CN110093070A - A kind of coating and preparation method thereof - Google Patents
A kind of coating and preparation method thereof Download PDFInfo
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- CN110093070A CN110093070A CN201810082978.5A CN201810082978A CN110093070A CN 110093070 A CN110093070 A CN 110093070A CN 201810082978 A CN201810082978 A CN 201810082978A CN 110093070 A CN110093070 A CN 110093070A
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- titanium dioxide
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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
- C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
- C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C09D127/16—Homopolymers or copolymers of vinylidene fluoride
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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
- C09D5/24—Electrically-conducting paints
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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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
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
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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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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Abstract
The present invention relates to a kind of coating, the coating includes following components: A) nano-complex particle of surface modified titanium dioxide and grapheme material；And B) film-forming components.It include preparing the nano-complex particle of the modified titanium dioxide in surface and grapheme material and further preparing coating the invention further relates to the method for preparing the coating.In coating of the invention the nano-complex particle of titanium dioxide and grapheme material with it is netted it is evenly dispersed be conducive to the maximum physical and chemical performance for playing graphene in the coating so that the coating prepared has excellent impact resistance, wearability and weatherability；Titanium dioxide forms conductive network in coating system, enhances the electric conductivity of coating.
Description
Technical field
The present invention relates to a kind of coating, relate more specifically to the nano-complex particle containing titanium dioxide and grapheme material
Coating.The invention further relates to the methods for preparing the coating.
Background technique
Six side's honeycomb two-dimension nano materials that grapheme material is made of single layer of carbon atom, special two-dimensional structure
Excellent physical and chemical performance is made it have, the research boom of a new round has been caused.Grapheme material application range is very wide, applies
Material is an important component in the numerous application fields of current grapheme material.Due to grapheme material specific surface area very
Height, therefore there is very strong adsorption capacity.After adding grapheme material in coating, netted knot is formed during film curing
Structure significantly enhances the caking property of paint film and ground, and paint film is more stable, and intensity is more preferable.
The main mode for being separated into and adding graphene in current coating is blended in liquid, but due to the ratio table of grapheme material
Face can be big, is very easy to reunite or by pigment, filler embedding without being dispersed in coating in coating.
Summary of the invention
In view of above-mentioned prior art situation, the present inventor has carried out extensively in the paint field containing grapheme material
General in-depth study is distributed in coating therein to a kind of grapheme material uniform particle to be obtained, and is obtained by the coating
The coating obtained shows excellent functionality, especially good impact strength, wearability, weatherability and electric conductivity.As a result, it has been found that
It a kind of nano-complex particle of the titanium dioxide and grapheme material modified comprising surface and film-forming components, optional pigment and fills out
The coating of material and optional auxiliary agent meets above-mentioned requirements.The present invention is based on above-mentioned discovery and is accomplished.
The object of the present invention is to provide the nano combined grains of a kind of titanium dioxide and grapheme material modified containing surface
The coating of son, the coating have good impact strength, wearability, weatherability and electric conductivity.
It is a further object of the present invention to provide a kind of methods for preparing above-mentioned coating.
Realize that the technical solution of the object of the invention can be summarized as follows:
A kind of coating, the coating include following components:
A) the nano-complex particle of surface modified titanium dioxide and grapheme material；With
B) film-forming components；
Wherein the modified titanium dioxide in surface and the nano-complex particle of grapheme material and the weight ratio of film-forming components are
1:9-1:99；
Wherein the nano-complex particle of the modified titanium dioxide in surface and grapheme material is by the titanium dioxide as matrix
It is formed with the nano-complex particle of grapheme material and dispersing agent, which receives titanium dioxide and grapheme material
On rice compound particle surface.Wherein the weight of nano-complex particle of the dispersing agent based on titanium dioxide and grapheme material is 0.1-
8.0 weight %；
Wherein the nano-complex particle of titanium dioxide and grapheme material is by the titanium dioxide nano-particle and work as core
It is formed for the grapheme material of shell, the weight ratio of titanium dioxide and grapheme material is 100:1-1:1.
The weight of the nano-complex particle and film-forming components of the modified titanium dioxide in surface and grapheme material in the coating
Than for 1:12-1:60；The weight of nano-complex particle of the content of dispersing agent based on titanium dioxide and grapheme material is 0.3-
6.0 weight %；The weight ratio of titanium dioxide and grapheme material is 50:1-2:1.
The nano-complex particle and film forming of the preferred coating titanium dioxide and grapheme material that wherein surface is modified
The weight ratio of component is 1:15-1:40；Nano-complex particle of the content of dispersing agent based on titanium dioxide and grapheme material
Weight is 0.5-4.0 weight %；The weight ratio of titanium dioxide and grapheme material is 20:1-2.5:1.
Dispersing agent is selected from compound, oleic acid and calgon with alkoxysilane groups in the coating.
Film-forming components are selected from fluorocarbon resin, polyurethane resin, alkyd resin, thermosetting acrylic resin, phenol in the coating
Urea formaldehyde, nitrocotton, chlorinated rubber, pitch, modified rosin resin and thermoplastic acrylic resin, preferably fluorocarbon resin, it is more excellent
Choosing is selected from polyvinyl fluoride, Kynoar, vinylidene fluoride-hexafluoropropylene copolymer, hexafluoropropylene (HFP)/tetrafluoroethylene (TFE)-vinylidene
Copolymer, tetrafluoroethylene propylene copolymer, tetrafluoroethene-vinylidene fluoride-propylene acid copolymer fluorocarbon resin.
The partial size of titanium dioxide described in the coating is 1-20nm, preferably 1-10nm, more preferable 3-6nm.
The preparation method of the coating the following steps are included:
I) grapheme material is provided；Grapheme material is added to the aqueous solution of n-hydroxysuccinimide and carbodiimide salt
In；
Ii) titanium dioxide nano-particle is dispersed in aqueous solution of alcohol, wherein the concentration of aqueous solution of alcohol is 0.01-
3mol/L；
Iii) grapheme material of step i) is added to the alcohol water dispersion by the obtained titanium dioxide nano-particle of step ii)
In body, the temperature of system is controlled at 55-95 DEG C；
Iv) gained reaction mixture is post-processed to the nano-complex particle for obtaining titanium dioxide and grapheme material；
V) the modified surface that obtains in the nano-complex particle surface of titanium dioxide and grapheme material is modified using dispersing agent
Titanium dioxide and grapheme material nano-complex particle；With
Vi) by nano-complex particle, film-forming components, the optional pigment of surface modified titanium dioxide and grapheme material
It is mixed to get coating in a solvent with filler and optional auxiliary agent.
Step i) additionally includes that n-hydroxysuccinimide and carbon is added in grapheme material in the preparation method of the coating
In the aqueous solution of diimmonium salt.
Carbodiimide salt described in the preparation method of the coating is carbodiimide hydrochloride, preferably 1- (3- dimethylamino third
Base) -3- ethyl-carbodiimide hydrochloride.
Step ii in the preparation method of the coating) in aqueous solution of alcohol concentration be 0.1-0.5mol/L, in step
Iii it is controlled by the temperature of disperse systems at 60-90 DEG C in).
In the preparation method of the coating alcohol used in aqueous solution of alcohol be selected from methanol, ethyl alcohol, propyl alcohol and its isomers,
Butanol and its isomers and ethylene glycol.
The nano-complex particle of titanium dioxide and grapheme material is dispersed in painting with netted in coating of the invention
In layer, be conducive to the maximum physical and chemical performance for playing graphene, so that the coating prepared has excellent impact resistance, wear-resisting
Property and weatherability；Titanium dioxide forms conductive network in coating system, enhances the electric conductivity of coating.
Specific embodiment
Coating of the present invention includes following components:
A) the nano-complex particle of surface modified titanium dioxide and grapheme material；With
B) film-forming components；
Wherein the modified titanium dioxide in surface and the nano-complex particle of grapheme material and the weight ratio of film-forming components are
1:9-1:99；
Wherein the nano-complex particle of the modified titanium dioxide in surface and grapheme material is by the titanium dioxide as matrix
With the nano-complex particle of grapheme material and be coated on the nano-complex particle surface of titanium dioxide and grapheme material
Dispersing agent composition, wherein the weight of nano-complex particle of the dispersing agent based on titanium dioxide and grapheme material is 0.1-8.0 weight
Measure %；
Wherein the nano-complex particle of titanium dioxide and grapheme material is by the titanium dioxide nano-particle and work as core
It is formed for the grapheme material of shell, the weight ratio of titanium dioxide and grapheme material is 100:1-1:1.
The weight of the nano-complex particle and film-forming components of the modified titanium dioxide in surface and grapheme material in the coating
Than for 1:12-1:60, preferably 1:15-1:40；Nano combined grain of the content of dispersing agent based on titanium dioxide and grapheme material
The weight of son is 0.3-6.0 weight %, preferably 0.5-4.0 weight %；The weight ratio of titanium dioxide and grapheme material is 50:1-
2:1, preferably 20:1-2.5:1.
Grapheme material can be selected from graphene, graphene oxide and its mixture in the coating.
" graphite " refers to the carbon that the flat layer being stacked on one another by many is formed in the present invention, and the layer is by sp2Hydridization carbon is former
The fused six-membered rings of son is formed.
For stringent, " graphene " is understood to mean that the single carbon layer with graphite-structure, i.e., hexagonal arrangement by 6
A sp2The single layer of the fused rings of hydbridized carbon atoms composition.However, according to the present invention, " graphene " also refers to by most 10 layers, preferably
At most 5 layers, more preferably up to 2 layers, especially by 1 layer of hexagonal arrangement by 6 sp2The fused rings of hydbridized carbon atoms composition
The material of formation.
" graphite oxide " is understood to mean that the three-dimensional structure of stratiform in the present invention, and single layer is by with carbonyl, carboxyl, alcohol
Base and the functionalized condensed C in epoxy group part6Ring is formed.Herein, graphite is not flat like that for another example for single layer, but according to oxidation
Degree partially or completely to protrude from plane in a zigzag.
