WO2018036422A1 - Modified white graphene composite anti-corrosion coating and preparation thereof - Google Patents

Modified white graphene composite anti-corrosion coating and preparation thereof Download PDF

Info

Publication number
WO2018036422A1
WO2018036422A1 PCT/CN2017/098063 CN2017098063W WO2018036422A1 WO 2018036422 A1 WO2018036422 A1 WO 2018036422A1 CN 2017098063 W CN2017098063 W CN 2017098063W WO 2018036422 A1 WO2018036422 A1 WO 2018036422A1
Authority
WO
WIPO (PCT)
Prior art keywords
parts
white graphene
modified white
anticorrosive coating
resin
Prior art date
Application number
PCT/CN2017/098063
Other languages
French (fr)
Chinese (zh)
Inventor
段曦东
赵涛楠
毛志浩
Original Assignee
广东纳路纳米科技有限公司
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 广东纳路纳米科技有限公司 filed Critical 广东纳路纳米科技有限公司
Publication of WO2018036422A1 publication Critical patent/WO2018036422A1/en

Links

Classifications

    • 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
    • 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
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
    • 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
    • C08K3/38—Boron-containing compounds
    • 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
    • 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
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C09D163/10—Epoxy resins modified by unsaturated 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
    • 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
    • C09D5/18—Fireproof paints including high temperature resistant paints
    • 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
    • C08K3/38—Boron-containing compounds
    • C08K2003/382—Boron-containing compounds and nitrogen
    • C08K2003/385—Binary compounds of nitrogen with boron

Definitions

  • the invention relates to the technical field of materials, in particular to a modified white graphene composite anticorrosive coating and a preparation thereof.
  • Metal materials occupy an important position in human life.
  • metal structural parts are highly corrosive due to constant contact with high temperature gas, moisture and smoke, thus significantly reducing the mechanical properties of metal materials and destroying the geometry of metal structural parts. Shorten the service life of the equipment and cause huge economic losses. Therefore, finding effective technical means to achieve the anti-corrosion of metal materials has become the focus of attention of all countries in the world.
  • Anti-corrosion coating is the best material to protect metal structural parts from corrosion at low cost. It is mainly used in various anti-corrosion environments such as construction industry, steel facilities, railway bridges, oil pipelines, ships and marine engineering. Since the anticorrosive coating separates the metal structural member from the external environment, the anticorrosive coating is required to have excellent adhesion, high temperature resistance, salt spray resistance, abrasion resistance and mechanical strength. However, the existing anticorrosive coatings are susceptible to failure under the influence of high temperature, high humidity, light, acid rain and the like, thereby losing the antiseptic effect on the equipment.
  • a modified white graphene composite anticorrosive coating the raw material comprises: 18-68.5 parts of matrix resin by weight, 5-20 parts of pigment filler, 0.4-1.5 parts of dispersant, 0.1-0.5 parts of antifoaming agent, 20-30 parts of solvent, 1-20 parts of modified white graphene, 0-10 parts of curing agent.
  • the matrix resin comprises one or more of an epoxy resin, an alkyd resin, a saturated polyester, and an acrylic resin;
  • the pigment filler comprises one or more of titanium white powder, carbon black, iron oxide red, indigo blue, medium chromium yellow, talc powder, calcium carbonate and barium sulfate;
  • the dispersing agent includes one of a synthetic polymer, a polyvalent carboxylic acid, and a silicate;
  • the antifoaming agent includes one of a silicone type and an acrylate type
  • the solvent includes one or more of water, a mixed solvent of xylene/n-butanol/ethyl acetate, propylene glycol methyl ether, and a ketone;
  • the curing agent includes one of an amine resin, a polyisocyanate resin, and an amino resin.
  • the preparation of the modified white graphene composite anticorrosive coating of the invention comprises:
  • Step 1) Preparation of modified white graphene: 5-10 layers of white graphene are treated with a surfactant to obtain a modified white graphene dispersion;
  • Step 2) dissolving the matrix resin, the pigment filler, the dispersing agent and the antifoaming agent in a solvent to obtain a matrix resin solution; and stirring the modified white graphene dispersion obtained in the step 1) with the matrix resin solution; The curing agent is stirred and mixed uniformly to prepare the anticorrosive coating.
  • the surfactant treatment method of the step 1) is to soak for 24 hours in an aqueous solution of a surfactant having a mass concentration of 0.1%.
  • the surfactant according to the step 1) includes one of a long-chain Lewis base, a long-chain Lewis acid, a quaternary ammonium compound, a sulfonate, and a nonionic surfactant.
  • the long-chain Lewis base is an amine
  • the long-chain Lewis acid is a borane
  • the quaternary ammonium compound is an alkyltrimethyl quaternary ammonium salt, an alkyldimethylbenzyl quaternary ammonium salt, One of dialkyl dimethyl quaternary ammonium salts
  • the sulfonate is sodium dodecyl benzene sulfonate, sodium dodecyl sulfonate, lignosulfonic acid One of sodium or sodium glycocholate
  • the nonionic surfactant is one of a polyether, a polyester, a polyvinyl alcohol, and a cellulose derivative.
  • the modified white graphene has good gas barrier properties and high strength.
  • the modified white graphene of atomic thickness can further reduce the coating thickness, increase the adhesion to the substrate, and improve the resistance of the coating. Grinding performance, salt spray resistance and mechanical strength without affecting other properties;
  • the anticorrosive coating of the invention has higher anticorrosive performance than the existing heavy anticorrosive coating, and has a real green environmental protection function, and can be widely applied to coating protection in the fields of marine engineering, transportation, large industrial equipment and municipal engineering facilities.
  • white graphene is widely used in metal anti-corrosion because of its unique properties.
  • white graphene is a single layer or a small layer of hexagonal boron nitride. It has a two-dimensional characteristic of the atomic thickness of graphene. It has a strong ability to block gases and can form a physical barrier layer between the metal structural member and the active medium to prevent diffusion and penetration.
  • white graphene has chemical inertness and thermal stability, and can be stable under the influence of high temperature, high humidity, light, acid rain and other factors.
  • white graphene has very high strength and is not available in common coatings. Abrasion resistance and mechanical strength.
  • the invention adopts the modified white graphene to be used in the anticorrosive coating, and can greatly improve various functions of the anticorrosive coating.
  • Step 1) Preparation of modified white graphene: 5-10 layers of white graphene with 0.1% long chain borane water The solution was immersed for 24 hours to obtain a long chain borane-modified white graphene solution.
  • Step 2 Dissolve 43.9 parts of alkyd resin, 12 parts of calcium carbonate, 7.5 parts of titanium dioxide, 0.5 part of carbon black, 1 part of BYK UMEN, 0.1 part of BYK 065 in 25 parts of xylene/n-butanol/ethyl acetate mixed solvent
  • the base resin solution is uniformly obtained by stirring; the 5 parts of the modified white graphene dispersion prepared in the step 1) and the above-mentioned base resin solution are uniformly stirred to obtain a high-performance alkyd resin anticorrosive paint of the composite modified white graphene.
  • Step 1) Preparation of modified white graphene: 5-10 layers of white graphene were soaked in a 0.1% aqueous oleylamine solution for 24 hours to obtain an oleylamine-modified white graphene solution.
  • Step 2) 33 parts of epoxy modified acrylic resin, 12 parts of barium sulfate, 8 parts of iron oxide red, 1.5 parts of Tego 740W, 0.5 parts of Tego 810 are dissolved in 30 parts of water and stirred to obtain a matrix resin; Step 1) is obtained.
  • the 10 parts of the modified white graphene dispersion and the above-mentioned base resin liquid are uniformly stirred to obtain a high performance epoxy modified acrylic resin anticorrosive coating of the composite modified white graphene.
  • Step 1) Preparation of modified white graphene: 5-10 layers of white graphene were soaked with 0.1% sodium dodecyl sulfate for 24 hours to obtain a long-chain borane-modified white graphene solution.
  • Step 2 Dissolve 43.9 parts of epoxy resin, 12 parts of talc, 8 parts of iron oxide red, 1 part of BYK P-104, 0.1 part of BYK 066N in 20 parts of xylene/n-butanol/ethyl acetate mixed solvent. Uniform; 15 parts of the modified white graphene dispersion prepared in step 1) and the epoxy resin solution are uniformly stirred; 10 parts of diethylenetriamine is further added, and the mixture is uniformly stirred to obtain a high composite modified white graphene. Performance epoxy resin anti-corrosion coating.
  • Step 1) Preparation of modified white graphene: 5-10 layers of white graphene were soaked in a 0.1% aqueous solution of polyvinyl alcohol for 24 hours to obtain an oleylamine-modified white graphene solution.
  • Step 2 20 parts epoxy emulsion, 6 parts talc, 6 parts barium sulfate, 2 parts indigo blue, 4 parts titanium White powder, 1.5 parts BYK 155/35, 0.5 parts Tego 810 dissolved in 30 parts of water and stirred uniformly; 20 parts of the modified white graphene dispersion prepared in step 1) is mixed with the epoxy resin solution, and stirred evenly; A Dow EH-3 curing agent (containing 70% by mass of poly-methylenecyclohexylamine) is stirred and mixed uniformly to obtain a high performance waterborne epoxy anticorrosive coating of composite modified white graphene.
  • a Dow EH-3 curing agent containing 70% by mass of poly-methylenecyclohexylamine
  • the present invention and the comparative sample were subjected to performance tests, and the comparative samples included Comparative Examples 1-4, and the formulations and preparation methods used in Comparative Examples 1-4 were the same as those in Examples 1-4, respectively, the only difference being No modified white graphene was added.
  • Table 1 shows the performance parameters of the high performance anticorrosive coating prepared in Examples 1-4 and the white graphene-free coating prepared in Comparative Examples 1-4:
  • the preparation method of the present invention can greatly improve the salt spray resistance, adhesion and mechanical strength of the anticorrosive coating.

Abstract

A modified white graphene composite anti-corrosion coating, the raw materials thereof comprising, on the basis of weight parts: 18-68.5 parts of a matric resin, 5-20 parts of a color filler, 0.4-1.5 parts of a dispersant, 0.1-0.5 parts of a defoamer, 20-30 parts of a solvent, 1-20 parts of white graphene, and 0-10 parts of a curing agent.

Description

一种改性白石墨烯复合防腐涂料及其制备Modified white graphene composite anticorrosive coating and preparation thereof 技术领域Technical field
本发明涉及材料技术领域，具体涉及一种改性白石墨烯复合防腐涂料及其制备。The invention relates to the technical field of materials, in particular to a modified white graphene composite anticorrosive coating and a preparation thereof.
背景技术Background technique
金属材料在人类生活中占据重要地位，在工业生产中，金属结构件因常年接触高温气体、湿气和烟尘，极易腐蚀，从而显著降低金属材料的力学性能、破坏金属结构件的几何形状、缩短设备的使用寿命，造成巨大的经济损失。因此寻找有效的技术手段来实现金属材料的防腐成为全球各国关注的目标。Metal materials occupy an important position in human life. In industrial production, metal structural parts are highly corrosive due to constant contact with high temperature gas, moisture and smoke, thus significantly reducing the mechanical properties of metal materials and destroying the geometry of metal structural parts. Shorten the service life of the equipment and cause huge economic losses. Therefore, finding effective technical means to achieve the anti-corrosion of metal materials has become the focus of attention of all countries in the world.
在众多防腐技术中，涂料的防腐技术应用最为广泛。防腐涂料是低成本保护金属结构件远离腐蚀的最佳材料，主要用于各类建筑行业、钢铁设施、铁路桥梁、输油管道、船舶及海洋工程等防腐环境中。由于防腐涂料是将金属结构件与外部环境隔绝开来，因此要求防腐涂料具有优异的附着力、耐高温、耐盐雾性、耐磨性和机械强度。而现有的防腐涂料在高温、高湿、光照、酸雨等因素的影响下防腐涂层容易失效，从而失去对设备的防腐作用。Among the many anti-corrosion technologies, coating anti-corrosion technology is the most widely used. Anti-corrosion coating is the best material to protect metal structural parts from corrosion at low cost. It is mainly used in various anti-corrosion environments such as construction industry, steel facilities, railway bridges, oil pipelines, ships and marine engineering. Since the anticorrosive coating separates the metal structural member from the external environment, the anticorrosive coating is required to have excellent adhesion, high temperature resistance, salt spray resistance, abrasion resistance and mechanical strength. However, the existing anticorrosive coatings are susceptible to failure under the influence of high temperature, high humidity, light, acid rain and the like, thereby losing the antiseptic effect on the equipment.
发明内容Summary of the invention
有鉴于此，有必要针对上述现有防腐涂料的不足，提供一种具有优异的附着力、耐高温、耐盐雾性、耐磨性和机械强度性能的改性白石墨烯复合防腐涂料及其制备。In view of this, it is necessary to provide a modified white graphene composite anticorrosive coating with excellent adhesion, high temperature resistance, salt spray resistance, wear resistance and mechanical strength performance against the above-mentioned deficiencies of the existing anticorrosive coatings. preparation.
为实现上述目的，本发明采取以下的技术方案：In order to achieve the above object, the present invention adopts the following technical solutions:
一种改性白石墨烯复合防腐涂料，原料按重量份包括：18-68.5份基体树脂， 5-20份颜填料，0.4-1.5份分散剂，0.1-0.5份消泡剂，20-30份溶剂，1-20份改性白石墨烯，0-10份固化剂。A modified white graphene composite anticorrosive coating, the raw material comprises: 18-68.5 parts of matrix resin by weight, 5-20 parts of pigment filler, 0.4-1.5 parts of dispersant, 0.1-0.5 parts of antifoaming agent, 20-30 parts of solvent, 1-20 parts of modified white graphene, 0-10 parts of curing agent.
进一步的，所述的基体树脂包括环氧树脂、醇酸树脂、饱和聚酯、丙烯酸树脂中的一种或几种；Further, the matrix resin comprises one or more of an epoxy resin, an alkyd resin, a saturated polyester, and an acrylic resin;
所述的颜填料包括钛白粉、炭黑、氧化铁红、酞青蓝、中铬黄、滑石粉、碳酸钙、硫酸钡中的一种或几种；The pigment filler comprises one or more of titanium white powder, carbon black, iron oxide red, indigo blue, medium chromium yellow, talc powder, calcium carbonate and barium sulfate;
所述的分散剂包括合成高分子类、多价羧酸类、硅酸盐类中的一种；The dispersing agent includes one of a synthetic polymer, a polyvalent carboxylic acid, and a silicate;
所述的消泡剂包括有机硅类、丙烯酸脂类中的一种；The antifoaming agent includes one of a silicone type and an acrylate type;
所述的溶剂包括水、二甲苯/正丁醇/醋酸乙酯混合溶剂、丙二醇甲醚、酮类中的一种或几种；The solvent includes one or more of water, a mixed solvent of xylene/n-butanol/ethyl acetate, propylene glycol methyl ether, and a ketone;
所述的固化剂包括胺类树脂、多异氰酸酯树脂、氨基树脂中的一种。The curing agent includes one of an amine resin, a polyisocyanate resin, and an amino resin.
本发明的改性白石墨烯复合防腐涂料的制备，包括：The preparation of the modified white graphene composite anticorrosive coating of the invention comprises:
步骤1)改性白石墨烯的制备：将5-10层的白石墨烯用表面活性剂处理，得到改性白石墨烯分散液；Step 1) Preparation of modified white graphene: 5-10 layers of white graphene are treated with a surfactant to obtain a modified white graphene dispersion;
步骤2)将基体树脂、颜填料、分散剂、消泡剂溶于溶剂中搅拌均匀得到基体树脂溶液；将步骤1)制得的改性白石墨烯分散液与基体树脂溶液搅拌均匀；再加入固化剂，搅拌混合均匀，即制得所述防腐涂料。Step 2) dissolving the matrix resin, the pigment filler, the dispersing agent and the antifoaming agent in a solvent to obtain a matrix resin solution; and stirring the modified white graphene dispersion obtained in the step 1) with the matrix resin solution; The curing agent is stirred and mixed uniformly to prepare the anticorrosive coating.
