WO2019095642A1 - Anti-corrosion coating composition, method for preparing anti-corrosion coating, and anti-corrosion coating - Google Patents

Anti-corrosion coating composition, method for preparing anti-corrosion coating, and anti-corrosion coating Download PDF

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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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French (fr)
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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    • 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.

Abstract

Disclosed are an anti-corrosion coating composition, a method for preparing an anti-corrosion coating, and the anti-corrosion coating. The composition comprises 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 material 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, and the content of the auxiliary agent is 0.1-10 parts by weight. The anti-corrosion coating of the present invention has relatively high chemical stability as well as anti-corrosive and wear-resisting performances, and can realize deactivation and corrosion inhibition of a metal base material. The anti-corrosion coating is environment-friendly, simple to prepare, and suitable for large-scale industrial production.

Description

防腐涂料组合物及制备防腐涂料的方法和防腐涂料Anticorrosive coating composition and method for preparing anticorrosive coating and anticorrosive coating 技术领域Technical field
本发明涉及涂料领域，具体地，涉及一种防腐涂料组合物及制备防腐涂料的方法和防腐涂料。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.
背景技术Background technique
海洋环境是十分严酷的腐蚀环境，船舶长期处于这样的海洋环境中，腐蚀极其严重，而涂料一直是其最主要的防腐手段。为了解决海洋防腐和防污的两大问题，海洋涂料的设计根据各种设施的使用环境和要求不同，又衍生出各种系列产品，例如，船舶涂料、海洋工程设施用重防腐涂料等。其中，氟碳树脂是近年来广受关注的新型材料，它具有极优异的耐候性、耐沾污性、耐化学品性、耐溶剂性等，是超耐候性建筑涂料及重防腐涂料的优良材料。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. In order to solve the two problems of marine anti-corrosion and anti-fouling, 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. Among them, 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.
为了防止海洋生韧在船底附着并由此带来对涂层的腐蚀，船底防腐和防污漆中有意掺入对生物有毒的物质，以一种渐释的形式抑制生物在漆面上生长。世界经济飞速发展，船运业日趋兴旺，海洋航运量也随之增加。然而，随之而来的问题是这些大小船只的船身都涂有含各种毒料、重金属化合物等有害物质的防腐涂料和防污涂料。涂料在施工使用和固化过程中会释放出有机溶剂，对环境和人身健康构成了严重的威胁。In order to prevent the marine toughness from adhering to the bottom of the ship and thereby causing corrosion to the coating, 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. However, 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.
石墨烯具有一系列优良的物化性能，包括1)优异的电学性能：石墨烯在二维平面上的电阻率为10 -6Ω/cm，小于最佳的金属导体银(银的电阻率力1.58×10 -6Ω/cm)，而其导电密度是铜的一百万倍；2)机械性能：石墨烯是最薄、最坚硬的物质。美国哥伦比亚大学James Hone等人最近发现，石墨烯的硬度比钻石还高，强度比世界上最好的钢铁还要高上100倍；3)化学 性能：石墨烯具有稳定的sp 2化学结构，耐腐蚀，耐高温，化学稳定性好；4)高比表面积：比表面积≥2650m 2/g。易于修饰及大规模生产等；5)抑制细菌生长；6)抗紫外辐射的功能。由于上述的这些优异的特性，石墨烯产品的应用研究近年来迅猛发展，但其作为防腐涂料的研究尚处于初级阶段。 Graphene has a series of excellent physicochemical properties, including 1) excellent electrical properties: graphene has a resistivity of 10 -6 Ω/cm on a two-dimensional plane, which is smaller than the optimal metal conductor silver (silver resistivity force of 1.58) ×10 -6 Ω/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. Corrosion, high temperature resistance, good chemical stability; 4) High specific surface area: specific surface area ≥ 2650m 2 /g. Easy to modify and mass production; 5) inhibit bacterial growth; 6) anti-ultraviolet radiation function. Due to these excellent characteristics, the application research of graphene products has developed rapidly in recent years, but its research as an anticorrosive coating is still in its infancy.
为了适应时代的发展和环境保护的要求，开发环保型涂料，并且在涂料技术的开发中要达到高性能、节省资源及适应生态环境成为船舶涂料研究生产的主要目标。In order to adapt to the development of the times and the requirements of environmental protection, the development of environmentally friendly coatings, and in the development of coating technology to achieve high performance, save resources and adapt to the ecological environment has become the main goal of research and production of marine coatings.
发明内容Summary of the invention
本发明的目的是提供一种防腐涂料组合物及制备防腐涂料的方法和防腐涂料，该防腐涂料具有优异的防腐耐磨性能。It is an object of the present invention to provide an anticorrosive coating composition and a method of preparing an anticorrosive coating and an anticorrosive coating which has excellent corrosion resistance and wear resistance.
为了实现上述目的，本发明第一方面：提供一种防腐涂料组合物，该组合物含有树脂、石墨烯/聚氨酯复合材料、填料、溶剂和助剂，相对于100重量份的所述树脂，所述石墨烯/聚氨酯复合材料的含量为1-25重量份，所述填料的含量为5-30重量份，所述溶剂的含量为1-20重量份，所述助剂的含量为0.1-10重量份。In order to achieve the above object, a first aspect of the present invention provides 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, and the content of the auxiliary agent is 0.1-10. Parts by weight.
可选地，相对于100重量份的所述树脂，所述石墨烯/聚氨酯复合材料的含量为5-15重量份，所述填料的含量为10-15重量份，所述溶剂的含量为5-15重量份，所述助剂的含量为1-5重量份。Optionally, 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, and 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.
