CN114410171B - Water-based paint - Google Patents
Water-based paint Download PDFInfo
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- CN114410171B CN114410171B CN202210296303.7A CN202210296303A CN114410171B CN 114410171 B CN114410171 B CN 114410171B CN 202210296303 A CN202210296303 A CN 202210296303A CN 114410171 B CN114410171 B CN 114410171B
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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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/062—Copolymers with monomers not covered by C09D133/06
- C09D133/066—Copolymers with monomers not covered by C09D133/06 containing -OH groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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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
- 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
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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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
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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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- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The invention discloses a water-based paint which is prepared from the following raw materials in parts by weight: 40-70 parts of carbon nanotube modified fluorine-containing polyacrylate emulsion; 0.2-0.5 part of defoaming agent; 0.2-0.5 part of leveling agent; 2-5 parts of a film-forming assistant; 15-30 parts of deionized water, and the modification effect and positive effect of the carbon nano tube modified fluorine-containing polyacrylate emulsion in the coating are effectively verified through a coating contact angle performance test, a coating hardness performance test, an adhesive force test, a weather resistance test and an electrochemical corrosion resistance test.
Description
Technical Field
The invention relates to a water-based paint, in particular to a preparation method of a carbon nano tube modified fluorine-containing polyacrylate emulsion paint.
Background
According to the classification of polymer resins, the current water-based paint applied to corrosion protection mainly comprises water-based acrylic acid anticorrosive paint, water-based epoxy anticorrosive paint, water-based polyurethane anticorrosive paint and water-based inorganic zinc-rich paint, and the water-based anticorrosive paint of acrylic resin is the paint which is developed most rapidly and applied most widely in all four types.
The acrylic resin can be modified according to application conditions and environmental requirements to prepare the water-based paint with excellent corrosion resistance, the water-based acrylic resin anticorrosive paint can be quickly dried within 1 hour at the use temperature of 5 ℃, the acrylic resin polymer contains groups with stronger hydrophilicity, the neutral salt fog resistance does not exceed 500 hours, and the water-based acrylic resin anticorrosive paint is usually used in light-corrosion and smart-medium anticorrosive environments.
Carbon atoms in the carbon nanotubes are mainly sp2 hybridized, 1 carbon atom is connected with 3 adjacent carbon atoms to form a hexagonal network structure which is divided into multi-wall carbon nanotubes (MWCNTs) and single-wall carbon nanotubes (SWCNTs), and the carbon nanotubes have excellent physical properties such as high mechanical properties (the average Young modulus of the MWCNTs is 1.8 TPa, the bending strength is 14.2 GPa),
Good conductivity (the current density is 103A/cm) 2 ) Good thermal conductivity (coefficient of thermal conductivity is about 3000W/(m.K)), and high chemical stability (whenA temperature of less than 973K, stable in an oxidizing or corrosive environment), and the like. The characteristics also enable the carbon nano tube to have wider application prospect in the fields of electronics, catalyst carriers, composite materials, biological medicine carrying and the like, and the application of the carbon nano tube in the field of corrosion prevention is gradually expanded.
For example, CN2013101272066 discloses a preparation method of a carbon nanotube modified acrylate resin light-resistant coating, which aims to solve the technical problems of esterification of a hydroxylated carbon nanotube, improvement of light resistance of acrylate resin by using the free radical reaction of the esterified carbon nanotube and an acrylate monomer, and improvement of adhesiveness of the acrylate resin by using bentonite and xanthan gum to modify the acrylate monomer.
For example, CN2011102038508 discloses a graphene carbon nanotube hybrid polymer composite material and a manufacturing method thereof, which is prepared by solution blending or mechanical blending graphene, carbon nanotubes and a polymer matrix material. The obtained composite material with high conductivity and high mechanical property can be used as an antistatic and electromagnetic shielding material to be made into conductive carpets, packages of electronic products, parts of mobile phones, antistatic tread rubber for tires, electromagnetic shielding coatings of aerospace devices and the like, and has wide application value.
For example, CN2013105603443 discloses a nano heat-insulating ultraviolet-curing paint, which comprises the following components in percentage by weight: 20 to 50 percent of resin; 10 to 40 percent of monomer; nanometer ITO powder 3~7%; carbon nanotubes 2~8%; 10 to 20 percent of filler; photoinitiator 3~5%; 0.2 to 0.5 percent of dispersant; 0.5 to 1 percent of auxiliary agent. According to the nano heat-insulation ultraviolet curing paint disclosed by the invention, the added nano material enables the coating to have excellent heat-conducting property, so that the coating cannot crack after long-time heat absorption, and has a good heat-insulation effect.
In addition, for example, CN2007100469048 discloses a carbon nanotube-containing aqueous polyurethane conductive coating and a preparation method thereof. The conductive coating is prepared by the following method: firstly, the carbon nano tube is chemically modified to lead the surface of the carbon nano tube to carry a certain amount of hydroxyl, carboxyl or amidoThen introducing the mixture into polyester polyol or isocyanate-terminated polyurethane prepolymer by a chemical bonding method, preparing a water-based polyurethane dispersion containing carbon nano tubes by a self-emulsifying method, finally adding deionized water and an auxiliary agent, and stirring at a high speed to obtain the conductive coating. The volume resistivity of the coating film of the conductive coating is 1 multiplied by 10 -5 ～4×10 -4 Omega. Cm, surface resistivity of 1X 10 -1 ～2×10 2 Omega, adhesive force is 0 grade, shielding effectiveness is 70-85 dB, and the paint can still keep stable after being placed for a long time. The invention has simple process, no pollution, environmental protection, high coating quality and low cost, and the product can be applied to the fields of electronic industry, inner wall of oil tank, aerospace, optical wave communication, electromagnetic shielding, building heating and the like.