" graphene oxide " is understood to mean that by most 10 layers, preferably up to 5 layers, more preferably up to 2 layers in the present invention,
The material especially formed by single layer, the layer is by with the thick of oxygen functional group group such as epoxy group, alcohol radical, carboxyl and/or carbonyl
Close C6Ring is formed.
Graphene can be produced by the removing of graphite or leafing.
The preparation of graphene oxide is known to the person skilled in the art.For example, graphene oxide can be by graphite oxidation
Object preparation, then makes it separate (removing).Graphite oxide and graphene oxide band due to the oxygen functional group in the presence of it
There is negative electrical charge, therefore graphite oxide can be separated into graphene oxide in polar solvent.This can be for example by using ultrasonic wave
And promote.Graphite oxide is hydrophilic.The graphene oxide of removing, which is formed, disperses fabulous aqueous suspension.
The preparation of graphite oxide is equally known to the person skilled in the art；Graphite oxide usually passes through graphite
It aoxidizes and prepares.Oxygen atom is introduced into graphite by the oxidation；Particularly form alcohol radical, epoxy group, carbonyl and carboxyl.These groups
Increase the distance between each layer, the layer can be more easily separated from each other.In addition, graphite oxidation nitride layer is due to oxygen-containing group
Reason and become it is more hydrophilic and have better water dispersible.
The example of graphite includes mineral and synthetic graphite, and there are also expanded graphites and intercalated graphite.
Graphite oxide usually passes through with oxidant and acid, especially strong acid treatment graphite and prepares.Oxidant used is outstanding
It is chlorate and permanganate；Acid used in particular sulfuric acid and nitric acid.
L.Staudenmaier, Ber.Dt.Chem.Ges.31, (1898), 1481 and L.Staudenmaier,
Ber.Dt.Chem.Ges.32, (1899), 1394 describe by having graphite and potassium chlorate in fuming nitric aicd and the concentrated sulfuric acid
It is lower reaction and prepare graphite oxide (this referred to herein as graphitic acid).
W.S.Hummers, R.E.Offeman, J.Am.Chem.Soc.80 (1958), 1339 describe by make graphite with
Sodium nitrate and potassium permanganate react in the presence of sulphuric acid and prepare graphite oxide.
It can also be used expansible graphite as precursor to prepare graphite oxide.In this case, make in the first step
Graphite expansion.Then, products therefrom is for example ground in the ball mill.Final step is by thermal oxide or by depositing in sulfuric acid
Chemical modification is carried out in lower oxidation.
Dispersing agent is selected from compound, oleic acid and calgon with alkoxysilane groups in the coating.
Compound in the coating with alkoxysilane groups can be selected from vinyltriethoxysilane, γ-methyl
Acryloyloxypropyltrimethoxysilane, Alpha-Methyl acryloyl methyl diethoxymethylsilane, Alpha-Methyl acryloyl-oxy
Ylmethyl triethoxysilane, α-acryloyloxymethyl diethoxymethylsilane, α-acryloyloxymethyl triethoxy
Silane, methyltrimethoxysilane, propyl trimethoxy silicane, 2- trimethoxysilyl propyl methacrylate oxysilane, 2,4,4- trimethyl penta
Base trimethoxy silane, octyl trimethoxy silane, hexadecyl trimethoxy silane, octadecyl trimethoxysilane, ring
Hexyl trimethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysila,e, 3- glycidyloxypropyl front three
Oxysilane, 2- (3,4- expoxycyclohexyl)-ethyl trimethoxy silane, 3- methacryloxypropyl trimethoxy silicon
Alkane and 3- acryloyloxypropyltrimethoxysilane.
Film-forming components are selected from fluorocarbon resin, polyurethane resin, alkyd resin, thermosetting acrylic resin, phenol in the coating
Urea formaldehyde, nitrocotton, chlorinated rubber, pitch, modified rosin resin and thermoplastic acrylic resin, preferably fluorocarbon resin, it is more excellent
Choosing is selected from polyvinyl fluoride, Kynoar, vinylidene fluoride-hexafluoropropylene copolymer, hexafluoropropylene (HFP)/tetrafluoroethylene (TFE)-vinylidene
Copolymer, tetrafluoroethylene propylene copolymer, tetrafluoroethene-vinylidene fluoride-propylene acid copolymer fluorocarbon resin.
The partial size of titanium dioxide described in the coating is 1-20nm, preferably 1-10nm, more preferable 3-6nm.
The coating also may include solvent.Solvent for use be or mixtures thereof common solvent, including but not limited to aromatic hydrocarbons such as
Dimethylbenzene, toluene etc.；Esters such as ethyl acetate, butyl acetate, isoamyl acetate etc.；Alcohols such as butanol, isobutanol, benzyl alcohol
Deng；Ethers such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol diethyl ether etc.；Ketone for example methyl iso-butyl ketone (MIBK), acetophenone,
Isophorone etc..Those skilled in the art can such as paintability of the performance according to needed for the coating etc. determine the amount of solvent for use.
