WO2019095642A1 - Composition de revêtement anticorrosion, procédé de préparation d'un revêtement anticorrosion et revêtement anticorrosion - Google Patents

Composition de revêtement anticorrosion, procédé de préparation d'un revêtement anticorrosion et revêtement anticorrosion Download PDF

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Publication number
WO2019095642A1
WO2019095642A1 PCT/CN2018/085470 CN2018085470W WO2019095642A1 WO 2019095642 A1 WO2019095642 A1 WO 2019095642A1 CN 2018085470 W CN2018085470 W CN 2018085470W WO 2019095642 A1 WO2019095642 A1 WO 2019095642A1
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weight
parts
graphene
resin
filler
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PCT/CN2018/085470
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English (en)
Chinese (zh)
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曹熙辰
郭馥宁
郭骏逸
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曹熙辰
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Publication of WO2019095642A1 publication Critical patent/WO2019095642A1/fr

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    • 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
    • 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
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

Definitions

  • the invention relates to the field of coatings, in particular to an anticorrosive coating composition and a method for preparing an anticorrosive coating and an anticorrosive coating.
  • the marine environment is a very harsh corrosive environment.
  • the ship has been in such a marine environment for a long time, and the corrosion is extremely serious, and the paint has always been its main anti-corrosion means.
  • the design of marine coatings is different according to the environment and requirements of various facilities, and various series of products are derived, for example, marine coatings and heavy-duty anti-corrosion coatings for marine engineering facilities.
  • fluorocarbon resin is a new type of material that has received much attention in recent years. It has excellent weather resistance, stain resistance, chemical resistance, solvent resistance, etc. It is excellent for super weather resistant architectural coatings and heavy anticorrosive coatings. material.
  • the bottom anticorrosive and antifouling paint intentionally incorporates a substance that is toxic to the organism, and inhibits the growth of the organism on the paint surface in a gradually releasing form.
  • the world economy is developing at a rapid pace, the shipping industry is booming, and the volume of ocean shipping is also increasing.
  • the ensuing problem is that the hulls of these large and small vessels are coated with anticorrosive coatings and antifouling coatings containing various toxic substances, heavy metal compounds and the like. Paints release organic solvents during construction and curing, posing a serious threat to the environment and human health.
  • Graphene has a series of excellent physicochemical properties, including 1) excellent electrical properties: graphene has a resistivity of 10 -6 ⁇ /cm on a two-dimensional plane, which is smaller than the optimal metal conductor silver (silver resistivity force of 1.58) ⁇ 10 -6 ⁇ /cm), and its conductive density is a million times that of copper; 2) Mechanical properties: Graphene is the thinnest and hardest substance. James Hone and others at Columbia University recently discovered that graphene has a higher hardness than diamonds and is 100 times stronger than the world's best steel. 3) Chemical properties: graphene has a stable sp 2 chemical structure and resistance.
  • a first aspect of the present invention provides an anticorrosive coating composition
  • an anticorrosive coating composition comprising a resin, a graphene/polyurethane composite material, a filler, a solvent, and an auxiliary agent, with respect to 100 parts by weight of the resin,
  • the content of the graphene/polyurethane composite is 1-25 parts by weight
  • the content of the filler is 5-30 parts by weight
  • the content of the solvent is 1-20 parts by weight
  • the content of the auxiliary agent is 0.1-10. Parts by weight.
  • the graphene/polyurethane composite is contained in an amount of 5 to 15 parts by weight
  • the filler is contained in an amount of 10 to 15 parts by weight
  • the solvent is contained in an amount of 5 parts by weight based on 100 parts by weight of the resin.
  • the amount of the auxiliary agent is 1-5 parts by weight based on -15 parts by weight.
  • w graphene/polyurethane composite
  • w (filler) means parts by weight relative to 100 parts by weight of the filler of the resin
  • w (solvent) means parts by weight relative to 100 parts by weight of the solvent of the resin
  • w (auxiliary) means parts by weight relative to 100 parts by weight of the auxiliary agent of the resin.
  • the resin is at least one selected from the group consisting of epoxy resins, fluorocarbon resins, phenol resins, and alkyd resins.
  • the resin is an epoxy resin and a fluorocarbon resin
  • the epoxy resin has a weight average molecular weight of 2000-20000
  • the fluorocarbon resin has a weight average molecular weight of 1000-5000
  • the epoxy resin and The weight ratio of the fluorocarbon resin is 1: (0.1-1).
  • the weight ratio of graphene to polyurethane is 1: (10-100).