It can be concluded from the above documents that the carbon nanotubes are usually added in the coating in the prior art to improve the hardness, flexibility, impact strength, adhesion and corrosion resistance of the coating, but especially the preparation method can conclude that the carbon nanotubes are rarely surface-treated to improve the dispersion of the inorganic material of the carbon nanotubes in the coating by hydroxylation or carboxylation, so that the obtained carbon nanotubes have unstable dispersibility in the coating solution, have limited dispersion effect improvement capability, and still easily re-agglomerate into carbon nanotube bundles after standing in the solution for a period of time, thereby not only affecting the stability but also restricting the practical application value of the performance.
Disclosure of Invention
Based on the problems, the invention provides a water-based paint, which is prepared by preparing a multi-heterocyclic quinoline modified carbon nanotube dispersion liquid through an electrochemical polymerization method, wherein the carbon nanotubes are highly dispersed in the solution and do not settle within three months, and the dispersion liquid is used for preparing a fluorine-containing polyacrylate emulsion paint, so that the stability, the mechanical property, the antibacterial property, the corrosion resistance and the artificial weather aging resistance of a coating can be effectively improved.
The water-based paint comprises the following raw materials in parts by weight:
40-70 parts of carbon nano tube modified fluorine-containing polyacrylate emulsion;
0.2-0.5 part of defoaming agent;
0.2-0.5 part of leveling agent;
2-5 parts of a film-forming assistant;
15-30 parts of deionized water;
the preparation method of the carbon nano tube modified fluorine-containing polyacrylate emulsion comprises the following steps:
(1) Preparing modified carbon tube dispersion liquid: (a) Adding 20-40ml of 3-methyl-8-quinoline sulfonic acid, a proper amount of hydroxylated carbon nanotube sodium hydroxide solution with the pH value of 8-9, 0.1-0.15mg of dichloro pentamethyl cyclopentadienyl rhodium dimer, isopropanol and water deionized water into a three-neck flask, and stirring for 10-15min at the temperature of 20-25 ℃; (b) Adding an inert metal anode and an inert metal cathode into a three-mouth bottle, performing electrochemical synthesis under the conditions that the direct current is 10-20mA at the temperature of 45-50 ℃ and the time is 10-15h, and removing part of the solvent by using a rotary evaporator after the reaction is finished to obtain the modified carbon tube dispersion liquid.
(2) Adding 0.5-0.8g of sorbitan monooleate nonionic surfactant and 0.5-0.8g of sodium dodecyl benzene sulfonate anionic surfactant into 30-50g of deionized water solution, heating to 35-40 ℃, stirring for 10-15min, and cooling to room temperature. (3) Adding 0.025-0.05g of ammonium persulfate, 7-8g of methyl methacrylate, 5-6g of butyl acrylate, 0.3-0.4g of ethyl methacrylate, 1.5-1.8g of hydroxypropyl acrylate and 1.4-1.8g of dodecafluoroheptyl methacrylate into the solution obtained in the step (2) in sequence, and fully stirring to obtain solution A;
(4) Adding 0.5-0.8g of sorbitan monooleate nonionic surfactant and 0.5-0.8g of sodium dodecyl benzene sulfonate anionic surfactant into a four-neck flask, adding the mixture into 30-50g of deionized water solution, heating to 35-40 ℃, stirring for 10-15min, cooling to room temperature, introducing protective gas, adding 0.025-0.05g of ammonium persulfate, 3.5-4g of methyl methacrylate, 2.5-3g of butyl acrylate, 0.15-0.2g of ethyl methacrylate, 0.75-0.9g of hydroxypropyl acrylate, 0.7-0.9g of dodecafluoro heptyl methacrylate and 10-15ml of 2-3wt.% modified carbon tube dispersion liquid, fully stirring, and heating to 75-80 ℃ to obtain a liquid B;
(5) Dropwise adding the solution A obtained in the step (3) into the solution B obtained in the step (4), controlling the dropwise adding time to be within 2-2.5h at the temperature of 75-80 ℃, keeping the temperature for 2-3h after the dropwise adding is stopped, cooling to 30-40 ℃, and adjusting the pH value to be neutral to obtain the carbon nano tube modified fluorine-containing polyacrylate emulsion;
(6) Adding the carbon-containing nanotube acrylate copolymer emulsion, the defoaming agent, the leveling agent, the film-forming assistant and the deionized water into a reaction kettle, and stirring at the rotating speed of 600-800r/min for 10min to disperse and defoam the mixture to obtain the coating composition.
Further, the defoaming agent is a mineral oil defoaming agent or an organic silicon defoaming agent, and the leveling agent is a modified polysiloxane leveling agent.
Further, the film-forming assistant is alcohol ester twelve, ethylene glycol butyl ether or dipropylene glycol butyl ether.
Further, the preparation process of the hydroxylated carbon nanotube sodium hydroxide solution is as follows: adding 1-2g of carbon nano tube and 150-200ml of sodium hydroxide into a three-necked bottle, heating to 100 +/-3 ℃ under stirring at 500-600rpm, carrying out constant-temperature reflux treatment for 2-4h, naturally cooling to room temperature, adding distilled water, and filtering and washing for multiple times until the pH concentration is reached.
Further, when the coating composition is used, the Bayer curing agent is firstly emulsified by deionized water, the Bayer curing agent emulsion is added into the coating composition, the mixture is stirred for 10min at the rotating speed of 600-800r/min, and then the mixture is sprayed on the surface of a base material to be treated, and the coating is obtained after drying and curing at room temperature.
Further, the thickness of the coating is 25 +/-2 μm.
Further, the volume ratio of the isopropanol to the water deionized water is 3-4:1.
Further, the preparation process of the hydroxylated carbon nanotube sodium hydroxide solution is as follows: adding 1-2g of carbon nano tube and 150-200ml of sodium hydroxide into a three-necked bottle, heating to 100 +/-3 ℃ under stirring at 500-600rpm, carrying out constant-temperature reflux treatment for 2-4h, naturally cooling to room temperature, adding distilled water, and filtering and washing for multiple times until the pH concentration is reached.
Further, the coating comprises the following raw materials in parts by weight:
40-70 parts of carbon nano tube modified fluorine-containing polyacrylate emulsion;
0.2-0.5 part of defoaming agent;
0.2-0.5 part of leveling agent;
2-5 parts of a film-forming assistant;
15-30 parts of deionized water;
the defoaming agent is a mineral oil defoaming agent or an organic silicon defoaming agent.
The leveling agent is a modified polysiloxane leveling agent.
The film-forming assistant is alcohol ester dodeca, ethylene glycol butyl ether or dipropylene glycol butyl ether.
Possible principles for preparing the polybasic heterocyclic quinoline modified carbon nanotube dispersion liquid are as follows:
the structure of 3-methyl-8-quinolinesulfonic acid is as follows:
under electrochemical conditions, the reaction is shown in figure 1.
It can be seen that hydroxyl is condensed, and in the electrode reaction process, the cathode can observe that H2 gas is emitted, the methyl quinoline derivatives are condensed, the methyl quinoline derivatives and the surface of the hydroxylated carbon tube are subjected to condensation dehydrogenation, so that the dispersibility of the carbon nanotube is effectively modified, the pi bond of quinoline is bonded with the pi on the carbon nanotube, and the dispersion effect of the carbon nanotube is further improved.
Before the nanotube is subjected to electrochemical reaction, hydroxylation treatment is required to be carried out, amorphous impurities such as five-membered rings and seven-membered ring carbons adhered to the inside and outside of the wall of the carbon nanotube exist on the surface of the carbon nanotube, so that the stability and the solvent affinity of the carbon nanotube are reduced, the stable performance of the subsequent carbon nanotube in a coating is influenced, the seven-membered rings and five-membered ring carbons on the surface of the carbon nanotube can be effectively removed through hydroxylation treatment under a strong alkali condition, the stable carbon nanotube cannot be influenced, and after the mixed carbon and the impurities on the surface are removed, the surface of the carbon nanotube can be effectively reserved, and the bonding of the hydroxyl groups is facilitated.
Advantageous technical effects
(1) According to the invention, the carbon nanotube is treated by high-temperature condensation reflux, so that the surface of the carbon tube is effectively cleaned, and meanwhile, hydroxyl is introduced to the surface of the carbon tube, and the hydroxyl is used as a bonding site for subsequent electrochemical treatment, so that the dispersity of the carbon nanotube can be effectively improved.
(2) The 3-methyl-8-quinoline sulfonic acid is electrochemically treated, quinoline derivatives are effectively dehydrogenated and condensed to form a large benzene ring, and pi-pi bonding is formed between the large benzene ring and the carbon nano tube to improve the dispersity of the carbon nano tube.
(3) The electrochemical dispersion carbon nano tube is simple, green and environment-friendly, and has high conversion rate.
(4) By adopting a solution polymerization method, taking acrylate monomers and organic fluorine monomers as raw materials, successfully synthesizing an organic fluorine acrylic resin solution, and modifying through high-dispersion carbon nano tubes, the physicochemical property of the coating is effectively improved.
(5) The modification effect and positive effect of the carbon nano tube modified fluorine-containing polyacrylate emulsion in the coating are effectively verified through a coating contact angle performance test, a coating hardness performance test, an adhesion force test, a weather resistance test and an electrochemical corrosion resistance performance test.
Drawings
FIG. 1 shows the reaction formula of the present invention for electrochemically dispersing carbon nanotubes.
FIG. 2 polarization curve test of electrochemical corrosion resistance of the present invention.
FIG. 3 is an SEM topography of the coating of the present invention.
Detailed Description
Example 1
The water-based paint is characterized by comprising the following raw materials in parts by weight:
40 parts of carbon nano tube modified fluorine-containing polyacrylate emulsion.
0.2 part of defoaming agent.
0.2 part of leveling agent.
And 2 parts of a film-forming assistant.
And 15 parts of deionized water.
A method of preparing a coating composition comprising the steps of:
(1) Pretreating the carbon nano tube: adding 1g of carbon nano tube and 150l of sodium hydroxide into a three-necked flask, heating to 100 +/-3 ℃ under the stirring of 500rpm, carrying out constant-temperature reflux treatment for 2h, naturally cooling to room temperature, adding distilled water, filtering and washing for multiple times until the solution is neutral, and then adjusting to the required pH concentration by using NaOH to obtain a hydroxylated carbon nano tube sodium hydroxide solution.
(2) Adding 20ml of 3-methyl-8-quinoline sulfonic acid, a proper amount of hydroxylated carbon nanotube sodium hydroxide solution with the pH value of 8-9, 0.1mg of dichloropentamethyl cyclopentadienyl rhodium dimer, isopropanol and water deionized water, wherein the volume ratio of the isopropanol to the water deionized water is 3:1, stirring for 10min, and keeping the temperature at 20 ℃; and then adding an inert metal anode and an inert metal cathode into the three-neck flask, carrying out electrochemical synthesis at 45 ℃ under direct current of 10mA for 10 hours, and removing part of the solvent by using a rotary evaporator after the reaction is finished to obtain the modified carbon tube dispersion liquid.
(3) 0.5g of sorbitan monooleate nonionic surfactant and 0.5g of sodium dodecyl benzene sulfonate anionic surfactant are added into 30g of deionized water solution, the temperature is raised to 35 ℃, the stirring is carried out for 10min, and the temperature is reduced to the room temperature.
(4) 0.025g of ammonium persulfate, 7g of methyl methacrylate, 5g of butyl acrylate, 0.3g of ethyl methacrylate, 1.5g of hydroxypropyl acrylate and 1.4g of dodecafluoroheptyl methacrylate are added to the solution obtained in the step (3) in sequence, and the mixture is fully stirred to obtain a solution A.
(5) Adding 0.5g of sorbitan monooleate nonionic surfactant and 0.5g of sodium dodecyl benzene sulfonate anionic surfactant into a 30g deionized water solution in a four-neck flask, heating to 35 ℃, stirring for 10min, cooling to room temperature, introducing protective gas, adding 0.025g of ammonium persulfate, 3.5g of methyl methacrylate, 2.5g of butyl acrylate, 0.15g of ethyl methacrylate, 0.75g of hydroxypropyl acrylate, 0.7g of dodecafluoroheptyl methacrylate and 1ml of 2wt.% modified carbon tube dispersion liquid, fully stirring, and heating to 75 ℃ to obtain liquid B.
(6) Dropwise adding the solution A obtained in the step (4) into the solution B obtained in the step (5), controlling the dropwise adding time within 2 hours at the temperature of 75 ℃, keeping the temperature for 2 hours after stopping dropwise adding, cooling to 30 ℃, and adjusting the pH value to be neutral to obtain the carbon nano tube modified fluorine-containing polyacrylate emulsion.
(7) Adding the carbon-containing nanotube acrylate copolymer emulsion, the organic silicon defoamer, the leveling agent, the film forming assistant and the deionized water into a reaction kettle, and stirring at the rotating speed of 600r/min for 10min to disperse and defoam the mixture to obtain the coating composition.
When the coating composition is used, firstly, a Bayer curing agent XP2655 is emulsified by deionized water, then Bayer curing agent emulsion is added into the coating composition, stirred for 10min at the rotating speed of 600r/min, then sprayed on the surface of a base material to be treated, and dried and cured at room temperature to obtain a coating.
Example 2
The water-based paint is characterized by comprising the following raw materials in parts by weight:
60 parts of carbon nano tube modified fluorine-containing polyacrylate emulsion.
0.35 part of defoaming agent.
0.35 part of leveling agent.
3.5 parts of a film-forming assistant.
22.5 parts of deionized water.
A method of preparing a coating composition comprising the steps of:
(1) Pretreating the carbon nano tube: adding 1.5g of carbon nano tube and 175ml of sodium hydroxide into a three-mouth bottle, heating to 100 +/-3 ℃ under stirring at 550rpm, carrying out constant-temperature reflux treatment for 3h, naturally cooling to room temperature, adding distilled water, filtering and washing for multiple times until the solution is neutral, and then adjusting the pH to the required concentration by using NaOH to obtain the hydroxylated carbon nano tube sodium hydroxide solution.
(2) Adding 30ml of 3-methyl-8-quinoline sulfonic acid, a proper amount of hydroxylated carbon nanotube sodium hydroxide solution with the pH of 8-9, 0.125mg of dichloropentamethyl cyclopentadienyl rhodium dimer, isopropanol and water deionized water into a three-neck flask, wherein the volume ratio of the isopropanol to the water deionized water is 3.5; and then adding an inert metal anode and an inert metal cathode into the three-neck flask, carrying out electrochemical synthesis at 47.5 ℃ under direct current of 15mA for 12.5h, and removing part of the solvent by using a rotary evaporator after the reaction is finished to obtain the modified carbon tube dispersion liquid.
(3) 0.65g of sorbitan monooleate nonionic surfactant and 0.65g of sodium dodecyl benzene sulfonate anionic surfactant are added into 40g of deionized water solution, the temperature is raised to 37.5 ℃, the stirring is carried out for 12.5min, and the temperature is reduced to the room temperature.
(4) 0.0375g of ammonium persulfate, 7.5g of methyl methacrylate, 5.5g of butyl acrylate, 0.35g of ethyl methacrylate, 1.65g of hydroxypropyl acrylate and 1.6g of dodecafluoroheptyl methacrylate were added to the solution obtained in the step (3) in this order, and the mixture was sufficiently stirred to obtain solution A.
(5) Adding 0.65g of sorbitan monooleate nonionic surfactant and 0.65g of sodium dodecyl benzene sulfonate anionic surfactant into a four-neck flask, adding the mixture into 40g of deionized water solution, heating to 37.5 ℃, stirring for 12.5min, cooling to room temperature, introducing protective gas, adding 0.0375g of ammonium persulfate, 3.75g of methyl methacrylate, 2.75g of butyl acrylate, 0.175g of ethyl methacrylate, 0.825g of hydroxypropyl acrylate, 0.8g of dodecafluoroheptyl methacrylate and 12.5ml of 2.5wt.% modified carbon tube dispersion, fully stirring, and heating to 77.5 ℃ to obtain liquid B.
