CN106564175B - A kind of graphene conductive masterbatch and preparation method thereof - Google Patents
A kind of graphene conductive masterbatch and preparation method thereof Download PDFInfo
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- CN106564175B CN106564175B CN201610918490.2A CN201610918490A CN106564175B CN 106564175 B CN106564175 B CN 106564175B CN 201610918490 A CN201610918490 A CN 201610918490A CN 106564175 B CN106564175 B CN 106564175B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 178
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 119
- 239000004594 Masterbatch (MB) Substances 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 64
- 239000010439 graphite Substances 0.000 claims abstract description 64
- 239000000463 material Substances 0.000 claims abstract description 61
- 239000012943 hotmelt Substances 0.000 claims abstract description 49
- 238000010008 shearing Methods 0.000 claims abstract description 40
- 239000002994 raw material Substances 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 13
- 230000000694 effects Effects 0.000 claims abstract description 9
- 238000005453 pelletization Methods 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 20
- 229920001971 elastomer Polymers 0.000 claims description 16
- 239000005060 rubber Substances 0.000 claims description 16
- 239000000654 additive Substances 0.000 claims description 15
- 230000000996 additive effect Effects 0.000 claims description 15
- 239000010410 layer Substances 0.000 claims description 15
- 239000004831 Hot glue Substances 0.000 claims description 13
- -1 graphite Alkene Chemical class 0.000 claims description 11
- 239000011347 resin Substances 0.000 claims description 11
- 229920005989 resin Polymers 0.000 claims description 11
- 238000002844 melting Methods 0.000 claims description 10
- 230000008018 melting Effects 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 8
- 239000006185 dispersion Substances 0.000 claims description 8
- 230000007423 decrease Effects 0.000 claims description 7
- 239000002356 single layer Substances 0.000 claims description 7
- 239000004698 Polyethylene Substances 0.000 claims description 5
- 239000002270 dispersing agent Substances 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 229920000728 polyester Polymers 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 238000004227 thermal cracking Methods 0.000 claims description 3
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims description 2
- 235000007164 Oryza sativa Nutrition 0.000 claims description 2
- 241000826860 Trapezium Species 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- VIKNJXKGJWUCNN-XGXHKTLJSA-N norethisterone Chemical compound O=C1CC[C@@H]2[C@H]3CC[C@](C)([C@](CC4)(O)C#C)[C@@H]4[C@@H]3CCC2=C1 VIKNJXKGJWUCNN-XGXHKTLJSA-N 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 235000009566 rice Nutrition 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 235000013339 cereals Nutrition 0.000 claims 1
- 239000000843 powder Substances 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000004743 Polypropylene Substances 0.000 description 5
- 238000004806 packaging method and process Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000004604 Blowing Agent Substances 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229920003020 cross-linked polyethylene Polymers 0.000 description 1
- 239000004703 cross-linked polyethylene Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000320 mechanical mixture Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920001596 poly (chlorostyrenes) Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- MZSDGDXXBZSFTG-UHFFFAOYSA-M sodium;benzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1 MZSDGDXXBZSFTG-UHFFFAOYSA-M 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/50—Details of extruders
- B29C48/505—Screws
- B29C48/59—Screws characterised by details of the thread, i.e. the shape of a single thread of the material-feeding screw
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2507/00—Use of elements other than metals as filler
- B29K2507/04—Carbon
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Conductive Materials (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention provides a kind of graphene conductive masterbatch and preparation method thereof.The Strong shear screw extruder that the present invention has shearing tooth using one, graphite raw material is uniformly mixed with hot melt material, it is acted on using the Strong shear of shearing tooth, graphite is removed into graphene, and graphene is evenly spread out along screw rod direction of rotation, finely dispersed graphene fusant is obtained, finally by extruding pelletization, obtains graphene conductive masterbatch.The present invention, which provides the above method and overcomes, to be prepared graphene conductive master batch as raw material by using graphene dry powder in the prior art and leads to high production cost, it is big using risk, the bad dispersibility of graphene in the conducting masterbatch of preparation, the low technical problem of yield rate, the dispersibility for improving graphene while production cost is greatly reduced in masterbatch is realized, is easy to the technical effect of graphene efficiently utilized, further, raw material and product are easy to store, highly-safe.
