巯基苯并噻唑改性氧化石墨烯复合防腐涂料
取20份改性氧化石墨烯、70份丙烯酸树脂、0.8份有机硅、1份消泡剂BYK302、1份分散剂BYK101、0.8份乙二醇苯醚、20份醋酸乙酯混合，在分散机上均匀分散4h，过滤后即可得到2-巯基苯并噻唑改性氧化石墨烯复合防腐涂料。其防腐性能如表1所示。
表1实施例1至3的防腐涂料腐蚀性能测试

Claims (8)

1.一种2-巯基苯并噻唑改性氧化石墨烯防腐涂料，其特征在于，按质量比原料包括：
其中，所述的2-巯基苯并噻唑改性氧化石墨烯，结构如下：
2.如权利要求1所述的一种2-巯基苯并噻唑改性氧化石墨烯防腐涂料，其特征在于所述基体树脂选自环氧树脂、氟碳树脂、氨基树脂、丙烯酸树脂、聚氨酯树脂、醇酸树脂、聚酯树脂中的至少一种。
3.如权利要求1所述的一种2-巯基苯并噻唑改性氧化石墨烯防腐涂料，所述流平剂选自有机硅、丙烯酸类、单丁醚类中的一种。
4.如权利要求1所述的一种2-巯基苯并噻唑改性氧化石墨烯防腐涂料，所述消泡剂选自有机硅类消泡剂、无机硅类消泡剂、非有机硅消泡剂中的一种，包括德国毕克公司生产的BYK302、BYK065、BYK20、BYK011、BYK053或埃夫卡公司生产的Efka2018中的一种。
5.如权利要求1所述的一种2-巯基苯并噻唑改性氧化石墨烯防腐涂料，所述分散剂选自熔性分散剂或润湿分散剂，包括德国毕克公司生产的BYK101，BYK161，BYK163，或埃夫卡公司生产的Efka5044。
6.如权利要求1所述的一种2-巯基苯并噻唑改性氧化石墨烯防腐涂料，所述成膜助剂选自丁基卞醇乙酸酯、乙二醇丁醚醇酸脂、乙二醇苯醚、二元酸二甲酯类、丙二醇丙醚、二元酸二乙酯类中的一种。
7.如权利要求1所述的一种2-巯基苯并噻唑改性氧化石墨烯防腐涂料，所述稀释剂选自1,4-丁二醇二缩水甘油醚、乙二醇二缩水甘油醚、丙酮、二甲苯、正丁醇、甲基异丁基酮、无水乙醇、醋酸乙酯、醋酸丁酯中的至少一种。
8.如权利要求1～7中所述的一种2-巯基苯并噻唑改性氧化石墨烯防腐涂料的制备方法，包括如下步骤：
(1)制备2-巯基苯并噻唑改性氧化石墨烯：
步骤1、取一定量的氧化石墨烯、三聚氯氰、碳酸氢钠于烧瓶中，取一定体积N，N-二甲基甲酰胺将其分散，室温下搅拌0.5～4h小时，升温至50℃搅拌10～24h，冷却并过滤得到沉淀物；其中氧化石墨烯、三聚氯氰、碳酸氢钠按照投料比为氧化石墨烯：三聚氯氰：碳酸氢钠＝1～30g：1～8mol：1～20mol，N，N-二甲基甲酰胺体积为100～2000ml；
步骤2、取步骤1中沉淀物、2-巯基苯并噻唑、氢氧化钾于烧瓶，取一定体积丙酮将其分散，反应6～10小时，冷却并过滤；其中沉淀物、2-巯基苯并噻唑、氢氧化钾的投料比为沉淀物：2-巯基苯并噻唑：氢氧化钾＝1～30g：1～8mol:1～8mol，丙酮体积为100～2000ml；
(2)将各组分分散混合后1～4h，过滤后即得2-巯基苯并噻唑改性氧化石墨烯复合防腐涂料。
CN201611036205.0A 2016-11-23 2016-11-23 一种2-巯基苯并噻唑改性氧化石墨烯防腐涂料及其制备方法 Active CN106700823B (zh)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN201611036205.0A CN106700823B (zh) 2016-11-23 2016-11-23 一种2-巯基苯并噻唑改性氧化石墨烯防腐涂料及其制备方法
US16/463,771 US10843926B2 (en) 2016-11-23 2017-11-23 2-mercaptobenzothiazole modified graphene oxide anti-corrosion coating and method for preparation thereof
PCT/CN2017/112586 WO2018095364A1 (zh) 2016-11-23 2017-11-23 一种2-巯基苯并噻唑改性氧化石墨烯防腐涂料及其制备方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201611036205.0A CN106700823B (zh) 2016-11-23 2016-11-23 一种2-巯基苯并噻唑改性氧化石墨烯防腐涂料及其制备方法

Publications (2)

Publication Number Publication Date
CN106700823A true CN106700823A (zh) 2017-05-24
CN106700823B CN106700823B (zh) 2018-12-18

Family

ID=58940211

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201611036205.0A Active CN106700823B (zh) 2016-11-23 2016-11-23 一种2-巯基苯并噻唑改性氧化石墨烯防腐涂料及其制备方法

Country Status (3)

Country Link
US (1) US10843926B2 (zh)
CN (1) CN106700823B (zh)
WO (1) WO2018095364A1 (zh)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107805438A (zh) * 2017-07-08 2018-03-16 厦门捌斗新材料科技有限公司 一种2‑氨基‑5‑巯基‑1,3,4‑噻二唑/石墨烯树脂浆料及其制备方法和应用
WO2018095364A1 (zh) * 2016-11-23 2018-05-31 厦门大学 一种2-巯基苯并噻唑改性氧化石墨烯防腐涂料及其制备方法
EP3476905A1 (en) * 2017-10-24 2019-05-01 The Boeing Company Compositions with coated carbon fibers and methods for manufacturing compositions with coated carbon fibers
CN109722147A (zh) * 2019-01-22 2019-05-07 江苏冠军科技集团股份有限公司 持久香型石墨烯改性水性醇酸树脂重防腐涂料的制备方法
CN112080329A (zh) * 2020-09-21 2020-12-15 中国科学院兰州化学物理研究所 一种多壁碳纳米管类纳米减摩剂及其应用
CN113637391A (zh) * 2021-08-20 2021-11-12 西安石油大学 一种石墨烯自修复无溶剂环氧防腐涂料及其制备方法和使用方法
CN115386205A (zh) * 2022-09-21 2022-11-25 容鑫新材料(江苏)有限公司 一种可降解抗菌园林膜及其制备方法
CN115517182A (zh) * 2022-09-20 2022-12-27 福建晋江优宏五金制品有限公司 一种具有防腐功能的电焊网
CN115572518A (zh) * 2022-09-26 2023-01-06 厦门大学 一种水系混凝土防护涂料组合物及其制备方法
CN117363134A (zh) * 2023-10-31 2024-01-09 浙江鱼童新材料股份有限公司 一种环氧带锈涂料

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113214632B (zh) * 2021-04-20 2023-04-28 兴业皮革科技股份有限公司 一种阻燃型三聚氯氰改性石墨烯/聚氨酯复合材料及其制备方法、应用
CN114015048B (zh) * 2021-11-02 2023-10-27 国科广化精细化工孵化器(南雄)有限公司 一种可用于水性防腐涂层中的缓蚀剂及其制备方法和应用

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105255353A (zh) * 2015-10-09 2016-01-20 安徽嘉年华漆业有限公司 一种高强度耐冲击油漆

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1221768A (zh) 1997-12-30 1999-07-07 北京红狮涂料公司 一种耐油防腐抗静电涂料及其制备方法
CN101108947A (zh) 2006-07-21 2008-01-23 靳一名 一种镀银铜粉导电涂料及其制备方法
CN102604533A (zh) 2012-03-14 2012-07-25 哈尔滨工程大学 一种基于聚苯胺与石墨烯复合材料的防腐涂料及制备方法
CN102978625A (zh) 2012-09-29 2013-03-20 吴雅萍 铝合金低温防腐保护剂及防腐方法
US20150064451A1 (en) 2013-08-29 2015-03-05 General Electric Company Coating, coating method, and coated article
CN104629603B (zh) 2015-02-11 2017-09-12 上海理工大学 含石墨烯的金属表面处理剂以及耐腐蚀性涂层制备方法
CN105482533B (zh) 2015-12-25 2018-05-11 西南石油大学 一种甲硝唑改性氧化石墨烯复合材料及其制备方法
CN105820645A (zh) 2016-05-23 2016-08-03 安徽易能新材料科技有限公司 一种乙二胺改性石墨烯及含有该乙二胺改性石墨烯的涂料
CN106700823B (zh) 2016-11-23 2018-12-18 厦门大学 一种2-巯基苯并噻唑改性氧化石墨烯防腐涂料及其制备方法

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105255353A (zh) * 2015-10-09 2016-01-20 安徽嘉年华漆业有限公司 一种高强度耐冲击油漆

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018095364A1 (zh) * 2016-11-23 2018-05-31 厦门大学 一种2-巯基苯并噻唑改性氧化石墨烯防腐涂料及其制备方法
US10843926B2 (en) 2016-11-23 2020-11-24 Xiamen University 2-mercaptobenzothiazole modified graphene oxide anti-corrosion coating and method for preparation thereof
CN107805438B (zh) * 2017-07-08 2020-08-18 厦门捌斗新材料科技有限公司 一种2-氨基-5-巯基-1,3,4-噻二唑/石墨烯树脂浆料及其制备方法和应用
CN107805438A (zh) * 2017-07-08 2018-03-16 厦门捌斗新材料科技有限公司 一种2‑氨基‑5‑巯基‑1,3,4‑噻二唑/石墨烯树脂浆料及其制备方法和应用
EP3476905A1 (en) * 2017-10-24 2019-05-01 The Boeing Company Compositions with coated carbon fibers and methods for manufacturing compositions with coated carbon fibers
CN109722147B (zh) * 2019-01-22 2020-12-29 江苏冠军科技集团股份有限公司 持久香型石墨烯改性水性醇酸树脂重防腐涂料的制备方法
CN109722147A (zh) * 2019-01-22 2019-05-07 江苏冠军科技集团股份有限公司 持久香型石墨烯改性水性醇酸树脂重防腐涂料的制备方法
CN112080329A (zh) * 2020-09-21 2020-12-15 中国科学院兰州化学物理研究所 一种多壁碳纳米管类纳米减摩剂及其应用
CN113637391A (zh) * 2021-08-20 2021-11-12 西安石油大学 一种石墨烯自修复无溶剂环氧防腐涂料及其制备方法和使用方法
CN115517182A (zh) * 2022-09-20 2022-12-27 福建晋江优宏五金制品有限公司 一种具有防腐功能的电焊网
CN115386205A (zh) * 2022-09-21 2022-11-25 容鑫新材料(江苏)有限公司 一种可降解抗菌园林膜及其制备方法
CN115386205B (zh) * 2022-09-21 2023-12-08 容鑫新材料(江苏)有限公司 一种可降解抗菌园林膜及其制备方法
CN115572518A (zh) * 2022-09-26 2023-01-06 厦门大学 一种水系混凝土防护涂料组合物及其制备方法
CN117363134A (zh) * 2023-10-31 2024-01-09 浙江鱼童新材料股份有限公司 一种环氧带锈涂料

Also Published As

Publication number Publication date
WO2018095364A1 (zh) 2018-05-31
US10843926B2 (en) 2020-11-24
US20190276318A1 (en) 2019-09-12
CN106700823B (zh) 2018-12-18

Similar Documents

Publication Publication Date Title
CN106700823A (zh) 一种2‑巯基苯并噻唑改性氧化石墨烯防腐涂料及其制备方法
CN102746766B (zh) 一种水性防腐涂料及其制备方法
CN102627903B (zh) 一种环保型水性防腐导静电涂料及其制备方法
CN105860790A (zh) 一种改良的耐高温涂料
CN101935487A (zh) 一种自动控温红外辐射涂料及其应用
CN106752726A (zh) 水性环氧煤沥青防腐涂料
KR20090086417A (ko) 저감된 수준의 휘발성 유기 화합물을 함유한 수성 필름 형성 조성물
CN104725969B (zh) 一种水性防腐漂浮型银粉漆及其制备方法
CN108129966B (zh) 一种氯醚乳液水性防腐涂料
KR20110003480A (ko) 감소된 휘발성 유기 화합물 수준과 증가된 오픈 타임을 나타내는 수성 코팅 조성물
CN110938350A (zh) 轨道交通用环氧底漆及其制备方法
EP2281017A2 (en) Aqueous polymer compositions exhibiting increased open time with reduced levels of volatile organic compounds
CN106366832A (zh) 一种硼改性酚醛树脂底漆
CN112375463A (zh) 一种储罐内壁环保型高固含重防腐涂料及其制备方法
CN109370383A (zh) 一种耐盐雾快干水性涂料及其制备方法
CN108276864A (zh) 一种磷酸酯/聚氨酯改性水性醇酸防腐涂料
CN109181480A (zh) 一种包含改性二氧化钛的环氧富锌涂料及制备方法和用途
CN105219215A (zh) 一种工程机械用高性能环氧底漆的制备方法
CN112457697A (zh) 一种超细矿渣微粉防锈底漆及其制备方法
CN112126293A (zh) 一种石墨烯改性丙烯酸树脂基防腐阻尼涂料及其制备方法
CN106634439A (zh) 一种高粘结强度配电柜外壳用双组份环氧涂料
CN106317461A (zh) 一种插层聚合高效无毒环保钙锌稳定剂的合成制备方法
CN114437610A (zh) 一种水性双组份环氧底面合一涂料及其制备方法
CN109608975A (zh) 一种氟-磷酸酯改性醇酸水性防腐涂料
CN110627097A (zh) 插层材料的制备及其在极地水性防腐涂料中的应用

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant