CN108034078A - A kind of fluorinated carbon material/basic zirconium phosphate binary composite, preparation method and applications - Google Patents
A kind of fluorinated carbon material/basic zirconium phosphate binary composite, preparation method and applications Download PDFInfo
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Abstract
The invention discloses a kind of fluorinated carbon material/basic zirconium phosphate binary composite, preparation method and applications, belong to technical field of composite preparation.The method of the present invention includes：Fluorinated carbon material and basic zirconium phosphate are added in the solvent that scion grafting thing is used as, mixes, binary composite is prepared.The present invention is by by fluorographite or the fluorination fluorinated carbon material such as carbon black, it is compound by difunctional or polyfunctional molecule with sheet nanometer basic zirconium phosphate, the binary composite being prepared can be very good to be dispersed in high molecular material matrix, the mechanical performances such as the tensile strength of high molecular material matrix can be improved, and improve the performances such as the antifriction scrape along anticorrosion of polymeric coating material.The method of the present invention is simple, and easy to operate, cost is low, is adapted to industrialized production.
Description
Technical field
The invention belongs to technical field of composite preparation, is related to a kind of binary composite, preparation method and applications,
More particularly to a kind of fluorinated carbon material/basic zirconium phosphate binary composite, preparation method and applications.
Background technology
Inorganic powder particle is widely used in including rubber, plastics, coating, paint, ink, profit as packing material
In the various products such as lubricating oil fat, these inorganic powder particles include, but are not limited to talcum powder, kaolin, clay, carbonic acid
Calcium, carbon black, white carbon, titanium dioxide etc..With the development of nanometer science and technology, due to Gao Bibiao caused by nano material
The excellent physicochemical properties such as area so that inorganic powder filled material towards become more meticulous, the direction of nanosizing is constantly sent out
Exhibition.In the development of inorganic nanometer powder granular materials, on the one hand since the improvement of synthesis preparation method is so that traditional is inorganic
Granular materials constantly diminishes and nanosizing；On the other hand numerous novel high-performance nano materials is also constantly found, and should
For granular filling material, such as carbon nanotubes, graphene, quantum dot, nano clay.
Either traditional inorganic powder particle or nano particle, the main function as packing material is to improve matrix
Performance, is such as added in rubber and plastics and improves its mechanical strength and barrier property；It is added in paint etc. and improves
Covering power and durability of matrix etc.；It is added to the lubrication abrasion resistance that oil phase is improved in lubricant grease.
Basic zirconium phosphate (also referred to as phosphoric acid hydrogen zirconium, Zirconium Phosphate, Zirconium Hydrogen Phosphate)
It is a kind of Two-dimensional Inorganic sheet granular materials, is usually synthesized by hydro-thermal method or circumfluence method, its piece size dimension is in nanoscale
To micron order, and its thickness is usually nanoscale, and basic zirconium phosphate is also referred to as zirconium phosphate nano sheet (Zirconium Phosphate
Nanoplatelets).Basic zirconium phosphate is a kind of high-performance inorganic packing material, can be as the addition of plastics and lubricant grease etc.
Agent, improves its performance.
Fluorinated carbon material is usually perfluorinated by carbon material and obtains, including fluorination carbon black, fluorographite, fluorocarbons nanometer
Pipe, fluorination carbon ball etc..Their general hydrophobic oleophobics, it is corrosion-resistant, and be a kind of high with performances such as excellent lubrication, dielectrics
Performance and multifunctional packing material, but its expensive and bad dispersibility seriously constrains their application.
The content of the invention
For the above-mentioned problems in the prior art, it is an object of the invention to provide a kind of binary composite, system
Preparation Method and its application, especially a kind of fluorinated carbon material/basic zirconium phosphate binary composite, preparation method and its prepare binary
Application in composite material reinforced epoxy and binary composite coating.The binary composite of the present invention can be very good
It is dispersed in high molecular material matrix, the mechanical performances such as the tensile strength of high molecular material matrix can be improved, and improve macromolecule
The performances such as the antifriction scrape along anticorrosion of coating material.
" fluorinated carbon material/basic zirconium phosphate binary composite " of the present invention refers to：Fluorinated carbon material and basic zirconium phosphate complex
Into binary composite.
In order to achieve the above object, the present invention uses following technical scheme：
In a first aspect, the present invention provides a kind of binary composite, the binary composite is fluorinated carbon material and phosphorus
The binary composite that sour zirconium is compounded to form.
Preferably, the fluorinated carbon material is to connect realization by scion grafting thing with the compound of basic zirconium phosphate, and the connection is excellent
Elect covalent attachment as.
Preferably, the scion grafting thing contains the organic matter of at least two amino for end, and at least two hydroxyl is contained in end
Organic matter, or end contain in the organic matter of at least one amino and 1 hydroxyl any one or at least two combination.
" end " of the present invention had not only included the end of main chain, but also the end including side chain.
Preferably, the fluorinated carbon material is connected by fluorine atom with the amino and/or hydroxyl of scion grafting thing, the basic zirconium phosphate
It is connected by hydroxyl with the amino and/or hydroxyl of scion grafting thing.
" basic zirconium phosphate " of the present invention is the basic zirconium phosphate with hydroxyl, and the present invention is not construed as limiting its preparation method, it can
To be common method disclosed in the prior art, prepared by the method that those skilled in the art can refer to the prior art.More preferably
Ground, basic zirconium phosphate is prepared using circumfluence method or hydro-thermal method.
A preferred preparation scheme as basic zirconium phosphate, prepares basic zirconium phosphate using circumfluence method, specifically includes following steps：Will
15.0g zirconyl chlorides (ZrOCl2.8·H2O) and 150.0mL concentration be 3.0mol/L phosphoric acid (H3PO4) mix and pour into glass burning
In bottle, magnetic agitation is uniform, is placed in being heated to 100 DEG C, when reaction reflux 24 is small in oil bath pan.After reaction, will react
Product is washed with water three times, by the way that product is collected by centrifugation, then, obtained sample is dried 24h at 65 DEG C.Then by drying
Product afterwards is ground into fine powder, obtains phosphoric acid zirconium powder.
A preferred preparation scheme as basic zirconium phosphate, prepares basic zirconium phosphate using hydro-thermal method, specifically includes following steps：
In the hydrothermal reaction kettle (Teflon Godson) that volume is about 150ml, by the ZrOCl of 10.0g2.8·H2O and 100ml concentration is
The phosphoric acid mixing of 9.0mol/L is poured into wherein.Reaction kettle is positioned over after closed in 200 DEG C of baking oven and reacts 2h, treats natural cooling
Reaction kettle is taken out after to room temperature, reaction product is washed with water three times, by the way that product is collected by centrifugation, then, the sample that will be obtained
The dry 24h at 65 DEG C.Then dried product is ground into fine powder, obtains phosphoric acid zirconium powder.
As the optimal technical scheme of binary composite of the present invention, the scion grafting thing is the scion grafting thing of liquid.Institute
State scion grafting thing preferably include it is any one in the polymer of diamines, polyamines, glycol, polyalcohol, hydramine, ether amines, polyetheramine or alcohol
Kind or at least two combination, further preferably include polyetheramine D230, polyetheramine D2000, polyetheramine T403, ethylenediamine, third
In diamines, phenylenediamine, monoethanolamine, ethylene glycol or polyethylene glycol any one or at least two combination.
It is highly preferred that the scion grafting thing is any one in polyetheramine, diamines or hydramine or at least two combination.
As the optimal technical scheme of binary composite of the present invention, the fluorinated carbon material include fluorographite,
Any one in fluorinated graphene, fluorination carbon black, fluorination coke, carbon fluoride nano-tube or fluorinated fullerene or at least two
Combination, but the above-mentioned fluorinated carbon material enumerated is not limited to, other fluorocarbons that can reach constructed effect commonly used in the art
Material can also be used for the present invention.
Fluorinated carbon material of the present invention can be commercially available fluorinated carbon material or the fluorination being directly prepared
Carbon material (preparation method is referring to method disclosed in the prior art), those skilled in the art can make choice as needed.
Preferably, the size of the basic zirconium phosphate is 10nm~100 μm, for example, 10nm, 30nm, 65nm, 100nm, 150nm,
200nm、400nm、600nm、800nm、1μm、3μm、5μm、10μm、20μm、30μm、40μm、50μm、60μm、70μm、80μm、
90 μm or 100 μm etc..
Preferably, the basic zirconium phosphate is any one in alpha zirconium phosphate, θ-basic zirconium phosphate or γ-basic zirconium phosphate or at least two
Combination.
Second aspect, the present invention provide the preparation method of binary composite as described in relation to the first aspect, the method bag
Include：
Fluorinated carbon material and basic zirconium phosphate are added in the solvent that scion grafting thing is used as, mixes, binary composite wood is prepared
Material.