Description
Technical field
The present invention relates to grapheme material fields, and in particular to a kind of graphene conductive masterbatch and preparation method thereof.
Background technique
In order to protect electric power transmission cable insulation from concentrated as electric field stress and caused by destruction, while in order to press down
Charge inducing processed, in electric power transmission cable, voltage rating 3.6/6.6 (7.2) kV's or more uses EP rubbers and polychlorostyrene
Ethylene is as the cable of insulating layer and use crosslinked polyethylene and the polyethylene of voltage rating 1.8/3.0 (3.6) kV or more
Cable as insulating layer should all have conductor shielding and insulation screen.One layer of semiconductive is respectively designed in outside in insulating layer respectively
Shielded layer.The quality of semiconductive shieldin material is played a crucial role to cable using safe and service life.Semiconductive
Composite material used in shielded layer must keep stable lower level at different temperatures and in long-term use process.Usually
The semiconducting rubber shielded layer seen is to be prepared by rubber and conductive black by mechanical mixture, is also had at present by stone
Black alkene is used for semi-conductive screen rubber.And the modified semi-conductive shielding material of current graphene is directly to divide graphene dry powder
It dissipates in high molecular material, the dispersion for causing graphene is uneven, and the shield effectiveness of cable is poor, and yield rate is low.And use stone
Additive of the black alkene conductive agglomerate as shielded layer, will substantially improve the conductive capability of shielded layer, greatly improves the finished product of cable
Rate.
Chinese invention patent application number 201510200391.6 discloses a kind of graphene conductive master batch and preparation method thereof
And application, the invention are related to a kind of preparation method of graphene conductive master batch, and antistatic agent dissolution is obtained in organic solvent
Graphene is put into organic solvent for ultrasonic dispersion by solution A, and solution A is added under ultrasound and mechanical stirring, and concentration removes organic
Solvent obtains paste, finally by paste heating melting, then by the paste of melting through freely falling body drippage, cooling institute to obtain the final product
The graphene conductive master batch stated.The graphene conductive master batch being prepared has excellent volume resistivity, in the application can
Form the high-effective conductive network of rotation section phase separation structure.However, graphene is easy to reunite, complicated preparation process easily leads to graphene
Dispersion is uneven, and it is uneven to further result in conductive network.
Chinese invention patent application number 201410042709.8 discloses a kind of graphene modified polypropylene agglomerate and its system
Preparation Method.Polypropylene particles are first passed through the graphene dry powder spraying with electrostatic and are modified by the invention, then will be modified poly-
Propylene particle and additive component are sent into double screw extruder after mixing and carry out melting mixing, finally pass through die head extruding pelletization.
The invention makes polypropylene material in the case where heating conduction is greatly improved, while also improving its power in certain amplitude
Learn performance.But graphene dry powder is directly used in the invention, lead at high cost, nothing during graphene covering polypropylene particles
Method accomplishes uniformly to be completely covered, and results in later period graphene being unevenly distributed in master batch, yield rate is low.
Chinese invention patent application number 201510035628.X disclose a kind of resin/graphite alkene conductive plastic base particle and its
Preparation method and purposes, the invention is by water, the resin/graphite conducting master batch, physical blowing agent, interleaving agent together in autoclave
Quick low voltage is released after middle heating, makes to obtain the resin/graphite alkene conductive plastics foaming master batch of blasting stripping method preparation.The conduction
Plastic foamed master batch again can resin/graphite alkene conductive plastic base particle through twin-screw extrusion deaeration.This method uses graphite for original
Material, solves the problems, such as that graphene is not easy to disperse, while using the solvability of overcritical physical blowing agent, when it penetrates into graphite
Lamella expands and exfoliated graphite layer in unexpected discharge.But the invention is not easy to grasp the intensity of explosion, there are some
Security risk.
According to above-mentioned, the preparation of graphene conductive master batch at present mostly uses greatly graphene dry powder as raw material, at high cost, makes
Big with risk, the bad dispersibility of graphene in the conducting masterbatch of preparation causes the conductive capability of conducting masterbatch low, yield rate
It is low.And exist in the form of powder or slurry mechanically direct obtained graphene of removing, easily reunite or be layered to sink and gathers,
Cause the very big inconvenience used.If, can be in mechanical stripping graphene directly by preparing graphite alkene conducting masterbatch
While solve the problems, such as the evenly dispersed of graphene, be easy to the efficient utilization of graphene, and be easy to store, it is highly-safe.
Summary of the invention
Preparation for the graphene conductive master batch obtained at present by mechanically direct removing mostly uses greatly graphene dry powder
At high cost as raw material, big using risk, the bad dispersibility of graphene, leads to conducting masterbatch in the conducting masterbatch of preparation
Conductive capability is low, the low technical problem of yield rate, and the present invention proposes a kind of graphene conductive masterbatch and preparation method thereof, passes through spiral shell
Graphite and hot melt material are carried out the effect of Strong shear power in the case where heating colloidal state, obtain a kind of graphene conductive by bar extruder
Masterbatch, conducting masterbatch prepared by the present invention can be used as the additive of conductive coating, good dispersion of the graphene in conducting masterbatch,
It will not reunite or heavy poly-, be made after masterbatch, be easy to store, the safety is improved.
On the one hand, the present invention provides a kind of preparation method of graphene conductive masterbatch, using cutting by force with shearing tooth
Screw extruder is cut, graphite raw material is sheared into grinding under colloidal state with hot melt material to prepare, the specific method is as follows：
（1）By mass percent be 15-29 graphite raw material and mass percent be 0-1 dispersing agent, mass percent
Dispersion 10-25min is mixed with the revolving speed of 600-1200rpm in a high speed mixer for the hot melt material of 70-85, is premixed
Object；
（2）By step（1）Obtained pre-composition is added in the Strong shear screw extruder, the Strong shear Screw Extrusion
Machine sets gradually conveying reduction stage, removing section, stirring section from feed end to discharge end, and screw rod is revolved with the revolving speed of 100-1200rpm
When turning, in the conveying section, it is 120-140 DEG C that this section of temperature, which is arranged, and the partial size of graphite raw material decreases below 1 milli in pre-composition
Rice, and be gradually fed forward together with the hot melt material；
In the removing section, it is 160-180 DEG C that this section of temperature, which is arranged, and screw machine screw thread is prolonging the corresponding unit of the first screw pitch
N number of opening is respectively distributed a shearing tooth in screw thread extensions, and hot melt material is extruded under the Strong shear power effect of the shearing tooth,
The hot melt material being adhered on the graphite raw material removes the graphite raw material at graphene by shearing motion, keeps graphite former
Material removing forms the graphene of single-layer or multi-layer large scale area, forms the hot melt material of graphene doping, wherein described first
Screw pitch is the screw pitch of the removing section screw thread, and N is the integer more than or equal to 1；
In the stirring section, it is 180-200 DEG C that this section of temperature, which is arranged, and hot melt material is in the higher molten condition of temperature,
Graphene is evenly spread out in melting hot-melt object material along screw rod direction of rotation, obtains finely dispersed graphene fusant, and
Gradually it is fed forward；
（3）Step（2）Obtained graphene fusant obtains graphene conductive masterbatch by extruding pelletization, cooling.
Preferably, the graphite raw material is crystalline flake graphite, expanded graphite, highly oriented graphite, thermal cracking graphite, graphite oxide
At least one of, the graphite raw material partial size is less than or equal to 10 millimeters.
Preferably, the hot melt material is EVA hot-melt adhesive, PA hot melt adhesive, PES polyester hot-melt adhesive, PE polyethylene hot-melt adhesive
One or more of, the partial size of the hot melt material is 3-50 mm.
Preferably, the dispersing agent be lauryl sodium sulfate, neopelex, polyvinylpyrrolidone,
At least one of 1- pyridine acid.
Preferably, the Strong shear screw extruder further includes：
Second screw pitch of the conveying reduction stage screw thread is 8-10cm, and lead angle is 45-60 °, wherein described second
Screw pitch is the screw pitch of the conveying reduction stage screw thread；
First screw pitch of the removing section screw thread is 3-8cm, and lead angle is 30-45 °；
The shearing tooth is one of square column type, arc-shaped, involute, and the facewidth of the shearing tooth is less than or equal to institute
State Opening length；
The third screw pitch of the stirring section screw thread is 2-5cm, and lead angle is 25-35 °, and the third screw pitch is described
Remove the screw pitch of section screw thread.
Preferably, the section of the spiral shell rib of the screw thread is one of triangular structure, rectangular configuration and trapezium structure.
