CN106566175A - Special semiconductive shielded graphene masterbatch for electric cables, and a preparation method thereof - Google Patents
Special semiconductive shielded graphene masterbatch for electric cables, and a preparation method thereof Download PDFInfo
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- 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
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- 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
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- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
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Abstract
The invention provides a semiconductive shielded graphene masterbatch for electric cables, and a preparation method thereof. According to the present invention, a semiconductive shielded graphene masterbatch is prepared by using an engaging screw machine, wherein graphite can form sheet-shaped orientation and can be subjected to directional shear stripping through the engaging block thread element in a shear stripping region when the material continuously passes through a screw extrusion chamber so as to form the radial large size area and high quality graphene, the radial large size area and high quality graphene and a masterbatch carrier are subjected to shear dispersion, and the graphene and the masterbatch carrier are further mixed and uniformly dispersed in a dispersing and mixing region so as to solve the defects of dispersion and compatibility and obtain the semiconductive shielded graphene masterbatch for electric cables; and the technical problems that the cost is high and the environmental pollution is generated during the production process in the prior art are overcome, such that the low-cost, pollution-free and large-scale preparation of the graphene electric cable masterbatch is achieved so as to further promote the mass production of the graphene electric cable.
Description
Technical field
The present invention relates to cable material field, and in particular to a kind of special semi-conductive screen Graphene masterbatch of cable and preparation
Method.
Background technology
2004, Univ Manchester UK physicss professor Geim etc. was peeled off and observed with a kind of extremely simple method
Quasi- two-dimensional material --- the Graphene of carbon is arrived, its special structure makes it have perfect quantum tunneling effect, half whole
The series of properties such as several quantum hall effect, the electrical conductivity for never disappearing cause the huge interest of scientific circles.Since graphite
After alkene is found, possess because its light transmission is good, heat conductivity is high, electron mobility is high, resistivity is low, mechanical strength is high etc.
The performance that numerous common materials do not possess, is expected to various fields and extensively applies, and is one of most promising advanced material, Graphene
Performance and huge market application foreground caused the research boom in the fields such as physics and material science.
Cable has the feature of interior energization, external insulation.Such as power cable, control cable, compensating cable, shielded cable, height
Warm cable, computer cable, signal cable, coaxial cable, fire-resisting cable, cable for ship, mine cable and aluminium alloy cable etc.,
Apply is used to connect circuit, electrical equipment etc. in power system, information transfer and instrument system.The 10KV seen in prior art
And the power cable of the above typically has conductor shield and insulation screen, to reach the effect of homogenizing electric field, and it is most of
Using semiconducting rubber as screen layer, semiconducting rubber screen layer is usually by rubber and conduction to shield type rubber flexible cable
White carbon black is prepared from through mechanical mixture, and in recent years, Graphene is used for semiconductive as a kind of special material of cable material
Shielding rubber.
Chinese invention patent application number 201410172273.4 discloses a kind of CABLE MATERIALS containing Graphene, by by stone
Black alkene is added in the raw materials such as resin, polyethylene, EVA, polyethyleneglycol diacrylate, by raw material mix homogeneously, in twin screw
The cable containing Graphene is prepared in mixing, pelletize in extruder.
Chinese invention patent application number 201410487326.1 discloses a kind of modified graphene CABLE MATERIALS, first by stone
Black alkene is modified, and obtains modified graphene, then modified graphene and other additives is added through plasticating as raw material
In the raw materials such as natural rubber nitrile rubber, ethylene-vinyl acetate copolymer afterwards, Graphene cable is prepared by Screw Extrusion
Material.
Chinese invention patent application number 201510439101.3 discloses a kind of graphene semiconductor shielding material, first prepares
Finely dispersed graphene nanometer sheet (GR) aqueous solution, stirring is lower to add ethylene-vinyl acetate (EVA) emulsion, obtains GR/
The molding on vulcanizing press after EVA solid rubber master batch, is sufficiently mixed by double roller cylinder mill, plus vulcanizing agent is processed, obtains stone
Black alkene shield semiconductors material.
Chinese invention patent application number 201410697240.1 discloses a kind of cable Graphene semiconductive shieldin material
Preparation method, by the way that Graphene and resin are mixed respectively with organic solution tetrahydrofuran, dimethylbenzene, chloroform etc., so
Graphene solution is mixed with mixed resin solution afterwards, the mixed solution of Graphene and resin is obtained, then in noble gases
Under protection, cable semiconductive shieldin material is obtained by spray drying granulation.Due to needing addition a large amount of organic in preparation process
Thing solvent, the type organic is poisonous and inflammable and explosive to human body, is also easy to produce environmental pollution, causes the presence of safe asking in commercial production
Topic and environmental problem.
It follows that directly using graphene nano material as Raw material processing Graphene CABLE MATERIALS in prior art, by
It is expensive in Graphene, Graphene is directly increased into Graphene CABLE MATERIALS production cost directly as raw materials for production, it is unfavorable
In large-scale promotion application.Additionally, in process of production by the use of Organic substance as solvent, being detrimental to health and causing environment
Pollution, it is difficult to carry out large-scale production, therefore, developing low-cost, prepare to scale Graphene cable masterbatch and meet Graphene
Cable market demand.
The content of the invention
For at present directly by the use of Graphene as the raw material for producing cable, high cost, cannot large-scale production defect,
The present invention proposes a kind of special semi-conductive screen Graphene masterbatch of cable and preparation method, overcomes cost in prior art and holds high
It is expensive, the technical problem of the environmental pollution of the generation of preparation process, so as to realizing low cost, preparing to scale Graphene cable mother
Material, the mass production for further having promoted Graphene cable is produced.
To solve the above problems, on the one hand, the present invention is employed the following technical solutions：
A kind of special semi-conductive screen Graphene masterbatch of cable, the masterbatch is prepared from by the raw material of following weight percents：
Masterbatch carrier 85-93%
Graphite 5-10%
Plasticizer 1.5-3%
Dispersant 0.5-2%
Wherein, described masterbatch carrier is ABS resin, PE resins, PP resins, HIPS polystyrene resins, polyvinyl chloride resin, EVA
The mixture of one or more of resin, natural rubber and nitrile rubber；Described graphite raw material be graphite powder, crystalline flake graphite,
At least one in expanded graphite, highly oriented graphite, thermal cracking graphite, graphite oxide；Described plasticizer be epoxy soybean oil,
One or more mixture of o-phthalic acid dibutyl ester, dioctyl sebacate, diisooctyl phthalate；Described dispersion
Agent is polyamide wax, polypropylene wax, EVA waxes, calcium stearate and magnesium stearate, ethylene group bis-stearamides, oleamide, erucic acid
Amide, 10PE27, phthalic acid ester, citrate, acetyl citrate, monoglyceride and pentaerythritol ester
The mixture of one or more.
On the other hand, the present invention discloses a kind of preparation method of the special semi-conductive screen Graphene masterbatch of cable, using rotation
Turn engagement screws machine by the stripping of shearing force to prepare, concrete grammar is as follows：
（1）Masterbatch carrier, plasticizer and dispersant are mixed into dispersion 10- in high-speed mixer with the rotating speed of 600-1200rpm
25min, obtains pre-composition；In terms of 100% mass fraction, wherein rubber carrier mass fraction is 80 to the quality sum of pre-composition
~ 90%, plasticizer mass fraction is 1.5-3%, and dispersant mass fraction is 0.5-1%；
（2）By step（1）The pre-composition and graphite for obtaining is separately added into the rotation engagement screws machine, extrusion from two spouts
Machine spout is connected with flow mixing device entrance, and material converges through flow mixing device, obtains masterbatch carrier and graphite mixture material, and then squeezes
Enter to rotate engagement screws machine extrusion within the chamber, mixed material is dispersed along screw rod direction of rotation, forms uniform random distribution,
And gradually to discharge end conveying, wherein, it is 100-200 DEG C that the flow mixing device arranges temperature；
Wherein, the extrusion within the chamber is divided into shearing stripping area and dispersion mixing area from feed end to discharge end, in the shearing
In stripping area, arrange least one set rotation engagement screws group, the screw rod group rotating shaft hang down parallel to the feed end with it is described go out
Material end line, in dispersion mixing area arrange least one set rotation engagement screws group, the screw rod group rotating shaft perpendicular to it is described enter
Material end and the discharge end line.
（3）Step（2）Finely dispersed material continues through natural cooling, pelletizing, air drying process, that is, obtain cable special
Semi-conductive screen Graphene masterbatch.