In the method for the present invention, scion grafting thing is not only used as functional molecular, but also is used as solvent, realizes fluorinated carbon material and phosphoric acid
Zirconium it is compound.In the binary composite, the fluorinated carbon material is connected by fluorine atom with the amino of scion grafting thing, the phosphorus
Sour zirconium is connected by hydroxyl with the amino and/or hydroxyl of scion grafting thing.
Scion grafting thing of the present invention is functional molecular, can be bi-functional molecule or multi-functional molecule,
But it must is fulfilled at least one in the following conditions：1. at least two amino is contained in the scion grafting thing end；2. the scion grafting thing
Contain at least two hydroxyl in end；3. at least one amino and 1 hydroxyl are contained in the scion grafting thing end.
As the optimal technical scheme of the present invention for preparing binary composite method, described be mixed into stirs evenly.
The ratio between the gross mass of the fluorographite and basic zirconium phosphate and the volume of scion grafting thing solvent are (1~4):10, such as 1:
10、1.5:10、2:10、2.5:10、3:10、3.2:10、3.5:10 or 4:10 etc., be preferably (1.5~3):10.
Preferably, the mass ratio of the fluorographite and basic zirconium phosphate is 1:0.001~1:1000, such as 1:0.001、1:
0.005、1:0.01、1:0.05、1:0.1、1:0.5、1:1、1:5、1:10、1:50、1:100、1:200、1:300、1:400、1:
500、1:600、1:700、1:800、1:900 or 1:1000 etc., it is preferably 1:(0.5~2).
Preferably, the method further includes the step washed and dried after blending.The purpose of the washing is
Unnecessary scion grafting thing is got rid of, so that the binary composite purified.
As the further preferred technical solution of the present invention for preparing binary composite method, the described method includes：
Fluorinated carbon material and basic zirconium phosphate are added in the solvent that scion grafting thing is used as, mixed, is washed out removing scion grafting thing, and it is dry,
The binary composite of purifying is prepared.
The third aspect, the present invention provide a kind of binary composite enhancing high molecular material, and the binary composite increases
The binary composite described in first aspect is included in the preparing raw material of strong high molecular material.
Preferably, the high molecular material include epoxy resin, polyethers, polyamide or polyester in any one or at least
Two kinds of combination, is preferably epoxy resin.
Fourth aspect, the present invention provide the preparation side of the binary composite enhancing high molecular material as described in the third aspect
Method, the described method includes：Binary composite described in first aspect, curing agent and high molecular material are mixed, stirs evenly, obtains
Binary composite strengthens high molecular material.
Preferably, during preparing binary composite enhancing high molecular material, the curing agent is polyetheramine.
Preferably, prepare binary composite enhancing high molecular material during, the binary composite quality with
The ratio between curing agent and high molecular material gross mass are 0.01:128~128:128, such as 0.01:128、0.1:128、1:128、5:
128、10:128、20:128、30:128、40:128、50:128、60:128、70:128、80:128、90:128、100:128 or
128:128 etc., it is preferably 6.7:1.28.
Preferably, during preparing binary composite enhancing high molecular material, the curing carries out in a mold, institute
Stating cured condition is preferably：First cure 2h at 80 DEG C, then cure 2h at 120 DEG C.
Preferably, the mould is the stainless steel mould for coating releasing agent in advance.
5th aspect, the present invention provide a kind of binary composite enhancing macromolecule material coating, and the coating binary is answered
The binary composite described in first aspect is included in the preparing raw material of condensation material enhancing macromolecule material coating.
Preferably, the high molecular material include epoxy resin, polyethers, polyamide or polyester in any one or at least
Two kinds of combination, is preferably epoxy resin.
6th aspect, the binary composite that the present invention is provided as described in terms of the 5th strengthen the system of macromolecule material coating
Preparation Method, the described method includes：Binary composite described in first aspect is dissolved in organic solvent, adds curing agent
And high molecular material, stir evenly, be coated to matrix surface, cure, obtain binary composite coating.
Preferably, during preparing binary composite enhancing macromolecule material coating, the curing agent is polyetheramine.
Preferably, during preparing binary composite enhancing macromolecule material coating, the binary composite matter
Amount is 0.6 with the ratio between curing agent and high molecular material gross mass:1.28.
Preferably, the gross mass of the binary composite, curing agent and high molecular material and the volume of organic solvent it
Than for 0.001g/50ml~50g/50ml, such as 0.001g/50ml, 0.01g/50ml, 0.1g/50ml, 1g/50ml, 5g/
50ml、10g/50ml、15g/50ml、20g/50ml、25g/50ml、30g/50ml、35g/50ml、40g/50ml、45g/50ml
Or 50g/50ml etc., it is preferably 1.88g/50ml.