可选地，通过下式计算得到的R为8-12.5：Alternatively, the R calculated by the following formula is 8-12.5:
R＝1.1w(石墨烯/聚氨酯复合材料)-0.32w(填料)+0.106w(溶剂)+0.055w(助剂)，R=1.1w (graphene/polyurethane composite)-0.32w (filler)+0.106w (solvent)+0.055w (auxiliary),
其中，w(石墨烯/聚氨酯复合材料)表示相对于100重量份树脂的石墨烯/聚氨酯复合材料的重量份，Wherein w (graphene/polyurethane composite) represents a part by weight of the graphene/polyurethane composite relative to 100 parts by weight of the resin,
w(填料)表示相对于100重量份树脂的填料的重量份，w (filler) means parts by weight relative to 100 parts by weight of the filler of the resin,
w(溶剂)表示相对于100重量份树脂的溶剂的重量份，w (solvent) means parts by weight relative to 100 parts by weight of the solvent of the resin,
w(助剂)表示相对于100重量份树脂的助剂的重量份。w (auxiliary) means parts by weight relative to 100 parts by weight of the auxiliary agent of the resin.
可选地，所述树脂为选自环氧树脂、氟碳树脂、酚醛树脂和醇酸树脂中的至少一种。Optionally, the resin is at least one selected from the group consisting of epoxy resins, fluorocarbon resins, phenol resins, and alkyd resins.
可选地，所述树脂为环氧树脂和氟碳树脂，所述环氧树脂的重均分子量为2000-20000，所述氟碳树脂的重均分子量为1000-5000，所述环氧树脂和氟碳树脂的重量比为1：(0.1-1)。Optionally, the resin is an epoxy resin and a fluorocarbon resin, the epoxy resin has a weight average molecular weight of 2000-20000, and 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).
可选地，所述石墨烯/聚氨酯复合材料中，石墨烯和聚氨酯的重量比为1：(10-100)。Optionally, in the graphene/polyurethane composite, the weight ratio of graphene to polyurethane is 1: (10-100).
可选地，所述填料为选自石墨、碳纤维、活性炭、导电炭黑、导电云母、滑石粉和有机膨润土中的至少一种。Optionally, 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.
可选地，所述填料为活性炭，所述活性炭包括粒径为20-50目的第一活性炭和粒径为100-200目的第二活性炭，所述第一活性炭和第二活性炭的重量比为1：(10-50)。Optionally, the filler is activated carbon, and 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).
可选地，所述溶剂为选自乙醇、乙二醇、丙三醇、正丁醇、乙酸乙酯、丙酮、甲苯、二甲苯和四氢呋喃中的至少一种。Optionally, 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.
可选地，所述助剂为选自分散剂和/或消泡剂。Optionally, the adjuvant is selected from the group consisting of dispersants and/or defoamers.
本发明第二方面：提供一种采用本发明第一方面所述的组合物制备防腐涂料的方法，该方法包括：将所述树脂、填料、溶剂和助剂混合均匀后研磨，然后将所得的混合物再与石墨烯/聚氨酯复合材料混合，分散均匀后得到防腐涂料。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.
本发明第三方面：提供一种由本发明第二方面所述的方法制备得到的防腐涂料。A third aspect of the invention provides an anticorrosive coating prepared by the method of the second aspect of the invention.
通过上述技术方案，本发明的防腐涂料具有较高的化学稳定性和防腐 耐磨性，可以实现金属基材的敦化和缓蚀，且对环境无污染，同时制备方法简单，有利于大规模工业生产。Through the above technical solution, 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. .
本发明的其他特征和优点将在随后的具体实施方式部分予以详细说明。Other features and advantages of the invention will be described in detail in the detailed description which follows.
具体实施方式Detailed ways
以下对本发明的具体实施方式进行详细说明。应当理解的是，此处所描述的具体实施方式仅用于说明和解释本发明，并不用于限制本发明。Specific embodiments of the present invention will be described in detail below. It is to be understood that the specific embodiments described herein are merely illustrative and not restrictive.
本发明第一方面：提供一种防腐涂料组合物，该组合物含有树脂、石墨烯/聚氨酯复合材料、填料、溶剂和助剂，相对于100重量份的所述树脂，所述石墨烯/聚氨酯复合材料的含量为1-25重量份，所述填料的含量为5-30重量份，所述溶剂的含量为1-20重量份，所述助剂的含量为0.1-10重量份。优选情况下，相对于100重量份的所述树脂，所述石墨烯/聚氨酯复合材料的含量为5-15重量份，所述填料的含量为10-15重量份，所述溶剂的含量为5-15重量份，所述助剂的含量为1-5重量份。A first aspect of the present invention provides an anticorrosive coating composition 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, and the content of the auxiliary agent is 0.1 to 10 parts by weight. Preferably, 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, and 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.
根据本发明，为了进一步提高防腐涂料的化学稳定性和防腐耐磨性，通过下式计算得到的R可以为8-12.5：According to the present invention, in order to further improve the chemical stability and corrosion resistance of the anticorrosive coating, the R calculated by the following formula may be 8-12.5:
R＝1.1w(石墨烯/聚氨酯复合材料)-0.32w(填料)+0.106w(溶剂)+0.055w(助剂)，R=1.1w (graphene/polyurethane composite)-0.32w (filler)+0.106w (solvent)+0.055w (auxiliary),
其中，w(石墨烯/聚氨酯复合材料)表示相对于100重量份树脂的石墨烯/聚氨酯复合材料的重量份，Wherein w (graphene/polyurethane composite) represents a part by weight of the graphene/polyurethane composite relative to 100 parts by weight of the resin,
w(填料)表示相对于100重量份树脂的填料的重量份，w (filler) means parts by weight relative to 100 parts by weight of the filler of the resin,
w(溶剂)表示相对于100重量份树脂的溶剂的重量份，w (solvent) means parts by weight relative to 100 parts by weight of the solvent of the resin,
w(助剂)表示相对于100重量份树脂的助剂的重量份。w (auxiliary) means parts by weight relative to 100 parts by weight of the auxiliary agent of the resin.
根据本发明，所述树脂可以为选自环氧树脂、氟碳树脂、酚醛树脂和 醇酸树脂中的至少一种。为了进一步提高防腐涂料的化学稳定性和防腐耐磨性，在本公开的一种优选的实施方式中，所述树脂可以为环氧树脂和氟碳树脂。其中，所述环氧树脂的重均分子量可以为2000-20000，例如为双酚A型环氧树脂；所述氟碳树脂的重均分子量可以为1000-5000。在该优选的实施方式中，所述环氧树脂和氟碳树脂的重量比可以为1：(0.1-1)。According to the invention, the resin may be at least one selected from the group consisting of epoxy resins, fluorocarbon resins, phenol resins, and alkyd resins. In order to further improve the chemical stability and corrosion resistance of the anticorrosive coating, in a preferred embodiment of the present disclosure, the resin may be an epoxy resin and a fluorocarbon resin. Wherein, 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. In this preferred embodiment, the weight ratio of the epoxy resin to the fluorocarbon resin may be 1: (-1 - 1).
根据本发明，所述石墨烯/聚氨酯复合材料为将石墨烯经过可选的改性和/或还原后在聚氨酯基体中形成纳米级分散所得到的材料，其可商购得到，也可以采用任意制备石墨烯/聚氨酯复合材料的现有技术制备得到，优选地，所述石墨烯/聚氨酯复合材料中，石墨烯和聚氨酯的重量比可以为1：(10-100)。例如，所述石墨烯/聚氨酯复合材料可以参考专利CN102153877B所公开的方法制备得到：a)将石墨烯与有机硅烷在有机溶剂和水的混合溶液中反应，得到有机硅烷修饰的石墨烯；b)将所述有机硅烷修饰的石墨烯和聚氨酯混合，得到石墨烯复合材料。According to the present invention, 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. Preferably, in the graphene/polyurethane composite material, the weight ratio of graphene to polyurethane may be 1: (10-100). For example, 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.
根据本发明，所述填料可以为制备防腐涂料的常见填料，例如为选自石墨、碳纤维、活性炭、导电炭黑、导电云母、滑石粉和有机膨润土中的至少一种。According to the present invention, 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.
在本发明的一种优选的实施方式中，所述填料为活性炭，所述活性炭包括粒径为20-50目的第一活性炭和粒径为100-200目的第二活性炭，所述第一活性炭和第二活性炭的重量比可以为1：(10-50)。采用具有上述粒径的活性炭的组合作为填料能够进一步优化防腐涂料的性能。In a preferred embodiment of the present invention, the filler is activated carbon, and 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.
根据本公开，所述溶剂可以为本领域常规的，例如为选自乙醇、乙二醇、丙三醇、正丁醇、乙酸乙酯、丙酮、甲苯、二甲苯和四氢呋喃中的至少一种。According to the present disclosure, 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.
根据本公开，所述助剂可以为制备防腐涂料的常见种类，如润湿剂、分散剂、流平剂、消泡剂、增稠剂、成膜剂、防沉剂、防霉防藻剂、附着 力促进剂等。优选情况下，所述助剂可以为选自分散剂和/或消泡剂。上述助剂均可商购得到，例如所述分散剂可以为购自德国毕克化学公司的Disperbyk163、Disperbyk 111、Disperbyk 115、Disperbyk 192、Disperbyk 191、Disperbyk 190等，消泡剂如德国毕克化学公司的BYK-053、BYK-065、BYK-055、BYK-053等。According to the present disclosure, 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. Preferably, the adjuvant may be selected from the group consisting of dispersants and/or antifoaming agents. The above-mentioned auxiliary agents are commercially available. For example, 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.
本公开第二方面：提供一种采用本公开第一方面所述的组合物制备防腐涂料的方法，其特征在于，该方法包括：将所述树脂、填料、溶剂和助剂混合均匀后研磨，然后将所得的混合物再与石墨烯/聚氨酯复合材料混合，分散均匀后得到防腐涂料。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.
本公开第三方面：提供一种由本公开第二方面所述的方法制备得到的防腐涂料。A third aspect of the present disclosure provides an anticorrosive coating prepared by the method of the second aspect of the present disclosure.
本发明的防腐涂料具有较高的化学稳定性和防腐耐磨性，可以实现金属基材的敦化和缓蚀，且对环境无污染，同时制备方法简单，有利于大规模工业生产。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.
下面通过实施例进一步描述本发明，但是本发明并不因此而受到任何限制。本发明的下述实施例中，所使用的试剂均为市售产品。The invention is further described by the following examples, but the invention is not limited thereby. In the following examples of the invention, the reagents used were all commercially available products.
实施例中，防腐涂料的耐磨性按照GB/T 1768的方法进行检测；防腐性能按照GB/T 1763的方法进行检测。In the examples, 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.
实施例1Example 1
将0.5g石墨烯粉末加入100mlN，N-二甲基甲酰胺中，以20赫兹的频率超声分散2小时，然后加入0.5gγ-氨丙基三甲氧基硅烷和0.5g蒸馏水，在25℃下机械搅拌，反应24小时，反应结束后采用抽滤方法得到黑色粉末状固体产物，即有机硅烷修饰的石墨烯；将0.3g上述有机硅烷修饰的石墨烯加入80mlN，N-二甲基甲酰胺中，然后加入10g聚氨酯，以20赫兹的频 率超声分散2小时，然后机械搅拌24小时，除去N，N-二甲基甲酰胺，得到石墨烯/聚氨酯复合材料。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 γ-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. 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.
将50重量份的双酚A型环氧树脂(重均分子量为10000)，50重量份的氟碳树脂(重均分子量为5000)，0.5重量份的20-50目的第一活性炭，10重量份的100-200目的第二活性炭，11重量份的溶剂正丁醇，1重量份的分散剂(Disperbyk191)，和1重量份的消泡剂(BYK 053)混合搅拌30min，然后在磨砂机中进行研磨，然后将所得的混合物再与12重量份的石墨烯/聚氨酯复合材料混合搅拌1h，得到本实施例制备的防腐涂料。50 parts by weight of bisphenol A type epoxy resin (weight average molecular weight: 10,000), 50 parts by weight of fluorocarbon resin (weight average molecular weight: 5000), 0.5 parts by weight of 20-50 mesh first activated carbon, 10 parts by weight 100-200 mesh of second activated carbon, 11 parts by weight of solvent n-butanol, 1 part by weight of dispersant (Disperbyk 191), and 1 part by weight of antifoaming agent (BYK 053) were mixed and stirred for 30 min, and then carried out in a sander After grinding, the resulting mixture was further mixed with 12 parts by weight of the graphene/polyurethane composite material for 1 hour to obtain an anticorrosive paint prepared in the present example.
检测该防腐涂料的耐磨性和防腐性能，测试结果见表1。The abrasion resistance and corrosion resistance of the anticorrosive coating were tested, and the test results are shown in Table 1.
实施例2Example 2
本实施例的石墨烯/聚氨酯复合材料与实施例1一致。The graphene/polyurethane composite material of this example is identical to that of Example 1.
将60重量份的双酚A型环氧树脂(重均分子量为10000)，40重量份的氟碳树脂(重均分子量为5000)，0.3重量份的20-50目的第一活性炭，12重量份的100-200目的第二活性炭，6重量份的溶剂乙二醇，2重量份的分散剂(Disperbyk191)，和1重量份的消泡剂(BYK 053)混合搅拌30min，然后在磨砂机中进行研磨，然后将所得的混合物再与11重量份的石墨烯/聚氨酯复合材料混合搅拌1h，得到本实施例制备的防腐涂料。60 parts by weight of bisphenol A type epoxy resin (weight average molecular weight: 10,000), 40 parts by weight of fluorocarbon resin (weight average molecular weight: 5000), 0.3 parts by weight of 20-50 mesh of first activated carbon, 12 parts by weight 100-200 mesh of second activated carbon, 6 parts by weight of solvent glycol, 2 parts by weight of dispersant (Disperbyk 191), and 1 part by weight of antifoaming agent (BYK 053) were mixed and stirred for 30 min, and then carried out in a sander After grinding, the resulting mixture was further mixed with 11 parts by weight of the graphene/polyurethane composite material for 1 hour to obtain an anticorrosive paint prepared in the present example.
检测该防腐涂料的耐磨性和防腐性能，测试结果见表1。The abrasion resistance and corrosion resistance of the anticorrosive coating were tested, and the test results are shown in Table 1.
实施例3Example 3
本实施例的石墨烯/聚氨酯复合材料与实施例1一致。The graphene/polyurethane composite material of this example is identical to that of Example 1.
将50重量份的双酚A型环氧树脂(重均分子量为10000)，50重量份的氟碳树脂(重均分子量为5000)，0.5重量份的20-50目的第一活性炭，25重量份的100-200目的第二活性炭，2重量份的溶剂正丁醇，0.1重量份 的分散剂(Disperbyk191)，和0.1重量份的消泡剂(BYK 053)混合搅拌30min，然后在磨砂机中进行研磨，然后将所得的混合物再与18重量份的石墨烯/聚氨酯复合材料混合搅拌1h，得到本实施例制备的防腐涂料。50 parts by weight of bisphenol A type epoxy resin (weight average molecular weight: 10,000), 50 parts by weight of fluorocarbon resin (weight average molecular weight: 5000), 0.5 parts by weight of 20-50 mesh first activated carbon, 25 parts by weight 100-200 mesh second activated carbon, 2 parts by weight of solvent n-butanol, 0.1 part by weight of dispersant (Disperbyk 191), and 0.1 part by weight of antifoaming agent (BYK 053) were mixed and stirred for 30 min, and then carried out in a sander After grinding, the resulting mixture was further mixed with 18 parts by weight of the graphene/polyurethane composite material for 1 hour to obtain an anticorrosive paint prepared in the present example.
检测该防腐涂料的耐磨性和防腐性能，测试结果见表1。The abrasion resistance and corrosion resistance of the anticorrosive coating were tested, and the test results are shown in Table 1.
实施例4Example 4
本实施例的石墨烯/聚氨酯复合材料与实施例1一致。The graphene/polyurethane composite material of this example is identical to that of Example 1.
将50重量份的双酚A型环氧树脂(重均分子量为10000)，50重量份的氟碳树脂(重均分子量为5000)，0.5重量份的20-50目的第一活性炭，10重量份的100-200目的第二活性炭，11重量份的溶剂正丁醇，1重量份的分散剂(Disperbyk191)，和1重量份的消泡剂(BYK 053)混合搅拌30min，然后在磨砂机中进行研磨，然后将所得的混合物再与5重量份的石墨烯/聚氨酯复合材料混合搅拌1h，得到本实施例制备的防腐涂料。50 parts by weight of bisphenol A type epoxy resin (weight average molecular weight: 10,000), 50 parts by weight of fluorocarbon resin (weight average molecular weight: 5000), 0.5 parts by weight of 20-50 mesh first activated carbon, 10 parts by weight 100-200 mesh of second activated carbon, 11 parts by weight of solvent n-butanol, 1 part by weight of dispersant (Disperbyk 191), and 1 part by weight of antifoaming agent (BYK 053) were mixed and stirred for 30 min, and then carried out in a sander After grinding, the resulting mixture was further mixed with 5 parts by weight of the graphene/polyurethane composite material for 1 hour to obtain an anticorrosive paint prepared in the present example.
检测该防腐涂料的耐磨性和防腐性能，测试结果见表1。The abrasion resistance and corrosion resistance of the anticorrosive coating were tested, and the test results are shown in Table 1.
实施例5Example 5
本实施例的石墨烯/聚氨酯复合材料与实施例1一致。The graphene/polyurethane composite material of this example is identical to that of Example 1.
