CN105820276B - A kind of preparation method of super High conductivity graphene modified poly (methyl methacrylate) composite material - Google Patents
A kind of preparation method of super High conductivity graphene modified poly (methyl methacrylate) composite material 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
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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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
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/10—Esters
- C08F120/12—Esters of monohydric alcohols or phenols
- C08F120/14—Methyl esters, e.g. methyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
Abstract
The present invention relates to a kind of preparation methods of super High conductivity graphene modified poly (methyl methacrylate) composite material.This method comprises the following steps：（1）The graphite intercalation compound that expanded graphite progress slight oxidation is expanded first（EGIC）；（2）MEGIC after being modified EGIC with silane coupling agent；（3）MEGIC and methyl methacrylate, dibenzoyl peroxide are added in 1 methyl, 2 pyrrolidinone solvent, first stirring at normal temperatures is for a period of time, then reaction temperature is risen to again carries out polymerisation, product is poured into methanol after reaction and centrifuged, washed and is dried in vacuo, the polymethyl methacrylate compound of graphene modification is obtained.In the present invention, when mEGIC contents reach 10 wt%, the glass transition temperature of compound can be improved 18 DEG C than pure polymethyl methacrylate, and elastic storage modulus improves about 300%, and conductivity can reach 1700 S/m or more.
Description
Technical field
The present invention relates to a kind of preparation method of simple graphene/polymer complex, specifically a kind of silanization is light
The preparation method for spending the graphene modified poly (methyl methacrylate) compound of oxidation, belongs to field of nanocomposite materials.
Background technology
Graphene is a kind of two-dimentional carbon nanomaterial of only monoatomic thickness.Because the peculiar property that it has is such as very big
Specific surface area（2630 m2g-1), very high Young's modulus（~1TPa）, pyroconductivity (5100 Wm of superelevation-1K-1) and it is excellent
Good electrical property etc. is favored by many researchers.Graphene by its excellent comprehensive performance make its electronic device,
The fields such as polymer complex have a wide range of applications.Especially in polymer composites field, graphene is at present
As most popular one of high performance material.
However, improvement, the obtained graphene-polymer haveing excellent performance to realization graphene to polymer comprehensive performance
Composite material, the critical issue of core be to solve graphene dispersion in a polymer matrix and graphene and polymer it
Between interfacial interaction.In past many researchs, people usually require to prepare graphene first, then again to graphene into
The various modifications of row are finally carried out with polymer compound again.This preparation method long flow path, it is complicated for operation, and with graphene
The increase of content, the dispersion effect in composite material material significantly deteriorate, this proposes challenge for its actual scale application.
Polymethyl methacrylate（PMMA）It is a kind of widely applied a kind of high molecular material, has fabulous transparent
Property, resistance to ag(e)ing outstanding and desired mechanical strength, and relative low price.In existing a few thing, people
The mechanics and electric property of polymethyl methacrylate are improved with graphene is had been attempted with.Although however, modified
Many performances of PMMA composite materials show improvement trend, but method and process long flow path, complicated for operation mostly, cannot be satisfied work
The actual needs of industry application.The present invention propose it is a kind of it is simple, effectively prepare graphene/polymethyl methacrylate compound
New method, this method need not prepare graphene in advance, but directly use the expanded graphite of silane idol chain agent modification mild oxidation,
And it and MMA are directly subjected to in-situ polymerization, the expanded graphite in composite material can be in subsequent extrusion or mixed process
It is removed and realizes evenly dispersed, greatly simplified the preparation process flow of composite material, also it is enable really to realize
Scale application.In the course of the polymerization process, since there are silane coupled agent molecules on expanded graphite surface, thus MMA can be penetrated into
Enter EGIC interlayers occur interlayer polymerisation, and by MMA EGIC interlayers polymerisation it is spontaneous by EGIC remove at graphite
Alkene, moreover, the stripping of graphene can also it is follow-up squeeze out and mixed process in further be strengthened and be homogenized, thus from root
Solves the problems such as dispersion and processing of the graphene in PMMA in sheet.Further, since part PMMA strands can polymerize
It is grafted on mEGIC in journey, enhances graphene and the interfacial interaction of PMMA, but also the PMMA composite material tables prepared
Reveal excellent mechanics and electrical properties.The technological process that this method prepares PMMA- graphene composite materials is short, easy to operate,
With good actual application value.
Invention content
The purpose of the present invention is to provide a kind of a kind of silanization suboxides journeys can significantly improve PMMA comprehensive performances
Spend the preparation method of graphite modified polymethyl methacrylate compound.
The present invention is the suboxides degree expanded graphite using silanization（mEGIC）Improve PMMA by in-situ polymerization
Performance.When mEGIC contents reach 10 wt%, the glass transition temperature of composite material improves 18 DEG C compared to pure PMMA, elasticity storage
Energy modulus improves about 300%, and conductivity reaches 1719 surprising S/m, is one of highest polymer complex of current conductivity.
The present invention adopts the following technical scheme that realization：
A kind of preparation method of the graphite modified polymethyl methacrylate compound of silanization suboxides degree, specific steps
It is as follows：
（1）1 ~ 3 g expanded graphites are subjected to slight oxidation with 200 ~ 600 mL concentrated sulfuric acids and 1 ~ 3 g strong oxidizers；
（2）By the expanded graphite of slight oxidation（EGIC）It is added to 50 ~ 150 mL deionized waters and 100 ~ 300 mL ethyl alcohol
Mixed solution in stirred evenly at 60 ~ 70 DEG C, obtain the mixed solution of EGIC；By 2.5 ~ 7.5 mL silane coupling agents in pH
Hydrolysis is stirred in the aqueous solution of=4 ~ 5 40 ~ 120 mL；Silane coupler solution after thorough hydrolysis is poured into above-mentioned EGIC's
In mixed solution, is reacted 2 hours at 60 ~ 70 DEG C, finally filter product methanol and water washing to obtain mEGIC.
（3）By mEGIC, methyl methacrylate（MMA）And dibenzoyl peroxide（BPO）It is added in nmp solvent, in
It after stirring a period of time under room temperature, is warming up to 70 ~ 90 DEG C and reacts 7 ~ 12 hours, product is poured into methanol by centrifugation, washing
And vacuum drying, obtain modified PMMA composite materials.Wherein：Methyl methacrylate（MMA）And dibenzoyl peroxide
（BPO）Mass ratio be 100 ~ 300：1.
In the present invention, step（1）Described in expanded graphite be to thermally expand graphite or chemically expansible graphite.
In the present invention, step（1）In oxidant used be potassium permanganate, potassium bichromate, the concentrated sulfuric acid/concentrated nitric acid mixture
（Volume ratio 1-5:1）, potassium ferrate, oxidant and raw material expanded graphite mass ratio are 1-5：1.
In the present invention, step（2）In silane coupling agent used be 3-（Methacryloxypropyl）Propyl trimethoxy silicane
（MPS）, vinyltrimethoxysilane, vinyl three（2- methoxy ethoxies）Silane or vinyltriethoxysilane etc. contain
Have any in the silane coupling agent of double bond.
In the present invention, step（2）In silane coupler solution used a concentration of 0.02 ~ 0.2 g/mL.
In the present invention, step（3）Stirring a period of time refers to stirring 0.1 ~ 10 hour at normal temperatures under middle room temperature.
The beneficial effects of the present invention are：The present invention directly silane coupling agent is modified after slight oxidation expanded graphite
（mEGIC）The polymer composites that in-situ polymerization can be had excellent performance are carried out with MMA.When mEGIC contents reach 10
When wt%, the glass transition temperature of composite material improves 18 DEG C than pure PMMA, and elastic storage modulus improves about 300%, and conductivity is reachable
1700 S/m or more are one of highest polymer composites of current conductivity.The method need not prepare graphene first, make
Standby flow is short, easy to operate, has good industrial application value.
Description of the drawings
Fig. 1 is the expanded graphite of slight oxidation（EGIC）With the heat of the expanded graphite mEGIC after silane coupling agent is modified
It is weightless（TGA）Curve.
Fig. 2（a）、（b）、（c）、（d）、（e）、（f）PMMA composite materials respectively containing 1,4,10 wt% mEGIC and
The ultra-thin section transmission electron microscope picture of PMMA composite materials containing 1,4,10 wt% EGIC.
Fig. 3（a）、（b）PMMA composite materials respectively containing 1,4,10 wt% mEGIC and contain 1,4,10 wt%
The dynamic thermomechanical of the PMMA composite materials of EGIC is analyzed（DMA）Curve.
Specific implementation mode
Following embodiment will the present invention is further illustrated in conjunction with attached drawing.It should be appreciated that these examples are only used for
It is bright the present invention rather than limit the scope of the invention.For those skilled in the art without prejudice to spirit of that invention and protection
The other changes and modifications made in the case of range, are included within the scope of the present invention.
Embodiment 1
It is added in 500 mL three-necked flasks after 2 g expanded graphites, the 350 mL concentrated sulfuric acids, 2g potassium permanganate are mixed,
It is reacted 1 hour at 35 DEG C, obtains the expanded graphite of suboxides degree（EGIC）.
The half of above-mentioned EGIC is taken to be added to three mouthfuls of the mixed solvent containing 50 mL deionized waters and 100 mL ethyl alcohol
In flask, stirred at 62 DEG C.Then 2.5 mL silane coupling agents MPS are added in 40 mL deionized waters of pH=4 and are stirred
Hydrolysis, after MPS has been hydrolyzed, 2 h that are added in the mixed solution of above-mentioned EGIC at 62 DEG C that the reaction was continued.100 mL of product
It is filtered after being washed with 200 mL deionized waters, obtains modified mEGIC
The above-mentioned mEGIC of 0.5 g, 30 g MMA, 0.15 g BPO are added to 500 mL containing 100 mL nmp solvents
In three-necked flask, in 1 h of room temperature and stirred under nitrogen atmosphere.Then, terminate after being warming up to 80 DEG C of 7 h of reaction.It will be produced after reaction
Object pours into 500 mL methanol, there is black solid particle generation.It centrifuges, leaves and takes lower sediment, it is more with ethyl alcohol and water washing
It is after secondary that product is 24 hours dry in 80 DEG C of convection ovens, obtain black powder solid, as target product silane fossil
The PMMA composite materials that black alkene is modified, wherein the content of graphene in the composite is 1 wt%.
Fig. 1 is the thermogravimetric curve of EGIC and mEGIC, it can be seen that since MPS is grafted in the oxygen-containing functional group of EGIC
So that mEGIC initial decomposition temperatures improve 30 DEG C or so.Fig. 2 is electric by the ultra-thin trimming transmission of the modified composite materials of mEGIC
Mirror figure, it can be seen that graphene is well dispersed in the composite.Fig. 3 a are that the DMA of each group mEGIC modified composite materials schemes, can be with
See that, when mEGIC contents are 1 wt%, the storage modulus of composite material increases 26%.
Embodiment 2
It is added in 500 mL three-necked flasks after 2 g expanded graphites, the 350 mL concentrated sulfuric acids, 2 g potassium bichromates are mixed,
It is reacted 1 hour at 35 DEG C, obtains the expanded graphite of mild oxidation（EGIC）.
The half of above-mentioned EGIC is taken to be added to three mouthfuls of the mixed solvent containing 50 mL deionized waters and 100 mL ethyl alcohol
In flask, stirred at 62 DEG C.Then by 2.5 mL silane coupling agents（Vinyltrimethoxysilane）It is added to the 40 of pH=4
Hydrolysis is stirred in mL deionized waters, after silane coupling agent has hydrolyzed, is added in the mixed solution of above-mentioned EGIC at 62 DEG C
The reaction was continued 2 h.Product filters after being washed with 100 mL and 200 mL deionized waters, obtains modified mEGIC
The above-mentioned mEGIC of 0.5 g, 30 g MMA, 0.15 g BPO are added to 500 mL containing 100 mL nmp solvents
In three-necked flask, 4 h are first stirred at normal temperatures, in nitrogen protection.Then, terminate after being warming up to 80 DEG C of 12 h of reaction.It will reaction
Product pours into 500 mL methanol afterwards, there is black solid particle generation.It centrifuges, lower sediment is left and taken, with ethyl alcohol and washing
It is after washing repeatedly that product is 24 hours dry in 80 DEG C of convection ovens, obtain black powder solid, as target product silane
The PMMA composite materials that graphite alkene is modified, wherein the content of graphene in the composite is 1 wt%.
Composite structure performance obtained by the present embodiment is suitable with embodiment 1.
Embodiment 3
1）It is added in 500 mL three-necked flasks after 1g expanded graphites, the 200 mL concentrated sulfuric acids, 1 g potassium permanganate are mixed,
It is reacted 1 hour at 35 DEG C, obtains the expanded graphite of slight oxidation（EGIC）.
2）Above-mentioned EGIC is added in the three-necked flask of the mixed solvent containing 50 mL deionized waters and 100 mL ethyl alcohol,
It is stirred at 62 DEG C.Then by 3 mL silane coupling agents（Vinyl three（2- methoxy ethoxies）Silane）It is added to the 50 of pH=5
In mL deionized waters stir hydrolysis, be added to after silane coupling agent has hydrolyzed in the mixed solution of above-mentioned EGIC at 62 DEG C after
2 h of continuous reaction.After product is washed with 100 mL and 200 mL deionized waters, suction filtration obtains modified mEGIC
3）Tri- mouthfuls of 500 mL containing 100 mL nmp solvents is added in the above-mentioned mEGIC of 1g, 30 g MMA, 0.15 g BPO
In flask, 5 h are stirred in room temperature and nitrogen protection.Then, be warming up to 80 DEG C reaction 7h after reaction was completed.Then, by product
It pours into 500 mL methanol, there is black solid particle generation.It centrifuges, leaves and takes lower sediment, it is multiple with ethyl alcohol and water washing
It is afterwards that product is 24 hours dry in 80 DEG C of convection ovens, obtain black powder solid, as target product silane graphite
Alkene modified PMMA composite material.The content of graphene in the composite is 4 wt%.
The thermogravimetric curve of the present embodiment mEGIC and EGIC are also shown in Fig. 1.The transmission electron microscope results of composite material are as schemed
Shown in 2, it can be seen that graphene has good dispersibility in the composite.The results are shown in Figure 3 by the DMA of composite material, can
To see composite material storage modulus increase about 100%.
Embodiment 4
1）It is added in 500 mL three-necked flasks after 1g expanded graphites, the 200 mL concentrated sulfuric acids, 1 g potassium ferrates are mixed,
It is reacted 1 hour at 35 DEG C, obtains the expanded graphite of slight oxidation（EGIC）.
2）Above-mentioned EGIC is added in the three-necked flask of the mixed solvent containing 50 mL deionized waters and 100 mL ethyl alcohol,
It is stirred at 62 DEG C.Then by 3 mL silane coupling agents（Vinyl three（2- methoxy ethoxies）Silane）It is added to the 50 of pH=5
In mL deionized waters stir hydrolysis, be added to after silane coupling agent has hydrolyzed in the mixed solution of above-mentioned EGIC at 62 DEG C after
2 h of continuous reaction.After product is washed with 100 mL and 200 mL deionized waters, suction filtration obtains modified mEGIC
3）Tri- mouthfuls of 500 mL containing 100 mL nmp solvents is added in the above-mentioned mEGIC of 1g, 30 g MMA, 0.15 g BPO
In flask, 0.1 h is stirred in room temperature and nitrogen protection.Then, be warming up to 80 DEG C reaction 7h after reaction was completed.Then, it will produce
Object pours into 500 mL methanol, there is black solid particle generation.It centrifuges, leaves and takes lower sediment, it is more with ethyl alcohol and water washing
It is after secondary that product is 24 hours dry in 80 DEG C of convection ovens, obtain black powder solid, as target product silane fossil
Black alkene modified PMMA composite material.The content of graphene in the composite is 4 wt%.
The structural behaviour of composite material obtained by the present embodiment is suitable with embodiment 3.
Embodiment 5
1）It is added in 500 mL three-necked flasks after 2g expanded graphites, the 350 mL concentrated sulfuric acids, 2g potassium permanganate are mixed,
It is reacted 1 hour at 35 DEG C, obtains the expanded graphite of suboxides degree（EGIC）.
2）Above-mentioned EGIC is added to the three-necked flask of the mixed solvent containing 50 mL deionized waters and 100 mL ethyl alcohol
In, it is stirred at 62 DEG C.Then by 16 mL silane coupling agents（Vinyltrimethoxysilane）80 mL for being added to pH=5 are gone
Hydrolysis is stirred in ionized water, is added to after silane coupling agent has hydrolyzed in the mixed solution of above-mentioned EGIC and is continued instead at 62 DEG C
Answer 2 h.After product is washed with 100 mL and 200 mL deionized waters, suction filtration obtains modified mEGIC
3）500 mL tri- containing 100 mL nmp solvents are added in the above-mentioned mEGIC of 1.5g, 30 g MMA, 0.15 g BPO
In mouthful flask, in 10 h of room temperature and stirred under nitrogen atmosphere, then heat to after 80 DEG C of reaction 7h that reaction was completed.Then, it will produce
Object pours into 500 mL methanol, there is black solid particle generation.It centrifuges, leaves and takes lower sediment, it is more with ethyl alcohol and water washing
It is after secondary that product is 24 hours dry in 80 DEG C of convection ovens, obtain black powder solid, as target product silane fossil
The PMMA composite materials that black alkene is modified.The content of graphene in the composite is 10 wt%.
The thermogravimetric curve of the present embodiment mEGIC and EGIC are as shown in Figure 1.The transmission electron microscope results of composite material such as Fig. 2
It is shown, it can be seen that graphene is slightly assembled in the composite.The results are shown in Figure 3 by the DMA of composite material, and storage modulus increases
Add about 300%.
Embodiment 6
1）It is added in 500 mL three-necked flasks after 2g expanded graphites, the 300 mL concentrated sulfuric acids, 50 mL concentrated nitric acids are mixed,
It is reacted 1 hour at 55 DEG C, obtains the expanded graphite of suboxides degree（EGIC）.
2）Above-mentioned EGIC is added to the three-necked flask of the mixed solvent containing 50 mL deionized waters and 100 mL ethyl alcohol
In, it is stirred at 62 DEG C.Then by 5 mL silane coupling agents（Vinyltriethoxysilane）Be added to pH=5 80 mL go from
Hydrolysis is stirred in sub- water, is added in the mixed solution of above-mentioned EGIC that the reaction was continued at 62 DEG C after silane coupling agent has hydrolyzed
2 h.After product is washed with 100 mL and 200 mL deionized waters, suction filtration obtains modified mEGIC
3）500 mL tri- containing 100 mL nmp solvents are added in the above-mentioned mEGIC of 1.5g, 30 g MMA, 0.15 g BPO
In mouthful flask, in 6 h of room temperature and stirred under nitrogen atmosphere, then heat to after 80 DEG C of reaction 7h that reaction was completed.Then, by product
It pours into 500 mL methanol, there is black solid particle generation.It centrifuges, leaves and takes lower sediment, it is multiple with ethyl alcohol and water washing
It is afterwards that product is 24 hours dry in 80 DEG C of convection ovens, obtain black powder solid, as target product silane graphite
The PMMA composite materials that alkene is modified.The content of graphene in the composite is 10 wt%.
Composite structure and performance obtained by the present embodiment are suitable with embodiment 5.
Comparative example 1
It is added in 500 mL three-necked flasks after 2 g expanded graphites, the 350 mL concentrated sulfuric acids, 2g potassium permanganate are mixed,
It is reacted 1 hour at 35 DEG C, obtains the expanded graphite of suboxides degree（EGIC）.
The above-mentioned unmodified EGIC of 0.5 g, 30 g MMA, 0.15 g BPO are added to containing 100 mL nmp solvents
500 mL three-necked flasks in, in 4 h of room temperature and stirred under nitrogen atmosphere, then heat to after 80 DEG C of 7 h of reaction that reaction was completed.
Then product is poured into 500 mL methanol, there is black solid particle generation.Centrifuge, leave and take lower sediment, with ethyl alcohol and
It is after water washing is multiple, product is 24 hours dry in 80 DEG C of convection ovens, black powder solid is obtained, as graphene changes
Property PMMA composite materials, wherein the content of graphene be 1 wt%.
The thermogravimetric curve of the present embodiment mEGIC and EGIC are also as shown in Figure 1.The transmission electron microscope knot of composite material
Fruit is as shown in Figure 2, it can be seen that the dispersion of graphene in the composite is obviously not as good as composite material modified mEGIC.This is
Because unmodified EGIC, which is unfavorable for MMA, enters the reaction of EGIC interlayers, thus can not realize the stripping of graphene well.It is multiple
The results are shown in Figure 3 by the DMA of condensation material, it can be seen that compound storage modulus is not substantially change.
Comparative example 2
1）It is added in 500 mL three-necked flasks after 1 g expanded graphites, the 200 mL concentrated sulfuric acids, 1 g potassium permanganate are mixed,
It is reacted 1 hour at 35 DEG C, obtains the expanded graphite of mild oxidation（EGIC）.
2）The above-mentioned unmodified EGIC of 1g, 30 g MMA, 0.15 g BPO additions are contained into 100 mL nmp solvents
In 500 mL three-necked flasks, in 5 h of room temperature and stirred under nitrogen atmosphere, then heat to after 80 DEG C of 7 h of reaction that reaction was completed.With
Afterwards, product is poured into 500 mL methanol, there is black solid particle generation.It centrifuges, lower sediment is left and taken, with second alcohol and water
It is after washing repeatedly that product is 24 hours dry in 80 DEG C of convection ovens, obtain black powder solid, as target product stone
The PMMA composite materials that black alkene is modified, wherein the content of graphene is 4 wt%.
The thermogravimetric curve of the present embodiment mEGIC and EGIC are as shown in Figure 1.The transmission electron microscope of PMMA composite materials
The results are shown in Figure 2, it can be seen that the dispersion of graphene in the composite is obviously not as good as composite material modified mEGIC.This
It is because unmodified EGIC is unfavorable for MMA and enters the reaction of EGIC interlayers, thus cannot achieve the abundant stripping to EGIC.
The DMA data of PMMA composite materials is as shown in Figure 3, it can be seen that compound storage modulus increase about 58%.
Comparative example 3
1）It is added in 500 mL three-necked flasks after 2 g expanded graphites, the 350 mL concentrated sulfuric acids, 2 g potassium permanganate are mixed,
It is reacted 1 hour at 35 DEG C, obtains the expanded graphite of mild oxidation（EGIC）.
2）The above-mentioned unmodified EGIC of 1.5 g, 30 g MMA, 0.15 g BPO are added and contain 100 mL nmp solvents
500 mL three-necked flasks in, in 6 h of room temperature and stirred under nitrogen atmosphere, then heat to after 80 DEG C of 7 h of reaction that reaction was completed.
Then, product is poured into 500 mL methanol, there is black solid particle generation.Centrifuge, leave and take lower sediment, with ethyl alcohol and
It is after water washing is multiple that product is 24 hours dry in 80 DEG C of convection ovens, obtain black powder solid, as target product
The PMMA composite materials that graphene is modified, wherein the content of graphene is 10 wt%.
The thermogravimetric curve of the present embodiment mEGIC and EGIC are as shown in Figure 1.The transmission electron microscope of PMMA composite materials
The results are shown in Figure 2, it can be seen that the dispersion of graphene in the composite is obviously not as good as composite material modified mEGIC.
This is because unmodified EGIC, which is unfavorable for MMA, enters the reaction of EGIC interlayers, thus the generation of EGIC cannot fully be removed
Effect.The DMA data of PMMA composite materials is as shown in Figure 3, it can be seen that compound storage modulus increases by 108%.
Claims (6)
1. a kind of preparation method of super High conductivity graphene modified poly (methyl methacrylate) composite material, which is characterized in that
It is as follows：
（1）By 1 ~ 3 g expanded graphites 200 ~ 600 mL concentrated sulfuric acids and oxidant slight oxidation；
（2）By the expanded graphite after slight oxidation（EGIC）It is added to 50 ~ 150 mL deionized waters and 100 ~ 300 mL ethanol groups
At mixed solution in, stirred evenly at 60 ~ 70 DEG C, obtain the mixed solution of EGIC；By the silane coupled of 2.5 ~ 7.5 mL
Hydrolysis is stirred in agent in the aqueous solution of 40 ~ 120 mL of pH=4 ~ 5, then pours into the silane coupler solution after thorough hydrolysis
The reaction was continued 2 hours at 60 ~ 70 DEG C in the mixed solution of the EGIC, and product methanol and water washing are filtered, silicon is obtained
Siloxane modified expanded graphite（mEGIC）；
（3）By step（2）Obtained mEGIC, methyl methacrylate（MMA）And dibenzoyl peroxide（BPO）It is added to N-
Methyl pyrrolidone（NMP）In solvent, and a period of time is stirred under room temperature, reacted 7 ~ 12 hours after being warming up to 70 ~ 90 DEG C, it will
Product, which is poured into methanol, to be centrifuged, is washed and vacuum drying treatment, and modified PMMA compounds are obtained；It is multiple in gained PMMA
It closes in object, the mass fraction that mEGIC accounts for entire PMMA compounds is 1% ~ 10%, methyl methacrylate and diphenyl peroxide first
Acyl mass ratio is 100 ~ 300：1.
2. according to the method described in claim 1, it is characterized in that step（1）Described in expanded graphite be to thermally expand graphite or change
Learn expanded graphite.
3. according to the method described in claim 1, it is characterized in that step（1）In oxidant used be potassium permanganate, dichromic acid
Potassium, volume ratio 1:It is any in 1 concentrated sulfuric acid/concentrated nitric acid mixture or potassium ferrate, oxidant and raw material expanded graphite matter
Amount is than being (1-5)：1.
4. according to the method described in claim 1, it is characterized in that step（2）In silane coupling agent used be 3-（Metering system
Acyl-oxygen）Propyl trimethoxy silicane（MPS）, vinyltrimethoxysilane, vinyl three（2- methoxy ethoxies）Silane or
It is any in vinyltriethoxysilane.
5. according to the method described in claim 1, it is characterized in that step（2）In silane coupler solution used it is a concentration of
0.02 ~0.2 g/mL。
6. according to the method described in claim 1, it is characterized in that step（3）Stirring a period of time is at normal temperatures under middle room temperature
Stirring 0.5 ~ 6 hour.
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| PCT/CN2017/082040 WO2017186127A1 (en) | 2016-04-26 | 2017-04-26 | Method for preparing graphene-modified polymethyl methacrylate composite material having ultra-high conductivity |
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| CN105820276B (en) * | 2016-04-26 | 2018-08-07 | 复旦大学 | A kind of preparation method of super High conductivity graphene modified poly (methyl methacrylate) composite material |
| CN111777728B (en) * | 2020-07-10 | 2022-06-03 | 陕西科技大学 | Preparation method of graphene oxide reinforced polymethyl methacrylate/carbon microsphere composite material |
| CN114478935A (en) * | 2020-11-12 | 2022-05-13 | 中国石油化工股份有限公司 | Temperature-resistant salt-resistant shape memory material particle system and preparation method thereof |
| CN113399117B (en) * | 2021-06-02 | 2023-12-19 | 杭州诗蓝过滤科技有限公司 | Progressive dust-holding electrostatic filter cotton with good adsorption performance |
| CN114636775B (en) * | 2022-03-02 | 2024-03-29 | 中国检验检疫科学研究院 | Separation and ionization integrated extraction device for carbamate compounds and application thereof |
| CN114685995B (en) * | 2022-05-16 | 2023-03-14 | 慈溪埃弗龙密封件有限公司 | High-strength graphite composite gasket for condenser and preparation method thereof |
| CN114989467A (en) * | 2022-07-22 | 2022-09-02 | 中山大学 | Ultrahigh molecular weight polyethylene/graphite composite material and preparation method thereof |
| CN115559131B (en) * | 2022-08-08 | 2023-11-07 | 浙江圣山科纺有限公司 | Thermochromic cooling heat-resistant fabric and preparation method thereof |
| CN116519493B (en) * | 2023-05-06 | 2024-01-19 | 天津大学 | High-temperature creep vacuum/atmosphere environment device |
| CN116884698B (en) * | 2023-07-11 | 2024-01-19 | 广东万东伟业电线电缆有限公司 | Network cable for monitoring equipment and preparation process thereof |
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| CN105273114B (en) * | 2015-11-23 | 2018-10-16 | 复旦大学 | A kind of preparation method of suboxides degree graphene modified poly (methyl methacrylate) composite material |
| CN105820276B (en) * | 2016-04-26 | 2018-08-07 | 复旦大学 | A kind of preparation method of super High conductivity graphene modified poly (methyl methacrylate) composite material |
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