进一步的，步骤1)所述表面活性剂处理方式为在质量浓度为0.1％的表面活性剂水溶液浸泡24h。Further, the surfactant treatment method of the step 1) is to soak for 24 hours in an aqueous solution of a surfactant having a mass concentration of 0.1%.
进一步的，步骤1)所述的表面活性剂包括长链路易斯碱、长链路易斯酸、季铵化物、磺酸化物、非离子型表面活性剂中的一种。Further, the surfactant according to the step 1) includes one of a long-chain Lewis base, a long-chain Lewis acid, a quaternary ammonium compound, a sulfonate, and a nonionic surfactant.
进一步的，所述长链路易斯碱为胺类；所述长链路易斯酸为硼烷类；所述季铵化物为烷基三甲基季铵盐、烷基二甲基苄基季铵盐、二烷基二甲基季铵盐中的一种；所述磺酸化物为十二烷基苯磺酸钠、十二烷基磺酸钠、木质素磺酸 钠、甘胆酸钠中的一种；所述非离子型表面活性剂为聚醚、聚酯、聚乙烯醇、纤维素衍生物中的一种。Further, the long-chain Lewis base is an amine; the long-chain Lewis acid is a borane; the quaternary ammonium compound is an alkyltrimethyl quaternary ammonium salt, an alkyldimethylbenzyl quaternary ammonium salt, One of dialkyl dimethyl quaternary ammonium salts; the sulfonate is sodium dodecyl benzene sulfonate, sodium dodecyl sulfonate, lignosulfonic acid One of sodium or sodium glycocholate; the nonionic surfactant is one of a polyether, a polyester, a polyvinyl alcohol, and a cellulose derivative.
本发明的有益效果为：The beneficial effects of the invention are:
(1)经过改性的白石墨烯有良好的隔离气体的性能和高的强度，原子级厚度的改性白石墨烯能进一步降低涂层厚度，增加对基材的附着力，提升涂料的耐磨性能、耐盐雾性能和机械强度而其他性能不受影响；(1) The modified white graphene has good gas barrier properties and high strength. The modified white graphene of atomic thickness can further reduce the coating thickness, increase the adhesion to the substrate, and improve the resistance of the coating. Grinding performance, salt spray resistance and mechanical strength without affecting other properties;
(2)本发明的防腐涂料防腐性能超过现有的重防腐涂料，并具有真正的绿色环保功能，可广泛应用于海洋工程、交通运输、大型工业设备及市政工程设施等领域的涂装保护。(2) The anticorrosive coating of the invention has higher anticorrosive performance than the existing heavy anticorrosive coating, and has a real green environmental protection function, and can be widely applied to coating protection in the fields of marine engineering, transportation, large industrial equipment and municipal engineering facilities.
具体实施方式detailed description
为使本发明的目的、技术方案和优点更加清楚，下面将结合本发明实施例，对本发明的技术方案作进一步清楚、完整地描述。需要说明的是，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。In order to make the objects, the technical solutions and the advantages of the present invention more clearly, the technical solutions of the present invention will be further clearly and completely described below in conjunction with the embodiments of the present invention. It should be noted that the described embodiments are only a part of the embodiments of the invention, and not all of the embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative efforts are within the scope of the present invention.
白石墨烯作为一种新型材料，因其独特的性能在金属防腐领域应用广泛。首先白石墨烯为单层或少层六方氮化硼，具有石墨烯原子级厚度的二维特性，阻隔气体的能力非常强，能在金属结构件和活性介质间形成物理阻隔层，阻止扩散渗透的进行；其次，白石墨烯具有化学惰性和热稳定性，在高温、高湿、光照、酸雨等因素的影响下都能保持稳定；另外，白石墨烯强度非常高，具有普通涂料所不具备的耐磨性和机械强度。本发明采用改性后的白石墨烯应用于防腐涂料中，能够大大改善防腐涂料的各项功能。As a new material, white graphene is widely used in metal anti-corrosion because of its unique properties. First, white graphene is a single layer or a small layer of hexagonal boron nitride. It has a two-dimensional characteristic of the atomic thickness of graphene. It has a strong ability to block gases and can form a physical barrier layer between the metal structural member and the active medium to prevent diffusion and penetration. Secondly, white graphene has chemical inertness and thermal stability, and can be stable under the influence of high temperature, high humidity, light, acid rain and other factors. In addition, white graphene has very high strength and is not available in common coatings. Abrasion resistance and mechanical strength. The invention adopts the modified white graphene to be used in the anticorrosive coating, and can greatly improve various functions of the anticorrosive coating.
实施例1Example 1
步骤1)改性白石墨烯的制备：将5-10层的白石墨烯用0.1％的长链硼烷水 溶液浸泡24h，得到长链硼烷改性的白石墨烯溶液。Step 1) Preparation of modified white graphene: 5-10 layers of white graphene with 0.1% long chain borane water The solution was immersed for 24 hours to obtain a long chain borane-modified white graphene solution.
步骤2)将43.9份醇酸树脂、12份碳酸钙、7.5份钛白粉、0.5份炭黑、1份BYK UMEN、0.1份BYK 065溶于25份二甲苯/正丁醇/醋酸乙酯混合溶剂中搅拌均匀得到基体树脂溶液；将步骤1)制得的5份改性白石墨烯分散液与上述基体树脂溶液搅拌均匀，即制得复合改性白石墨烯的高性能醇酸树脂防腐涂料。Step 2) Dissolve 43.9 parts of alkyd resin, 12 parts of calcium carbonate, 7.5 parts of titanium dioxide, 0.5 part of carbon black, 1 part of BYK UMEN, 0.1 part of BYK 065 in 25 parts of xylene/n-butanol/ethyl acetate mixed solvent The base resin solution is uniformly obtained by stirring; the 5 parts of the modified white graphene dispersion prepared in the step 1) and the above-mentioned base resin solution are uniformly stirred to obtain a high-performance alkyd resin anticorrosive paint of the composite modified white graphene.
实施例2Example 2
步骤1)改性白石墨烯的制备：将5-10层的白石墨烯用0.1％的油胺水溶液浸泡24h，得到油胺改性的白石墨烯溶液。Step 1) Preparation of modified white graphene: 5-10 layers of white graphene were soaked in a 0.1% aqueous oleylamine solution for 24 hours to obtain an oleylamine-modified white graphene solution.
步骤2)将33份环氧改性丙烯酸树脂、12份硫酸钡、8份氧化铁红、1.5份Tego 740W、0.5份Tego 810溶于30份水中搅拌均匀得到基体树脂；将步骤1)制得的10份改性白石墨烯分散液与上述基体树脂液搅拌均匀，即制得复合改性白石墨烯的高性能环氧改性丙烯酸树脂防腐涂料。Step 2) 33 parts of epoxy modified acrylic resin, 12 parts of barium sulfate, 8 parts of iron oxide red, 1.5 parts of Tego 740W, 0.5 parts of Tego 810 are dissolved in 30 parts of water and stirred to obtain a matrix resin; Step 1) is obtained. The 10 parts of the modified white graphene dispersion and the above-mentioned base resin liquid are uniformly stirred to obtain a high performance epoxy modified acrylic resin anticorrosive coating of the composite modified white graphene.
实施例3Example 3
步骤1)改性白石墨烯的制备：将5-10层的白石墨烯用0.1％的十二烷基磺酸钠浸泡24h，得到长链硼烷改性的白石墨烯溶液。Step 1) Preparation of modified white graphene: 5-10 layers of white graphene were soaked with 0.1% sodium dodecyl sulfate for 24 hours to obtain a long-chain borane-modified white graphene solution.
步骤2)将43.9份环氧树脂、12份滑石粉、8份氧化铁红、1份BYK P-104、0.1份BYK 066N溶于20份二甲苯/正丁醇/醋酸乙酯混合溶剂中搅拌均匀；将步骤1)制得的15份改性白石墨烯分散液与环氧树脂溶液搅拌均匀；再加入10份二乙烯三胺，搅拌混合均匀，即制得复合改性白石墨烯的高性能环氧树脂防腐涂料。Step 2) Dissolve 43.9 parts of epoxy resin, 12 parts of talc, 8 parts of iron oxide red, 1 part of BYK P-104, 0.1 part of BYK 066N in 20 parts of xylene/n-butanol/ethyl acetate mixed solvent. Uniform; 15 parts of the modified white graphene dispersion prepared in step 1) and the epoxy resin solution are uniformly stirred; 10 parts of diethylenetriamine is further added, and the mixture is uniformly stirred to obtain a high composite modified white graphene. Performance epoxy resin anti-corrosion coating.
实施例4Example 4
步骤1)改性白石墨烯的制备：将5-10层的白石墨烯用0.1％的聚乙烯醇水溶液浸泡24h，得到油胺改性的白石墨烯溶液。Step 1) Preparation of modified white graphene: 5-10 layers of white graphene were soaked in a 0.1% aqueous solution of polyvinyl alcohol for 24 hours to obtain an oleylamine-modified white graphene solution.
步骤2)将20份环氧乳液、6份滑石粉、6份硫酸钡、2份酞青蓝、4份钛 白粉、1.5份BYK 155/35、0.5份Tego 810溶于30份水中搅拌均匀；将步骤1)制得的20份改性白石墨烯分散液与环氧树脂溶液混合，搅拌均匀；再加入10份陶氏EH-3固化剂(含质量百分百为70％的聚-亚甲基环己胺)，搅拌混合均匀，即制得复合改性白石墨烯的高性能水性环氧防腐涂料。Step 2) 20 parts epoxy emulsion, 6 parts talc, 6 parts barium sulfate, 2 parts indigo blue, 4 parts titanium White powder, 1.5 parts BYK 155/35, 0.5 parts Tego 810 dissolved in 30 parts of water and stirred uniformly; 20 parts of the modified white graphene dispersion prepared in step 1) is mixed with the epoxy resin solution, and stirred evenly; A Dow EH-3 curing agent (containing 70% by mass of poly-methylenecyclohexylamine) is stirred and mixed uniformly to obtain a high performance waterborne epoxy anticorrosive coating of composite modified white graphene.
为验证本发明的技术效果，将本发明与对比样品进行性能测试，对比样品包括对比例1-4，对比例1-4所用配方与制法分别与实施例1-4相同，唯一区别是其中未加入改性白石墨烯。In order to verify the technical effects of the present invention, the present invention and the comparative sample were subjected to performance tests, and the comparative samples included Comparative Examples 1-4, and the formulations and preparation methods used in Comparative Examples 1-4 were the same as those in Examples 1-4, respectively, the only difference being No modified white graphene was added.
表1中为测定实施例1-4中所制备得到的高性能防腐涂料及对比例1-4制备的未加白石墨烯的涂料的性能参数：Table 1 shows the performance parameters of the high performance anticorrosive coating prepared in Examples 1-4 and the white graphene-free coating prepared in Comparative Examples 1-4:
表1各实施例所得的高性能防腐涂料的性能数据Table 1 Performance data of high performance anticorrosive coatings obtained in each example
Figure PCTCN2017098063-appb-000001
Figure PCTCN2017098063-appb-000001
从上表可知，本发明的制备方法可以大幅度提高防腐涂料的耐盐雾性能、附着力和机械强度。As can be seen from the above table, the preparation method of the present invention can greatly improve the salt spray resistance, adhesion and mechanical strength of the anticorrosive coating.
以上所述实施例仅表达了本发明的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对本发明专利范围的限制。应当指出的是，对于本领域 的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。 The above-mentioned embodiments are merely illustrative of several embodiments of the present invention, and the description thereof is more specific and detailed, but is not to be construed as limiting the scope of the invention. It should be noted that for the field A person skilled in the art can make several modifications and improvements without departing from the spirit and scope of the invention. Therefore, the scope of the invention should be determined by the appended claims.

