CN109280120A - A kind of graphite/styrene copolymerized composite pellets and preparation method thereof of silica solution cladding - Google Patents
A kind of graphite/styrene copolymerized composite pellets and preparation method thereof of silica solution cladding Download PDFInfo
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- CN109280120A CN109280120A CN201810984943.0A CN201810984943A CN109280120A CN 109280120 A CN109280120 A CN 109280120A CN 201810984943 A CN201810984943 A CN 201810984943A CN 109280120 A CN109280120 A CN 109280120A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—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 an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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Abstract
The invention discloses a kind of graphite/styrene copolymerized composite pellets and preparation method thereof of silica solution cladding.The preparation method includes: the preparation of the 1) graphite of copolymerizable double bond type silica solution cladding;2) graphite/styrene copolymerized composite pellets preparation of silica solution cladding.The present invention reacts the polymerization inhibitor that two levels solve the problems, such as graphite in graphite/polystyrene synthesis from physical shielding and chemical copolymerization, forms fine and close physical shielding layer on graphite microparticles surface by ethyl orthosilicate in-situ hydrolysis, effectively shields the polymerization inhibitor group of graphite surface;On the other hand, silica solution graphite powder containing double bonds is obtained using the directly modification of the hydrophobic modifier containing copolymerizable double bond, the double bond on graphite powder surface improves the activity that chemical reaction is copolymerized with styrene monomer, eliminates inhibition to coat shielding inhibition in physics and improve chemical copolymerization two levels of reaction.
Description
Technical field
The invention belongs to energy-saving and heat-insulating material technical fields, more particularly, to a kind of graphite/benzene second of silica solution cladding
Copolymerized bead of alkene and preparation method thereof.
Background technique
For the heat-insulation and heat-preservation and flame retardant property for further increasing expanded polystyrene (EPS) (EPS), often introduced in EPS have every
The hot factor, infrared radiation reflecting and the graphite powder for reducing heat transport properties, so that preparation has the stone of excellent thermal insulation performance
Black EPS thermal insulation material.But there are probelem in two aspects for the graphite EPS thermal insulation material for utilizing suspension polymerization to prepare.On the one hand,
Graphite surface contains the quinoids group such as benzoquinones, and quinoid group is typical radical scavenger, and therefore, graphite is in vinyl-type monomer
As styrene and methyl methacrylate monomer polymerization in there is significant polymerization inhibitor phenomenon so that needed for graphite EPS when polymerization
Between extend, the bad stability of polymerization system, properties of product can also reduce, while increase industrialized production technology controlling and process
Difficulty and manufacturing cost hinder high performance graphite EPS product marketization and promote and apply.On the other hand, graphite is in styrene
Dispersibility in monomer be also determine graphite EPS properties of product most want factor, graphite bad dispersibility in styrene monomer, group
Poly- serious, dispersion stabilization is poor, affects mechanics, the heat-insulated and flame retardant effect of graphite EPS.
Summary of the invention
The purpose of the present invention is to solve the above problem, suspends from physical shielding and chemical copolymerization reaction dual-layer face shielding poly-
The inhibition of graphite in legal synthetic graphite polystyrene sphere synthesis, and the synchronous graphite that solves disperses in styrene monomer
Property seriously affect caused by poor, reunion is serious and dispersion stabilization difference graphite polystyrene foamed material mechanics, it is heat-insulated and
The problems such as flame retardant effect.
To achieve the goals above, the first aspect of the present invention provides the graphite of a kind of silica solution cladding/styrene copolymerized
The preparation method of composite pellets, the preparation method include:
1) preparation of the graphite of copolymerizable double bond type silica solution cladding
Polyvinylpyrrolidone is dissolved in dehydrated alcohol under stirring, is added at one time graphite, water, NH3·H2O, into
Row first stirs, and ethyl orthosilicate is added in property again, carries out the second stirring, copolymerizable double bond type hydrophobically modified is then added
Agent, the reaction was continued, then after separation of solid and liquid, washing, drying, obtains the graphite of the copolymerizable double bond type silica solution cladding;
2) graphite/styrene copolymerized composite pellets preparation of silica solution cladding
In the reaction vessel be added water, the aqueous solution of surfactant, the first Inorganic suspending agent, polymer suspension agent water
Solution adds the copolymerizable double bond type silica solution cladding obtained by styrene monomer, initiator and step 1) after mixing evenly
Graphite composition oily phase, system is heated under stirring, copolymerizable double bond type silicon is realized by in-situ suspension polymerization
The copolymerization of the graphite of Sol-gel Coated and styrene monomer molecule adds the second Inorganic suspending agent, styrene monomer in reaction process
After conversion completely, stops heating, graphite/styrene copolymerized composite pellets of silica solution cladding are obtained after cooling.
As a preferred embodiment of the present invention,
In step 1), on the basis of dehydrated alcohol, relative to every 100mL dehydrated alcohol, the dosage of each component is respectively as follows:
0.1~1.0g of polyvinylpyrrolidone, 1.0~20.0g of graphite, 0.5~3.0mL of water, NH3·H2O1~6.0mL,
0.5~7.0mL of ethyl orthosilicate, 0.1~2.0mL of copolymerizable double bond type hydrophobic modifier;
According to the present invention, in step 1), graphite, water, NH are added at one time by above-mentioned dosage3·H2It O and is added at one time
Ethyl orthosilicate can reach the purpose of control hydrolysis time, obtain the graphite of the copolymerizable double bond type silica solution cladding.
In step 2), on the basis of water, relative to every 100~200mL water, the dosage of each component is respectively as follows: surface-active
1~8mL of aqueous solution of agent, first 0.1~2g of Inorganic suspending agent, polymer suspension agent 5~10mL of aqueous solution, styrene monomer
10~100mL, 0.1~1.0g of initiator, 0.05~3.0g of copolymerizable double bond type silica solution, the second Inorganic suspending agent 0.1~
2.0g;Wherein, the mass fraction of the aqueous solution of surfactant is 0.02-0.1wt%, the matter of the aqueous solution of polymer suspension agent
Amount score is 4~10wt%.
As a preferred embodiment of the present invention, the graphite is laminated structure, and partial size is 0.1~50 μm.Select partial size
It is that the small silica solution that is conducive to of graphite composite powder partial size is coated and is modified for the beneficial effect of 0.1~50 μm of laminated structure graphite,
Be conducive to improve its dispersibility and stability in styrene monomer, to be uniformly dispersed in polystyrene sphere, improve
Fire-retardant, the heat-insulated and mechanical property of graphite/styrene copolymerized bead of silica solution cladding.
As a preferred embodiment of the present invention, in step 1), the copolymerizable double bond type hydrophobic modifier is selected from 3- (three
Methoxy methyl silicon substrate) in propyl methacrylate, vinyltrimethoxysilane and vinyltriethoxysilane at least one
Kind.
As a preferred embodiment of the present invention, in step 2), the surfactant be selected from neopelex,
At least one of lauryl sodium sulfate and nonyl phenol polyethenoxy ether.
As a preferred embodiment of the present invention, the Inorganic suspending agent is selected from calcium phosphate, kaolin, barium sulfate and talcum
At least one of powder.
As a preferred embodiment of the present invention, the polymer suspension agent is selected from polyvinyl alcohol, hydroxyethyl cellulose, hydroxyl
At least one of propyl methocel, carboxymethyl cellulose and Sodium Polyacrylate.
As a preferred embodiment of the present invention, the initiator is azodiisobutyronitrile and/or benzoyl peroxide.
As a preferred embodiment of the present invention,
In step 1), the time of the first stirring is 1~10min;The time of second stirring is 1~7h;When the reaction was continued
Between be 1~4h;
In step 2), the speed of stirring is 100~300 revs/min, and being heated to temperature is 80~90 DEG C.
The graphite of the second aspect of the present invention offer cladding of the silica solution as made from above-mentioned preparation method/styrene copolymerized
Composite pellets.
According to the present invention, the solid-liquid separation means that those skilled in the art routinely use can be used in the separation of solid and liquid, wrap
It includes but is not limited to filter, be centrifuged.
Beneficial effects of the present invention:
The present invention reacts the resistance that two levels solve graphite in graphite/polystyrene synthesis from physical shielding and chemical copolymerization
Poly- problem forms fine and close physical shielding layer in graphite surface by ethyl orthosilicate in-situ hydrolysis, effectively shielding graphite surface
Polymerization inhibitor group;On the other hand, using the hydrophobic modifier containing copolymerizable double bond, directly modified to obtain silicon containing double bonds molten
Glue coated graphite powder, the double bond on graphite powder surface improve the activity that chemical reaction is copolymerized with styrene monomer, thus
Physics cladding shielding inhibition and raising chemical copolymerization react two levels and eliminate inhibition.
The present invention can not only improve dispersibility and stability of the graphite in styrene monomer, improve the fire-retardant of composite material
Performance can also eliminate the inhibition in the synthesis of graphite polystyrene sphere.Specifically, on the one hand, nano silica has
Preferable resistance to acid and alkali and heat-resistant stability, silica can scatters ultraviolet there is preferable weatherability, therefore, silica solution
The graphite composite powder of cladding equally has preferable resistance to acid and alkali, heat-resistant stability and weatherability.On the other hand, the two of graphite surface
Silica sol can be used as thermal insulation layer and be gathered in contact of the molten polymer surface reduction polymer with combustion flame, thus
Improve graphite/polystyrene material flame retardant property to a certain extent.Furthermore, it is most important that nano silica coats stone
After ink powder body, the color of graphite composite powder itself has been still maintained, has not influenced graphite/benzene second while shielding graphite inhibition
The color of the copolymerized bead of alkene.
Other features and advantages of the present invention will then part of the detailed description can be specified.
Detailed description of the invention
Fig. 1 shows scanning electron microscope of the graphite of copolymerizable double bond type silica solution cladding produced by the present invention under 1000 times
Picture;
Fig. 2 shows scanning electricity of the graphite of copolymerizable double bond type silica solution cladding produced by the present invention under 30000 times
Mirror picture;
Fig. 3 shows the element energy spectrum diagram of the graphite of copolymerizable double bond type silica solution cladding produced by the present invention;
Fig. 4 shows dispersion of the graphite of copolymerizable double bond type silica solution cladding produced by the present invention in styrene monomer
Property comparison diagram;
Fig. 5 shows graphite/styrene copolymerized composite pellets photo of silica solution cladding produced by the present invention.
Specific embodiment
The preferred embodiment of the present invention is described in more detail below.Although the following describe preferred implementations of the invention
Mode, however, it is to be appreciated that may be realized in various forms the present invention without that should be limited by the embodiments set forth herein.Phase
Instead, these embodiments are provided so that the present invention is more thorough and complete, and can be by the scope of the present invention completely
It is communicated to those skilled in the art.
Embodiment 1
1) preparation of copolymerizable double bond type silica solution coated graphite
0.3g polyvinylpyrrolidone is dissolved in 100mL dehydrated alcohol under stiring, be added at one time 3.0g graphite,
0.9mL ultrapure water, 2.0mL NH3·H2O, after stirring 3min, 1.0mL ethyl orthosilicate, magnetic agitation reaction is added in property again
After 3.0h, 3- (trimethoxy first silicon substrate) propyl methacrylate 0.2mL is directly added into above-mentioned system, the reaction was continued 2.0h
Afterwards, filter, wash, being dried to obtain the graphite of the copolymerizable double bond type silica solution cladding of hydrophobicity.
2) graphite/styrene copolymerized composite pellets synthesis of silica solution cladding
In the four-hole bottle for being equipped with mechanical stirring and condensing unit, distilled water 110mL, mass fraction 0.04% is added
Sodium dodecyl benzene sulfonate aqueous solution 5.5mL, calcium phosphate 0.4g and mass fraction be 6% polyvinyl alcohol aqueous solution 6mL,
Speed of agitator is 160 revs/min, after stirring, will contain 40mL styrene monomer, 0.4g benzoyl peroxide and 0.4g
The oil of the copolymerizable double bond type silica solution coated graphite of hydrophobicity is added in above-mentioned reaction system, and being kept stirring revolving speed is 160
Rev/min, heating water bath is warming up to 85 DEG C, 0.3g calcium phosphate is added in reaction process, polymerization system is kept to stablize, monomer has converted
Quan Hou stops heating, graphite/styrene copolymerized composite pellets of silica solution cladding is obtained after cooling.
Embodiment 2
1) preparation of copolymerizable double bond type silica solution coated graphite
0.5g polyvinylpyrrolidone is dissolved in 100mL dehydrated alcohol under stiring, be added at one time 6.0g graphite,
2.0mL ultrapure water, 3.0mL NH3·H2O, after stirring 4min, 2.0mL ethyl orthosilicate, magnetic agitation reaction is added in property again
After 3.5h, 3- (trimethoxy first silicon substrate) propyl methacrylate 0.3mL is directly added into above-mentioned system, the reaction was continued 2.0h
Afterwards, it filters, wash, being dried to obtain the copolymerizable double bond type silica solution coated graphite of hydrophobicity.
2) graphite/styrene copolymerized composite pellets synthesis of silica solution cladding
In the four-hole bottle for being equipped with mechanical stirring and condensing unit, distilled water 120mL is sequentially added, mass fraction is
The hydroxypropyl methyl fiber that 0.04% sodium dodecyl benzene sulfonate aqueous solution 6.0mL, calcium phosphate 0.6g and mass fraction is 7%
The aqueous solution 7.0mL of element, speed of agitator are 180 revs/min, after stirring, will contain 40mL styrene monomer, 0.4g mistake
The oil of Benzoyl Oxide and the copolymerizable double bond type silica solution coated graphite of 0.6g hydrophobicity is added in above-mentioned reaction system, is protected
Holding speed of agitator is 180 revs/min, and heating water bath is warming up to 85 DEG C, and 0.4g calcium phosphate is added in reaction process and keeps polymerization system
Stablize, after monomer conversion completely, stops heating, graphite/styrene copolymerized composite pellets of silica solution cladding are obtained after cooling.
Embodiment 3
1) preparation of copolymerizable double bond type silica solution coated graphite
0.6g polyvinylpyrrolidone is dissolved in 100mL dehydrated alcohol under magnetic stirring, is added at one time 9.0g
Graphite, 2.8mL ultrapure water, 4.0mL NH3·H2O, after stirring 6min, 3.0mL ethyl orthosilicate is added in property again, and magnetic force stirs
After mixing reaction 6.0h, vinyltriethoxysilane 0.4mL is directly added into above-mentioned system, after the reaction was continued 1.5h, filter,
It washs, be dried to obtain the copolymerizable double bond type silica solution coated graphite of hydrophobicity.
2) graphite/styrene copolymerized composite pellets synthesis of silica solution cladding
In the four-hole bottle for being equipped with mechanical stirring and condensing unit, distilled water 120mL is sequentially added, mass fraction is
The carboxymethyl cellulose that 0.04% lauryl sodium sulfate aqueous solution 6.5mL, kaolin 0.8g and mass fraction is 5.5%
Aqueous solution 7.0mL, speed of agitator are 190 revs/min, after stirring, will contain 40mL styrene monomer, 0.4g azo two
The oil of isobutyronitrile and the copolymerizable double bond type silica solution coated graphite of 0.8g hydrophobicity is added in above-mentioned reaction system, keeps stirring
Mixing revolving speed is 190 revs/min, and heating water bath is warming up to 85 DEG C, 0.5g kaolin is added in reaction process, polymerization system is kept to stablize,
After monomer conversion completely, stops heating, graphite/styrene copolymerized composite pellets of silica solution cladding are obtained after cooling.
Embodiment 4
1) preparation of copolymerizable double bond type silica solution coated graphite
0.6g polyvinylpyrrolidone is dissolved in 100mL dehydrated alcohol under magnetic stirring, is added at one time 12.0g
Graphite, 2.95mL ultrapure water, 5.0mL NH3·H2O, after stirring 8min, 4.0mL ethyl orthosilicate is added in property again, and magnetic force stirs
After mixing reaction 5.0h, vinyltriethoxysilane 0.6mL is directly added into above-mentioned system, after the reaction was continued 1.5h, filter,
It washs, be dried to obtain the copolymerizable double bond type silica solution coated graphite of hydrophobicity.
2) graphite/styrene copolymerized composite pellets synthesis of silica solution cladding
In the four-hole bottle for being equipped with mechanical stirring and condensing unit, distilled water 160mL is sequentially added, mass fraction is
The water for the Sodium Polyacrylate that 0.06% lauryl sodium sulfate aqueous solution 6.0mL, barium sulfate 0.9g and mass fraction is 5.0%
Solution 8.0mL, speed of agitator are 200 revs/min, after stirring, will contain 40mL styrene monomer, 0.4g benzoyl peroxide
The oil of formyl and the copolymerizable double bond type silica solution coated graphite of 1.2g hydrophobicity is added in above-mentioned reaction system, is kept stirring
Revolving speed is 200 revs/min, and heating water bath is warming up to 85 DEG C, 0.55g barium sulfate is added in reaction process, polymerization system is kept to stablize,
After monomer conversion completely, stops heating, graphite/styrene copolymerized composite pellets of silica solution cladding are obtained after cooling.
