CN106479110A - A kind of preparation method of heat-conductivity conducting graphene composite material - Google Patents
A kind of preparation method of heat-conductivity conducting graphene composite material Download PDFInfo
- Publication number
- CN106479110A CN106479110A CN201610928372.XA CN201610928372A CN106479110A CN 106479110 A CN106479110 A CN 106479110A CN 201610928372 A CN201610928372 A CN 201610928372A CN 106479110 A CN106479110 A CN 106479110A
- Authority
- CN
- China
- Prior art keywords
- heat
- composite material
- graphene
- conductivity conducting
- graphene composite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
-
- 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
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/06—Elements
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/08—Materials not undergoing a change of physical state when used
- C09K5/14—Solid materials, e.g. powdery or granular
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The present invention discloses a kind of preparation method of heat-conductivity conducting graphene composite material, comprises the steps：Resin, Graphene and other Carbon Materials are dissolved in solvent mixture A is obtained；Mixture A is carried out with high pressure homogenize process to wherein no granule, prepared mixture B；Mixture B is dried with process, removes solvent therein, prepared heat-conductivity conducting graphene composite material.Resin, Graphene and Carbon Materials are carried out high efficiency dispersion and mixing under solution state by the present invention, thus obtaining graphene uniform dispersion have preferable heat-conductivity conducting and the polymer composite of good mechanical performance.
Description
Technical field
The invention belongs to field of composite material preparation, it is more particularly to a kind of preparation of heat-conductivity conducting graphene composite material
Method.
Background technology
Graphene has larger specific surface area, higher thermal conductivity and electrical conductivity and excellent mechanical property, by stone
Black alkene is added in high polymer as functional stuffing or additive, can improve the thermal and electric conductivity properties of polymer.But in graphite
Find in the application process of alkene, Graphene easily occurs to reunite and is difficult to be dispersed into well in composite.Conventional by stone
In the composite that black alkene, resin and auxiliary agent are prepared through mechanical fusion mixing method, Graphene is unable to reach good dispersion, its
Result causes the excellent physical property of Graphene can not fully play, and the mechanical performance of composite is affected simultaneously.Separately
There is outward the method for some common chemical grafts to grapheme material modifying surface it is intended that improving Graphene in polyphosphazene polymer
Dispersibility in compound, but this method often destroys the crystal structure of Graphene, thus have impact on the entirety of composite
Performance.
Content of the invention
It is an object of the invention to provide a kind of not only can improve dispersive property in high polymer for the Graphene but also will not destroy
The preparation technology of the heat-conductivity conducting graphene composite material of the crystal structure of Graphene.
According to an aspect of the invention, it is provided a kind of preparation method of heat-conductivity conducting graphene composite material, including
Following steps：
Resin, Graphene and other Carbon Materials are dissolved in solvent mixture A is obtained；
Mixture A is carried out with high pressure homogenize process to wherein no granule, prepared mixture B；
Mixture B is dried with process, removes solvent therein, prepared heat-conductivity conducting graphene composite material.
According to another aspect of the present invention, there is provided a kind of preparation method of heat-conductivity conducting graphene composite material, wrap
Include following steps：
Graphene and/or resin are carried out pretreatment, it is ultrasonic that the pretreatment of Graphene is included with infiltration, intercalation, premix,
Pretreatment to resin includes chemical graft, modified and modification；
Resin, Graphene and other Carbon Materials are dissolved in solvent mixture A is obtained；
Mixture A is reprocessed, reprocessing includes sand milling, nanorize, filtration；
The mixture A carrying out reprocessing is carried out with high pressure homogenize process to wherein no granule, prepared mixture B；
Mixture B is dried with process, removes solvent therein, prepared heat-conductivity conducting graphene composite material.
In some embodiments, resin is the resin containing phenyl ring, and the resin containing phenyl ring is selected from Merlon, gathers to benzene two
One of formic acid diethyl alcohol ester, acrylonitrile-butadiene-styrene copolymer, polyether sulfone, polyphenylene sulfide and polyether-ketone or many
Kind.
In some embodiments, solvent be selected from water, ethanol, methanol, dimethylformamide, N-Methyl pyrrolidone, third
One or more of ketone, ethyl acetate, dimethyl carbonate, oxolane, dichloromethane and chloroform.
In some embodiments, other Carbon Materials are selected from one of white carbon black, graphite, carbon fiber and CNT or many
Kind.
In some embodiments, resin and the mass ratio of solvent are 2:1-1:30.
In some embodiments, heat-conductivity conducting graphene composite material includes the stone that mass percent is 0.5%-30%
Black alkene.
In some embodiments, surfactant or coupling agent, surfactant or coupling agent are also included in mixture A
Mass percent with Graphene is 0.1%-10%.
In some embodiments, high pressure homogenize process pressure be 500-2000Bar, high pressure homogenize process time be
10-300 minute.
In some embodiments, dried includes high temperature drying drying or/and drying at room temperature or/and cold drying
Or/and aeration-drying or/and vacuum drying or/and supercritical drying, the time of dried is 6-48 hour.
Its advantage is：The present invention carries out pretreatment to raw material first, by resin, Graphene and Carbon Materials in solution
Carry out high efficiency dispersion and mixing, thus obtaining graphene uniform dispersion there is preferable heat-conductivity conducting and good machine under state
The polymer composite of tool performance.
Pretreatment is carried out to Graphene and resin, the resistance that graphene dispersion enters resin can be reduced, increase Graphene
Adhesion with interlaminar resin.
Mixture A is reprocessed it is ensured that no granule and bubble is so that resin, Graphene and other Carbon Materials exist in slurry
Evenly, slurry more refines solvent dispersion.
Graphene has similar benzene ring structure, and according to similar compatibility principle, Graphene is easy in the resin solution containing phenyl ring
Compatible with dispersion.
Aqueous solvent, ethanol, methanol, dimethylformamide, N-Methyl pyrrolidone, acetone, ethyl acetate, carbonic acid diformazan
Ester, oxolane and dichloromethane and chloroform enable resin, Graphene, Carbon Materials to be more easy to make mixed liquor.
Using the synergism of other Carbon Materials white carbon blacks, graphite, carbon fiber and CNT and Graphene, preferably play
The superiority of Graphene.
Mass ratio is 2:1-1:30 resin is beneficial to the dissolving of resin and the dispersion of Graphene with solvent.
Heat-conductivity conducting graphene composite material includes the Graphene that mass percent is 0.5%-30%.
Based on grapheme material bulk density is little and the big feature of specific surface area, Graphene accounted for heat-conductivity conducting Graphene and is combined
The mass percent of material controls within 0.5%-30%, both can guarantee that the performance of Graphene is played, by can prevent set
Fat becomes powder not have mechanical performance value.
The addition of the surfactant of 0.1%-10% or coupling agent can make dispersion in organic media for the Graphene more
Uniformly, and increased the compatibility between Graphene and polymer and adhesion in composite.
The present invention makes the Graphene of reunion and other Carbon Materials solution coalescences be distributed to and contain by the process for dispersing of high pressure homogenize
Phenyl ring, in the liquid resin of pretreatment.Under the external force of high pressure acts on, graphene layer intermolecular forces are weakened, simultaneously
The model ylid bloom action power of the hexagonal structure by Graphene and the interlaminar resin containing phenyl ring is so that be originally in the stone of aggregating state
Black alkene gradually realizes depolymerization, reaches good dispersity, then forms uniform and stable heat transfer network, makes prepared being combined
Material conducts heat is uniform.
Specific embodiment
Embodiment one
50g acrylonitrile-butadiene-styrene copolymer is put in 300g dimethyl carbonate, the above-mentioned mixing of ultrasonic agitation
Thing 2h, is completely dissolved to acrylonitrile-butadiene-styrene copolymer.Add the graphene powder of 1.85g, the Carbon fibe of 3.7g
Powder, is filtered after ultrasonic homogenizing stirring 2h.After mixed liquor is disperseed under the conditions of the 1250Bar through high-pressure homogeneous device, pour into
In mould, aeration-drying removes solvent, obtains the heat-conductivity conducting graphene composite material that Graphene content is 3.3%.
Embodiment two
60g acrylonitrile-butadiene-styrene copolymer is put in 550g dimethyl carbonate, in 50 DEG C of stirring at low speed bars
Under part, heated and stirred said mixture 3h, it is completely dissolved to acrylonitrile-butadiene-styrene copolymer.Add the graphite of 3.3g
The carbon fiber powder body of alkene powder body and 3.37g, ultrasonic homogenizing stirring mixing 2h, by mixed liquor through high-pressure homogeneous device in 1000Bar
Under the conditions of disperse after, pour in mould 50 DEG C into and dry and remove solvent, obtain the composite that Graphene content is 5%.
Embodiment three
50g acrylonitrile-butadiene-styrene copolymer is put in 340g dimethyl carbonate, in 60 DEG C of stirring at low speed bars
Under part, heated and stirred said mixture 4h, it is completely dissolved to acrylonitrile-butadiene-styrene copolymer.Add the stone of 5.55g
Black alkene powder body, is filtered after ultrasonic homogenizing stirring 1h.Mixed liquor is disperseed under the conditions of 1500Bar through high-pressure homogeneous device
Afterwards, pour 80 DEG C of drying in mould into and remove solvent, obtain the composite that Graphene content is 10%.
Example IV
200g acrylonitrile-butadiene-styrene copolymer is put in 1500g dimethyl carbonate, ultrasonic agitation is above-mentioned mixed
Compound 2h, is completely dissolved to acrylonitrile-butadiene-styrene copolymer.Add the graphene powder of 50g, continue ultrasonic homogenizing
Stop stirring after stirring 1h and continue ultrasonic 2h.After mixed liquor is disperseed under the conditions of the 2000Bar through high-pressure homogeneous device, pour mould into
Aeration-drying in tool, obtains the composite that Graphene content is 20%.
In above example, the heat conductivity of obtained composite reaches more than 25W/m K, and square resistance can achieve
Less than 10 Ω.
Described above has fully disclosed the specific embodiment of the present invention.It is pointed out that being familiar with this field
Any change that technical staff is done to the specific embodiment of the present invention is all without departing from the scope of claims of the present invention.
Correspondingly, the scope of the claim of the present invention is also not limited only to previous embodiment.
Claims (10)
1. the preparation method of heat-conductivity conducting graphene composite material is it is characterised in that comprise the steps：
Resin, Graphene and other Carbon Materials are dissolved in solvent mixture A is obtained；
Mixture A is carried out with high pressure homogenize process to wherein no granule, prepared mixture B；
Mixture B is dried with process, removes solvent therein, prepared heat-conductivity conducting graphene composite material.
2. the preparation method of heat-conductivity conducting graphene composite material according to claim 1 is it is characterised in that include as follows
Step：
Graphene and/or resin are carried out pretreatment, it is ultrasonic that the pretreatment of described Graphene is included with infiltration, intercalation, premix,
Pretreatment to described resin includes chemical graft, modified and modification；
Resin, Graphene and other Carbon Materials are dissolved in solvent mixture A is obtained；
Mixture A is reprocessed, described reprocessing includes sand milling, nanorize, filtration；
The mixture A carrying out reprocessing is carried out with high pressure homogenize process to wherein no granule, prepared mixture B；
Mixture B is dried with process, removes solvent therein, prepared heat-conductivity conducting graphene composite material.
3. the preparation method of heat-conductivity conducting graphene composite material according to claim 1 is it is characterised in that described resin
It is the resin containing phenyl ring, the described resin containing phenyl ring is selected from Merlon, poly terephthalic acid diethyl alcohol ester, acrylonitrile-benzene second
One or more of alkene-butadiene copolymer, polyether sulfone, polyphenylene sulfide and polyether-ketone.