  • the filler is at least one selected from the group consisting of graphite, carbon fiber, activated carbon, conductive carbon black, conductive mica, talc, and organic bentonite.
  • the filler is activated carbon
  • the activated carbon comprises a first activated carbon having a particle diameter of 20-50 mesh and a second activated carbon having a particle diameter of 100-200 mesh, and the weight ratio of the first activated carbon to the second activated carbon is 1 :(10-50).
  • the solvent is at least one selected from the group consisting of ethanol, ethylene glycol, glycerol, n-butanol, ethyl acetate, acetone, toluene, xylene, and tetrahydrofuran.
  • the adjuvant is selected from the group consisting of dispersants and/or defoamers.
  • a second aspect of the present invention provides a method for preparing an anticorrosive coating using the composition of the first aspect of the invention, the method comprising: uniformly mixing the resin, the filler, the solvent and the auxiliary agent, and then grinding the resulting The mixture is then mixed with the graphene/polyurethane composite and dispersed to obtain an anticorrosive coating.
  • a third aspect of the invention provides an anticorrosive coating prepared by the method of the second aspect of the invention.
  • the anticorrosive coating of the invention has high chemical stability and anti-corrosion and wear resistance, can realize dendification and corrosion inhibition of the metal substrate, and has no pollution to the environment, and the preparation method is simple, and is favorable for large-scale industrial production. .
  • a first aspect of the present invention provides an anticorrosive coating composition
  • a resin comprising a resin, a graphene/polyurethane composite, a filler, a solvent, and an auxiliary agent, the graphene/polyurethane relative to 100 parts by weight of the resin
  • the content of the composite material is 1 to 25 parts by weight
  • the content of the filler is 5 to 30 parts by weight
  • the content of the solvent is 1 to 20 parts by weight
  • the content of the auxiliary agent is 0.1 to 10 parts by weight.
  • the content of the graphene/polyurethane composite is 5 to 15 parts by weight
  • the content of the filler is 10 to 15 parts by weight
  • the content of the solvent is 5 with respect to 100 parts by weight of the resin.
  • the amount of the auxiliary agent is 1-5 parts by weight based on -15 parts by weight.
  • the R calculated by the following formula may be 8-12.5:
  • w graphene/polyurethane composite
  • w (filler) means parts by weight relative to 100 parts by weight of the filler of the resin
  • w (solvent) means parts by weight relative to 100 parts by weight of the solvent of the resin
  • w (auxiliary) means parts by weight relative to 100 parts by weight of the auxiliary agent of the resin.
  • the resin may be at least one selected from the group consisting of epoxy resins, fluorocarbon resins, phenol resins, and alkyd resins.
  • the resin may be an epoxy resin and a fluorocarbon resin.
  • the epoxy resin may have a weight average molecular weight of 2000-20000, for example, a bisphenol A type epoxy resin; and the fluorocarbon resin may have a weight average molecular weight of 1000-5000.
  • the weight ratio of the epoxy resin to the fluorocarbon resin may be 1: (-1 - 1).
  • the graphene/polyurethane composite material is a material obtained by subjecting graphene to nano-scale dispersion in a polyurethane matrix after optional modification and/or reduction, which is commercially available or may be used arbitrarily.
  • the prior art for preparing a graphene/polyurethane composite material is prepared.
  • the weight ratio of graphene to polyurethane may be 1: (10-100).
  • the graphene/polyurethane composite material can be prepared by the method disclosed in the patent CN102153877B: a) reacting graphene with an organosilane in a mixed solution of an organic solvent and water to obtain an organosilane-modified graphene; b) The organosilane-modified graphene and the polyurethane are mixed to obtain a graphene composite material.
  • the filler may be a common filler for preparing an anticorrosive paint, for example, at least one selected from the group consisting of graphite, carbon fiber, activated carbon, conductive carbon black, conductive mica, talc, and organic bentonite.
  • the filler is activated carbon
  • the activated carbon comprises a first activated carbon having a particle diameter of 20-50 mesh and a second activated carbon having a particle diameter of 100-200 mesh, the first activated carbon and The weight ratio of the second activated carbon may be 1: (10-50).
  • the use of a combination of activated carbon having the above particle diameter as a filler can further optimize the performance of the anticorrosive coating.
  • the solvent may be conventional in the art, for example, at least one selected from the group consisting of ethanol, ethylene glycol, glycerin, n-butanol, ethyl acetate, acetone, toluene, xylene, and tetrahydrofuran.
  • the auxiliary agent may be a common type of anticorrosive coating, such as a wetting agent, a dispersing agent, a leveling agent, an antifoaming agent, a thickening agent, a film forming agent, an anti-settling agent, a mildewproof and an algicide. , adhesion promoters, etc.
  • the adjuvant may be selected from the group consisting of dispersants and/or antifoaming agents.
  • the above-mentioned auxiliary agents are commercially available.
  • the dispersing agent may be Disperbyk 163, Disperbyk 111, Disperbyk 115, Disperbyk 192, Disperbyk 191, Disperbyk 190, etc., which are commercially available from BYK Chemical Co., Ltd., and defoaming agents such as BYK Chemical The company's BYK-053, BYK-065, BYK-055, BYK-053 and so on.
  • a second aspect of the present disclosure provides a method for preparing an anticorrosive paint by using the composition of the first aspect of the present disclosure, characterized in that the method comprises: uniformly mixing the resin, the filler, the solvent and the auxiliary agent, and then grinding, The resulting mixture is then mixed with the graphene/polyurethane composite and dispersed to obtain an anticorrosive coating.
  • a third aspect of the present disclosure provides an anticorrosive coating prepared by the method of the second aspect of the present disclosure.
  • the anticorrosive coating of the invention has high chemical stability and anti-corrosion and wear resistance, can realize Dunhua and corrosion inhibition of the metal substrate, and has no pollution to the environment, and has a simple preparation method and is favorable for large-scale industrial production.
  • the abrasion resistance of the anticorrosive coating was tested according to the method of GB/T 1768; the anticorrosive property was tested according to the method of GB/T 1763.
  • 0.5 g of graphene powder was added to 100 ml of N,N-dimethylformamide, ultrasonically dispersed at a frequency of 20 Hz for 2 hours, then 0.5 g of ⁇ -aminopropyltrimethoxysilane and 0.5 g of distilled water were added, and mechanically at 25 ° C. After stirring for 24 hours, after the reaction, a black powdery solid product, that is, organosilane-modified graphene, was obtained by suction filtration; 0.3 g of the above organosilane-modified graphene was added to 80 ml of N,N-dimethylformamide.
  • the graphene/polyurethane composite material of this example is identical to that of Example 1.
  • the graphene/polyurethane composite material of this example is identical to that of Example 1.
  • the graphene/polyurethane composite material of this example is identical to that of Example 1.
  • the graphene/polyurethane composite material of this example is identical to that of Example 1.
  • the graphene/polyurethane composite material of this example is identical to that of Example 1.
  • the graphene/polyurethane composite material of this example is identical to that of Example 1.
  • the graphene/polyurethane composite material of this example is identical to that of Example 1.
  • the graphene/polyurethane composite material of this example is identical to that of Example 1.
  • the graphene/polyurethane composite material of this example is identical to that of Example 1.
  • a black powdery solid product that is, organosilane-modified graphene
  • organosilane-modified graphene was obtained by suction filtration; 0.3 g of the above organosilane-modified graphene was added to 80 ml of N,N-dimethylformamide, and then 10 g of polyurethane was added, ultrasonically dispersed at a frequency of 20 Hz for 2 hours, and then mechanically stirred for 24 hours to remove N,N-dimethylformamide to obtain a graphene/polyurethane composite.
  • 0.5 g of graphene powder was added to 100 ml of N,N-dimethylformamide, ultrasonically dispersed at a frequency of 20 Hz for 2 hours, then 0.5 g of ⁇ -aminopropyltrimethoxysilane and 0.5 g of distilled water were added, and mechanically at 25 ° C. After stirring for 24 hours, after the reaction, a black powdery solid product, that is, organosilane-modified graphene, was obtained by suction filtration; 0.3 g of the above organosilane-modified graphene was added to 80 ml of N,N-dimethylformamide.
  • Example 1 the same weight fraction of graphene powder as in Example 1 was used instead of the graphene/polyurethane composite material of Example 1, and otherwise, in the same manner as in Example 1, the anticorrosive paint of the present comparative example was prepared.
  • the anticorrosive coating of the present disclosure has high chemical stability and corrosion resistance.
  • the epoxy resin when the resin is an epoxy resin and a fluorocarbon resin, the epoxy resin has a weight average molecular weight of 2,000 to 20,000, and the fluorocarbon resin has a weight.
  • the average molecular weight is 1000-5000, and when the weight ratio of the epoxy resin to the fluorocarbon resin is 1: (0.1-1), the chemical stability and corrosion resistance of the anticorrosive coating can be further improved.
  • the activated carbon when the filler is activated carbon, includes a first activated carbon having a particle diameter of 20-50 mesh and a second activated carbon having a particle diameter of 100-200 mesh.
  • the weight ratio of the first activated carbon to the second activated carbon is 1: (10-50)
  • the chemical stability and corrosion resistance of the anticorrosive coating can be further improved.
  • Example 11 when the weight ratio of graphene to polyurethane in the graphene/polyurethane composite is 1: (10-100), the chemical stability of the anticorrosive coating can be further improved. Sex and anti-corrosion resistance.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Paints Or Removers (AREA)

