CN106543675A - A kind of preparation method of Graphene 3D printing wire rod - Google Patents
A kind of preparation method of Graphene 3D printing wire rod Download PDFInfo
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- CN106543675A CN106543675A CN201610928371.5A CN201610928371A CN106543675A CN 106543675 A CN106543675 A CN 106543675A CN 201610928371 A CN201610928371 A CN 201610928371A CN 106543675 A CN106543675 A CN 106543675A
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- graphene
- wire rod
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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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
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The present invention discloses a kind of preparation method of Graphene 3D printing wire rod, comprises the steps：Resin a, Graphene and other Carbon Materials dissolvings are distributed in solvent and obtain mixed liquor；Make mixed liquor dispersed by high pressure homogenize process；Dry mixed liquid removes solvent, and masterbatch is obtained；The masterbatch of certain proportioning, resin b and auxiliary agent Jing mixed at high speed are obtained into compound；By compound Jing melt blending extruding pelletizations/into line.The present invention carries out pretreatment to raw material first, resin, Graphene and other Carbon Materials are carried out into high efficiency dispersion and mixing under solution state again, i.e. from the Graphene of high concentration to the process of low concentration Graphene transition, compare, the mechanical strength of wire rod is higher, so as to obtain 3D printing wire rod of the graphene uniform dispersion with preferable thermal conductivity and good mechanical performance.
Description
Technical field
The invention belongs to 3D printing wire rod preparation field, is more particularly to a kind of preparation side of Graphene 3D printing wire rod
Method.
Background technology
3D printing technique is rapid shaping technique, is a kind of high-new manufacturing technology based on material stacking method, using three-dimensional
The data of CAD, by rapidform machine, by material stacking from level to level into physical prototypes method.3D printing is made due to which
Quickly, can completely online 3-D effect the advantages of, gradually apply in fields such as medical science, aviation, buildings.
With the expansion of 3D printing industry, market is gradually stepped up to the performance requirement of the parts of 3D printing, international market
On whether the giant enterprise of 3D printing or the consumptive material manufacturer of new master sight has been invested 3D printing engineering plastics field all, make
Obtain the new research and development of 3D printing consumptive material and the application of technical grade receives much concern.Currently for feature 3D printing engineering plastics
Research and development and using less, this field is needed badly and makes up and expand this field, the invention is intended to develop new towards heat conduction/lead
The preparation technology of the 3D printing engineering plastics wire rod of electrical domain.
The content of the invention
It is an object of the invention to provide a kind of preparation method of the 3D printing engineering plastics wire rod with thermal conductivity function.
According to an aspect of the invention, there is provided a kind of preparation method of Graphene 3D printing wire rod, including following step
Suddenly：
(1) resin a, Graphene and other Carbon Materials dissolvings are distributed in solvent and obtain mixed liquor；
(2) make mixed liquor dispersed by high pressure homogenize process；
(3) dry mixed liquid removes solvent, and masterbatch is obtained；
(4) masterbatch, resin b and auxiliary agent Jing mixed at high speed are obtained into compound；
(5) compound Jing melt blendings are extruded into into line.
In some embodiments, through pretreatment before dissolving is distributed in solvent, pretreatment is for resin a and Graphene
Chemical graft, modified, infiltration, intercalation, modification, premix ultrasound, mixed liquor is passed through in high pressure homogenize before processing and is reprocessed, then is located
Reason includes sand milling, nanorize, filtration.
In some embodiments, resin a is selected from Merlon, polyethylene terephthalate, acrylonitrile-benzene second
One or more in alkene-butadiene copolymer, polyether sulfone, polyphenylene sulfide and polyether-ketone.
In some embodiments, solvent is selected from water, ethanol, methanol, dimethylbenzene, DMF, N, N- bis-
Methylacetamide, N-Methyl pyrrolidone, acetone, ethyl acetate, dimethyl carbonate, tetrahydrofuran, dichloromethane and three chloromethanes
One or more in alkane.
In some embodiments, the one kind or many of other Carbon Materials selected from white carbon black, graphite, carbon fiber and CNT
Kind.
In some embodiments, surfactant or coupling agent, surfactant or coupling agent are also included in mixed liquor
The percentage ratio of quality of quality and Graphene be 0.1%-10%.
In some embodiments, high pressure homogenize process pressure be 500-2000Bar, high pressure homogenize process time be
10-300 minutes.
In some embodiments, in masterbatch, the mass content of Graphene is 10%-50%.
In some embodiments, resin b is selected from Merlon, polyethylene terephthalate, acrylonitrile-benzene second
Alkene-butadiene copolymer, polypropylene, polyvinyl alcohol, polrvinyl chloride, polymethyl methacrylate, polyformaldehyde, polyether sulfone, polyphenyl
One or more in thioether and polyether-ether-ketone, polyamide.
In some embodiments, compound Jing melt blendings pass through double-screw extruding pelletizing machine or Single screw extrusion into line
Machine extruding pelletization or into line.
Its advantage is：The present invention carries out pretreatment first to raw material, then resin, Graphene and other Carbon Materials are existed
Carry out high efficiency dispersion and mixing, the i.e. Graphene from high concentration to compare to the process of low concentration Graphene transition under solution state
The preparation of low concentration graphene composite material is prepared directly, the mechanical strength of wire rod is higher, so as to obtain graphene uniform dispersion
3D printing wire rod with preferable thermal conductivity and good mechanical performance.Resin a is conducive to Graphene in liquid resin
In preferably dispersion and merge with which, there is the effect for promoting to the intensity of 3D printing wire rod, and resin b can then improve resin
The synergism of the performance of a, i.e. performance.
The Graphene of reunion and other Carbon Materials solution coalescences are made to be distributed to containing phenyl ring, Jing by high pressure homogenize process for dispersing
Cross in the liquid resin a of pretreatment.Resin a in the raw material of pretreatment includes dissolved state, its structure there occurs orientation
The change of property.When they are in the presence of the external force such as high pressure, graphene layer intermolecular forces are weakened, while tying by its hexagon
Model ylid bloom action power between structure and the resin a containing phenyl ring so that the Graphene in aggregating state gradually realizes depolymerization originally, reaches
Then uniform and stable heat transfer network is formed to good dispersity, realized with this new towards thermal conductivity field
The exploitation of feature 3D printing wire rod.
Specific embodiment
The invention provides a kind of preparation method of Graphene 3D printing wire rod, comprises the steps：(1) by resin a, stone
Black alkene is distributed in solvent with other Carbon Materials dissolvings and obtains mixed liquor；(2) make mixed liquor dispersed by high pressure homogenize process；
(3) dry mixed liquid removes solvent, and masterbatch is obtained；(4) masterbatch of certain proportioning, resin b and auxiliary agent Jing mixed at high speed are obtained
Compound；(5) compound Jing melt blendings are obtained into Graphene 3D printing wire rod.
Wherein, resin a is selected from Merlon, polyethylene terephthalate, acrylonitrile-styrene-butadiene copolymer
One or more in thing, polyether sulfone, polyphenylene sulfide and polyether-ether-ketone, polyamide.Solvent is selected from water, ethanol, methanol, diformazan
Benzene, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, N-Methyl pyrrolidone, acetone, ethyl acetate, dimethyl carbonate,
One or more in tetrahydrofuran, dichloromethane and chloroform.Other Carbon Materials are selected from white carbon black, graphite, carbon fiber and carbon
One or more of nanotube.Resin disperses molten by way of one or more method such as heating, ultrasound and stirring combines
To in solvent, the time that resin is completely dissolved is 1-24h to solution.Also include surfactant or coupling agent in mixed liquor, surface is lived
Property agent or the percentage ratio of quality of quality and Graphene of coupling agent be 0.1%-10%.High pressure homogenize process pressure be
500-2000Bar, the time of high pressure homogenize process is 10-300 minutes.In masterbatch, the mass content of Graphene is 10%-50%.
Resin b is selected from Merlon, polyethylene terephthalate, acrylonitrile-butadiene-styrene copolymer, polypropylene, poly- second
In enol, polrvinyl chloride, polymethyl methacrylate, polyformaldehyde, polyether sulfone, polyphenylene sulfide and polyether-ether-ketone, polyamide one
Plant or various.Auxiliary agent is surfactant or coupling agent, and surfactant is in sodium lauryl sulphate and sodium stearate
One or two, one or more in KH570, SG-Si900 and NDZ-201 of coupling agent.The melt blending of compound can
Melt kneading, mill mixing etc. to realize by single screw rod melt blending, double-screw melt blending, banbury, more preferably
Be double-screw melt blending.The preferred Single screw extrusion of molding of Graphene 3D printing wire rod is into line machine.
Embodiment 1
200g acrylonitrile-butadiene-styrene copolymers are put in 1500g dimethyl carbonate, ultrasonic agitation is above-mentioned mixed
Compound 2h, is completely dissolved to acrylonitrile-butadiene-styrene copolymer.The graphene powder of 50g, ultrasonic agitation 1h is added to stop
Only stirring continues ultrasound 2h.The bubble on slurry surface is removed, mixed liquor Jing high-pressure homogeneous devices are disperseed under the conditions of 2000Bar
Afterwards, pour aeration-drying in mould into and remove solvent, obtain the composite that Graphene content is 20%.
Weigh the thermal conductivity masterbatch that 200g Graphene contents are 20%, the PC masterbatch of 1800g, the KH570 of 1g is at a high speed
After mixing 20min in mixer, line is extruded into via single screw extrusion machine melt blending.Single screw extrusion machine includes feeding successively
Section, melt zone, discharge boost section and take-up section.Feeding section temperature：180-190℃；The temperature of melt zone：190-200℃；Discharge
The temperature of supercharging：190℃；Main frame speed is 20HZ；Take-up hauling speed is 29HZ, and it is 2% to finally give Graphene content
Thermal conductivity wire rod.
In the present embodiment, the heat conductivity of obtained functional polymer composites reaches more than 20W/mK, square electricity
Resistance is capable of achieving 0.5-30 Ω, a diameter of 1.70mm of wire rod, can be applicable to the CubePro Trio of 3D systems companies of the U.S.
Type 3D printer.
Embodiment 2
200g acrylonitrile-butadiene-styrene copolymers are put in 1800g dimethyl carbonate, in 60 DEG C of stirring at low speed
Under the conditions of, heated and stirred said mixture 5h is completely dissolved to acrylonitrile-butadiene-styrene copolymer.Add 85.7g's
Graphene powder, ultrasonic agitation 1.5h stop stirring and continue ultrasound 2h.The bubble on slurry surface is removed, by mixed liquor Jing high pressure
After homogeneous device disperses under the conditions of 1500Bar, pour 80 DEG C of drying in mould into and remove solvent, Graphene content is obtained for 30%
Composite.
Weigh the thermal conductivity masterbatch that 200g Graphene contents are 30%, the ABS masterbatch of 1000g, the KH570 of 1g is at a high speed
After mixing 20min in mixer, via double screw extruder melt blending extruding pelletization.Double screw extruder include feeding section,
Dispersion homogenizing zone, melt zone, discharge boost section and take-up section.
The major function of feeding section is to eat material, and material is conveyed.Dispersion homogenizing zone is that feeding section is conveyed
The material for coming over carries out melt and flavoring agent, infiltrates and break up.Melt zone is to mix the melt resin that dispersion homogenizing zone conveying comes
Compound is fully melted and carries out preliminary mixing.Discharge boost section is that compression melt sets up a stable pressure area, is melt
Prepare from the die extrusion of double screw extruder.
One or two area's feeding section temperature：175-180℃；345 distinguish scattered homogenizing zone temperature：185-195℃；6th 78 area
Melt zone temperature：195-210℃；90 area's discharges increase temperature section：185-190℃.Engine speed 100RPM, rate of feeding
7RPM, pelletizing speed 450r/min.Pellet is extruded into into line into line machine through Single screw extrusion, Graphene content is obtained for 5%
Thermal conductivity 3D printing wire rod.
In the present embodiment, the heat conductivity of obtained functional polymer composites reaches more than 20W/mK, square electricity
Resistance is capable of achieving 0.5-30 Ω, a diameter of 1.70mm of wire rod, can be applicable to the CubePro Trio of 3D systems companies of the U.S.
Type 3D printer.
Described above has fully disclosed the specific embodiment of the present invention.It is pointed out that being familiar with the field
Scope of any change that technical staff is done to the specific embodiment of the present invention all without departing from claims of the present invention.
Correspondingly, the scope of claim of the invention is also not limited only to previous embodiment.
Claims (10)
1. a kind of preparation method of Graphene 3D printing wire rod, it is characterised in that comprise the steps：
(1) resin a, Graphene and other Carbon Materials dissolvings are distributed in solvent and obtain mixed liquor；
(2) make mixed liquor dispersed by high pressure homogenize process；
(3) dry mixed liquid removes solvent, and masterbatch is obtained；
(4) masterbatch, resin b and auxiliary agent Jing mixed at high speed are obtained into compound；
(5) compound Jing melt blendings are extruded into into line.
2. the preparation method of Graphene 3D printing wire rod according to claim 1, it is characterised in that the resin a and stone
Black alkene before dissolving is distributed in solvent through pretreatment, the pretreatment be chemical graft, modified, infiltration, intercalation, modification,
Premix ultrasound, in high pressure homogenize before processing through reprocessing, the reprocessing includes sand milling, nanorize, mistake to the mixed liquor
Filter.
3. the preparation method of Graphene 3D printing wire rod according to claim 1, it is characterised in that the resin a is selected from
Merlon, polyethylene terephthalate, acrylonitrile-butadiene-styrene copolymer, polyether sulfone, polyphenylene sulfide and poly-
One or more in ether ketone.
4. the preparation method of Graphene 3D printing wire rod according to claim 1, it is characterised in that the solvent is selected from
Water, ethanol, methanol, dimethylbenzene, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, N-Methyl pyrrolidone, acetone, second
One or more in acetoacetic ester, dimethyl carbonate, tetrahydrofuran, dichloromethane and chloroform.