(6) Dropwise adding the solution A obtained in the step (4) into the solution B obtained in the step (5), controlling the dropwise adding time within 2.25h at the temperature of 77.5 ℃, keeping the temperature for 2.5h after stopping dropwise adding, cooling to 35 ℃, and adjusting the pH value to be neutral to obtain the carbon nano tube modified fluorine-containing polyacrylate emulsion.
(7) Adding the carbon-containing nanotube acrylate copolymer emulsion, the organic silicon defoamer, the leveling agent, the film forming assistant and the deionized water into a reaction kettle, and stirring at the rotating speed of 700r/min for 10min to disperse and defoam the mixture to obtain the coating composition.
When the coating composition is used, firstly, a Bayer curing agent XP2655 is emulsified by deionized water, then, bayer curing agent emulsion is added into the coating composition, stirred for 10min at the rotating speed of 700r/min, then, sprayed on the surface of a base material to be treated, and dried and cured at room temperature to obtain a coating.
Example 3
The water-based paint is characterized by comprising the following raw materials in parts by weight:
60 parts of carbon nano tube modified fluorine-containing polyacrylate emulsion.
0.35 part of defoaming agent.
0.35 part of leveling agent.
3.5 parts of a film-forming assistant.
22.5 parts of deionized water.
A method of preparing a coating composition comprising the steps of:
(1) Pretreating the carbon nano tube: adding 2g of carbon nano tube and 200ml of sodium hydroxide into a three-neck flask, heating to 100 +/-3 ℃ under stirring at 600rpm, carrying out constant-temperature reflux treatment for 4h, naturally cooling to room temperature, adding distilled water, filtering and washing for multiple times until the solution is neutral, and then adjusting to the required pH concentration by using NaOH to obtain the hydroxylated carbon nano tube sodium hydroxide solution.
(2) Adding 40ml of 3-methyl-8-quinoline sulfonic acid, a proper amount of hydroxylated carbon nanotube sodium hydroxide solution with the pH value of 8-9, 0.15mg of dichloro pentamethyl cyclopentadienyl rhodium dimer, isopropanol and water deionized water, wherein the volume ratio of the isopropanol to the water deionized water is 4:1, stirring for 15min, and the temperature is 25 ℃; and then adding an inert metal anode and an inert metal cathode into the three-neck flask, carrying out electrochemical synthesis at 50 ℃ under direct current of 20mA for 15h, and removing part of the solvent by using a rotary evaporator after the reaction is finished to obtain the modified carbon tube dispersion liquid.
(3) Adding 0.8g of sorbitan monooleate nonionic surfactant and 0.8g of sodium dodecyl benzene sulfonate anionic surfactant into 50g of deionized water solution, heating to 40 ℃, stirring for 15min, and cooling to room temperature.
(4) 0.05g of ammonium persulfate, 8g of methyl methacrylate, 6g of butyl acrylate, 0.4g of ethyl methacrylate, 1.8g of hydroxypropyl acrylate and 1.8g of dodecafluoroheptyl methacrylate are added to the solution obtained in the step (3) in sequence, and the mixture is fully stirred to obtain a solution A.
(5) Adding 0.8g of sorbitan monooleate nonionic surfactant and 0.8g of sodium dodecyl benzene sulfonate anionic surfactant into a 50g deionized water solution in a four-neck flask, heating to 40 ℃, stirring for 10-15min, cooling to room temperature, introducing protective gas, adding 0.05g of ammonium persulfate, 4g of methyl methacrylate, 3g of butyl acrylate, 0.2g of ethyl methacrylate, 0.9g of hydroxypropyl acrylate, 0.9g of dodecafluoroheptyl methacrylate and 15ml of 3wt.% modified carbon tube dispersion liquid, fully stirring, and heating to 80 ℃ to obtain liquid B.
(6) And (5) dropwise adding the solution A obtained in the step (4) into the solution B obtained in the step (5), controlling the dropwise adding time within 2.5 hours at the temperature of 80 ℃, keeping the temperature for 3 hours after the dropwise adding is stopped, cooling to 40 ℃, and adjusting the pH value to be neutral to obtain the carbon nano tube modified fluorine-containing polyacrylate emulsion.
(7) Adding the carbon-containing nanotube acrylate copolymer emulsion, the organic silicon defoamer, the leveling agent, the film forming assistant and the deionized water into a reaction kettle, and stirring at the rotating speed of 800r/min for 10min to disperse and defoam the mixture to obtain the coating composition.
When the coating composition is used, firstly, a Bayer curing agent XP2655 is emulsified by deionized water, then, bayer curing agent emulsion is added into the coating composition, stirred for 10min at the rotating speed of 800r/min, then, sprayed on the surface of a base material to be treated, and dried and cured at room temperature to obtain a coating.
Comparative example 1
The water-based paint is characterized by comprising the following raw materials in parts by weight:
60 parts of fluorine-containing polyacrylate emulsion.
0.35 part of defoaming agent.
And 0.35 part of a leveling agent.
3.5 parts of a film-forming assistant.
22.5 parts of deionized water.
A method of preparing a coating composition comprising the steps of:
(1) 0.65g of sorbitan monooleate nonionic surfactant and 0.65g of sodium dodecyl benzene sulfonate anionic surfactant are added into 40g of deionized water solution, the temperature is raised to 37.5 ℃, the stirring is carried out for 12.5min, and the temperature is reduced to the room temperature.
(2) 0.0375g of ammonium persulfate, 7.5g of methyl methacrylate, 5.5g of butyl acrylate, 0.35g of ethyl methacrylate, 1.65g of hydroxypropyl acrylate and 1.6g of dodecafluoroheptyl methacrylate are sequentially added to the solution obtained in the step (1), and the mixture is fully stirred to obtain a solution A.
(3) Adding 0.65g of sorbitan monooleate nonionic surfactant and 0.65g of sodium dodecyl benzene sulfonate anionic surfactant into a four-neck flask, adding the mixture into 40g of deionized water solution, heating to 37.5 ℃, stirring for 12.5min, cooling to room temperature, introducing protective gas, adding 0.0375g of ammonium persulfate, 3.75g of methyl methacrylate, 2.75g of butyl acrylate, 0.175g of ethyl methacrylate, 0.825g of hydroxypropyl acrylate and 0.8g of dodecafluoroheptyl methacrylate, fully stirring, and heating to 77.5 ℃ to obtain liquid B.
(4) Dropwise adding the solution A obtained in the step (2) into the solution B obtained in the step (3), controlling the dropwise adding time within 2.25h at the temperature of 77.5 ℃, keeping the temperature for 2.5h after stopping dropwise adding, cooling to 35 ℃, and adjusting the pH value to be neutral to obtain the carbon nano tube modified fluorine-containing polyacrylate emulsion.
(5) Adding the carbon-containing nanotube acrylate copolymer emulsion, the organic silicon defoamer, the leveling agent, the film forming assistant and the deionized water into a reaction kettle, and stirring at the rotating speed of 700r/min for 10min to disperse and defoam the mixture to obtain the coating composition.
When the coating composition is used, firstly, a Bayer curing agent XP2655 is emulsified by deionized water, then Bayer curing agent emulsion is added into the coating composition, stirred for 10min at the rotating speed of 700r/min, then sprayed on the surface of a base material to be treated, and dried and cured at room temperature to obtain a coating.
Comparative example 2
The water-based paint is characterized by comprising the following raw materials in parts by weight:
60 parts of carbon nano tube modified fluorine-containing polyacrylate emulsion.
0.35 part of defoaming agent.
0.35 part of leveling agent.
3.5 parts of a film-forming assistant.
22.5 parts of deionized water.
A method of preparing a coating composition comprising the steps of:
(1) Adding 30ml of 3-methyl-8-quinoline sulfonic acid, a carbon nano tube sodium hydroxide solution, 0.125mg of dichloro pentamethyl cyclopentadienyl rhodium dimer, isopropanol and water deionized water into a three-neck flask, wherein the volume ratio of the isopropanol to the water deionized water is 3.5; and then adding an inert metal anode and an inert metal cathode into the three-neck flask, carrying out electrochemical synthesis at 47.5 ℃ under direct current of 15mA for 12.5h, and removing part of the solvent by using a rotary evaporator after the reaction is finished to obtain the modified carbon tube dispersion liquid.
(2) 0.65g of sorbitan monooleate nonionic surfactant and 0.65g of sodium dodecyl benzene sulfonate anionic surfactant are added into 40g of deionized water solution, the temperature is raised to 37.5 ℃, the stirring is carried out for 12.5min, and the temperature is reduced to the room temperature.
(3) 0.0375g of ammonium persulfate, 7.5g of methyl methacrylate, 5.5g of butyl acrylate, 0.35g of ethyl methacrylate, 1.65g of hydroxypropyl acrylate and 1.6g of dodecafluoroheptyl methacrylate are sequentially added to the solution obtained in the step (2), and the mixture is fully stirred to obtain a solution A.
(4) Adding 0.65g of sorbitan monooleate nonionic surfactant and 0.65g of sodium dodecyl benzene sulfonate anionic surfactant into a four-neck flask, adding the mixture into 40g of deionized water solution, heating to 37.5 ℃, stirring for 12.5min, cooling to room temperature, introducing protective gas, adding 0.0375g of ammonium persulfate, 3.75g of methyl methacrylate, 2.75g of butyl acrylate, 0.175g of ethyl methacrylate, 0.825g of hydroxypropyl acrylate, 0.8g of dodecafluoroheptyl methacrylate and 12.5ml of 2.5wt.% modified carbon tube dispersion, fully stirring, and heating to 77.5 ℃ to obtain liquid B.
(5) Dropwise adding the solution A obtained in the step (3) into the solution B obtained in the step (4), controlling the dropwise adding time within 2.25h at the temperature of 77.5 ℃, keeping the temperature for 2.5h after stopping dropwise adding, cooling to 35 ℃, and adjusting the pH value to be neutral to obtain the carbon nano tube modified fluorine-containing polyacrylate emulsion.
(6) Adding the carbon-containing nanotube acrylate copolymer emulsion, the organic silicon defoamer, the leveling agent, the film forming assistant and the deionized water into a reaction kettle, and stirring at the rotating speed of 700r/min for 10min to disperse and defoam the mixture to obtain the coating composition.
When the coating composition is used, firstly, a Bayer curing agent XP2655 is emulsified by deionized water, then, bayer curing agent emulsion is added into the coating composition, stirred for 10min at the rotating speed of 700r/min, then, sprayed on the surface of a base material to be treated, and dried and cured at room temperature to obtain a coating.