4. the preparation method of heat-conductivity conducting graphene composite material according to claim 1 is it is characterised in that described solvent
Selected from water, ethanol, methanol, dimethylformamide, N-Methyl pyrrolidone, acetone, ethyl acetate, dimethyl carbonate, tetrahydrochysene furan
Mutter, one or more of dichloromethane and chloroform.
5. heat-conductivity conducting graphene composite material according to claim 1 preparation method it is characterised in that described other
Carbon Materials are selected from one or more of white carbon black, graphite, carbon fiber and CNT.
6. the preparation method of heat-conductivity conducting graphene composite material according to claim 1 is it is characterised in that described resin
Mass ratio with solvent is 2:1-1:30.
7. the preparation method of heat-conductivity conducting graphene composite material according to claim 1 is it is characterised in that described heat conduction
Conductive graphene composite includes the Graphene that mass percent is 0.5%-30%.
8. the preparation method of heat-conductivity conducting graphene composite material according to claim 1 is it is characterised in that described mixing
Surfactant or coupling agent is also included, described surfactant or coupling agent with the mass percent of Graphene are in thing A
0.1%-10%.
9. the preparation method of heat-conductivity conducting graphene composite material according to claim 1 is it is characterised in that described high pressure
The pressure of sterilization treatment is 500-2000Bar, and the time that described high pressure homogenize is processed is 10-300 minute.
10. the preparation method of heat-conductivity conducting graphene composite material according to claim 1 is it is characterised in that described do
Dry process includes high temperature dry drying or/and drying at room temperature or/and cold drying or/and aeration-drying or/and vacuum drying or/
And supercritical drying, the time of described dried is 6-48 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610928372.XA CN106479110A (en) | 2016-10-31 | 2016-10-31 | A kind of preparation method of heat-conductivity conducting graphene composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610928372.XA CN106479110A (en) | 2016-10-31 | 2016-10-31 | A kind of preparation method of heat-conductivity conducting graphene composite material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106479110A true CN106479110A (en) | 2017-03-08 |
Family
ID=58271226
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610928372.XA Pending CN106479110A (en) | 2016-10-31 | 2016-10-31 | A kind of preparation method of heat-conductivity conducting graphene composite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106479110A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107119338A (en) * | 2017-05-15 | 2017-09-01 | 苏州介观智造新材料有限公司 | Graphene produces conductive fiber formula |
| CN111690194A (en) * | 2019-03-14 | 2020-09-22 | 新奥石墨烯技术有限公司 | Polymer composite material and preparation method thereof |
| CN112143072A (en) * | 2020-09-02 | 2020-12-29 | 新奥（内蒙古）石墨烯材料有限公司 | Graphene/polyethylene heat conduction material, preparation method thereof, pipe using heat conduction material and ground source heat pump |
| CN112745565A (en) * | 2019-10-30 | 2021-05-04 | 中国石油化工股份有限公司 | Polypropylene graphene antibacterial composite material and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102807737A (en) * | 2012-08-07 | 2012-12-05 | 上海交通大学 | Preparation method of graphene/carbon nano tube disperse system high-polymer based composite material |
| CN104419107A (en) * | 2013-08-29 | 2015-03-18 | 合肥杰事杰新材料股份有限公司 | Polymer-based electromagnetic shielding material based on carbon fiber and graphene and preparation method of polymer-based electromagnetic shielding material |
| CN106009787A (en) * | 2016-05-18 | 2016-10-12 | 中国科学院山西煤炭化学研究所 | Graded dispersion method and device for preparing graphene-based waterborne dispersion liquid |
-
2016
- 2016-10-31 CN CN201610928372.XA patent/CN106479110A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102807737A (en) * | 2012-08-07 | 2012-12-05 | 上海交通大学 | Preparation method of graphene/carbon nano tube disperse system high-polymer based composite material |