The coating also may include other components known to those skilled in the art, such as pigment；Filler, such as talcum
Powder, calcium carbonate, barium sulfate, titanium dioxide etc.；Auxiliary agent, such as defoaming agent, wetting agent, dispersing agent, emulsifier, anti-settling agent, stabilization
Agent, anti skinning agent, levelling agent, drier, anti-sagging agent, plasticizer, delustering agent, fire retardant, fungicide etc..Those skilled in the art
Member can determine the concrete type and its dosage of other components used by performance such as bactericidal property needed for coating etc. according to the present invention.
The solid content of the coating can be 20-60 weight %, preferably 30-50 weight %.
The preparation method of the coating the following steps are included:
I) grapheme material is added in the aqueous solution of n-hydroxysuccinimide and carbodiimide salt；
Ii) titanium dioxide nano-particle is dispersed in aqueous solution of alcohol, wherein the concentration of aqueous solution of alcohol is 0.01-
3mol/L；
Iii) grapheme material of step i) is added to the alcohol water dispersion by the obtained titanium dioxide nano-particle of step ii)
In body, the temperature of system is controlled at 55-95 DEG C；
Iv) gained reaction mixture is post-processed to the nano-complex particle for obtaining titanium dioxide and grapheme material；
V) the modified surface that obtains in the nano-complex particle surface of titanium dioxide and grapheme material is modified using dispersing agent
Titanium dioxide and grapheme material nano-complex particle；With
Vi) by nano-complex particle, film-forming components, the optional pigment of surface modified titanium dioxide and grapheme material
It is mixed to get coating in a solvent with filler and optional auxiliary agent.
It can be in the form of grapheme material dispersion, such as aqueous dispersion or graphene for grapheme material of the invention
The dispersion of material in organic solvent.The organic solvent can be methanol, ethyl alcohol, isopropanol, DMSO, DMF and NMP etc..
The concentration of the dispersion can be 0.05-5g/L, preferably 0.1-2g/L.
In a preferred embodiment of the invention, step i) additionally includes that N- hydroxysuccinimidyl is added in grapheme material
In the aqueous solution of acid imide and carbodiimide salt.In the aqueous solution, n-hydroxysuccinimide and carbodiimide salt it is dense
Degree can be 0.02-0.5mol/L, preferably 0.05-0.2ml/L.It is preferred that carbodiimide salt is carbodiimide hydrochloride, more preferably
1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride.Grapheme material, which is distributed in the aqueous solution, to be led to
It crosses method well known to those skilled in the art and such as stirs progress.Mixing time can be 10 minutes to 5 hours, and preferably 20 minutes extremely
2 hours.
Carbodiimide salt described in the preparation method for coating is carbodiimide hydrochloride, preferably 1- (3- dimethylamino third
Base) -3- ethyl-carbodiimide hydrochloride.
Step ii in the preparation method for coating) in the concentration of aqueous solution of alcohol be 0.1-0.5mol/L, the alcohol-containing is water-soluble
Alcohol used in liquid is selected from methanol, ethyl alcohol, propyl alcohol and its isomers, butanol and its isomers and ethylene glycol.Titanium dioxide is received
Rice corpuscles is dispersed in aqueous solution of alcohol can such as stir progress by method well known to those skilled in the art.Mixing time can be with
It is 10 minutes to 5 hours, preferably 20 minutes to 2 hours.
The step iii of the preparation method for coating) in, grapheme material is added and is received by the titanium dioxide that step ii) is obtained
In the alcohol aqueous dispersion of rice corpuscles.The charging usually carries out under stiring, and stirring rate is, for example, 100-500rpm, preferably
200-400rpm.The charging generally remains slow progress.During charging, the temperature of system is controlled at 60-90 DEG C.?
After charging is completed, continue to stir 10-48h, preferably 20-30h at said temperatures.In a preferred embodiment, adding
During material, the pH of system is controlled in 8.8-9.2,8.9-9.2 is preferably controlled in, more preferably control is in 9-9.1.
In order to ensure being sufficiently mixed, system can also be ultrasonically treated simultaneously.In the context of the present invention, for
Ultrasonic treatment does not specially require, such as power is 100-500w, preferably 200-400w；Such as the frequency of ultrasonic treatment is 40-
70KHz, preferably 45-65KHz.
The step iv of the preparation method for coating) in, dioxy will be obtained by the reaction mixture post-processing that step iii) is obtained
Change the nano-complex particle of titanium and grapheme material.Such as it is carried out and by the centrifugation of gained reaction mixture, washing and drying
Post-processing.The drying can carry out at decompression (such as 2.67kPa or less) and raising temperature such as 70-100 DEG C.
In the step v) of the preparation method for coating, using dispersing agent by the nano combined grain of titanium dioxide and grapheme material
The modified nano-complex particle for obtaining surface modified titanium dioxide and grapheme material in sublist face.The step v) can specifically such as
Lower progress:
A) optionally, the nano-complex particle as the titanium dioxide of matrix and grapheme material is moistened using wetting agent
It is wet；
B) nano-complex particle of dispersing agent and titanium dioxide and grapheme material is mixed in wetting agent；With
C) optionally filtering and drying.
Step a) can be carried out, it can also without step a) and direct receiving dispersing agent and titanium dioxide and grapheme material
Rice compound particle is added in wetting agent together.Wetting agent used can be common low boiling point solvent such as ethyl alcohol and acetone etc..Institute
Weight ratio with wetting agent and the nano-complex particle of titanium dioxide and grapheme material is 2:1-10:1, preferably 3:1-5:1.It can
By conventional method such as by the nano-complex particle of titanium dioxide and grapheme material be added in wetting agent and by titanium dioxide and
The nano-complex particle of grapheme material soaks.In order to ensure the nano-complex particle of titanium dioxide and grapheme material is abundant
And uniform wet, it can be as shaking, stirring receiving for titanium dioxide and grapheme material such as obtained by mechanical stirring and/or ultrasonic treatment
Dispersion of the rice compound particle in wetting agent.
Dispersing agent and the nano-complex particle of titanium dioxide and grapheme material are being moistened by stirring and/or being ultrasonically treated
It is mixed well in humectant, to ensure that dispersing agent is uniformly coated on the nano-complex particle surface of titanium dioxide and grapheme material
On.
Can carry out step c), can also without step c) and directly using the modified titanium dioxide in surface obtained by step b) and
Dispersion of the nano-complex particle of grapheme material in wetting agent.It is preferred that carrying out step c).In step c), drying can be
It is carried out at room temperature or raised temperature such as 70-100 DEG C and under normal pressure or decompression (such as 2.67kPa or less).It is suitable dry
Method is, for example, to be dried under reduced pressure at raised temperature such as 70-100 DEG C.
The step vi of the preparation method for coating) in by the nano combined grain of surface modified titanium dioxide and grapheme material
Son, film-forming components, optional pigment and filler and optional auxiliary agent are mixed to get coating in a solvent.
Coating of the present invention can be applied to substrate table to be coated by any appropriate method well known to those skilled in the art
Face, such as roller coating, spraying, dipping, brushing, blade coating etc..
Embodiment
The present invention is specifically described below with reference to embodiment, but the embodiment is not to scope of the invention structure
At any restrictions.
Comparative example 1
By 43Kg Kynoar-hexafluoropropylene copolymer (being purchased from Shanghai Dong Fu Chemical Industry Science Co., Ltd, T-1) dispersion
Fluorocarbon resin dispersion is formed in the admixture solvent that the volume ratio of dimethylbenzene, butyl acetate and isophorone is 7:2:1,
Its solid content is 40 weight %.0.25kg graphene (being purchased from the poly- carbon composite Co., Ltd in Zhuhai, CPG-1406) is added
Enter in gained fluorocarbon resin dispersion and mix and obtains graphene fluorocarbon resin coating.
Embodiment 1
The titanium dioxide nano-particle that 1.25kg partial size is 3-6 nanometers is added to the ethanol water of 25L0.25mol/L under stirring
In solution, continue stirring 1 hour at normal temperature.Meanwhile the graphene of 500L 0.5g/L (is purchased from the poly- carbon composite in Zhuhai
Co., Ltd, CPG-1406) aqueous dispersion is added to 0.1mol/L n-hydroxysuccinimide and 0.1mol/L 1- (3- diformazan
Aminopropyl) -3- ethyl-carbodiimide hydrochloride aqueous solution (1.5L) in, stirring 30min obtain graphene dispersion body.?
Graphene dispersion body is added to by above-mentioned titanium dioxide nano granule with the feed rate of 0.5L/min under the mixing speed of 300rpm
The temperature of dispersion and pH value are remained 65 DEG C and 9 in fill process in the dispersion in ethanol water by son respectively.
After charging, simultaneously ultrasonic (300w, 65kHz) is stirred 24 hours.By gained reactant centrifugation, wash and in 50 DEG C and 2.5kPa
Obtain within lower drying 5 hours the nano-complex particle 1.49kg of titanium dioxide and graphene.At 800 rpm, by gained titanium dioxide
It is dispersed with stirring in 7.5kg acetone with the nano-complex particle of graphene, continues stirring 1 hour.By 12.5g vinyl under stirring
The nano combined of titanium dioxide and graphene is added in triethoxysilane KH-550 (be purchased from Changzhou Run Xiang Chemical Co., Ltd.)
Particle continues stirring 2 hours in the dispersion of acetone.Gained mixture is filtered and small under 2.5kPa dry 3 at 50 DEG C
When obtain the nano-complex particle 1.51kg of surface modified titanium dioxide and graphene.By 43kg biasfluoroethylene-hexafluoropropylene
Copolymer (being purchased from Shanghai Dong Fu Chemical Industry Science Co., Ltd, T-1) is dispersed in the volume of dimethylbenzene, butyl acetate and isophorone
Than forming fluorocarbon resin dispersion in the admixture solvent for 7:2:1, solid content is 40 weight %.Gained surface is changed
Property titanium dioxide and graphene nano compound particle be added in gained fluororesin dispersion and mix and obtain coating of the present invention.
Embodiment 2
The titanium dioxide nano-particle that 1.25kg partial size is 3-6 nanometers is added to the ethanol water of 25L0.25mol/L under stirring
In solution, continue stirring 1 hour at normal temperature.Meanwhile the graphene of 500L 1.0g/L (is purchased from the poly- carbon composite in Zhuhai
Co., Ltd, CPG-1406) aqueous dispersion is added to 0.1mol/L n-hydroxysuccinimide and 0.1mol/L 1- (3- diformazan
Aminopropyl) -3- ethyl-carbodiimide hydrochloride aqueous solution (1.5L) in, stirring 30min obtain graphene dispersion body.?
Graphene dispersion body is added to by above-mentioned titanium dioxide nano granule with the feed rate of 0.5L/min under the mixing speed of 300rpm
The temperature of dispersion and pH value are remained 65 DEG C and 9 in fill process in the dispersion in ethanol water by son respectively.
After charging, simultaneously ultrasonic (300w, 65kHz) is stirred 24 hours.By gained reactant centrifugation, wash and in 50 DEG C and 2.5kPa
Obtain within lower drying 5 hours the nano-complex particle 1.74kg of titanium dioxide and graphene.At 800 rpm, by gained titanium dioxide
It is dispersed with stirring in 7.5kg acetone with the nano-complex particle of graphene, continues stirring 1 hour.By 12.5g vinyl under stirring
The nano combined of titanium dioxide and graphene is added in triethoxysilane KH-550 (be purchased from Changzhou Run Xiang Chemical Co., Ltd.)
Particle continues stirring 2 hours in the dispersion of acetone.Gained mixture is filtered and small under 2.5kPa dry 3 at 50 DEG C
When obtain the nano-complex particle 1.75kg of surface modified titanium dioxide and graphene.By 42.5kg vinylidene-hexafluoro third
Alkene copolymer (being purchased from Shanghai Dong Fu Chemical Industry Science Co., Ltd, T-1) is dispersed in the body of dimethylbenzene, butyl acetate and isophorone
Product is than to form fluorocarbon resin dispersion in the admixture solvent of 7:2:1, solid content is 40 weight %.By gained surface
Modified titanium dioxide and graphene nano compound particle are added in gained fluororesin dispersion and mix the acquisition present invention and apply
Material.
Embodiment 3
The titanium dioxide nano-particle that 1.25kg partial size is 3-6 nanometers is added to the ethanol water of 25L0.25mol/L under stirring
In solution, continue stirring 1 hour at normal temperature.Meanwhile the graphene of 500L 0.5g/L (is purchased from the poly- carbon composite in Zhuhai
Co., Ltd, CPG-1406) aqueous dispersion is added to 0.1mol/L n-hydroxysuccinimide and 0.1mol/L 1- (3- diformazan
Aminopropyl) -3- ethyl-carbodiimide hydrochloride aqueous solution (1.5L) in, stirring 30min obtain graphene dispersion body.?
Graphene dispersion body is added to by above-mentioned titanium dioxide nano granule with the feed rate of 0.5L/min under the mixing speed of 300rpm
The temperature of dispersion and pH value are remained 65 DEG C and 9 in fill process in the dispersion in ethanol water by son respectively.
After charging, simultaneously ultrasonic (300w, 65kHz) is stirred 24 hours.By gained reactant centrifugation, wash and in 50 DEG C and 2.5kPa
Obtain within lower drying 5 hours the nano-complex particle 1.48kg of titanium dioxide and graphene.At 800 rpm, by gained titanium dioxide
It is dispersed with stirring in 7.5kg acetone with the nano-complex particle of graphene, continues stirring 1 hour.By 32.5g vinyl under stirring
The nano combined of titanium dioxide and graphene is added in triethoxysilane KH-550 (be purchased from Changzhou Run Xiang Chemical Co., Ltd.)
Particle continues stirring 2 hours in the dispersion of acetone.Gained mixture is filtered and small under 2.5kPa dry 3 at 50 DEG C
When obtain the nano-complex particle 1.51kg of surface modified titanium dioxide and graphene.By 85kg biasfluoroethylene-hexafluoropropylene
Copolymer (being purchased from Shanghai Dong Fu Chemical Industry Science Co., Ltd, T-1) is dispersed in the volume of dimethylbenzene, butyl acetate and isophorone
Than forming fluorocarbon resin dispersion in the admixture solvent for 7:2:1, solid content is 40 weight %.Gained surface is changed
Property titanium dioxide and graphene nano compound particle be added in gained fluororesin dispersion and mix and obtain coating of the present invention.
Embodiment 4
The titanium dioxide nano-particle that 1.25kg partial size is 3-6 nanometers is added to the ethanol water of 25L0.25mol/L under stirring
In solution, continue stirring 1 hour at normal temperature.Meanwhile the graphene of 500L 0.5g/L (is purchased from the poly- carbon composite in Zhuhai
Co., Ltd, CPG-1406) aqueous dispersion is added to 0.1mol/L n-hydroxysuccinimide and 0.1mol/L 1- (3- diformazan
Aminopropyl) -3- ethyl-carbodiimide hydrochloride aqueous solution (1.5L) in, stirring 30min obtain graphene dispersion body.?
Graphene dispersion body is added to by above-mentioned titanium dioxide nano granule with the feed rate of 0.5L/min under the mixing speed of 300rpm
The temperature of dispersion and pH value are remained 65 DEG C and 9 in fill process in the dispersion in ethanol water by son respectively.
After charging, simultaneously ultrasonic (300w, 65kHz) is stirred 24 hours.By gained reactant centrifugation, wash and in 50 DEG C and 2.5kPa
Obtain within lower drying 5 hours the nano-complex particle 1.50kg of titanium dioxide and graphene.At 800 rpm, by gained titanium dioxide
It is dispersed with stirring in 15kg acetone with the nano-complex particle of graphene, continues stirring 1 hour.By 12.5g γ-methyl under stirring
Titanium dioxide and stone is added in acryloyloxypropyltrimethoxysilane KH-570 (being purchased from Changzhou Run Xiang Chemical Co., Ltd.)
The nano-complex particle of black alkene continues stirring 2 hours in the dispersion of acetone.Gained mixture is filtered and at 50 DEG C and
The nano-complex particle 1.51kg of surface modified titanium dioxide and graphene is obtained within dry 3 hours under 2.5kPa.By 42.5kg
Vinylidene fluoride-hexafluoropropylene copolymer (being purchased from Shanghai Dong Fu Chemical Industry Science Co., Ltd, T-1) is dispersed in dimethylbenzene, acetic acid fourth
The volume ratio of ester and isophorone is that fluorocarbon resin dispersion, solid content 40 are formed in the admixture solvent of 7:2:1
Weight %.The modified titanium dioxide in gained surface and graphene nano compound particle are added in gained fluororesin dispersion simultaneously
It mixes and obtains coating of the present invention.
(sample for test is according to HGT as in the table below for the performance of the coating obtained by embodiment 1-4 and comparative example 1
In 3793-2005 hot melt type fluor resin PVDF coating prepared by method for making sample):
Table:
| Comparative example 1 | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | |
| Impact strength (J) | 40 | 90 | 80 | 70 | 90 |
| Wearability (L/pm) | 2.8 | 3.6 | 3.4 | 3.1 | 3.6 |
| Weatherability (artificial weathering aging) (h) | 2000 | 4500 | 4000 | 3500 | 4500 |
| Sheet resistance (Ω) | 1.1х104 | 2.3х104 | 2.3х104 | 2.1х104 | 2.4х104 |
Impact strength test: according to 2002 paint and varnish rapid deformation (impact resistance) of ISO 6272-2e test the 2nd
Part: drop weight test (small area formed punch)；
Wearability test: the wearability of organic coating, GB/T are tested according to ASTMD 968-93 (2001) knockout method
The ranking method of 1766-1995 paint and varnish coating aging；
Weatherability test: GB/T 1865-1997 paint and varnish artificial weathering aging and man-made radiation expose (filtration
The radiation of ammonia arc) (eqvISO 11341:1994)；
Electric conductivity test: the measurement of GB/T33328-2016 paint and varnish conductivity and resistance.
It is in table the results show that showing the impact resistance improved, wearability, resistance to by the coating that coating of the present invention obtains
Time property and electric conductivity.
Claims (11)
1. a kind of coating, the coating includes following components:
A) the nano-complex particle of surface modified titanium dioxide and grapheme material；With
B) film-forming components；
Wherein the weight ratio of the nano-complex particle and film-forming components of the modified titanium dioxide in surface and grapheme material is 1:9-
1:99；
Wherein the nano-complex particle of the modified titanium dioxide in surface and grapheme material is by the titanium dioxide and stone as matrix
The nano-complex particle of black alkene material and the dispersion being coated on the nano-complex particle surface of titanium dioxide and grapheme material
Agent composition, wherein the weight of nano-complex particle of the dispersing agent based on titanium dioxide and grapheme material is 0.1-8.0 weight %；
Wherein the nano-complex particle of titanium dioxide and grapheme material is by the titanium dioxide nano-particle as core and as shell
Grapheme material composition, the weight ratio of titanium dioxide and grapheme material is 100:1-1:1.
2. coating according to claim 1, wherein the nano-complex particle of the modified titanium dioxide in surface and grapheme material with
The weight ratio of film-forming components is 1:12-1:60；Nano combined grain of the content of dispersing agent based on titanium dioxide and grapheme material
The weight of son is 0.3-6.0 weight %；The weight ratio of titanium dioxide and grapheme material is 50:1-2:1.
3. coating according to claim 2, wherein the nano-complex particle of the modified titanium dioxide in surface and grapheme material with
The weight ratio of film-forming components is 1:15-1:40；Nano combined grain of the content of dispersing agent based on titanium dioxide and grapheme material
The weight of son is 0.5-4.0 weight %；The weight ratio of titanium dioxide and grapheme material is 20:1-2.5:1.
4. according to claim 1 or 2 or 3 coating, wherein dispersing agent is selected from compound, oleic acid with alkoxysilane groups
And calgon.