5. the preparation method of Graphene 3D printing wire rod according to claim 1, it is characterised in that described other Carbon Materials
Selected from one or more of white carbon black, graphite, carbon fiber and CNT.
6. the preparation method of Graphene 3D printing wire rod according to claim 1, it is characterised in that in the mixed liquor also
Including the quality and the percentage ratio of the quality of Graphene of surfactant or coupling agent, the surfactant or coupling agent it is
0.1%-10%.
7. the preparation method of Graphene 3D printing wire rod according to claim 1, it is characterised in that at the high pressure homogenize
The pressure of reason is 500-2000Bar, and the time that the high pressure homogenize is processed is 10-300 minutes.
8. the preparation method of Graphene 3D printing wire rod according to claim 1, it is characterised in that graphite in the masterbatch
The mass content of alkene is 10%-50%.
9. the preparation method of Graphene 3D printing wire rod according to claim 1, it is characterised in that the resin b is selected from
Merlon, polyethylene terephthalate, acrylonitrile-butadiene-styrene copolymer, polypropylene, polyvinyl alcohol, polychlorostyrene
One or more in ethylene, polymethyl methacrylate, polyformaldehyde, polyether sulfone, polyphenylene sulfide and polyether-ether-ketone, polyamide.
10. the preparation method of Graphene 3D printing wire rod according to claim 1, it is characterised in that the compound Jing
Melt blending passes through double-screw extruding pelletizing machine or Single screw extrusion into line machine extruding pelletization or into line.
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| CN201610928371.5A CN106543675A (en) | 2016-10-31 | 2016-10-31 | A kind of preparation method of Graphene 3D printing wire rod |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107610803A (en) * | 2017-09-11 | 2018-01-19 | 中山大学 | A kind of 3D printing composite conducting wire rod and preparation method thereof |
| CN107987444A (en) * | 2017-12-12 | 2018-05-04 | 常州工程职业技术学院 | A kind of graphene/PMMA heat-conductive composite materials, preparation method and applications |
| CN108384213A (en) * | 2018-03-22 | 2018-08-10 | 疆合材料科技（苏州）有限公司 | A kind of polycarbonate composite material of high conductivity and preparation method thereof |
| CN109081891A (en) * | 2018-06-29 | 2018-12-25 | 深圳光韵达光电科技股份有限公司 | 3D printing photocuring slurry and preparation method thereof |
| CN110157140A (en) * | 2018-04-10 | 2019-08-23 | 广东华斓汽车材料研究院 | A kind of electric conductivity and the 3D printing material of satisfactory mechanical property and preparation method thereof |
| CN110386776A (en) * | 2018-04-20 | 2019-10-29 | 杭州万杵材料科技有限公司 | A kind of novel heat-conducting plastics and preparation method thereof |
| CN113897078A (en) * | 2021-11-25 | 2022-01-07 | 新疆德欣精细化工有限公司 | Processing technology of low-energy-consumption environment-friendly carbon black |
-
2016
- 2016-10-31 CN CN201610928371.5A patent/CN106543675A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107610803A (en) * | 2017-09-11 | 2018-01-19 | 中山大学 | A kind of 3D printing composite conducting wire rod and preparation method thereof |
| CN107987444A (en) * | 2017-12-12 | 2018-05-04 | 常州工程职业技术学院 | A kind of graphene/PMMA heat-conductive composite materials, preparation method and applications |
| CN108384213A (en) * | 2018-03-22 | 2018-08-10 | 疆合材料科技（苏州）有限公司 | A kind of polycarbonate composite material of high conductivity and preparation method thereof |
| CN110157140A (en) * | 2018-04-10 | 2019-08-23 | 广东华斓汽车材料研究院 | A kind of electric conductivity and the 3D printing material of satisfactory mechanical property and preparation method thereof |
| CN110386776A (en) * | 2018-04-20 | 2019-10-29 | 杭州万杵材料科技有限公司 | A kind of novel heat-conducting plastics and preparation method thereof |
| CN109081891A (en) * | 2018-06-29 | 2018-12-25 | 深圳光韵达光电科技股份有限公司 | 3D printing photocuring slurry and preparation method thereof |
| CN109081891B (en) * | 2018-06-29 | 2021-02-09 | 深圳光韵达光电科技股份有限公司 | 3D printing photocuring slurry and preparation method thereof |
| CN113897078A (en) * | 2021-11-25 | 2022-01-07 | 新疆德欣精细化工有限公司 | Processing technology of low-energy-consumption environment-friendly carbon black |
| CN113897078B (en) * | 2021-11-25 | 2022-04-29 | 新疆德欣精细化工有限公司 | Processing technology of low-energy-consumption environment-friendly carbon black |
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