The mode of coating is not construed as limiting in the present invention, such as can be spraying or spin coating.
Preferably, described matrix is glass.
Preferably, first organic solvent is made to volatilize before the curing.
Compared with the prior art, the present invention has the advantages that：
(1) present invention with sheet nanometer basic zirconium phosphate by by fluorographite or the fluorination fluorinated carbon material such as carbon black, passing through
Difunctional or polyfunctional molecule is compound, and a kind of new binary composite has been prepared, and is specifically fluorocarbons/basic zirconium phosphate two
First composite material.This binary composite can be very good to be dispersed in high molecular material matrix, can improve high molecular material
The mechanical performances such as the tensile strength of matrix, and improve the performances such as the antifriction scrape along anticorrosion of polymeric coating material.
(2) preparation method of the invention is simple, and easy to operate, cost is low, is adapted to industrialized production.
Brief description of the drawings
Fig. 1 is basic zirconium phosphate XRD spectra prepared by 1 circumfluence method of embodiment.
Fig. 2 is the SEM image of basic zirconium phosphate prepared by 1 circumfluence method of embodiment.
Fig. 3 is the XRD spectra of basic zirconium phosphate prepared by 2 hydro-thermal method of embodiment.
Fig. 4 is the TEM image of basic zirconium phosphate prepared by 2 hydro-thermal method of embodiment.
Fig. 5 is the SEM image of 1 fluorographite of embodiment.
Fig. 6 is the SEM image for fluorographite/basic zirconium phosphate binary composite that embodiment 1 is prepared by polyetheramine D230.
Fig. 7 is the SEM image for fluorographite/basic zirconium phosphate binary composite that embodiment 2 is prepared by polyetheramine T403.
Fig. 8 is the SEM image that embodiment 3 is fluorinated carbon black.
Fig. 9 is the SEM image for fluorination carbon black/basic zirconium phosphate binary composite that embodiment 3 is prepared by monoethanolamine.
Embodiment
Further illustrate technical scheme below with reference to the accompanying drawings and specific embodiments.
Embodiment 1
The present embodiment provides a kind of fluorographite/basic zirconium phosphate binary composite
(1) zirconium phosphate nano sheet is prepared using circumfluence method：
By 15.0g zirconyl chlorides (ZrOCl2.8·H2O) and 150.0mL concentration be 3.0mol/L phosphoric acid (H3PO4) mixing
Pour into glass flask, magnetic agitation is uniform, is placed in being heated to 100 DEG C, when reaction reflux 24 is small in oil bath pan.Reaction terminates
Afterwards, reaction product is washed with water three times, by the way that product is collected by centrifugation, then, obtained sample is dried into 24h at 65 DEG C.
Then dried product is ground into fine powder, and obtained phosphoric acid zirconium powder is subjected to XRD (x-ray diffraction) and SEM (scannings
Electron microscope) detection.The XRD spectra for the basic zirconium phosphate sample that circumfluence method obtains is shown in Fig. 1 and Fig. 2 respectively with SEM image, can by figure
To find out, prepared basic zirconium phosphate has sheet crystal structure, and diameter is in below 100nm.
(2) binary composite (fluorographite/basic zirconium phosphate binary composite) is prepared：
1g fluorographites and 1g circumfluence method basic zirconium phosphates are added in 10ml polyetheramines D230, stirs evenly, is fluorinated
Graphite basic zirconium phosphate binary composite.By the mixture of fluorographite, basic zirconium phosphate and polyetheramine D230 ethanol eccentric cleaning 3
It is secondary, to remove unnecessary polyetheramine D230, and it is dried to obtain the fluorographite basic zirconium phosphate binary composite of purifying.
In the present embodiment, polyetheramine D230 is the bifunctional molecule that both ends are amino, can be distinguished by the amino at both ends
Fluorographite and basic zirconium phosphate are connected, to prepare fluorographite/basic zirconium phosphate binary composite.
In the present embodiment, fluorographite and the fluorographite/basic zirconium phosphate binary composite prepared by polyetheramine D230
SEM image see Fig. 5 and Fig. 6 respectively, as seen from the figure, fluorographite particle size be less than 10 microns, about at 3-8 microns
Between；Fluorographite has carried out good grafting with two kinds of components of basic zirconium phosphate by polyetheramine D230, forms stable binary
Composite material.