Claims (6)

  1. 一种改性白石墨烯复合防腐涂料，其特征在于，原料按重量份包括：18-68.5份基体树脂，5-20份颜填料，0.4-1.5份分散剂，0.1-0.5份消泡剂，20-30份溶剂，1-20份改性白石墨烯，0-10份固化剂。A modified white graphene composite anticorrosive coating, characterized in that the raw material comprises, by weight: 18-68.5 parts of matrix resin, 5-20 parts of pigment filler, 0.4-1.5 parts of dispersant, 0.1-0.5 parts of antifoaming agent, 20-30 parts of solvent, 1-20 parts of modified white graphene, 0-10 parts of curing agent.
  2. 根据权利要求1所述的改性白石墨烯复合防腐涂料，其特征在于，The modified white graphene composite anticorrosive coating according to claim 1, wherein
    所述的基体树脂包括环氧树脂、醇酸树脂、饱和聚酯、丙烯酸树脂中的一种或几种；The matrix resin comprises one or more of an epoxy resin, an alkyd resin, a saturated polyester, and an acrylic resin;
    所述的颜填料包括钛白粉、炭黑、氧化铁红、酞青蓝、中铬黄、滑石粉、碳酸钙、硫酸钡中的一种或几种；The pigment filler comprises one or more of titanium white powder, carbon black, iron oxide red, indigo blue, medium chromium yellow, talc powder, calcium carbonate and barium sulfate;
    所述的分散剂包括合成高分子类、多价羧酸类、硅酸盐类中的一种；The dispersing agent includes one of a synthetic polymer, a polyvalent carboxylic acid, and a silicate;
    所述的消泡剂包括有机硅类、丙烯酸脂类中的一种；The antifoaming agent includes one of a silicone type and an acrylate type;
    所述的溶剂包括水、二甲苯/正丁醇/醋酸乙酯混合溶剂、丙二醇甲醚、酮类中的一种或几种；The solvent includes one or more of water, a mixed solvent of xylene/n-butanol/ethyl acetate, propylene glycol methyl ether, and a ketone;
    所述的固化剂包括胺类树脂、多异氰酸酯树脂、氨基树脂中的一种。The curing agent includes one of an amine resin, a polyisocyanate resin, and an amino resin.
  3. 一种权利要求1或2所述的改性白石墨烯复合防腐涂料的制备，其特征在于，包括：A preparation of the modified white graphene composite anticorrosive coating according to claim 1 or 2, which comprises:
    步骤1)改性白石墨烯的制备：将5-10层的白石墨烯用表面活性剂处理，得到改性白石墨烯分散液；Step 1) Preparation of modified white graphene: 5-10 layers of white graphene are treated with a surfactant to obtain a modified white graphene dispersion;
    步骤2)将基体树脂、颜填料、分散剂、消泡剂溶于溶剂中搅拌均匀得到基体树脂溶液；将步骤1)制得的改性白石墨烯分散液与基体树脂溶液搅拌均匀；再加入固化剂，搅拌混合均匀，即制得所述防腐涂料。Step 2) dissolving the matrix resin, the pigment filler, the dispersing agent and the antifoaming agent in a solvent to obtain a matrix resin solution; and stirring the modified white graphene dispersion obtained in the step 1) with the matrix resin solution; The curing agent is stirred and mixed uniformly to prepare the anticorrosive coating.
  4. 根据权利要求3所述的改性白石墨烯复合防腐涂料的制备，其特征在于，步骤1)所述表面活性剂处理方式为在质量浓度为0.1％的表面活性剂水溶液浸 泡24h。The preparation of the modified white graphene composite anticorrosive coating according to claim 3, wherein the surfactant is treated in the step 1) by a surfactant aqueous solution having a mass concentration of 0.1%. Soak for 24h.
  5. 根据权利要求3所述的改性白石墨烯复合防腐涂料的制备，其特征在于，步骤1)所述的表面活性剂包括长链路易斯碱、长链路易斯酸、季铵化物、磺酸化物、非离子型表面活性剂中的一种。The preparation of the modified white graphene composite anticorrosive coating according to claim 3, wherein the surfactant in the step 1) comprises a long-chain Lewis base, a long-chain Lewis acid, a quaternary ammonium compound, a sulfonate, One of the nonionic surfactants.
  6. 根据权利要求5所述的改性白石墨烯复合防腐涂料的制备，其特征在于，所述长链路易斯碱为胺类；所述长链路易斯酸为硼烷类；所述季铵化物为烷基三甲基季铵盐、烷基二甲基苄基季铵盐、二烷基二甲基季铵盐中的一种；所述磺酸化物为十二烷基苯磺酸钠、十二烷基磺酸钠、木质素磺酸钠、甘胆酸钠中的一种；所述非离子型表面活性剂为聚醚、聚酯、聚乙烯醇、纤维素衍生物中的一种。 The modified white graphene composite anticorrosive coating according to claim 5, wherein the long-chain Lewis base is an amine; the long-chain Lewis acid is a borane; and the quaternary ammonium compound is an alkane One of a trimethyl quaternary ammonium salt, an alkyl dimethyl benzyl quaternary ammonium salt, and a dialkyl dimethyl quaternary ammonium salt; the sulfonate is sodium dodecyl benzene sulfonate, twelve One of sodium alkyl sulfonate, sodium lignosulfonate, and sodium glycocholate; the nonionic surfactant is one of a polyether, a polyester, a polyvinyl alcohol, and a cellulose derivative.
PCT/CN2017/098063 2016-08-22 2017-08-18 Modified white graphene composite anti-corrosion coating and preparation thereof WO2018036422A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201610705377.6A CN106243943B (en) 2016-08-22 2016-08-22 A kind of modified white graphite alkene composite anticorrosion coating and its preparation
CN201610705377.6 2016-08-22

Publications (1)

Publication Number Publication Date
WO2018036422A1 true WO2018036422A1 (en) 2018-03-01

Family

ID=57595011

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2017/098063 WO2018036422A1 (en) 2016-08-22 2017-08-18 Modified white graphene composite anti-corrosion coating and preparation thereof

Country Status (2)

Country Link
CN (1) CN106243943B (en)
WO (1) WO2018036422A1 (en)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111423801A (en) * 2019-01-10 2020-07-17 沈阳化工研究院有限公司 Water-based nano heavy-duty coating for chemical sewage tank and preparation thereof
CN113265185A (en) * 2021-05-24 2021-08-17 广州市上善纳米材料有限公司 Self-repairing graphene composite titanium nano heavy-duty anticorrosive material and preparation and use methods thereof
CN113777174A (en) * 2021-08-20 2021-12-10 湖北省建筑科学研究设计院股份有限公司 Ultrasonic flaw detection coupling agent for building or bridge steel structure and preparation method thereof
CN114044880A (en) * 2021-09-28 2022-02-15 昆明国松特种涂料有限公司 Polycarbonate epoxy resin, solvent-free anticorrosive paint and application
CN114517047A (en) * 2022-03-03 2022-05-20 江南大学 Preparation method of water-based epoxy-modified graphene oxide nano composite coating
CN114921145A (en) * 2022-06-10 2022-08-19 洛阳大豫实业有限公司 Modified graphene anticorrosive paint and preparation method thereof
CN115232530A (en) * 2022-08-17 2022-10-25 山东玉皇新能源科技有限公司 Water-based graphene-based composite anticorrosive paint and preparation method thereof
CN115491128A (en) * 2022-08-31 2022-12-20 山东之诺新材料科技有限公司 Formula of JJY-1 graphene modified high-temperature-resistant abrasion-resistant heavy-duty anticorrosive nano ceramic coating
CN117089256A (en) * 2023-10-19 2023-11-21 北京易净星科技有限公司 High-performance protective paint for highway guardrails and preparation method thereof

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106824596A (en) * 2016-12-28 2017-06-13 芜湖顺景自动化设备有限公司 A kind of architectural finish machine device with corrosion-resistant coating
CN107103768A (en) * 2017-05-27 2017-08-29 宁波力泰电子科技有限公司 A kind of energy-saving traffic signal lamp control device
CN107268245A (en) * 2017-05-27 2017-10-20 宁波奇尘电子科技有限公司 A kind of clothes hanger of acid rain preventing intelligent control
CN107418371B (en) * 2017-07-03 2019-08-06 陕西省石油化工研究设计院 A kind of preparation method of the fluorine-carbon modified thermally conductive anticorrosive paint suitable for wet crude heating
GB2565048B (en) * 2017-07-26 2023-04-19 Talga Tech Limited Functionalised graphene composition
CN107964103A (en) * 2017-09-01 2018-04-27 福建师范大学 A kind of graphene dispersion agent and the preparation method of graphene/raw lacquer composite anticorrosion coating
CN107880732A (en) * 2017-12-21 2018-04-06 芜湖品度电子科技有限公司 Numerical control cutting and folding machine improved abrasion resistant coating and preparation method thereof
CN108276877B (en) * 2018-01-05 2019-12-27 广东纳路纳米科技有限公司 Composite anti-scale coating containing modified white graphene and application thereof
CN108219628B (en) * 2018-01-09 2024-02-02 河北晨阳工贸集团有限公司 Marine corrosion-resistant aircraft engine deionized water paint and preparation method thereof
CN108585634A (en) * 2018-05-04 2018-09-28 砺剑防务技术集团有限公司 Boron nitride fire-resistant anticorrosion paint and preparation method thereof
CN108659671B (en) * 2018-05-14 2020-06-09 重庆中科检测技术服务有限公司 Lignin/graphene-based composite anticorrosive coating and preparation method and application thereof
CN109233497A (en) * 2018-08-09 2019-01-18 钱兴 A kind of graphene water soluble acrylic acid anticorrosive paint
CN109181490B (en) * 2018-11-01 2020-01-03 海洋化工研究院有限公司 Water-based epoxy anticorrosive paint and preparation method thereof
CN109880483A (en) * 2019-02-20 2019-06-14 朱冬梅 A kind of bi-component epoxide-resin complex abrasion-proof coating
CN110484116A (en) * 2019-08-30 2019-11-22 西北工业大学 Hexagonal boron nitride anti-corrosion polyurethane coating and preparation method thereof, corrosion-inhibiting coating

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6426438A (en) * 1987-07-23 1989-01-27 Kobe Steel Ltd Rust proof steel sheet with organic coating
CN102061121A (en) * 2010-12-06 2011-05-18 老虎粉末涂料制造（太仓）有限公司 Environmental-protection anti-corrosive heat-dissipation powder paint, and preparation method and application thereof
CN103589281A (en) * 2013-11-04 2014-02-19 上海电力学院 High temperature resistant anticorrosion coating based on graphene and preparation method thereof
CN104327670A (en) * 2014-11-05 2015-02-04 侨健新能源科技（苏州）有限公司 Impact-resistant cold-resistant anticorrosive paint
CN104629510A (en) * 2015-02-03 2015-05-20 大连理工大学 Preparation method of stripping boron nitride anticorrosive coating, coating obtained by preparation method and application of coating
CN104817930A (en) * 2015-05-05 2015-08-05 济宁利特纳米技术有限责任公司 Heat-conductive and anti-corrosion coating based on graphene functional material and preparation method of same

