CN106986960A - It is a kind of to prepare graphene three-dimensional construction method of the powder body material containing carbon polymer - Google Patents
It is a kind of to prepare graphene three-dimensional construction method of the powder body material containing carbon polymer Download PDFInfo
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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
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/26—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a solid phase from a macromolecular composition or article, e.g. leaching out
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- C08J2325/00—Characterised by the use of 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 an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2325/02—Homopolymers or copolymers of hydrocarbons
- C08J2325/04—Homopolymers or copolymers of styrene
- C08J2325/08—Copolymers of styrene
- C08J2325/14—Copolymers of styrene with unsaturated esters
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Abstract
Graphene three-dimensional construction method of the powder body material containing carbon polymer is prepared the invention discloses a kind of, belong to Polymer Synthesizing field, its step is that (1) adds crosslinkers monomers and initiator monomer in polymerized monomer, produces monomer mixed phase, then adds pore-foaming agent；(2) aqueous solution is added in a kettle., dispersant is then added, and monomer mixed phase, which is added drop-wise in reactor, reacts；(3) cool, washing etc. obtains copolymer；(4) pore-foaming agent is removed with extractant again, copolymer, which is hydrolyzed, obtains graphene three-dimensional construction powder body material containing carbon polymer.The present invention prepare graphene three-dimensional construction powder body material contain carbon polymer, this have the advantage that easily incorporation transition metal ions be used to low temperature graphitization, after being handled through high temperature graphitization, formed stereochemical structure three-dimensional grapheme powder, disintegration rate be more than 98%；The inventive method has high purity, product quality stabilization, advantage easy to operate.
Description
Technical field
The present invention relates to Polymer Synthesizing field, more particularly to one kind prepares graphene three-dimensional construction powder body material containing carbon poly
The method of compound.
Background technology
Since 2010 Nobel Prizes in physics being obtained from A.K.Geim and K.S.Novoselov in 2010 because of grapheme material,
Graphene receives the extensive concern of whole world scientist, and the relation technological researching of graphene enters fast-developing track, domestic
Also the sixth of the twelve Earthly Branches by graphene write " 13 " planning, graphene by《Made in China 2025》One of frontier material is classified as, into
For the prior development direction of field of new materials.
Graphene is a kind of two dimensional crystal formed by the plane carbon atom of hexagon ordered arrangement, only one atomic layer
Thickness.Main Types are；Point single-layer graphene, bilayer graphene (2 layer by layer spacing 0.34nm) few layer graphene (3-10 layers),
More than 10 layers are graphite.Graphene has special performance；Hardness 130GPa, Stability Analysis of Structures；The theory of graphene compares surface
Product is up to 2630m2/g；Graphene has higher light transmittance, and the absorptivity to light is only 2.3%；The fracture strength of graphene
It is more than 100 times of steel for 42N/m；Graphene theoretical electronic transfer rate is 20000cm2/ (Vs), high conductivity 10-6
Ω cm, electric conductivity is better than copper；The thermal conductivity factor of graphene reaches 5000W/ (m K), is more than 10 times of copper.Thus with stone
Black alkene prepares the development of level and the development of graphene application technology level, and grapheme material can be applied in the production of more downstreams
In product and field, graphene will be mainly used in following field：Military equipment, Aero-Space, energy management, electric automobile,
Mobile electron, ultracapacitor field, lithium ion battery, touch-screen, enhanced type composite material, sensor, thin film solar electricity
Pond, Special rubber plastic material and the field such as fabric and high-performance computer, sapecial coating, the market space are wide.
Graphene prepares main method；Mechanical stripping method；It is a kind of repeatedly on graphite it is difficult to control size and the number of plies
Paste and take adhesive glue off and bring the method for preparing graphene, the graphene film of number mm square can only be obtained reluctantly.Its advantage
It is that can obtain the very high quality graphene film that can not be realized during using other method.Solvent stripping method:In strength ultrasonication
Graphite layers are inserted by solvent to be peeled off, prepare graphene down；Shortcoming：The yield of preparation is very low, is not suitable for mass
Production.Chemical vapour deposition technique；Process is complicated, cost is high, can manufacture large-area graphene.It is by methane etc. in vacuum tank
Carbon source, which is heated to 1000 DEG C or so, decomposes it, and the technology of graphene film is then formed in the metal foils such as Ni and Cu.But, exist
The technique used under 1000 DEG C of high temperature can only be promoted in the way of batch processing, and this is the bottleneck of the manufacturing process.And technique
Also there is the problem of being easily mixed into defect and impurity during transferring repeatedly.Whard to control, cost is high.Epitaxial growth method；Plus
Hot carborundum (SiC) substrate removes the silicon (Si) on surface, and remaining carbon (C) spontaneously reconfigures to form graphene.Shortcoming：It is non-
Often high treatment temperature, involves great expense, yields poorly, and is unsuitable for industrialization and large-scale production.Graphene oxide reducing process；It is first
Graphite powder first is aoxidized, is then placed in solution and disperses, it is reduced again after very thin one layer is coated on substrate.Due to using
The problem of folding the construction of multiple tens nanometer square parts, and can not reduce completely, therefore exist is it is difficult to ensure that fully
Electric conductivity and the transparency.These are the main methods for producing two-dimensional graphene material in the market.In addition, the above method is closed
Into graphene generally by Van der Waals force or dangling bond effect influenceed, be made after powder sample, it is easy to accumulation or reunite, easily reunite
Into graphite flake, many good characteristics of original grapheme material are lost, thus need to be scattered in stabilizer before use, concentration is very
Low, it synthesizes cost height, complex process.Therefore it is unfavorable for widely using for graphene.In addition, the graphene ratio of commercial powder sample
Surface area is typically smaller than 100m2/ g, it synthesizes cost height, complex process.
The information for being disclosed in the background section is merely intended to understanding of the increase to the general background of the present invention, without answering
When the prior art for being considered as recognizing or implying the information structure in any form well known to persons skilled in the art.
The content of the invention
The present invention be directed to above-mentioned technical problem, invent it is a kind of prepare graphene three-dimensional construction powder body material contain carbon polymer
Method, synthetically using the advantage of suspension polymerisation, by suitably changing preparation condition, only from use identical and different polymer
Monomer Formations are started with, and the carbon containing polymer beads of a variety of required performances are easily made using suspension polymerization.
To achieve the above object, the technical scheme that the present invention is provided is as follows：
It is a kind of to prepare graphene three-dimensional construction method of the powder body material containing carbon polymer, include following operating procedure：
(1) polymerized monomer 87%~99%, crosslinkers monomers 0.5%~10%, initiator are weighed according to percentage by weight
0.5%~3.0%, crosslinkers monomers and initiator monomer are then added in polymerized monomer, is sufficiently stirred for making initiator monomer
Dissolving, produces monomer mixed phase, then adds pore-foaming agent, stir；
(2) aqueous solution is added in a kettle., dispersant is then added, under conditions of continuously stirring, by step (1)
Middle gained monomer mixed phase is added drop-wise in reactor, continues to stir 120min after dripping, keeping temperature is 60~95 DEG C of reactions 5
~6 hours；
(3) gained mass temperature is down to room temperature after step (2) is reacted, obtained white spherical copolymer, through using repeatedly
Deionized water washing, dehydration, drying, that is, remove the Free water in gained copolymer, and it is the spherical of 0.15~1.2mm to obtain particle diameter
Copolymer；
(4) cleaned, then using water with the pore-foaming agent contained in the copolymer of gained in extractant removing step (3) again
Gained copolymer is hydrolyzed for solution agent, washes, dries, that is, removes the Free water in gained copolymer, obtain graphene three-dimensional
Construct powder body material and contain carbon polymer.
Wherein, the polymerized monomer described in step (1) is styrene (S), acrylic acid, acrylonitrile, methyl acrylate, butylbenzene
Rubber/polystyrene/polyacrylic acid N-butyl performed polymer, polyurethane (PU)/poly- N-butyl acrylic acid (PBMA) performed polymer, first
Base hydroxy-ethyl acrylate (MEG), double diurethanes (OUDM), three isocyanic acid glycol esters, polyethers (polyester) dihydric alcohol, first
Base acrylic acid binaryglycol ester (EGDMA), 2,4 toluene diisocyanate (TDI)/N-butyl acrylic acid (PBMA) performed polymer or
One or more kinds of mixtures in polyurethane (PU)/NIPA performed polymer；Wherein, styrene is made
For main body monomer.
Wherein, cross-linking monomer described in step (1) is divinylbenzene (DVB), isocyanic acid triallyl (TAIC) or clothing health
One or more kinds of mixtures in sour α-allyl ester.
Wherein, initiator monomer described in step (1) is benzoyl peroxide (BPO) and/or azo diethyl fourth eyeball.
Wherein, pore-foaming agent described in step (1) is toluene, atoleine or 200#One kind in gasoline, consumption is step
(1) the 20~40% of gained monomer mixed phase percentage by weight in.
Wherein, dispersant described in step (2) is one kind or one in animal gelatin, polyvinyl alcohol or hydroxyethyl cellulose
Thing mixed above is planted, consumption accounts for the 0.4~6% of step (2) reclaimed water solution weight percentage.
Wherein, 1.25 times of amount of the aqueous solution added in step (2) monomer mixed phase weight obtained by step (1).
Wherein, the keeping temperature described in step (2) is that 60~95 DEG C of reactions 5~6 hours are that keeping temperature is 60 DEG C anti-
Answer 1.5~2 hours, 95 DEG C are then warming up to again and is incubated 2.5~4 hours.
Wherein, the extractant described in step (3) is one kind in toluene, ethyl acetate, acetone or vapor, and consumption is institute
Obtain the 300~400% of copolymer dry weight percentage by weight.
Wherein, the sodium hydroxide that step (3) described hydrolytic reagent is diethylenetriamine and/or mass concentration is 15~35% is molten
Liquid, consumption is 1.65 times of gained monomer mixed phase weight in step (1).
Compared with prior art, the present invention has the advantages that：
The present invention prepare graphene three-dimensional construction powder body material contain carbon polymer, this have the advantage that and easily mixed
Metal ion is crossed to low temperature graphitization, after being handled through high temperature graphitization, the three-dimensional grapheme powder of stereochemical structure, disintegration is formed
Rate is more than 98%；Further, the present invention prepares products obtained therefrom steady quality, due to not to the chain transfer reaction of solvent, production
The molecular weight of thing is higher than solution polymer, and product is in regular ball particle, and the big I of spherolite is adjusted as requested, is inhaled on polymer
Attached dispersant is few, easily removing, and the inventive method has high purity, product quality stabilization, advantage easy to operate.
Embodiment
It is described in detail with reference to embodiment, it is to be understood that protection scope of the present invention is not by specific
The limitation of embodiment.
Embodiment 1
A kind of to prepare graphene three-dimensional construction method of the powder body material containing carbon polymer, operating procedure is as follows：
(1) polymerized monomer styrene (S) 34.4%, acrylic acid 11%, acrylonitrile 44% are weighed according to percentage by weight, handed over
Join agent monomer divinylbenzene (DVB) 4.5%, isocyanic acid triallyl (TAIC) 4%, itaconic acid α-allyl ester 1%, initiator mistake
BP (BPO) 0.4%, azo diethyl fourth eyeball 0.2%, then add crosslinkers monomers and initiator in polymerized monomer
Monomer, is sufficiently stirred for dissolving initiator monomer, produces monomer mixed phase, then adds gained monomer mixed phase percentage by weight
35% pore-foaming agent toluene, stir；
(2) 1.25 times of the aqueous solution of monomer mixed phase weight obtained by step (1) is added in a kettle., is then added again and is accounted for
3.7% polyethylene of dispersing agent alcohol 2.3%, the hydroxyethyl cellulose 1.4% of the aqueous solution percentage by weight of addition, are continuously being stirred
Under conditions of mixing, gained monomer mixed phase in step (1) is added drop-wise in reactor, continues to stir 120min after dripping, protects
Hold temperature to react 1.5~2 hours for 60 DEG C, after heat to be polymerized, be progressively warming up to 95 DEG C and be incubated 2.5 hours；
(3) gained mass temperature is down to room temperature after step (2) is reacted, obtained white spherical copolymer, through using repeatedly
Deionized water washing, dehydration, drying, that is, remove the Free water in gained copolymer, and it is the spherical of 0.15~1.2mm to obtain particle diameter
Copolymer；
(4) again with institute in 400% extractant vapor removing step (3) of gained copolymer dry weight percentage by weight
The pore-foaming agent contained in the copolymer obtained, is washed with deionized water net, gained monomer mixed phase in then using consumption for step (1)
Gained copolymer is hydrolyzed for 25% sodium hydroxide solution for 1.65 times of hydrolytic reagent mass concentration of weight, then spends
Ionized water is cleaned, and drying removes the Free water in gained copolymer, is obtained graphene three-dimensional construction powder body material and is contained carbon polymer.
Embodiment 2
A kind of to prepare graphene three-dimensional construction method of the powder body material containing carbon polymer, operating procedure is as follows：
(1) polymerized monomer styrene (S) 75.4%, methyl acrylate 6.8%, butylbenzene rubber are weighed according to percentage by weight
Glue/polystyrene/polyacrylic acid N-butyl performed polymer 8.2%, crosslinkers monomers isocyanic acid triallyl (TAIC) 9%, initiation
Then agent benzoyl peroxide (BPO) 2.5% adds crosslinkers monomers and draws in polymerized monomer styrene and methyl acrylate
Agent monomer is sent out, is sufficiently stirred for dissolving initiator monomer, then gathers gained addition polymerized monomer butadiene-styrene rubber/polystyrene/
In n-butyl acrylate performed polymer, it is mixed evenly, produces monomer mixed phase, then adds gained monomer mixed phase weight hundred
Divide 38% pore-foaming agent 200 of ratio#Gasoline, stirs；
(2) 1.25 times of the aqueous solution of monomer mixed phase weight obtained by step (1) is added in a kettle., is then added again and is accounted for
6% dispersant animal gelatin of the aqueous solution percentage by weight of addition, under conditions of continuously stirring, by institute in step (1)
Obtain monomer mixed phase to be added drop-wise in reactor, continue to stir 120min after dripping, keeping temperature is that 60 DEG C of reactions 1.5~2 are small
When, it is to be polymerized heat after, be progressively warming up to 95 DEG C be incubated 4 hours；
(3) gained mass temperature is down to room temperature after step (2) is reacted, obtained white spherical copolymer, through using repeatedly
Deionized water washing, dehydration, drying, that is, remove the Free water in gained copolymer, and it is the spherical of 0.15~1.2mm to obtain particle diameter
Copolymer；
(4) institute in 300% extractant ethyl acetate removing step (3) of gained copolymer dry weight percentage by weight is added again
The pore-foaming agent contained in the copolymer obtained, is washed with deionized water net, gained monomer mixed phase in then using consumption for step (1)
Gained copolymer is hydrolyzed 1.65 times of hydrolytic reagent diethylenetriamine of weight, is then cleaned with deionized water, drying is removed
The Free water gone in gained copolymer, obtains graphene three-dimensional construction powder body material and contains carbon polymer.
Embodiment 3
A kind of to prepare graphene three-dimensional construction method of the powder body material containing carbon polymer, operating procedure is as follows：(1) according to
Percentage by weight weighs polymerized monomer styrene (S) 59.2%, polyurethane (PU)/poly- N-butyl acrylic acid (PBMA) performed polymer
5.5%th, hydroxyethyl methacrylate (MEG) 6%, the isocyanic acid glycol ester of double diurethanes (OUDM) 7.8%, three
10.5%, crosslinkers monomers divinylbenzene (DVB) 2.4%, isocyanic acid triallyl (TAIC) 3.6%, initiator benzoyl peroxide
Formyl (BPO) 1.4%, azo diethyl fourth eyeball 1.6%, then in polymerized monomer styrene (S), hydroxyethyl methacrylate
(MEG) crosslinkers monomers and initiator monomer, are added in double diurethanes (OUDM) and three isocyanic acid glycol esters, fully
Stirring dissolves initiator monomer, and gained then is added into polyurethane (PU)/poly- N-butyl acrylic acid (PBMA) performed polymer mixes
Stir, produce monomer mixed phase, then add 40% pore-foaming agent atoleine of gained monomer mixed phase percentage by weight,
Stir；
(2) 1.25 times of the aqueous solution of monomer mixed phase weight obtained by step (1) is added in a kettle., is then added again and is accounted for
(wherein polyvinyl alcohol is accounted for the 0.4% polyethylene of dispersing agent alcohol and hydroxyethyl cellulose of the aqueous solution percentage by weight of addition
0.2%, 0.2%) hydroxyethyl cellulose is accounted for, under conditions of continuously stirring, and gained monomer mixed phase in step (1) is added drop-wise to
Continue to stir 120min in reactor, after dripping, keeping temperature is 60 DEG C and reacted 1.5~2 hours, after heat to be polymerized, by
Step is warming up to 95 DEG C and is incubated 3 hours；
(3) gained mass temperature is down to room temperature after step (2) is reacted, obtained white spherical copolymer, through using repeatedly
Deionized water washing, dehydration, drying, that is, remove the Free water in gained copolymer, and it is the spherical of 0.15~1.2mm to obtain particle diameter
Copolymer；
(4) again plus obtained by 350% extractant toluene removing step (3) of gained copolymer dry weight percentage by weight
Copolymer in the pore-foaming agent that contains, be washed with deionized water net, then use consumption monomer mixed phase obtained by step (1) is middle
Gained copolymer is hydrolyzed the sodium hydroxide solution of 1.65 times of hydrolytic reagent 20% of weight, then clear with deionized water
Wash, drying removes the Free water in gained copolymer, obtain graphene three-dimensional construction powder body material and contain carbon polymer.
Embodiment 4
A kind of to prepare graphene three-dimensional construction method of the powder body material containing carbon polymer, operating procedure is as follows：
(1) polymerized monomer styrene (S) 46.9%, polyethers (polyester) dihydric alcohol 4.5%, first are weighed according to percentage by weight
Base acrylic acid binaryglycol ester (EGDMA) 8.8%, 2,4 toluene diisocyanate (TDI)/N-butyl acrylic acid (PBMA) are pre-
Aggressiveness 4.8%, acrylonitrile 34.0%, crosslinkers monomers divinylbenzene (DVB) 8%, isocyanic acid triallyl (TAIC) 2%, draw
Agent benzoyl peroxide (BPO) 2.2% is sent out, then in polymerized monomer styrene (S), polyethers (polyester) dihydric alcohol, metering system
Add in acid diethylene glycol ester (EGDMA), acrylonitrile, crosslinkers monomers divinylbenzene (DVB), isocyanic acid triallyl (TAIC)
Enter crosslinkers monomers and initiator monomer, be sufficiently stirred for dissolving initiator monomer, it is different that gained then is added into 2,4- toluene two
In cyanate (TDI)/N-butyl acrylic acid (PBMA) performed polymer, continue to stir, produce monomer mixed phase, then add institute
20% pore-foaming agent atoleine of monomer mixed phase percentage by weight is obtained, is stirred；
(2) 1.25 times of the aqueous solution of monomer mixed phase weight obtained by step (1) is added in a kettle., is then added again and is accounted for
3% dispersant animal gelatin, polyvinyl alcohol and hydroxyethyl cellulose mixture (its of the aqueous solution percentage by weight of addition
In, 1%) animal gelatin, polyvinyl alcohol and hydroxyethyl cellulose respectively account for respectively, under conditions of continuously stirring, by step (1)
Gained monomer mixed phase is added drop-wise in reactor, continues to stir 120min after dripping, keeping temperature is 60 DEG C of reactions 1.5~2
Hour, after heat to be polymerized, progressively it is warming up to 95 DEG C and is incubated 3.5 hours；
(3) gained mass temperature is down to room temperature after step (2) is reacted, obtained white spherical copolymer, through using repeatedly
Deionized water washing, dehydration, drying, that is, remove the Free water in gained copolymer, and it is the spherical of 0.15~1.2mm to obtain particle diameter
Copolymer；
(4) institute in 400% extractant water vapour removing step (3) of gained copolymer dry weight percentage by weight is added again
The pore-foaming agent contained in the copolymer obtained, is washed with deionized water net, gained monomer mixed phase in then using consumption for step (1)
Gained copolymer is hydrolyzed for 15% sodium hydroxide solution for 1.65 times of hydrolytic reagent mass concentration of weight, then spends
Ionized water is cleaned, and drying removes the Free water in gained copolymer, is obtained graphene three-dimensional construction powder body material and is contained carbon polymer.
Embodiment 5
A kind of to prepare graphene three-dimensional construction method of the powder body material containing carbon polymer, operating procedure is as follows：
(1) polymerized monomer styrene (S) 54.2%, polyurethane (PU)/poly- N-butyl propylene are weighed according to percentage by weight
Sour (PBMA) performed polymer 32.8%, crosslinkers monomers divinylbenzene (DVB) 0.38%, isocyanic acid triallyl 0.12%, initiation
Agent benzoyl peroxide (BPO) 0.25%, azo diethyl fourth eyeball (AIBN) 0.25%, then in polymerized monomer styrene (S)
Add crosslinkers monomers and initiator monomer, be sufficiently stirred for dissolving initiator monomer, then by gained add polyurethane (PU)/
It is uniformly mixed in poly- N-butyl acrylic acid (PBMA) performed polymer, produces monomer mixed phase, then adds gained monomer mixing
30% pore-foaming agent 200 of phase percentage by weight#Gasoline, stirs；
(2) 1.25 times of the aqueous solution of monomer mixed phase weight obtained by step (1) is added in a kettle., is then added again and is accounted for
The 6% polyethylene of dispersing agent alcohol and hydroxyethyl cellulose mixture (wherein, polyvinyl alcohol of the aqueous solution percentage by weight of addition
Respectively account for 3%), under conditions of continuously stirring, gained monomer mixed phase in step (1) is added drop-wise to respectively with hydroxyethyl cellulose
Continue to stir 120min in reactor, after dripping, keeping temperature is 60 DEG C and reacted 1.5~2 hours, after heat to be polymerized, by
Step is warming up to 95 DEG C and is incubated 2.5~4 hours；
(3) gained mass temperature is down to room temperature after step (2) is reacted, obtained white spherical copolymer, through using repeatedly
Deionized water washing, dehydration, drying, that is, remove the Free water in gained copolymer, and it is the spherical of 0.15~1.2mm to obtain particle diameter
Copolymer；
(4) again plus obtained by 200% extractant water vapour removing step (3) of gained copolymer dry weight percentage by weight
Copolymer in the pore-foaming agent that contains, be washed with deionized water net, then use consumption monomer mixed phase weight obtained by step (1) is middle
Gained copolymer is hydrolyzed for 35% sodium hydroxide solution for 1.65 times of hydrolytic reagent mass concentration of amount, then spend from
Sub- water cleaning, drying removes the Free water in gained copolymer, obtains graphene three-dimensional construction powder body material and contains carbon polymer.
Detection：
Above-described embodiment 1~5 is prepared into products obtained therefrom and carries out properties detection, the data obtained is as shown in table 1：
Table 1
It is foregoing to the present invention specific illustrative embodiment description be in order to illustrate and illustration purpose.These descriptions
It is not wishing to limit the invention to disclosed precise forms, and it will be apparent that according to above-mentioned teaching, can be much changed
And change.The purpose of selecting and describing the exemplary embodiment is that explaining that the certain principles and its reality of the present invention should
With so that those skilled in the art can realize and using the present invention a variety of exemplaries and
A variety of selections and change.The scope of the present invention is intended to be limited by claims and its equivalents.