On the other hand, the present invention provides a kind of graphene conductive masterbatch, and the graphene conductive masterbatch is by claim 1-6
The solid mixt that the method is prepared, as additive application in rubber, resin.
A kind of graphene conductive masterbatch of the present invention and preparation method thereof, compared with prior art, the feature that protrudes and excellent
Different effect is：
1, the present invention produces graphene conductive masterbatch using screw extruder, and production cost is greatly reduced, and produces
Journey non-environmental-pollution, yield is high, has significant market application value.
2, removing is sheared by the screw machine of specific structure and prepares graphene, in Continuous Extrusion Process, graphite is by cutting
Removing is cut, high-quality graphene is formed, and heats colloid and has buffered mechanical shock process, shear force is mildly transmitted, protects
Graphene integrality, improves the electric conductivity of conducting masterbatch.
3, in graphene conductive masterbatch prepared by the present invention, the good dispersion of graphene will not reunite or heavy poly-, and electric current passes
It is few to pass obstacle, resistance is low.
4, graphene conductive masterbatch prepared by the present invention, is easy to store, the safety is improved.
Detailed description of the invention
For the preparation method for further illustrating a kind of graphene conductive masterbatch, it is illustrated by attached drawing.
Attached drawing 1 is that embodiment 1 removes section screw-rod structure schematic diagram.
Wherein：1- screw thread；2- shearing tooth.
Specific embodiment
In the following, the present invention will be further described in detail by way of specific embodiments, but this should not be interpreted as to the present invention
Range be only limitted to example below.Without departing from the idea of the above method of the present invention, according to ordinary skill
The various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Embodiment 1
（1）It is 15 by mass percent, the dodecyl that the crystalline flake graphite and mass percent that partial size is 10mm are 0.1
Sodium sulphate, mass percent 84.9, the EVA hot-melt adhesive that partial size is 3 mm are mixed in a high speed mixer with the revolving speed of 600rpm
Disperse 10min, obtains pre-composition；
（2）By step（1）Obtained pre-composition is added in Strong shear screw extruder, cuts the spiral shell rib of screw machine screw thread by force
Section is triangular structure, and Strong shear screw extruder sets gradually conveying reduction stage from feed end to discharge end, removing section, stirs
Section is mixed, when screw rod is rotated with the revolving speed of 100rpm, in the conveying section, the second screw pitch for conveying reduction stage screw thread is 8cm, screw thread
Lift angle is 45 °, and it is 120 DEG C that this section of temperature, which is arranged, and the partial size of graphite raw material decreases below 1 millimeter in pre-composition, and with it is described
Hot melt material is gradually fed forward together；
As shown in Figure 1, first screw pitch of removing section screw thread is 3cm in the removing section, lead angle is 30 °, spiral shell
Bar machine screw thread 1 opening on prolonging the corresponding unit screw thread extensions of the first screw pitch is respectively distributed a shearing tooth, and shearing tooth is square column
The facewidth of shape, shearing tooth is less than the Opening length, and it is 160 DEG C that this section of temperature, which is arranged, in the Strong shear masterpiece of the shearing tooth
It is extruded with lower hot melt material, the hot melt material being adhered on the graphite raw material shells the graphite raw material by shearing motion
From at graphene, so that graphite raw material is removed the graphene to form single-layer or multi-layer large scale area, form the heat of graphene doping
Fusant material；
In the stirring section, the third screw pitch of stirring section screw thread is 2cm, and lead angle is 25 °, this section of temperature, which is arranged, is
180 DEG C, hot melt material is in the molten condition of higher temperature, and graphene is uniform in melting hot-melt object material along screw rod direction of rotation
It scatter, obtains finely dispersed graphene fusant, and be gradually fed forward；
（3）Step（2）Obtained graphene fusant obtains graphene conductive masterbatch by extruding pelletization, cooling.
Graphene conductive masterbatch manufactured in the present embodiment can be used as additive application in rubber, resin, improve its conduction
Property, more preferably it is applied to integrated circuit packaging, electromagnetic wave shielding utilizes.It can by graphene conductive masterbatch prepared in embodiment one
As additive application in second the third insulated cable rubber, it is as shown in table 1 that performance parameter is obtained after tested.