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104974640A (en) * 2013-11-01 2015-10-14 天津大学 Preparation method of graphene-containing marine anticorrosive antifouling paint
CN104231815A (en) * 2014-09-30 2014-12-24 济宁利特纳米技术有限责任公司 Functionalized antifouling anticorrosive graphene paint as well as preparation method and painting method thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6426438A (en) * 1987-07-23 1989-01-27 Kobe Steel Ltd Rust proof steel sheet with organic coating
CN102061121A (en) * 2010-12-06 2011-05-18 老虎粉末涂料制造（太仓）有限公司 Environmental-protection anti-corrosive heat-dissipation powder paint, and preparation method and application thereof
CN103589281A (en) * 2013-11-04 2014-02-19 上海电力学院 High temperature resistant anticorrosion coating based on graphene and preparation method thereof
CN104327670A (en) * 2014-11-05 2015-02-04 侨健新能源科技（苏州）有限公司 Impact-resistant cold-resistant anticorrosive paint
CN104629510A (en) * 2015-02-03 2015-05-20 大连理工大学 Preparation method of stripping boron nitride anticorrosive coating, coating obtained by preparation method and application of coating
CN104817930A (en) * 2015-05-05 2015-08-05 济宁利特纳米技术有限责任公司 Heat-conductive and anti-corrosion coating based on graphene functional material and preparation method of same

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111423801A (en) * 2019-01-10 2020-07-17 沈阳化工研究院有限公司 Water-based nano heavy-duty coating for chemical sewage tank and preparation thereof
CN113265185A (en) * 2021-05-24 2021-08-17 广州市上善纳米材料有限公司 Self-repairing graphene composite titanium nano heavy-duty anticorrosive material and preparation and use methods thereof
CN113265185B (en) * 2021-05-24 2022-02-11 广州市上善纳米材料有限公司 Self-repairing graphene composite titanium nano heavy-duty anticorrosive material and preparation and use methods thereof
CN113777174A (en) * 2021-08-20 2021-12-10 湖北省建筑科学研究设计院股份有限公司 Ultrasonic flaw detection coupling agent for building or bridge steel structure and preparation method thereof
CN114044880B (en) * 2021-09-28 2024-01-09 昆明国松特种涂料有限公司 Polycarbonate epoxy resin, solvent-free anticorrosive paint and application
CN114044880A (en) * 2021-09-28 2022-02-15 昆明国松特种涂料有限公司 Polycarbonate epoxy resin, solvent-free anticorrosive paint and application
CN114517047A (en) * 2022-03-03 2022-05-20 江南大学 Preparation method of water-based epoxy-modified graphene oxide nano composite coating
CN114921145A (en) * 2022-06-10 2022-08-19 洛阳大豫实业有限公司 Modified graphene anticorrosive paint and preparation method thereof
CN114921145B (en) * 2022-06-10 2023-07-18 洛阳大豫实业有限公司 Modified graphene anticorrosive paint and preparation method thereof
CN115232530A (en) * 2022-08-17 2022-10-25 山东玉皇新能源科技有限公司 Water-based graphene-based composite anticorrosive paint and preparation method thereof
CN115232530B (en) * 2022-08-17 2024-02-23 山东玉皇新能源科技有限公司 Water-based graphene-based composite anticorrosive paint and preparation method thereof
CN115491128A (en) * 2022-08-31 2022-12-20 山东之诺新材料科技有限公司 Formula of JJY-1 graphene modified high-temperature-resistant abrasion-resistant heavy-duty anticorrosive nano ceramic coating
CN117089256A (en) * 2023-10-19 2023-11-21 北京易净星科技有限公司 High-performance protective paint for highway guardrails and preparation method thereof

Also Published As

Publication number Publication date
CN106243943B (en) 2018-07-20
CN106243943A (en) 2016-12-21

Similar Documents

Publication Publication Date Title
WO2018036422A1 (en) Modified white graphene composite anti-corrosion coating and preparation thereof
WO2017201770A1 (en) Graphene heavy-duty anti-corrosion environmentally friendly hard repair coating and preparation method therefor
CN103834209B (en) A kind of polyaniline paint and preparation method thereof hindering control chloride permeability
CN105419626A (en) Macromolecule aluminum alloy anti-corrosion Czochralski collosol and preparation method thereof
CN113265185B (en) Self-repairing graphene composite titanium nano heavy-duty anticorrosive material and preparation and use methods thereof
CN114921145B (en) Modified graphene anticorrosive paint and preparation method thereof
CN109337454B (en) High-corrosion-resistance anti-corrosion paste suitable for marine atmospheric environment and preparation method and application thereof
CN111500148A (en) Graphene-modified functional heavy-duty water-based paint for steel, and preparation method and application method thereof
CN110819193A (en) Self-flame-retardant acrylic resin water-based anticorrosive paint
CN108727961A (en) Heat insulating and corrosion coating and preparation method thereof
CN202952600U (en) High temperature and strong acid resistant anticorrosion coating
CN105694667B (en) Thick coated type epoxy insulation antiseptic paint
CN113372791A (en) Marine heavy-duty anticorrosive paint and preparation method thereof
CN108178984B (en) High-temperature-resistant heavy-duty anticorrosive paint for stainless steel
CN108329794B (en) Self-repairing anticorrosive coating based on polysilazane microcapsule and preparation method thereof
CN112852260B (en) Durable epoxy resin anticorrosive paint and preparation method and application thereof
CN111378347A (en) High-temperature-resistant anti-condensation coating for high-temperature flue gas treatment equipment and preparation method thereof
CN106398535B (en) A kind of cable erosion shield
CN105296995A (en) Long-acting aluminum alloy anti-corrosion lifting sol and preparation method thereof
CN109135500A (en) A kind of preparation method of antifouling anticorrosive paint peculiar to vessel
CN105062355B (en) Nano-composite water durably anticorrosion paint preparation method for ship
CN113429812A (en) Composite anticorrosive paint and preparation method thereof
WO2016175367A1 (en) Aqueous colored pigment composition mixed with plate-like zinc powder
RU2549844C1 (en) Composition of anti-salt compound for coating metal surface, primarily of housings and components of submerged pumps for oil extraction and method for preparation thereof
CN105331266A (en) Aluminium section coating pretreatment agent

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 17842845

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 17842845

Country of ref document: EP

Kind code of ref document: A1