CN109575398A - Mining type graphene, carbon black, polyethylene composite pipe and preparation method thereof - Google Patents

Mining type graphene, carbon black, polyethylene composite pipe and preparation method thereof Download PDF

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Publication number
CN109575398A
CN109575398A CN201811366872.4A CN201811366872A CN109575398A CN 109575398 A CN109575398 A CN 109575398A CN 201811366872 A CN201811366872 A CN 201811366872A CN 109575398 A CN109575398 A CN 109575398A
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carbon black
graphene
parts
polyethylene
antioxidant
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Inventor
田振宇
杨万庆
谢卫宏
白国伟
王晓华
张寿明
张博
李文学
司书鑫
瞿研
刘平
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SIXTH ELEMENT (CHANGZHOU) Ltd
Shandong Fangda New Mstar Technology Ltd
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SIXTH ELEMENT (CHANGZHOU) Ltd
Shandong Fangda New Mstar Technology Ltd
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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
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K2003/026—Phosphorus
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • C08K2003/3045—Sulfates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/04—Antistatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/18—Applications used for pipes
    • 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
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/06—Properties of polyethylene
    • C08L2207/062—HDPE

Abstract

The present invention provides a kind of mining type graphene, carbon black, polyethylene compound particle, each component is by weight, comprising: 100 parts of high density polyethylene (HDPE), 0.1~2 part of graphene, 1~10 part of carbon black, 4~15 parts of fire retardant, 0.5~3 part of dispersion liquid, 0.5~4 part of nucleating agent, 2~10 parts of toughener, 0.5~4 part of antioxidant.The present invention also provides the preparation methods and purposes of mining type graphene, carbon black, polyethylene compound particle.The graphene that the present invention is prepared/polyethylene tensile strength is up to 25MPa, disconnected column elongation up to 402%.Its mechanical property fully achieves GB/T8804-2003 in colliery industry standard MT558.1-2005 " measurement of thermoplastic plastic pipe tensile property ": tensile strength >=9MPa, elongation at break >=300%.

Description

Mining type graphene, carbon black, polyethylene composite pipe and preparation method thereof
Technical field
The present invention relates to a kind of efficient mining type pipe materials and preparation method thereof, belong to high polymer material technology and processing Field.
Background technique
Polyethylene (PE) tubing has many advantages, such as good corrosion resistance, long service life, light weight, easy for construction, extensive Use applied to every field, especially in coal mining.But the PE tubing of underground mine use is in antistatic and flame retardant property side The requirement in face is extremely harsh, and needs to have good mechanical mechanics property.
Currently, the pertinent literature about anti-electrostatic fire retardant mineral polyethylene piping materials also has been reported that.CN 104277279 A A kind of fire retardant, antistatic polyethylene pipe material and preparation method thereof is disclosed, the conductive black addition of 20wt%~40wt% is supreme In density polyethylene matrix, under the promoter effects such as coupling agent, reach antistatic property.High additive amount carbon black leads to drawing pipe And the mechanical properties degradation such as elongation at break, compared to for pure PE tubing, elongation at break has dropped 50%~60%, needs Add the deficiency that appropriate toughener makes up tensile toughness.Material melt viscosity is got higher again simultaneously, is turned round during tube extrusion Square is excessive, squeezes out phenomena such as unstable.The carbon black of high additive amount can also make tubing matter double wall thick, and rough surface can not meet mining The demand of downhole tubular goods；CN104151664B discloses a kind of preparation method of polyethylene composite pipe modified with graphene, Graphene/polyethylene master batch is prepared using modified graphene powder, then female with graphene/polyethylene of 1-100 parts by weight Grain after mixing evenly, is added to obtained graphite in plastic pipe extruder with the polyethylene composite pipe material of 100 parts by weight Alkene modified poly ethylene composite pipe.In this technology, graphene is modified processing with a large amount of surfactant first, processing Process uses ultrasonic disperse, and graphene obtained in this technology/polyethylene master batch cannot be needed directly as pipe material again Further organic polymer dilution technique is wanted, just can be used as pipe material.It is complex technical process, at high cost, and ultrasound point It dissipates since its noise pollution causes large-scale production limited.CN102010540B and CN102775669A are individually disclosed for mine With the antistatic constituent and Expandable flame-retardant coal mine downhole polyethylene tube of flame-proof polyethylene, two patents utilize graphite Respectively as conductive filler and fire retardant, prepared antistatic and anti-flammability meets mining standard, and defect is that additive amount is larger, Performance boost is unobvious；CN104262740A discloses a kind of hdpe pipe, prepares stone using screw extruder The powder-modified hdpe pipe of black alkene, but the graphene powder specific surface area of high-quality is larger, density is small, and its The additive amount of graphene is larger, and direct Screw Extrusion is blended graphene powder and is not easy to be added in plastics system, cause to disperse it is poor, The sheet resistance of the tubing of final production is 1.0 × 106Ω or more does not meet pipe material for coal mine standard.
The stringent definition of graphene (Graphene) be one kind by carbon atom with sp2The two-dimensional surface knot that hybrid form is formed Structure.With the difference of technique in graphene production preparation, and in order to realize that the graphene for obtaining different performance in process produces Product may be connected to minimal amount of oxygen-containing group on the graphene C atom in the disclosure, or by multilayer two-dimension planar structure Graphene is stacked the graphene product of the multilayered structure to be formed.Graphene is to be currently known conductive best material at room temperature Material, electron mobility can reach 2 × 105cm2/ Vs, 140 times of electron mobility about in silicon, resistivity is up to 10-8 Ω m is lower than copper and Yin Geng.Graphene has more excellent electric property than conventional conductive filler, leads as novel Electric filler introduces powdery paints, is bound to that the more excellent conductive powder paint of electric conductivity can be prepared.
The technology contents listed in the prior art only represent the technology that inventor is grasped, and are not considered naturally It is the prior art and is used to evaluate novelty and creativeness of the invention.
Summary of the invention
It is an object of the invention in view of the above-mentioned problems, providing the mining type stone that a kind of graphene additive amount is small, at low cost Black alkene, carbon black, polyethylene compound particle and preparation method thereof.
It is a further object of the present invention to provide the mining type graphenes, carbon black, poly- second with the direct extrusion bar of above-mentioned particle Alkene composite pipe and preparation method thereof.
The purpose of the present invention is achieved by the following technical scheme:
A kind of mining type graphene, carbon black, polyethylene compound particle, each component is by weight, comprising: high-density polyethylene 100 parts of alkene, 0.1~2 part of graphene, 1~10 part of carbon black, 4~15 parts of fire retardant, 0.5~3 part of dispersion liquid, nucleating agent 0.5~4 Part, 2~10 parts of toughener, 0.5~4 part of antioxidant.
As above-mentioned mining type graphene, carbon black, polyethylene compound particle preferred embodiment, each component by weight, It include: 100 parts of high density polyethylene (HDPE), 0.3~1.8 part of graphene, 1~5 part of carbon black, 4~8 parts of fire retardant, dispersion liquid 1~2.5 Part, 1~3.5 part of nucleating agent, 2.5~8 parts of toughener, 1~3.5 part of antioxidant.
As the preferred plan of above-mentioned mining type graphene, carbon black, polyethylene compound particle, each component by weight, Include: 100 parts of high density polyethylene (HDPE), 1.6 parts of graphene, 4 parts of carbon black, 6 parts of fire retardant, 1.5 parts of dispersion liquid, 2 parts of nucleating agent, increase Tough dose 5 parts, 2.5 parts of antioxidant.
According to an aspect of the present invention, specific surface area BET >=250m of the graphene2/ g, preferably BET >=487m2/ g。
According to an aspect of the present invention, the partial size of the graphene is D50≤27 μm.
According to an aspect of the present invention, in the graphene oxygen mass fraction O% < 1%.The wherein matter of the oxygen Amount score refers to the mass fraction of oxygen atom in the graphene.
According to an aspect of the present invention, the number of plies≤10 layer of the graphene, preferably≤3 layer.
According to an aspect of the present invention, the carbon black is nanoscale superconduction carbon black, and partial size is 50nm or less.
According to an aspect of the present invention, the fire retardant is red phosphorus, magnesium hydroxide, aluminium hydroxide, hexabromocyclododecane Or at least one of antimony oxide.
According to an aspect of the present invention, the dispersed phase of the dispersion liquid is white oil.
According to an aspect of the present invention, the decentralized medium of the dispersion liquid is PE wax, EBS, hyper-dispersant A8021 or super At least one of dispersing agent R1618.
According to an aspect of the present invention, the concentration of decentralized medium is 8-12wt%, preferably 10wt% in the dispersion liquid.
According to an aspect of the present invention, the nucleating agent is in calcium stearate, barium sulfate, silicate or titanium dioxide It is at least one.
According to an aspect of the present invention, the toughener be LLDPE, SEBS, SBS, DOP, POE or EVA at least It is a kind of.
According to an aspect of the present invention, the antioxidant be BASF B215, antioxidant 1010, antioxidant 264 or anti- At least one of oxygen agent B225.
BASF B215 is four (β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol esters (abbreviation: antioxidant 1010) with three [2,4- di-tert-butyl-phenyl] phosphite esters (referred to as: irgasfos 168) with compound obtained by the mass ratio of 1:2 Referred to as；
Antioxidant 1010 is the abbreviation of four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters；
Antioxidant 264 is the abbreviation of 2,6 di tert butyl 4 methyl phenol；
Antioxidant B225 is four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters (abbreviation: antioxidant 1010) with three (2,4- di-tert-butyl-phenyl) phosphite esters (referred to as: irgasfos 168) with compound obtained by the mass ratio of 1:1 Referred to as.
According to an aspect of the present invention, the molecular weight of the high density polyethylene (HDPE) is 4 × 105G/mol~3 × 106g/ Mol, preferably 4 × 105G/mol~6 × 105g/mol。
Invention additionally discloses the preparation methods of a kind of mining type graphene, carbon black, polyethylene compound particle, according to above-mentioned each Component and proportion relation,
By high density polyethylene (HDPE), antioxidant, fire retardant and toughener melt blending, extruding pelletization, the poly- second of flame retardant type is obtained Alkene particle；
Flame retardant type polyethylene particles, dispersion liquid, graphene, carbon black and nucleating agent are mixed；With
By said mixture melt blending, extruding pelletization to get.
According to an aspect of the present invention, described to dissolve high density polyethylene (HDPE), antioxidant, fire retardant and toughener altogether Mixed, extruding pelletization is carried out using dual-screw pelletizer.
Preferably, the high density polyethylene (HDPE), antioxidant, fire retardant and toughener are added sequentially to dual-screw pelletizer In, the rate of feeding of dual-screw pelletizer is 10~30r/min, preferably 15~28r/min.
Preferably, dual-screw pelletizer Heating Zone Temperature be respectively as follows: 240 DEG C, 240 DEG C, 245 DEG C, 245 DEG C, 245 DEG C and 240℃。
Preferably, the screw speed of dual-screw pelletizer is 60~100r/min, preferably 65~85r/min.
According to an aspect of the present invention, described by flame retardant type polyethylene particles, dispersion liquid, graphene, carbon black and nucleation Agent mixing is carried out using high-speed mixer.
Preferably, flame retardant type polyethylene particles, dispersion liquid, graphene, carbon black and nucleating agent high speed is added sequentially to mix It is mixed in conjunction machine.
Preferably, the mixed temperature is 10 DEG C~70 DEG C, preferably 25 DEG C~40 DEG C.
Preferably, the mixed revolving speed is 300~800r/min, preferably 350~650r/min.
Preferably, the mixed incorporation time is 5~60min, preferably 10~30min.
According to an aspect of the present invention, described to be granulated said mixture melt blending, extruding pelletization using twin-screw Machine carries out.
Preferably, the rate of feeding of the dual-screw pelletizer is 10~30r/min, preferably 15~28r/min.
Preferably, dual-screw pelletizer Heating Zone Temperature be respectively as follows: 240 DEG C, 240 DEG C, 245 DEG C, 245 DEG C, 245 DEG C and 240℃。
Preferably, the screw speed of dual-screw pelletizer is 60~100r/min, preferably 65~85r/min.
A kind of mining type graphene, carbon black, polyethylene composite pipe, including above-mentioned mining type graphene, carbon black, poly- second The each component of alkene compound particle.
A kind of preparation method of mining type graphene, carbon black, polyethylene composite pipe, by above-mentioned mining type graphene, Carbon black, polyethylene compound particle are squeezed out through pipe extruder.
The technology of the present invention principle:
It needs to add a large amount of conductive filler with anti-electrostatic fire retardant type PE tubing in view of current mine and fire retardant passes through Twin-screw extrusion is prepared, and conductive filler usually uses (expansion) graphite, conductive black, carbon fiber and high molecular polymer etc., Additive amount accounts for 15~25wt% of matrix or so, and tubing wall is blocked up, and pipe is just at high cost, and rough surface, persistence is poor, and General Life is only There is 3-5, and mechanical mechanics property is insufficient；Fire retardant usually with fire retardants such as bromine system, phosphorus system and silicon systems, additive amount 15~ 20wt% or so, effect on environment is more serious, and reduces matrix mechanical property.Graphene has excellent electric conductivity, high resistant Fire the characteristics such as performance and high strength and modulus.Graphene specific surface area is bigger, and easier to form perfect conductive network, what is obtained answers Condensation material electric conductivity is also better；But it is studied through the present inventor, the usual vibration density of the graphene product of large specific surface area It spends very little (in 0.1g/cm3 or less), under same quality, volume can be relatively large；And under equal volume, quality can be compared with Gently, it easily blows out in feeding procedure, is difficult with the composite material that common processing method realizes high additive amount graphene.This hair It is bright to compound highly conductive graphene with carbon black, most carbon black is substituted with a small amount of graphene, avoids high additive amount graphene Utilize the problem for the addition difficulty that twin-screw processing occurs；It is acted synergistically by graphene and carbon black and unique structure is set up, So that preferably being contacted between graphene and carbon black structure, so that perfect conductive path is more readily formed, by material surface Electrostatic charge is evacuated rapidly；Synergistic effect is played using graphene high flame-retardant property and fire retardant simultaneously, burning is more likely formed densification Layer of charcoal carry out barrier protection, flame retardant effect compare single fire retardant preparation anti-flaming tubular product better effect.Meanwhile present invention benefit Graphene is compounded with carbon black, fire retardant with high-speed mixer and screw extruder, is melted after being uniformly dispersed using dispersion liquid Melt blending extrusion, it is few and have both excellent antistatic, anti-flammability and mechanical force to prepare the additive amounts such as a kind of antistatic agent, fire retardant Learn the mining PE tubing of performance.
The technology of the present invention effect:
(1) present invention utilizes graphene high flame retardant and its architectural characteristic, and the graphene/polyethylene being prepared answers material Oxygen index (OI) improves 20%~40% compared to pure polyethylene, and after compounding with fire retardant, the anti-flammability of the polyvinyl piping materials of preparation is accorded with The MT181-88 " plastic pipe for coal mine Safety Inspection specification " in colliery industry standard MT558.1-2005 is closed, relatively In existing flame retardant type PE tubing, amount of flame-retardant agent reduces 15wt% or so, and it is conductive to tubing and mechanical property to reduce it It influences；
(2) graphene high conductivity characteristic, the carbon black loading of 50% or more substitution are utilized.Under the two synergistic effect, tubing Surface resistivity 106Ω hereinafter, and tube surfaces it is smooth, antistatic property is more longlasting；
(3) graphene/polyethylene tensile strength that the present invention is prepared is reachable up to 25MPa, disconnected column elongation 402%, 430%.Its mechanical property fully achieves the " heat of GB/T8804-2003 in colliery industry standard MT558.1-2005 The performance measurement of thermoplastic plastic drawing pipe ": tensile strength >=9MPa, elongation at break >=300%；
(4) graphene/polyethylene answers the excellent mechanical property of material, so that extruding pipe material is in same nominal pressure and outer diameter Lower corresponding wall thickness reduces 10~15%, reduces the dosage of unit length, save the cost, and improves transfer efficiency.
Specific embodiment
Hereinafter, certain illustrative embodiments are simply just described.As one skilled in the art will recognize that As, without departing from the spirit or scope of the present invention, the various not Tongfangs such as increase, deletion, modification can be passed through Formula modifies described embodiment.Therefore, description is considered essentially illustrative rather than restrictive.
In the description of the present invention, term " effect is more preferable " cannot simply be understood to group according to specific embodiment Part, formula, technological parameter etc. it is obtained the result is that preferably, for those of ordinary skills, in concrete condition Under, term " effect is more preferable " should also comprehensively consider the factors such as economy, environment, time.
In an embodiment of the invention, a kind of mining type graphene, carbon black, polyethylene compound particle are provided, respectively Component is by weight, comprising: 100 parts of high density polyethylene (HDPE), 0.1~2 part of graphene, 1~10 part of carbon black, fire retardant 4~15 Part, 0.5~3 part of dispersion liquid, 0.5~4 part of nucleating agent, 2~10 parts of toughener, 0.5~4 part of antioxidant.
Such as: 100 parts of high density polyethylene (HDPE), 0.1 part of graphene, 10 parts of carbon black, 1 part of fire retardant, 3 parts of dispersion liquid, nucleation 0.5 part of agent, 10 parts of toughener, 0.5 part of antioxidant；100 parts of high density polyethylene (HDPE), 2 parts of graphene, 1 part of carbon black, fire retardant 12 Part, 0.5 part of dispersion liquid, 4 parts of nucleating agent, 2 parts of toughener, 4 parts of antioxidant；100 parts of high density polyethylene (HDPE), 1 part of graphene, carbon black 5 parts, 6 parts of fire retardant, 2 parts of dispersion liquid, 3 parts of nucleating agent, 5 parts of toughener, 2 parts of antioxidant, etc..
According to a preferred embodiment of the present invention, each group of above-mentioned mining type graphene, carbon black, polyethylene compound particle Point by weight, comprising: 100 parts of high density polyethylene (HDPE), 0.3~1.8 part of graphene, 1~5 part of carbon black, 1~8 part of fire retardant, 1~2.5 part of dispersion liquid, 1~3.5 part of nucleating agent, 2.5~8 parts of toughener, 1~3.5 part of antioxidant.
Such as: 100 parts of high density polyethylene (HDPE), 0.3 part of graphene, 5 parts of carbon black, 1 part of fire retardant, 2.5 parts of dispersion liquid, nucleation 1 part of agent, 8 parts of toughener, 1 part of antioxidant；100 parts of high density polyethylene (HDPE), 1.8 parts of graphene, 1 part of carbon black, fire retardant 8 part, point 1 part of dispersion liquid, 3.5 parts of nucleating agent, 2.5 parts of toughener, 3.5 parts of antioxidant；100 parts of high density polyethylene (HDPE), 1 part of graphene, carbon black 2.5 parts, 4 parts of fire retardant, 2 parts of dispersion liquid, 2 parts of nucleating agent, 5 parts of toughener, 2 parts of antioxidant, etc..
According to a preferred embodiment of the present invention, above-mentioned mining type graphene, carbon black, polyethylene compound particle ground each group Divide by weight, comprising: 100 parts of high density polyethylene (HDPE), 1.6 parts of graphene, 4 parts of carbon black, 6 parts of fire retardant, dispersion liquid 1.5 Part, 2 parts of nucleating agent, 5 parts of toughener, 2.5 parts of antioxidant.
According to a preferred embodiment of the present invention, specific surface area BET >=250m of the graphene2/ g, when BET >= 487m2Effect is more preferable when/g.
According to a preferred embodiment of the present invention, the partial size of the graphene is D50≤27 μm.
According to a preferred embodiment of the present invention, the mass fraction O% < 1% of the oxygen of the graphene, wherein described The mass fraction of oxygen refers to the mass fraction of oxygen atom in graphene.
According to a preferred embodiment of the present invention, the number of plies≤10 layer of the graphene, such as 10 layers, 9 layers, 8 layers, 7 Layer, 6 layers, 5 layers, 4 layers, 3 layers, 2 layers, 1 layer etc., when the number of plies of graphene is≤3 layers, effect is more preferable.
According to a preferred embodiment of the present invention, the carbon black is nanoscale superconduction carbon black, and partial size is 50nm or less.
According to a preferred embodiment of the present invention, the fire retardant is red phosphorus, magnesium hydroxide, aluminium hydroxide, hexabromo ring At least one of dodecane or antimony oxide.
According to a preferred embodiment of the present invention, the dispersed phase of the dispersion liquid is white oil.
According to a preferred embodiment of the present invention, the decentralized medium of the dispersion liquid is PE wax, EBS, hyper-dispersant At least one of A8021 or hyper-dispersant R1618.
According to a preferred embodiment of the present invention, in the dispersion liquid decentralized medium concentration be 8-12wt%, when point When the concentration of dispersion media is 10wt%, effect is more preferable.
According to a preferred embodiment of the present invention, the nucleating agent is calcium stearate, barium sulfate, silicate or titanium dioxide At least one of titanium.
According to a preferred embodiment of the present invention, the toughener is in LLDPE, SEBS, SBS, DOP, POE or EVA At least one.
According to a preferred embodiment of the present invention, the antioxidant is BASF B215, antioxidant 1010, antioxidant At least one of 264 or antioxidant B225.
According to a preferred embodiment of the present invention, the molecular weight of the high density polyethylene (HDPE) is 4 × 105G/mol~3 × 106G/mol, the molecular weight of the high density polyethylene (HDPE) are 4 × 105G/mol~6 × 105Effect is more preferable when g/mol.
In an embodiment of the invention, a kind of mining type graphene, carbon black, polyethylene compound particle are also provided Preparation method, according to above-mentioned each component and proportion relation,
By high density polyethylene (HDPE), antioxidant, fire retardant and toughener melt blending, extruding pelletization, the poly- second of flame retardant type is obtained Alkene particle；
Flame retardant type polyethylene particles, dispersion liquid, graphene, carbon black and nucleating agent are mixed；With
By said mixture melt blending, extruding pelletization to get.
According to a preferred embodiment of the present invention, described to melt high density polyethylene (HDPE), antioxidant, fire retardant and toughener Melt blending, extruding pelletization is carried out using dual-screw pelletizer.
According to a preferred embodiment of the present invention, by the high density polyethylene (HDPE), antioxidant, fire retardant and toughener according to Secondary to be added in dual-screw pelletizer, the rate of feeding of dual-screw pelletizer is 10~30r/min, such as: 10r/min, 15r/ Min, 20r/min, 25r/min, 30r/min etc., effect is more preferable when the rate of feeding is 15~28r/min, such as: 15r/ Min, 18r/min, 21r/min, 24r/min, 27r/min, 28r/min etc..
According to a preferred embodiment of the present invention, the dual-screw pelletizer Heating Zone Temperature is respectively as follows: 240 DEG C, 240 DEG C, 245 DEG C, 245 DEG C, 245 DEG C and 240 DEG C.
According to a preferred embodiment of the present invention, the screw speed of the dual-screw pelletizer is 60~100r/min, Such as: the screw speed of 60r/min, 70r/min, 80r/min, 90r/min, 100r/min etc., the dual-screw pelletizer are Effect is more preferable when 65~85r/min, such as: 65r/min, 70r/min, 75r/min, 80r/min, 85r/min.
According to a preferred embodiment of the present invention, described by flame retardant type polyethylene particles, dispersion liquid, graphene, carbon black It is carried out with nucleating agent mixing using high-speed mixer.
According to a preferred embodiment of the present invention, by the flame retardant type polyethylene particles, dispersion liquid, graphene, carbon black It is added sequentially to mix in high-speed mixer with nucleating agent.
According to a preferred embodiment of the present invention, the mixed temperature be 10 DEG C~70 DEG C, such as: 10 DEG C, 20 DEG C, 30 DEG C, 40 DEG C, 50 DEG C, 60 DEG C, 70 DEG C etc., effect is more preferable when mixing temperature is 25 DEG C~40 DEG C, such as: 25 DEG C, 30 DEG C, 35 DEG C, 40 DEG C etc..
According to a preferred embodiment of the present invention, the mixed revolving speed is 300~800r/min, such as: 300r/ Min, 400r/min, 500r/min, 600r/min, 700r/min, 800r/min etc., the mixed revolving speed are 350~650r/ Effect is more preferable when min, such as: 350r/min, 400r/min, 450r/min, 500r/min, 550r/min, 600r/min, 650r/min etc..
According to a preferred embodiment of the present invention, the mixed incorporation time is 5~60min, such as: 5min, 10min, 20min, 30min, 40min, 50min, 60min etc., effect is more preferable when the incorporation time is 10~30min, such as: 10min, 15min, 20min, 25min, 30min etc..
According to a preferred embodiment of the present invention, described that said mixture melt blending, extruding pelletization are used into double spiral shells Bar pelletizer carries out.
According to a preferred embodiment of the present invention, said mixture is added in dual-screw pelletizer, twin-screw is made The rate of feeding of grain machine is 10~30r/min, such as: 10r/min, 15r/min, 20r/min, 25r/min, 30r/min etc., institute State rate of feeding be 15~28r/m when effect it is more preferable, such as: 15r/min, 18r/min, 21r/min, 24r/min, 27r/min, 28r/min etc..
According to a preferred embodiment of the present invention, the dual-screw pelletizer Heating Zone Temperature is respectively as follows: 240 DEG C, 240 DEG C, 245 DEG C, 245 DEG C, 245 DEG C and 240 DEG C.
According to a preferred embodiment of the present invention, the screw speed of the dual-screw pelletizer is 60~100r/min, Such as: the screw speed of 60r/min, 70r/min, 80r/min, 90r/min, 100r/min etc., the dual-screw pelletizer are Effect is more preferable when 65~85r/min, such as: 65r/min, 70r/min, 75r/min, 80r/min, 85r/min.
In an embodiment of the invention, a kind of mining type graphene, carbon black, polyethylene composite pipe are also provided, Including above-mentioned mining type graphene, carbon black, polyethylene compound particle each component.
In an embodiment of the invention, a kind of mining type graphene, carbon black, polyethylene composite pipe are also provided Preparation method, including squeezing out above-mentioned mining type graphene, carbon black, polyethylene compound particle through pipe extruder.
Hereinafter, preferred embodiments of the present invention will be described, it should be understood that preferred embodiment described herein is only used In the description and interpretation present invention, it is not intended to limit the present invention.
Following embodiment is that present inventor's preparation method according to the invention and application method have carried out specific reality It tests.
In following embodiment, the graphene is the graphene powder prepared using oxidation-reduction method, by hexa-atomic material 6 kinds have been randomly selected in the product of a variety of different models of material limited liability company production, in this 6 kinds of graphene products, graphite The alkene number of plies is no more than 10 layers, and graphene partial size is D50≤27 μm, and the nitrogen adsorption methods measurement the specific area of the graphene is equal For 250~550m2/ g, graphene carbon content >=98%.
In following embodiment, in related component substances, except graphene is raw by hexa-atomic cellulosic material limited liability company It produces, can be bought from market.
Embodiment 1:
It (1) is 3.5 parts, 8 parts of fire retardant antimony oxide and toughener by 100 parts of high density polyethylene (HDPE), antioxidant B225 LLDPE is added sequentially to progress melt blending extrusion pelletizing in screw extruder for 2.5 parts and prepares flame retardant type polyethylene particles. Dual-screw pelletizer Heating Zone Temperature is respectively as follows: 240 DEG C, 240 DEG C, 245 DEG C, 245 DEG C, 245 DEG C, 240 DEG C；Screw speed exists 65r/min, rate of feeding is in 15r/min.
(2) by above-mentioned flame retardant type polyethylene particles, 1 part of white oil dispersion liquid, graphene (BET:487m2/ g, D50:27 μm, O% < 1.0%) it is added sequentially to mix in high-speed mixer for 0.3 part, 1 part of carbon black, 3.5 parts of nucleating agent calcium stearate, it mixes Temperature is 25 DEG C, revolving speed 350r/min；Incorporation time is 10min.
(3) (2) resulting mixture is added in dual-screw pelletizer and carries out abundant melt blending extrusion pelletizing, double spiral shells Bar granulator heating area temperature is respectively as follows: 240 DEG C, 240 DEG C, 245 DEG C, 245 DEG C, 245 DEG C, 240 DEG C；Screw speed is in 65r/ Min, rate of feeding are squeezed out in 15r/min, particle through pipe extruder, and graphene/carbon black/PE tubing is made.
Embodiment 2:
(1) be 2.5 parts by 100 parts of high density polyethylene (HDPE), antioxidant B215,6.0 parts of red phosphorus and toughener SEBS be 5 parts according to It is secondary be added in screw extruder carry out melt blending squeeze out pelletizing prepare flame retardant type polyethylene particles.Dual-screw pelletizer adds Hot zone temperature is respectively as follows: 240 DEG C, 240 DEG C, 245 DEG C, 245 DEG C, 245 DEG C, 240 DEG C；Screw speed is in 80r/min, rate of feeding In 16r/min.
(2) by above-mentioned flame retardant type polyethylene particles, 1.5 parts of EBS white oil dispersion liquid, graphene (BET:550m2/ g, D50:8 μm, O% < 1.0%) it is added sequentially to mix in high-speed mixer for 1.6 parts, 4 parts of carbon black, 2 parts of barium sulfate, mixing temperature is 35℃；Revolving speed is 600r/min；Incorporation time is 20min.
(3) (2) resulting mixture is added in dual-screw pelletizer and carries out abundant melt blending extrusion pelletizing, double spiral shells Bar granulator heating area temperature is respectively as follows: 240 DEG C, 240 DEG C, 245 DEG C, 245 DEG C, 245 DEG C, 240 DEG C；Screw speed is in 80r/ Min, rate of feeding are squeezed out in 16r/min, particle through pipe extruder, and graphene/carbon black/PE tubing is made.
Embodiment 3:
It (1) is 1.0 parts, 1 part of fire retardant aluminium hydroxide and toughener EVA by 100 parts of high density polyethylene (HDPE), antioxidant 264 Progress melt blending extrusion pelletizing in screw extruder, which is added sequentially to, for 8 parts prepares flame retardant type polyethylene particles.Twin-screw Granulator heating area temperature is respectively as follows: 240 DEG C, 240 DEG C, 245 DEG C, 245 DEG C, 245 DEG C, 240 DEG C；Screw speed in 85r/min, Rate of feeding is in 28r/min.
(2) by above-mentioned flame retardant type polyethylene particles, 2.5 parts of A8021 white oil dispersion liquid, graphene (BET:520m2/ g, D50:24 μm, O% < 1.0%) it is added sequentially to mix in high-speed mixer for 1.8 parts, 5.0 parts of carbon black, 1 part of barium sulfate, it mixes Closing temperature is 40 DEG C；Revolving speed is 650r/min；Incorporation time is 30min.
(3) (2) resulting mixture is added in dual-screw pelletizer and carries out abundant melt blending extrusion pelletizing, double spiral shells Bar granulator heating area temperature is respectively as follows: 240 DEG C, 240 DEG C, 245 DEG C, 245 DEG C, 245 DEG C, 240 DEG C；Screw speed is in 85r/ Min, rate of feeding are squeezed out in 28r/min, particle through pipe extruder, and graphene/carbon black/PE tubing is made.
Embodiment 4:
It (1) is 0.5 part, 12 parts of fire retardant aluminium hydroxide and toughener by 100 parts of high density polyethylene (HDPE), antioxidant B215 EVA is added sequentially to progress melt blending extrusion pelletizing in screw extruder for 2 parts and prepares flame retardant type polyethylene particles.Double spiral shells Bar granulator heating area temperature is respectively as follows: 240 DEG C, 240 DEG C, 245 DEG C, 245 DEG C, 245 DEG C, 240 DEG C；Screw speed is in 100r/ Min, rate of feeding is in 10r/min.
(2) by above-mentioned flame retardant type polyethylene particles, 0.5 part of EBS white oil dispersion liquid, graphene (BET:250m2/ g, D50: 26 μm, O% < 1.0%) it is added sequentially to mix in high-speed mixer for 2 parts, 10 parts of carbon black, 0.5 part of barium sulfate, mixing temperature It is 70 DEG C；Revolving speed is 300r/min；Incorporation time is 5min.
(3) (2) resulting mixture is added in dual-screw pelletizer and carries out abundant melt blending extrusion pelletizing, double spiral shells Bar granulator heating area temperature is respectively as follows: 240 DEG C, 240 DEG C, 245 DEG C, 245 DEG C, 245 DEG C, 240 DEG C；Screw speed is in 100r/ Min, rate of feeding are squeezed out in 10r/min, particle through pipe extruder, and graphene/carbon black/PE tubing is made.
Embodiment 5:
(1) be 4 parts by 100 parts of high density polyethylene (HDPE), antioxidant B225,1 part of fire retardant aluminium hydroxide and toughener EVA are 10 parts are added sequentially to progress melt blending extrusion pelletizing in screw extruder and prepare flame retardant type polyethylene particles.Twin-screw is made Grain machine Heating Zone Temperature is respectively as follows: 240 DEG C, 240 DEG C, 245 DEG C, 245 DEG C, 245 DEG C, 240 DEG C；Screw speed is fed in 60r/min Expect speed in 30r/min.
(2) by above-mentioned flame retardant type polyethylene particles, 3 parts of EBS white oil dispersion liquid, graphene (BET:505m2/ g, D50:10 μ M, O% < 1.0%) it is added sequentially to mix in high-speed mixer for 0.1 part, 1 part of carbon black, 4 parts of barium sulfate, mixing temperature 10 ℃；Revolving speed is 800r/min；Incorporation time is 60min.
(3) (2) resulting mixture is added in dual-screw pelletizer and carries out abundant melt blending extrusion pelletizing, double spiral shells Bar granulator heating area temperature is respectively as follows: 240 DEG C, 240 DEG C, 245 DEG C, 245 DEG C, 245 DEG C, 240 DEG C；Screw speed is in 60r/ Min, rate of feeding are squeezed out in 30r/min, particle through pipe extruder, and graphene/carbon black/PE tubing is made.
Graphene/carbon black/polyethylene made from each embodiment is answered material to be tested for the property, and is not added with graphite with existing Carbon black/polyvinyl piping materials (D1 in following table) of alkene and a kind of hdpe pipe according to disclosed in CN104262740A (under D2 in table) performance parameter compare, as a result referring to following table:
It is multiple to can be seen that mining type graphene provided by the invention, carbon black, polyethylene from the data of above-described embodiment and table Tubing is closed with excellent antistatic, fire-retardant and mechanical property, compared with D1, the tubing of all embodiments its smooth in appearance, Smooth, bubble-free, uniform color；The tensile strength of mining type graphene provided by the invention, carbon black, polyethylene composite pipe It greatly, is 23-25MPa, the tensile strength 11MPa of significantly larger than D1, and the average tensile strength of the tubing of each embodiment is greater than The tensile strength 22Mpa of D2；Mining type graphene provided by the invention, carbon black, the elongation at break of polyethylene composite pipe are high, For 330%-430%, elongation at break 310% higher than D1, the farther elongation at break 150% much higher than D2；The present invention mentions The mining type graphene of confession, carbon black, the sheet resistance of polyethylene composite pipe are low, 105Ω or so, the generally lower than surface of D1 Resistance 8.9 × 105The surface resistivity 4 × 10 of Ω and D26Ω。
Finally, it should be noted that the foregoing is only a preferred embodiment of the present invention, it is not intended to restrict the invention, Although the present invention is described in detail referring to the foregoing embodiments, for those skilled in the art, still may be used To modify the technical solutions described in the foregoing embodiments or equivalent replacement of some of the technical features. All within the spirits and principles of the present invention, any modification, equivalent replacement, improvement and so on should be included in of the invention Within protection scope.

Claims (10)

1. a kind of mining type graphene, carbon black, polyethylene compound particle, each component is by weight, comprising: high density polyethylene (HDPE) 100 parts, 0.1~2 part of graphene, 1~10 part of carbon black, 4~15 parts of fire retardant, 0.5~3 part of dispersion liquid, 0.5~4 part of nucleating agent, 2~10 parts of toughener, 0.5~4 part of antioxidant.
2. mining type graphene according to claim 1, carbon black, polyethylene compound particle, each component by weight, is wrapped Include: 100 parts of high density polyethylene (HDPE), 0.3~1.8 part of graphene, 1~5 part of carbon black, 4~8 parts of fire retardant, 1~2.5 part of dispersion liquid, 1~3.5 part of nucleating agent, 2.5~8 parts of toughener, 1~3.5 part of antioxidant；
Preferably, the mining type graphene, carbon black, polyethylene compound particle each component by weight, comprising: it is highly dense Spend 100 parts of polyethylene, 1.6 parts of graphene, 4 parts of carbon black, 6 parts of fire retardant, 1.5 parts of dispersion liquid, 2 parts of nucleating agent, 5 parts of toughener, 2.5 parts of antioxidant.
3. mining type graphene according to claim 1 or 2, carbon black, polyethylene compound particle, which is characterized in that described BET >=250m of graphene2/ g, preferably BET >=487m2/g；And/or the partial size of the graphene is D50≤27 μm；And/or The mass fraction O% < 1% of oxygen；And/or the number of plies≤10 layer of the graphene, preferably≤3 layer；
And/or the carbon black is nanoscale superconduction carbon black, partial size is 50nm or less；
And/or the fire retardant be red phosphorus, magnesium hydroxide, aluminium hydroxide, hexabromocyclododecane or antimony oxide at least It is a kind of；
And/or the dispersed phase of the dispersion liquid is white oil；
And/or the decentralized medium of the dispersion liquid be PE wax, EBS, hyper-dispersant A8021 or hyper-dispersant R1618 at least It is a kind of；
And/or the concentration of decentralized medium is 8-12wt%, preferably 10wt% in the dispersion liquid；
And/or the nucleating agent is at least one of calcium stearate, barium sulfate, silicate or titanium dioxide；
And/or the toughener is at least one of LLDPE, SEBS, SBS, DOP, POE or EVA；
And/or the antioxidant is at least one in BASF B215, antioxidant 1010, antioxidant 264 or antioxidant B225 Kind.
4. mining type graphene according to claim 1 or 2, carbon black, polyethylene compound particle, which is characterized in that described The molecular weight of high density polyethylene (HDPE) is 4 × 105~3 × 106G/mol, preferably 4 × 105~6 × 105g/mol。
5. the preparation method of a kind of mining type graphene, carbon black, polyethylene compound particle, which is characterized in that according to claim Any one of 1-4 each component and proportion relation,
By high density polyethylene (HDPE), antioxidant, fire retardant and toughener melt blending, extruding pelletization, flame retardant type polyethylene grain is obtained Son；
Flame retardant type polyethylene particles, dispersion liquid, graphene, carbon black and nucleating agent are mixed；With
By said mixture melt blending, extruding pelletization to get.
6. the preparation method of mining type graphene according to claim 5, carbon black, polyethylene compound particle, feature exist In described that high density polyethylene (HDPE), antioxidant, fire retardant and toughener are dissolved blending, extruding pelletization using dual-screw pelletizer It carries out；Preferably, the high density polyethylene (HDPE), antioxidant, fire retardant and toughener are added sequentially in dual-screw pelletizer, double The rate of feeding of screw pelletizer is 10~30r/min；Preferably 15~28r/min, dual-screw pelletizer Heating Zone Temperature point Not are as follows: 240 DEG C, 240 DEG C, 245 DEG C, 245 DEG C, 245 DEG C and 240 DEG C；The screw speed of dual-screw pelletizer is 60~100r/ Min, preferably 65~85r/min.
7. the preparation method of mining type graphene according to claim 5, carbon black, polyethylene compound particle, feature exist In described mix flame retardant type polyethylene particles, dispersion liquid, graphene, carbon black and nucleating agent is carried out using high-speed mixer；It is excellent Flame retardant type polyethylene particles, dispersion liquid, graphene, carbon black and nucleating agent are added sequentially to mix in high-speed mixer by selection of land； Preferably, the mixed temperature is 10 DEG C~70 DEG C, preferably 25 DEG C~40 DEG C；Preferably, the mixed revolving speed be 300~ 800r/min, preferably 350~650r/min；Preferably, the mixed incorporation time is 5~60min, preferably 10~30min.
8. the preparation method of mining type graphene according to claim 5, carbon black, polyethylene compound particle, feature exist In described to carry out said mixture melt blending, extruding pelletization using dual-screw pelletizer；Preferably, the twin-screw is made The rate of feeding of grain machine is 10~30r/min；Preferably 15~28r/min, dual-screw pelletizer Heating Zone Temperature are respectively as follows: 240 DEG C, 240 DEG C, 245 DEG C, 245 DEG C, 245 DEG C and 240 DEG C；The screw speed of dual-screw pelletizer is 60~100r/min, excellent 65~85r/min of selection of land.
9. a kind of mining type graphene, carbon black, polyethylene composite pipe, which is characterized in that including of any of claims 1 or 2 Mining type graphene, carbon black, polyethylene compound particle each component.
10. the preparation method of a kind of mining type graphene, carbon black, polyethylene composite pipe, which is characterized in that by claim 1 Or mining type graphene, carbon black described in 2, polyethylene compound particle are squeezed out through pipe extruder.
CN201811366872.4A 2017-11-16 2018-11-16 Mining type graphene, carbon black, polyethylene composite pipe and preparation method thereof Pending CN109575398A (en)

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