| CN104419107A (en) * | 2013-08-29 | 2015-03-18 | 合肥杰事杰新材料股份有限公司 | Polymer-based electromagnetic shielding material based on carbon fiber and graphene and preparation method of polymer-based electromagnetic shielding material |
| CN106009787A (en) * | 2016-05-18 | 2016-10-12 | 中国科学院山西煤炭化学研究所 | Graded dispersion method and device for preparing graphene-based waterborne dispersion liquid |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107119338A (en) * | 2017-05-15 | 2017-09-01 | 苏州介观智造新材料有限公司 | Graphene produces conductive fiber formula |
| CN111690194A (en) * | 2019-03-14 | 2020-09-22 | 新奥石墨烯技术有限公司 | Polymer composite material and preparation method thereof |
| CN112745565A (en) * | 2019-10-30 | 2021-05-04 | 中国石油化工股份有限公司 | Polypropylene graphene antibacterial composite material and preparation method thereof |
| CN112745565B (en) * | 2019-10-30 | 2023-10-24 | 中国石油化工股份有限公司 | Polypropylene graphene antibacterial composite material and preparation method thereof |
| CN112143072A (en) * | 2020-09-02 | 2020-12-29 | 新奥（内蒙古）石墨烯材料有限公司 | Graphene/polyethylene heat conduction material, preparation method thereof, pipe using heat conduction material and ground source heat pump |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106479110A (en) | A kind of preparation method of heat-conductivity conducting graphene composite material | |
| CN105504469B (en) | A kind of graphene/polyolefin elastomer masterbatch, graphene anti-static composite material and preparation method | |
| CN102618107B (en) | Conductive graphite cream and preparation method thereof | |
| CN103937234B (en) | Heat-conducting plastic of a kind of applying modified carbon material and preparation method thereof | |
| CN103739903B (en) | A kind of High-conductivity carbon nanotube/rubber nanocomposite and preparation method thereof | |
| KR101157451B1 (en) | Effective dispersion of carbon nano material to generate electrically high performance polymer | |
| CN107057192A (en) | Functionalization graphene strengthens the preparation method of composite polyolefine material | |
| CN102424705A (en) | Preparation method of polymer/graphene nano composite material | |
| CN107141698A (en) | A kind of graphene is combined multi-functional resins of ABS and preparation method thereof | |
| CN106543675A (en) | A kind of preparation method of Graphene 3D printing wire rod | |
| CN104693464A (en) | Preparation method of lignin-nanocelluose reinforced polylactic acid composite film | |
| CN106674825A (en) | Preparation method of master batch for graphene/PVC (Polyvinyl Chloride) composite material and master batch | |
| CN105400109B (en) | A kind of modified polyvinylalcohol foamed plastics and preparation method thereof | |
| CN103554598B (en) | The preparation method of halogen-free flameproof high density polyethylene(HDPE)/ethylene-vinyl acetate copolymer | |
| CN105949536A (en) | {0><}0{>Preparation method of high-strength natural rubber (NR)/carbon nano tube (CNT) conductive composite film | |
| CN105883805B (en) | A kind of preparation method of the high-specific surface area carbosphere based on tea seed shell base | |
| CN108864570A (en) | A kind of novel environment friendly Wood plastic wall board and preparation method thereof | |
| CN104513485B (en) | Carbon nanotube/polyetherimide/thermosetting resin dielectric composite material and preparation method thereof | |
| CN102504558B (en) | Method for preparing carbon grain wrapped plant fiber stuffing in manner of steam explosion | |
| KR101771588B1 (en) | Environmentally friendly filaments using biomass and method for manufacturing the same | |
| CN104844795A (en) | High strength thermal conductivity nylon 6 and preparation method thereof | |
| CN103342869A (en) | Modified carbon black/PVA (polyvinyl alcohol) film and preparation method thereof | |
| CN106398122A (en) | Graphene and epoxy resin composite foam material and preparation method thereof | |
| CN110698801A (en) | High-fluidity graphene modified polystyrene composite material and preparation method thereof | |
| JP2009001739A (en) | Thermoplastic resin composition and molded product thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |