CN109694549A - A kind of preparation method of Graphene epoxy resin composite material - Google Patents
A kind of preparation method of Graphene epoxy resin composite material Download PDFInfo
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- CN109694549A CN109694549A CN201710990252.7A CN201710990252A CN109694549A CN 109694549 A CN109694549 A CN 109694549A CN 201710990252 A CN201710990252 A CN 201710990252A CN 109694549 A CN109694549 A CN 109694549A
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- epoxy resin
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- graphite
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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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
Abstract
The invention belongs to technical field of composite materials, more particularly to a kind of preparation method of Graphene epoxy resin composite material, it is fully ground in mechano-chemical reation dress device this method comprises: graphite-like raw material is added in epoxy resin, so that graphite flake layer is removed to obtain graphene using power chemistry and evenly dispersed forms slurry in the epoxy, later by the slurry and curing agent bubble removing after mixing, directly structural member can be used as by curing molding when using, it can also be compound with carbon fiber or as adhesive.The excellent in mechanical performance of the composite material, the epoxide resin material performance for comparing not containing graphene are greatly improved, and the technology of preparing route of composite material is simple, do not use organic solvent, pollution is small, low in cost.
Description
Technical field
The present invention relates to a kind of manufacturing process of composite material, belong to epoxy resin composite material technical field, specifically relate to
And a kind of preparation method of Graphene epoxy resin composite material.
Background technique
Epoxy resin is the organic compound referred in molecule containing epoxy group, is contained in epoxy molecule structure
Active epoxide group can be crosslinked with curing agent reacts and forms the insoluble high polymer with three-dimensional network.Epoxy resin
It is a kind of big, cheap, widely used one of the high molecular material of yield, there is high intensity, insulation, fire-retardant, corrosion-resistant etc.
Excellent performance is widely used in the fields such as national defence, electronics, binder and communication.However epoxide resin material is due to crosslink density
Height, poor toughness are easy cracking, so as to cause practical application failure.
Graphene is a kind of two-dimensional layer material being made of carbon atom.It is the most thin and tough material being currently known
Material, 200 times more taller than steel of breaking strength.Therefore in field of compound material, graphene is used frequently as nanofiller to mention
The mechanical property of high composite material.
But in the preparation process of current Graphene epoxy resin composite material, often first with physics or change
Method prepares graphene, later again by the graphene dispersion prepared into solvent and epoxy resin and curing agent mixing,
Solidify after removing solvent after being uniformly dispersed.Such preparation process is cumbersome in addition to graphene preparation process, need to expend a large amount of water,
Outside solvent or energy, solvent is also difficult completely out, and remaining solvent will form product defect and cause product quality problem.
Graphene microchip and organic solvent are mixed to get dispersion liquid by patent application CN106009514A, point obtained later
Dispersion liquid mixes again with epoxy resin, and mixed liquor is carried out vacuum revolving to remove organic solvent, will finally remove the mixed of solvent
It closes and curing agent reconciliation is added in object, resolidification obtains Graphene epoxy resin composite material.This method is removed using vacuum revolving
Solvent, although most of solvent can be removed, as the abjection system viscosity of solvent rises, some inevitable solvent is difficult to
It is removed to influence the performance of cured product.Patent application CN106751522A, which mixes graphene oxide and dehydroabietic acid, to be divided
It is scattered in solvent, cosolvent is removed by evaporation, graphene oxide dehydroabietic acid powder is obtained, by graphene oxide/dehydrogenation fir
Sour powder, which is placed in graphene oxide reducing agent, to be reacted, and obtains graphene/dehydroabietic acid powder, then by graphene/dehydrogenation
Abietic acid powder is reacted to obtain graphene/abietyl polyamine with polyamine；By graphene/abietyl polyamine and asphalt mixtures modified by epoxy resin
Rouge progress is mixing cured to obtain graphene/epoxy resin composite material.This method in order to be uniformly dispersed still used it is a large amount of molten
Agent, although solvent is possible to remove more clean, technical process is excessively cumbersome and complicated, the cost undoubtedly greatly improved.Specially
Mechanical stripping is blended in carbon materials and inorganic solid particles and liquid-working-medium ternary system by benefit application CN101857221A
Graphene is removed into a liquid from by carbon materials, is removed liquid medium later and is obtained the composite wood of graphene and solid particle
Material.The effect of this method is maximum the problem still exists in liquid medium is solvent, need to finally remove liquid after the completion of graphite removing
Body medium, and remove the solvent greatest problem that exactly graphene application link is faced.
About by graphite-like raw material, direct mechanical stripping is at graphene and evenly dispersed in the epoxy, later and epoxy
Resin curing agent mixing, solidification preparation Graphene epoxy resin composite material are not all appeared in the newspapers at home and abroad.
Summary of the invention
The purpose of the present invention is to provide a kind of Graphene epoxy resin composite materials and preparation method thereof, can effectively solve
Certainly poly- graphene disperses difficult problem in the epoxy.Graphite or expanded graphite are from a wealth of sources, cheap；Mechanical force and chemical
Operation is simple, green non-pollution.Also, mechanical force and chemical process can sufficiently remove graphite-like raw material into graphene and equal
It is even to disperse in the epoxy, and epoxy molecule serves as protectant effect during mechanical force and chemical, prevents from removing
The graphene film opened is milled to amorphous carbon easily.Therefore, the present invention will significantly improve Graphene epoxy resin composite material
Mechanical property.
Technical scheme is as follows:
The preparation method of Graphene epoxy resin composite material of the invention, comprising the following steps:
(1) by graphite-like raw material and epoxy blend, mechanical stripping is carried out to graphite-like raw material, is prepared and uniformly divides
Scattered graphene epoxy resin slurry；
(2) graphene epoxy resin slurry obtained above and epoxy curing agent are blended, are sufficiently mixed rear degasification
Graphene epoxy resin composite material is made in bubble.
Preparation method according to the present invention, wherein the graphite-like raw material, including crystalline flake graphite, expanded graphite
And expansible graphite.
Preparation method according to the present invention, wherein the epoxy resin is the epoxy for being under room temperature liquid
The mixture of one or more of resin.For example, it may be but being not limited to bisphenol A type epoxy resin, bisphenol F type epoxy tree
Rouge, bisphenol-s epoxy resin, halogenated epoxy resin, glycerol epoxy resin, organotitanium epoxy resin and cycloaliphatic epoxy resin etc..
Preparation method according to the present invention, wherein the mechanical stripping in mechano-chemical reation device into
Row, wherein the mechano-chemical reation device includes planetary ball mill, abrasive disk type Mechanico-chemical reactor or co-vibration mill.
It is further preferred that step (1) is carried out mechanical stripping 2~48 hours using planetary type ball-milling or co-vibration mill, alternatively,
It is carried out mechanical stripping 10~100 times using abrasive disk type co-vibration mill.
Preparation method according to the present invention, wherein the epoxy curing agent include acid anhydride type curing agent and/
Or amine curing agent.Acid anhydride type curing agent can be, but not limited to phthalic anhydride, trimellitic anhydride, maleic anhydride,
One or more of methyl tetrahydro phthalic anhydride, methyl tetrahydro phthalate anhydride, methyl hexahydrophthalic acid anhydride etc..The amine is solid
Agent can be, but not limited to ethylenediamine, diethylenetriamines, diethyl toluene diamine (DETD), m-phenylene diamine (MPD), diamino hexichol
One or more of methane, diaminodiphenylsulfone, dicyandiamide etc..
Preparation method according to the present invention, wherein preferably, the graphite-like raw material is epoxy resin and asphalt mixtures modified by epoxy resin
0.2wt%~2.5wt% of rouge curing agent gross mass.
Preparation method according to the present invention, wherein the weight ratio of the epoxy resin and curing agent is by epoxy
The amount of required curing agent is calculated in the epoxide number of resin, and specifically, the calculation formula is as follows:
100g epoxy resin needs amine curing agent dosage=curing agent molecular weight * epoxide number/active hydrogen number
100g epoxy resin needs acid anhydride type curing agent dosage=k* curing agent molecular weight * epoxide number, wherein K is preferably
0.5~1.1 empirical value, further preferably 0.85.
Preparation method according to the present invention, wherein Graphene epoxy resin composite material produced by the present invention makes
Used time directly can be used as structural member by curing molding, can also be compound with carbon fiber or as adhesive.
When traditionally, using graphene reinforced epoxy composite material, usually first by graphene raw material and asphalt mixtures modified by epoxy resin
Rouge is distributed to respectively in organic solvent of the same race, later by two kinds of solution blendings, is vacuumized removing organic solvent later, is made graphene
It is dispersed in epoxy-resin systems, adds curing agent or straight forming later, or is compound or as gluing with carbon fiber
Agent uses.The most important problem of this technical process is to need using a large amount of solvent, and later period solvent completely removes very
Difficulty, even if minimal amount of solvent will also result in the defect of material, to influence final performance.And the present invention is by graphene
Preparation and dispersion carry out simultaneously in the epoxy, and do not use organic solvent completely, therefore not only technical process is simple, product
Performance is high, and environmentally protective.
Method of the invention has the advantages that
1, technical solution provided by the invention is using epoxy resin as the dispersing agent of graphene and protective agent, by graphene
Preparation and dispersion at the same carry out.
2, technical solution provided by the invention avoids chemistry using the method preparation of mechanical force and chemical and dispersed graphite alkene
High temperature needed for method prepares a large amount of acid and oxidant and CVD method preparation required for graphene, energy conservation and environmental protection.
3, technical solution provided by the invention is avoided graphene dispersion into epoxy-resin systems frequently in technique
Used a large amount of organic solvents, it is environmentally protective.
4, technical solution provided by the invention, simple process are environmental-friendly.
Detailed description of the invention
Fig. 1 is 400 times of scanning electron microscope enlarged drawings of crystalline flake graphite in embodiment 1.
Fig. 2 is that crystalline flake graphite is stripped into the transmission electron microscope photo after graphene in embodiment 1.
Fig. 3 is 3500 times of scanning electron microscope enlarged drawings of expanded graphite in embodiment 2.
Specific embodiment
The present invention is further explained in the light of specific embodiments.
Embodiment 1
0.2516g graphite (Fig. 1) and 100g bisphenol f type epoxy resin DER354 epoxy resin are mixed, are added planetary
In ball grinder, abundant ball milling 12 hours obtains thick slurry.Obtained slurry and 25.8gDETD curing agent are mixed, in height
It is sufficiently mixed in fast blender, removes bubble.Obtained mixture of viscous form is poured curing molding.A small amount of slurry is taken to be distributed to
In acetone, sample preparation is under transmission electron microscope it has been observed that graphite is stripped into graphene film (Fig. 2).
Embodiment 2
4g expanded graphite (Fig. 3) and 100g bisphenol A type epoxy resin E51 are mixed, are added in disc mill, mill 30 times,
Obtain thick slurry.Obtained slurry and 100g curing agent methyl tetrahydro phthalic anhydride are mixed, it is sufficiently mixed in high-speed mixer
It closes, removes bubble.Obtained mixture of viscous form is poured curing molding.
Embodiment 3
0.5325g graphite and 100g bisphenol A type epoxy resin E44 epoxy resin are mixed, are added in co-vibration mill, is sufficiently shaken
Dynamic removing 24 hours, obtains thick slurry.Obtained slurry and 6.5g ethylenediamine curing agent are mixed, in high-speed mixer
It is sufficiently mixed, removes bubble.Obtained mixture of viscous form is poured curing molding.
Embodiment 4
1.68g expanded graphite and 100g bisphenol A type epoxy resin E54 are mixed, it is small that ball milling 6 in planetary ball mill is added
When, obtain thick slurry.Obtained slurry and 67.98g phthalic acid anhydride curing agents are mixed, filled in high-speed mixer
Divide mixing, removes bubble.Obtained mixture of viscous form is poured curing molding.
Certainly, the present invention can also there are many embodiments, without deviating from the spirit and substance of the present invention, are familiar with
Those skilled in the art can disclosure according to the present invention make various corresponding changes and modification, but these it is corresponding change and
Deformation all should fall within the scope of protection of the appended claims of the present invention.
Claims (9)
1. a kind of preparation method of Graphene epoxy resin composite material, comprising the following steps:
(1) by graphite-like raw material and epoxy blend, mechanical stripping is carried out to graphite-like raw material, is prepared evenly dispersed
Graphene epoxy resin slurry；
(2) graphene epoxy resin slurry obtained above and epoxy curing agent are blended, are sufficiently mixed rear bubble removing, made
Obtain Graphene epoxy resin composite material.
2. preparation method according to claim 1, which is characterized in that the graphite-like raw material, including it is crystalline flake graphite, swollen
Swollen graphite and expansible graphite.
3. preparation method according to claim 1, which is characterized in that the epoxy resin be under room temperature be liquid
One or more of epoxy resin.
4. preparation method according to claim 3, which is characterized in that the epoxy resin is bisphenol A epoxide resin, bis-phenol
F epoxy resin, bisphenol-s epoxy resin, halogenated epoxy resin, glycerol epoxy resin, organotitanium epoxy resin and alicyclic epoxy
The mixture of one or more of resin.
5. preparation method according to claim 1, which is characterized in that the graphite-like raw material is epoxy resin and asphalt mixtures modified by epoxy resin
0.2wt%~2.5wt% of rouge curing agent gross mass.
6. preparation method according to claim 1, which is characterized in that the mechanical stripping is filled in mechano-chemical reation
Set interior progress, wherein the mechano-chemical reation device includes planetary ball mill, abrasive disk type Mechanico-chemical reactor or resonance
Mill.
7. preparation method according to claim 6, which is characterized in that step (1) using planetary type ball-milling or co-vibration mill into
Row mechanical stripping 2~48 hours, alternatively, being carried out mechanical stripping 10~100 times using abrasive disk type co-vibration mill.
8. a kind of Graphene epoxy resin composite material according to claims 1 and preparation method thereof, which is characterized in that institute
The epoxy curing agent stated includes acid anhydride type curing agent and/or amine curing agent.
9. a kind of Graphene epoxy resin composite material according to claims 1 and preparation method thereof, which is characterized in that institute
The amount of required curing agent is calculated by the epoxide number of epoxy resin for the weight ratio of the epoxy resin and curing agent stated.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710990252.7A CN109694549A (en) | 2017-10-23 | 2017-10-23 | A kind of preparation method of Graphene epoxy resin composite material |
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| CN201710990252.7A CN109694549A (en) | 2017-10-23 | 2017-10-23 | A kind of preparation method of Graphene epoxy resin composite material |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110963491A (en) * | 2019-12-24 | 2020-04-07 | 沈阳航空航天大学 | Graphene precursor and preparation method and application thereof |
| CN111560207A (en) * | 2020-05-14 | 2020-08-21 | 哈尔滨鑫科纳米科技发展有限公司 | Biological adhesion-preventing nontoxic nano coating and preparation method thereof |
| CN111592815A (en) * | 2020-05-14 | 2020-08-28 | 哈尔滨鑫科纳米科技发展有限公司 | Multifunctional weld joint anticorrosive paint and preparation method thereof |
| CN111748063A (en) * | 2020-06-05 | 2020-10-09 | 薛俊峰 | Graphene resin and preparation method thereof |
| CN113088037A (en) * | 2021-04-13 | 2021-07-09 | 珠海昌意新材料科技有限公司 | Heat dissipation material with high heat conductivity coefficient and high radiation coefficient and preparation method thereof |
| WO2022185344A1 (en) * | 2021-03-05 | 2022-09-09 | Log 9 Materials Scientific Pvt. Ltd. | A system and method for synthesizing low-cost epoxy composites for electromagnetic interference shielding applications |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110963491A (en) * | 2019-12-24 | 2020-04-07 | 沈阳航空航天大学 | Graphene precursor and preparation method and application thereof |
| CN110963491B (en) * | 2019-12-24 | 2022-02-01 | 沈阳航空航天大学 | Graphene precursor and preparation method and application thereof |
| CN111560207A (en) * | 2020-05-14 | 2020-08-21 | 哈尔滨鑫科纳米科技发展有限公司 | Biological adhesion-preventing nontoxic nano coating and preparation method thereof |
| CN111592815A (en) * | 2020-05-14 | 2020-08-28 | 哈尔滨鑫科纳米科技发展有限公司 | Multifunctional weld joint anticorrosive paint and preparation method thereof |
| CN111748063A (en) * | 2020-06-05 | 2020-10-09 | 薛俊峰 | Graphene resin and preparation method thereof |
| WO2022185344A1 (en) * | 2021-03-05 | 2022-09-09 | Log 9 Materials Scientific Pvt. Ltd. | A system and method for synthesizing low-cost epoxy composites for electromagnetic interference shielding applications |
| CN113088037A (en) * | 2021-04-13 | 2021-07-09 | 珠海昌意新材料科技有限公司 | Heat dissipation material with high heat conductivity coefficient and high radiation coefficient and preparation method thereof |
| CN113088037B (en) * | 2021-04-13 | 2022-11-11 | 珠海昌意新材料科技有限公司 | Heat dissipation material with high heat conductivity coefficient and high radiation coefficient and preparation method thereof |
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Application publication date: 20190430 |