Embodiment 2
（1）It is 20 by mass percent, the detergent alkylate that the expanded graphite and mass percent that partial size is 8mm are 0.5
Sodium sulfonate, mass percent 79.5, the EVA hot-melt adhesive that partial size is 10 mm are mixed with the revolving speed of 800rpm in a high speed mixer
With dispersion 15min, pre-composition is obtained；
（2）By step（1）Obtained pre-composition is added in Strong shear screw extruder, cuts the spiral shell rib of screw machine screw thread by force
Section is triangular structure, and Strong shear screw extruder sets gradually conveying reduction stage from feed end to discharge end, removing section, stirs
Section is mixed, when screw rod is rotated with the revolving speed of 400rpm, in the conveying section, the second screw pitch for conveying reduction stage screw thread is 9cm, screw thread
Lift angle is 50 °, and it is 130 DEG C that this section of temperature, which is arranged, and the partial size of graphite raw material decreases below 1 millimeter in pre-composition, and with it is described
Hot melt material is gradually fed forward together；
In the removing section, first screw pitch for removing section screw thread is 4cm, and lead angle is 35 °, and screw machine screw thread exists
Prolong 3 openings in the corresponding unit screw thread extensions of the first screw pitch and be respectively distributed a shearing tooth, shearing tooth is involute, shearing tooth
The facewidth be less than the Opening length, in the present embodiment, 3 opening be opposite position i.e. 3 be open perpendicular to screw rod edge
The vertical line angle in line direction is 120 °, and it is other positions that certain those skilled in the art, which can according to need 3 openings of setting,；If
Setting this section of temperature is 170 DEG C, and hot melt material is extruded under the Strong shear power effect of the shearing tooth, and it is former to be adhered to the graphite
Hot melt material on material removes the graphite raw material at graphene by shearing motion, make graphite raw material remove to be formed single layer or
The graphene of multilayer large scale area forms the hot melt material of graphene doping；
In the stirring section, the third screw pitch of stirring section screw thread is 3cm, and lead angle is 28 °, this section of temperature, which is arranged, is
190 DEG C, hot melt material is in the molten condition of higher temperature, and graphene is uniform in melting hot-melt object material along screw rod direction of rotation
It scatter, obtains finely dispersed graphene fusant, and be gradually fed forward；
（3）Step（2）Obtained graphene fusant obtains graphene conductive masterbatch by extruding pelletization, cooling.
Graphene conductive masterbatch manufactured in the present embodiment can be used as additive application in rubber, resin, improve its conduction
Property, more preferably it is applied to integrated circuit packaging, electromagnetic wave shielding utilizes.Graphene conductive masterbatch prepared in embodiment two is made
It is additive application in second the third insulated cable rubber, it is as shown in table 1 obtains performance parameter after tested.
Embodiment 3
（1）It is 24 by mass percent, the dodecyl that the highly oriented graphite and mass percent that partial size is 6mm are 0.5
Benzene sulfonic acid sodium salt, mass percent 75.5, partial size are the PA hot melt adhesive of 20 mm in a high speed mixer with the revolving speed of 1000rpm
Dispersion 20min is mixed, pre-composition is obtained；
（2）By step（1）Obtained pre-composition is added in Strong shear screw extruder, cuts the spiral shell rib of screw machine screw thread by force
Section is rectangular configuration, and Strong shear screw extruder sets gradually conveying reduction stage, removing section, stirring from feed end to discharge end
Section, when screw rod is rotated with the revolving speed of 800rpm, in the conveying section, the second screw pitch for conveying reduction stage screw thread is 9cm, screw thread liter
Angle is 55 °, and it is 130 DEG C that this section of temperature, which is arranged, and the partial size of graphite raw material decreases below 1 millimeter in pre-composition, and with the heat
Fusant material is gradually fed forward together；
In the removing section, first screw pitch for removing section screw thread is 6cm, and lead angle is 40 °, and screw machine screw thread exists
Prolong 3 openings in the corresponding unit screw thread extensions of the first screw pitch and be respectively distributed a shearing tooth, shearing tooth is involute, shearing tooth
The facewidth be less than the Opening length, in the present embodiment, 3 opening be opposite position i.e. 3 be open perpendicular to screw rod edge
The vertical line angle in line direction is 120 °, and it is other positions that certain those skilled in the art, which can according to need 3 openings of setting,；If
Setting this section of temperature is 170 DEG C, and hot melt material is extruded under the Strong shear power effect of the shearing tooth, and it is former to be adhered to the graphite
Hot melt material on material removes the graphite raw material at graphene by shearing motion, make graphite raw material remove to be formed single layer or
The graphene of multilayer large scale area forms the hot melt material of graphene doping；
In the stirring section, the third screw pitch of stirring section screw thread is 4cm, and lead angle is 30 °, this section of temperature, which is arranged, is
190 DEG C, hot melt material is in the molten condition of higher temperature, and graphene is uniform in melting hot-melt object material along screw rod direction of rotation
It scatter, obtains finely dispersed graphene fusant, and be gradually fed forward；
（3）Step（2）Obtained graphene fusant obtains graphene conductive masterbatch by extruding pelletization, cooling.
Graphene conductive masterbatch manufactured in the present embodiment can be used as additive application in rubber, resin, improve its conduction
Property, more preferably it is applied to integrated circuit packaging, electromagnetic wave shielding utilizes.It can by graphene conductive masterbatch prepared in embodiment three
As additive application in second the third insulated cable rubber, it is as shown in table 1 that performance parameter is obtained after tested.
Embodiment 4
（1）It is 27 by mass percent, the detergent alkylate that the highly oriented graphite and mass percent that partial size is 6mm are 1
Sodium sulfonate, mass percent 72, the PA hot melt adhesive that partial size is 30 mm are mixed in a high speed mixer with the revolving speed of 1200rpm
Disperse 20min, obtains pre-composition；
（2）By step（1）Obtained pre-composition is added in Strong shear screw extruder, cuts the spiral shell rib of screw machine screw thread by force
Section is rectangular configuration, and Strong shear screw extruder sets gradually conveying reduction stage, removing section, stirring from feed end to discharge end
Section, when screw rod is rotated with the revolving speed of 800rpm, in the conveying section, the second screw pitch for conveying reduction stage screw thread is 9cm, screw thread liter
Angle is 55 °, and it is 130 DEG C that this section of temperature, which is arranged, and the partial size of graphite raw material decreases below 1 millimeter in pre-composition, and with the heat
Fusant material is gradually fed forward together；
In the removing section, first screw pitch for removing section screw thread is 6cm, and lead angle is 40 °, and screw machine screw thread exists
Prolong 4 openings in the corresponding unit screw thread extensions of the first screw pitch and be respectively distributed a shearing tooth, shearing tooth is square column type, shearing tooth
The facewidth is less than the Opening length, and in the present embodiment, 4 openings are that opposite position i.e. 4 are open along perpendicular to screw rod
The vertical line angle in direction is 90 °, and it is other positions that certain those skilled in the art, which can according to need 4 openings of setting,；Setting
This section of temperature is 170 DEG C, and hot melt material is extruded under the Strong shear power effect of the shearing tooth, is adhered to the graphite raw material
On hot melt material by shearing motion by the graphite raw material remove at graphene, make graphite raw material remove to form single layer or more
The graphene of layer large scale area, forms the hot melt material of graphene doping；
In the stirring section, the third screw pitch of stirring section screw thread is 4cm, and lead angle is 30 °, this section of temperature, which is arranged, is
190 DEG C, hot melt material is in the molten condition of higher temperature, and graphene is uniform in melting hot-melt object material along screw rod direction of rotation
It scatter, obtains finely dispersed graphene fusant, and be gradually fed forward；
（3）Step（2）Obtained graphene fusant obtains graphene conductive masterbatch by extruding pelletization, cooling.
Graphene conductive masterbatch manufactured in the present embodiment can be used as additive application in rubber, resin, improve its conduction
Property, more preferably it is applied to integrated circuit packaging, electromagnetic wave shielding utilizes.It can by graphene conductive masterbatch prepared in example IV
As additive application in second the third insulated cable rubber, it is as shown in table 1 that performance parameter is obtained after tested.