Preferably, the screw rod of shearing stripping area screw rod group from feed end to discharge end set gradually dispersion orientation section,
Section is peeled off in shearing carbonization section, shearing, and screw slenderness ratio peels off section length less than the shearing in shearing stripping area screw rod group,
Screw diameter is 20-180mm；
Described dispersion orientation section conveys the engagement spiral shell that screwing element, two groups of teeth shape disk, four groups of oblique angles are 60 ° by two group 56/56
Texel part, four groups of reverse 56/56 conveying screwing element compositions；
Described shearing carbonization Duan Yousi groups oblique angle be 45 ° engagement screwing element, engagement screw thread that four groups of oblique angles are 60 ° it is first
Part, four groups reverse 45 ° of engagement screwing element composition；
It is first that the engagement screw thread that the engagement screwing element that Duan Yousi groups oblique angle is 30 °, four groups of oblique angles are 45 ° is peeled off in described shearing
Part, four groups reverse 45 ° of engagement screwing element group, four groups 90 ° of right angle engagement screwing element, four groups reverse 60 ° of engagement spiral shell
Texel part is constituted.
Preferably, the screw rod in the dispersion mixing district screw rod group is made up of four groups 90 ° of right angle engagement screwing element, institute
State screw slenderness ratio in dispersion mixing district screw rod group and be more than 10/1, screw diameter is 50-200mm.
Preferably, the screw rod in the screw rod group is rotated with the rotating speed of 100-1200rpm, and the rotation engagement screws machine sets
Temperature is put for 170-240 DEG C.
Graphene cable performance prepared by semi-conductive screen Graphene masterbatch prepared by the present invention, as shown in table 1.
Table 1：
| Performance indications | Tensile strength | Elongation at break | 20 DEG C of volume resistances | Melt index (pressure 20KG) |
| Graphene cable | 10.5MPa | 280% | 28.4Ω•cm | 1.0g/10min |
The method that a kind of utilization screw machine shearing of the present invention continuously prepares grapheme material, compared with prior art, what it was projected
Feature and excellent effect are：
1st, the inventive method directly adopts the materials such as graphite and resin as masterbatch carrier for raw material, using the engagement in the present invention
, for semi-conductive screen Graphene masterbatch, raw material sources are extensively, with low cost, with the significant market competitiveness for screw mechanism.
2nd, the engagement screws machine in the present invention is realized continuous as the reactor for preparing semi-conductive screen Graphene masterbatch
Prepare with scale semi-conductive screen Graphene masterbatch, and non-environmental-pollution, yield are high, have further promoted Graphene cable
Extensive industrialized development.
3rd, the engagement screws machine in the present invention prepares semi-conductive screen Graphene masterbatch, is continuing through Screw Extrusion chamber
During, first graphite can form the orientation of piece shape, and by shearing the gear block screwing element of stripping area in the side of orientation
To stripping is sheared, disperse so as to defining the high-quality graphene of radial direction large scale area and shearing with masterbatch carrier, dividing
Graphene can further be mixed and is uniformly dispersed by scattered mixed zone with masterbatch carrier again, solve dispersion, compatible defect, obtain one
Plant the special semi-conductive screen Graphene masterbatch of cable.
Description of the drawings
For the further special semi-conductive screen Graphene masterbatch preparation process of clear and definite cable, illustrated by accompanying drawing.
Accompanying drawing 1：Engage three screw machine appearance schematic diagrams.
1- spouts 1；2- spouts 2；3- flow mixing devices；4- shears stripping area；5- dispersion mixings area；6- discharging openings；7- spiral shells
Bar group 1；8- screw rod groups 2.
Specific embodiment
Below by way of specific embodiment, the present invention is described in further detail, but this should not be interpreted as into the present invention
Scope be only limitted to Examples below.In the case of without departing from said method thought of the present invention, according to ordinary skill
Various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Embodiment 1
（1）ABS resin and PE resins that mass fraction is 85% are taken, mass fraction is 2% o-phthalic acid dibutyl ester and quality
Fraction is that 3% polyamide wax mixes dispersion 10min in high-speed mixer with the rotating speed of 600rpm, obtains pre-composition.
（2）By step（1）The pre-composition and mass fraction for obtaining is that 10% crystalline flake graphite adds respectively from two spouts
Enter to rotate engagement screws machine, as shown in figure 1, extruder spout 1 and spout 2 are connected with the entrance of flow mixing device 3, material is through mixed
Flow device 3 to converge, flow mixing device 3 arranges temperature and obtains masterbatch carrier and crystalline flake graphite mixed material for 100 DEG C, and then clamp-on rotation and nibble
Screw machine extrusion within the chamber is closed, extrusion within the chamber is divided into shearing stripping area 4 and dispersion mixing area 5 from feed end to discharge end,
In shearing stripping area 4, it is screw rod group 1 to arrange one group of rotation engagement screws group, and the rotating shaft of screw rod group 1 is hung down parallel to feed end and discharging
End line, screw slenderness ratio peels off section length less than the shearing in screw rod group 1, and screw diameter is 20mm.The shearing spiral shell of stripping area 4
The screw rod of bar group is set gradually dispersion orientation section, shearing carbonization section, is sheared and peel off section from feed end to discharge end, dispersion orientation section
The engagement screwing element, four groups reverse 56/56 that screwing element, two groups of teeth shape disk, four groups of oblique angles are 60 ° is conveyed by two group 56/56
Conveying screwing element composition, shearing carbonization Duan Yousi groups oblique angle is 45 ° and engages the engagement that screwing element, four groups of oblique angles are 60 °
The engagement screw thread unit that Duan Yousi groups oblique angle is 30 ° is peeled off in screwing element, four groups reverse 45 ° of engagement screwing element composition, shearing
Part, four groups of oblique angles are 45 ° of engagement screwing element, four groups reverse 45 ° of engagement screwing element group, the engagement of four groups 90 ° of right angle
Screwing element, four groups reverse 60 ° of engagement screwing element composition.The compound of pre-composition and crystalline flake graphite composition is through shearing stripping
Behind area, crystalline flake graphite is sheared broken, acquisition big size graphene, mixes with raw materials such as the ABS resin and PE resins after shearing
Compound to dispersion mixing area conveys.
It is screw rod group 2 that three groups of rotation engagement screws groups are arranged in dispersion mixing area 5, and the rotating shaft of screw rod group 2 is perpendicular to described
Feed end and discharge end line, the screw rod in the screw rod group of dispersion mixing area 5 is made up of four groups 90 ° of right angle engagement screwing element,
Screw slenderness ratio is 15/1 in screw rod group 2, and screw diameter is 50mm.After shearing-crushing, material in the dispersion mixing area 5 after
Continuous shearing dispersion, unbroken graphite is further broken up into Graphene, and Graphene can further in ABS resin and PE trees
It is uniformly dispersed in the raw mixtures such as fat.In the present embodiment extrude within the chamber two regions in screw rod group screw rod with 100rpm
Rotating speed rotation, it is 170 DEG C to arrange rotation engagement screws machine temperature.
（3）Step（2）Finely dispersed material continues through natural cooling, pelletizing, air drying process, that is, obtain cable special
Semi-conductive screen Graphene masterbatch.
Through test, the cable material prepared using the special semi-conductive screen Graphene masterbatch of cable in embodiment one
Can be as shown in table 2.
Embodiment 2
（1）ABS resin and PE resins that mass fraction is 90% are taken, mass fraction is 1.5% o-phthalic acid dibutyl ester and matter
Amount fraction is that 0.5% polyamide wax mixes dispersion 10min in high-speed mixer with the rotating speed of 600rpm, obtains pre-composition.
（2）By step（1）The pre-composition and mass fraction for obtaining is that 8% expanded graphite is separately added into from two spouts
Rotation engagement screws machine, extruder spout is connected with flow mixing device entrance, and material converges through flow mixing device, and flow mixing device arranges temperature
Masterbatch carrier and expanded graphite mixed material are obtained for 150 DEG C, and then clamp-ons rotation engagement screws machine extrusion within the chamber, extruding cavity
It is indoor to be divided into shearing stripping area and dispersion mixing area from feed end to discharge end, in shearing stripping area, one group of rotation is set and is nibbled
Screw rod group is closed, screw rod group rotating shaft is hung down parallel to the feed end and discharge end line, screw rod major diameter in shearing stripping area screw rod group
Than peeling off section length less than the shearing, screw diameter is 100mm.The screw rod of shearing stripping area screw rod group is from feed end to discharging
End set gradually dispersion orientation section, shearing carbonization section, shearing peel off section, dispersion orientation section by two group 56/56 convey screwing element,
Two groups of teeth shape disk, four groups of oblique angles are 60 ° of engagement screwing element, convey screwing elements composition, shearing carbonization for four groups reverse 56/56
Duan Yousi groups oblique angle is 45 ° of engagement screwing element, engagement screwing element, four groups of reverse 45 ° of the engagements that four groups of oblique angles are 60 °
Screwing element is constituted, and shearing is peeled off Duan Yousi groups oblique angles and is 30 ° and engages the engagement screw thread that screwing element, four groups of oblique angles are 45 °
Element, four groups reverse 45 ° of engagement screwing element group, four groups 90 ° of right angle engagement screwing element, four groups of reverse 60 ° of engagements
Screwing element is constituted.After the compound of pre-composition and graphite composition is through shearing stripping area, crystalline flake graphite is sheared broken, acquisition
Big size graphene, conveys with raw mixtures such as the ABS resin and PE resins after shearing to dispersion mixing area.
Three groups of rotation engagement screws groups are set in dispersion mixing area, and screw rod group rotating shaft is perpendicular to the feed end and discharging
End line, the screw rod in dispersion mixing district screw rod group is made up of four groups 90 ° of right angle engagement screwing element, dispersion mixing district screw rod
Screw slenderness ratio is 15/1 in group, and screw diameter is 100mm.After shearing-crushing, material continues to cut in dispersion mixing area
Cutting dissipates, and unbroken graphite is further broken up into Graphene, and Graphene can further in ABS resin and PE resins etc.
It is uniformly dispersed in raw mixture.Screw rod group screw rod turning with 500rpm in two regions of within the chamber is extruded in the present embodiment
Speed rotation, it is 170 DEG C to arrange rotation engagement screws machine temperature.
（3）Step（2）Finely dispersed material continues through natural cooling, pelletizing, air drying process, that is, obtain cable special
Semi-conductive screen Graphene masterbatch.
Through test, the cable material prepared using the special semi-conductive screen Graphene masterbatch of cable in embodiment two
Can be as shown in table 2.
Embodiment 3
（1）Nitrile rubber and natural rubber that mass fraction is 85% are taken, mass fraction is 2% dioctyl sebacate and quality
Fraction is that 3% erucyl amide mixes dispersion 10min in high-speed mixer with the rotating speed of 600rpm, obtains pre-composition.
（2）By step（1）The pre-composition and mass fraction for obtaining is that 10% crystalline flake graphite adds respectively from two spouts
Enter to rotate engagement screws machine, extruder spout is connected with flow mixing device entrance, and material converges through flow mixing device, flow mixing device arranges temperature
Spend and obtain masterbatch carrier and crystalline flake graphite mixed material for 200 DEG C, and then clamp-on rotation engagement screws machine extrusion within the chamber, extrusion
Within the chamber is divided into shearing stripping area and dispersion mixing area from feed end to discharge end, in shearing stripping area, arranges one group of rotation
Engagement screws group, screw rod group rotating shaft is hung down parallel to the feed end and discharge end line, and screw rod is long in shearing stripping area screw rod group
Footpath ratio peels off section length less than the shearing, and screw diameter is 150mm.The screw rod of shearing stripping area screw rod group is from feed end to going out
Material end sets gradually and disperses orientation section, shearing carbonization section, shearing stripping section, dispersion orientation section to convey screw thread unit by two group 56/56
Part, two groups of teeth shape disk, four groups of oblique angles are 60 ° of engagement screwing element, convey screwing elements composition, shearing for four groups reverse 56/56
Carbonization Duan Yousi groups oblique angle be 45 ° engagement screwing element, four groups of oblique angles be 60 ° engage screwing element, four groups reverse 45 °
Engagement screwing element composition, shearing is peeled off Duan Yousi groups oblique angles and is 30 ° and engages the engagement that screwing element, four groups of oblique angles are 45 °
Screwing element, four groups reverse 45 ° of engagement screwing element group, four groups 90 ° of right angle engagement screwing element, four groups reverse 60 °
Engagement screwing element composition.Pre-composition and graphite composition compound through shearing stripping area after, crystalline flake graphite be sheared it is broken,
Big size graphene is obtained, is conveyed to dispersion mixing area with raw mixtures such as the nitrile rubbers and natural rubber after shearing.
Three groups of rotation engagement screws groups are set in dispersion mixing area, and screw rod group rotating shaft is perpendicular to the feed end and discharging
End line, the screw rod in dispersion mixing district screw rod group is made up of four groups 90 ° of right angle engagement screwing element, dispersion mixing district screw rod
Screw slenderness ratio is 15/1 in group, and screw diameter is 50mm.
After shearing-crushing, material continues shearing dispersion in dispersion mixing area, and unbroken crystalline flake graphite is further
It is broken into Graphene, and Graphene further can be uniformly dispersed in the raw mixtures such as nitrile rubber and natural rubber.
Screw rod group screw rod in two regions of within the chamber is extruded in the present embodiment to rotate with the rotating speed of 1000rpm, and rotation engagement is set
Screw machine temperature is 200 DEG C.
（3）Step（2）Finely dispersed material continues through natural cooling, pelletizing, air drying process, that is, obtain cable special
Semi-conductive screen Graphene masterbatch.
Through test, the cable material prepared using the special semi-conductive screen Graphene masterbatch of cable in embodiment three
Can be as shown in table 2.
Embodiment 4
（1）ABS resin and PE resins that mass fraction is 90% are taken, mass fraction is 1.5% o-phthalic acid dibutyl ester and matter
Amount fraction is that 0.5% polyamide wax mixes dispersion 25min in high-speed mixer with the rotating speed of 600rpm, obtains pre-composition.
（2）By step（1）The pre-composition and mass fraction for obtaining is that 8% expanded graphite is separately added into from two spouts
Rotation engagement screws machine, extruder spout is connected with flow mixing device entrance, and material converges through flow mixing device, and flow mixing device arranges temperature
Masterbatch carrier and expanded graphite mixed material are obtained for 150 DEG C, and then clamp-ons rotation engagement screws machine extrusion within the chamber, extruding cavity
It is indoor to be divided into shearing stripping area and dispersion mixing area from feed end to discharge end, in shearing stripping area, one group of rotation is set and is nibbled
Screw rod group is closed, screw rod group rotating shaft is hung down parallel to the feed end and discharge end line, screw rod major diameter in shearing stripping area screw rod group
Than peeling off section length less than the shearing, screw diameter is 180mm.The screw rod of shearing stripping area screw rod group is from feed end to discharging
End set gradually dispersion orientation section, shearing carbonization section, shearing peel off section, dispersion orientation section by two group 56/56 convey screwing element,
Two groups of teeth shape disk, four groups of oblique angles are 60 ° of engagement screwing element, convey screwing elements composition, shearing carbonization for four groups reverse 56/56
Duan Yousi groups oblique angle is 45 ° of engagement screwing element, engagement screwing element, four groups of reverse 45 ° of the engagements that four groups of oblique angles are 60 °
Screwing element is constituted, and shearing is peeled off Duan Yousi groups oblique angles and is 30 ° and engages the engagement screw thread that screwing element, four groups of oblique angles are 45 °
Element, four groups reverse 45 ° of engagement screwing element group, four groups 90 ° of right angle engagement screwing element, four groups of reverse 60 ° of engagements
Screwing element is constituted.After the compound of pre-composition and graphite composition is through shearing stripping area, crystalline flake graphite is sheared broken, acquisition
Big size graphene, conveys with raw mixtures such as the ABS resin and PE resins after shearing to dispersion mixing area.
Four groups of rotation engagement screws groups are set in dispersion mixing area, and screw rod group rotating shaft is perpendicular to the feed end and discharging
End line, the screw rod in dispersion mixing district screw rod group is made up of four groups 90 ° of right angle engagement screwing element, dispersion mixing district screw rod
Screw slenderness ratio is 15/1 in group, and screw diameter is 100mm.After shearing-crushing, material continues to cut in dispersion mixing area
Cutting dissipates, and unbroken graphite is further broken up into Graphene, and Graphene can further in ABS resin and PE resins etc.
It is uniformly dispersed in raw mixture.In the present embodiment extrude within the chamber two regions in screw rod group screw rod with 1200rpm's
Rotating speed rotates, and it is 240 DEG C to arrange rotation engagement screws machine temperature.
（3）Step（2）Finely dispersed material continues through natural cooling, pelletizing, air drying process, that is, obtain cable special
Semi-conductive screen Graphene masterbatch.
Through test, the cable material prepared using the special semi-conductive screen Graphene masterbatch of cable in example IV
Can be as shown in table 2.
Embodiment 5
（1）Polyvinyl chloride resin, EVA resin, PP resin compounds that mass fraction is 90% are taken, mass fraction is 1.5% adjacent benzene two
Formic acid dibutyl ester and mass fraction are that 0.5% polyamide wax mixes dispersion in high-speed mixer with the rotating speed of 600rpm
25min, obtains pre-composition.
（2）By step（1）The pre-composition and mass fraction for obtaining is that 8% expanded graphite is separately added into from two spouts
Rotation engagement screws machine, extruder spout is connected with flow mixing device entrance, and material converges through flow mixing device, and flow mixing device arranges temperature
Masterbatch carrier and expanded graphite mixed material are obtained for 150 DEG C, and then clamp-ons rotation engagement screws machine extrusion within the chamber, extruding cavity
It is indoor to be divided into shearing stripping area and dispersion mixing area from feed end to discharge end, in shearing stripping area, one group of rotation is set and is nibbled
Screw rod group is closed, screw rod group rotating shaft is hung down parallel to the feed end and discharge end line, screw rod major diameter in shearing stripping area screw rod group
Than peeling off section length less than the shearing, screw diameter is 180mm.The screw rod of shearing stripping area screw rod group is from feed end to discharging
End set gradually dispersion orientation section, shearing carbonization section, shearing peel off section, dispersion orientation section by two group 56/56 convey screwing element,
Two groups of teeth shape disk, four groups of oblique angles are 60 ° of engagement screwing element, convey screwing elements composition, shearing carbonization for four groups reverse 56/56
Duan Yousi groups oblique angle is 45 ° of engagement screwing element, engagement screwing element, four groups of reverse 45 ° of the engagements that four groups of oblique angles are 60 °
Screwing element is constituted, and shearing is peeled off Duan Yousi groups oblique angles and is 30 ° and engages the engagement screw thread that screwing element, four groups of oblique angles are 45 °
Element, four groups reverse 45 ° of engagement screwing element group, four groups 90 ° of right angle engagement screwing element, four groups of reverse 60 ° of engagements
Screwing element is constituted.After the compound of pre-composition and graphite composition is through shearing stripping area, crystalline flake graphite is sheared broken, acquisition
Big size graphene, it is defeated to dispersion mixing area with raw mixtures such as polyvinyl chloride resin, EVA resin, the PP resin compounds after shearing
Send.
Two groups of rotation engagement screws groups are set in dispersion mixing area, and screw rod group rotating shaft is perpendicular to the feed end and discharging
End line, the screw rod in dispersion mixing district screw rod group is made up of four groups 90 ° of right angle engagement screwing element, dispersion mixing district screw rod
Screw slenderness ratio is 15/1 in group, and screw diameter is 100mm.After shearing-crushing, material continues to cut in dispersion mixing area
Cutting dissipates, and unbroken graphite is further broken up into Graphene, and Graphene can further polyvinyl chloride resin, EVA resin,
It is uniformly dispersed in the raw mixtures such as PP resin compounds.Screw rod group spiral shell in two regions of within the chamber is extruded in the present embodiment
Bar is rotated with the rotating speed of 1200rpm, and it is 240 DEG C to arrange rotation engagement screws machine temperature.
（3）Step（2）Finely dispersed material continues through natural cooling, pelletizing, air drying process, that is, obtain cable special
Semi-conductive screen Graphene masterbatch.
Through test, the cable material prepared using the special semi-conductive screen Graphene masterbatch of cable in embodiment five
Can be as shown in table 2.
Table 2
| Performance indications | Tensile strength | Elongation at break | 20 DEG C of volume resistances | Melt index (pressure 20KG) |
| Embodiment one | 10.5MPa | 280% | 28.4Ω•cm | 1.0g/10min |
| Embodiment two | 11.3MPa | 310% | 26.3Ω•cm | 1.4g/10min |
| Embodiment three | 10.7MPa | 250% | 24.4Ω•cm | 2.2g/10min |
| Example IV | 14.5MPa | 370% | 30.4Ω•cm | 1.7g/10min |
| Embodiment five | 12.2MPa | 290% | 29.4Ω•cm | 3.2g/10min |
Claims (5)
1. the special semi-conductive screen Graphene masterbatch of a kind of cable, it is characterised in that the masterbatch by following masses fraction original
Material is prepared from：
Masterbatch carrier 85-93%
Graphite raw material 5-10%
Plasticizer 1.5-3%
Dispersant 0.5-2%
Wherein, described masterbatch carrier is ABS resin, PE resins, PP resins, HIPS polystyrene resins, polyvinyl chloride resin, EVA
The mixture of one or more of resin, natural rubber and nitrile rubber；Described graphite raw material is crystalline flake graphite, expansion stone
At least one in black, highly oriented graphite, thermal cracking graphite, graphite oxide；Described plasticizer is epoxy soybean oil, adjacent benzene two
One or more mixture of formic acid dibutyl ester, dioctyl sebacate, diisooctyl phthalate；Described dispersant is poly-
Amide waxe, polypropylene wax, EVA waxes, calcium stearate and magnesium stearate, ethylene group bis-stearamides, oleamide, erucyl amide,
One kind of 10PE27, phthalic acid ester, citrate, acetyl citrate, monoglyceride and pentaerythritol ester
Or several mixture.
2. the preparation method of the special semi-conductive screen Graphene masterbatch of a kind of cable, it is characterised in that using rotation engagement screws
Machine is prepared by the stripping of shearing force, and concrete grammar is as follows：
（1）By mass fraction be 85-93% masterbatch carriers, 1.5-3% plasticizers and 0.5-2% dispersants in high-speed mixer with
The rotating speed of 600-1200rpm mixes dispersion 10-25min, obtains pre-composition；
（2）By step（1）The pre-composition for obtaining and mass fraction are separately added into described for the graphite of 5-10% from two spouts
Rotation engagement screws machine, extruder spout is connected with flow mixing device entrance, and material converges through flow mixing device, obtain masterbatch carrier and
Graphite mixture material, and then rotation engagement screws machine extrusion within the chamber is clamp-oned, mixed material is dispersed along screw rod direction of rotation,
Uniform random distribution is formed, and gradually to discharge end conveying, wherein, it is 100-200 DEG C that the flow mixing device arranges temperature；
Wherein, the extrusion within the chamber is divided into shearing stripping area and dispersion mixing area from feed end to discharge end, in the shearing
In stripping area, arrange least one set rotation engagement screws group, the screw rod group rotating shaft hang down parallel to the feed end with it is described go out
Material end line, in dispersion mixing area arrange least one set rotation engagement screws group, the screw rod group rotating shaft perpendicular to it is described enter
Material end and the discharge end line；
（3）Step（2）Finely dispersed material continues through natural cooling, pelletizing, air drying process, that is, obtain that cable is special partly to lead
Electric screen Graphene masterbatch.
3. the preparation method of the special semi-conductive screen Graphene masterbatch of a kind of cable as claimed in claim 2, it is characterised in that
The screw rod of shearing stripping area screw rod group sets gradually dispersion orientation section, shearing carbonization section, shearing from feed end to discharge end
Section is peeled off, screw slenderness ratio peels off section length less than the shearing in shearing stripping area screw rod group, and screw diameter is 20-
180mm；
Described dispersion orientation section conveys the engagement spiral shell that screwing element, two groups of teeth shape disk, four groups of oblique angles are 60 ° by two group 56/56
Texel part, four groups of reverse 56/56 conveying screwing element compositions；
Described shearing carbonization Duan Yousi groups oblique angle be 45 ° engagement screwing element, engagement screw thread that four groups of oblique angles are 60 ° it is first
Part, four groups reverse 45 ° of engagement screwing element composition；
It is first that the engagement screw thread that the engagement screwing element that Duan Yousi groups oblique angle is 30 °, four groups of oblique angles are 45 ° is peeled off in described shearing
Part, four groups reverse 45 ° of engagement screwing element group, four groups 90 ° of right angle engagement screwing element, four groups reverse 60 ° of engagement spiral shell
Texel part is constituted.
4. the preparation method of the special semi-conductive screen Graphene masterbatch of a kind of cable as claimed in claim 3, it is characterised in that
Screw rod in the dispersion mixing district screw rod group is made up of four groups 90 ° of right angle engagement screwing element, dispersion mixing area spiral shell
Screw slenderness ratio is more than 10/1 in bar group, and screw diameter is 50-200mm.
5. the preparation method of the special semi-conductive screen Graphene masterbatch of a kind of cable as claimed in claim 4, it is characterised in that
Screw rod in the screw rod group is rotated with the rotating speed of 100-1200rpm, and it is 170-240 that the rotation engagement screws machine arranges temperature
℃。
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| CN107358999A (en) * | 2017-07-31 | 2017-11-17 | 武汉大学 | A kind of electromagnetic shielding cable |
| CN108624009A (en) * | 2018-05-25 | 2018-10-09 | 郭跃 | A kind of preparation method of the wear-resisting compound conductive plastic of low resistance |
| CN109233100A (en) * | 2018-09-07 | 2019-01-18 | 安徽华网电缆有限公司 | A kind of special plastic substitution shielding material and its manufacturing method |
| CN109370027A (en) * | 2018-09-18 | 2019-02-22 | 特变电工(德阳)电缆股份有限公司 | A kind of compound semi-conductive shielding material of graphene, preparation method and applications |
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| CN107358999A (en) * | 2017-07-31 | 2017-11-17 | 武汉大学 | A kind of electromagnetic shielding cable |
| CN107358999B (en) * | 2017-07-31 | 2019-09-10 | 武汉大学 | A kind of electromagnetic shielding cable |
| CN108624009A (en) * | 2018-05-25 | 2018-10-09 | 郭跃 | A kind of preparation method of the wear-resisting compound conductive plastic of low resistance |
| CN109233100A (en) * | 2018-09-07 | 2019-01-18 | 安徽华网电缆有限公司 | A kind of special plastic substitution shielding material and its manufacturing method |
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| CN109651754A (en) * | 2018-12-06 | 2019-04-19 | 安徽集虹材料科技有限公司 | A kind of antistatic high tenacity ABS plastic of low sizing content and preparation method thereof |
| CN109651754B (en) * | 2018-12-06 | 2021-05-25 | 安徽集虹材料科技有限公司 | Antistatic high-toughness ABS plastic with low filler content and preparation method thereof |
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