CN103012973B - High heat conductivity nanocomposite rubber - Google Patents
High heat conductivity nanocomposite rubber Download PDFInfo
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- CN103012973B CN103012973B CN201210573979.2A CN201210573979A CN103012973B CN 103012973 B CN103012973 B CN 103012973B CN 201210573979 A CN201210573979 A CN 201210573979A CN 103012973 B CN103012973 B CN 103012973B
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Abstract
The invention discloses a high heat conductivity nanocomposite rubber. The raw materials comprise one or more of the following components: ethylene-propylene-diene-terpolymer (EPDM) rubber, anti-aging agents, carbon black, sulfur, accelerants, plasticizers, paraffin oil, an organic active agent PEG4000, inorganic active agents and dispersing agents. The nanocomposite rubber has the beneficial effects that the heat conductivity of the composite material is greatly improved by using the mixed fillers; granules and whiskers with certain length-diameter ratios are utilized to form a continuous heat conduction network chain; the fillers in different grain sizes are selected and combined to achieve higher filling density; a coupling agent is utilized to improve the interfaces of the fillers and the matrix to reduce the heat resistance on the interfaces; the heat conductivity is improved by filling the rubber with nano materials; molecule interaction forces between the thermoplastic rubber and the fillers are improved by utilizing unique molecular design; and a heat channel is formed through efficient contact between the fillers, thus greatly improving the heat conductivity.
Description
Technical field
The present invention relates to nanometer new material technology field, particularly relate to a kind of High heat conductivity nanocomposite rubber.
Background technology
Now, because electronic product is more and more tending towards miniaturization, therefore those easily integrated and miniaturization and the good compounded rubber substrate of snappiness are widely used, but because the multiple stratification of the highly integrated and laminate of unicircuit certainly leads to heat release problem, therefore the task of top priority is just become to the requirement of the heat conductivility of these materials.
Terpolymer EP rubber (EPDM) is the terpolymer of ethene, propylene and diene-based monomer, and the introducing of diene is to realize sulfuration, and the type of diene has: dicyclopentadiene (DCPD), l, 4 one hexadienes.EPDM is better than common ethylene-propylene rubber(EPR) toughness.
People are with dielectric metal oxide and other compound filled polymers in recent years, tentatively solve this problem.The filler of insulated type heat conductive rubber mainly comprises: metal oxide is as BeO, MgO, A1
2o
3, CaO, NIO; Metal nitride is as AlN, BN etc.; Carbide is as SiC, B
4c
3deng.They have higher thermal conductivity, and what is more important compares the electrical insulating property having excellence with metal powder, and therefore they can ensure that end article has good electrical insulating property, and this is vital in electronic apparatus industry.
Investigation and application for heat conductive rubber is a lot, can be divided into: metal filled type, metal oxide filled-type, metal nitride filled-type, inorganic non-metallic filled-type, fiber filled type heat conductive rubber by the kind of particle filled composite; Also can divide according to a certain character of heat conductive rubber, such as can be divided into insulated type heat conductive rubber and nonisulated type heat conductive rubber according to its electrical insulation capability.
Because rubber itself has insulativity, the therefore electrical insulation capability of most heat conductive rubber is finally determined by the insulating property of particle filled composite.Filler for nonisulated type heat conductive rubber is usually metal powder, graphite, carbon black, carbon fiber etc., the feature of this kind of filler has good thermal conductivity, material easily can be made to obtain high heat conductivility, but also make the decreasing insulating of material even become electro-conductive material simultaneously.Therefore at the Working environment of material in the less demanding situation of electrical insulating property, above-mentioned filler can be applied.And also necessarily require heat conductive rubber to have low electrical insulating property to meet specific requirement, as electromagnetic shielding material etc. under certain conditions.
Information industry flourish in the last few years, new requirement is proposed to the performance of macromolecular material, especially for the development of heat conductive rubber provides development space, the application of heat conductive rubber on computer fittings will improve the heat dissipation problem of computer and improve its travelling speed and stability, as CPU, notebook computer shell and various surface-mounted integrated circuit, these materials all require heat conductive insulating.Macromolecular material insulate, but as thermally conductive material, pure macromolecular material is generally inefficient, because macromolecular material is the poor conductor of heat mostly, macromolecular material thermal conductivity is about the 1/500-1/600 of metal.Modification must be carried out to macromolecular material.The thermal conductivity of metal and metal oxide is in Table 1-1, table 1-2.
The thermal conductivity of table 1-1 metal and metal oxide
Metal and the mineral filler that can be used as conductive particle have following several substantially:
(l) metal powder filler: copper powder, aluminium powder, bronze, silver powder.
(2) metal oxide: aluminum oxide, is oxidized secret, barium oxide, magnesium oxide, zinc oxide.
(3) metal nitride: aluminium nitride, boron nitride.
(4) inorganic non-metallic: graphite, silicon carbide.
When ceramic is as heat conductive filler filled high polymer material matrix, the quality of filling effect depends primarily on following factor: the kind of (l) polymeric matrix, characteristic; (2) shape, particle diameter, the distribution of sizes of filler; (3) interface binding characteristic of filler and matrix and the interaction of two-phase.
The thermal conductivity of some packing materials of table 1-2
Due to adding of filler, the mechanical property of material is declined.Therefore, the conductivity not only will considered in the design of matrix material, and require that stability of material is good, nontoxic, satisfactory mechanical property and inexpensive.The polymkeric substance that use itself has good heat conductive performance relative to another selection of filled polymer, but the expensive and deficient in stability in performance of this type of material price, become their main drawback on using.Rubber is the material that in macromolecular material, output is maximum.
The market requirement of conductivity macromolecular material is annual all in growth, and wherein the market demand of heat conductive rubber increases faster.Therefore the research of rubber heat conductivility has been caused to the interest of various countries investigator, and done good work.The research of current fillibility heat conductive rubber, the method that major part adopts physics to fill, heat conductivility is poor, and mechanical property declines serious, and production cost is high.But along with the market of expanding day and going deep into of research, heat conductive rubber will have a large development, especially the research and development of nano heat-conductive material, the preparation of high heat-conductive body polymer materials, the discussion of polymer bond mechanism should become the developing direction of heat-conducting polymer material.
Summary of the invention
Technical problem to be solved by this invention is, electric packaged material requires heat conduction, insulation have lower specific inductivity, good heat-conductive characteristic and low thermal expansivity.This type of material is the application market that heat-conducting polymer material is larger.The present invention is by inorganic particulate filler Ultrafine, and when even arriving nano-scale, the change of matter can occur because of the change of interatomic distance in particle and structure for itself thermal conductivity.Thermal conductivity as aluminium nitride is about 36w/ (m.K), and the thermal conductivity of nano level aluminium nitride can reach 320w/ (m.K).The trickle magnesium oxide of high purity, its thermal conductivity is not less than 50w/ (m.K), is equivalent to 4 times of silicon oxide, 3 times of aluminum oxide.
For solving the problems of the technologies described above, obtaining the matrix material of high thermal conductivity, the invention provides a kind of high heat conducting nano compounded rubber, its raw material comprise in following component one or more: terpolymer EP rubber, anti-aging agent, carbon black, sulphur, promotor, softening agent, paraffin oil, organic active agent PEG4000, inorganic active agent, dispersion agent.
Described material content proportioning is preferably by weight:
Terpolymer EP rubber 150-200 part,
Anti-aging agent 1-4 part,
Carbon black 40-80 part,
Sulphur 1-3 part,
Promotor 1-3 part,
Softening agent 6-10 part,
Paraffin oil 40-80 part,
Organic active agent PEG4000,3-8 part
Inorganic active agent 6-12 part,
Dispersion agent 1-4 part.
Described anti-aging agent be preferably in following reagent one or more: 6-oxyethyl group-2,2,4-trimethylammonium-1,2-dihyaroquinoline; 2,2,4-trimethylammonium 1,2-dihydro quinoline polymer; N-phenyl-α-aniline; N-Phenyl beta naphthylamine; N-phenyl-N`-cyclohexyl Ursol D; N-phenyl-N`-sec.-propyl-Ursol D.; N-N`-diphenyl-p-phenylenediamine.