Embodiment 5
（1）It is 29 by mass percent, thermal cracking graphite that partial size is 5mm and the 1- pyridine acid that mass percent is 1,
Mass percent is 72, and the PES polyester hot-melt adhesive that partial size is 50 mm, which is mixed in a high speed mixer with the revolving speed of 1200rpm, to be divided
25min is dissipated, pre-composition is obtained；
（2）By step（1）Obtained pre-composition is added in Strong shear screw extruder, cuts the spiral shell rib of screw machine screw thread by force
Section is rectangular configuration, and Strong shear screw extruder sets gradually conveying reduction stage, removing section, stirring from feed end to discharge end
Section, when screw rod is rotated with the revolving speed of 1200rpm, in the conveying section, the second screw pitch for conveying reduction stage screw thread is 10cm, screw thread
Lift angle is 60 °, and it is 140 DEG C that this section of temperature, which is arranged, and the partial size of graphite raw material decreases below 1 millimeter in pre-composition, and with it is described
Hot melt material is gradually fed forward together；
In the removing section, first screw pitch for removing section screw thread is 8cm, and lead angle is 45 °, and screw machine screw thread exists
Prolong 4 openings in the corresponding unit screw thread extensions of the first screw pitch and be respectively distributed a shearing tooth, shearing tooth be it is arc-shaped, shearing tooth
The facewidth is less than the Opening length, and in the present embodiment, 4 openings are that opposite position i.e. 4 are open along perpendicular to screw rod
The vertical line angle in direction is 90 °, and it is other positions that certain those skilled in the art, which can according to need 4 openings of setting,；Setting
This section of temperature is 180 DEG C, and hot melt material is extruded under the Strong shear power effect of the shearing tooth, is adhered to the graphite raw material
On hot melt material by shearing motion by the graphite raw material remove at graphene, make graphite raw material remove to form single layer or more
The graphene of layer large scale area, forms the hot melt material of graphene doping；
In the stirring section, the third screw pitch of stirring section screw thread is 5cm, and lead angle is 35 °, this section of temperature, which is arranged, is
200 DEG C, hot melt material is in the molten condition of higher temperature, and graphene is uniform in melting hot-melt object material along screw rod direction of rotation
It scatter, obtains finely dispersed graphene fusant, and be gradually fed forward；
（3）Step（2）Obtained graphene fusant obtains graphene conductive masterbatch by extruding pelletization, cooling.
Graphene conductive masterbatch manufactured in the present embodiment can be used as additive application in rubber, resin, improve its conduction
Property, more preferably it is applied to integrated circuit packaging, electromagnetic wave shielding utilizes.It can by graphene conductive masterbatch prepared in embodiment five
As additive application in second the third insulated cable rubber, it is as shown in table 1 that performance parameter is obtained after tested.
Table 1
| Performance indicator | Volume resistivity（Ω•m） | Peel strength/MPa | Insulating surface remains after removing |
| Embodiment one | 157 | 17 | Nothing |
| Embodiment two | 179 | 20 | Nothing |
| Embodiment three | 123 | 15 | Nothing |
| Example IV | 107 | 18 | Nothing |
| Embodiment five | 92 | 19 | Nothing |
Claims (6)
1. a kind of preparation method of graphene conductive masterbatch, which is characterized in that squeezed using a Strong shear screw rod with shearing tooth
Graphite raw material is sheared grinding under colloidal state with hot melt material to prepare by machine out, and the specific method is as follows：
（1）By mass percent be 15-29 graphite raw material and mass percent be 0-1 dispersing agent, mass percent 70-
85 hot melt material mixes dispersion 10-25min in a high speed mixer with the revolving speed of 600-1200rpm, obtains pre-composition；
（2）By step（1）Obtained pre-composition is added in the Strong shear screw extruder, the Strong shear screw extruder by
Feed end sets gradually conveying reduction stage, removing section, stirring section to discharge end, when screw rod is rotated with the revolving speed of 100-1200rpm,
In the conveying reduction stage, it is 120-140 DEG C that this section of temperature, which is arranged, and the partial size of graphite raw material decreases below 1 milli in pre-composition
Rice, and be gradually fed forward together with the hot melt material；The second screw pitch for conveying reduction stage screw thread is 8-10cm, lead angle
It is 45-60 °, wherein second screw pitch is the screw pitch of the conveying reduction stage screw thread；
In the removing section, it is 160-180 DEG C that this section of temperature, which is arranged, and screw machine screw thread is prolonging the corresponding unit screw thread of the first screw pitch
N number of opening is respectively distributed a shearing tooth in extensions, and hot melt material is extruded under the Strong shear power effect of the shearing tooth, adheres to
Hot melt material on the graphite raw material removes the graphite raw material at graphene by shearing motion, shells graphite raw material
From the graphene for forming single-layer or multi-layer large scale area, the hot melt material of graphene doping is formed, wherein first screw pitch
For the screw pitch of the removing section screw thread, N is the integer more than or equal to 1；First screw pitch for removing section screw thread is 3-8cm, spiral shell
Line lift angle is 30-45 °；The shearing tooth is one of square column type, arc-shaped, involute, and the facewidth of the shearing tooth is small
In equal to the Opening length；
In the stirring section, it is 180-200 DEG C that this section of temperature, which is arranged, and hot melt material is in the higher molten condition of temperature, graphite
Alkene is evenly spread out in melting hot-melt object material along screw rod direction of rotation, obtains finely dispersed graphene fusant, and gradually
It is fed forward；The third screw pitch of stirring section screw thread is 2-5cm, and lead angle is 25-35 °；
（3）Step（2）Obtained graphene fusant obtains graphene conductive masterbatch by extruding pelletization, cooling.
