CN110093071A - A kind of coating and preparation method thereof - Google Patents
A kind of coating and preparation method thereof Download PDFInfo
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- CN110093071A CN110093071A CN201810083239.8A CN201810083239A CN110093071A CN 110093071 A CN110093071 A CN 110093071A CN 201810083239 A CN201810083239 A CN 201810083239A CN 110093071 A CN110093071 A CN 110093071A
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- sol particles
- grapheme material
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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
-
- 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
-
- 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
- C09D7/63—Additives non-macromolecular organic
-
- 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
- C09D7/66—Additives characterised by particle size
- C09D7/67—Particle size smaller than 100 nm
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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
- C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
-
- 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
-
- 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
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
- C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond
-
- 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
Abstract
The present invention relates to a kind of coating, the coating includes following components: A) the modified Si in surfaceXOX‑1(OH)X‑1(OC2H5)X‑1The nano-complex particle of sol particles and grapheme material；And B) film-forming components；The invention further relates to the method for preparing the coating, this method includes preparing the modified Si in surfaceXOX‑1(OH)X‑1(OC2H5)X‑1The nano-complex particle of sol particles and grapheme material and further prepare coating.The Si in coating of the inventionXOX‑1(OH)X‑1(OC2H5)X‑1The nano-complex particle of sol particles 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；SiXOX‑1(OH)X‑1(OC2H5)X‑1Sol particles performance in coating system is stablized, and does not reunite.
Description
Technical field
The present invention relates to a kind of coating, relate more specifically to containing SiXOX-1(OH)X-1(OC2H5)X-1Sol particles and graphite
The coating of the nano-complex particle of alkene material.The invention further relates to the methods for preparing the coating.
Background technique
Graphene is a kind of two dimensional crystal, is arranged by carbon atom according to hexagon, is connected with each other, and carbon point is formed
Son, structure are highly stable；As the amount of carbon atom connected is increasing, this two-dimensional carbon molecules plane constantly expands
Greatly, molecule also constantly becomes larger.The thickness of only one carbon atom of single-layer graphene, i.e., 0.335 nanometer are equivalent to a hair
The thickness of 20 a ten thousandths will nearly have 1,500,000 layers or so of graphene in the graphite of 1 millimeters thick.Graphene be it is known most
A kind of thin material, and have many advantages, such as high specific surface area, superpower thermal conductivity and intensity.The presence of above-mentioned advantage makes
It possesses good market prospects.Grapheme material application range is very wide, and coating is the numerous applications of current grapheme material
An important component in field.Since the specific surface area of grapheme material is very high, there is very strong adsorption capacity.It applies
After adding grapheme material in material, reticular structure is formed during film curing, significantly enhances paint film and ground
Caking property, 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 and weatherability.As a result, it has been found that one kind includes
The modified Si in surfaceXOX-1(OH)X-1(OC2H5)X-1The nano-complex particle of sol particles and grapheme material and film-forming components are appointed
The pigment and filler of choosing and the coating of optional auxiliary agent meet above-mentioned requirements.The present invention is based on above-mentioned discovery and has been able to
At.
The object of the present invention is to provide a kind of Sis modified containing surfaceXOX-1(OH)X-1(OC2H5)X-1Sol particles and stone
The coating of the nano-complex particle of black alkene material, the coating have good impact strength, wearability and weatherability.
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 modified Si in surfaceXOX-1(OH)X-1(OC2H5)X-1The nano-complex particle of sol particles and grapheme material；With
B) film-forming components；
X is the integer greater than 2；
The wherein modified Si in surfaceXOX-1(OH)X-1(OC2H5)X-1The nano-complex particle of sol particles and grapheme material
Weight ratio with film-forming components is 1:9-1:99；
The wherein modified Si in surfaceXOX-1(OH)X-1(OC2H5)X-1The nano-complex particle of sol particles and grapheme material
By the Si as matrixXOX-1(OH)X-1(OC2H5)X-1It the nano-complex particle of sol particles and grapheme material and is coated on
SiXOX-1(OH)X-1(OC2H5)X-1Dispersing agent composition on the nano-complex particle surface of sol particles and grapheme material, wherein
Dispersing agent is based on SiXOX-1(OH)X-1(OC2H5)X-1The weight of the nano-complex particle of sol particles and grapheme material is 0.1-
8.0 weight %；
Wherein SiXOX-1(OH)X-1(OC2H5)X-1The nano-complex particle of sol particles and grapheme material is by as core
SiXOX-1(OH)X-1(OC2H5)X-1Sol particles and as shell grapheme material form, SiXOX-1(OH)X-1(OC2H5)X-1Colloidal sol
The weight ratio of particle and grapheme material is 100:1-1:1.
The modified Si in surface in the coatingXOX-1(OH)X-1(OC2H5)X-1Sol particles and grapheme material it is nano combined
The weight ratio of particle and film-forming components are as follows: 12-1:60, preferably 1:15-1:40；The content of dispersing agent is based on SiXOX-1(OH)X-1
(OC2H5)X-1The weight of the nano-complex particle of sol particles and grapheme material is 0.3-6.0 weight %, preferably 0.5-4.0 weight
Measure %；SiXOX-1(OH)X-1(OC2H5)X-1The weight ratio of sol particles and grapheme material is 50:1-2:1, preferably 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.
Si described in the coatingXOX-1(OH)X-1(OC2H5)X-1The partial size of sol particles is 1-20nm, preferably 1-10nm.
The preparation method of the coating the following steps are included:
I) grapheme material is provided；
Ii aqueous solution of alcohol is mixed into equipped with Si (OC under) stirring2H5)4Reactor in, then plus dilute hydrochloric acid to solution
In, reaction temperature is controlled in room temperature with circulated refrigerated water, 10-20min is stirred, obtains SiXOX-1(OH)X-1(OC2H5)X-1Colloidal sol
The aqueous solution of alcohol of particle, wherein the concentration of aqueous solution of alcohol is 0.01-3mol/L；
Iii) grapheme material of step i) is added to the Si obtained by step ii)XOX-1(OH)X-1(OC2H5)X-1Colloidal sol grain
In the alcohol aqueous dispersion of son, the temperature of system is controlled at 55-95 DEG C；
Iv) gained reaction mixture is post-processed and obtains SiXOX-1(OH)X-1(OC2H5)X-1Sol particles and grapheme material
Nano-complex particle；
V) utilize dispersing agent by SiXOX-1(OH)X-1(OC2H5)X-1The nano-complex particle of sol particles and grapheme material
Surface is modified to obtain the modified Si in surfaceXOX-1(OH)X-1(OC2H5)X-1The nano-complex particle of sol particles and grapheme material；
Vi) the Si that surface is modifiedXOX-1(OH)X-1(OC2H5)X-1The nano combined grain of sol particles and grapheme material
Son, film-forming components, optional pigment and filler and optional auxiliary agent are mixed to get coating in a solvent.
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.
Step ii in the preparation method of the coating) in aqueous solution of alcohol concentration be 0.05-2mol/L, preferably 0.1-
0.5mol/L, the concentration of dilute hydrochloric acid are 0.01-0.5mol/L, preferably 0.05-0.1mol/L, Si (OC2H5)4With rubbing for dilute hydrochloric acid
You are than being 1:0.2-4, preferably 1:0.3-3；The temperature of disperse systems is controlled at 60-90 DEG C in step iii).
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.
Carbodiimide salt described in the preparation method of the coating is carbodiimide hydrochloride, preferably 1- (3- dimethylamino third
Base) -3- ethyl-carbodiimide hydrochloride.
The Si in coating of the inventionXOX-1(OH)X-1(OC2H5)X-1The nano combined grain of sol particles and grapheme material
Son with it is netted it is evenly dispersed in the coating, be conducive to the maximum physical and chemical performance for playing graphene, so that the coating prepared has
Excellent impact resistance, wearability and weatherability；SiXOX-1(OH)X-1(OC2H5)X-1Sol particles performance in coating system
Stablize, does not reunite.
Specific embodiment
A kind of coating, the coating include following components: A) the modified Si in surfaceXOX-1(OH)X-1(OC2H5)X-1Colloidal sol grain
The nano-complex particle of son and grapheme material；And B) film-forming components, wherein X is the integer greater than 2.
The wherein modified Si in surfaceXOX-1(OH)X-1(OC2H5)X-1The nano-complex particle of sol particles and grapheme material
Weight ratio with film-forming components is 1:9-1:99, preferably 1:12-1:60, more preferable 1:15-1:40；The modified Si in surfaceXOX-1
(OH)X-1(OC2H5)X-1The nano-complex particle of sol particles and grapheme material is by the Si as matrixXOX-1(OH)X-1
(OC2H5)X-1The nano-complex particle of sol particles and grapheme material and it is coated on SiXOX-1(OH)X-1(OC2H5)X-1Colloidal sol grain
Dispersing agent composition on the nano-complex particle surface of son and grapheme material, wherein dispersing agent is based on SiXOX-1(OH)X-1
(OC2H5)X-1The weight of the nano-complex particle of sol particles and grapheme material is 0.1-8.0 weight %, preferably 0.3-6.0 weight
Measure %, more preferable 0.5-4.0 weight %；SiXOX-1(OH)X-1(OC2H5)X-1The nano combined grain of sol particles and grapheme material
Son is by the Si as coreXOX-1(OH)X-1(OC2H5)X-1Sol particles and as shell grapheme material form, SiXOX-1(OH)X-1
(OC2H5)X-1The weight ratio of sol particles and grapheme material is 100:1-1:1；It is preferred that 50:1-2:1, more preferable 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.
Si described in the coatingXOX-1(OH)X-1(OC2H5)X-1The partial size of sol particles is 1-20nm, preferably 1-10nm.
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 etc.；Auxiliary agent, such as defoaming agent, wetting agent, dispersing agent, emulsifier, anti-settling agent, stabilizer, anti-skinning
Agent, levelling agent, drier, anti-sagging agent, plasticizer, delustering agent, fire retardant, fungicide etc..Those skilled in the art can basis
Such as bactericidal property of performance needed for coating of the present invention etc. determines the concrete type and its dosage of other components used.
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 provided；
Ii aqueous solution of alcohol is mixed into equipped with Si (OC under) stirring2H5)4Reactor in, then plus dilute hydrochloric acid to solution
In, reaction temperature is controlled in room temperature with circulated refrigerated water, 10-20min is stirred, obtains SiXOX-1(OH)X-1(OC2H5)X-1Colloidal sol
The aqueous solution of alcohol of particle, wherein the concentration of aqueous solution of alcohol is 0.01-3mol/L；
Iii) grapheme material of step i) is added to the Si obtained by step ii)XOX-1(OH)X-1(OC2H5)X-1Colloidal sol grain
In the alcohol aqueous dispersion of son, the temperature of system is controlled at 55-95 DEG C；
Iv) gained reaction mixture is post-processed and obtains SiXOX-1(OH)X-1(OC2H5)X-1Sol particles and grapheme material
Nano-complex particle；
V) utilize dispersing agent by SiXOX-1(OH)X-1(OC2H5)X-1The nano-complex particle of sol particles and grapheme material
Surface is modified to obtain the modified Si in surfaceXOX-1(OH)X-1(OC2H5)X-1The nano-complex particle of sol particles and grapheme material；
Vi) the Si that surface is modifiedXOX-1(OH)X-1(OC2H5)X-1The nano combined grain of sol particles and grapheme material
Son, film-forming components, optional pigment and filler and optional auxiliary agent are mixed to get coating in a solvent.
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.By SiXOX-1
(OH)X-1(OC2H5)X-1Sol particles are dispersed in aqueous solution of alcohol can be by method well known to those skilled in the art as stirred
It carries out.Step ii in the preparation method for coating) in dilute hydrochloric acid concentration be 0.01-0.5mol/L, preferably 0.05-0.1mol/
L.Step ii in the preparation method for coating) Si (OC2H5)4Molar ratio with dilute hydrochloric acid is 1:0.2-4, preferably 1:0.3-3.
The step iii of the preparation method for coating) in, grapheme material is added to the Si obtained by step ii)XOX-1
(OH)X-1(OC2H5)X-1In the alcohol aqueous dispersion of sol particles.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, by the temperature of system
Control is at 60-90 DEG C.After the addition was complete, continue to stir 10-48h, preferably 20-30h at said temperatures.Preferably at one
In embodiment, during charging, the pH of system is controlled in 8.8-9.2,8.9-9.2 is preferably controlled in, more preferably controlled
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, it will be post-processed and be obtained by the reaction mixture that step iii) is obtained
SiXOX-1(OH)X-1(OC2H5)X-1The nano-complex particle of sol particles and grapheme material.Such as reacting mixing by obtained by
Object centrifugation washs and dries and post-processed.The drying can decompression (such as 2.67kPa or less) and increase temperature such as
It is carried out at 70-100 DEG C.
In the step v) of the preparation method for coating, using dispersing agent by SiXOX-1(OH)X-1(OC2H5)X-1Sol particles and stone
The nano-complex particle surface of black alkene material is modified to obtain the modified Si in surfaceXOX-1(OH)X-1(OC2H5)X-1Sol particles and stone
The nano-complex particle of black alkene material.The step v) specific as follows can be carried out:
It a) optionally, will be as the Si of matrix using wetting agentXOX-1(OH)X-1(OC2H5)X-1Sol particles and graphene material
The nano-complex particle of material soaks；
B) by dispersing agent and SiXOX-1(OH)X-1(OC2H5)X-1The nano-complex particle of sol particles and grapheme material exists
It is mixed in wetting agent；With
C) optionally filtering and drying.
Step a) can be carried out, it can also be without step a) and directly by dispersing agent and SiXOX-1(OH)X-1(OC2H5)X-1Colloidal sol
The nano-complex particle of particle and grapheme material is added in wetting agent together.Wetting agent used can be common low boiling point solvent
Such as ethyl alcohol and acetone etc..Wetting agent and Si usedXOX-1(OH)X-1(OC2H5)X-1The nanometer of sol particles and grapheme material is multiple
The weight ratio for closing particle is 2:1-10:1, preferably 3:1-5:1.It can be by conventional method such as by SiXOX-1(OH)X-1(OC2H5)X-1It is molten
The nano-complex particle of micelle and grapheme material is added in wetting agent and by SiXOX-1(OH)X-1(OC2H5)X-1Sol particles
It is soaked with the nano-complex particle of grapheme material.In order to ensure by SiXOX-1(OH)X-1(OC2H5)X-1Sol particles and graphene
The nano-complex particle of material sufficiently and uniform wet, can be as shaking, stirring such as obtained by mechanical stirring and/or ultrasonic treatment
SiXOX-1(OH)X-1(OC2H5)X-1Dispersion of the nano-complex particle of sol particles and grapheme material in wetting agent.
By stirring dispersing agent and Si and/or being ultrasonically treatedXOX-1(OH)X-1(OC2H5)X-1Sol particles and graphene material
The nano-complex particle of material mixes well in wetting agent, to ensure that dispersing agent is uniformly coated on SiXOX-1(OH)X-1
(OC2H5)X-1On the nano-complex particle surface of sol particles and grapheme material.
Step c) can be carried out, the Si that can also be modified without step c) and directly using surface obtained by step b)XOX-1
(OH)X-1(OC2H5)X-1Dispersion of the nano-complex particle of sol particles and grapheme material in wetting agent.It is preferred that being walked
It is rapid c).In step c), drying can at room temperature or raised temperature such as 70-100 DEG C and normal pressure or decompression (such as
2.67kPa or less) under carry out.Suitable drying means 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 Si that surface is modifiedXOX-1(OH)X-1(OC2H5)X-1Sol particles and stone
Nano-complex particle, film-forming components, optional pigment and the filler of black alkene material and optional auxiliary agent mix in a solvent
To coating.
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
25L 0.25mol/L ethanol water is mixed into equipped with 1.25kgSi (OC under stirring2H5)4Reactor in, then
Add 36L 0.05mol/L dilute hydrochloric acid into solution, reaction temperature is controlled in room temperature with circulated refrigerated water, 20min is stirred, obtains
SiXOX-1(OH)X-1(OC2H5)X-1The aqueous solution of alcohol of sol particles.Meanwhile the graphene of 500L 1.0g/L (is purchased from Zhuhai
Poly- carbon composite Co., Ltd, CPG-1406) aqueous dispersion be added to 0.1mol/L n-hydroxysuccinimide and
In the aqueous solution (1.5L) of 0.1mol/L 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride, stirring 30min is obtained
To graphene dispersion body.Graphene dispersion body is added to the feed rate of 0.5L/min under the mixing speed of 300rpm
State SiXOX-1(OH)X-1(OC2H5)X-1Sol particles are in the dispersion in ethanol water, by dispersion in fill process
Temperature and pH value remain 65 DEG C and 9 respectively.After charging, simultaneously ultrasonic (300w, 65kHz) is stirred 24 hours.Gained is anti-
Answer object centrifugation, washing and dry 5 hours acquisition Si under 50 DEG C and 2.5kPaXOX-1(OH)X-1(OC2H5)X-1Sol particles and stone
The nano-complex particle 1.75kg of black alkene.At 800 rpm, by gained SiXOX-1(OH)X-1(OC2H5)X-1Sol particles and graphite
The nano-complex particle of alkene is dispersed with stirring in 7.5kg acetone, continues stirring 1 hour.By three ethoxy of 12.5g vinyl under stirring
Si is added in base silane KH-550 (being purchased from Changzhou Run Xiang Chemical Co., Ltd.)XOX-1(OH)X-1(OC2H5)X-1Sol particles and stone
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
Obtain the modified Si in surface within dry 3 hours under 2.5kPaXOX-1(OH)X-1(OC2H5)X-1Sol particles and graphene it is nano combined
Particle 1.76kg.By 42.5kg vinylidene fluoride-hexafluoropropylene copolymer (being purchased from Shanghai Dong Fu Chemical Industry Science Co., Ltd, T-1)
The volume ratio for being dispersed in dimethylbenzene, butyl acetate and isophorone is that fluorocarbon resin dispersion is formed in the admixture solvent of 7:2:1
System, solid content are 40 weight %.By the modified Si in gained surfaceXOX-1(OH)X-1(OC2H5)X-1Sol particles and graphite
Alkene nano-complex particle, which is added in gained fluororesin dispersion and mixes, obtains coating of the present invention.
Embodiment 2
25L 0.25mol/L ethanol water is mixed into equipped with 1.25kgSi (OC under stirring2H5)4Reactor in, then
Add 18L 0.1mol/L dilute hydrochloric acid into solution, reaction temperature is controlled in room temperature with circulated refrigerated water, 20min is stirred, obtains
SiXOX-1(OH)X-1(OC2H5)X-1The aqueous solution of alcohol of sol particles.Meanwhile the graphene of 500L 0.5g/L (is purchased from Zhuhai
Poly- carbon composite Co., Ltd, CPG-1406) aqueous dispersion be added to 0.1mol/L n-hydroxysuccinimide and
In the aqueous solution (1.5L) of 0.1mol/L 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride, stirring 30min is obtained
To graphene dispersion body.Graphene dispersion body is added to the feed rate of 0.5L/min under the mixing speed of 300rpm
State SiXOX-1(OH)X-1(OC2H5)X-1Sol particles are in the dispersion in ethanol water, by dispersion in fill process
Temperature and pH value remain 65 DEG C and 9 respectively.After charging, simultaneously ultrasonic (300w, 65kHz) is stirred 24 hours.Gained is anti-
Answer object centrifugation, washing and dry 5 hours acquisition Si under 50 DEG C and 2.5kPaXOX-1(OH)X-1(OC2H5)X-1Sol particles and stone
The nano-complex particle 1.50kg of black alkene.At 800 rpm, by gained SiXOX-1(OH)X-1(OC2H5)X-1Sol particles and graphite
The nano-complex particle of alkene is dispersed with stirring in 7.5kg acetone, continues stirring 1 hour.By three ethoxy of 12.5g vinyl under stirring
Si is added in base silane KH-550 (being purchased from Changzhou Run Xiang Chemical Co., Ltd.)XOX-1(OH)X-1(OC2H5)X-1Sol particles and stone
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
Obtain the modified Si in surface within dry 3 hours under 2.5kPaXOX-1(OH)X-1(OC2H5)X-1Sol particles and graphene it is nano combined
Particle 1.51kg.By 43kg vinylidene fluoride-hexafluoropropylene copolymer (being purchased from Shanghai Dong Fu Chemical Industry Science Co., Ltd, T-1) point
The volume ratio for being dispersed in dimethylbenzene, butyl acetate and isophorone is that fluorocarbon resin dispersion is formed in the admixture solvent of 7:2:1
System, solid content are 40 weight %.By the modified Si in gained surfaceXOX-1(OH)X-1(OC2H5)X-1Sol particles and graphene
Nano-complex particle, which is added in gained fluororesin dispersion and mixes, obtains coating of the present invention.