Embodiment 2
The present embodiment provides a kind of fluorographite/basic zirconium phosphate binary composite
(1) zirconium phosphate nano sheet is prepared using hydro-thermal method：
In the hydrothermal reaction kettle for being about 150ml in volume (Teflon Godson), by the ZrOCl of 10.0g2.8·H2O and 100ml
The phosphoric acid mixing that concentration is 9.0mol/L is poured into wherein.Reaction kettle is positioned over after closed in 200 DEG C of baking oven and reacts 2h, is treated certainly
Reaction kettle is taken out after being so cooled to room temperature, reaction product is washed with water three times, by the way that product is collected by centrifugation, then, will be obtained
Sample at 65 DEG C dry 24h.Then dried product is ground into fine powder, and obtained phosphoric acid zirconium powder is carried out
XRD and TEM (transmission electron microscope) detections.The XRD spectra for the basic zirconium phosphate sample that hydro-thermal method obtains is shown in figure respectively with TEM image
3 and Fig. 4, as seen from the figure, basic zirconium phosphate prepared by this method has laminar structured, and particle size is more than 1 micron mostly.
(2) binary composite (fluorographite/basic zirconium phosphate binary composite) is prepared：
1g fluorographites and 0.5g circumfluence method basic zirconium phosphates are added in 10ml polyetheramines T403, stirs evenly, obtains fluorine
Graphite basic zirconium phosphate binary composite.By the mixture of fluorographite, basic zirconium phosphate and polyetheramine T403 ethanol eccentric cleaning 3
It is secondary, to remove unnecessary polyetheramine T403, and it is dried to obtain the fluorographite basic zirconium phosphate binary composite of purifying.
In the present embodiment, polyetheramine T403 is three functional moleculars that three end groups are amino, can pass through three end groups
Amino connects fluorographite and basic zirconium phosphate respectively, to prepare fluorographite/basic zirconium phosphate binary composite.
In the present embodiment, the SEM image of the fluorographite/basic zirconium phosphate binary composite prepared by polyetheramine D403 is shown in
Fig. 7, as seen from the figure, fluorographite have carried out good grafting with two kinds of components of basic zirconium phosphate by polyetheramine D403, are formed
The binary composite stablized.
Embodiment 3
The present embodiment provides one kind to be fluorinated carbon black/basic zirconium phosphate binary composite
(1) preparation method of basic zirconium phosphate is same as Example 2；
(2) binary composite (fluorination carbon black/basic zirconium phosphate binary composite) is prepared：
1g fluorination carbon blacks are added in 10ml monoethanolamines with 2g hydro-thermal method basic zirconium phosphates, stirs evenly, obtains fluorination carbon black
Basic zirconium phosphate binary composite.The mixture ethanol eccentric cleaning 3 times of carbon black, basic zirconium phosphate and monoethanolamine will be fluorinated, to remove
Unnecessary alcohol amine, and it is dried to obtain fluorination carbon black/basic zirconium phosphate binary composite of purifying.
In the present embodiment, monoethanolamine is that one end is the bifunctional molecule that amino one end is hydroxyl, can pass through the ammonia at both ends
Base and hydroxyl connect fluorination carbon black and basic zirconium phosphate respectively, and carbon black basic zirconium phosphate binary composite is fluorinated to prepare.
In the present embodiment, fluorination carbon black and the SEM of the fluorination carbon black basic zirconium phosphate binary composite prepared by monoethanolamine
Image is shown in Fig. 8 and Fig. 9 respectively, as seen from the figure, is fluorinated the size of carbon black about between 10-20 microns；And it is fluorinated carbon black
Good grafting has been carried out by monoethanolamine with two kinds of components of basic zirconium phosphate, has formd stable binary composite.
Embodiment 4
In addition to polyetheramine is replaced with propane diamine, other methods and condition are same as Example 1.
Embodiment 5
In addition to polyetheramine T403 is replaced with polyethylene glycol, other methods and condition are same as Example 2.
Embodiment 6
In addition to polyetheramine T403 is replaced with phenylenediamine, other methods and condition are same as Example 3.
The method of 1-6 of the embodiment of the present invention can successfully prepare fluorinated carbon material and be answered with the compound intact binary of basic zirconium phosphate
Condensation material.
Embodiment 7
The present embodiment provides a kind of fluorographite/basic zirconium phosphate binary composite reinforced epoxy material, binary are compound
The concentration of material in the epoxy is~5%.
Preparation method：
Fluorographite prepared by 6.7g embodiments 1/basic zirconium phosphate binary composite is equal with being stirred in 32g polyetheramines D230
It is added to after even in 96g epoxy resin E44, the stainless steel mould for coating releasing agent in advance is poured into after three is stirred
In, it is then placed in baking oven and cures.Condition of cure is 80 DEG C of 120 DEG C two hours after two hours.Room temperature is naturally cooled to after curing,
Sample is removed from the molds and carries out Mechanical Properties Tensile experimental test.Tensile testing samples are prepared with reference to ASTM D638 standards,
Fracture toughness test sample is prepared with reference to ASTM D5045 standards.
Comparative example 1
In this comparative example, contrast sample is pure epoxy resin (being free of any filler).
Comparative example 2
In this comparative example, the fluorographite in embodiment 7/basic zirconium phosphate binary composite is replaced with etc. to the fluorination of quality
The contrast sample of graphite, i.e. this comparative example is the epoxy resin of 5% fluorographite of addition.
Comparative example 3
In this comparative example, the fluorographite in embodiment 7/basic zirconium phosphate binary composite is replaced with etc. to the phosphoric acid of quality
The contrast sample of zirconium, i.e. this comparative example is the epoxy resin of 5% basic zirconium phosphate of addition.
The preparation process of the contrast sample of comparative example 1-3 and binary composite reinforced epoxy material described in embodiment 7
The preparation process of material is identical.The measuring mechanical property result of the sample of embodiment 7 and comparative example 1-3 is shown in Table 1.
1 measuring mechanical property comparing result of table
As can be seen from Table 1, epoxy resin is filled using binary composite provided by the invention and can significantly carried
Rise the mechanical performance of epoxide resin material.
Embodiment 8
The present embodiment provides a kind of fluorographite/basic zirconium phosphate binary composite reinforced epoxy material coating, binary
The concentration of composite material in the epoxy is~30%.
Preparation method：
Fluorographite prepared by 0.6g embodiments 1/basic zirconium phosphate binary composite is dissolved in 50ml acetone solns, then
Sequentially add 0.32g polyetheramines and 0.96g epoxy resin E44.After above-mentioned solution is stirred, glass table is sprayed to
Face, is put into baking oven cures after the solvent is volatilized.Condition of cure is 80 DEG C of 120 DEG C two hours after two hours.It is naturally cold after curing
But room temperature is arrived, sample is subjected to mantle friction test.
Comparative example 4
In this comparative example, contrast sample is pure epoxy resin (being free of any filler) coating.
Comparative example 5
In this comparative example, the fluorographite in embodiment 8/basic zirconium phosphate binary composite is replaced with etc. to the fluorination of quality
The contrast sample of graphite, i.e. this comparative example is the epoxy coating of 30% fluorographite of addition.
Comparative example 6
In this comparative example, the fluorographite in embodiment 8/basic zirconium phosphate binary composite is replaced with etc. to the phosphoric acid of quality
The contrast sample of zirconium, i.e. this comparative example is the epoxy coating of 30% basic zirconium phosphate of addition.
The preparation process of the contrast sample of comparative example 4-6 and binary composite reinforced epoxy material described in embodiment 8
Expect that the preparation process of coating is identical.The coating surface friction coefficient of the sample of embodiment 8 and comparative example 4-6 is according to national standard GB/
T10006 is tested, and surface contact angle is measured by contact angle tester.The surface test of the sample of embodiment 8 and comparative example 4-6
It the results are shown in Table 2.
2 surface property test comparison result of table
As can be seen from Table 2, epoxy coating is prepared using binary composite provided by the invention, can significantly improved
The surface property of coating.
Applicant states that the present invention illustrates the method detailed of the present invention, but not office of the invention by above-described embodiment
It is limited to above-mentioned method detailed, that is, does not mean that the present invention has to rely on above-mentioned method detailed and could implement.Technical field
Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to each raw material of product of the present invention
Addition, selection of concrete mode etc., all fall within protection scope of the present invention and the open scope.
Claims (10)
1. a kind of binary composite, it is characterised in that the binary composite is fluorinated carbon material and basic zirconium phosphate complex
Into binary composite.
2. binary composite according to claim 1, it is characterised in that the fluorinated carbon material and basic zirconium phosphate it is compound
It is to connect to realize by scion grafting thing, the connection is preferably to be covalently attached；
Preferably, the scion grafting thing contains the organic matter of at least two amino for end, and the organic of at least two hydroxyl is contained in end
Thing, or end contain in the organic matter of at least one amino and 1 hydroxyl any one or at least two combination；
Preferably, the fluorinated carbon material is connected by fluorine atom with the amino and/or hydroxyl of scion grafting thing, and the basic zirconium phosphate passes through
Hydroxyl is connected with the amino and/or hydroxyl of scion grafting thing；
Preferably, the scion grafting thing be liquid scion grafting thing, the scion grafting thing preferably include diamines, polyamines, glycol, polyalcohol,
Hydramine, ether amines, polyetheramine or alcohol polymer in any one or at least two combination, further preferably including polyetheramine
In D230, polyetheramine D2000, polyetheramine T403, ethylenediamine, propane diamine, phenylenediamine, monoethanolamine, ethylene glycol or polyethylene glycol
Any one or at least two combination；
Preferably, the scion grafting thing is any one in polyetheramine, diamines or hydramine or at least two combination.
3. method according to claim 1 or 2, it is characterised in that the fluorinated carbon material includes fluorographite, fluorination stone
Black alkene, any one being fluorinated in carbon black, fluorination coke, carbon fluoride nano-tube or fluorinated fullerene or at least two combination；
Preferably, the size of the basic zirconium phosphate is 10nm~100 μm；
Preferably, the basic zirconium phosphate is any one in alpha zirconium phosphate, θ-basic zirconium phosphate or γ-basic zirconium phosphate or at least two group
Close.
4. such as the preparation method of claim 1-3 any one of them binary composites, it is characterised in that the method bag
Include：
Fluorinated carbon material and basic zirconium phosphate are added in the solvent that scion grafting thing is used as, mixes, binary composite is prepared.
5. according to the method described in claim 4, it is characterized in that, described be mixed into stirs evenly；
Preferably, the ratio between the gross mass of the fluorographite and basic zirconium phosphate and the volume of scion grafting thing solvent are (1~4):10, preferably
For (1.5~3):10；
Preferably, the mass ratio of the fluorographite and basic zirconium phosphate is 1:0.001~1:1000, it is preferably 1:(0.5~2)；
Preferably, the method further includes the step washed and dried after blending.
6. method according to claim 4 or 5, it is characterised in that the described method includes：By fluorinated carbon material and basic zirconium phosphate
It is added in the solvent that scion grafting thing is used as, mixes, is washed out removing scion grafting thing, and it is dry, and the binary that purifying is prepared is answered
Condensation material.
7. a kind of binary composite strengthens high molecular material, it is characterised in that the binary composite strengthens macromolecule material
Claim 1-3 any one of them binary composites are included in the preparing raw material of material；
Preferably, the high molecular material includes any one in epoxy resin, polyether-polyamide or polyester or at least two
Combination, be preferably epoxy resin.
8. the preparation method of binary composite enhancing high molecular material as claimed in claim 7, it is characterised in that the side
Method includes：Claim 1-4 any one of them binary composite, curing agent and high molecular material are mixed, stirred evenly, then
Using curing agent solidification, binary composite enhancing high molecular material is obtained；
Preferably, during preparing binary composite enhancing high molecular material, the curing agent is polyetheramine；
Preferably, during preparing binary composite enhancing high molecular material, the binary composite quality is with curing
The ratio between agent and high molecular material gross mass are 0.01:128~128:128, it is preferably 6.7:128；
Preferably, during preparing binary composite enhancing high molecular material, the curing carries out in a mold, described solid
The condition of change is preferably：First cure 2h at 80 DEG C, then cure 2h at 120 DEG C；
Preferably, the mould is the stainless steel mould for coating releasing agent in advance.
9. a kind of binary composite strengthens macromolecule material coating, it is characterised in that the binary composite strengthens high score
Claim 1-4 any one of them binary composites are included in the preparing raw material of sub- material coating；
Preferably, the high molecular material includes any one in epoxy resin, polyethers, polyamide or polyester or at least two
Combination, be preferably epoxy resin.
10. the preparation method of binary composite enhancing macromolecule material coating as claimed in claim 9, it is characterised in that
The described method includes：Claim 1-4 any one of them binary composites are dissolved in organic solvent, add curing
Agent and high molecular material, stir evenly, and are coated to matrix surface, cure, obtain binary composite coating；
Preferably, during preparing binary composite enhancing macromolecule material coating, the curing agent is polyetheramine；
Preferably, prepare binary composite enhancing macromolecule material coating during, the binary composite quality with
The ratio between curing agent and high molecular material gross mass are 0.6:1.28；
Preferably, the ratio between the gross mass of the binary composite, curing agent and high molecular material and the volume of organic solvent are
0.001g/50ml~50g/50ml, is preferably 1.88g/50ml；
Preferably, the mode of the coating is any one in spraying or spin coating；
Preferably, described matrix is glass；
Preferably, first organic solvent is made to volatilize before the curing.
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| CN201711353727.8A CN108034078B (en) | 2017-12-15 | 2017-12-15 | Carbon fluoride material/zirconium phosphate binary composite material, preparation method and application thereof |
| PCT/CN2018/110923 WO2019114414A1 (en) | 2017-12-15 | 2018-10-19 | Fluorinated carbon material/zirconium phosphate binary composite material, preparation method and application thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108997517A (en) * | 2018-07-05 | 2018-12-14 | 四川大学 | A kind of application of fluorinated graphene method of modifying and fluorinated graphene as radical initiator |
| WO2019114414A1 (en) * | 2017-12-15 | 2019-06-20 | 深圳南科二维复材科技有限公司 | Fluorinated carbon material/zirconium phosphate binary composite material, preparation method and application thereof |
| CN110229708A (en) * | 2019-06-26 | 2019-09-13 | 包头协同纳米新材科技有限公司 | Carbon nanotube/two-dimension nano materials composite material and its preparation method and application |
| CN112812628A (en) * | 2021-02-08 | 2021-05-18 | 南方科技大学 | LIS coating and preparation method and application thereof |
| CN114958102A (en) * | 2022-06-23 | 2022-08-30 | 中北大学 | Bottom surface integrated composite coating and preparation method and coating method thereof |
| CN115558370A (en) * | 2022-04-08 | 2023-01-03 | 中国船舶重工集团公司第七一一研究所 | Antifriction and wear-resistant coating for sliding bearing, preparation method of antifriction and wear-resistant coating and preparation method of coating |
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| WO2008053694A1 (en) * | 2006-10-27 | 2008-05-08 | Toagosei Co., Ltd. | Novel lamellar zirconium phosphate |
| CN106010133A (en) * | 2016-07-29 | 2016-10-12 | 王小凤 | Acid and alkali resistant antibacterial paint for municipal drainage and sewage pipelines |
| CN107312162A (en) * | 2017-07-31 | 2017-11-03 | 南方科技大学 | A kind of epoxy curing agent, a kind of epoxide resin material and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108034078B (en) * | 2017-12-15 | 2020-04-28 | 深圳南科二维复材科技有限公司 | Carbon fluoride material/zirconium phosphate binary composite material, preparation method and application thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008053694A1 (en) * | 2006-10-27 | 2008-05-08 | Toagosei Co., Ltd. | Novel lamellar zirconium phosphate |
| CN106010133A (en) * | 2016-07-29 | 2016-10-12 | 王小凤 | Acid and alkali resistant antibacterial paint for municipal drainage and sewage pipelines |
| CN107312162A (en) * | 2017-07-31 | 2017-11-03 | 南方科技大学 | A kind of epoxy curing agent, a kind of epoxide resin material and preparation method thereof |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019114414A1 (en) * | 2017-12-15 | 2019-06-20 | 深圳南科二维复材科技有限公司 | Fluorinated carbon material/zirconium phosphate binary composite material, preparation method and application thereof |
| CN108997517A (en) * | 2018-07-05 | 2018-12-14 | 四川大学 | A kind of application of fluorinated graphene method of modifying and fluorinated graphene as radical initiator |
| CN108997517B (en) * | 2018-07-05 | 2019-12-03 | 四川大学 | A kind of application of fluorinated graphene method of modifying and fluorinated graphene as radical initiator |
| CN110229708A (en) * | 2019-06-26 | 2019-09-13 | 包头协同纳米新材科技有限公司 | Carbon nanotube/two-dimension nano materials composite material and its preparation method and application |
| CN112812628A (en) * | 2021-02-08 | 2021-05-18 | 南方科技大学 | LIS coating and preparation method and application thereof |
| CN115558370A (en) * | 2022-04-08 | 2023-01-03 | 中国船舶重工集团公司第七一一研究所 | Antifriction and wear-resistant coating for sliding bearing, preparation method of antifriction and wear-resistant coating and preparation method of coating |
| CN114958102A (en) * | 2022-06-23 | 2022-08-30 | 中北大学 | Bottom surface integrated composite coating and preparation method and coating method thereof |
Also Published As
| Publication number | Publication date |
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| WO2019114414A1 (en) | 2019-06-20 |
| CN108034078B (en) | 2020-04-28 |
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