Abstract

L'invention concerne une composition de revêtement anticorrosion, un procédé de préparation d'un revêtement anticorrosion et le revêtement anticorrosion. La composition comprend une résine, un matériau composite à base de graphène/polyuréthane, une charge, un solvant et un agent auxiliaire. Sur la base de 100 parties en poids de la résine, la teneur en matériau composite à base de graphène/polyuréthane est de 1 à 25 parties en poids, la teneur en charge est de 5 à 30 parties en poids, la teneur en solvant est de 1 à 20 parties en poids et la teneur en agent auxiliaire est 0,1 à 10 parties en poids. Le revêtement anticorrosion de la présente invention présente une stabilité chimique relativement élevée ainsi que des performances anticorrosion et de résistance à l'usure et peut réaliser une désactivation et une inhibition de la corrosion d'un matériau de base métallique. Le revêtement anticorrosion est respectueux de l'environnement, simple à préparer et approprié pour une production industrielle à grande échelle.
PCT/CN2018/085470 2017-11-20 2018-05-03 Composition de revêtement anticorrosion, procédé de préparation d'un revêtement anticorrosion et revêtement anticorrosion WO2019095642A1 (fr)

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CN201711160547.8A CN107955490B (zh) 2017-11-20 2017-11-20 防腐涂料组合物及制备防腐涂料的方法和防腐涂料
CN201711160547.8 2017-11-20

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CN113717603A (zh) * 2021-10-11 2021-11-30 广西民族大学 一种改性氟碳防腐涂料及其制备方法
CN114149721A (zh) * 2021-11-26 2022-03-08 湖南航天三丰科工有限公司 一种组合涂料及其制备、涂装方法

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CN107955490B (zh) * 2017-11-20 2019-05-31 曹熙辰 防腐涂料组合物及制备防腐涂料的方法和防腐涂料
CN113462258A (zh) * 2021-07-28 2021-10-01 西安建筑科技大学 一种耐高温防腐涂料及其制备方法
CN113755086A (zh) * 2021-09-03 2021-12-07 中星防腐工程技术(广东)有限公司 一种基于聚氨酯的环保阻燃防腐涂料及其制备方法

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CN111394039A (zh) * 2020-05-21 2020-07-10 重庆索梦得新材料科技有限公司 一种石墨烯纳米三防胶及其制备方法
CN113717603A (zh) * 2021-10-11 2021-11-30 广西民族大学 一种改性氟碳防腐涂料及其制备方法
CN113717603B (zh) * 2021-10-11 2022-07-12 广西民族大学 一种改性氟碳防腐涂料及其制备方法
CN114149721A (zh) * 2021-11-26 2022-03-08 湖南航天三丰科工有限公司 一种组合涂料及其制备、涂装方法

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