将50重量份的双酚A型环氧树脂(重均分子量为10000)，50重量份的氟碳树脂(重均分子量为5000)，0.5重量份的20-50目的第一活性炭，10重量份的100-200目的第二活性炭，15重量份的溶剂正丁醇，1重量份的分散剂(Disperbyk191)，和2重量份的消泡剂(BYK 053)混合搅拌30min，然后在磨砂机中进行研磨，然后将所得的混合物再与15重量份的石墨烯/聚氨酯复合材料混合搅拌1h，得到本实施例制备的防腐涂料。50 parts by weight of bisphenol A type epoxy resin (weight average molecular weight: 10,000), 50 parts by weight of fluorocarbon resin (weight average molecular weight: 5000), 0.5 parts by weight of 20-50 mesh first activated carbon, 10 parts by weight 100-200 mesh second activated carbon, 15 parts by weight of solvent n-butanol, 1 part by weight of dispersant (Disperbyk 191), and 2 parts by weight of antifoaming agent (BYK 053) were mixed and stirred for 30 min, and then carried out in a sander After grinding, the resulting mixture was further mixed with 15 parts by weight of the graphene/polyurethane composite material for 1 hour to obtain an anticorrosive paint prepared in the present example.
检测该防腐涂料的耐磨性和防腐性能，测试结果见表1。The abrasion resistance and corrosion resistance of the anticorrosive coating were tested, and the test results are shown in Table 1.
实施例6Example 6
本实施例的石墨烯/聚氨酯复合材料与实施例1一致。The graphene/polyurethane composite material of this example is identical to that of Example 1.
将100重量份的双酚A型环氧树脂(重均分子量为10000)，0.5重量份的20-50目的第一活性炭，10重量份的100-200目的第二活性炭，11重量份的溶剂正丁醇，1重量份的分散剂(Disperbyk191)，和1重量份的消泡剂(BYK 053)混合搅拌30min，然后在磨砂机中进行研磨，然后将所得的混合物再与12重量份的石墨烯/聚氨酯复合材料混合搅拌1h，得到本实施例制备的防腐涂料。100 parts by weight of bisphenol A type epoxy resin (weight average molecular weight: 10,000), 0.5 parts by weight of 20-50 mesh first activated carbon, 10 parts by weight of 100-200 mesh second activated carbon, and 11 parts by weight of solvent Butanol, 1 part by weight of a dispersant (Disperbyk 191), and 1 part by weight of an antifoaming agent (BYK 053) were mixed and stirred for 30 minutes, then ground in a sander, and then the resulting mixture was further mixed with 12 parts by weight of graphene. The polyurethane composite was mixed and stirred for 1 hour to obtain an anticorrosive coating prepared in this example.
检测该防腐涂料的耐磨性和防腐性能，测试结果见表1。The abrasion resistance and corrosion resistance of the anticorrosive coating were tested, and the test results are shown in Table 1.
实施例7Example 7
本实施例的石墨烯/聚氨酯复合材料与实施例1一致。The graphene/polyurethane composite material of this example is identical to that of Example 1.
将100重量份的氟碳树脂(重均分子量为5000)，0.5重量份的20-50目的第一活性炭，10重量份的100-200目的第二活性炭，11重量份的溶剂正丁醇，1重量份的分散剂(Disperbyk191)，和1重量份的消泡剂(BYK 053)混合搅拌30min，然后在磨砂机中进行研磨，然后将所得的混合物再与12重量份的石墨烯/聚氨酯复合材料混合搅拌1h，得到本实施例制备的防腐涂料。100 parts by weight of fluorocarbon resin (weight average molecular weight: 5000), 0.5 parts by weight of 20-50 mesh first activated carbon, 10 parts by weight of 100-200 mesh second activated carbon, 11 parts by weight of solvent n-butanol, 1 Parts by weight of dispersant (Disperbyk 191), and 1 part by weight of antifoaming agent (BYK 053) were mixed and stirred for 30 min, then ground in a sander, and then the resulting mixture was further mixed with 12 parts by weight of graphene/polyurethane composite. The mixture was stirred for 1 hour to obtain an anticorrosive paint prepared in this example.
检测该防腐涂料的耐磨性和防腐性能，测试结果见表1。The abrasion resistance and corrosion resistance of the anticorrosive coating were tested, and the test results are shown in Table 1.
实施例8Example 8
本实施例的石墨烯/聚氨酯复合材料与实施例1一致。The graphene/polyurethane composite material of this example is identical to that of Example 1.
将50重量份的双酚A型环氧树脂(重均分子量为1000)，50重量份的氟碳树脂(重均分子量为6000)，0.5重量份的20-50目的第一活性炭，10重量份的100-200目的第二活性炭，11重量份的溶剂正丁醇，1重量份的分 散剂(Disperbyk191)，和1重量份的消泡剂(BYK 053)混合搅拌30min，然后在磨砂机中进行研磨，然后将所得的混合物再与12重量份的石墨烯/聚氨酯复合材料混合搅拌1h，得到本实施例制备的防腐涂料。50 parts by weight of bisphenol A type epoxy resin (weight average molecular weight of 1000), 50 parts by weight of fluorocarbon resin (weight average molecular weight of 6000), 0.5 part by weight of 20-50 mesh of first activated carbon, 10 parts by weight 100-200 mesh of second activated carbon, 11 parts by weight of solvent n-butanol, 1 part by weight of dispersant (Disperbyk 191), and 1 part by weight of antifoaming agent (BYK 053) were mixed and stirred for 30 min, and then carried out in a sander After grinding, the resulting mixture was further mixed with 12 parts by weight of the graphene/polyurethane composite material for 1 hour to obtain an anticorrosive paint prepared in the present example.
检测该防腐涂料的耐磨性和防腐性能，测试结果见表1。The abrasion resistance and corrosion resistance of the anticorrosive coating were tested, and the test results are shown in Table 1.
实施例9Example 9
本实施例的石墨烯/聚氨酯复合材料与实施例1一致。The graphene/polyurethane composite material of this example is identical to that of Example 1.