Embodiment 5
1) preparation of copolymerizable double bond type silica solution coated graphite
0.6g polyvinylpyrrolidone is dissolved in 100mL dehydrated alcohol under magnetic stirring, is added at one time graphite
16.0g, 2.95mL ultrapure water, 5.5mL NH3·H2O, after stirring 9min, 6.0mL ethyl orthosilicate, magnetic force is added in property again
After being stirred to react 5.0h, it is directly added into vinyltrimethoxysilane 0.9mL into above-mentioned system, after the reaction was continued 3.0h, takes out
It filters, wash, being dried to obtain the copolymerizable double bond type silica solution coated graphite of hydrophobicity.
2) graphite/styrene copolymerized composite pellets synthesis of silica solution cladding
In the four-hole bottle for being equipped with mechanical stirring and condensing unit, distilled water 170mL is sequentially added, mass fraction is
The hydroxy ethyl fiber that 0.04% nonyl phenol polyethenoxy ether aqueous solution 7.0mL, talcum powder 0.8g and mass fraction is 4.0%
The aqueous solution 9.0mL of element, speed of agitator are 220 revs/min, after stirring, will be even containing 40mL styrene monomer, 0.4g
The oil of nitrogen bis-isobutyronitrile and the copolymerizable double bond type silica solution coated graphite of 1.6g hydrophobicity is added in above-mentioned reaction system, is protected
Holding speed of agitator is 220 revs/min, and heating water bath is warming up to 85 DEG C, and 0.6g talcum powder is added in reaction process and keeps polymerization system
Stablize, after monomer conversion completely, stops heating, graphite/styrene copolymerized composite pellets of silica solution cladding are obtained after cooling.
Comparative example (synthesis of unmodified graphite polystyrene material)
In the four-hole bottle for being equipped with mechanical stirring and condensing unit, distilled water 160mL, mass fraction 0.06% is added
Lauryl sodium sulfate aqueous solution 6.0mL, barium sulfate 0.9g and mass fraction be 5.0% Sodium Polyacrylate aqueous solution
8.0mL, speed of agitator are 200 revs/min, after stirring, will contain 40mL styrene monomer, 0.4g benzoyl peroxide
It is added in above-mentioned reaction system with the oil of 1.2g raw graphite, being kept stirring revolving speed is 200 revs/min, heating water bath heating
To 85 DEG C, 0.65g barium sulfate is added in reaction process, polymerization system is kept to stablize, after monomer conversion completely, stop heating, it is cooling
After obtain graphite/polystyrene sphere.
Under the conditions of monomer, initiator, polymerization temperature are consistent, the production that is prepared using embodiment 1-5 and comparative example
Product investigate the influence of the graphite and raw graphite of the copolymerizable double bond type silica solution cladding of addition hydrophobicity to polymerization time, by table 1
It is found that the present invention effectively shields stone during suspension polymerization synthetic graphite polystyrene sphere the time required to middle polymerization reaction
The inhibition of ink.
Table 1
* remarks: the graphite that comparative example uses is unmodified raw graphite.
Fig. 1 shows scanning electron microscope of the graphite of copolymerizable double bond type silica solution cladding produced by the present invention under 1000 times
Picture, modified graphite is laminated structure as can be seen from the picture, without obvious agglomeration.
Fig. 2 shows scanning electricity of the graphite of copolymerizable double bond type silica solution cladding produced by the present invention under 30000 times
Mirror picture, from picture it can be observed how there is the silicon dioxide granule of many 40~100nm on modified graphite surface, particle forms cause
Close clad.
Fig. 3 shows the element energy spectrum diagram of the graphite of copolymerizable double bond type silica solution cladding produced by the present invention, in addition to spray
Outside the Au element that gold pretreatment introduces, it can be observed that contain only C, Si and O, these elements from graphite and silica at
Point.
Fig. 4 shows dispersion of the graphite of copolymerizable double bond type silica solution cladding produced by the present invention in styrene monomer
Property comparison diagram, figure a be raw graphite in styrene monomer dispersion stand 5min after photo, it can be found that graphite obviously sinks
Drop.Figure b is the graphite of silica solution cladding, and silica solution has preferable hydrophily with hydroxyl abundant, cannot be in styrene list
Disperse in body, therefore stands substantially all sedimentation bottom after 5min.Figure c is the stone of the copolymerizable double bond type silica solution cladding of hydrophobicity
Ink disperses to stand the picture after 5min in styrene monomer, because showing hydrophobicity after silica solution grafted hydrophobic modifying agent,
Therefore there is preferable compatibility and dispersion stabilization in styrene monomer, prepare silica solution cladding for next step suspension polymerisation
Graphite/styrene copolymerized composite pellets provide safeguard.
Fig. 5 shows graphite/styrene copolymerized composite pellets photo of silica solution cladding produced by the present invention, can see
Composite pellets partial size is more uniform out, average grain diameter about 1.1mm, in addition, having still maintained the original of graphite after silica solution coated graphite
There is color.
Various embodiments of the present invention are described above, above description is exemplary, and non-exclusive, and
It is not limited to disclosed each embodiment.Without departing from the scope and spirit of illustrated each embodiment, for this skill
Many modifications and changes are obvious for the those of ordinary skill in art field.
Claims (10)
1. a kind of graphite/styrene copolymerized composite pellets preparation method of silica solution cladding, which is characterized in that the preparation method
Include:
1) preparation of the graphite of copolymerizable double bond type silica solution cladding
Polyvinylpyrrolidone is dissolved in dehydrated alcohol under stirring, is added at one time graphite, water, NH3·H2O carries out the
One stirring, ethyl orthosilicate is added in property again, carries out the second stirring, copolymerizable double bond type hydrophobic modifier is then added, after
Continuous reaction, then after separation of solid and liquid, washing, drying, obtain the graphite of the copolymerizable double bond type silica solution cladding;
2) graphite/styrene copolymerized composite pellets preparation of silica solution cladding
In the reaction vessel be added water, the aqueous solution of surfactant, the first Inorganic suspending agent, polymer suspension agent it is water-soluble
Liquid adds the copolymerizable double bond type silica solution cladding obtained by styrene monomer, initiator and step 1) after mixing evenly
The oily phase of graphite composition, heats system under stirring, realizes that copolymerizable double bond type silicon is molten by in-situ suspension polymerization
The copolymerization of the graphite and styrene monomer molecule of glue cladding, the second Inorganic suspending agent is added in reaction process, and styrene monomer turns
After changing completely, stops heating, graphite/styrene copolymerized composite pellets of silica solution cladding are obtained after cooling.
2. preparation method according to claim 1, wherein
In step 1), on the basis of dehydrated alcohol, relative to every 100mL dehydrated alcohol, the dosage of each component is respectively as follows:
0.1~1.0g of polyvinylpyrrolidone, 1.0~20.0g of graphite, 0.5~3.0mL of water, NH3·H2O1~6.0mL, positive silicon
0.5~7.0mL of acetoacetic ester, 0.1~2.0mL of copolymerizable double bond type hydrophobic modifier;
In step 2), on the basis of water, relative to every 100~200mL water, the dosage of each component is respectively as follows: surfactant
1~8mL of aqueous solution, first 0.1~2g of Inorganic suspending agent, 5~10mL of aqueous solution of polymer suspension agent, styrene monomer 10~
100mL, 0.1~1.0g of initiator, 0.05~3.0g of copolymerizable double bond type silica solution, second 0.1~2.0g of Inorganic suspending agent;Its
In, the mass fraction of the aqueous solution of surfactant is 0.02-0.1wt%, the mass fraction of the aqueous solution of polymer suspension agent
For 4~10wt%.
3. preparation method according to claim 1, wherein the graphite is laminated structure, and partial size is 0.1~50 μm.
4. preparation method according to claim 1, wherein in step 1), the copolymerizable double bond type hydrophobic modifier choosing
From in 3- (trimethoxy first silicon substrate) propyl methacrylate, vinyltrimethoxysilane and vinyltriethoxysilane
It is at least one.
5. preparation method according to claim 1, wherein in step 2), the surfactant is selected from detergent alkylate
At least one of sodium sulfonate, lauryl sodium sulfate and nonyl phenol polyethenoxy ether.
6. preparation method according to claim 1, wherein the Inorganic suspending agent is selected from calcium phosphate, kaolin, barium sulfate
At least one of with talcum powder.
7. preparation method according to claim 1, wherein it is fine that the polymer suspension agent is selected from polyvinyl alcohol, ethoxy
Tie up at least one of element, hydroxypropyl methyl cellulose, carboxymethyl cellulose and Sodium Polyacrylate.
8. preparation method according to claim 1, wherein the initiator is azodiisobutyronitrile and/or benzoyl peroxide
Formyl.
9. preparation method according to claim 1, wherein
In step 1), the time of the first stirring is 1~10min;The time of second stirring is 1~7h;The time that the reaction was continued is 1
~4h;
In step 2), the speed of stirring is 100~300 revs/min, and being heated to temperature is 80~90 DEG C.
10. the graphite of the cladding of silica solution made from the preparation method as described in any one of claim 1-9/styrene copolymerized
Composite pellets.
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