CN105570560A - Graphene-enhanced thermal conductance composite polyolefin pipe - Google Patents
Graphene-enhanced thermal conductance composite polyolefin pipe Download PDFInfo
- Publication number
- CN105570560A CN105570560A CN201610148355.4A CN201610148355A CN105570560A CN 105570560 A CN105570560 A CN 105570560A CN 201610148355 A CN201610148355 A CN 201610148355A CN 105570560 A CN105570560 A CN 105570560A
- Authority
- CN
- China
- Prior art keywords
- graphene
- polyolefin
- tubing
- boron nitride
- layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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 invention provides a high-strength pipe. The high-strength pipe comprises a polyolefin outer layer, a polyolefin inner layer and a graphene-polyolefin blending middle layer.
Description
Technical field
The present invention relates to a kind of tubing, particularly a kind of Graphene increased thermal conductivity compound polyolefin tubing.
Background technique
As everyone knows, metallic conduit has perishable, easy fouling, and working life is short, installs the shortcomings such as difficulty.Trend is become to mould Dai Gang, therefore plastic pipe has irreplaceable effect in work China Democratic National Construction Association field, and such as PP-R/PE/PVC/PE-RT pipe is widely used in the fields such as building water supply and drainage, heating pipe system, central air-conditioning pipe system, chemical engineering piping systems, electrical protective sleeve pipe.
Due to Environmental Conditions, often there are some problems in these pipelines: it is inadequate 1, to bear pressure; 2, high temperature condition is shorter for lower working life.Special in polyolefin pipe, often there is the shortcoming that insufficient strength is high.Simultaneously, in the process used, particularly in heating power transporting system and water heating system, often need tubing to have withstand voltage, resistant to elevated temperatures feature, can only maintain the underground pipe gallery construction proposed in a few year " 13 planning " in this case the working life of tubing has higher requirement to performances such as the mechanical index of tubing and working lifes.The working life of tubing is determined jointly by serviceability temperature and working pressure.Such as the most frequently used at present PP-R pipe is at 60 DEG C, can use 50 years under the environment of 1Mpa, so current existing polyolefin pipe can not at the environment Long-Time Service of 95 DEG C.Therefore need a kind of tubing badly, meet serviceability temperature 95 DEG C, working pressure 1.6MPa, the tubing in 50 years working life.The height developed especially at present, the utilization of new energy resources such as middle temperature solar and underground heat energy, are badly in need of High Temperature High Pressure long lifetime and the good polyolefin pipe of thermal conductivity
A kind of high strength is needed badly, the composite pipe with combination property of long service life while of high pressure resistant for above-mentioned situation.
Summary of the invention
For the problems referred to above, the invention provides a kind of polyolefin pipe of high strength long service life, comprise polyolefinic outer layer, polyolefin interior layer, the mesosphere of Graphene-polyolefin blends, described polyolefin pipe can in temperature at 95 DEG C, and pressure, under the condition being greater than 1.6MPa, reaches more than 50 years working life.
As a kind of mode of execution, described polyolefin is selected from least one in the group of the following composition: the homopolymer in the group of homopolymerisation polyethylene and homo-polypropylene composition; The random copolymer of one or more comonomer in the group selecting free ethylene, propylene, butylene, hexene and octene to form.
As a kind of preferred version, described polyolefin selects the copolymer of a kind of and ethylene copolymer in propylene, hexene and octene.
As a kind of mode of execution, the ratio of described polyolefin interior layer and outer layer thickness sum and Graphene-polyolefin blends intermediate layer thickness is (2 ~ 70): 1.
As a kind of mode of execution, the Thickness Ratio of polyolefinic outer layer and polyolefin interior layer is (1 ~ 5): (1 ~ 5).
As a kind of mode of execution, described Graphene is Nomex modified graphene, and the weight ratio of Nomex and Graphene is (10 ~ 30): 1.
As a kind of preferred version, described Graphene-polyolefin layer comprises boron nitride, and the weight ratio of described boron nitride and Graphene is 1:(5 ~ 20).
As a kind of mode of execution, described Graphene-polyolefin layer comprises boron nitride, and the weight ratio of described boron nitride and Graphene is 1:(10 ~ 20).
As a kind of mode of execution, described polyolefin interior layer and the stretched orientation process of skin, and draw ratio is 3 ~ 8.
As a kind of mode of execution, described polyolefin interior layer and the stretched orientation process of skin, and draw ratio is 3 ~ 5.
Embodiment
The detailed description of the following preferred implementation methods of the present invention of participation in the election and the embodiment comprised can more easily understand content of the present invention.Unless otherwise defined, all technology used herein and scientific terminology have the identical implication usually understood with one skilled in the art of the present invention.When there is contradiction, be as the criterion with the definition in this specification.
Term as used herein " by ... preparation " and " comprising " synonym.Term used herein " comprises ", " comprising ", " having ", " containing " or its other distortion any, be intended to cover the comprising of non-exclusionism.Such as, comprise the composition of listed elements, step, method, goods or device and need not be only limitted to those key elements, but other key element of clearly not listing or the intrinsic key element of this kind of composition, step, method, goods or device can be comprised.
Conjunction " by ... composition " get rid of any key element, step or the component do not pointed out.If in claim, this phrase will make claim be closed, make it not comprise material except those materials described, but except relative customary impurities.When phrase " by ... composition " to appear in the clause of claim main body instead of immediately preceding after theme time, it is only limited to the key element described in this clause; Other key element is not excluded outside described claim as a whole.
During the Range Representation that equivalent, concentration or other value or parameter limit with scope, preferable range or a series of upper limit preferred value and lower preferable values, this is appreciated that all scopes specifically disclosing and formed by arbitrary pairing of any range limit or preferred value and any range lower limit or preferred value, no matter and whether this scope separately discloses.Such as, when disclosing scope " 1 to 5 ", described scope should be interpreted as comprising scope " 1 to 4 ", " 1 to 3 ", " 1 to 2 ", " 1 to 2 and 4 to 5 ", " 1 to 3 and 5 " etc.When number range is described in this article, unless otherwise indicated, otherwise this scope intention comprises its end value and all integers within the scope of this and mark.
Singulative comprises plural number and object is discussed, unless clearly indicated in addition in context." optional " or " any one " refer to that the item that describes thereafter or event can occur or not occur, and this description comprises situation that event occurs and the situation that event does not occur.
Approximate term in specification and claims is used for modifying quantity, represents that the present invention is not limited to this concrete quantity, also comprises close to this quantity acceptable and can not cause the part of the correction of the change of relevant fundamental function.Accordingly, modify a numerical value with " approximately ", " about " etc., mean and the invention is not restricted to this exact numerical.In some example, approximate term may correspond to the precision of the instrument measuring numerical value.In present specification and claims, scope limits and can combine and/or exchange, if do not illustrate that these scopes comprise contained all subranges therebetween in addition.
In addition, the indefinite article " one " before key element of the present invention or component and " one " are to quantitative requirement (i.e. occurrence number) unrestriction of key element or component.Therefore " one " or " one " should be read as and comprise one or at least one, and the key element of singulative or component also comprise plural form, unless the obvious purport of described quantity refers to singulative.
" polymer " means the polymerizable compound prepared by the monomer by being polymerized identical or different type.General tems " polymer " comprises term " homopolymer ", " copolymer ", " terpolymer " and " copolymer ".
" copolymer " means the polymer prepared by polymerization at least two kinds of different monomers.General tems " copolymer " comprises term " copolymer " (it is generally in order to refer to the polymer prepared by two kinds of different monomers) and term " terpolymer " (it is generally in order to refer to the polymer prepared by three kinds of different monomers).It also comprises plants monomer and the polymer that manufactures by being polymerized four or more." blend " mean two or more polymer by physics or the method for chemistry jointly mix and the polymer formed.
The invention provides a kind of Graphene increased thermal conductivity compound polyolefin tubing, comprise polyolefinic outer layer, polyolefin interior layer, the mesosphere of Graphene-polyolefin blends, described polyolefin pipe can in temperature at 95 DEG C, and pressure, under the condition being greater than 1.6MPa, reaches more than 50 years working life.
In order to solve the problem, the invention provides a kind of Graphene increased thermal conductivity compound polyolefin tubing, comprising polyolefinic outer layer, polyolefin interior layer, the mesosphere of Graphene-polyolefin blends.
As a kind of mode of execution, described polyolefin is selected from least one in the group of the following composition: the homopolymer in the group of homopolymerisation polyethylene and homo-polypropylene composition; The random copolymer of one or more comonomer in the group selecting free ethylene, propylene, butylene, hexene and octene to form.
polyolefin:
Polyolefin described in the present invention is selected from least one in the group of the following composition: the homopolymer in the group of homopolymerisation polyethylene and homo-polypropylene composition; The random copolymer of one or more comonomer in the group selecting free ethylene, propylene, butylene, hexene and octene to form.
Can be such as: the random copolymer of ethene and propylene; The random copolymer of ethene and butylene; The random copolymer of ethene and hexene; The random copolymer of ethene and octene; The random copolymer of propylene and butylene; The random copolymer of propylene and hexene; The random copolymer of propylene and octene; The random copolymer of butylene and hexene; The random copolymer of butylene and octene; The random copolymer of ethene, propylene and butylene; The random copolymer of ethene, propylene and hexene; The random copolymer of ethene, propylene and octene; The random copolymer of ethene, butylene and hexene; The random copolymer of ethene, butylene and octene; The random copolymer of propylene, butylene and hexene; The random copolymer of propylene, butylene and octene; The random copolymer of butylene, hexene and octene.
Described polyolefin can be homo-polypropylene, or by the random copolymer of propylene monomer and 12mol% or less ethene or the monomer copolymerization based on C4-C10 alkene.
Described polyolefin can be the copolymer of the vinyl monomer of the propylene monomer 1-12mol% of 88-99mol%.
Described vistanex can use has melt index lower than 0.3g/10min(230 DEG C, 2.16Kg) polyolefin.
Polyolefin refers to the polymer containing the monomeric unit deriving from alkene.Can such as: polyethylene based polymers.
As polyethylene based polymers, polyethylene can be illustrated.Be not particularly limited as polyethylene, Low Density Polyethylene, LLDPE, medium density polyethylene, high density polyethylene (HDPE) etc. can be used.
As polyethylene based polymers, the copolymer of ethene and other alkene preferably can be illustrated.As at this " other alkene ", propylene, butylene, hexene, octene etc. can be preferably.These " other alkene " can be used alone a kind or combinationally use two or more.As polyethylene based polymers, more specifically, optimal ethylene-propylene copolymer, ethylene-hexene co-polymers, ethylene-octene copolymer etc., wherein, be especially preferably ethylene-hexene co-polymers.
The molecular weight of said polyolefins polymer is not particularly limited, and such as, weight average molecular weight is preferably in the scope of 20000 ~ 6000000, more preferably in the scope of 30000 ~ 6000000, preferred in the scope of 100000 ~ 5000000 further.
When polyolefinic weight average molecular weight is more than 20000, obtain tubing weatherability can improve better.In addition, when polyolefinic weight average molecular weight is less than 6000000, the shaping operation of the tubing obtained can become easier.
In addition, this weight average molecular weight passes through: prepare the chloroformic solution that polyolefinic concentration is 0.5 quality %, uses high performance liquid chromatography to measure, compare, the value calculated thus with the polystyrene that the weight average molecular weight measured under the same conditions is known.In addition, condition determination is as follows.
Post: GPC post
Column temperature: 40 DEG C
Eluent: chloroform
Flow velocity: 1ml/ minute
The melt flow rate (MFR) (MFR, unit: g/10min) that the mobility of resin is such as measured by the method utilizing JIS7210:1999 to specify represents.
Polyolefin described in the present invention can prepare for any one method well known by persons skilled in the art.Such as prepare the copolymer of ethene and propylene.
Ethene and propylene mix in advance in proportion in gas holder.Be aggregated in the tubular type there-necked flask that slotting bill kept on file body canal, outtake tube and mechanical agitation 100ml are housed and carry out.First vacuumized by polymerization bottle, logical monomer replaces twice so continuously, then vacuum bakes bottle 5 minutes.By reactor as in water bath with thermostatic control, once add normal heptane, cocatalyst, external electron donor, pass into mixed gas continuous bubbling, reach after dissolution equilibrium until monomer, add primary catalyst initiated polymerization.Polymerization terminates the ethanol cessation reaction of rear acidifying, and after filtration, washing, at 60 DEG C, vacuum drying is to constant weight, weighs for polymer.
Polyolefin polymer described in the present invention also can buy the polyolefin pipe PP Pipe Compound that any market has existed.Such as: PE-RT (heat-proof polythene), PPR (atactic copolymerized polypropene), PEX (crosslinked polyethylene), PE (polyethylene) etc.Polyolefin described in the present invention is preferably PE-RT II, and described PE-RT II type refers to the copolymer of ethene and hexene, is preferably the copolymer of high density ethylene and hexene.
In the present invention, described polyolefin interior layer and polyolefinic outer layer can be same polyolefin, also can be different polyolefin.Polyolefin interior layer and polyolefinic outer layer are in same polyolefinic situation, such as, polyolefin interior layer and polyolefinic outer layer are all copolymer from ethylene and propylene, the ratio of ethene and propylene can be different, can be such as the weight portion of weight portion more than propylene of ethene in polyolefinic outer layer, in polyolefin interior layer, the weight portion of propylene be greater than the weight portion of ethene.
In the present invention, also containing epoxy resin in described polyolefin polymer.
The Adding Way of described epoxy resin is as follows: mixed in a solvent with a certain amount of epoxy resin, curing agent by the above-mentioned polyolefin polymer prepared; Under nitrogen protection effect, be warming up to 100 ~ 125 DEG C, warming velocity controls at 0.5 ~ 5 DEG C/min, stirs simultaneously, be incubated 0.5 ~ 2 hour with the speed of 30 ~ 60 turns/min, obtains suspension, then carries out follow-up extrusion process.
In said method, described epoxy resin and polyolefinic weight ratio are 1:(10 ~ 100), be preferably 1:(20 ~ 50).
In the present invention, described epoxy resin refers to the material containing two or more epoxy group.
In the present invention, described epoxy resin is one or more in diglycidyl ether type epoxy resin, cycloaliphatic epoxy resin, aliphatic epoxy resin, glycolylurea epoxide resin.
In the present invention, described epoxy resin can also be one or more in organic epoxy resin of the elements such as glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, imide ring epoxy resins, phenol aldehyde type epoxy resin, polyurethane-type epoxy resin, siliceous, phosphorus.
In the present invention, described epoxy resin is bisphenol A type epoxy resin, methyl epoxy resin, 2,3-epoxy resin-2,3-dihydro-1,4-naphthoquinones, two (7-oxabicyclo [4.1.0] 3-methyl in heptan) adipate ester, 1,2,5,6-diepoxy resin cyclooctane, ethyl (2S, 3S)-2, one or more in 3-epoxy resin-3-methylpropane acid esters, hexane-1,6-diglycidyl ether, diethylene glycol diglycidyl glycerin ether, tripropyleneglycol diglycidyl ether, neopentylglycol diglycidyl ether.
In addition, epoxy resin in the present invention can also be other epoxy resin compounds, such as bisphenol f type epoxy resin can be enumerated, cresol novolak type epoxy resin, phenol novolak type epoxy, biphenyl type epoxy resin, stilbene type epoxy resin, hydroquinone type epoxy resin, naphthalene matrix type epoxy resin, four phenolic group ethane type epoxy resin, DPP type epoxy resin, three hydroxyphenyl methane type epoxy resin, bicyclopentadiene phenol-type epoxy resin, the diglycidyl ether of bisphenol A epoxy ethane additive product, the diglycidyl ether of bisphenol A propylene oxide addition product, phenyl glycidyl ether, phenyl glycidyl ethers etc. have the glycidol ether of an epoxide group.
In addition, the nuclear hydrogenation epoxy resin of the nuclear hydrogenation compound as these epoxy resin can also be enumerated.
In the present invention, described epoxy resin can adopt any one preparation method known to those skilled in the art to prepare.
In the present invention, the principle of the preparation method of described epoxy resin can be divided into two classes substantially: (1) carbon-carbon double bond is oxidized to epoxy bond; (2) substrate reactions containing epoxy bond.
In the present invention, described polyolefinic outer layer can contain epoxy resin, and polyolefin interior layer is not containing epoxy resin; Also can be that polyolefinic outer layer does not contain epoxy resin, polyolefin interior layer contains epoxy resin; Also can be that polyolefin interior layer and polyolefinic outer layer are all containing epoxy resin.
As a kind of mode of execution, the stretched orientation process of tubing described in the present invention.
Described process is that the tubing prepared is heated to melt temperature, under elastomeric state, carry out planar stretch to tubing, and after being stretched to certain length, carry out cooling process, described cooling process can be lowered the temperature gradually, also can be instantaneous temperature reduction.The intensity of the tubing after stretched orientation increases all to some extent.
As a kind of mode of execution, in the present invention, vistanex is through plasma treatment.
Low temperature plasma contains a large amount of electronics, excited atom and molecule and free radicals isoreactivity particle, these active particles make material surface cause the physical and chemical reactions such as etching, oxidation, reduction, cracking, crosslinked and polymerization, thus realize the modification to material surface.Because the energy of particle in low temperature plasma is generally several to tens electron-volts, be greater than macromolecular material several to tens electron-volts in conjunction with bond energy, can make completely the bond of organic macromolecule material rupture and form new key; But its bond energy is far below the energy of high-energy radiation, therefore surface plasma process only occurs in the surface of material.Plasma treatment can improve the surface energy of polyolefin master batch, and plasma can not affect the structure of polyolefin master batch.
During low-temperature plasma process, described preferably low-temperature plasma process operating procedure particularly: polyolefin master batch is placed in GPT-3 type plasma treatment instrument, closeall air intake valve vacuumizes, in time being extracted into air pressure to 10Pa, gas washing is carried out with oxygen, repeating gas washing 2 ~ 3, then by regulating air intake valve, passing into the pressure that oxygen reaches certain.Close thermocouple vacuum gauge, open radio frequency power source and discharge, discharge the regular hour under different capacity.After end, put into air directly in plasma vacuum chamber, take out sample.Wherein the power of glow discharge is 30 ~ 120W, and the electro discharge treatment time is 1 ~ 10min, and pressure is 20 ~ 100Pa.
graphene-polyolefin blends mesosphere:
Graphene be a kind of by carbon atom with sp
2the monoatomic layer two dimensional crystal that hydridization is connected to form, what carbon atom was regular is arranged among honeycomb lattice element of construction.Each carbon atom is except being connected with σ key and other three carbon atoms, and the pi-electron of remaining pi-electron and other carbon atoms forms the large π key of delocalization, and electronics can move freely in this region, thus makes Graphene have excellent electric conductivity.Meanwhile, this closelypacked cellular structure is also the elementary cell of other material with carbon elements of structure, and the Graphene of monoatomic layer can be wrapped to form the fullerene of zero dimension, and the Graphene of individual layer or multilayer can curl into the carbon nano-tube of single wall or many walls.
Because each carbon atom in Graphene is all combined into very strong σ key with adjacent three carbon atoms, therefore Graphene shows excellent mechanical property equally.Recently, Columbia University scientist utilizes atom force microscope directly to test the mechanical property of single-layer graphene, and find that the Young's modulus of Graphene is about 1100GPa, rupture strength reaches 130GPa especially, more taller than best iron and steel 100 times.
Graphene is a kind of excellent heat conductor equally, and its thermal conductivity, up to 5000W/ (mK), is better than carbon nano-tube, especially than some common metal, as contour more than 10 times of gold, silver, copper.
The preparation method of Graphene: mechanical stripping method, epitaxial growth method, Low Pressure Chemical Vapor Deposition, chemical synthesis, graphene oxide reduction method and longitudinal cutting carbon tube method etc. are several.
Mechanical stripping method: utilize micromechanics stripping method to isolate Graphene from graphite, ultrasonic stripping graphite is the method for another conventional stripping graphite in the liquid phase.
Epitaxial growth method: utilize from carbide silicon chip (SiC) surface high temperature (1200 ~ 1500 ° of C) to distil and remove silicon atom, thus obtain epitaxially grown Graphene.
Low Pressure Chemical Vapor Deposition: Low Pressure Chemical Vapor Deposition refers at high temperature cracking carbon source (as hydrocarbon) and is deposited on solid substrate surface, and substrate is generally the transition metal such as Ni, Ru.
Graphene oxide reduction method: use the most extensive at present, also be a kind of method preparing Graphene being hopeful to take the lead in realizing heavy industrialization be most utilize graphene oxide for precursor, by hot deoxidizing or electronation, the oxy radical of surface of graphene oxide is removed.Although this method can not obtain perfect Graphene, the intrinsic performance of Graphene can be recovered to a great extent.Meanwhile, relative to other graphene preparation methods, the abundant raw material of graphene oxide reduction method, simply, the workability of the Graphene prepared is good, therefore receives much concern for equipment and operating process.
Graphene oxide reduction method comprises again thermal expansion reduction method, chemical reduction method.
Longitudinally cutting carbon tube method: be that to prepare Graphene be a kind of novel method preparing Graphene that development in recent years is got up to raw material with carbon nano-tube, from be that isotropic graphite alkene lamella prepared by raw material is different with graphite, what cutting carbon nanotubes obtained is anisotropic banded Graphene.
In the present invention, the preparation method of Graphene can adopt any one method known in the art to prepare, the method for preferred redox graphene in the present invention.
Graphene oxide is a kind of derivative of Graphene, comprises C, H, O tri-kinds of elements with the Graphene after strong oxidizer process.With graphite-phase seemingly, graphite oxide is similarly two-dimensional layered structure, and graphene oxide is by active force stacked in multi-layers such as the hydrogen bonds of interlayer together.But surface of graphene oxide contains a large amount of oxy radicals, makes it show stronger hydrophily and can be dispersed in water completely.
The preparation method of graphene oxide: current three kinds of commonly using prepare the method for graphite oxide, i.e. Brodie method, Staudenmaier method and Hummers method is all utilize the combination of oxidation reinforced dose of strong acid to process graphite.Strong protonic acid enters into graphite layers and forms graphite intercalation compound (graphiteintercalationcompounds), and strong oxidizer carries out being oxidized introducing oxygen-containing functional group hydrophilic in a large number to graphite and forms graphene oxide to graphenic surface and edge subsequently.Due to the hydrophily that oxy radical is stronger, graphene oxide can be peeled off completely and be dispersed in the middle of the aqueous solution.
In the present invention, described graphene oxide is the product of powdered graphite after chemical oxidation and stripping, and graphene oxide is single atomic layer, can expand to some tens of pm at any time on transverse dimension, therefore, its construct trans typical size of general chemistry and materials science.Graphene oxide can be considered a kind of flexible material of non-traditional kenel, has polymer, colloid, film, and amphiphilic characteristic.After oxidation processes, graphite oxide still keeps the stratiform structure of graphite, but on the Graphene monolithic of every one deck, introduce many oxygen base functional groups.Graphene oxide is generally oxidized through strong acid by graphite and obtains.Mainly contain the method that three kinds are prepared graphite oxide: Brodie method, Staudenmaier method and Hummers method.Wherein Hummers method preparation process ageing relatively better and also safer in preparation process, be one the most frequently used at present.Potassium permanganate in its employing concentrated sulphuric scid and powdered graphite are after oxidation reaction, obtain the brown graphite flake having derivative carboxylic acid group at edge and be mainly phenolic hydroxyl group and epoxide group in the plane, this graphene layers can be peeled off as graphene oxide through ultrasonic or high shearing vigorous stirring, and in water, form single-layer graphene oxide suspension that is stable, sundown.Because conjugate network is subject to serious functionalized, graphene oxide thin slice has the speciality of insulation.Can partial reduction be carried out through reduction treatment, obtain the graphene platelet of chemical modification.At present, prepare graphene oxide new method and emerged in an endless stream, be divided into top-down approach and the large class of Bottom-up approach two substantially.The former thinking splits crystalline flake graphite etc. to prepare graphene oxide, improves one's methods as representative with traditional three methods, also comprises method of fractionation (breaking) carbon nano-tube etc.The latter is the method for synthesizing by various carbon source, and concrete grammar is multifarious, of a great variety.
In the present invention, Graphene-polyolefin blends refers to and is undertaken blended by the Graphene prepared and poly-system, then blending extrusion in extruder.In Graphene-polyolefin blends, the content of Graphene accounts for 0.1-10wt%.
As a kind of mode of execution, in the present invention, mesosphere can also be graphene oxide and polyolefin blends.In described graphene oxide and polyolefinic blend, the content of described graphene oxide accounts for 0.1-8wt%.
As a kind of mode of execution, in Graphene-polyolefin mesosphere, Graphene is through Nomex modification.
Concrete preparation method: the Graphene 1, adding under 180 DEG C of vacuum dry 24 hours in the there-necked flask of 500ml, is about the silane coupler of 0.1-1wt% Graphene and the anhydrous dimethyl benzene of silane dosage 200 times.There-necked flask is furnished with paddle and condensation tube and is positioned in the oil bath of 110-120 DEG C and processes more than at least 4 hours.Then Graphene is filtered out, and dry 2 hours of the vacuum drying cabinet being placed in 120 DEG C; 2, by as follows for the further process of grafting of Graphene after silane-modified: the graphene dispersion after first that previous step is silane-modified is in 1-METHYLPYRROLIDONE; Then quantitative 3,5-diaminobenzoic acids, pyridine and triphenyl phosphite are joined in solution, react 3 hours under 100 DEG C of nitrogen atmospheres.Then reaction liquid is cooled to room temperature, cooled reaction liquid is poured in the methanol solvate of the lithium chloride containing methanol solvate mass ratio 0.1% and carry out precipitating, filter to isolate nano-graphene, use N respectively again, dinethylformamide and washed with methanol 3 times, to remove 3,5-unnecessary diaminobenzoic acid monomers.
As a kind of mode of execution, the weight ratio of described Nomex and Graphene is (10 ~ 100): 1, is preferably (10 ~ 50): 1, is more preferably (20 ~ 40): 1.
As a kind of mode of execution, the weight average molecular weight of described Nomex is 200000-6000000, is preferably 300000-1000000, is more preferably 300000-900000.
As a kind of mode of execution, described in the present invention, Graphene-polyolefin layer comprises boron nitride.
Six side's layered nitride boron (h-BN) belong to hexagonal system, and its B-N key is SP
2hydridization bonding.H-BN is more similar with cell parameter with the structure of Graphene, is therefore called as " white graphite alkene ".Hexagonal boron nitride belongs to hexagonal crystal system, its structure is similar to the stratiform structure of graphite, its layer of inside is alternately arranged by boron atom and nitrogen-atoms and forms the unlimited hexagonal gridding extended, and hexagonal boron nitride is perpendicular to C axle direction having quite high thermal conductivity [60W/ (mK)], lower thermal expansion coefficient [(0 ~ 2.6) × 10
– 4/ K] and very high tension stress intensity.
Hexagonal boron nitride preparation method: mechanical phonograph recorder separation, Low Pressure Chemical Vapor Deposition, solvent-thermal method, high temperature and high pressure method.
Mechanical phonograph recorder separation: the hexagonal boron nitride powder adhesive tape of particle diameter average out to 10 μm is attached in the silica substrate that thickness is 300nm, then by force boron nitride is separated into less fragment, finally obtain the two-dimentional boron nitride of only several atom thick.
Low Pressure Chemical Vapor Deposition: by adopting hot wall type reactor, the gaseous feed of boracic, nitrogen is imported in a vacuum reaction chamber via carrier gas, making gaseous feed generation chemical reaction finally generate hexagonal boron nitride is at high temperature heat stratiform ultrathin film, and wherein boron source material generally adopts BF
3, BCl
3, BBr
3, B
2h
6with B (OCH
3)
3deng boron-containing compound, nitrogenous source generally adopts ammonia or nitrogen.
Water (solvent) thermal synthesis method: by adopting water (or organic solvent) as the medium of reaction, and autoclave is heated, under high temperature, condition of high voltage, make usually to be difficult to molten or insoluble,practically material and occur to dissolve and react the new crystalline solid of generation.
Solvent stripping method: this method is the surface tension utilizing organic solvent stronger, destroys boron nitride powder Van der Waals force between layers by ultrasound condition and reaches the object peeling off hexagonal boron nitride.
Borax-urea (ammonium chloride) method: thermal response will be added after borax anhydrous and urea (ammonium chloride) Homogeneous phase mixing and obtain hexagonal boron nitride powder under ammonia flow effect.
Any one method that in the present invention, the preparation method of boron nitride adopts those skilled in the art known prepares.
In the present invention, in Graphene-polyolefin layer, adding of boron nitride by simple physical mixed, also can adopt the connection between chemical bond.
Such as: can be the simple mixing between Graphene, polyolefin, boron nitride three; Also can be carry out physical mixed with polyolefin after Graphene and boron nitride carry out compound; Also can be Graphene after Nomex modification, then carry out physical mixed with Graphene, boron nitride; Also can be boron nitride after Nomex modification, then carry out physical mixed with Graphene, boron nitride; Also can be after Graphene and boron nitride carry out compound, then through Nomex modification, then carry out physical mixed with polyolefin.In combinations thereof, described polyolefin can be any kind, and also can there is epoxy resin in described polyolefin.
The preparation process of Graphene/boron nitride compound: the boron nitride of different proportion and Graphene are mixed according to different proportion, is then dissolved in DMF solution, carries out ultrasonic and centrifugal, finally obtains the composite of Graphene/boron nitride.
The preparation process of Nomex modification boron nitride: the boron nitride 1, adding under 180 DEG C of vacuum dry 24 hours in the there-necked flask of 500ml, is about the silane coupler of 0.1-1wt% boron nitride and the anhydrous dimethyl benzene of silane dosage 200 times.There-necked flask is furnished with paddle and condensation tube and is positioned in the oil bath of 110-120 DEG C and processes more than at least 4 hours.Then boron nitride is filtered out, and dry 2 hours of the vacuum drying cabinet being placed in 120 DEG C; 2, by as follows for the further process of grafting of boron nitride after silane-modified: the boron nitride after first that previous step is silane-modified is distributed in 1-METHYLPYRROLIDONE; Then quantitative 3,5-diaminobenzoic acids, pyridine and triphenyl phosphite are joined in solution, react 3 hours under 100 DEG C of nitrogen atmospheres.Then reaction liquid is cooled to room temperature, cooled reaction liquid is poured in the methanol solvate of the lithium chloride containing methanol solvate mass ratio 0.1% and carry out precipitating, filter to isolate nm-class boron nitride, use N respectively again, dinethylformamide and washed with methanol 3 times, to remove 3,5-unnecessary diaminobenzoic acid monomers.
As a kind of mode of execution.The weight ratio of described boron nitride and Graphene is 1:(5 ~ 20), more preferably 1:(10 ~ 20).
Another aspect of the present invention provides the method preparing described high strength linepipe, and the present invention adopts the method for extruding and moulding to prepare.
Extrusion molding, extruding, extrusion molding are again in extruding and moulding of the present invention.Be the extrusion by screw rod or plunger, make the uniform plastics of plasticizing be forced through mouthful mould and become the continuous goods with constant cross-section.
Described extrusion process comprises reinforced, plasticizing, extruding and moulding, vacuum sizing, cooling, traction, cutting.
Concrete steps are:
S1: the preparation of Nomex graft modification Graphene: the Graphene 1, adding under 180 DEG C of vacuum dry 24 hours in the there-necked flask of 500ml, is about the silane coupler of 0.1-1wt% Graphene and the anhydrous dimethyl benzene of silane dosage 200 times.There-necked flask is furnished with paddle and condensation tube and is positioned in the oil bath of 110-120 DEG C and processes more than at least 4 hours.Then Graphene is filtered out, and dry 2 hours of the vacuum drying cabinet being placed in 120 DEG C; 2, by as follows for the further process of grafting of Graphene after silane-modified: the graphene dispersion after first that previous step is silane-modified is in 1-METHYLPYRROLIDONE; Then quantitative 3,5-diaminobenzoic acids, pyridine and triphenyl phosphite are joined in solution, react 3 hours under 100 DEG C of nitrogen atmospheres.Then reaction liquid is cooled to room temperature, cooled reaction liquid is poured in the methanol solvate of the lithium chloride containing methanol solvate mass ratio 0.1% and carry out precipitating, filter to isolate nano-graphene, use N respectively again, dinethylformamide and washed with methanol 3 times, to remove 3,5-unnecessary diaminobenzoic acid monomers.
S2: the preparation of modified graphene/polyolefin blend particle: by the Nomex graft modification Graphene described in S1, join in polyolefin powder, add additive again, utilize banbury to mix dispersion, then blend is joined extruding pelletization in double screw extruder and obtain modified graphene/polyolefin blend particle;
S3: the preparation of polyolefin pipe: extruder described in the present invention has three hoppers, polyolefin particles is placed on outer hopper, modified graphene described in described S2/polyolefin blend particle is placed on mesosphere hopper, described polyolefin particles is placed on internal layer hopper, then obtains three layers of compound polyolefin tubing through plasticizing co-extrusion.
As a kind of mode of execution, the ratio of described polyolefin interior layer and outer layer thickness sum and Graphene-polyolefin blends intermediate layer thickness is (2 ~ 70): 1, is preferably (10 ~ 70): 1, is more preferably (50-70): 1.
As a kind of mode of execution, tell polyolefinic outer layer and polyolefin interior layer Thickness Ratio be (1 ~ 5): (1 ~ 5), is preferably (1 ~ 3): (1 ~ 5), is more preferably 3:(1 ~ 5).
As a kind of mode of execution, Graphene-polyolefin blends described in the present invention also can at outer or internal layer.When described Graphene-polyolefin blends is at skin, when extruding, described Graphene-polyolefin blends layered material bucket outside, polyolefin particles is at internal layer hopper and mesosphere hopper, at the polyolefin that the polyolefin particles of internal layer hopper and mesosphere hopper can be the different trade mark, different types of polyolefin, is not specifically limited here, then jointly extrudes.
additive:
When not affecting the invention, according to circumstances additive can be selected.Typical additives has anti-impact modifier, antimicrobial agent, light stabilizer, antioxidant, tackifier, bulking agent, strengthening agent, stuffing, nanometer material.
Described anti-impact modifier is the mixing of a kind of in ethylene propylene diene rubber, styrene butadiene rubber, neoprene, natural rubber, styrene-butadiene-styrene, ethylene-vinyl acetate copolymer, acrylonitrile-butadiene-phenylethylene copolymer, haloflex or more than two kinds;
Described light stabilizer is the mixing of a kind of in benzophenone, benzoate, benzotriazole, salicylate, aminodithioformic acid nickel salt, thiobisphenol, phosphate monoester nickel, hindered amine, carbon black, titanium dioxide, zine oxide, iron oxide or more than two kinds;
Described antioxidant is the one or more kinds of mixing in phosphorous acid antioxidant, thioesters antioxidant, phenolic antioxidant;
Described nanometer material is the mixing of a kind of in active nano-calcium carbonate, silica, titanium dioxide, French chalk, mica, silica sand, sericite, potter's clay, silicate, limestone or more than two kinds;
Described tackifier are polyisobutene co-polymer, polystyrene resin;
Described bulking agent is polypropylene-caprolactone graft copolymer, polypropylene-styrene graft copolymer, maleic anhydride graft copolymer, large molecule silane coupler, large molecule aluminium titanium coupling agent, large molecule titanate coupling agent, polypropylene-methacrylic acid ester graft copolymer, polypropylene-acrylonitrile graft copolymer, polypropylene-methacrylic acid graft copolymer, 1-chloro-4-methyl-benzene graft copolymer, acrylic acid graft copolymer, ethylene-propylene graft copolymer, acrylic acid epoxy ester graft copolymer, maleic anhydride graft copolymer, the mixing of a kind of in ethylene-vinyl acetate copolymer or more than two kinds,
Described reinforcing material is the mixing of any one or more than two kinds in activity glass fiber, carbon fiber, aramid fibre, whisker nylon fiber, polyester fibre, boron fiber;
Described stuffing is the mixing of a kind of in calcium carbonate, silica, titanium dioxide, French chalk, mica, silica sand, sericite, potter's clay, silicate, limestone or more than two kinds.
Tubing of the present invention may be used for every field, such as chemical pipeline, water supply pipe, hot spring pipeline etc.
Present inventor finds unexpectedly, Nomex connects and can improve tubing at high temperature (95 DEG C) adding of modification branch Graphene, working life (38 years) under high pressure (1.6MPa), adding of Nomex be possible reason can improve polyolefinic orientation and amount of crystals, simultaneously the adding of Nomex and epoxy resin, further increase product at high temperature (95 DEG C), working life (52 years) under high pressure (2.0MPa), possible reason is induction force between Nomex and epoxy resin and dipole-dipole force, make to define large network structure, thus improve the working life of product.
Below by embodiment, the present invention is specifically described.What be necessary to herein means out is; following examples are only for the invention will be further described; limiting the scope of the invention can not be interpreted as; some nonessential improvement and adjustment that the professional and technical personnel in this field makes according to the content of the invention described above, still belong to protection scope of the present invention.
In addition, if do not have other to illustrate, raw materials used is all commercially available.
Embodiment 1: tubing is all made up of PE-RT I, and regardless of skin, middle level and internal layer, the trade mark of described PE-RT I is PE-RTDX800, and business men is Korea S SK.
Test result:
Embodiment 2: tubing is all by the blend of PE-RT I and Graphene, and regardless of skin, middle level and internal layer, the trade mark of described PE-RT I is PE-RTDX800, and business men is Korea S SK.The weight part ratio of Graphene and PE-RT I is 1:100.
Described manufacturing step is:
The preparation of S1: Graphene/PE-RT I blended particles: PE-RT I and Graphene are put into high-speed mixer, be warming up to 70-90 DEG C, mix and blend, then put into cold mixer and be cooled to room temperature, obtain PE-RT I and Graphene mixture, again mixture to be added in granulating extruder through plastifying, extrude, cool, pelletizing, obtain compound particles;
S2: the preparation of polyolefin pipe:: the pellet prepared by step S1 joins the internal layer of three-layer composite pipe material extruder, mesosphere, outer hopper respectively, obtains three-layer composite pipe material through plasticizing co-extrusion.
Test result:
Embodiment 3: outer: PE-RT I; Internal layer: PE-RT I; Mesosphere: Graphene and PE-RT I, the trade mark of described PE-RT I is PE-RTDX800, and business men is Korea S SK.
The preparation of S1: Graphene/PE-RT I blended particles: by Graphene, join in PE-RT I, then add additive, utilize banbury to mix dispersion, again mixture to be added in granulating extruder through plastifying, extrude, cool, pelletizing, obtain compound particles;
S2: the preparation of polyolefin pipe: the pellet prepared by step S1 joins the mesosphere hopper of three-layer composite pipe material extruder, inside and outside layered material bucket adds PE-RT I particle.Three-layer composite pipe material is obtained through plasticizing co-extrusion.
Test result:
The ratio of tubing thickness proportion: PE-RT I internal layer and outer layer thickness sum and Graphene-PE-RT I blend intermediate layer thickness is 40:1; In Graphene-PE-RT I mesosphere, the weight ratio of Graphene and PE-RT I is 1:100;
PE-RT I Thickness Ratio that is outer and PE-RT I internal layer is 1:2.
Embodiment 4: outer: PE-RT I; Internal layer: PE-RT I; Mesosphere: the blend of Graphene, Nomex and PE-RT I, the trade mark of described PE-RT I is PE-RTDX800, and business men is Korea S SK.
S1: the preparation of Graphene/Nomex/PE-RT I blended particles: Nomex, Graphene are joined in PE-RT I powder, add additive again, banbury is utilized to mix dispersion, again mixture to be added in granulating extruder through plastify, extrude, cool, pelletizing, obtain Graphene/Nomex/PE-RT I blended particles;
S2: the preparation of polyolefin pipe: the mesosphere hopper Graphene described in S1/Nomex/PE-RT I blended particles being joined three-layer composite pipe material extruder, inside and outside layered material bucket adds PE-RT I particle.Three-layer composite pipe material is obtained through plasticizing co-extrusion.
Test result:
The ratio of tubing thickness proportion: PE-RT I internal layer and outer layer thickness sum and Graphene-PE-RT I blend intermediate layer thickness is 60:1; In Graphene-PE-RT I mesosphere, the weight ratio of Graphene and PE-RT I is 1:50, and the weight ratio of Nomex and Graphene is 10:1;
PE-RT I Thickness Ratio that is outer and PE-RT I internal layer is 2:1.
Embodiment 5: outer: PE-RT I; Internal layer: PE-RT I; Mesosphere: the blend of Nomex/Graphene and PE-RT I, the trade mark of described PE-RT I is PE-RTDX800, and business men is Korea S SK.
Nomex/Graphene is Nomex graft modification Graphene.
S1: the preparation of Nomex graft modification Graphene: the Graphene 1, adding under 180 DEG C of vacuum dry 24 hours in the there-necked flask of 500ml, is about the silane coupler of 0.1-1wt% Graphene and the anhydrous dimethyl benzene of silane dosage 200 times.There-necked flask is furnished with paddle and condensation tube and is positioned in the oil bath of 110-120 DEG C and processes more than at least 4 hours.Then Graphene is filtered out, and dry 2 hours of the vacuum drying cabinet being placed in 120 DEG C; 2, by as follows for the further process of grafting of Graphene after silane-modified: the graphene dispersion after first that previous step is silane-modified is in 1-METHYLPYRROLIDONE; Then quantitative 3,5-diaminobenzoic acids, pyridine and triphenyl phosphite are joined in solution, react 3 hours under 100 DEG C of nitrogen atmospheres.Then reaction liquid is cooled to room temperature, cooled reaction liquid is poured in the methanol solvate of the lithium chloride containing methanol solvate mass ratio 0.1% and carry out precipitating, filter to isolate nano-graphene, use N respectively again, dinethylformamide and washed with methanol 3 times, to remove 3,5-unnecessary diaminobenzoic acid monomers.
The preparation of S2: modified graphene/PE-RT I blended particles: by the Nomex graft modification Graphene described in S1, join in PE-RT I powder, add additive again, utilize banbury to mix dispersion, then blend is joined extruding pelletization in granulating extruder and obtain the blended master batch of modified graphene/PE-RT I;
S3: the preparation of polyolefin pipe: mesosphere hopper modified graphene/PE-RT I blended particles described in S2 being joined three-layer composite pipe material extruder, inside and outside layered material bucket adds PE-RT I particle.Three-layer composite pipe material is obtained through plasticizing co-extrusion.
Test result:
The ratio of tubing thickness proportion: PE-RT I internal layer and outer layer thickness sum and Graphene-PE-RT I blend intermediate layer thickness is 60:1; In Graphene-PE-RT I mesosphere, the weight ratio of Graphene and PE-RT I is 1:50, and the weight ratio of Nomex and Graphene is 10:1;
PE-RT I Thickness Ratio that is outer and PE-RT I internal layer is 2:1.
Embodiment 6: outer: PE-RT I; Internal layer: PE-RT I; Mesosphere: the blend of Nomex/Graphene and PE-RT I, the trade mark of described PE-RT I is PE-RTDX800, and business men is Korea S SK.
Nomex/Graphene is Nomex graft modification Graphene.
S1: the preparation of Nomex graft modification Graphene: the Graphene 1, adding under 180 DEG C of vacuum dry 24 hours in the there-necked flask of 500ml, is about the silane coupler of 0.1-1wt% Graphene and the anhydrous dimethyl benzene of silane dosage 200 times.There-necked flask is furnished with paddle and condensation tube and is positioned in the oil bath of 110-120 DEG C and processes more than at least 4 hours.Then Graphene is filtered out, and dry 2 hours of the vacuum drying cabinet being placed in 120 DEG C; 2, by as follows for the further process of grafting of Graphene after silane-modified: the graphene dispersion after first that previous step is silane-modified is in 1-METHYLPYRROLIDONE; Then quantitative 3,5-diaminobenzoic acids, pyridine and triphenyl phosphite are joined in solution, react 3 hours under 100 DEG C of nitrogen atmospheres.Then reaction liquid is cooled to room temperature, cooled reaction liquid is poured in the methanol solvate of the lithium chloride containing methanol solvate mass ratio 0.1% and carry out precipitating, filter to isolate nano-graphene, use N respectively again, dinethylformamide and washed with methanol 3 times, to remove 3,5-unnecessary diaminobenzoic acid monomers.
The preparation of S2: modified graphene/PE-RT I blended particles: by the Nomex graft modification Graphene described in S1, join in PE-RT I powder, add additive again, utilize banbury to mix dispersion, then blend is joined extruding pelletization in granulating extruder and obtain modified graphene/PE-RT I blended particles;
S3: the preparation of polyolefin pipe: mesosphere hopper modified graphene/PE-RT I blended particles described in S2 being joined three-layer composite pipe material extruder, inside and outside layered material bucket adds PE-RT I particle.Three-layer composite pipe material is obtained through plasticizing co-extrusion.
Test result:
The ratio of tubing thickness proportion: PE-RT I internal layer and outer layer thickness sum and Graphene-PE-RT I blend intermediate layer thickness is 60:1; In Graphene-PE-RT I mesosphere, the weight ratio of Graphene and PE-RT I is 1:50, and the weight ratio of Nomex and Graphene is 150:1;
PE-RT I Thickness Ratio that is outer and PE-RT I internal layer is 2:1.
Embodiment 7: outer: PE-RT I; Internal layer: PE-RT I; Mesosphere: the blend of Graphene, boron nitride and PE-RT I, the trade mark of described PE-RT I is PE-RTDX800, and business men is Korea S SK.
S1: the preparation of Graphene/boron nitride/PE-RT I blended particles: Graphene, boron nitride are joined in PE-RT I powder, add additive again, utilize banbury to mix dispersion, then blend is joined extruding pelletization in granulating extruder and obtain Graphene/boron nitride/PE-RT I blended particles;
S2: the preparation of polyolefin pipe: the mesosphere hopper Graphene described in S1/boron nitride/PE-RT I blended particles being joined three-layer composite pipe material extruder, inside and outside layered material bucket adds PE-RT I particle.Three-layer composite pipe material is obtained through plasticizing co-extrusion.
Test result:
The ratio of tubing thickness proportion: PE-RT I internal layer and outer layer thickness sum and Graphene-PE-RT I blend intermediate layer thickness is 60:1; In Graphene-PE-RT I mesosphere, the weight ratio of Graphene and PE-RT I is 1:75, and the weight ratio of boron nitride and Graphene is 1:10;
PE-RT I Thickness Ratio that is outer and PE-RT I internal layer is 2:1.
Embodiment 8: outer: PE-RT I; Internal layer: PE-RT I; Mesosphere: the blend of Graphene, boron nitride and PE-RT I, the trade mark of described PE-RT I is PE-RTDX800, and business men is Korea S SK.
S1: the preparation of Graphene/boron nitride/PE-RT I blended particles: Graphene, boron nitride are joined in PE-RT I powder, add additive again, utilize banbury to mix dispersion, then blend is joined extruding pelletization in granulating extruder and obtain Graphene/boron nitride/PE-RT I blended particles;
S2: the preparation of polyolefin pipe: the mesosphere hopper Graphene described in S1/boron nitride/PE-RT I blended particles being joined three-layer composite pipe material extruder, inside and outside layered material bucket adds PE-RT I particle.Three-layer composite pipe material is obtained through plasticizing co-extrusion.
Test result:
The ratio of tubing thickness proportion: PE-RT I internal layer and outer layer thickness sum and Graphene-PE-RT I blend intermediate layer thickness is 45:1; In Graphene-PE-RT I mesosphere, the weight ratio of Graphene and PE-RT I is 1:65, and the weight ratio of boron nitride and Graphene is 1:15;
PE-RT I Thickness Ratio that is outer and PE-RT I internal layer is 3:1.
Embodiment 9: be with the difference of embodiment 8, and described mesosphere is the blend of Nomex/Graphene, boron nitride and PE-RT I.
Test result:
The ratio of tubing thickness proportion: PE-RT I internal layer and outer layer thickness sum and Graphene-PE-RT I blend intermediate layer thickness is 65:1; In Graphene-PE-RT I mesosphere, the weight ratio of Graphene and PE-RT I is 1:100, and the weight ratio of Nomex and Graphene is 35:1; The weight ratio of boron nitride and Graphene is 1:20;
PE-RT I Thickness Ratio that is outer and PE-RT I internal layer is 4:1.
Embodiment 10: be with the difference of embodiment 9,
The ratio of tubing thickness proportion: PE-RT I internal layer and outer layer thickness sum and Graphene-PE-RT I blend intermediate layer thickness is 70:1; In Graphene-PE-RT I mesosphere, the weight ratio of Graphene and PE-RT I is 1:100, and the weight ratio of Nomex and Graphene is 45:1; The weight ratio of boron nitride and Graphene is 1:18;
PE-RT I Thickness Ratio that is outer and PE-RT I internal layer is 1:1.
Test result:
Embodiment 11: be with the difference of embodiment 9, and described skin and internal layer are the blend of PE-RT I and epoxy resin.
Test result:
The ratio of tubing thickness proportion: PE-RT I internal layer and outer layer thickness sum and Graphene-PE-RT I blend intermediate layer thickness is 55:1; The weight ratio of epoxy resin and PE-RT I is 1:10; The epoxide number of described epoxy resin is 0.48mol/100g.
PE-RT I Thickness Ratio that is outer and PE-RT I internal layer is 1:1.
Embodiment 12: be with the difference of embodiment 9, and through overstretching process after described tube extrusion, and draw ratio is 3 times.
Test result:
Embodiment 13: be with the difference of embodiment 9, and described PE-RT I master batch is before extrusion through plasma treatment.
Test result:
Embodiment 14: embodiment 1: tubing is all made up of PE-RT II, and regardless of skin, middle level and internal layer, the trade mark of described PE-RT II is DOWLEX2388, and business men is Tao Shi.
Test result:
Embodiment 15: be with the difference of embodiment 11, and described skin and internal layer are the blend of PE-RT II and epoxy resin.
Test result:
Above data can be found out, compared with not using the product of Graphene, boron nitride, Nomex, material prepared by the present invention is possessing compared with high ambient temperature, oxygen barrier and while bearing high pressure, also there is longer working life, because herein is provided Advantageous Effects of the present invention, polyolefin pipe of the present invention can in temperature at 95 DEG C, and pressure, under the condition being greater than 1.6MPa, reaches more than 50 years working life.
Aforesaid example is only illustrative, for explaining some features of feature of the present disclosure.Appended claim is intended to the scope wide as far as possible that requirement it is contemplated that, and the embodiment presented herein is only the explanation of the mode of execution of the selection of combination according to all possible embodiment.Therefore, the purpose of claimant is the selectional restriction that appended claim is not illustrated the example of feature of the present invention.And progress in science and technology is not replaced to be formed due to the inaccurate reason of language performance by the possible equivalent considered at present or son, and these changes also should be interpreted as being covered by appended claim in the conceived case.
Claims (10)
1. Graphene increased thermal conductivity compound polyolefin tubing, comprises polyolefinic outer layer, polyolefin interior layer, the mesosphere of Graphene-polyolefin blends.
2. tubing described in claim 1, described polyolefin is selected from least one in the group of the following composition: the homopolymer in the group of homopolymerisation polyethylene and homo-polypropylene composition; The random copolymer of one or more comonomer in the group selecting free ethylene, propylene, butylene, hexene and octene to form.
3. tubing described in claim 1, described polyolefin selects the copolymer of a kind of and ethylene copolymer in propylene, hexene and octene.
4. tubing described in claim 1, the ratio of described polyolefin interior layer and outer layer thickness sum and Graphene-polyolefin blends intermediate layer thickness is (2 ~ 70): 1.
5. tubing described in claim 1, the Thickness Ratio of polyolefinic outer layer and polyolefin interior layer is (1 ~ 5): (1 ~ 5).
6. tubing described in claim 1, described Graphene is Nomex modified graphene, and the weight ratio of Nomex and Graphene is (10 ~ 100): 1.
7. tubing described in claim 1, described Graphene-polyolefin layer comprises boron nitride, and the weight ratio of described boron nitride and Graphene is 1:(5 ~ 20).
8. tubing described in claim 1, described Graphene-polyolefin layer comprises boron nitride, and the weight ratio of described boron nitride and Graphene is 1:(10 ~ 20).
9. tubing described in claim 1, the stretched orientation process of described tubing, and draw ratio is 3 ~ 8.
10. tubing described in claim 1, the stretched orientation process of described tubing, and draw ratio is 3 ~ 5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610148355.4A CN105570560B (en) | 2016-03-16 | 2016-03-16 | Graphene increased thermal conductivity compound polyolefin tubing |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610148355.4A CN105570560B (en) | 2016-03-16 | 2016-03-16 | Graphene increased thermal conductivity compound polyolefin tubing |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105570560A true CN105570560A (en) | 2016-05-11 |
| CN105570560B CN105570560B (en) | 2019-03-19 |
Family
ID=55881017
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610148355.4A Active CN105570560B (en) | 2016-03-16 | 2016-03-16 | Graphene increased thermal conductivity compound polyolefin tubing |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105570560B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN107906270A (en) * | 2017-10-24 | 2018-04-13 | 佛山科学技术学院 | A kind of mica powder, graphene composite and flexible pipe |
| 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 |
| 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 |
| CN115027102A (en) * | 2022-05-12 | 2022-09-09 | 临海伟星新型建材有限公司 | High-strength medium conveying pipeline with temperature and preparation method thereof |
| CN115232360A (en) * | 2022-08-17 | 2022-10-25 | 山东玉皇新能源科技有限公司 | Graphene composite reinforcing agent and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
2016
- 2016-03-16 CN CN201610148355.4A patent/CN105570560B/en active Active
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 |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN107906270A (en) * | 2017-10-24 | 2018-04-13 | 佛山科学技术学院 | A kind of mica powder, graphene composite and flexible pipe |
| 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 |
| CN115027102A (en) * | 2022-05-12 | 2022-09-09 | 临海伟星新型建材有限公司 | High-strength medium conveying pipeline with temperature and preparation method thereof |
| 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 |
| CN115232360A (en) * | 2022-08-17 | 2022-10-25 | 山东玉皇新能源科技有限公司 | Graphene composite reinforcing agent 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105570560B (en) | 2019-03-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105570560A (en) | Graphene-enhanced thermal conductance composite polyolefin pipe | |
| EP4063465A1 (en) | Flexible multi-level phase change material having cross-linked network structure and preparation method therefor | |
| US8563109B2 (en) | Pressureless polymer pipe, a compositon therefore, and a process for preparing it | |
| CN102050993B (en) | Flame-retardant PP/nylon corrugated tube composite material and preparation method thereof | |
| CN102286207B (en) | A kind of thermoplastic polymer based thermal conductive composite and preparation method thereof | |
| KR102042966B1 (en) | Fiber Reinforced Polypropylene Composite | |
| CN102884093A (en) | Propylene homopolymer having high melt strength and preparation method thereof | |
| EA022216B1 (en) | Heterophasic propylene with excellent creep performance | |
| CN102627796B (en) | Polyethylene composition for manufacturing lithium battery diaphragm | |
| UA125156C2 (en) | Fiber reinforced polypropylene composition | |
| CN108373559A (en) | A kind of graphene/carbon nano-tube collaboration enhancing polyethylene pipe and preparation method thereof | |
| US9228068B2 (en) | Increased output of a film extrusion process | |
| JP2019515970A (en) | Modified polyethylene resin and method for producing the same | |
| CN107200902A (en) | A kind of graft modification IXPE heat-resisting pipes and preparation method thereof | |
| CN107189318A (en) | A kind of power cable sheath special material for pipeline and preparation method thereof | |
| CN101987892B (en) | Heat-shrinkable tubing and material thereof | |
| US11177051B2 (en) | Insulation layer for cables | |
| CN115583081A (en) | Enhanced polypropylene double-wall corrugated pipe and processing technology thereof | |
| CN103360716B (en) | Cold water tubing block polypropylene, its composition and compound auxiliary system | |
| CN105605339A (en) | High-strength antibacterial oxygen-resistant PP-RCT composite pipe | |
| CN116120666A (en) | High-flame-retardance modified polypropylene composite material and preparation method and application thereof | |
| CN107325411B (en) | Flame-retardant antistatic random copolymerization polypropylene composition and pipe | |
| CN105801991A (en) | Halogen-free heat shrinkable casing pipe and preparation method thereof | |
| CN106009157B (en) | A kind of high-performance polyethylene based composites and its preparation method and application | |
| KR20230174224A (en) | biaxially oriented film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20190716 Address after: Building 61 Jian'an Road, Fengjing Town, Jinshan District, Shanghai, 201501 Patentee after: Shanghai Zhongsu Pipe Industry Co., Ltd. Address before: 100000 Beijing city Chaoyang District Shuangqiao Road No. 60 hospital HEIZHUANGHU shuangxu Park Residency Gurgaon No. 120 1 floor East households Patentee before: Liu Zhiguang |
|
| TR01 | Transfer of patent right |