将50重量份的双酚A型环氧树脂(重均分子量为1000)，50重量份的氟碳树脂(重均分子量为6000)，10.5重量份的20-50目的第一活性炭，11重量份的溶剂正丁醇，1重量份的分散剂(Disperbyk191)，和1重量份的消泡剂(BYK 053)混合搅拌30min，然后在磨砂机中进行研磨，然后将所得的混合物再与12重量份的石墨烯/聚氨酯复合材料混合搅拌1h，得到本实施例制备的防腐涂料。50 parts by weight of bisphenol A type epoxy resin (weight average molecular weight of 1000), 50 parts by weight of fluorocarbon resin (weight average molecular weight of 6000), 10.5 parts by weight of 20-50 mesh of first activated carbon, 11 parts by weight Solvent n-butanol, 1 part by weight of dispersant (Disperbyk 191), and 1 part by weight of antifoaming agent (BYK 053) were mixed and stirred for 30 min, then ground in a sander, and then the resulting mixture was further mixed with 12 parts by weight. The graphene/polyurethane composite material was mixed and stirred for 1 hour to obtain an anticorrosive coating prepared in this example.
检测该防腐涂料的耐磨性和防腐性能，测试结果见表1。The abrasion resistance and corrosion resistance of the anticorrosive coating were tested, and the test results are shown in Table 1.
实施例10Example 10
本实施例的石墨烯/聚氨酯复合材料与实施例1一致。The graphene/polyurethane composite material of this example is identical to that of Example 1.
将50重量份的双酚A型环氧树脂(重均分子量为1000)，50重量份的氟碳树脂(重均分子量为6000)，10.5重量份的100-200目的第二活性炭，11重量份的溶剂正丁醇，1重量份的分散剂(Disperbyk191)，和1重量份的消泡剂(BYK 053)混合搅拌30min，然后在磨砂机中进行研磨，然后将所得的混合物再与12重量份的石墨烯/聚氨酯复合材料混合搅拌1h，得到本实施例制备的防腐涂料。50 parts by weight of bisphenol A type epoxy resin (weight average molecular weight of 1000), 50 parts by weight of fluorocarbon resin (weight average molecular weight of 6000), 10.5 parts by weight of 100-200 mesh of second activated carbon, 11 parts by weight Solvent n-butanol, 1 part by weight of dispersant (Disperbyk 191), and 1 part by weight of antifoaming agent (BYK 053) were mixed and stirred for 30 min, then ground in a sander, and then the resulting mixture was further mixed with 12 parts by weight. The graphene/polyurethane composite material was mixed and stirred for 1 hour to obtain an anticorrosive coating prepared in this example.
检测该防腐涂料的耐磨性和防腐性能，测试结果见表1。The abrasion resistance and corrosion resistance of the anticorrosive coating were tested, and the test results are shown in Table 1.
实施例11Example 11
将2g石墨烯粉末加入100mlN，N-二甲基甲酰胺中，以20赫兹的频率超声分散2小时，然后加入0.5gγ-氨丙基三甲氧基硅烷和0.5g蒸馏水，在25℃下机械搅拌，反应24小时，反应结束后采用抽滤方法得到黑色粉末状固体产物，即有机硅烷修饰的石墨烯；将0.3g上述有机硅烷修饰的石墨烯加入80mlN，N-二甲基甲酰胺中，然后加入10g聚氨酯，以20赫兹的频率超声分散2小时，然后机械搅拌24小时，除去N，N-二甲基甲酰胺，得到石墨烯/聚氨酯复合材料。2 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 γ-aminopropyltrimethoxysilane and 0.5 g of distilled water were added, and mechanically stirred at 25 ° C. After reacting 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, 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.
将50重量份的双酚A型环氧树脂(重均分子量为10000)，50重量份的氟碳树脂(重均分子量为5000)，0.5重量份的20-50目的第一活性炭，10重量份的100-200目的第二活性炭，11重量份的溶剂正丁醇，1重量份的分散剂(Disperbyk191)，和1重量份的消泡剂(BYK 053)混合搅拌30min，然后在磨砂机中进行研磨，然后将所得的混合物再与12重量份的石墨烯/聚氨酯复合材料混合搅拌1h，得到本实施例制备的防腐涂料。50 parts by weight of bisphenol A type epoxy resin (weight average molecular weight: 10,000), 50 parts by weight of fluorocarbon resin (weight average molecular weight: 5000), 0.5 parts by weight of 20-50 mesh first activated carbon, 10 parts by weight 100-200 mesh of second activated carbon, 11 parts by weight of solvent n-butanol, 1 part by weight of dispersant (Disperbyk 191), and 1 part by weight of antifoaming agent (BYK 053) were mixed and stirred for 30 min, and then carried out in a sander After grinding, the resulting mixture was further mixed with 12 parts by weight of the graphene/polyurethane composite material for 1 hour to obtain an anticorrosive paint prepared in the present example.
检测该防腐涂料的耐磨性和防腐性能，测试结果见表1。The abrasion resistance and corrosion resistance of the anticorrosive coating were tested, and the test results are shown in Table 1.
实施例11Example 11
将0.5g石墨烯粉末加入100mlN，N-二甲基甲酰胺中，以20赫兹的频率超声分散2小时，然后加入0.5gγ-氨丙基三甲氧基硅烷和0.5g蒸馏水，在25℃下机械搅拌，反应24小时，反应结束后采用抽滤方法得到黑色粉末状固体产物，即有机硅烷修饰的石墨烯；将0.3g上述有机硅烷修饰的石墨烯加入80mlN，N-二甲基甲酰胺中，然后加入60g聚氨酯，以20赫兹的频率超声分散2小时，然后机械搅拌24小时，除去N，N-二甲基甲酰胺，得到石墨烯/聚氨酯复合材料。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 γ-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. Then, 60 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.
将50重量份的双酚A型环氧树脂(重均分子量为10000)，50重量份 的氟碳树脂(重均分子量为5000)，0.5重量份的20-50目的第一活性炭，10重量份的100-200目的第二活性炭，11重量份的溶剂正丁醇，1重量份的分散剂(Disperbyk191)，和1重量份的消泡剂(BYK 053)混合搅拌30min，然后在磨砂机中进行研磨，然后将所得的混合物再与12重量份的石墨烯/聚氨酯复合材料混合搅拌1h，得到本实施例制备的防腐涂料。50 parts by weight of bisphenol A type epoxy resin (weight average molecular weight: 10,000), 50 parts by weight of fluorocarbon resin (weight average molecular weight: 5000), 0.5 parts by weight of 20-50 mesh first activated carbon, 10 parts by weight 100-200 mesh of second activated carbon, 11 parts by weight of solvent n-butanol, 1 part by weight of dispersant (Disperbyk 191), and 1 part by weight of antifoaming agent (BYK 053) were mixed and stirred for 30 min, and then carried out in a sander After grinding, the resulting mixture was further mixed with 12 parts by weight of the graphene/polyurethane composite material for 1 hour to obtain an anticorrosive paint prepared in the present example.
检测该防腐涂料的耐磨性和防腐性能，测试结果见表1。The abrasion resistance and corrosion resistance of the anticorrosive coating were tested, and the test results are shown in Table 1.
对比例1Comparative example 1
本对比例采用与实施例1相同重量份的石墨烯粉末代替实施例1中的石墨烯/聚氨酯复合材料，其他与实施例1一致，制备得到本对比例的防腐涂料。In the present comparative example, 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.
检测该防腐涂料的耐磨性和防腐性能，测试结果见表1。The abrasion resistance and corrosion resistance of the anticorrosive coating were tested, and the test results are shown in Table 1.
表1Table 1
Figure PCTCN2018085470-appb-000001
Figure PCTCN2018085470-appb-000001
Figure PCTCN2018085470-appb-000002
Figure PCTCN2018085470-appb-000002
由表1可见，本公开的防腐涂料具有较高的化学稳定性和防腐耐磨性。As can be seen from Table 1, the anticorrosive coating of the present disclosure has high chemical stability and corrosion resistance.
具体地，由实施例1-11和对比例1的对比可见，在防腐涂料组合物中采用石墨烯/聚氨酯复合材料能有效提高防腐涂料的化学稳定性和防腐耐磨性。Specifically, from the comparison of Examples 1-11 and Comparative Example 1, it can be seen that the use of the graphene/polyurethane composite material in the anticorrosive coating composition can effectively improve the chemical stability and corrosion resistance of the anticorrosive coating.
由实施例1-2和实施例3的对比可见，当相对于100重量份的所述树脂，所述石墨烯/聚氨酯复合材料的含量为5-15重量份，所述填料的含量为10-15重量份，所述溶剂的含量为5-15重量份，所述助剂的含量为1-5重量份时，能进一步提高防腐涂料的化学稳定性和防腐耐磨性。As can be seen from the comparison of Examples 1-2 and 3, when the content of the graphene/polyurethane composite is 5-15 parts by weight with respect to 100 parts by weight of the resin, the content of the filler is 10- 15 parts by weight, the solvent is contained in an amount of 5 to 15 parts by weight, and when the amount of the auxiliary agent is 1 to 5 parts by weight, the chemical stability and corrosion resistance of the anticorrosive coating can be further improved.
由实施例1-2和实施例4-5的对比可见，当通过R＝1.1w(石墨烯/聚氨酯复合材料)-0.32w(填料)+0.106w(溶剂)+0.055w(助剂)得到的R为8-12.5时，能进一步提高防腐涂料的化学稳定性和防腐耐磨性。From the comparison of Examples 1-2 and Examples 4-5, it can be seen that when R = 1.1w (graphene / polyurethane composite) - 0.32w (filler) + 0.106w (solvent) + 0.055w (auxiliary) is obtained. When R is 8-12.5, the chemical stability and corrosion resistance of the anticorrosive coating can be further improved.
由实施例1-2和实施例6-8的对比可见，当所述树脂为环氧树脂和氟碳树脂，所述环氧树脂的重均分子量为2000-20000，所述氟碳树脂的重均分子量为1000-5000，所述环氧树脂和氟碳树脂的重量比为1：(0.1-1)时，能进一步提高防腐涂料的化学稳定性和防腐耐磨性。As can be seen from the comparison of Examples 1-2 and Examples 6-8, 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.
由实施例1-2和实施例9-10的对比可见，当所述填料为活性炭，所述活 性炭包括粒径为20-50目的第一活性炭和粒径为100-200目的第二活性炭，所述第一活性炭和第二活性炭的重量比为1：(10-50)时，能进一步提高防腐涂料的化学稳定性和防腐耐磨性。As can be seen from the comparison of Examples 1-2 and Examples 9-10, when the filler is activated carbon, the 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. When 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.
由实施例1-2和实施例11的对比可见，当所述石墨烯/聚氨酯复合材料中，石墨烯和聚氨酯的重量比为1：(10-100)时，能进一步提高防腐涂料的化学稳定性和防腐耐磨性。It can be seen from the comparison between Example 1-2 and Example 11 that 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.
以上详细描述了本发明的优选实施方式，但是，本发明并不限于上述实施方式中的具体细节，在本发明的技术构思范围内，可以对本发明的技术方案进行多种简单变型，这些简单变型均属于本发明的保护范围。The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solutions of the present invention within the scope of the technical idea of the present invention. These simple variants All fall within the scope of protection of the present invention.
另外需要说明的是，在上述具体实施方式中所描述的各个具体技术特征，在不矛盾的情况下，可以通过任何合适的方式进行组合。为了避免不必要的重复，本发明对各种可能的组合方式不再另行说明。It should be further noted that the specific technical features described in the above specific embodiments may be combined in any suitable manner without contradiction. In order to avoid unnecessary repetition, the present invention will not be further described in various possible combinations.
此外，本发明的各种不同的实施方式之间也可以进行任意组合，只要其不违背本发明的思想，其同样应当视为本发明所公开的内容。In addition, any combination of various embodiments of the invention may be made as long as it does not deviate from the idea of the invention, and it should be regarded as the disclosure of the invention.

Claims (10)

  1. 一种防腐涂料组合物，其特征在于，该组合物含有树脂、石墨烯/聚氨酯复合材料、填料、溶剂和助剂，相对于100重量份的所述树脂，所述石墨烯/聚氨酯复合材料的含量为1-25重量份，所述填料的含量为5-30重量份，所述溶剂的含量为1-20重量份，所述助剂的含量为0.1-10重量份。An anticorrosive coating composition comprising a resin, a graphene/polyurethane composite, a filler, a solvent and an auxiliary agent, wherein the graphene/polyurethane composite material is based on 100 parts by weight of the resin The content is 1 to 25 parts by weight, the filler is contained in an amount of 5 to 30 parts by weight, the solvent is contained in an amount of 1 to 20 parts by weight, and the auxiliary is contained in an amount of 0.1 to 10 parts by weight.
  2. 根据权利要求1所述的组合物，其中，相对于100重量份的所述树脂，所述石墨烯/聚氨酯复合材料的含量为5-15重量份，所述填料的含量为10-15重量份，所述溶剂的含量为5-15重量份，所述助剂的含量为1-5重量份。The composition according to claim 1, wherein the graphene/polyurethane composite is contained in an amount of 5 to 15 parts by weight, and the filler is contained in an amount of 10 to 15 parts by weight based on 100 parts by weight of the resin. The solvent is contained in an amount of 5 to 15 parts by weight, and the auxiliary agent is contained in an amount of 1 to 5 parts by weight.
  3. 根据权利要求1或2所述的组合物，其中，通过下式计算得到的R为8-12.5：The composition according to claim 1 or 2, wherein the R calculated by the following formula is 8-12.5:
    R＝1.1w(石墨烯/聚氨酯复合材料)-0.32w(填料)+0.106w(溶剂)+0.055w(助剂)，R=1.1w (graphene/polyurethane composite)-0.32w (filler)+0.106w (solvent)+0.055w (auxiliary),
    其中，w(石墨烯/聚氨酯复合材料)表示相对于100重量份树脂的石墨烯/聚氨酯复合材料的重量份，Wherein w (graphene/polyurethane composite) represents a part by weight of the graphene/polyurethane composite relative to 100 parts by weight of the resin,
    w(填料)表示相对于100重量份树脂的填料的重量份，w (filler) means parts by weight relative to 100 parts by weight of the filler of the resin,
    w(溶剂)表示相对于100重量份树脂的溶剂的重量份，w (solvent) means parts by weight relative to 100 parts by weight of the solvent of the resin,
    w(助剂)表示相对于100重量份树脂的助剂的重量份。w (auxiliary) means parts by weight relative to 100 parts by weight of the auxiliary agent of the resin.
  4. 根据权利要求1或2所述的组合物，其中，所述树脂为选自环氧树脂、氟碳树脂、酚醛树脂和醇酸树脂中的至少一种。The composition according to claim 1 or 2, wherein the resin is at least one selected from the group consisting of epoxy resins, fluorocarbon resins, phenol resins, and alkyd resins.
  5. 根据权利要求4所述的组合物，其中，所述树脂为环氧树脂和氟碳 树脂，所述环氧树脂的重均分子量为2000-20000，所述氟碳树脂的重均分子量为1000-5000，所述环氧树脂和氟碳树脂的重量比为1：(0.1-1)。The composition according to claim 4, wherein the resin is an epoxy resin and a fluorocarbon resin, the epoxy resin has a weight average molecular weight of from 2,000 to 20,000, and the fluorocarbon resin has a weight average molecular weight of from 1,000 to 10,000. 5000, the weight ratio of the epoxy resin to the fluorocarbon resin is 1: (0.1-1).
  6. 根据权利要求1或2所述的组合物，其中，所述石墨烯/聚氨酯复合材料中，石墨烯和聚氨酯的重量比为1：(10-100)。The composition according to claim 1 or 2, wherein a weight ratio of graphene to polyurethane in the graphene/polyurethane composite material is 1: (10-100).
  7. 根据权利要求1或2所述的组合物，其中，所述填料为选自石墨、碳纤维、活性炭、导电炭黑、导电云母、滑石粉和有机膨润土中的至少一种；The composition according to claim 1 or 2, wherein 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;
    当所述填料为活性炭时，所述活性炭包括粒径为20-50目的第一活性炭和粒径为100-200目的第二活性炭，所述第一活性炭和第二活性炭的重量比为1：(10-50)。When 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).
  8. 根据权利要求1或2所述的组合物，其中，所述溶剂为选自乙醇、乙二醇、丙三醇、正丁醇、乙酸乙酯、丙酮、甲苯、二甲苯和四氢呋喃中的至少一种；The composition according to claim 1 or 2, wherein the solvent is at least one selected from the group consisting of ethanol, ethylene glycol, glycerin, n-butanol, ethyl acetate, acetone, toluene, xylene, and tetrahydrofuran. Species
    所述助剂为选自分散剂和/或消泡剂。The auxiliaries are selected from the group consisting of dispersants and/or antifoaming agents.
  9. 一种采用权利要求1所述的组合物制备防腐涂料的方法，其特征在于，该方法包括：将所述树脂、填料、溶剂和助剂混合均匀后研磨，然后将所得的混合物再与石墨烯/聚氨酯复合材料混合，分散均匀后得到防腐涂料。A method for preparing an anticorrosive coating using the composition according to claim 1, characterized in that the method comprises: uniformly mixing the resin, the filler, the solvent and the auxiliary agent, and then grinding the obtained mixture with the graphene The polyurethane composite is mixed and evenly dispersed to obtain an anticorrosive coating.
  10. 一种由权利要求9所述的方法制备得到的防腐涂料。An anticorrosive coating prepared by the method of claim 9.
PCT/CN2018/085470 2017-11-20 2018-05-03 Anti-corrosion coating composition, method for preparing anti-corrosion coating, and anti-corrosion coating WO2019095642A1 (en)

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