CN105570560B - Graphene increased thermal conductivity compound polyolefin tubing - Google Patents
Graphene increased thermal conductivity compound polyolefin tubing Download PDFInfo
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- CN105570560B CN105570560B CN201610148355.4A CN201610148355A CN105570560B CN 105570560 B CN105570560 B CN 105570560B CN 201610148355 A CN201610148355 A CN 201610148355A CN 105570560 B CN105570560 B CN 105570560B
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- graphene
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- epoxy resin
- nomex
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Classifications
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
- F16L9/00—Rigid pipes
- F16L9/12—Rigid pipes of plastics with or without reinforcement
- F16L9/121—Rigid pipes of plastics with or without reinforcement with three layers
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
- F16L11/00—Hoses, i.e. flexible pipes
- F16L11/04—Hoses, i.e. flexible pipes made of rubber or flexible plastics
- F16L11/06—Hoses, i.e. flexible pipes made of rubber or flexible plastics with homogeneous wall
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
- F16L11/00—Hoses, i.e. flexible pipes
- F16L11/04—Hoses, i.e. flexible pipes made of rubber or flexible plastics
- F16L11/12—Hoses, i.e. flexible pipes made of rubber or flexible plastics with arrangements for particular purposes, e.g. specially profiled, with protecting layer, heated, electrically conducting
Abstract
The present invention provides a kind of high strength linepipe, including polyolefinic outer layer, polyolefin interior layer, graphene-polyolefin blends middle layer.
Description
Technical field
The present invention relates to a kind of tubing, in particular to a kind of graphene increased thermal conductivity compound polyolefin tubing.
Background technique
It is well known that metallic conduit have it is perishable, easy fouling, service life is short, it is difficult to install the disadvantages of.To mould Dai Gang
As trend, therefore plastic conduit has irreplaceable role in work China Democratic National Construction Association field, such as PP-R/PE/PVC/PE-RT is managed
It is widely used in building water supply and drainage, heating pipe system, central air-conditioning pipe system, chemical engineering piping systems, electrical protective sleeve pipe etc.
Field.
Due to use environment, often there are some problems in these pipelines: 1, it is inadequate to bear pressure；2, high temperature
Under the conditions of service life it is shorter.Especially in polyolefin pipe, often have the shortcomings that intensity is not high enough.Meanwhile it using
In the process, especially in heating power transportation system and hot-water heating system, generally require tubing have the characteristics that pressure resistance, it is resistant to high temperature, this
The service life of tubing can be only sustained at the underground pipe gallery proposed in several years " 13 planning " and build to pipe in the case of kind
The performances such as the mechanical index of material and service life have higher requirement.The service life of tubing is by using temperature and operating pressure
It codetermines.Such as most common PP-R pipe can be used 50 years in the environment of 1Mpa at 60 DEG C, so existing at present
There is polyolefin pipe that cannot be used for a long time in 95 DEG C of environment.Therefore a kind of tubing is needed, meets and uses 95 DEG C of temperature, work pressure
Power 1.6MPa, 50 years tubing of service life.The height being especially currently being deployed, the new energy such as middle temperature solar and underground heat energy
It utilizes, is badly in need of high temperature and pressure long-life and the good polyolefin pipe of thermal conductivity
A kind of high intensity, the multiple tube high pressure resistant while with long service life with comprehensive performance are needed for above situation
Material.
Summary of the invention
In view of the above-mentioned problems, the present invention provides a kind of high intensity polyolefin pipe with long service life, including outside polyolefin
Layer, polyolefin interior layer, graphene-polyolefin blends middle layer, the polyolefin pipe can be in temperature at 95 DEG C, pressure
Under conditions of being greater than 1.6MPa, service life reaches 50 years or more.
As an implementation, the polyolefin is selected from least one of the group of the following terms composition: the poly- second of homopolymerization
Homopolymer in the group of alkene and homopolypropylene composition；It selects one in the group of free ethylene, propylene, butylene, hexene and octene composition
The random copolymer of kind or a variety of comonomers.
As a preferred embodiment, the polyolefin selects the copolymerization of one of propylene, hexene and octene and ethylene copolymer
Object.
As an implementation, the sum of the polyolefin interior layer and outer layer thickness in graphene-polyolefin blends
The ratio of interbed thickness is (2~70): 1.
As an implementation, the thickness of polyolefinic outer layer and polyolefin interior layer ratio is (1~5): (1~5).
As an implementation, the graphene is Nomex modified graphene, and Nomex and graphene
Weight ratio is (10~30): 1.
As a preferred embodiment, the graphene-polyolefin layer includes boron nitride, and the boron nitride and graphene
Weight ratio is 1:(5~20).
As an implementation, the graphene-polyolefin layer includes boron nitride, and the boron nitride and graphene
Weight ratio is 1:(10~20).
As an implementation, the polyolefin interior layer and the stretched orientation process of outer layer, and draw ratio be 3~
8。
As an implementation, the polyolefin interior layer and the stretched orientation process of outer layer, and draw ratio be 3~
5。
Specific embodiment
The detailed description for preferred implementation method of the invention below of participating in the election of and including embodiment this hair can be more easily to understand
Bright content.Unless otherwise defined, all technologies used herein and scientific term have common with fields of the present invention
The normally understood identical meaning of technical staff.When there is a conflict, the definition in this specification shall prevail.
As used herein term " by ... preparation " it is synonymous with "comprising".Term "comprising" used herein, " comprising ",
" having ", " containing " or its any other deformation, it is intended that cover non-exclusionism includes.For example, the combination comprising listed elements
Object, step, method, product or device are not necessarily limited to those elements, but may include not expressly listed other elements or
Such composition, step, method, product or the intrinsic element of device.
Conjunction " Consists of " excludes any element that do not point out, step or component.If in claim, this
Phrase will make claim closed, so that it is not included the material in addition to the material of those descriptions, but relative normal
Except rule impurity.When being rather than immediately following after theme in the clause that phrase " Consists of " appears in claim main body,
It is only limited to element described in the clause；Other elements are not excluded except the claim as a whole.
Equivalent, concentration or other values or parameter are excellent with range, preferred scope or a series of upper limit preferred values and lower limit
When the Range Representation that choosing value limits, this should be understood as specifically disclosing by any range limit or preferred value and any range
Any pairing of lower limit or preferred value is formed by all ranges, regardless of whether the range separately discloses.For example, when open
When range " 1 to 5 ", described range should be interpreted as including range " 1 to 4 ", " 1 to 3 ", " 1 to 2 ", " 1 to 2 and 4 to
5 ", " 1 to 3 and 5 " etc..When numberical range is described herein, unless otherwise stated, otherwise the range is intended to include its end
Value and all integers and score in the range.
Singular includes that plural number discusses object, unless the context clearly dictates otherwise." optional " or it is " any
It is a kind of " refer to that the item described thereafter or event may or may not occur, and the description include situation that event occurs and
The situation that event does not occur.
Approximate term in specification and claims is used to modify quantity, and it is specific to indicate that the present invention is not limited to this
Quantity further includes the acceptable modified part without will lead to the change of dependency basis this function close with the quantity.Phase
It answers, modifies a numerical value with " about ", " about " etc., mean that the present invention is not limited to the exact numericals.In some examples, approximate
Term likely corresponds to the precision of the instrument of measurement numerical value.In present specification and claims, range limits can be with
Combination and/or exchange, these ranges if not stated otherwise include all subranges contained therebetween.
In addition, indefinite article "an" before element of the present invention or component and "one" quantitative requirement to element or component
(i.e. frequency of occurrence) unrestriction.Therefore "one" or "an" should be read as including one or at least one, and odd number
The element or component of form also include plural form, unless the obvious purport of the quantity refers to singular.
" polymer " means polymerizable compound prepared by the monomer by the identical or different type of polymerization.Generic term
" polymer " includes term " homopolymer ", " copolymer ", " terpolymer " and " copolymer ".
" copolymer " means the polymer by polymerization at least two different monomers preparation.Generic term " copolymer " includes
(it is general with term " terpolymer " for term " copolymer " (it is generally to refer to the polymer prepared by two kinds of different monomers)
To refer to the polymer prepared by three kinds of different monomers).It also includes the polymerization manufactured by polymerization four or more monomer
Object." blend " means that two or more polymer mixes the polymerization to be formed by physics or chemical method jointly
Object.
The present invention provides a kind of graphene increased thermal conductivity compound polyolefin tubing, including polyolefinic outer layer, in polyolefin
Layer, graphene-polyolefin blends middle layer, the polyolefin pipe can be in temperature at 95 DEG C, and pressure is being greater than
Under conditions of 1.6MPa, service life reaches 50 years or more.
To solve the above-mentioned problems, the present invention provides a kind of graphene increased thermal conductivity compound polyolefin tubing, including poly-
Olefinic outer layer, polyolefin interior layer, graphene-polyolefin blends middle layer.
As an implementation, the polyolefin is selected from least one of the group of the following terms composition: the poly- second of homopolymerization
Homopolymer in the group of alkene and homopolypropylene composition；It selects one in the group of free ethylene, propylene, butylene, hexene and octene composition
The random copolymer of kind or a variety of comonomers.
Polyolefin:
Heretofore described polyolefin is selected from least one of the group of the following terms composition: homopolymerisation polyethylene and homopolymerization are poly-
Homopolymer in the group of propylene composition；It selects one or more total in the group of free ethylene, propylene, butylene, hexene and octene composition
The random copolymer of polycondensation monomer copolymerization.
Such as it may is that the random copolymer of ethylene and propylene；The random copolymer of ethylene and butylene；Ethylene and hexene
Random copolymer；The random copolymer of ethylene and octene；The random copolymer of propylene and butylene；The random copolymerization of propylene and hexene
Object；The random copolymer of propylene and octene；The random copolymer of butylene and hexene；The random copolymer of butylene and octene；Ethylene,
The random copolymer of propylene and butylene；The random copolymer of ethylene, propylene and hexene；The random copolymerization of ethylene, propylene and octene
Object；The random copolymer of ethylene, butylene and hexene；The random copolymer of ethylene, butylene and octene；Propylene, butylene and hexene
Random copolymer；The random copolymer of propylene, butylene and octene；The random copolymer of butylene, hexene and octene.
The polyolefin can be homopolypropylene, or by propylene monomer and 12mol% or less ethylene or be based on C4-
The random copolymer of the monomer copolymerization of C10 alkene.
The polyolefin can be the copolymer of the vinyl monomer of the propylene monomer 1-12mol% of 88-99mol%.
The polyolefin resin can be used poly- lower than 0.3 g/10 min(230 DEG C, 2.16Kg) with melt index
Alkene.
Polyolefin refers to the polymer containing the monomeric unit from alkene.It can be such as: polyethylene based polymers.
As polyethylene based polymers, polyethylene may be exemplified.It is not particularly limited, can be used low close as polyethylene
Spend polyethylene, linear low density polyethylene, medium density polyethylene, high density polyethylene (HDPE) etc..
As polyethylene based polymers, the copolymer of ethylene He other alkene may be preferably exemplified.As " other in this
Alkene " can be preferably propylene, butylene, hexene, octene etc..These " other alkene " can be used alone or be applied in combination
Two or more.As polyethylene based polymers, more specifically, optimal ethylene-propylene copolymer, ethylene-hexene co-polymers, second
Alkene-octene copolymer etc., wherein especially preferably ethylene-hexene co-polymers.
The molecular weight of said polyolefins polymer is not particularly limited, for example, weight average molecular weight preferably 20000~
In the range of 6000000, more preferably in the range of 30000~6000000, further preferably 100000~5000000
In range.
When the weight average molecular weight of polyolefin is 20000 or more, the weatherability of acquired tubing can be improved preferably.Separately
Outside, when the weight average molecular weight of polyolefin is 6000000 or less, the processing and forming of obtained tubing can be become easier to.
In addition, the weight average molecular weight is to pass through: the concentration for preparing polyolefin is the chloroformic solution of 0.5 mass %, using efficient
Liquid chromatogram is measured, and is compared with polystyrene known to the weight average molecular weight measured under the same conditions, is thus counted
The value of calculating.In addition, determination condition is as follows.
Column: GPC column
Column temperature: 40 DEG C
Eluent: chloroform
Flow velocity: 1ml/ minutes
Melt flow rate (MFR) (MFR, the list that the mobility of the resin such as method as defined in using JIS7210:1999 measures
Position: g/10 min) it indicates.
Heretofore described polyolefin can be prepared for any method well known by persons skilled in the art.Such as
Prepare the copolymer of ethylene and propylene.
Ethylene and propylene mix in air accumulator in proportion in advance.It is aggregated in equipped with slotting bill kept on file body canal, outtake tube
It is carried out in the tubular type there-necked flask of mechanical stirring 100ml.First polymerization bottle is vacuumized, logical monomer is so continuously replaced twice, connect
Vacuum bake bottle 5 minutes.Reactor is led to as normal heptane, co-catalyst, external electron donor in water bath with thermostatic control, is once added
Enter gaseous mixture continuous bubbling, after monomer reaches dissolution equilibrium, major catalyst is added and causes polymerization.With acidification after polymerization
Ethyl alcohol terminates reaction, and polymer is filtered, and washs, constant weight is dried under vacuum at 60 DEG C, weighs.
Heretofore described polyolefin polymer can also buy the already existing polyolefin pipe PP Pipe Compound in any market.
Such as: PE-RT (heat-proof polythene), PPR (atactic copolymerized polypropene), PEX (crosslinked polyethylene), PE (polyethylene) etc..This hair
Polyolefin described in bright is preferably PE-RT II, and II type of PE-RT refers to the copolymer of ethylene and hexene, preferably high density
The copolymer of ethylene and hexene.
In the present invention, the polyolefin interior layer and polyolefinic outer layer can be same polyolefin, be also possible to different
Polyolefin.In the case that polyolefin interior layer and polyolefinic outer layer are same polyolefin, for example, outside polyolefin interior layer and polyolefin
Layer is all copolymer from ethylene and propylene, and the ratio of both ethylene and propylene can be different, such as can be second in polyolefinic outer layer
The parts by weight of alkene are more than the parts by weight of propylene, and the parts by weight of propylene are greater than the parts by weight of ethylene in polyolefin interior layer.
In the present invention, also contain epoxy resin in the polyolefin polymer.
The Adding Way of the epoxy resin is as follows: by the above-mentioned polyolefin polymer prepared and a certain amount of asphalt mixtures modified by epoxy resin
Rouge, curing agent are uniformly mixed in a solvent；Under nitrogen protection effect, 100~125 DEG C are warming up to, heating rate is controlled 0.5
~5 DEG C/min, while with the stirring of the speed of 30~60 turns/min, 0.5~2 hour is kept the temperature, suspension is obtained, then carries out subsequent
Extrusion process.
In the above method, the weight ratio of the epoxy resin and polyolefin is 1:(10~100), preferably 1:(20~
50).
In the present invention, the epoxy resin refers to the substance containing two or more epoxy groups.
In the present invention, the epoxy resin is diglycidyl ether type epoxy resin, cycloaliphatic epoxy resin, aliphatic epoxy
One of resin, glycolylurea epoxide resin are a variety of.
In the present invention, the epoxy resin can also be glycidyl ester type epoxy resin, glycidyl amine epoxy tree
The organic resin epoxy of the elements such as rouge, acid imide epoxy resin, phenol aldehyde type epoxy resin, polyurethane-type epoxy resin, siliceous, phosphorus
One of or it is a variety of.
In the present invention, the epoxy resin is bisphenol A type epoxy resin, methyl epoxy resin, 2,3- epoxy resin -2,3-
Dihydro -1,4- naphthoquinones, bis- (7- oxabicyclo [4.1.0] 3- methyl in heptan) adipate esters, 1,2,5,6- diepoxy resin cyclooctane,
Ethyl (2S, 3S) -2,3- epoxy resin -3- methylpropane acid esters, hexane -1,6- diglycidyl ether, diethylene glycol diglycidyl
One of glycerin ether, tripropyleneglycol diglycidyl ether, neopentylglycol diglycidyl ether are a variety of.
In addition, the epoxy resin in the present invention can also be other epoxy resin compounds, such as Bisphenol F type ring can be enumerated
Oxygen resin, cresol novolak type epoxy resin, phenol novolak type epoxy, biphenyl type epoxy resin, stilbene type epoxy resin, quinhydrones
Type epoxy resin, naphthalene skeleton type epoxy resin, four phenolic group ethane type epoxy resin, DPP type epoxy resin, three oxybenzene methylmethane types
Epoxy resin, bicyclopentadiene phenol-type epoxy resin, the diglycidyl ether of bisphenol A epoxy ethane additive product, bisphenol-A epoxy third
Diglycidyl ether, phenyl glycidyl ether, phenyl glycidyl ether of alkane addition product etc. have the shrink of an epoxy group
Glycerin ether.
Furthermore it is also possible to enumerate the nuclear hydrogenation epoxy resin of the nuclear hydrogenation compound as these epoxy resin.
In the present invention, the epoxy resin can be prepared using any preparation method known to those skilled in the art
It obtains.
In the present invention, the principle of the preparation method of the epoxy resin can be basically classified into two classes: (1) carbon-carbon double bond
It is oxidized to epoxy bond；(2) containing the substrate reactions of epoxy bond.
In the present invention, the polyolefinic outer layer can contain epoxy resin, and polyolefin interior layer does not contain epoxy resin；It can also
To be polyolefinic outer layer without containing epoxy resin, polyolefin interior layer contains epoxy resin；It is also possible to polyolefin interior layer and polyene
Hydrocarbon outer layer contains epoxy resin.
As an implementation, the stretched orientation process of heretofore described tubing.
The process is that the tubing prepared is heated to melting temperature, carries out planar stretch to tubing under elastomeric state,
It is stretched to after certain length, carries out cooling processing, the cooling processing can gradually cool down, and be also possible to instantaneous temperature reduction.
The intensity of tubing after stretched orientation increased.
As an implementation, polyolefin resin passes through corona treatment in the present invention.
Low temperature plasma contains a large amount of electronics, excited atom and molecule and free radical isoreactivity particle, these
Active particle makes material surface cause the physical and chemical reactions such as etching, oxidation, reduction, cracking, crosslinking and polymerization, to realize
Modification to material surface.Since the energy of particle in low temperature plasma is generally several to tens electron-volts, it is greater than
The combination bond energy that several to more than ten electron-volt of high molecular material can be such that the associative key of organic macromolecule material is broken completely
And form new keys；But its bond energy is far below the energy of high-energy radiation, therefore surface plasma processing only occurs in the table of material
Face.Corona treatment can improve the surface energy of polyolefin master batch, and plasma will not influence the structure of polyolefin master batch.
When low-temperature plasma processing, the preferably low-temperature plasma handles specifically operating procedure: by polyolefin master batch
It is placed in GPT-3 type corona treatment instrument, closes all air intake valves and vacuumize, when being extracted into air pressure to 10Pa, use oxygen
Gas carries out gas washing, repeats gas washing 2~3, then by adjusting air intake valve, is passed through the pressure that oxygen reaches certain.Close thermocouple
Vacuum meter opens radio frequency power source and discharges, discharges the regular hour under different capacity.After, directly to plasma
It is put into air in body vacuum chamber, takes out sample.Wherein the power of glow discharge be 30~120W, the discharge treatment time be 1~
10min, pressure are 20~100Pa.
Graphene-polyolefin blends middle layer:
Graphene be one kind by carbon atom with sp2Hydridization connects the monoatomic layer two dimensional crystal to be formed, and carbon atom is regular
It is arranged among honeycomb lattice structural unit.Each carbon atom remains other than being connected with σ key with other three carbon atoms
The pi-electron of remaining pi-electron and other carbon atoms forms the big pi bond of delocalization, and electronics can move freely in this area, thus
Make graphene that there is excellent electric conductivity.Meanwhile this closelypacked honeycomb structure is also to construct other carbon materials
Basic unit, the graphene of monoatomic layer can be wrapped to form the fullerene of zero dimension, and the graphene of single layer or multilayer can be rolled up
It is curved at single wall or the carbon nanotube of multi wall.
Since each carbon atom in graphene is combined into very strong σ key, stone with three adjacent carbon atoms
Black alkene equally shows excellent mechanical property.Recently, Columbia University scientist is directly tested using atomic force microscope
The mechanical property of single-layer graphene finds that the Young's modulus of graphene is about 1100GPa, and breaking strength is even more to reach
130GPa, 100 times more taller than best steel.
Graphene is equally a kind of excellent heat conductor, and thermal coefficient is up to 5000W/ (mK), is better than carbon nanometer
Pipe, even more than some common metals, such as high 10 times of gold, silver, copper or more.
The preparation method of graphene: mechanical stripping method, epitaxial growth method, chemical vapour deposition technique, chemical synthesis, oxidation
Graphene reduction method and longitudinally cutting carbon tube method etc. are several.
Mechanical stripping method: isolating graphene using micromechanics stripping method from graphite, in the liquid phase ultrasound removing graphite
It is the method for another common removing graphite.
Epitaxial growth method: former using (1200 ~ 1500 °C) distillation removal silicon of high temperature from the carbide silicon wafer surface (SiC)
Son, to obtain the graphene of epitaxial growth.
Chemical vapour deposition technique: chemical vapour deposition technique, which refers to, to be cracked carbon source (such as hydrocarbon) at high temperature and deposits
On solid substrate surface, substrate is usually the transition metal such as Ni, Ru.
Graphene oxide reduction method: use is most extensive at present, and is most hopeful to take the lead in realizing the system of heavy industrialization
It is presoma that a kind of method of standby graphene, which is using graphene oxide, by thermal reduction or electronation, by graphite oxide
The oxygen-containing group on alkene surface removes.Although this method cannot obtain perfect graphene, can largely restore
The intrinsic performance of graphene.Meanwhile relative to other graphene preparation methods, the abundant raw material of graphene oxide reduction method, if
Standby and operating process is simple, and the machinability for the graphene prepared is good, therefore is concerned.
Graphene oxide reduction method includes thermal expansion reduction method, chemical reduction method again.
Longitudinally cutting carbon tube method: preparing graphene as raw material using carbon nanotube is that one kind developed in recent years is novel
The method for preparing graphene, different from the isotropic graphite alkene lamella prepared using graphite as raw material, cutting carbon nanotubes obtain
Be anisotropic band-like graphene.
The preparation method of graphene can be prepared using any method known in the art in the present invention, this hair
The method of preferred redox graphene in bright.
Graphene oxide is a kind of derivative of graphene, includes C, H, O tri- with graphene of the strong oxidizer after processed
Kind element.It is similar to graphite, the effects of graphite oxide is similarly two-dimensional layered structure, and graphene oxide passes through the hydrogen bond of interlayer power
Stacked in multi-layers is together.But surface of graphene oxide contains a large amount of oxygen-containing group, it is made to show stronger hydrophily simultaneously
It can be completely dispersed in water.
The preparation method of graphene oxide: currently used three kinds of methods for preparing graphite oxide, i.e. Brodie method,
Staudenmaier method and Hummers method are to be handled using oxidation reinforced dose of strong acid of combination graphite.Strong proton
Acid enters graphite layers and forms graphite intercalation compound (graphite intercalation compounds), subsequent strong oxygen
Agent carries out oxidation to graphite and introduces a large amount of hydrophilic oxygen-containing functional groups to graphene surface and edge formation graphene oxide.By
In the stronger hydrophily of oxygen-containing group, graphene oxide can be removed completely and is dispersed in aqueous solution.
In the present invention, the graphene oxide is product of the powdered graphite after chemical oxidation and removing, graphene oxide
Be single atomic layer, some tens of pm can be expanded on lateral dimension at any time, therefore, the general chemistry of construct trans and
The typical size of material science.Graphene oxide can be considered a kind of flexible material of non-traditional kenel, have polymer, colloid,
The characteristic of film and amphiphatic molecule.After oxidation processes, graphite oxide still keeps the layer structure of graphite, but each
Many oxygroup functional groups are introduced on the graphene monolithic of layer.Graphene oxide is generally aoxidized through strong acid by graphite and is obtained.Mainly
There are three types of the methods for preparing graphite oxide: Brodie method, Staudenmaier method and Hummers method.The wherein system of Hummers method
The timeliness of standby process is relatively preferably and also relatively safer in preparation process, is most common one kind.It uses dense sulphur
For potassium permanganate and powdered graphite in acid after oxidation reaction, obtain brown has derivative carboxylic acid group and in the plane at edge
The predominantly graphite flake of phenolic hydroxyl group and epoxy group, this graphene layers can be vigorously stirred removing through ultrasound or high shear and be
Graphene oxide, and formed stablize in water, the single-layer graphene oxide suspension of sundown.Since conjugate network is by tight
The functionalization of weight, graphene oxide thin slice have the speciality of insulation.Partial reduction can be carried out through reduction treatment, obtains chemical modification
Graphene platelet.Had been emerging currently, preparing graphene oxide new method, be generally divided into top-down approach and
Bottom-up approach two major classes.The former thinking is to split crystalline flake graphite etc. to prepare graphene oxide, with changing for traditional three methods
It is representative into method, further includes the method etc. for splitting (breaking) carbon nanotube.The latter is with various carbon source synthetic methods, tool
Body method is multifarious, many kinds of.
Graphene-polyolefin blends refer to that the graphene that will be prepared and poly- system are blended in the present invention, then
The blending extrusion in extruding machine.In graphene-polyolefin blends, the content of graphene accounts for 0.1-10wt%.
As an implementation, middle layer can also be graphene oxide and polyolefin blends in the present invention.It is described
In the blend of graphene oxide and polyolefin, the content of the graphene oxide accounts for 0.1-8wt%.
As an implementation, graphene is modified by Nomex in graphene-polyolefin middle layer.
Specific preparation method: 1, being added dry 24 hours under 180 DEG C of vacuum graphenes in the three-necked flask of 500ml,
The about silane coupling agent of 0.1-1wt% graphene and 200 times of silane dosage of anhydrous dimethyl benzene.Three-necked flask is equipped with stirring
Paddle and condenser pipe and being placed in 110-120 DEG C of oil bath is handled at least 4 hours or more.Then graphene is filtered out, is placed in
It is 2 hours dry in 120 DEG C of vacuum drying oven；2, the further process of grafting of graphene after will be silane-modified is as follows: first
By graphene dispersion of the previous step after silane-modified into N-Methyl pyrrolidone；Then by quantitative 3,5- diaminobenzene first
Acid, pyridine and triphenyl phosphite are added in solution, are reacted 3 hours under 100 DEG C of nitrogen atmospheres.Then reaction solution is cooling
To room temperature, reaction solution after cooling is poured into the methanol solvate of the lithium chloride containing methanol solvate mass ratio 0.1% and sunk
Analysis, filters to isolate nano-graphene, then is rinsed 3 times with n,N-Dimethylformamide and methanol respectively, to remove extra 3,
5- diaminobenzoic acid monomer.
As an implementation, the weight ratio of the Nomex and graphene is (10~100): 1, preferably (10
~50): 1, more preferably (20~40): 1.
As an implementation, the weight average molecular weight of the Nomex is 200000-6000000, preferably
300000-1000000, more preferably 300000-900000.
As an implementation, heretofore described graphene-polyolefin layer includes boron nitride.
Six side's layered nitride boron (h-BN) belong to hexagonal crystal system, and B-N key is SP2Hydridization bonding.H-BN and graphene
Structure and cell parameter it is more similar, therefore be referred to as " white graphite alkene ".Hexagonal boron nitride belongs to hexaplanar, structure with
The layer structure of graphite is similar, and layer inside is alternately arranged the hexagonal gridding for forming and infinitely extending by boron atom and nitrogen-atoms,
Hexagonal boron nitride has quite high thermal conductivity [60 W/ (mK)], lower thermal expansion coefficient on perpendicular to C axis direction
[(0~2.6) × 10–4/ K] and very high tension stress intensity.
Hexagonal boron nitride preparation method: mechanical phonograph recorder separation, chemical vapour deposition technique, solvent-thermal method, high temperature and high pressure method.
Mechanical phonograph recorder separation: 10 μm of partial size average out to of hexagonal boron nitride powder is attached to adhesive tape with a thickness of 300 nm's
In silica substrate, boron nitride is then separated into lesser fragment by force, has finally obtained the two of only several atom thicks
Tie up boron nitride.
Chemical vapour deposition technique: by using hot wall type reaction kettle, the gaseous feed of boracic, nitrogen is imported into via carrier gas
One vacuum reaction is intracavitary, so that gaseous feed generation chemical reaction is ultimately generated hexagonal boron nitride stratiform at high temperature heat super
Very thin film, wherein boron source material generallys use BF3, BCl3, BBr3, B2H6With B (OCH3)3Equal boron-containing compounds, nitrogen source are generally adopted
With ammonia or nitrogen.
Water (solvent) thermal synthesis method: the medium by using water (or organic solvent) as reaction, and to autoclave
It is heated, under high temperature, condition of high voltage, so that being generally difficult to molten or insoluble,practically substance occurs to dissolve and react generation newly
Crystalline solid.
Solvent stripping method: this method is to destroy boron nitride powder by ultrasound condition using the stronger surface tension of organic solvent
End Van der Waals force between layers and achieve the purpose that remove hexagonal boron nitride.
Borax-urea (ammonium chloride) method: by borax anhydrous and urea (ammonium chloride) after evenly mixing under ammonia flow effect
Heating reacts and hexagonal boron nitride powder is made.
The preparation method of boron nitride is prepared using any one method known to those skilled in the art in the present invention.
The addition of boron nitride can also be adopted by simple physical mixed in graphene-polyolefin layer in the present invention
With the connection between chemical bond.
Such as: it can be graphene, polyolefin, being simply mixed between boron nitride three；It is also possible to graphene and nitrogen
After change boron progress is compound and polyolefin carries out physical mixed；Be also possible to graphene by Nomex it is modified and then and
Graphene, boron nitride carry out physical mixed；Be also possible to boron nitride by Nomex it is modified and then with graphene, nitridation
Boron carries out physical mixed；It is also possible to graphene and boron nitride is carried out compound and then is modified through Nomex, then and polyolefin
Carry out physical mixed.In said combination, the polyolefin can be any type, and there may also be epoxies in the polyolefin
Resin.
The compound preparation process of graphene/boron nitride: the boron nitride of different proportion and graphene are mixed according to different proportion
It closes, is then dissolved in DMF solution, carry out ultrasound and centrifugation, finally obtain graphene/boron nitride compound.
The preparation process of the modified boron nitride of Nomex: 1, it in the three-necked flask of 500ml is added dry under 180 DEG C of vacuum
The anhydrous dimethyl benzene of 200 times of 24 hours boron nitride, the about silane coupling agent of 0.1-1wt% boron nitride and silane dosage.Three
Mouth flask, which is furnished with agitating paddle and condenser pipe and is placed in 110-120 DEG C of oil bath, to be handled at least 4 hours or more.Then it filters out
Boron nitride is placed in 120 DEG C of vacuum drying oven 2 hours dry；2, the further graft reaction of boron nitride after will be silane-modified
Process is as follows: boron nitride of the previous step after silane-modified being distributed in N-Methyl pyrrolidone first；Then by quantitative 3,
5- diaminobenzoic acid, pyridine and triphenyl phosphite are added in solution, are reacted 3 hours under 100 DEG C of nitrogen atmospheres.Then
Reaction solution is cooled to room temperature, the methanol that reaction solution after cooling is poured into the lithium chloride containing methanol solvate mass ratio 0.1% is molten
Precipitating is carried out in agent, filters to isolate nm-class boron nitride, then is rinsed 3 times with n,N-Dimethylformamide and methanol respectively, to remove
Remove extra 3,5- diaminobenzoic acid monomer.
As an implementation.The weight ratio of the boron nitride and graphene is 1:(5~20), further preferably 1:
(10~20).
Another aspect of the present invention provides the method for preparing the high strength linepipe, the method that the present invention uses extrusion molding
Preparation.
Extrusion molding of the present invention is called extrusion molding, extruding, extrusion molding.It is to make by the extrusion of screw rod or plunger
With making to be plasticized uniform plastics and be forced through mouth mold and become the continuous product with constant cross-section.
The extrusion process includes charging, plasticizing, extrusion molding, vacuum sizing, cooling, traction, cutting.
Specific steps are as follows:
S1: it the preparation of Nomex graft modification graphene: 1, in the three-necked flask of 500ml is added 180 DEG C vacuum under
Dry 24 hours graphenes, the about silane coupling agent of 0.1-1wt% graphene and 200 times of silane dosage of anhydrous dimethyl
Benzene.Three-necked flask, which is furnished with agitating paddle and condenser pipe and is placed in 110-120 DEG C of oil bath, to be handled at least 4 hours or more.Then
Graphene is filtered out, is placed in 120 DEG C of vacuum drying oven 2 hours dry；2, the graphene after will be silane-modified further connects
Branch reaction process is as follows: the graphene dispersion first by previous step after silane-modified is into N-Methyl pyrrolidone；Then will determine
3,5- diaminobenzoic acid, pyridine and the triphenyl phosphite of amount are added in solution, and it is small that 3 are reacted under 100 DEG C of nitrogen atmospheres
When.Then reaction solution is cooled to room temperature, reaction solution after cooling is poured into the lithium chloride containing methanol solvate mass ratio 0.1%
Methanol solvate in carry out precipitating, filter to isolate nano-graphene, then rinse 3 with n,N-Dimethylformamide and methanol respectively
It is secondary, to remove extra 3,5- diaminobenzoic acid monomer.
S2: modified graphene/polyolefin blend particle preparation: by the graphite of Nomex graft modification described in S1
Alkene is added in polyolefin powder, adds additive, is mixed and is dispersed using mixer, then blend is added to twin-screw
Modified graphene/polyolefin blend particle is made in extruding pelletization in extruder；
S3: the preparation of polyolefin pipe: there are three hopper, polyolefin particles to be placed on outer layer for heretofore described extruder
Hopper, modified graphene described in the S2/polyolefin blend particle are placed on middle layer hopper, and the polyolefin particles are put
It sets in interior layered material bucket, then obtains three layers of compound polyolefin tubing by plasticizing co-extrusion.
As an implementation, the sum of the polyolefin interior layer and outer layer thickness in graphene-polyolefin blends
The ratio of interbed thickness is (2~70): 1, preferably (10~70): 1, more preferably (50-70): 1.
As an implementation, the thickness of told polyolefinic outer layer and polyolefin interior layer ratio is (1~5): (1~5), excellent
It is selected as (1~3): (1~5), more preferably 3:(1~5).
As an implementation, heretofore described graphene-polyolefin blends can also be in outer layer or internal layer.
When the graphene-polyolefin blends are in outer layer, when squeezing out, the graphene-polyolefin blends in outer layer material bucket,
Polyolefin particles can be difference in interior layered material bucket and middle layer hopper, in the polyolefin particles of interior layered material bucket and middle layer hopper
The polyolefin of the trade mark, different types of polyolefin, is not specifically limited here, then common to squeeze out.
Additive:
In the case where not influencing the invention, additive can be according to circumstances selected.Typical additives have anti-impact
Hit modifying agent, antibacterial agent, light stabilizer, antioxidant, tackifier, expanding material, reinforcing agent, filler material, nano material.
The anti-impact modifier is ethylene propylene diene rubber, butadiene-styrene rubber, neoprene, natural rubber, styrene-fourth
Diene-styrene copolymer, ethylene-vinyl acetate copolymer, acrylonitrile-butadiene-phenylethylene copolymer, in haloflex
One kind or two kinds or more of mixing；
The light stabilizer is benzophenone, benzoic ether, benzotriazole, salicylate, aminodithioformic acid nickel
One of salt, thiobisphenol, phosphate monoester nickel, hindered amine, carbon black, titanium dioxide, zinc oxide, iron oxide or two kinds or more
Mixing；
The antioxidant is one of phosphorous acid antioxidant, thioesters antioxidant, phenolic antioxidant or two or more
Mixing；
The nano material be active nano-calcium carbonate, silica, titanium dioxide, talcum powder, mica, quartz sand,
The mixing of one of sericite, clay, silicate, lime stone or two kinds or more；
The tackifier are polyisobutene co-polymer, polystyrene resin；
The expanding material is polypropylene-caprolactone graft copolymer, polypropylene-styrene graft copolymer, maleic acid
Acid anhydride graft copolymer, macromolecular silane coupling agent, macromolecular aluminium titanium coupling agent, macromolecular titanate coupling agent, polypropylene-methyl
Acrylate graft copolymers, polypropylene-acrylonitrile graft copolymer, polypropylene-methacrylic acid graft copolymer, chloromethyl
Phenylethene grafted copolymer, acrylic acid graft copolymer, ethylene-propylene graft copolymer, acrylic acid epoxy ester graft copolymer,
The mixing of one of maleic anhydride graft copolymer, ethylene-vinyl acetate copolymer or two kinds or more；
The reinforcing material is activity glass fiber, carbon fiber, aramid fiber, whisker nylon fiber, polyester fiber, boron
Any one or two kinds or more of mixing in fiber；
The filler material is calcium carbonate, silica, titanium dioxide, talcum powder, mica, quartz sand, sericite, pottery
The mixing of one of soil, silicate, lime stone or two kinds or more.
Tubing of the invention can be used for every field, such as chemical pipeline, water supply pipe, hot spring pipeline etc..
Present inventor is found surprisingly that tubing can be improved in height in the addition that Nomex connects modified branch graphene
Service life (38 years) under warm (95 DEG C), high pressure (1.6 MPa), the possible reason is the addition of Nomex can be improved it is poly-
The orientation and amount of crystals of alkene, while the addition of Nomex and epoxy resin further improve product in high temperature (95
DEG C), the service life (52 years) under high pressure (2.0MPa), the possible reason is the induction force between Nomex and epoxy resin
And dipole-dipole force, so that big network structure is formd, to improve the service life of product.
The present invention is specifically described below by embodiment.It is necessarily pointed out that following embodiment is only used
In the invention will be further described, it should not be understood as limiting the scope of the invention, professional and technical personnel in the field
The some nonessential modifications and adaptations made according to the content of aforementioned present invention, still fall within protection scope of the present invention.
In addition, if without other explanations, it is raw materials used to be all commercially available.
Embodiment 1: tubing is all made of PE-RT I, and regardless of outer layer, the trade mark of middle layer and internal layer, the PE-RT I is
PE-RT DX800, business men are South Korea SK.
Test result:
Embodiment 2: tubing is all by the blend of PE-RT I and graphene, regardless of outer layer, middle layer and internal layer, and the PE-
The trade mark of RT I is PE-RT DX800, and business men is South Korea SK.The weight part ratio of graphene and PE-RT I are 1:100.
The manufacturing step are as follows:
The preparation of S1: graphene/PE-RT I blended particles: being put into high-speed mixer for PE-RT I and graphene, heating
To 70-90 DEG C, it is mixed, is then placed in cold mixer and is cooled to room temperature, obtain PE-RT I and graphene mixture, then will mix
It closes object to be added in granulating extruder by plasticizing, squeeze out, cooling, pelletizing, obtains compound particles；
S2: the preparation of polyolefin pipe:: the step S1 pellet prepared is added separately to three-layer composite pipe material extruder
Internal layer, middle layer, outer layer hopper, through plasticizing co-extrusion obtain three-layer composite pipe material.
Test result:
Embodiment 3: outer layer: PE-RT I；Internal layer: PE-RT I；Middle layer: graphene and PE-RT I, the PE-RT I
The trade mark be PE-RT DX800, business men be South Korea SK.
The preparation of S1: graphene/PE-RT I blended particles: graphene is added in PE-RT I, adds addition
Agent is mixed using mixer and is dispersed, then is fed the mixture into granulating extruder by plasticizing, extrusion, cooling, pelletizing, is obtained
Compound particles；
S2: the preparation of polyolefin pipe: the step S1 pellet prepared is added in three-layer composite pipe material extruder
I particle of PE-RT is added in interbed hopper, inside and outside layered material bucket.Three-layer composite pipe material is obtained by being plasticized co-extrusion.
Test result:
Tubing thickness proportion: the sum of I internal layer of PE-RT and outer layer thickness and thickness among I blend of graphene-PE-RT
The ratio of degree is 40:1；The weight ratio of graphene and PE-RT I are 1:100 in I middle layer of graphene-PE-RT；
The thickness ratio of I internal layer of I outer layer of PE-RT and PE-RT is 1:2.
Embodiment 4: outer layer: PE-RT I；Internal layer: PE-RT I；Middle layer: graphene, Nomex and PE-RT I are total to
Mixed object, the trade mark of the PE-RT I are PE-RT DX800, and business men is South Korea SK.
S1: Nomex, graphene the preparation of graphene/I blended particles of Nomex/PE-RT: are added to PE-
In I powder of RT, additive is added, is mixed and is dispersed using mixer, then is fed the mixture into granulating extruder by modeling
Change, squeeze out, cooling, pelletizing, graphene/I blended particles of Nomex/PE-RT are made；
S2: the preparation of polyolefin pipe: graphene described in S1/I blended particles of Nomex/PE-RT are added
To the middle layer hopper of three-layer composite pipe material extruder, I particle of PE-RT is added in inside and outside layered material bucket.It is obtained by being plasticized co-extrusion
Three-layer composite pipe material.
Test result:
Tubing thickness proportion: the sum of I internal layer of PE-RT and outer layer thickness and thickness among I blend of graphene-PE-RT
The ratio of degree is 60:1；In I middle layer of graphene-PE-RT the weight ratio of graphene and PE-RT I be 1:50, Nomex and
The weight ratio of graphene is 10:1；
The thickness ratio of I internal layer of I outer layer of PE-RT and PE-RT is 2:1.
Embodiment 5: outer layer: PE-RT I；Internal layer: PE-RT I；Middle layer: Nomex/graphene and PE-RT's I is total to
Mixed object, the trade mark of the PE-RT I are PE-RT DX800, and business men is South Korea SK.
Nomex/graphene is Nomex graft modification graphene.
S1: it the preparation of Nomex graft modification graphene: 1, in the three-necked flask of 500ml is added 180 DEG C vacuum under
Dry 24 hours graphenes, the about silane coupling agent of 0.1-1wt% graphene and 200 times of silane dosage of anhydrous dimethyl
Benzene.Three-necked flask, which is furnished with agitating paddle and condenser pipe and is placed in 110-120 DEG C of oil bath, to be handled at least 4 hours or more.Then
Graphene is filtered out, is placed in 120 DEG C of vacuum drying oven 2 hours dry；2, the graphene after will be silane-modified further connects
Branch reaction process is as follows: the graphene dispersion first by previous step after silane-modified is into N-Methyl pyrrolidone；Then will determine
3,5- diaminobenzoic acid, pyridine and the triphenyl phosphite of amount are added in solution, and it is small that 3 are reacted under 100 DEG C of nitrogen atmospheres
When.Then reaction solution is cooled to room temperature, reaction solution after cooling is poured into the lithium chloride containing methanol solvate mass ratio 0.1%
Methanol solvate in carry out precipitating, filter to isolate nano-graphene, then rinse 3 with n,N-Dimethylformamide and methanol respectively
It is secondary, to remove extra 3,5- diaminobenzoic acid monomer.
The preparation of S2: modified graphene/PE-RT I blended particles: by the graphite of Nomex graft modification described in S1
Alkene is added in I powder of PE-RT, adds additive, is mixed and is dispersed using mixer, then blend is added to granulation and is squeezed
Extruding pelletization is made modified graphene/PE-RT I and master batch is blended in machine out；
S3: I blended particles of modified graphene/PE-RT described in S2 the preparation of polyolefin pipe: is added to three layers
I particle of PE-RT is added in the middle layer hopper of composite pipe extruder, inside and outside layered material bucket.Through plasticizing co-extrusion obtain three layers it is compound
Tubing.
Test result:
Tubing thickness proportion: the sum of I internal layer of PE-RT and outer layer thickness and thickness among I blend of graphene-PE-RT
The ratio of degree is 60:1；In I middle layer of graphene-PE-RT the weight ratio of graphene and PE-RT I be 1:50, Nomex and
The weight ratio of graphene is 10:1；
The thickness ratio of I internal layer of I outer layer of PE-RT and PE-RT is 2:1.
Embodiment 6: outer layer: PE-RT I；Internal layer: PE-RT I；Middle layer: Nomex/graphene and PE-RT's I is total to
Mixed object, the trade mark of the PE-RT I are PE-RT DX800, and business men is South Korea SK.
Nomex/graphene is Nomex graft modification graphene.
S1: it the preparation of Nomex graft modification graphene: 1, in the three-necked flask of 500ml is added 180 DEG C vacuum under
Dry 24 hours graphenes, the about silane coupling agent of 0.1-1wt% graphene and 200 times of silane dosage of anhydrous dimethyl
Benzene.Three-necked flask, which is furnished with agitating paddle and condenser pipe and is placed in 110-120 DEG C of oil bath, to be handled at least 4 hours or more.Then
Graphene is filtered out, is placed in 120 DEG C of vacuum drying oven 2 hours dry；2, the graphene after will be silane-modified further connects
Branch reaction process is as follows: the graphene dispersion first by previous step after silane-modified is into N-Methyl pyrrolidone；Then will determine
3,5- diaminobenzoic acid, pyridine and the triphenyl phosphite of amount are added in solution, and it is small that 3 are reacted under 100 DEG C of nitrogen atmospheres
When.Then reaction solution is cooled to room temperature, reaction solution after cooling is poured into the lithium chloride containing methanol solvate mass ratio 0.1%
Methanol solvate in carry out precipitating, filter to isolate nano-graphene, then rinse 3 with n,N-Dimethylformamide and methanol respectively
It is secondary, to remove extra 3,5- diaminobenzoic acid monomer.
The preparation of S2: modified graphene/PE-RT I blended particles: by the graphite of Nomex graft modification described in S1
Alkene is added in I powder of PE-RT, adds additive, is mixed and is dispersed using mixer, then blend is added to granulation and is squeezed
I blended particles of modified graphene/PE-RT are made in extruding pelletization in machine out；
S3: I blended particles of modified graphene/PE-RT described in S2 the preparation of polyolefin pipe: is added to three layers
I particle of PE-RT is added in the middle layer hopper of composite pipe extruder, inside and outside layered material bucket.Three layers are obtained again by being plasticized co-extrusion
Close tubing.
Test result:
Tubing thickness proportion: the sum of I internal layer of PE-RT and outer layer thickness and thickness among I blend of graphene-PE-RT
The ratio of degree is 60:1；In I middle layer of graphene-PE-RT the weight ratio of graphene and PE-RT I be 1:50, Nomex and
The weight ratio of graphene is 150:1；
The thickness ratio of I internal layer of I outer layer of PE-RT and PE-RT is 2:1.
Embodiment 7: outer layer: PE-RT I；Internal layer: PE-RT I；Middle layer: the blending of graphene, boron nitride and PE-RT I
Object, the trade mark of the PE-RT I are PE-RT DX800, and business men is South Korea SK.
S1: graphene, boron nitride the preparation of graphene/I blended particles of boron nitride/PE-RT: are added to PE-RT I
In powder, additive is added, is mixed and is dispersed using mixer, then blend is added to extruding pelletization system in granulating extruder
Obtain graphene/I blended particles of boron nitride/PE-RT；
S2: the preparation of polyolefin pipe: graphene described in S1/I blended particles of boron nitride/PE-RT are added to
I particle of PE-RT is added in the middle layer hopper of three-layer composite pipe material extruder, inside and outside layered material bucket.Three are obtained by being plasticized co-extrusion
Layer composite pipe.
Test result:
Tubing thickness proportion: the sum of I internal layer of PE-RT and outer layer thickness and thickness among I blend of graphene-PE-RT
The ratio of degree is 60:1；The weight ratio of graphene and PE-RT I are 1:75, boron nitride and stone in I middle layer of graphene-PE-RT
The weight ratio of black alkene is 1:10；
The thickness ratio of I internal layer of I outer layer of PE-RT and PE-RT is 2:1.
Embodiment 8: outer layer: PE-RT I；Internal layer: PE-RT I；Middle layer: the blending of graphene, boron nitride and PE-RT I
Object, the trade mark of the PE-RT I are PE-RT DX800, and business men is South Korea SK.
S1: graphene, boron nitride the preparation of graphene/I blended particles of boron nitride/PE-RT: are added to PE-RT I
In powder, additive is added, is mixed and is dispersed using mixer, then blend is added to extruding pelletization system in granulating extruder
Obtain graphene/I blended particles of boron nitride/PE-RT；
S2: the preparation of polyolefin pipe: graphene described in S1/I blended particles of boron nitride/PE-RT are added to
I particle of PE-RT is added in the middle layer hopper of three-layer composite pipe material extruder, inside and outside layered material bucket.Three are obtained by being plasticized co-extrusion
Layer composite pipe.
Test result:
Tubing thickness proportion: the sum of I internal layer of PE-RT and outer layer thickness and thickness among I blend of graphene-PE-RT
The ratio of degree is 45:1；The weight ratio of graphene and PE-RT I are 1:65, boron nitride and stone in I middle layer of graphene-PE-RT
The weight ratio of black alkene is 1:15；
The thickness ratio of I internal layer of I outer layer of PE-RT and PE-RT is 3:1.
Embodiment 9: the difference with embodiment 8 is that the middle layer is Nomex/graphene, boron nitride and PE-RT
I blend.
Test result:
Tubing thickness proportion: the sum of I internal layer of PE-RT and outer layer thickness and thickness among I blend of graphene-PE-RT
The ratio of degree is 65:1；In I middle layer of graphene-PE-RT the weight ratio of graphene and PE-RT I be 1:100, Nomex and
The weight ratio of graphene is 35:1；The weight ratio of boron nitride and graphene is 1:20；
The thickness ratio of I internal layer of I outer layer of PE-RT and PE-RT is 4:1.
Embodiment 10: the difference with embodiment 9 is,
Tubing thickness proportion: the sum of I internal layer of PE-RT and outer layer thickness and thickness among I blend of graphene-PE-RT
The ratio of degree is 70:1；In I middle layer of graphene-PE-RT the weight ratio of graphene and PE-RT I be 1:100, Nomex and
The weight ratio of graphene is 45:1；The weight ratio of boron nitride and graphene is 1:18；
The thickness ratio of I internal layer of I outer layer of PE-RT and PE-RT is 1:1.
Test result:
Embodiment 11: the difference with embodiment 9 is, the outer layer and internal layer are the blending of PE-RT I and epoxy resin
Object.
Test result:
Tubing thickness proportion: the sum of I internal layer of PE-RT and outer layer thickness and thickness among I blend of graphene-PE-RT
The ratio of degree is 55:1；The weight ratio of epoxy resin and PE-RT I are 1:10；The epoxide number of the epoxy resin is 0.48mol/
100g。
The thickness ratio of I internal layer of I outer layer of PE-RT and PE-RT is 1:1.
Embodiment 12: the difference with embodiment 9 is, handles after the tube extrusion through overstretching, and draw ratio is 3
Times.
Test result:
Embodiment 13: the difference with embodiment 9 is that I master batch of PE-RT passes through corona treatment before extrusion.
Test result:
Embodiment 14: embodiment 1: tubing is all made of PE-RT II, regardless of outer layer, middle layer and internal layer, and the PE-RT
II trade mark is DOWLEX 2388, business men Tao Shi.
Test result:
Embodiment 15: the difference with embodiment 11 is, the outer layer and internal layer are PE-RT II and epoxy resin is total to
Mixed object.
Test result:
Above data can be seen that compared with the product for not using graphene, boron nitride, Nomex, present invention preparation
Material while having compared with high environment temperature, oxygen barrier and bearing high pressure, also there is longer service life, therefore mention
Advantageous effects of the invention are supplied, polyolefin pipe of the invention can be in temperature at 95 DEG C, and pressure is being greater than 1.6MPa
Under conditions of, service life reaches 50 years or more.
Example above-mentioned is merely illustrative, some features of the feature for explaining the disclosure.The attached claims
It is intended to the range as wide as possible for requiring to be contemplated that, and embodiments as presented herein is only according to all possible embodiment
Combined selection embodiment explanation.Therefore, the purpose of applicant is that the attached claims are not illustrated the present invention
Feature exemplary selectional restriction.And the progress in science and technology will be formed language express it is inaccurate due to and not
The possible equivalent being presently considered or son replacement, and these variations should also be interpreted in the conceived case by appended
Claim covering.
Claims (1)
1. graphene increased thermal conductivity compound polyolefin tubing, which is characterized in that
It includes the middle layer of the blend of Nomex graft modification graphene, boron nitride and PE-RT I；Outer layer and internal layer are equal
For the mixture of PE-RT II and epoxy resin；
Wherein, the ratio of the sum of internal layer and outer layer thickness and intermediate layer thickness is 55:1；II internal layer of II outer layer of PE-RT and PE-RT
Thickness ratio be 1:1；The weight ratio of epoxy resin and PE-RT II are 1:10；The epoxide number of the epoxy resin is 0.48mol/
100g；
In the middle layer, the weight ratio of the graphene and PE-RT I are 1:100, the weight ratio of Nomex and graphene
For 35:1；The weight ratio of boron nitride and graphene is 1:20；
Wherein, the Nomex graft modification graphene the preparation method is as follows:
Dry 24 hours under 180 DEG C of vacuum graphenes are added in the three-necked flask of 500ml, are the silicon of 0.1-1wt% graphene
Alkane coupling agent and 200 times of silane dosage of anhydrous dimethyl benzene；Three-necked flask is equipped with agitating paddle and condenser pipe and is placed in 110-
It is handled in 120 DEG C of oil bath at least 4 hours or more；Then graphene is filtered out, is placed in 120 DEG C of vacuum drying oven dry 2
Hour, obtain it is silane-modified after graphene；
The further process of grafting of graphene after will be silane-modified is as follows: the graphene first by previous step after silane-modified
It is distributed in N-Methyl pyrrolidone；Then quantitative 3,5- diaminobenzoic acid, pyridine and triphenyl phosphite are added to
In solution, is reacted 3 hours under 100 DEG C of nitrogen atmospheres, then reaction solution is cooled to room temperature, reaction solution after cooling is poured into
Precipitating is carried out in the methanol solvate of lithium chloride containing methanol solvate mass ratio 0.1%, filters to isolate nano-graphene, then divide
Not Yong n,N-Dimethylformamide and methanol rinse 3 times, to remove extra 3,5- diaminobenzoic acid monomer；The tubing warp
Overstretching orientation process, and draw ratio is 3.
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| CN106751477A (en) * | 2016-11-29 | 2017-05-31 | 太湖县金辉煌电子科技有限公司 | A kind of high-molecular-weight epoxy Heat Conduction Material and preparation method thereof |
| CN107103768A (en) * | 2017-05-27 | 2017-08-29 | 宁波力泰电子科技有限公司 | A kind of energy-saving traffic signal lamp control device |
| CN109486023A (en) * | 2017-09-12 | 2019-03-19 | 丹阳市丹达防腐设备有限公司 | A kind of steel lining plastic modified polypropylene material and preparation method thereof |
| CN107906270B (en) * | 2017-10-24 | 2020-08-11 | 佛山科学技术学院 | Mica powder and graphene composite flexible pipe |
| CN109943201A (en) * | 2019-02-12 | 2019-06-28 | 中国石油天然气集团有限公司 | It is less than oil pipe good antiscale property graphene modified epoxy coating and preparation method thereof of 50000ppm water injection well for salinity |
| CN115027102B (en) * | 2022-05-12 | 2024-03-19 | 临海伟星新型建材有限公司 | High-strength medium conveying pipeline with temperature and preparation method thereof |
| CN115232360B (en) * | 2022-08-17 | 2023-06-30 | 山东玉皇新能源科技有限公司 | Graphene composite reinforcing agent and preparation method thereof |
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| CN102496668A (en) * | 2011-12-26 | 2012-06-13 | 金虎 | Boron nitride-graphene composite material, preparation method and purpose thereof |
| CN102826539A (en) * | 2012-07-31 | 2012-12-19 | 上海交通大学 | Hyperbranched polyaramide functionalized graphene, as well as preparation method and applications of hyperbranched polyaramide functionalized graphene |
| CN203051984U (en) * | 2013-01-24 | 2013-07-10 | 河北建投宝塑管业有限公司 | Multilayer composite pipe preventing scratches and point loads |
| CN103480329A (en) * | 2013-09-05 | 2014-01-01 | 深圳先进技术研究院 | Hexagonal boron nitride/graphene oxide composite adsorption material and preparation method thereof |
| CN104093557A (en) * | 2011-12-06 | 2014-10-08 | 韦文有限公司 | Multi-layered pipe |
| CN104151696A (en) * | 2014-05-07 | 2014-11-19 | 武汉金牛经济发展有限公司 | Preparation method of graphene-modified polypropylene steel-plastic composite pipe |
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2016
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104093557A (en) * | 2011-12-06 | 2014-10-08 | 韦文有限公司 | Multi-layered pipe |
| CN102496668A (en) * | 2011-12-26 | 2012-06-13 | 金虎 | Boron nitride-graphene composite material, preparation method and purpose thereof |
| CN102826539A (en) * | 2012-07-31 | 2012-12-19 | 上海交通大学 | Hyperbranched polyaramide functionalized graphene, as well as preparation method and applications of hyperbranched polyaramide functionalized graphene |
| CN203051984U (en) * | 2013-01-24 | 2013-07-10 | 河北建投宝塑管业有限公司 | Multilayer composite pipe preventing scratches and point loads |
| CN103480329A (en) * | 2013-09-05 | 2014-01-01 | 深圳先进技术研究院 | Hexagonal boron nitride/graphene oxide composite adsorption material and preparation method thereof |
| CN104151696A (en) * | 2014-05-07 | 2014-11-19 | 武汉金牛经济发展有限公司 | Preparation method of graphene-modified polypropylene steel-plastic composite pipe |
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