5. according to claim 1 or 2 or 3 coating, wherein film-forming components be selected from fluorocarbon resin, polyurethane resin, alkyd resin,
Thermosetting acrylic resin, phenolic resin, nitrocotton, chlorinated rubber, pitch, modified rosin resin and thermoplastic acrylic tree
Rouge, preferably fluorocarbon resin are more preferably selected from polyvinyl fluoride, Kynoar, vinylidene fluoride-hexafluoropropylene copolymer, tetrafluoro second
Alkene-hexafluoropropene-vinylidene fluoride copolymers, tetrafluoroethylene propylene copolymer, tetrafluoroethene-vinylidene fluoride-propylene acid copolymer
Fluorocarbon resin.
6. according to claim 1 or 2 or 3 coating, wherein the partial size of the titanium dioxide is 1-20nm, preferably 1-10nm, it is more excellent
Select 3-6nm.
7. a kind of prepare the method such as 1~6 coating defined by any one in claim, the described method comprises the following steps:
I) grapheme material is provided；Grapheme material is added in the aqueous solution of n-hydroxysuccinimide and carbodiimide salt；
Ii) titanium dioxide nano-particle is dispersed in aqueous solution of alcohol, wherein the concentration of aqueous solution of alcohol is 0.01-3mol/
L；
Iii) grapheme material of step i) is added to the alcohol aqueous dispersion by the obtained titanium dioxide nano-particle of step ii)
In, the temperature of system is controlled at 55-95 DEG C；
Iv) gained reaction mixture is post-processed to the nano-complex particle for obtaining titanium dioxide and grapheme material；
V) be modified the modified acquisition surface in the nano-complex particle surface of titanium dioxide and grapheme material using dispersing agent two
The nano-complex particle of titanium oxide and grapheme material；With
Vi it) by the nano-complex particle of the modified titanium dioxide in surface and grapheme material, film-forming components, optional pigment and fills out
Material and optional auxiliary agent are mixed to get coating in a solvent.
8. method according to claim 7, wherein step i) includes additionally that n-hydroxysuccinimide is added in grapheme material
In the aqueous solution of carbodiimide salt.
9. according to the method in claim 8, wherein the carbodiimide salt is carbodiimide hydrochloride, preferably 1- (3- diformazan
Aminopropyl) -3- ethyl-carbodiimide hydrochloride.
10. method according to claim 7, wherein step ii) in the concentration of aqueous solution of alcohol be 0.1-0.5mol/L, in step
Rapid iii) in the temperature of disperse systems is controlled at 60-90 DEG C.
11. according to the method for any one of claim 7-10, wherein the alcohol used in aqueous solution of alcohol is selected from methanol, second
It is a kind of in alcohol, propyl alcohol and its isomers, butanol and its isomers and ethylene glycol.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113652154A (en) * | 2021-09-17 | 2021-11-16 | 苏州同构科技有限公司 | Wear-resistant color paste coating with high weather resistance and preparation method thereof |
| CN114836069A (en) * | 2022-06-14 | 2022-08-02 | 国网黑龙江省电力有限公司大兴安岭供电公司 | Super-hydrophobic corrosion-resistant coating for grounding electrode and preparation method of coating thereof |
| CN115181439A (en) * | 2022-05-16 | 2022-10-14 | 湖北巴司特科技股份有限公司 | Hybrid inorganic and graphene conductive coating and preparation method thereof |
| CN115895353A (en) * | 2023-01-07 | 2023-04-04 | 江苏考普乐新材料股份有限公司 | Preparation method of FEVE coating |
| CN115975444A (en) * | 2023-01-07 | 2023-04-18 | 江苏考普乐新材料股份有限公司 | FEVE coating |
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| CN103788413A (en) * | 2014-01-24 | 2014-05-14 | 济南大学 | Method for chemically modifying inorganic filler with graphene oxide, product and application |
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| CN107057568A (en) * | 2016-10-19 | 2017-08-18 | 北京恒通绿建节能科技有限公司 | A kind of ultra-hydrophobic conductive coating and preparation method thereof |
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| CN103788413A (en) * | 2014-01-24 | 2014-05-14 | 济南大学 | Method for chemically modifying inorganic filler with graphene oxide, product and application |
| US20160144348A1 (en) * | 2014-11-20 | 2016-05-26 | Korea Institute Of Science And Technology | Photocatalyst using semiconductor-carbon nanomaterial core-shell composite quantum dot and method for preparing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113652154A (en) * | 2021-09-17 | 2021-11-16 | 苏州同构科技有限公司 | Wear-resistant color paste coating with high weather resistance and preparation method thereof |
| CN115181439A (en) * | 2022-05-16 | 2022-10-14 | 湖北巴司特科技股份有限公司 | Hybrid inorganic and graphene conductive coating and preparation method thereof |
| CN114836069A (en) * | 2022-06-14 | 2022-08-02 | 国网黑龙江省电力有限公司大兴安岭供电公司 | Super-hydrophobic corrosion-resistant coating for grounding electrode and preparation method of coating thereof |
| CN115895353A (en) * | 2023-01-07 | 2023-04-04 | 江苏考普乐新材料股份有限公司 | Preparation method of FEVE coating |
| CN115975444A (en) * | 2023-01-07 | 2023-04-18 | 江苏考普乐新材料股份有限公司 | FEVE coating |
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Application publication date: 20190806 |