Embodiment 3
25L 0.25mol/L ethanol water is mixed into equipped with 1.25kgSi (OC under stirring2H5)4Reactor in, then
Add 18L 0.1mol/L dilute hydrochloric acid into solution, reaction temperature is controlled in room temperature with circulated refrigerated water, 20min is stirred, obtains
SiXOX-1(OH)X-1(OC2H5)X-1The aqueous solution of alcohol of sol particles.Meanwhile the graphene of 500L 0.5g/L (is purchased from Zhuhai
Poly- carbon composite Co., Ltd, CPG-1406) aqueous dispersion be added to 0.1mol/L n-hydroxysuccinimide and
In the aqueous solution (1.5L) of 0.1mol/L 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride, stirring 30min is obtained
To graphene dispersion body.Graphene dispersion body is added to the feed rate of 0.5L/min under the mixing speed of 300rpm
State SiXOX-1(OH)X-1(OC2H5)X-1Sol particles are in the dispersion in ethanol water, by dispersion in fill process
Temperature and pH value remain 65 DEG C and 9 respectively.After charging, simultaneously ultrasonic (300w, 65kHz) is stirred 24 hours.Gained is anti-
Answer object centrifugation, washing and dry 5 hours acquisition Si under 50 DEG C and 2.5kPaXOX-1(OH)X-1(OC2H5)X-1Sol particles and stone
The nano-complex particle 1.49kg of black alkene.At 800 rpm, by gained SiXOX-1(OH)X-1(OC2H5)X-1Sol particles and graphite
The nano-complex particle of alkene is dispersed with stirring in 7.5kg acetone, continues stirring 1 hour.By three ethoxy of 32.5g vinyl under stirring
Si is added in base silane KH-550 (being purchased from Changzhou Run Xiang Chemical Co., Ltd.)XOX-1(OH)X-1(OC2H5)X-1Sol particles and stone
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
Obtain the modified Si in surface within dry 3 hours under 2.5kPaXOX-1(OH)X-1(OC2H5)X-1Sol particles and graphene it is nano combined
Particle 1.52kg.By 85kg vinylidene fluoride-hexafluoropropylene copolymer (being purchased from Shanghai Dong Fu Chemical Industry Science Co., Ltd, T-1) point
The volume ratio for being dispersed in dimethylbenzene, butyl acetate and isophorone is that fluorocarbon resin dispersion is formed in the admixture solvent of 7:2:1
System, solid content are 40 weight %.By the modified Si in gained surfaceXOX-1(OH)X-1(OC2H5)X-1Sol particles and graphene
Nano-complex particle, which is added in gained fluororesin dispersion and mixes, obtains coating of the present invention.
Embodiment 4
25L 0.25mol/L ethanol water is mixed into equipped with 1.25kgSi (OC under stirring2H5)4Reactor in, then
Add 36L 0.05mol/L dilute hydrochloric acid into solution, reaction temperature is controlled in room temperature with circulated refrigerated water, 20min is stirred, obtains
SiXOX-1(OH)X-1(OC2H5)X-1The aqueous solution of alcohol of sol particles.Meanwhile the graphene of 500L 0.5g/L (is purchased from Zhuhai
Poly- carbon composite Co., Ltd, CPG-1406) aqueous dispersion be added to 0.1mol/L n-hydroxysuccinimide and
In the aqueous solution (1.5L) of 0.1mol/L 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride, stirring 30min is obtained
To graphene dispersion body.Graphene dispersion body is added to the feed rate of 0.5L/min under the mixing speed of 300rpm
State SiXOX-1(OH)X-1(OC2H5)X-1Sol particles are in the dispersion in ethanol water, by dispersion in fill process
Temperature and pH value remain 65 DEG C and 9 respectively.After charging, simultaneously ultrasonic (300w, 65kHz) is stirred 24 hours.Gained is anti-
Answer object centrifugation, washing and dry 5 hours acquisition Si under 50 DEG C and 2.5kPaXOX-1(OH)X-1(OC2H5)X-1Sol particles and stone
The nano-complex particle 1.49kg of black alkene.At 800 rpm, by gained SiXOX-1(OH)X-1(OC2H5)X-1Sol particles and graphite
The nano-complex particle of alkene is dispersed with stirring in 15kg acetone, continues stirring 1 hour.By 12.5g γ-methacryl under stirring
Si is added in oxygroup propyl trimethoxy silicane KH-570 (being purchased from Changzhou Run Xiang Chemical Co., Ltd.)XOX-1(OH)X-1
(OC2H5)X-1The nano-complex particle of sol particles and graphene continues stirring 2 hours in the dispersion of acetone.Gained is mixed
It closes object filtering and dry 3 hours under 50 DEG C and 2.5kPa obtains the modified Si in surfaceXOX-1(OH)X-1(OC2H5)X-1Sol particles
With the nano-complex particle 1.50kg of graphene.42.5kg vinylidene fluoride-hexafluoropropylene copolymer (is fluorinated work purchased from Shanghai east
Science and Technology Ltd., T-1) volume ratio of dimethylbenzene, butyl acetate and isophorone is dispersed in as in the admixture solvent of 7:2:1
Fluorocarbon resin dispersion is formed, solid content is 40 weight %.By the modified Si in gained surfaceXOX-1(OH)X-1
(OC2H5)X-1Sol particles and graphene nano compound particle are added in gained fluororesin dispersion and mix the acquisition present invention
Coating.
(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 | 80 | 90 | 70 | 90 |
| Wearability (L/pm) | 2.8 | 3.3 | 3.5 | 3.2 | 3.6 |
| Weatherability (artificial weathering aging) (h) | 2000 | 4500 | 4000 | 3800 | 4500 |
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)；
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
Hou Xing.
Claims (10)
1. a kind of coating, the coating includes following components:
A) the modified Si in surfaceXOX-1(OH)X-1(OC2H5)X-1The nano-complex particle of sol particles and grapheme material；With
B) film-forming components；
X is the integer greater than 2；
The wherein modified Si in surfaceXOX-1(OH)X-1(OC2H5)X-1The nano-complex particle of sol particles and grapheme material at
The weight ratio of membrane component is 1:9-1:99；
The wherein modified Si in surfaceXOX-1(OH)X-1(OC2H5)X-1The nano-complex particle of sol particles and grapheme material is by making
For the Si of matrixXOX-1(OH)X-1(OC2H5)X-1The nano-complex particle of sol particles and grapheme material and it is coated on SiXOX-1
(OH)X-1(OC2H5)X-1Dispersing agent on the nano-complex particle surface of sol particles and grapheme material forms, wherein dispersing agent
Based on SiXOX-1(OH)X-1(OC2H5)X-1The weight of the nano-complex particle of sol particles and grapheme material is 0.1-8.0 weight
Measure %；
Wherein SiXOX-1(OH)X-1(OC2H5)X-1The nano-complex particle of sol particles and grapheme material is by the Si as coreXOX-1
(OH)X-1(OC2H5)X-1Sol particles and as shell grapheme material form, SiXOX-1(OH)X-1(OC2H5)X-1Sol particles with
The weight ratio of grapheme material is 100:1-1:1.
2. coating according to claim 1, the Si that wherein surface is modifiedXOX-1(OH)X-1(OC2H5)X-1Sol particles and graphene
The nano-complex particle of material and the weight ratio of film-forming components are as follows: 12-1:60, preferably 1:15-1:40；The content of dispersing agent is based on
SiXOX-1(OH)X-1(OC2H5)X-1The weight of the nano-complex particle of sol particles and grapheme material is 0.3-6.0 weight %,
It is preferred that 0.5-4.0 weight %；SiXOX-1(OH)X-1(OC2H5)X-1The weight ratio of sol particles and grapheme material is 50:1-2:1,
It is preferred that 20:1-2.5:1.
3. coating according to claim 1 or 2, wherein dispersing agent be selected from compound with alkoxysilane groups, oleic acid and
Calgon.
4. the coating according to claim 1 or in 2, 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.
5. coating according to claim 1 or 2, wherein the SiXOX-1(OH)X-1(OC2H5)X-1The partial size of sol particles is 1-
20nm, preferably 1-10nm.
6. a kind of method for preparing the coating as defined in any one of claim 1-5, the described method comprises the following steps:
I) grapheme material is provided；
Ii aqueous solution of alcohol is mixed into equipped with Si (OC under) stirring2H5)4Reactor in, then plus dilute hydrochloric acid into solution, use
Circulated refrigerated water controls reaction temperature in room temperature, stirs 10-20min, obtains SiXOX-1(OH)X-1(OC2H5)X-1Sol particles
Aqueous solution of alcohol, wherein the concentration of aqueous solution of alcohol be 0.01-3mol/L；
Iii) grapheme material of step i) is added to the Si obtained by step ii)XOX-1(OH)X-1(OC2H5)X-1Sol particles
In alcohol aqueous dispersion, the temperature of system is controlled at 55-95 DEG C；
Iv) gained reaction mixture is post-processed and obtains SiXOX-1(OH)X-1(OC2H5)X-1Sol particles and grapheme material are received
Rice compound particle；
V) utilize dispersing agent by SiXOX-1(OH)X-1(OC2H5)X-1The nano-complex particle surface of sol particles and grapheme material
It is modified to obtain the modified Si in surfaceXOX-1(OH)X-1(OC2H5)X-1The nano-complex particle of sol particles and grapheme material；
Vi) the Si that surface is modifiedXOX-1(OH)X-1(OC2H5)X-1The nano-complex particle of sol particles and grapheme material, at
Membrane component, optional pigment and filler and optional auxiliary agent are mixed to get coating in a solvent.
7. method according to claim 6, wherein step i) includes additionally that n-hydroxysuccinimide is added in grapheme material
In the aqueous solution of carbodiimide salt.
8. the method for according to claim 6 or 7, wherein step ii) in the concentration of aqueous solution of alcohol be 0.05-2mol/L, it is excellent
0.1-0.5mol/L is selected, the concentration of dilute hydrochloric acid is 0.01-0.5mol/L, preferably 0.05-0.1mol/L, Si (OC2H5)4With dilute salt
The molar ratio of acid is 1:0.2-4, preferably 1:0.3-3；The temperature of disperse systems is controlled at 60-90 DEG C in step iii).
9. the method for according to claim 6 or 7, wherein the alcohol used in aqueous solution of alcohol be selected from methanol, ethyl alcohol, propyl alcohol and its
It is a kind of in isomers, butanol and its isomers and ethylene glycol.
10. method according to claim 7, wherein the carbodiimide salt is carbodiimide hydrochloride, preferably 1- (3- diformazan ammonia
Base propyl) -3- ethyl-carbodiimide hydrochloride.
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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 |
| CN104263358A (en) * | 2014-09-26 | 2015-01-07 | 重庆文理学院 | Magnetic-fluorescent difunctional graphene oxide nanocomposite and preparation method thereof |
| CN106479232A (en) * | 2015-08-25 | 2017-03-08 | 现代自动车株式会社 | Coated film containing Graphene and preparation method thereof |
| WO2017083804A1 (en) * | 2015-11-13 | 2017-05-18 | SiNode Systems, Inc. | Graphene-encapsulated electroactive material for use in a lithium ion electrochemical cell |
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2018
- 2018-01-29 CN CN201810083239.8A patent/CN110093071A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103788413A (en) * | 2014-01-24 | 2014-05-14 | 济南大学 | Method for chemically modifying inorganic filler with graphene oxide, product and application |
| CN104263358A (en) * | 2014-09-26 | 2015-01-07 | 重庆文理学院 | Magnetic-fluorescent difunctional graphene oxide nanocomposite and preparation method thereof |
| CN106479232A (en) * | 2015-08-25 | 2017-03-08 | 现代自动车株式会社 | Coated film containing Graphene and preparation method thereof |
| WO2017083804A1 (en) * | 2015-11-13 | 2017-05-18 | SiNode Systems, Inc. | Graphene-encapsulated electroactive material for use in a lithium ion electrochemical cell |
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