2. a kind of preparation method of graphene conductive masterbatch according to claim 1, which is characterized in that the graphite raw material
For at least one of crystalline flake graphite, expanded graphite, highly oriented graphite, thermal cracking graphite, graphite oxide, the graphite raw material grain
Diameter is less than or equal to 10 millimeters.
3. a kind of preparation method of graphene conductive masterbatch according to claim 1, which is characterized in that the hot melt material
For one or more of EVA hot-melt adhesive, PA hot melt adhesive, PES polyester hot-melt adhesive, PE polyethylene hot-melt adhesive, the hot melt material
Partial size be 3-50mm.
4. a kind of preparation method of graphene conductive masterbatch according to claim 1, which is characterized in that the dispersing agent
For at least one of lauryl sodium sulfate, neopelex, polyvinylpyrrolidone, 1- pyridine acid.
5. a kind of preparation method of graphene conductive masterbatch according to claim 1, which is characterized in that the spiral shell of the screw thread
The section of rib is one of triangular structure, rectangular configuration and trapezium structure.
6. a kind of graphene conductive masterbatch, which is characterized in that the graphene conductive masterbatch is as described in claim any one of 1-5
The solid mixt that is prepared of method, as additive application in rubber, resin.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP5688669B1 (en) * | 2014-09-09 | 2015-03-25 | グラフェンプラットフォーム株式会社 | Graphite-based carbon material used as graphene precursor, graphene dispersion containing the same, graphene composite, and method for producing the same |
| CN104592620A (en) * | 2015-01-26 | 2015-05-06 | 湖北工业大学 | Resin/graphene conductive plastic master batch as well as preparation method and use thereof |
| CN105324241A (en) * | 2013-04-18 | 2016-02-10 | 新泽西鲁特格斯州立大学 | In situ exfoliation method for preparing graphene-reinforced polymer matrix composites |
| CN105315538A (en) * | 2015-12-01 | 2016-02-10 | 厦门陆海环保股份有限公司 | Regenerated polyethylene-graphene composite conducting material and preparation method thereof |
| CN105502367A (en) * | 2015-12-31 | 2016-04-20 | 成都新柯力化工科技有限公司 | Method for preparing graphene by pulling jelly |
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|---|---|---|---|---|
| CN105324241A (en) * | 2013-04-18 | 2016-02-10 | 新泽西鲁特格斯州立大学 | In situ exfoliation method for preparing graphene-reinforced polymer matrix composites |
| JP5688669B1 (en) * | 2014-09-09 | 2015-03-25 | グラフェンプラットフォーム株式会社 | Graphite-based carbon material used as graphene precursor, graphene dispersion containing the same, graphene composite, and method for producing the same |
| CN104592620A (en) * | 2015-01-26 | 2015-05-06 | 湖北工业大学 | Resin/graphene conductive plastic master batch as well as preparation method and use thereof |
| CN105315538A (en) * | 2015-12-01 | 2016-02-10 | 厦门陆海环保股份有限公司 | Regenerated polyethylene-graphene composite conducting material and preparation method thereof |
| CN105502367A (en) * | 2015-12-31 | 2016-04-20 | 成都新柯力化工科技有限公司 | Method for preparing graphene by pulling jelly |
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