Described promotor be preferably in following reagent one or more: promotor T; The two thiamide of N, N-tetramethyl-two sulphur; Tetramethyl-thiuram disulfide; Thiram; Vulcanization accelerator TMTD; Tetramethyl-dithio thiuram; Vulcanization accelerator TMTD; Vulcanization accelerator TMTD-II; Promotor TT; Curing two (thiocarbonyl group dimethylamine); Tetramethyl TMTD; Tetramethyl-sulfo-peroxy dicarbonate diamide; Tetramethyl thiuram disulfide; TMTD; Altax; Accelerant B Z.
Described softening agent be preferably in following reagent one or more:: o-phthalic acid dibutyl ester; DEDB; Octyl adipate; Di-n-hexyl adipate; Butyl benzyl phthalate; Sebacic acid two (2-ethyl hexyl) ester.
Described promoting agent is preferably PEG4000; Described dispersion agent be preferably in following reagent one or more: triethyl hexyl phosphoric acid, sodium lauryl sulphate, methyl amyl alcohol, derivatived cellulose, polyacrylamide, guar gum, fatty acid polyglycol ester.
Described inorganic active agent be preferably in following reagent one or more: MgO, Al
2o
3, Si
3n
4, BN, AlN, ZnO, KAl (SO
4)
212H
2o, Al
2o
3-2SiO
2-2H
2o.
Described AlN is preferably: AlN whisker and AlN particle.
Described Si
3n
4be preferably highly heat-conductive silicon nitride; Described BN is nano silicon nitride boron particles, meets following index:
Described high heat conducting nano compounded rubber, prepare preferably by following steps:
The first step, synthetic rubber: by Banbury mixer by described Material synthesis rubber;
Second step, shaping: by mill, synthetic rubber is shaping;
3rd step, sulfuration: mould molded rubber being put into vulcanizer, pressurization scope is 150-210kgf/ ㎝
2, be warmed up to 220-230 DEG C, the time is 80-100 second, carries out sulfuration.
The present invention is by having carried out Experimental comparison to the thermal conduction capability of the filler of various different shapes and size raising polymer-based carbon used in combination, and filler comprises MgO, Al
2o
3, Si
3n
4, BN, AlN, ZnO, KAl (SO
4)
212H
2o(alum), Al
2o
3-2SiO
2-2H
2o(kaolin) etc.The present invention's mixed fillers makes the thermal conductivity of matrix material significantly improve.The present invention utilizes the particle, the whisker formation continuous print heat conduction network chain that there are certain length-to-diameter ratio; Select the filler combination of different particle diameters, reach higher filling density: utilize coupling agent to improve the interface of filler and matrix, to reduce the thermal resistance of interface; Thermal conductivity is improved with nanomaterial-filled rubber.High heat conductivity nanocomposite rubber of the present invention is the material of thermal conductivity up to 22.25 ~ 35.56w/mK.The technology of the present invention utilizes unique molecular designing, improves the interaction force of molecule between thermoplastic elastomer and filler, and filler high-level efficiency contact each other defines thermal pathways, has increased substantially thermal conductivity.
Embodiment
Describe embodiments of the present invention in detail below with reference to embodiment, to the present invention, how utilisation technology means solve technical problem whereby, and the implementation procedure reaching technique effect can fully understand and implement according to this.
Embodiment 1: the present embodiment high heat conducting nano high-speed vulcanization complex ternary ethylene-propylene rubber(EPR), each material component content proportioning is by weight:
Terpolymer EP rubber 150-200 part,
Anti-aging agent 1-4 part,
Carbon black 40-80 part,
Sulphur 1-3 part,
Promotor 1-3 part,
Softening agent 6-10 part,
Paraffin oil 40-80 part,
Organic active agent PEG4000,3-8 part
Inorganic active agent 6-12 part,
Dispersion agent 1-4 part,
And it is prepared by following steps:
The first step, synthetic rubber: by Banbury mixer by above-mentioned raw materials synthetic rubber;
Second step, shaping: by mill, synthetic rubber is shaping;
3rd step, sulfuration: mould molded rubber being put into vulcanizer, pressurization scope is 150-210kgf/ ㎝
2, be warmed up to 220-230 DEG C, the time is 80-100 second, carries out sulfuration.
