CN103524859A - Graphite-containing heat-conducting polyethylene master batch and preparation method and composition thereof - Google Patents
Graphite-containing heat-conducting polyethylene master batch and preparation method and composition thereof Download PDFInfo
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Abstract
The invention relates to a graphite-containing heat-conducting polyethylene master batch and a preparation method and a composition thereof, belongs to the field of processing and application of high-molecular materials, and mainly relates to the graphite-containing heat-conducting polyethylene master batch and the preparation method and the composition thereof. The graphite-containing heat-conducting polyethylene master batch is characterized by comprising the following components (in parts by weight): 100 parts of polyethylene powder, 60-300 parts of graphite, 0.3-15 parts of coupling agent, 0.3-300 parts of diluting agent and 0.01-5 parts of antioxidant, wherein the weight ratio of the coupling agent to the diluting agent is 1:(0.5-50). The prepared heat-conducting polyethylene composition ensures the excellent heat-conducting property, ensures the excellent mechanical property and saves the late-stage maintenance cost when being adopted to prepare a polyethylene pipe used for a ground source heat pump, and heat-conducting polyethylene radiating plate and sheet materials.
Description
Technical field
A kind of graphitiferous heat conduction polyethylene masterbatch and preparation method thereof and composition, the processing and the Application Areas that belong to macromolecular material, relate generally to a kind of graphitiferous heat conduction polyethylene masterbatch and preparation method thereof, and the heat conduction polyethylene composition that adopts this graphitiferous heat conduction polyethylene masterbatch to prepare.
Background technology
Earth source heat pump is a kind of energy-efficient air-conditioning system that not only can heat but also can freeze of utilizing earth shallow-layer resource (comprising soil, underground water, surface water or municipal middle water).It utilizes and is laid on the heat exchange pipeline in soil, surface water etc., realizes the heat exchange of air-conditioned room and soil, surface water etc., to reach the effect of building air conditioning.Ground source heat pump central air-conditioning system is state-of-the-art central air conditioner system in the world at present, can save a large amount of working costs and maintenance cost.Earth-source hot-pump system when work, the annual substantially constant of the temperature difference that heat transmits, and be far longer than the heat transfer temperature difference of air source heat pump.For improving earth-source hot-pump system heat exchange efficiency, should adopt the heat exchange pipeline of good heat conductivity, adopt high heat conduction heat exchange pipeline can reduce heat transfer tube quantity when reaching same heat transfer effect, while pipeline needs are withstand voltage, corrosion-resistant, have good long-term behaviour.For this reason, have in recent years many software engineering researchers invent height source heat pump system pipeline with heat conduction.Patent CN1102199321A proposes a kind of formula of high heat conduction polyethylene pipe, the polyethylene using in its formula, graphite, lubricant is different from the present invention, its content of graphite is different from content of graphite in heat conduction polyethylene composition of the present invention, its preparation method is different from the present invention, the high heat conduction polyethylene earth-source hot-pump system pipeline that patent CN1102199321A produces, heat-resistance coefficient can reach 0.65(W/m.K), the used for geothermal heat pump polyvinyl piping materials that the present invention produces and the heat conductivility of heat conduction polyethylene board or sheet material and mechanical property are far above patent CN1102199321A, excellent combination property, patent CN102128316A discloses a kind of heat-resisting polyethylene plastic pipe with high heat conductivity, by PE-RT and the moulding of thermally conductive material blending extrusion, it can be single-component individual layer, also can be the high thermal-conductive polyethylene pipe of multi-component and multi-layer, this patent is with patent CN1102199321A, thermally conductive material (graphite) and treatment process are not specifically studied and limited, and the kind of thermally conductive material and treatment process thereof are one of key factors affecting matrix material heat conductivility and composition mechanical property thereof, and to polyethylene, it is not further studied and requirement.Tubing, sheet material, sheet material, after provided underground, need expend a large amount of manpower and materials as broken down and excavate replacing, also can cause certain pollution and destruction to environment simultaneously.Especially thermal-conductive polyethylene pipe, as cold and hot water conveying pressure pipeline, requires highly to tubing over-all properties, tubing, when having higher heat conductivility, should have good mechanical property and voltage endurance capability.
Summary of the invention:
The technical problem to be solved in the present invention is: overcome the deficiencies in the prior art, a kind of graphitiferous heat conduction polyethylene masterbatch and preparation method thereof and composition are provided, the heat conduction polyethylene composition that adopts this graphitiferous heat conduction polyethylene masterbatch to prepare, be applicable to produce used for geothermal heat pump polyvinyl piping materials, high withstand voltage, heat conduction polyethylene board or sheet material, for earth-source hot-pump system and various interchanger.
The technical solution adopted for the present invention to solve the technical problems is: this kind of graphitiferous heat conduction polyethylene masterbatch, it is characterized in that, by 100 parts, (weight part) polyethylene powder, 60～300 parts, graphite, 0.3～15 part of coupling agent, 0.3～300 part of thinner, 0.01～5 part of composition of oxidation inhibitor, described coupling agent and thinner are by weight 1:(0.5～50) add.
Preferably, a kind of graphitiferous heat conduction polyethylene masterbatch, is characterized in that, by 100 parts, (weight part) polyethylene powder, 60～200 parts, graphite, 0.5～8 part of coupling agent, 0.5～160 part of thinner, 0.1～3 part of composition of oxidation inhibitor, described coupling agent and thinner are by weight 1:(1～20) add.
It is 50～400 orders that described graphite is selected particle diameter, and the expansible black lead of expansion multiplying power 100～400ml/g or particle diameter are 400～1200 object oildags.
It is 0.915～0.950g/cm that described polyethylene powder or pellet are selected density
3, melt mass flow rate is the ethene-alpha-olefin copolymer of (2.16Kg counterweight) 1～30g/10min.
Described coupling agent is selected a kind of in isopropyl tri (dioctylpyrophosphato)titanate, two (dioctylphosphato) metatitanic acid second diester, diisostearoyl ethylene titanate or γ-aminopropyl triethoxysilane.
Described thinner is selected a kind of of whiteruss, acetone or alcohol.
Described oxidation inhibitor is selected hindered phenol, hindered amine, phosphite or sulphur ester antioxidant.
Described oxidation inhibitor is selected four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, 2,6-toluene di-tert-butyl phenol, one or more compositions in tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester or Tyox B.
The preparation method of graphitiferous heat conduction polyethylene masterbatch of the present invention, is characterized in that, concrete technology step is: coupling agent and thinner are mixed in proportion, add in homogenizer together with graphite, be warming up to 40～80 ℃, stir 2～10min; Polyethylene powder and oxidation inhibitor are added in homogenizer, discharging after 5～15min high-speed mixing, adds the raw material being mixed in forcing machine again, and extruding pelletization at 160～250 ℃, obtains graphitiferous heat conduction polyethylene masterbatch.
A polyethylene composition, is characterized in that, each component proportion (weight part) is: 100 parts of polyethylene, graphitiferous heat conduction polyethylene masterbatch is 60～200 parts described in claim 1～8 any one, 0～20 part of processing aid.
Described processing aid is selected from fluoroelastomer or polyethylene wax.
The tensile strength of described heat conduction polyethylene composition > 15MPa, modulus in flexure > 1000MPa, oxidation induction period (OIT, 200 ℃) > 40min, thermal conductivity > 0.75W/m.k.
Production used for geothermal heat pump polyvinyl piping materials prepared by described heat conduction polyethylene composition.
Heat conduction polyethylene board or sheet material prepared by described heat conduction polyethylene composition.
Owing to requiring PE pressure pipe material to there is good long-term hydrostatic strength, its prediction hydrostatic strength confidence lower limit σ
lPLanswer>=6.3MPa of numerical value, preferably σ
lPL>=8.0MPa; The preferred heat-proof polythene of polyethylene of the present invention (PE-RT), has selected in embodiment and has met the PE-RT type Ⅱ resin that ISO 22391 requires.PE-RT, except having excellent voltage endurance capability, also with higher resistance toheat, is for the preferred base resin of earth source heat pump heat exchange tubing.
Traditional highly heat-conductive material is mainly metallic substance (as copper, aluminium), and the density of these materials is larger, and the coefficient of expansion is high, and thermal conductivity is not high enough.The thermal conductivity of three kinds of argents that wherein thermal conductivity is higher, copper, aluminium is respectively: 430W/m.k, 400W/m.k, 238W/m.k, reach 2200W/m.k and graphite has high thermal conductivity (graphite single facet is to thermal conductivity).Graphite has good mechanical property, and has advantages of that density is low, thermal expansivity is little.Contriver is by the discovery of concentrating on studies: graphite has more excellent heat conductivility with the high heat conduction polyethylene masterbatch that polyethylene blend makes after coupling agent treatment, the heat conduction polyethylene composition that preparation has practical value, and then the basis of preparing thermal-conductive polyethylene pipe, sheet material, sheet material.
Compared with prior art, graphitiferous heat conduction polyethylene masterbatch of the present invention and preparation method thereof with the beneficial effect that composition has is: graphitiferous heat conduction polyethylene masterbatch of the present invention has excellent heat conductivility, its thermal conductivity reaches 1.027～1.151W/m.k, when guaranteeing that tubing that place produces has good heat conductivility, can possess good mechanical property: the present invention adopts coupling agent to carry out pre-treatment to graphite in preparation process, by pretreated graphite prior to polyethylene powder and thinner, oxidation inhibitor carries out blend, make graphitiferous heat conduction polyethylene masterbatch of the present invention, again by graphitiferous heat conduction polyethylene masterbatch of the present invention and polyethylene, processing aid blend obtains heat conduction polyethylene composition of the present invention.Heat conduction polyethylene composition of the present invention has excellent mechanics, thermo oxidative aging and heat conductivility, tensile strength 15.6～19.8MPa, modulus in flexure 1010～1520MPa, oxidation induction period (OIT, 200 ℃) 42～68min, thermal conductivity 0.762～0.957W/m.k.Solved the defect that in prior art, heat conduction polyethylene composition resistance toheat is low, heat conductivility is poor.In large-scale commercial production, the situation that graphite, oxidation inhibitor are prone to skewness in composition affects pipe performance.Preparation method of the present invention, carries out to graphite the heat conductivility that pre-treatment has promoted graphite by coupling agent; By tune, convert graphitiferous heat conduction polyethylene masterbatch to heat conduction polyethylene composition, improved the degree of uniformity that graphite and oxidation inhibitor distribute in heat conduction polyethylene composition, make the mechanical property of heat conduction polyethylene composition simultaneously, with respect to graphitiferous heat conduction polyethylene masterbatch, obtained obvious lifting, in large-scale commercial production, solved each component skewness of composition, stir difficulty and the too high problem of energy consumption.
Graphitiferous heat conduction polyethylene masterbatch of the present invention and heat conduction polyethylene composition, be suitable for producing used for geothermal heat pump polyvinyl piping materials, also can be used for the fields such as heat conduction polyethylene board or sheet material.
When for the production of used for geothermal heat pump polyvinyl piping materials: the MFR(5kg of its heat conduction polyethylene composition) 0.2～3g/10min, preferably 0.4～2.5g/10min; Heat conduction polyethylene composition of the present invention can direct production used for geothermal heat pump polyvinyl piping materials and pipe fitting, also can produce as composite bed heat conduction tubing, that is, tubing internal layer adopts heat conduction polyethylene composition of the present invention to make, and skin is ultra-thin ultrahigh molecular weight polyethylene tubing.Ultrahigh molecular weight polyethylene tubing excellent in abrasion resistance plays the effect of effective protection internal layer heat pipe in construction process, when guaranteeing good heat conductivility, has improved mechanical property and the resistance to hydrostatic ability of composite pipe.When direct production used for geothermal heat pump polyvinyl piping materials and pipe fitting: the oxidation induction period of tubing (OIT, 200 ℃) > 40min, the hydrostatic test of tubing, press GB/T6111 test, under following test conditions tubing non-leakage, do not break: 20 ℃, ring stress 12.4MPa, is greater than 200h; 80 ℃, ring stress 5.5MPa, is greater than 500h; 80 ℃, ring stress 5.0MPa, is greater than 1000h; While becoming composite bed heat conduction tubing with ultrahigh molecular weight polyethylene: hydrostatic test, press GB/T6111 test, under corresponding test conditions tubing non-leakage, do not break.Resisting environmental stress and cracking test: 20 ℃, during ring stress 12.4MPa, be greater than 300h; 80 ℃, ring stress 5.5MPa, is greater than 600h; 80 ℃, ring stress 5.0MPa, is greater than 1500h.
When dispel the heat for the production of heat conduction polyethylene sheet material or sheet material can be used as dispelling the heat sheet material or sheet material: the MFR(5kg of its heat conduction polyethylene composition) 0.3～15g/10min, preferred 0.5～12g/10min, oxidation induction period (OIT, 200 ℃) > 30min, modulus in flexure > 1000MPa, resisting environmental stress and cracking > 1000h.Tubing, after provided underground, need expend a large amount of manpower and materials as broken down and excavate replacing.In sum, the heat conduction polyethylene composition that adopts graphitiferous heat conduction polyethylene masterbatch of the present invention to make, when preparing used for geothermal heat pump polyvinyl piping materials, heat conduction polyethylene heat radiation sheet material or sheet material, both tubing, sheet material, the good heat conductivility of sheet material had been guaranteed, guarantee again the mechanical property that it is excellent, saved the cost of later period maintenance simultaneously.
Embodiment
Embodiment 1～15 is specific embodiments of the invention.Wherein embodiment 5, embodiment 9 are most preferred embodiment of the present invention.
Embodiment 1
The component of the graphitiferous heat conduction polyethylene masterbatch of embodiment 1 is pressed following parts by weight:
Polyethylene powder: 100 parts of ethene and butene-1 copolymers, density 0.920g/cm
3, MFR(2.16Kg counterweight) and 2g/10min; Graphite: 150 parts of expansible black leads, 325 orders; Coupling agent: 2.0 parts of γ-aminopropyl triethoxysilanes; Thinner: 2.0 parts of whiterusss; Oxidation inhibitor: 0.8 part of four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, and 0.8 part of three ［ 2.4-di-tert-butyl-phenyl ］ phosphorous acid ester.
The component of embodiment 1 heat conduction polyethylene composition is pressed following parts by weight:
100 parts of ethene and butene-1 copolymers, PE80 level (σ
lPL=8.0MPa), density 0.943g/cm
3, MFR(2.16Kg counterweight) and 0.12g/10min; 100 parts of the graphitiferous heat conduction polyethylene masterbatch of embodiment 1; Processing aid: 0.5 part of Tyox B, and 0.5 part of tetramethylolmethane diphosphite two (2,4-di-tert-butyl phenyl) ester.
The preparation method of embodiment 1, according to the following steps:
1) masterbatch preparation technology: graphite coupling agent treatment: coupling agent is joined in thinner and mixed in proportion, join together with graphite in homogenizer, process 8min in homogenizer; Again the polyethylene powder of powdery, oxidation inhibitor are added in the homogenizer of just processing graphite in proportion, after 10min high-speed mixing, discharging obtains mixed ingredients again, mixed ingredients is added to extruding pelletization in forcing machine, and temperature range is 160～250 ℃, obtains graphitiferous heat conduction polyethylene masterbatch;
2) composition preparation technology: polyethylene, graphitiferous heat conduction polyethylene masterbatch, processing aid are added in homogenizer in proportion, the raw material that discharging obtains being mixed after 10min high-speed mixing, the raw material being mixed is added to extruding pelletization in forcing machine, and temperature range is 160～250 ℃.
Embodiment 2
The component of embodiment 2 heat conduction polyethylene compositions is pressed following parts by weight:
Polyethylene: 100 parts of ethene and 1-hexene copolymers, PE100 level (σ
lPL=10.0MPa),, density 0.945g/cm
3, MFR(2.16Kg counterweight) and 0.10g/10min; 200 parts of the graphitiferous heat conduction polyethylene masterbatch of embodiment 1; Processing aid: 1.5 parts of Tyox Bs, and 1.0 parts of tetramethylolmethane diphosphite two (2,4-di-tert-butyl phenyl) esters.
The masterbatch composition of embodiment 2, preparation technology and composition preparation technology are with embodiment 1.
Embodiment 3:
The component of embodiment 3 heat conduction polyethylene compositions is pressed following parts by weight:
Polyethylene: 100 parts of ethene and 1-hexene copolymers, PE100 level (σ
lPL=10.0MPa), density 0.945g/cm
3, MFR(2.16Kg counterweight) and 0.08g/10min; 80 parts of the graphitiferous heat conduction polyethylene masterbatch of embodiment 1.
The masterbatch composition of embodiment 3, preparation technology and composition preparation technology are with embodiment 1.
Embodiment 4:
The component of embodiment 4 heat conduction polyethylene compositions is pressed following parts by weight:
Polyethylene: 100 parts of ethene and 1-hexene copolymers, PE100 level (σ
lPL=10.0MPa), density 0.945g/cm
3, MFR(2.16Kg counterweight) and 0.08g/10min; 60 parts of the graphitiferous heat conduction polyethylene masterbatch of embodiment 1.
The masterbatch composition of embodiment 4, preparation technology and composition preparation technology are with embodiment 1.
Embodiment 5
The component of the graphitiferous heat conduction polyethylene masterbatch of embodiment 5 is pressed following parts by weight:
100 parts, polyethylene powder, density 0.945g/cm
3, MFR(2.16Kg counterweight) and 32g/10min; Expansible black lead: 150 parts, 200 orders; Coupling agent: 2.5 parts of sec.-propyl three (dioctylphyrophosphoric acid acyloxy) titanic acid ester; Thinner: 2.5 parts of ethanol; Oxidation inhibitor: 1.5 parts of Tyox Bs, and 1.0 parts of tetramethylolmethane diphosphite two (2,4-di-tert-butyl phenyl) esters.
The component of embodiment 5 heat conduction polyethylene compositions is pressed following parts by weight:
100 parts of polyethylene, PE100 level, ethene and butene-1 copolymer, density 0.947g/cm
3, MFR(2.16Kg counterweight) and 0.15g/10min; 150 parts of the graphitiferous heat conduction polyethylene masterbatch of embodiment 5; Processing aid: 1.5 parts of Tyox Bs, and 1.0 parts of tetramethylolmethane diphosphite two (2,4-di-tert-butyl phenyl) esters.
The preparation method of embodiment 5, according to the following steps:
1) masterbatch preparation technology: graphite coupling agent treatment: coupling agent is joined in thinner and mixed in proportion, join in homogenizer together with graphite, in homogenizer, process, homogenizer is warming up to 50 ℃, in homogenizer, process 10min; Again the polyethylene powder of powdery, oxidation inhibitor are added in the homogenizer of processing graphite in proportion, discharging after 15min high-speed mixing, the raw material being mixed is added to extruding pelletization in forcing machine, and temperature range is 160～250 ℃, obtains graphitiferous heat conduction polyethylene masterbatch;
2) composition preparation technology: polyethylene, graphitiferous heat conduction polyethylene masterbatch, processing aid are added in homogenizer in proportion, discharging after 5～15min high-speed mixing, the raw material being mixed is added to extruding pelletization in forcing machine, and temperature range is 160～250 ℃.
Embodiment 6
The component of embodiment 6 heat conduction polyethylene compositions is pressed following parts by weight:
Polyethylene: 100 parts of ethene and 1-hexene copolymers, PE100 level (σ
lPL=10.0MPa), density 0.947g/cm
3, MFR(2.16Kg counterweight) and 0.15g/10min; 250 parts of the graphitiferous heat conduction polyethylene masterbatch of embodiment 5; Processing aid: 1.5 parts of Tyox Bs, and 1.0 parts of tetramethylolmethane diphosphite two (2,4-di-tert-butyl phenyl) esters.
The masterbatch composition of embodiment 6, preparation technology and composition preparation technology are with embodiment 5.
Embodiment 7
The component of the graphitiferous heat conduction polyethylene masterbatch of embodiment 7 is pressed following parts by weight:
100 parts of ethene and butene-1 copolymers, density 0.918g/cm
3, MFR(2.16Kg counterweight) and 1.6g/10min); Oildag: 100 parts, 400 orders; Coupling agent: 3.5 parts of γ-aminopropyl triethoxysilanes; Thinner: 40 parts of ethanol; 0.5 part of oxidation inhibitor: 1,1,3-tri-(2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane, and 0.5 part of tetramethylolmethane diphosphite two (2,4-di-tert-butyl phenyl) ester.
The component of embodiment 7 heat conduction polyethylene compositions is pressed following parts by weight:
100 parts, heat-proof polythene PE-RT II type, ethene and 1-octene copolymer, density 0.942g/cm
3, MFR(2.16Kg counterweight) and 0.56g/10min; 100 parts of the graphitiferous heat conduction polyethylene masterbatch of embodiment 7
The masterbatch preparation technology of embodiment 7 and composition preparation technology are with embodiment 5.
Embodiment 8
The component of embodiment 8 heat conduction polyethylene compositions is pressed following parts by weight:
100 parts, heat-proof polythene PE-RT II type, ethene and 1-hexene copolymer, density 0.936g/cm
3, MFR(2.16Kg counterweight) and 0.62g/10min; 150 parts of the graphitiferous heat conduction polyethylene masterbatch of embodiment 7; Processing aid: 1.0 parts of Tyox Bs, and 1.0 parts of tetramethylolmethane diphosphite two (2,4-di-tert-butyl phenyl) esters.
The masterbatch composition of embodiment 8, preparation technology and composition preparation technology are with embodiment 5.
Embodiment 9:
The component of the graphitiferous heat conduction polyethylene masterbatch of embodiment 9 is pressed following parts by weight:
Polyethylene powder: 100 parts of ethene and butene-1 copolymers, density 0.918g/cm
3, MFR(2.16Kg counterweight) and 1.6g/10min); Oildag: 100 parts, 800 orders; Coupling agent: 3.5 parts of γ-aminopropyl triethoxysilanes; Thinner: 70 parts of ethanol; 1.5 parts of oxidation inhibitor: 1,1,3-tri-(2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane, and 1.5 parts of tetramethylolmethane diphosphite two (2,4-di-tert-butyl phenyl) esters.
The component of embodiment 9 heat conduction polyethylene compositions is pressed following parts by weight:
100 parts, heat-proof polythene PE-RT II type, ethene and butene-1 copolymer, density 0.948g/cm
3, MFR(2.16Kg counterweight) and 0.45g/10min; 200 parts of the graphitiferous heat conduction polyethylene masterbatch of embodiment 9.
The preparation method of embodiment 9, according to the following steps:
1) masterbatch preparation technology: graphite coupling agent treatment: coupling agent is joined in thinner and mixed in proportion, join together with graphite in homogenizer, homogenizer is warming up to 50 ℃, process 15min in homogenizer; Again the polyethylene powder of powdery, oxidation inhibitor are added in the homogenizer of processing graphite in proportion, discharging after 10min high-speed mixing, the raw material being mixed is added in Banbury mixer, discharging after mixing 10min clock, then make after crushed graphitiferous heat conduction polyethylene masterbatch;
2) composition preparation technology: polyethylene, graphitiferous heat conduction polyethylene masterbatch, processing aid are added in homogenizer in proportion, discharging after 10min high-speed mixing, the raw material being mixed is added to extruding pelletization in forcing machine, and temperature range is 160～250 ℃.
Embodiment 10:
The component of embodiment 10 heat conduction polyethylene compositions is pressed following parts by weight:
100 parts, heat-proof polythene PE-RT II type, ethene and 1-hexene copolymer, density 0.938g/cm
3, MFR(2.16Kg counterweight) and 0.62g/10min; 80 parts of the graphitiferous heat conduction polyethylene masterbatch of embodiment 9.
The masterbatch preparation technology of embodiment 10 and composition preparation technology are with embodiment 9.
Embodiment 11:
The component of the graphitiferous heat conduction polyethylene masterbatch of embodiment 11 is pressed following parts by weight:
Polyethylene powder: 100 parts of ethene and butene-1 copolymers, density 0.918g/cm
3, MFR(2.16Kg counterweight) and 1.6g/10min); Graphite: 100 parts of oildags, 1200 orders; Coupling agent: 3.5 parts of γ-aminopropyl triethoxysilanes; Thinner: 100 parts, acetone; 0.5 part of oxidation inhibitor: 1,1,3-tri-(2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane, and 0.5 part of tetramethylolmethane diphosphite two (2,4-di-tert-butyl phenyl) ester.
The component of embodiment 1 heat conduction polyethylene composition is pressed following parts by weight:
100 parts, heat-proof polythene PE-RT II type, ethene and 1-hexene copolymer, density: 0.938g/cm
3, MFR(2.16Kg counterweight) and 0.62g/10min; 66 parts of the graphitiferous heat conduction polyethylene masterbatch of embodiment 11, processing aid: fluoroelastomer (commercially available tube material rheological agent): 0.1 part.
The preparation method of embodiment 11, according to the following steps:
1) masterbatch preparation technology: graphite coupling agent treatment: coupling agent is joined in thinner and mixed in proportion, join together with graphite in homogenizer, homogenizer is warming up to 50 ℃, process 15min in homogenizer; Again the polyethylene powder of powdery, oxidation inhibitor are added in the homogenizer of processing graphite in proportion, discharging after 10min high-speed mixing, the raw material being mixed is added in Banbury mixer, discharging after mixing 10min clock, then make after crushed graphitiferous heat conduction polyethylene masterbatch;
2) composition preparation technology: polyethylene, graphitiferous heat conduction polyethylene masterbatch, processing aid are added in homogenizer in proportion, discharging after 10min high-speed mixing, the raw material being mixed is added to extruding pelletization in forcing machine, and temperature range is 160～250 ℃.
Comparative example 1
The component of comparative example 1 heat conduction polyethylene composition is pressed following parts by weight:
100 parts, heat-proof polythene PE-RT II type, ethene and 1-hexene copolymer, density: 0.938g/cm
3, MFR(2.16Kg counterweight) and 0.62g/10min; Contain embodiment 7 graphite masterbatch: 40 parts.
The masterbatch composition of comparative example 1, preparation technology and composition preparation technology are with embodiment 7.
Embodiment 1～11 and comparative example 1 performance test:
Table 1 embodiment 1～11 and comparative example 1 the performance test results
By table 1, can find out, with respect to comparative example 1, the density of embodiment 1～11, MFR, oxidation induction period, tensile strength are suitable, and compare the performance that ratio 1 height makes modulus in flexure, thermal conductivity and be obviously better than comparative example 1, excellent combination property owing to adding amount of master batch.
Embodiment 12:
Adopt the embodiment of the present invention 1 composition, extrude and prepare diameter 63mm tubing, tubing processing characteristics is good.
Embodiment 13:
Adopt the embodiment of the present invention 9 compositions, extrude and prepare diameter 110mm tubing, tubing processing characteristics is good.
Embodiment 14:
Adopt the embodiment of the present invention 9 compositions, extrude and prepare diameter 110mm tubing, tubing processing characteristics is good; The ultrahigh molecular weight polyethylene tubing of additional wall thickness 2mm.
Embodiment 15:
Adopt the embodiment of the present invention 6 compositions, extrude preparation heat conduction polyethylene 2mm thick sheet, processing characteristics is good.Embodiment 12～15 performance tests:
Embodiment 12～15 performances are in Table 2.Hydrostatic test in table 2, presses GB/T6111 test, under corresponding test conditions tubing non-leakage, do not break.
Table 2 embodiment 12～15 the performance test results
By table 2, can find out tubing and the sheet material of embodiment 12～15 for adopting heat conduction polyethylene composition of the present invention to prepare, the hydrostatic test of embodiment 12～15, modulus in flexure, the test result of resisting environmental stress and cracking time excellence.
The above, be only preferred embodiment of the present invention, is not invention to be done to the restriction of other form, and any those skilled in the art may utilize the technology contents of above-mentioned announcement to be changed or be modified as the equivalent embodiment of equivalent variations.But every technical solution of the present invention content that do not depart from, any simple modification, equivalent variations and the remodeling above embodiment done according to technical spirit of the present invention, still belong to the protection domain of technical solution of the present invention.
Claims (14)
1. a graphitiferous heat conduction polyethylene masterbatch, is characterized in that, by 100 parts, (weight part) polyethylene powder, 60～300 parts, graphite, 0.3～15 part of coupling agent, 0.3～300 part of thinner, 0.01～5 part of composition of oxidation inhibitor, described coupling agent and thinner are by weight 1:(0.5～50) add.
2. graphitiferous heat conduction polyethylene masterbatch according to claim 1, it is characterized in that: by 100 parts, (weight part) polyethylene powder, 60～200 parts, graphite, 0.5～8 part of coupling agent, 0.5～160 part of thinner, 0.1～3 part of composition of oxidation inhibitor, described coupling agent and thinner are by weight 1:(1～20) add.
3. graphitiferous heat conduction polyethylene masterbatch according to claim 1 and 2, is characterized in that: it is 50～400 orders that described graphite is selected particle diameter, and the expansible black lead of expansion multiplying power 100～400ml/g or particle diameter are 400～1200 object oildags.
4. graphitiferous heat conduction polyethylene masterbatch according to claim 1 and 2, is characterized in that: it is 0.915～0.950g/cm that described polyethylene powder or pellet are selected density
3, melt mass flow rate is the ethene-alpha-olefin copolymer of (2.16Kg counterweight) 1～30g/10min.
5. graphitiferous heat conduction polyethylene masterbatch according to claim 1 and 2, is characterized in that: described coupling agent is selected a kind of in isopropyl tri (dioctylpyrophosphato)titanate, two (dioctylphosphato) metatitanic acid second diester, diisostearoyl ethylene titanate or γ-aminopropyl triethoxysilane.
6. graphitiferous heat conduction polyethylene masterbatch according to claim 1 and 2, is characterized in that: described thinner is selected a kind of of whiteruss, acetone or alcohol.
7. graphitiferous heat conduction polyethylene masterbatch according to claim 1 and 2, is characterized in that: described oxidation inhibitor is selected hindered phenol, hindered amine, phosphite or sulphur ester antioxidant.
8. graphitiferous heat conduction polyethylene masterbatch according to claim 7, it is characterized in that: described oxidation inhibitor is selected four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, 2,6-toluene di-tert-butyl phenol, one or more compositions in tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester or Tyox B.
9. the preparation method of graphitiferous heat conduction polyethylene masterbatch described in claim 1～8 any one, it is characterized in that, concrete technology step is: coupling agent and thinner are mixed in proportion, add in homogenizer together with graphite, be warming up to 40～80 ℃, stir 2～10min; Polyethylene powder and oxidation inhibitor are added in homogenizer, discharging after 5～15min high-speed mixing, adds the raw material being mixed in forcing machine again, and extruding pelletization at 160～250 ℃, obtains graphitiferous heat conduction polyethylene masterbatch.
10. a heat conduction polyethylene composition, is characterized in that: each component proportion (weight part) is: 100 parts of polyethylene, graphitiferous heat conduction polyethylene masterbatch is 60～200 parts described in claim 1～8 any one, 0～20 part of processing aid.
11. heat conduction polyethylene compositions according to claim 10, is characterized in that, described processing aid is selected from fluoroelastomer or polyethylene wax.
12. heat conduction polyethylene compositions according to claim 10, is characterized in that the tensile strength of described heat conduction polyethylene composition > 15MPa, modulus in flexure > 1000MPa, oxidation induction period (OIT, 200 ℃) > 40min, thermal conductivity > 0.75W/m.k.
13. 1 kinds of production used for geothermal heat pump polyvinyl piping materials that adopt the heat conduction polyethylene composition described in claim 10～12 any one to prepare.
14. 1 kinds of heat conduction polyethylene board or sheet materials that adopt the heat conduction polyethylene composition described in claim 10～12 any one to prepare.
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