CN111808499A - Organic framework modified epoxy resin scratch-resistant water-based paint - Google Patents
Organic framework modified epoxy resin scratch-resistant water-based paint Download PDFInfo
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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
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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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/1851—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
- C23C18/1872—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment
- C23C18/1886—Multistep pretreatment
- C23C18/1893—Multistep pretreatment with use of organic or inorganic compounds other than metals, first
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/38—Coating with copper
- C23C18/40—Coating with copper using reducing agents
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- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- 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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- 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
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The invention discloses an organic framework modified epoxy resin scratch-resistant water-based paint, which relates to the technical field of paint processing, and specifically comprises the following processes: 1) carrying out chemical copper plating on the treated graphene oxide; 2) preparing a powdery organic metal framework material compound by using cobalt chloride, manganese nitrate, terephthalic acid and copper-plated graphene as precursors; 3) introducing an organic metal framework material compound in the synthesis process of the epoxy resin to obtain modified epoxy resin; 4) emulsifying the organic metal framework modified epoxy resin to obtain epoxy resin emulsion, and uniformly dispersing the epoxy resin emulsion and the prepared raw materials. According to the invention, the organic metal framework material compound with good stability and flexibility is introduced into the epoxy resin, so that a strong high-toughness chemical connection is formed in an epoxy resin polymer network, the molecular chain of the epoxy resin is not easy to slip, and the deformation can be completely recovered after the external force is removed, thereby realizing the improvement of the scratch resistance of the coating.
Description
Technical Field
The invention belongs to the technical field of paint treatment, and particularly relates to an organic framework modified epoxy resin scratch-resistant water-based paint.
Background
The epoxy resin coating is a high-performance coating and has wide application. It has many advantages including strong adhesion to various base materials, high hardness of coating, good water and chemical resistance, high wear resistance, etc., and can be used as terrace, floor coating, metal antirust primer, ship coating, etc. However, most of the epoxy resin coatings are solvent-based coatings at present, contain a large amount of volatile organic compounds, and the organic compounds are toxic and flammable, pollute the atmosphere and cause harm to the environment and human bodies. With the scientific progress, the requirement of people on environmental protection is increasingly improved, and the call for using water-based paint is increasingly rising.
The water-based epoxy resin coating has the characteristics of good chemical resistance, adhesiveness, physical and mechanical properties and electrical insulation of a solvent-based epoxy coating, low pollution, simple construction, low price and the like, and is a water-based coating which is developed quickly at present. In recent years, the demand for water-based coatings is more and more pursuing individualization and functionalization, and high-performance coatings are beginning to be sought after. The high performance of the coating comprises the performances of high decoration, heavy corrosion resistance, super durability, functionalization, good construction application and the like, wherein the scratch resistance is an important index for measuring the performance of the coating. In the using process of the paint, the coating is easy to scratch and damage, so that the coating loses luster and scratches, and the attractiveness of the coating is influenced, thereby reducing the using performance and the service life of the paint. At present, the common epoxy resin coating has small inter-molecular chain mobility, larger brittleness and poor scratch resistance because of high crosslinking generated in the curing process. Therefore, on the basis of meeting some basic performances of the coating, the scratch resistance of the epoxy resin coating is improved, and high decorative performance and high protection effect are achieved, so that the application purpose is achieved.
Disclosure of Invention
Aiming at the existing problems, the invention provides an organic framework modified epoxy resin scratch-resistant water-based paint, wherein an organic metal framework material compound with good stability and flexibility is introduced into epoxy resin, so that an epoxy resin polymer network forms strong high-toughness chemical connection, the formed high-toughness chemical connection enables epoxy resin molecular chains not to easily slide, and deformation can be completely recovered after external force is removed, so that the scratch resistance of a coating can be improved.
The invention is realized by the following technical scheme:
an organic framework modified epoxy resin scratch-resistant water-based paint comprises the following specific processes:
1) weighing a proper amount of graphene oxide, carrying out coarsening, sensitizing and activating treatment on the graphene oxide, selecting 8-12g/L copper sulfate, 0.6-1.0g/L nickel sulfate, 13-16g/L sodium citrate, 26-30g/L sodium hypophosphite and 25-30g/L boric acid to prepare a chemical plating solution, adding reduced graphene into the plating solution according to the mass-volume ratio of 1:30-40g/ml at room temperature, adjusting the pH value to 11-12, reacting for 3-7min, and carrying out natural precipitation, centrifugation, washing, drying, crushing and grinding after the reaction is finished to obtain the nano copper-plated graphene; according to the invention, graphene oxide is treated and then surface copper plating is carried out, so that the wettability of graphene and a metal organic framework substrate can be improved through copper plating treatment, the graphene can be in close contact with the metal organic framework substrate to be adsorbed, huge intermolecular acting force is formed on an interface, the bonding strength is improved, and the graphene can be firmly attached to the surface of the metal organic framework;
2) weighing 4-6 parts of cobalt chloride and 4-6 parts of manganese nitrate, dissolving in 100-150 parts of N, N-dimethylformamide solution, adding 8-12 parts of terephthalic acid and 0.5-1.5 parts of copper-plated graphene at room temperature, transferring to a polytetrafluoroethylene-lined stainless steel autoclave, reacting at 120-130 ℃ for 23-27h, cooling the product to room temperature, washing for 3-4 times with N, N-dimethylformamide solution, purifying the product with ethanol, exchanging an object N, N-dimethylformamide solvent for 24-28h, and finally activating in a vacuum drying oven at 80-90 ℃ for 12-15h to obtain a powdery organic metal framework material compound; according to the invention, cobalt chloride, manganese nitrate, terephthalic acid and copper-plated graphene are used as precursors, a compound with graphene is synthesized by adopting a simple one-pot method, the introduced nano copper-plated graphene can be attached to and grow on the surface of a metal organic framework, the agglomeration of metal organic framework materials can be effectively inhibited, and a copper-plated layer formed by depositing on the surface of the graphene is formed by arranging copper particles, the copper-plated layer formed by the deposition of the surface of the graphene is compact in structure but rough in surface due to the size difference among the copper particles, the graphene with the rough copper-plated layer surface can improve the 'bonding' effect, and the bonding property of the metal organic framework and epoxy resin molecules is improved;
3) dispersing a powdery organic metal framework material compound in deionized water to obtain dispersion liquid with the concentration of 5-10 per thousand, then adding bisphenol A and epoxy chloropropane into the dispersion liquid according to the mass ratio of 50-80:1 of bisphenol A to organic metal framework material compound and the molar ratio of 1:8-12 of bisphenol A to epoxy chloropropane, mixing for 30-50min at 70-80 ℃ to obtain mixed liquid, then adding a first part of initiator which accounts for 10-15% of the total mass of the initiator into the mixed liquid according to the molar ratio of 1.0-1.3:1 of the initiator to the epoxy chloropropane, reacting for 50-80min at 65-70 ℃, then adding the rest of initiator, reacting for 1-2h at 75-80 ℃, after the reaction is finished, washing for 3-4 times at 60-70 ℃, distilling to obtain organic skeleton modified epoxy resin; according to the invention, an in-situ polymerization method is adopted, an organic metal framework material compound is added from the initial synthesis stage, epoxy resin molecules are adsorbed on the surface of the organic metal framework material compound, and the epoxy resin molecules form cross-linking through the organic metal framework material compound;
4) weighing 40-45 parts of polyethylene glycol ether, 45-50 parts of alkyl polyoxyethylene ether and 170 parts of organic framework modified epoxy resin 140-65 parts by weight, adding the materials into a reaction kettle, heating the materials until the materials are completely dissolved, adding 55-65 parts of dimethylbenzene, uniformly stirring the materials, adding 15-18 parts of toluene diisocyanate at the temperature of 60-65 ℃, reacting the materials for 3.0-3.5 hours at the temperature of 80-90 ℃, raising the temperature to 110 ℃ and vacuumizing the materials, extracting the dimethylbenzene, cooling the temperature to 55-60 ℃, adding 55-60 parts of aliphatic glycidyl ether epoxy resin, uniformly stirring the materials to obtain an epoxy emulsifier, taking 130 parts of 100 parts of the prepared epoxy emulsifier, taking 180 parts of the organic framework modified epoxy resin 150-180 parts of aliphatic glycidyl ether epoxy resin 35-38 parts of the prepared epoxy emulsifier, adding the mixture into a reaction kettle, melting the mixture to be transparent at 70-75 ℃, discharging the mixture, cooling the mixture to normal temperature, slowly adding deionized water under high-speed stirring until the phase is changed to prepare 50-55% of epoxy resin emulsion, and then dispersing the epoxy resin emulsion 50-70%, the curing agent 10-20%, the film-forming auxiliary agent 5-10%, the defoaming agent 0.3-0.8%, the flatting agent 2-5%, the wetting agent 2-4% and the removed deionized water uniformly at the rotating speed of 500 plus 800r/min according to the mass fraction to obtain the required water-based coating.
Further, the roughening treatment is as follows: adding graphene oxide into a sodium hydroxide aqueous solution with the mass percentage of 35-40%, performing ultrasonic dispersion for 1-2h at 200-300W, heating for 30-50min under the water bath condition of 90-100 ℃, then performing centrifugal filtration on the mixture, repeatedly washing a filter cake to be neutral by deionized water, and drying to obtain the graphene oxide filter cake.
Further, the sensitization treatment is as follows: firstly, preparing a stannous chloride solution with the concentration of 30-40g/L and a hydrochloric acid solution with the concentration of 100-130mg/L, uniformly mixing the stannous chloride solution and the hydrochloric acid solution to form a sensitizing solution, then dispersing the coarsened graphene oxide into the sensitizing solution, carrying out 200-300W ultrasonic dispersion for 1-2h, heating for 15-25min at the temperature of 50-70 ℃, then washing with distilled water to be neutral, filtering and drying.
Further, the activation treatment is as follows: preparing a silver nitrate solution with the concentration of 30-40g/L, adding ammonia water with the mass concentration of 20-25% into the silver nitrate solution to prepare a silver ammonia solution, then putting the sensitized graphene oxide into the silver ammonia solution for ultrasonic dispersion and activation, then washing the activated graphene oxide to be neutral by using distilled water, and filtering and drying the activated graphene oxide.
Further, the initiator includes one or more of benzyltrimethylammonium chloride, tetramethylammonium bromide, tetraethylammonium bromide, and hexadecyltrimethylammonium bromide.
Further, the curing agent is a polyamide curing agent or an amide curing agent; the foaming agent is selected from at least one of C-885FBRA defoaming agent and 080 defoaming agent; the film-forming auxiliary agent adopts an ether film-forming auxiliary agent; the leveling agent is a BYK series leveling agent; the wetting agent is at least one selected from PM-WET 100, PM-WET 101 and PM-DISPERSANT 5040.
Compared with the prior art, the invention has the following advantages:
the water paint provided by the invention is prepared by modifying epoxy resin, adding organic metal framework material compound in the initial synthesis stage of the epoxy resin, the surface of the organic metal framework material compound is adsorbed with epoxy resin molecules, and the introduced organic metal framework material compound has good stability and flexibility, and has good cohesiveness with epoxy resin molecules, and the introduction of the flexible organic metal framework material compound leads the epoxy resin polymer network to form strong high-toughness chemical connection, so that the epoxy resin molecular chains are not easy to slip, the deformation can be completely recovered after the external force is removed, the coating is not easy to be damaged, therefore, the scratch resistance of the coating can be improved, the coating is not easy to be damaged by scratching, the attractiveness of the coating is improved, and the application of the coating is expanded.
Detailed Description
The present invention will be further described with reference to specific embodiments.
Example 1
An organic framework modified epoxy resin scratch-resistant water-based paint comprises the following specific processes:
1) weighing a proper amount of graphene oxide, carrying out coarsening, sensitizing and activating treatment on the graphene oxide, then selecting 8g/L copper sulfate, 0.6g/L nickel sulfate, 13g/L sodium citrate, 26g/L sodium hypophosphite and 25g/L boric acid to prepare a chemical plating solution, adding reduced graphene into the plating solution according to the mass-to-volume ratio of 1:30g/ml under the condition of room temperature, adjusting the pH value to 11, reacting for 7min, and carrying out natural precipitation, centrifugation, washing, drying, crushing and grinding after the reaction is finished to obtain the nanoscale copper-plated graphene;
2) weighing 4 parts of cobalt chloride and 4 parts of manganese nitrate, dissolving the cobalt chloride and the manganese nitrate in 100 parts of N, N-dimethylformamide solution, adding 8 parts of terephthalic acid and 0.5 part of copper-plated graphene at room temperature, transferring the mixture into a polytetrafluoroethylene-lined stainless steel autoclave, reacting at 120 ℃ for 23 hours, cooling the product to room temperature, washing the product for 3 times by using N, N-dimethylformamide solution, purifying the product by using ethanol, exchanging an object N, N-dimethylformamide solvent for 24 hours, and finally performing activation treatment in a vacuum drying oven at 80 ℃ for 12 hours to obtain a powdery organic metal framework material compound;
3) dispersing a powdery organic metal framework material compound in deionized water to obtain a dispersion liquid with the concentration of 5 per thousand, then adding bisphenol A and epoxy chloropropane into the dispersion liquid according to the mass ratio of 50:1 of bisphenol A to organic metal framework material compound and the molar ratio of 1:8 of bisphenol A to epoxy chloropropane, mixing for 30min at 70 ℃ to obtain a mixed liquid, then adding a first part of benzyl trimethyl ammonium chloride accounting for 10% of the total mass of the benzyl trimethyl ammonium chloride into the mixed liquid according to the molar ratio of 1.0:1 of benzyl trimethyl ammonium chloride to react for 50min at 65 ℃, then adding the rest of benzyl trimethyl ammonium chloride to react for 1h at 75 ℃, washing for 3 times at 60 ℃ after the reaction is finished, and distilling to obtain the organic framework modified epoxy resin;
4) weighing 40 parts by weight of polyethylene glycol ether, 45 parts by weight of alkyl polyoxyethylene ether and 140 parts by weight of organic framework modified epoxy resin, adding the mixture into a reaction kettle, heating the mixture until the mixture is completely dissolved, adding 55 parts by weight of dimethylbenzene, uniformly stirring the mixture, adding 15 parts by weight of toluene diisocyanate at 60 ℃, reacting the mixture for 3.0 hours at 80 ℃, raising the temperature to 100 ℃, vacuumizing the mixture, pumping out dimethylbenzene, cooling the mixture to 55 ℃, adding 55 parts by weight of fatty glycidyl ether epoxy resin, uniformly stirring the mixture to obtain an epoxy emulsifier, taking 100 parts by weight of the prepared epoxy emulsifier, taking 150 parts by weight of organic framework modified epoxy resin and 35 parts by weight of fatty glycidyl ether epoxy resin, adding the mixture into the reaction kettle, melting the mixture to a transparent state at 70 ℃, discharging the mixture to normal temperature, slowly adding deionized water under high-speed stirring until the phase is changed to obtain a 50% epoxy resin emulsion, then, according to the mass fraction, 60 percent of epoxy resin emulsion, 15 percent of polyamide curing agent, 5 percent of propylene glycol phenyl ether, 0.3 percent of C-885FBRA defoaming agent, 2 percent of BYK-323 flatting agent, 1002 percent of PM-WET and the removed deionized water are dispersed uniformly at the rotating speed of 500r/min, thus obtaining the required water-based paint.
Further, the roughening treatment is as follows: adding graphene oxide into a sodium hydroxide aqueous solution with the mass percentage of 35%, ultrasonically dispersing for 1h at 200W, heating for 30min under the condition of a water bath at 90 ℃, then centrifugally filtering the mixture, repeatedly washing a filter cake to be neutral by deionized water, and drying to obtain the graphene oxide filter cake.
Further, the sensitization treatment is as follows: firstly, preparing a stannous chloride solution with the concentration of 30g/L and a hydrochloric acid solution with the concentration of 100mg/L, uniformly mixing the stannous chloride solution and the hydrochloric acid solution to form a sensitizing solution, then dispersing the coarsened graphene oxide into the sensitizing solution, carrying out ultrasonic dispersion for 1h at 200W, heating for 15min at the temperature of 50 ℃, then washing the graphene oxide to be neutral by using distilled water, and filtering and drying the graphene oxide.
Further, the activation treatment is as follows: preparing a silver nitrate solution with the concentration of 30g/L, adding ammonia water with the mass concentration of 20% into the silver nitrate solution to prepare a silver-ammonia solution, putting the sensitized graphene oxide into the silver-ammonia solution for ultrasonic dispersion and activation, then washing the activated graphene oxide with distilled water to be neutral, and filtering and drying the activated graphene oxide.
Control group 1:
weighing 40 parts by weight of polyethylene glycol ether, 45 parts by weight of alkyl polyoxyethylene ether and 140 parts by weight of E-20 epoxy resin, adding the mixture into a reaction kettle, heating the mixture until the mixture is completely dissolved, adding 55 parts by weight of dimethylbenzene, uniformly stirring the mixture, adding 15 parts by weight of toluene diisocyanate at 60 ℃, reacting the mixture for 3.0 hours at 80 ℃, raising the temperature to 100 ℃, vacuumizing the mixture, pumping out dimethylbenzene, cooling the mixture to 55 ℃, adding 55 parts by weight of fatty glycidyl ether epoxy resin, uniformly stirring the mixture to obtain an epoxy emulsifier, taking 100 parts by weight of the prepared epoxy emulsifier, taking 150 parts by weight of E-20 epoxy resin and 35 parts by weight of fatty glycidyl ether epoxy resin, adding the mixture into the reaction kettle, melting the mixture to a transparent state at 70 ℃, discharging the mixture to normal temperature, slowly adding deionized water under high-speed stirring until the phase is changed to obtain a 50% epoxy resin emulsion, then, according to the mass fraction, 60 percent of epoxy resin emulsion, 15 percent of polyamide curing agent, 5 percent of propylene glycol phenyl ether, 0.3 percent of C-885FBRA defoaming agent, 2 percent of BYK-323 flatting agent, 1002 percent of PM-WET and the removed deionized water are dispersed uniformly at the rotating speed of 500r/min, thus obtaining the required water-based paint.
Scratch resistance test experiment of the coating:
the water paint provided in example 1 and control 1 was coated on tinplate and PC thin plate respectively, the coating thickness was 3mm, the coating was dried for 7 days at room temperature, the scratch resistance test of the coating was performed using a multi-fingered scratch tester (Taber 710 type, usa), the apparatus had 5 needles with different loads (2N, 3N, 5N, 6N, 7N), during the test, the sample was fixed on a horizontal table, then the load was applied, the horizontal table was rapidly moved linearly by an air pump, the scratch resistance value SR1 of the coating was determined as the load corresponding to the permanent scratch on the coating, and the results were as follows: the coating of the waterborne coating provided in control 1 had a SR1 of 3N, and the coating of the waterborne coating provided in example 1 had a SR1 of 7N.
Note: during the test, the water based paint of example 1 was coated on the tinplate sample and the PC sheet sample, and the water based paint of control 1 was coated on the tinplate sample and the PC sheet sample, each of which was 50 pieces.
Example 2
An organic framework modified epoxy resin scratch-resistant water-based paint comprises the following specific processes:
1) weighing a proper amount of graphene oxide, carrying out coarsening, sensitizing and activating treatment on the graphene oxide, selecting 10g/L copper sulfate, 0.8g/L nickel sulfate, 15g/L sodium citrate, 28g/L sodium hypophosphite and 27g/L boric acid to prepare a chemical plating solution, adding reduced graphene into the plating solution according to the mass-to-volume ratio of 1:35g/ml under the condition of room temperature, adjusting the pH value to 11, reacting for 7min, and carrying out natural precipitation, centrifugation, washing, drying, crushing and grinding after the reaction is finished to obtain the nanoscale copper-plated graphene;
2) weighing 5 parts of cobalt chloride and 5 parts of manganese nitrate, dissolving the cobalt chloride and the manganese nitrate in 120 parts of N, N-dimethylformamide solution, adding 10 parts of terephthalic acid and 1.0 part of copper-plated graphene at room temperature, transferring the mixture into a polytetrafluoroethylene-lined stainless steel autoclave, reacting for 25 hours at 125 ℃, cooling the product to room temperature, washing for 3 times with N, N-dimethylformamide solution, purifying the product with ethanol, exchanging an object N, N-dimethylformamide solvent for 25 hours, and finally performing activation treatment for 13 hours in a 85 ℃ vacuum drying oven to obtain a powdery organic metal framework material compound;
3) dispersing a powdery organic metal framework material compound in deionized water to obtain a dispersion liquid with the concentration of 7 per thousand, then adding bisphenol A and epoxy chloropropane into the dispersion liquid according to the mass ratio of 60:1 of the bisphenol A to the organic metal framework material compound and the molar ratio of 1:10 of the bisphenol A to the epoxy chloropropane, mixing for 40min at 75 ℃ to obtain a mixed liquid, then adding a first part of tetramethyl ammonium bromide into the mixed liquid according to the molar ratio of 1.1:1 of the tetramethyl ammonium bromide to the epoxy chloropropane, wherein the first part of tetramethyl ammonium bromide accounts for 12% of the total mass of the tetramethyl ammonium bromide, reacting for 60min at 67 ℃, then adding the rest of the tetramethyl ammonium bromide, reacting for 1.5h at 78 ℃, washing for 4 times by using water at 65 ℃ after the reaction is finished, and distilling to obtain the organic framework modified epoxy resin;
4) weighing 43 parts by weight of polyethylene glycol ether, 48 parts by weight of alkyl polyoxyethylene ether and 150 parts by weight of organic framework modified epoxy resin, adding the materials into a reaction kettle, heating the materials until the materials are completely dissolved, adding 60 parts by weight of dimethylbenzene, uniformly stirring the materials, adding 17 parts by weight of toluene diisocyanate at 63 ℃, reacting the materials for 3.2 hours at 75 ℃, raising the temperature to 105 ℃, vacuumizing the temperature, pumping out the dimethylbenzene, cooling the temperature to 56 ℃, adding 57 parts by weight of aliphatic glycidyl ether epoxy resin, uniformly stirring the materials to obtain an epoxy emulsifier, taking 120 parts by weight of the prepared epoxy emulsifier, taking 170 parts by weight of organic framework modified epoxy resin and 37 parts by weight of aliphatic glycidyl ether epoxy resin, adding the materials into the reaction kettle, melting the materials to a transparent state at 72 ℃, discharging the materials to normal temperature, slowly adding deionized water under high-speed stirring until the materials are phase-changed to obtain 52% epoxy resin emulsion, then, according to the mass fraction, 50 percent of epoxy resin emulsion, 20 percent of polyamide curing agent, 7 percent of propylene glycol phenyl ether, 0.5 percent of 080 defoaming agent, 3 percent of BYK-323 flatting agent, 1013 percent of PM-WET and deionized water are uniformly dispersed at the rotating speed of 500-800r/min, and the required water-based paint can be obtained.
Further, the roughening treatment is as follows: adding graphene oxide into a sodium hydroxide aqueous solution with the mass percentage of 36%, ultrasonically dispersing for 1.5h under 250W, heating for 40min under the condition of a water bath at 95 ℃, then centrifugally filtering the mixture, repeatedly washing a filter cake to be neutral by deionized water, and drying to obtain the graphene oxide filter cake.
Further, the sensitization treatment is as follows: firstly, preparing a stannous chloride solution with the concentration of 35g/L and a hydrochloric acid solution with the concentration of 120mg/L, uniformly mixing the stannous chloride solution and the hydrochloric acid solution to form a sensitizing solution, then dispersing the coarsened graphene oxide into the sensitizing solution, performing ultrasonic dispersion for 1.5h at 250W, heating for 20min at the temperature of 60 ℃, then washing with distilled water to be neutral, filtering and drying.
Further, the activation treatment is as follows: preparing a silver nitrate solution with the concentration of 35g/L, adding ammonia water with the mass concentration of 23% into the silver nitrate solution to prepare a silver-ammonia solution, putting the sensitized graphene oxide into the silver-ammonia solution for ultrasonic dispersion and activation, then washing the activated graphene oxide with distilled water to be neutral, and filtering and drying the activated graphene oxide.
Scratch resistance test experiment of the coating:
the water paint provided in example 2 and control 2 was coated on tinplate and PC thin plate respectively, the coating thickness was 3mm, and dried at room temperature for 7d, and the scratch resistance test of the coating was performed using a multi-finger scratch tester (Taber 710 type, usa), which has 5 needles with different loads (2N, 3N, 5N, 6N, 7N), during the test, the sample was fixed on a horizontal table, then the load was applied, the horizontal table was rapidly moved linearly by an air pump, and the load corresponding to the permanent scratch on the coating was changed to the scratch resistance SR1 of the coating, and the test results were as follows: the coating of the waterborne coating provided in control 2 had a SR1 of 3N, and the coating of the waterborne coating provided in example 2 had a SR1 of 7N.
Note: during the test, the water based paint of example 2 was coated on the tinplate sample and the PC sheet sample, and the water based paint of control 2 was coated on the tinplate sample and the PC sheet sample, each of which was 50 pieces.
Example 3
An organic framework modified epoxy resin scratch-resistant water-based paint comprises the following specific processes:
1) weighing a proper amount of graphene oxide, carrying out coarsening, sensitizing and activating treatment on the graphene oxide, then selecting 12g/L copper sulfate, 1.0g/L nickel sulfate, 16g/L sodium citrate, 30g/L sodium hypophosphite and 30g/L boric acid to prepare a chemical plating solution, adding reduced graphene into the plating solution according to the mass-to-volume ratio of 1:40g/ml under the condition of room temperature, adjusting the pH value to 12, reacting for 3min, and carrying out natural precipitation, centrifugation, washing, drying, crushing and grinding after the reaction is finished to obtain the nanoscale copper-plated graphene;
2) weighing 6 parts of cobalt chloride and 6 parts of manganese nitrate, dissolving the cobalt chloride and the manganese nitrate in 150 parts of N, N-dimethylformamide solution, adding 12 parts of terephthalic acid and 1.5 parts of copper-plated graphene at room temperature, transferring the mixture into a polytetrafluoroethylene-lined stainless steel autoclave, reacting for 27 hours at 130 ℃, cooling the product to room temperature, washing for 4 times with N, N-dimethylformamide solution, purifying the product with ethanol, exchanging an object N, N-dimethylformamide solvent for 28 hours, and finally activating for 15 hours in a vacuum drying oven at 80-90 ℃ to obtain a powdery organic metal framework material compound;
3) dispersing a powdery organic metal framework material compound in deionized water to obtain a dispersion liquid with the concentration of 10 per thousand, then adding bisphenol A and epoxy chloropropane into the dispersion liquid according to the mass ratio of the bisphenol A to the organic metal framework material compound of 80:1 and the molar ratio of the bisphenol A to the epoxy chloropropane of 1:12, mixing for 50min at 80 ℃ to obtain a mixed liquid, then adding a first part of tetraethylammonium bromide into the mixed liquid according to the molar ratio of the tetraethylammonium bromide to the epoxy chloropropane of 1.3:1 to react for 80min at 70 ℃, then adding the rest tetraethylammonium bromide to react for 2h at 80 ℃, washing for 4 times at 70 ℃ after the reaction is finished, and distilling to obtain the organic framework modified epoxy resin;
4) weighing 45 parts by weight of polyethylene glycol ether, 50 parts by weight of alkyl polyoxyethylene ether and 170 parts by weight of organic framework modified epoxy resin, adding the mixture into a reaction kettle, heating the mixture until the mixture is completely dissolved, adding 65 parts by weight of xylene, uniformly stirring the mixture, adding 18 parts by weight of toluene diisocyanate at 65 ℃, reacting the mixture for 3.5 hours at 90 ℃, raising the temperature to 110 ℃, vacuumizing the mixture, pumping out xylene, cooling the mixture to 60 ℃, adding 60 parts by weight of aliphatic glycidyl ether epoxy resin, uniformly stirring the mixture to obtain an epoxy emulsifier, taking 130 parts by weight of the prepared epoxy emulsifier, taking 180 parts by weight of organic framework modified epoxy resin and 38 parts by weight of aliphatic glycidyl ether epoxy resin, adding the mixture into the reaction kettle, melting the mixture to a transparent state at 75 ℃, discharging the mixture to a normal temperature, slowly adding deionized water under high-speed stirring until the mixture is phase-changed to prepare 55 percent epoxy resin emulsion, and then, according to the mass fraction, dispersing 70 percent of epoxy resin emulsion, 10 percent of polyamide curing agent, 5 percent of propylene glycol phenyl ether, 0.3 percent of 080 defoaming agent, 2 percent of BYK-323 flatting agent, PM-DISPERSANT 50402 percent and the removed amount of deionized water uniformly at the rotating speed of 800r/min to obtain the required water-based paint.
Further, the roughening treatment is as follows: adding graphene oxide into a 35-40% sodium hydroxide aqueous solution by mass, performing ultrasonic dispersion for 2h at 300W, heating for 50min under the condition of a water bath at 100 ℃, then performing centrifugal filtration on the mixture, repeatedly washing a filter cake to be neutral by deionized water, and drying to obtain the graphene oxide filter cake.
Further, the sensitization treatment is as follows: firstly, preparing a stannous chloride solution with the concentration of 40g/L and a hydrochloric acid solution with the concentration of 130mg/L, uniformly mixing the stannous chloride solution and the hydrochloric acid solution to form a sensitizing solution, then dispersing the coarsened graphene oxide into the sensitizing solution, carrying out ultrasonic dispersion for 2 hours at 300W, heating for 25min at the temperature of 70 ℃, then washing the graphene oxide to be neutral by using distilled water, and filtering and drying the graphene oxide.
Further, the activation treatment is as follows: preparing a silver nitrate solution with the concentration of 40g/L, adding ammonia water with the mass concentration of 25% into the silver nitrate solution to prepare a silver-ammonia solution, placing the sensitized graphene oxide into the silver-ammonia solution for ultrasonic dispersion and activation, then washing the activated graphene oxide with distilled water to be neutral, and filtering and drying the activated graphene oxide.
Scratch resistance test experiment of the coating:
the water paint provided in example 3 and control 3 was coated on tinplate and PC thin plate respectively, the coating thickness was 3mm, the coating was dried for 7 days at room temperature, the scratch resistance test of the coating was performed using a multi-fingered scratch tester (Taber 710 type, usa), the apparatus had 5 needles with different loads (2N, 3N, 5N, 6N, 7N), during the test, the sample was fixed on a horizontal table, then the load was applied, the horizontal table was driven by an air pump to move rapidly and linearly, and the scratch resistance value SR1 of the coating was determined as the load corresponding to the permanent scratch on the coating, and the test results were as follows: the coating of the waterborne coating provided in control 3 had a SR1 of 2N, and the coating of the waterborne coating provided in example 3 had a SR1 of 7N.
Note: during the test, the water based paint of example 3 was coated on the tinplate sample and the PC sheet sample, and the water based paint of control 3 was coated on the tinplate sample and the PC sheet sample, each of which was 50 pieces.
According to the test results, the water-based paint provided by the invention has excellent scratch resistance, so that the coating is not easy to be damaged by scratching, the attractiveness of the coating is improved, and the application of the paint is expanded.
The above description is only an embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that are not thought of through the inventive work should be included in the scope of the present invention.
Claims (10)
1. An organic framework modified epoxy resin scratch-resistant water-based paint is characterized by comprising the following specific processes:
1) weighing a proper amount of graphene oxide, carrying out coarsening, sensitizing and activating treatment on the graphene oxide, selecting 8-12g/L copper sulfate, 0.6-1.0g/L nickel sulfate, 13-16g/L sodium citrate, 26-30g/L sodium hypophosphite and 25-30g/L boric acid to prepare a chemical plating solution, adding reduced graphene into the plating solution according to the mass-volume ratio of 1:30-40g/ml at room temperature, adjusting the pH value to 11-12, reacting for 3-7min, and carrying out natural precipitation, centrifugation, washing, drying, crushing and grinding after the reaction is finished to obtain the nano copper-plated graphene;
2) weighing a proper amount of cobalt chloride and manganese nitrate, dissolving in an N, N-dimethylformamide solution, adding a proper amount of terephthalic acid and copper-plated graphene under the condition of room temperature, then transferring to a polytetrafluoroethylene-lined stainless steel autoclave, reacting at the temperature of 120 ℃ for 23-27h, cooling the product to room temperature, washing the product for 3-4 times by using the N, N-dimethylformamide solution, purifying the product by using ethanol, exchanging an object N, N-dimethylformamide solvent for 24-28h, and finally performing activation treatment in a vacuum drying oven at the temperature of 80-90 ℃ for 12-15h to obtain a powdery organic metal framework material compound;
3) dispersing the powdery organic metal framework material compound in deionized water to obtain dispersion liquid, adding bisphenol A and epoxy chloropropane, mixing to obtain mixed liquid, adding a first part of initiator into the mixed liquid, reacting at 65-70 ℃ for 50-80min, adding the rest of initiator, reacting at 75-80 ℃ for 1-2h, and after the reaction is finished, washing with water and distilling to obtain the organic metal framework modified epoxy resin;
4) emulsifying the organic metal framework modified epoxy resin to obtain epoxy resin emulsion, and then dispersing 50-70% of the epoxy resin emulsion, 10-20% of a curing agent, 5-10% of a film forming additive, 0.3-0.8% of a defoaming agent, 2-5% of a flatting agent, 2-4% of a wetting agent and a removal amount of deionized water uniformly at the rotating speed of 800r/min plus 500-.
2. The organic framework modified epoxy resin scratch-resistant water-based paint according to claim 1, wherein in the process step 1), the roughening treatment is as follows: adding graphene oxide into a sodium hydroxide aqueous solution with the mass percentage of 35-40%, performing ultrasonic dispersion for 1-2h at 200-300W, heating for 30-50min under the water bath condition of 90-100 ℃, then performing centrifugal filtration on the mixture, repeatedly washing a filter cake to be neutral by deionized water, and drying to obtain the graphene oxide filter cake.
3. The organic framework modified epoxy resin scratch-resistant water-based paint according to claim 1, characterized in that in the process step 1), the sensitization treatment is as follows: firstly, preparing a stannous chloride solution with the concentration of 30-40g/L and a hydrochloric acid solution with the concentration of 100-130mg/L, uniformly mixing the stannous chloride solution and the hydrochloric acid solution to form a sensitizing solution, then dispersing the coarsened graphene oxide into the sensitizing solution, carrying out 200-300W ultrasonic dispersion for 1-2h, heating for 15-25min at the temperature of 50-70 ℃, then washing with distilled water to be neutral, filtering and drying.
4. The organic framework modified epoxy resin scratch-resistant water-based paint according to claim 1, wherein in the process step 1), the activation treatment is as follows: preparing a silver nitrate solution with the concentration of 30-40g/L, adding ammonia water with the mass concentration of 20-25% into the silver nitrate solution to prepare a silver ammonia solution, then putting the sensitized graphene oxide into the silver ammonia solution for ultrasonic dispersion and activation, then washing the activated graphene oxide to be neutral by using distilled water, and filtering and drying the activated graphene oxide.
5. The organic framework modified epoxy resin scratch-resistant water-based paint as claimed in claim 1, wherein in the process step 2), the raw material components comprise, by weight, 4-6 parts of cobalt chloride, 4-6 parts of manganese nitrate, 100 parts of N, N-dimethylformamide solution, 8-12 parts of terephthalic acid and 0.5-1.5 parts of copper-plated graphene.
6. The organic framework modified epoxy resin scratch-resistant water-based paint as claimed in claim 1, wherein in the process step 3), the concentration of the dispersion liquid is 5-10 per mill; the mass ratio of the bisphenol A to the organic metal framework material compound is 50-80: 1; the molar ratio of the bisphenol A to the epichlorohydrin is 1: 8-12; the molar ratio of the initiator to the epichlorohydrin is 1.0-1.3: 1.
7. The organic framework modified epoxy resin scratch-resistant water-based paint as claimed in claim 1, wherein in the process step 3), the mixing temperature is 70-80 ℃, and the mixing time is 30-50 min; the first part of initiator accounts for 10-15% of the total mass of the initiator; the washing temperature is 60-70 ℃, and the washing times are 3-4.
8. The organic framework modified epoxy resin scratch-resistant waterborne coating of claim 1, wherein in process step 3), the initiator comprises one or more of benzyltrimethylammonium chloride, tetramethylammonium bromide, tetraethylammonium bromide and hexadecyltrimethylammonium bromide.
9. The organic framework modified epoxy resin scratch-resistant water-based paint according to claim 1, wherein in the process step 4), the preparation method of the epoxy resin emulsion comprises the following steps: weighing 40-45 parts of polyethylene glycol ether, 45-50 parts of alkyl polyoxyethylene ether and 170 parts of organic framework modified epoxy resin 140-65 parts by weight, adding the materials into a reaction kettle, heating the materials until the materials are completely dissolved, adding 55-65 parts of dimethylbenzene, uniformly stirring the materials, adding 15-18 parts of toluene diisocyanate at the temperature of 60-65 ℃, reacting the materials for 3.0-3.5 hours at the temperature of 80-90 ℃, raising the temperature to 110 ℃ and vacuumizing the materials, extracting the dimethylbenzene, cooling the temperature to 55-60 ℃, adding 55-60 parts of aliphatic glycidyl ether epoxy resin, uniformly stirring the materials to obtain an epoxy emulsifier, taking 130 parts of 100 parts of the prepared epoxy emulsifier, taking 180 parts of the organic framework modified epoxy resin 150-180 parts of aliphatic glycidyl ether epoxy resin 35-38 parts of the prepared epoxy emulsifier, adding into a reaction kettle, melting to transparent state at 70-75 deg.C, cooling to room temperature, stirring at high speed, slowly adding deionized water until phase transition, and making into 50-55% epoxy resin emulsion.
10. The organic framework modified epoxy resin scratch-resistant water-based paint according to claim 1, wherein in the process step 4), the curing agent is a polyamide curing agent or an amide curing agent; the foaming agent is selected from at least one of C-885FBRA defoaming agent and 080 defoaming agent; the film-forming auxiliary agent adopts an ether film-forming auxiliary agent; the leveling agent is a BYK series leveling agent; the wetting agent is at least one selected from PM-WET 100, PM-WET 101 and PM-DISPERSANT 5040.
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