Comparative example 3
The water-based paint is characterized by comprising the following raw materials in parts by weight:
60 parts of carbon nano tube modified fluorine-containing polyacrylate emulsion.
0.35 part of defoaming agent.
0.35 part of leveling agent.
3.5 parts of a film-forming assistant.
22.5 parts of deionized water.
A method of preparing a coating composition comprising the steps of:
(1) Pretreating the carbon nano tube: adding 1.5g of carbon nano tube and 175ml of sodium hydroxide into a three-mouth bottle, heating to 100 +/-3 ℃ under stirring at 550rpm, carrying out constant-temperature reflux treatment for 3h, naturally cooling to room temperature, adding distilled water, filtering and washing for multiple times until the solution is neutral, and then adjusting the pH to the required concentration by using NaOH to obtain the hydroxylated carbon nano tube sodium hydroxide solution.
(2) 0.65g of sorbitan monooleate nonionic surfactant and 0.65g of sodium dodecyl benzene sulfonate anionic surfactant are added into 40g of deionized water solution, the temperature is raised to 37.5 ℃, the stirring is carried out for 12.5min, and the temperature is reduced to the room temperature.
(3) 0.0375g of ammonium persulfate, 7.5g of methyl methacrylate, 5.5g of butyl acrylate, 0.35g of ethyl methacrylate, 1.65g of hydroxypropyl acrylate and 1.6g of dodecafluoroheptyl methacrylate are sequentially added to the solution obtained in the step (2), and the mixture is fully stirred to obtain a solution A.
(4) Adding 0.65g of sorbitan monooleate nonionic surfactant and 0.65g of sodium dodecyl benzene sulfonate anionic surfactant into a four-neck flask, adding the mixture into 40g of deionized water solution, heating to 37.5 ℃, stirring for 12.5min, cooling to room temperature, introducing protective gas, adding 0.0375g of ammonium persulfate, 3.75g of methyl methacrylate, 2.75g of butyl acrylate, 0.175g of ethyl methacrylate, 0.825g of hydroxypropyl acrylate, 0.8g of dodecafluoroheptyl methacrylate and 12.5ml of 2.5wt.% hydroxylated carbon nanotube sodium hydroxide solution, fully stirring, heating to 77.5 ℃, and obtaining solution B.
(5) Dropwise adding the solution A obtained in the step (3) into the solution B obtained in the step (4), controlling the dropwise adding time within 2.25h at the temperature of 77.5 ℃, keeping the temperature for 2.5h after stopping dropwise adding, cooling to 35 ℃, and adjusting the pH value to be neutral to obtain the carbon nano tube modified fluorine-containing polyacrylate emulsion.
(6) Adding the carbon-containing nanotube acrylate copolymer emulsion, the organic silicon defoamer, the leveling agent, the film forming assistant and the deionized water into a reaction kettle, and stirring at the rotating speed of 700r/min for 10min to disperse and defoam the mixture to obtain the coating composition.
When the coating composition is used, firstly, a Bayer curing agent XP2655 is emulsified by deionized water, then, bayer curing agent emulsion is added into the coating composition, stirred for 10min at the rotating speed of 700r/min, then, sprayed on the surface of a base material to be treated, and dried and cured at room temperature to obtain a coating.
Coating film contact angle test: the emulsion is coated on a glass plate to form a natural film, different areas of the film are tested for three times through a JJ2000B2 type contact angle tester, the average value of the average value is taken, the hydrophobicity of the coating can be evaluated through the size of a water contact angle, and the corrosion-resistant protection effect of the coating can be directly influenced through the hydrophobicity, if the hydrophobicity is stronger, corrosive solution or gas is difficult to permeate into the coating to penetrate through the coating, so that a metal substrate is protected.
As shown in the attached FIG. 3, the carbon nanotubes with different dispersities have different display modes on the surface of the coating, as can be seen from comparative example 1 and example 2, after part of the highly dispersed carbon nanotubes are added into the coating, a little uniform salient point appears on the surface coating, and if hydroxyl pretreatment and quinoline electrochemical modification treatment are not carried out, the agglomeration of the carbon nanotubes on the surface is serious as shown in comparative example 2 and comparative example 3.
And (3) testing pencil hardness: the test is carried out according to GB/T6739-2006 "pencil hardness method for measuring coating hardness of colored paint and varnish", the hardness of the coating is measured on a pencil hardness tester, and the evaluation method of the coating hardness grade comprises the following steps: five times of tests are carried out on pencils of the same type until two or more traces on the surface of the coating film have obvious defects, and the last bit of the pencil hardness type is the pencil of the coating film
Hardness, as can be seen from the above table of example 1 and comparative example 1, the addition of the carbon nanotubes does not significantly improve the hardness, and both are 3H hardness, mainly because the addition of the carbon nanotubes weakens the van der waals force between the macromolecular chain segments of the resin to a certain extent, and reduces the crosslinking density of the resin, as in comparative examples 2 and 3, the dispersion degree of the carbon nanotubes is reduced without hydroxylation treatment and quinoline modification, and further the crosslinking degree of the coating is seriously affected, and the hardness of the coating is reduced.
The test was carried out according to GB/T5210-2006 adhesion test by the pull-open method for paints and varnishes. The adhesion force of the coating is tested by using a digital display pull-off method adhesion force tester, and compared with the embodiment 2 and the comparative examples 2-3, the adhesion force of the coating is gradually increased along with the increase of the dispersion degree, because the high-dispersion carbon nano tube and the epoxy resin are wound and curled, the tightness degree inside the coating is improved, the adhesion force of the coating is increased, the binding force range of the coating is 6-8Mpa, if the dispersion degree of the carbon nano tube is reduced, the self agglomeration can occur, and the stable binding of the coating and the base material is obviously not facilitated.
According to GB/T1865-1997 color paint and varnish artificial weathering and artificial radiation exposure, the gloss retention rate is used for testing weather resistance, and the table shows that the gloss retention rate is about 92% after 1200 hours of artificial weathering resistance, and the weather resistance is excellent.
And (3) solution settleability, namely performing ultrasonic dispersion on the prepared carbon nanotube dispersion liquid, standing until visible dispersion occurs, and determining that settlement occurs, wherein the carbon nanotube dispersion liquid modified by the multi-heterocyclic quinoline has settleability of more than 3 months and extremely high dispersibility.
The electrochemical corrosion resistance test is carried out in 3.5% NaCl solution, a polarization curve and an electrochemical alternating-current impedance spectrum test are carried out by adopting a three-electrode system under an open-circuit potential, a saturated calomel electrode is taken as a reference electrode, a platinum electrode is taken as a counter electrode, a working electrode is a carbon steel sheet coated with coating, the effective working area is 1 cm, as can be seen from the above table, the coating material prepared by the method has extremely high corrosion resistance, and the electrochemical polarization curve is shown in figure 2.
The above embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core ideas; all other embodiments obtained by the idea of the invention without making creative efforts will belong to the protection scope of the present invention for the ordinary skilled person in the art. In view of the foregoing, the description is not to be taken in a limiting sense.
Claims (4)
1. The water-based paint is characterized by comprising the following raw materials in parts by weight:
40-70 parts of carbon nano tube modified fluorine-containing polyacrylate emulsion;
0.2-0.5 part of defoaming agent;
0.2-0.5 part of leveling agent;
2-5 parts of a film-forming assistant;
15-30 parts of deionized water;
the preparation method of the carbon nano tube modified fluorine-containing polyacrylate emulsion comprises the following steps:
(1) Preparing modified carbon tube dispersion liquid: (a) Adding 20-40mL of 3-methyl-8-quinoline sulfonic acid, a proper amount of hydroxylated carbon nanotube sodium hydroxide solution with the pH value of 8-9, 0.1-0.15mg of dichloro pentamethyl cyclopentadienyl rhodium dimer, isopropanol and deionized water into a three-neck flask, and stirring for 10-15min at the temperature of 20-25 ℃; (b) Adding an inert metal anode and an inert metal cathode into a three-neck flask, carrying out electrochemical synthesis at 45-50 ℃ under direct current of 10-20mA for 10-15h, and removing part of solvent by using a rotary evaporator after the reaction is finished to obtain modified carbon tube dispersion liquid;
(2) Adding 0.5-0.8g of sorbitan monooleate nonionic surfactant and 0.5-0.8g of sodium dodecyl benzene sulfonate anionic surfactant into 30-50g of deionized water solution, heating to 35-40 ℃, stirring for 10-15min, and cooling to room temperature;
(3) Sequentially adding 0.025-0.05g of ammonium persulfate, 7-8g of methyl methacrylate, 5-6g of butyl acrylate, 0.3-0.4g of ethyl methacrylate, 1.5-1.8g of hydroxypropyl acrylate and 1.4-1.8g of dodecafluoroheptyl methacrylate into the solution obtained in the step (2), and fully stirring to obtain solution A;
(4) Adding 0.5-0.8g of sorbitan monooleate nonionic surfactant and 0.5-0.8g of sodium dodecyl benzene sulfonate anionic surfactant into a four-neck flask, adding 30-50g of deionized water solution, heating to 35-40 ℃, stirring for 10-15min, cooling to room temperature, introducing protective gas, adding 0.025-0.05g of ammonium persulfate, 3.5-4g of methyl methacrylate, 2.5-3g of butyl acrylate, 0.15-0.2g of ethyl methacrylate, 0.75-0.9g of hydroxypropyl acrylate, 0.7-0.9g of dodecafluoro heptyl methacrylate and 10-15mL of 2-3wt.% modified carbon tube dispersion, fully stirring, and heating to 75-80 ℃ to obtain a solution B;
(5) Dropwise adding the solution A obtained in the step (3) into the solution B obtained in the step (4), controlling the dropwise adding time to be within 2-2.5h at the temperature of 75-80 ℃, keeping the temperature for 2-3h after the dropwise adding is stopped, cooling to 30-40 ℃, and adjusting the pH value to be neutral to obtain the carbon nano tube modified fluorine-containing polyacrylate emulsion;
(6) Adding the carbon nano tube modified fluorine-containing polyacrylate emulsion, a defoaming agent, a flatting agent, a film-forming assistant and deionized water into a reaction kettle, and stirring at the rotating speed of 600-800r/min for 10min to disperse and defoam the mixture to obtain the coating composition.
2. The aqueous coating of claim 1 wherein the defoamer is a mineral oil defoamer or a silicone defoamer.
3. The aqueous coating according to claim 1 wherein the leveling agent is a modified polysiloxane leveling agent.
4. The waterborne coating of claim 1, wherein said coalescent is an alcohol ester of twelve, ethylene glycol butyl ether, or dipropylene glycol butyl ether.
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