Claims (10)
1. a kind of prepare graphene three-dimensional construction method of the powder body material containing carbon polymer, it is characterised in that includes following operation
Step：
(1) polymerized monomer 87%~99%, crosslinkers monomers 0.5%~10%, initiator 0.5% are weighed according to percentage by weight
~3.0%, crosslinkers monomers and initiator monomer are then added in polymerized monomer, stirring produces monomer mixed phase, Ran Houjia
Enter pore-foaming agent, stir；
(2) aqueous solution is added in a kettle., then adds dispersant, it is under conditions of stirring, gained in step (1) is single
Body mixed phase is added drop-wise in reactor, and keeping temperature is 60~95 DEG C and reacted 5~6 hours；
(3) gained mass temperature is down to room temperature after step (2) is reacted, water washing, dehydration, drying, acquisition particle diameter for 0.15~
1.2mm copolymer；
(4) cleaned, then using hydrolytic reagent with the pore-foaming agent contained in the copolymer of gained in extractant removing step (3) again
Gained copolymer is hydrolyzed, washes, dry, graphene three-dimensional construction powder body material is obtained and contains carbon polymer.
2. according to the method described in claim 1, it is characterised in that：Polymerized monomer described in step (1) is styrene (S),
Acrylic acid, acrylonitrile, methyl acrylate, butadiene-styrene rubber/polystyrene/polyacrylic acid N-butyl performed polymer, polyurethane (PU)/poly-
N-butyl acrylic acid (PBMA) performed polymer, hydroxyethyl methacrylate (MEG), double diurethanes (OUDM), three isocyanic acids
Glycol ester, polyethers (polyester) dihydric alcohol, methacrylic acid binaryglycol ester (EGDMA), 2,4 toluene diisocyanate
(TDI) one in/N-butyl acrylic acid (PBMA) performed polymer or polyurethane (PU)/NIPA performed polymer
Plant or more than one mixtures；Wherein, styrene is used as main body monomer.
3. according to the method described in claim 1, it is characterised in that：Cross-linking monomer described in step (1) is divinylbenzene
(DVB), one or more kinds of mixtures in isocyanic acid triallyl (TAIC) or itaconic acid α-allyl ester.
4. according to the method described in claim 1, it is characterised in that：Initiator monomer described in step (1) is benzoyl peroxide first
Acyl (BPO) and/or azo diethyl fourth eyeball.
5. according to the method described in claim 1, it is characterised in that：Pore-foaming agent described in step (1) be toluene, atoleine or
200#One kind in gasoline, consumption is 20~40% of gained monomer mixed phase percentage by weight in step (1).
6. according to the method described in claim 1, it is characterised in that：Dispersant described in step (2) is animal gelatin, polyethylene
One or more kinds of mixtures in alcohol or hydroxyethyl cellulose, consumption accounts for the 0.4 of step (2) reclaimed water solution weight percentage
~6%.
7. according to the method described in claim 1, it is characterised in that：The aqueous solution added in step (2) is single obtained by step (1)
1.25 times of amount of body mixed phase weight.
8. according to the method described in claim 1, it is characterised in that：Keeping temperature described in step (2) is anti-for 60~95 DEG C
Answer be within 5~6 hours keeping temperature be 60 DEG C react 1.5~2 hours, be then warming up to again 95 DEG C be incubated 2.5~4 hours.
9. according to the method described in claim 1, it is characterised in that：Extractant described in step (3) is toluene, ethyl acetate,
One kind in acetone or vapor, consumption is the 300~400% of gained copolymer dry weight percentage by weight.
10. according to the method described in claim 1, it is characterised in that：Step (3) described hydrolytic reagent be diethylenetriamine and/or
Mass concentration is 15~35% sodium hydroxide solution, and consumption is 1.65 times of gained monomer mixed phase weight in step (1).
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