Embodiment 2: rubber disperse agent impels material particles to be dispersed in Rubber Media, forms the reagent of stable suspension.The rubber disperse agent used in the embodiment of the present invention is one or more in following reagent: triethyl hexyl phosphoric acid, sodium lauryl sulphate, methyl amyl alcohol, derivatived cellulose, polyacrylamide, guar gum, fatty acid polyglycol ester.
Embodiment 3:
The anti-aging agent that one embodiment of the invention uses is: 6-oxyethyl group-2,2,4-trimethylammonium-1,2-dihyaroquinoline.Its trade name is antioxidant A W.Antioxidant A W is brown viscous liquid, and sterling is light brown sticky cylinder liquid.Nontoxic, proportion is 1.029 ~ 1.030(25 DEG C), boiling point is 169 DEG C.Benzene, acetone, dichloroethane, tetracol phenixin, industrial naptha and ethanol can be dissolved in; Water insoluble.Shelf-stable.Be the anti-ozone anti-aging agent of special efficacy, also have protective effect to flex crack and thermo-oxidative ageing.The goods used under being specially adapted to dynamic condition.No blooming, has contaminative, is unsuitable for light color article.Little on sulfuration impact during consumption 1 ~ 2 part, increase to 3 parts and then significantly promote sulfuration, during use, promote that consumption should suitably reduce.
The anti-aging agent that another embodiment of the present invention uses is: 2,2,4-trimethylammonium 1,2-dihydro quinoline polymer.Trade name is anti-aging agent RD.Anti-aging agent RD be amber to canescence arborescens powder, nontoxic.Softening temperature is not less than 74 DEG C.Acetone, benzene, chloroform, dithiocarbonic anhydride can be dissolved in, be slightly soluble in petroleum hydrocarbon; Water insoluble.The oxidation that energy rejection condition is harsher, thermal ageing and Weather effect, but poor to flex crack protection effect.No blooming, there is light contamination.General amount ranges is 0.5 ~ 2 part, reaches as high as 3 compositions.
The anti-aging agent that yet another embodiment of the invention uses is: N-phenyl-α-aniline.Trade name is antioxidant A.Antioxidant A be tawny to purple crystal shape material, sterling is colorless plate crystal, because of containing a small amount of methyl naphthylamine and aniline, poisonous, can not with skin contact.Proportion is 1.16 ~ 1.17, and fusing point is not less than 52.0 DEG C.Be soluble in acetone, ethyl acetate, benzene, ethanol, chloroform, tetracol phenixin; Dissolve in gasoline; Water insoluble.Gradual change purple in daylight and air.Inflammable.Antioxidant A to heat, oxygen, to subdue and the solarization such as weather all has good protection effect, be the general anti-aging agent of natural rubber, synthetic rubber and reclaimed rubber.The performance that ozone-resistant is aging is had concurrently in chloroprene rubber; Also there is certain inhibition easily to disperse in dry glue to the solarization of variable valency metal ions and reclaimed rubber, be also easily scattered in water; Solubleness in rubber is up to 5%, larger than antioxidant D, and consumption is no blooming 3 ~ 4 parts time, therefore can increase consumption to improve protective benefits.Antioxidant A has contaminative and transport property.General amount ranges is 1 ~ 2 part, reaches as high as 5 parts.
The anti-aging agent that further embodiment of this invention uses is: N-Phenyl beta naphthylamine.Trade name is antioxidant D.Antioxidant D is light grey to light brown powder, and sterling is white powder.Proportion is 1.18, and fusing point is not less than 104 DEG C.Easy solvent is in acetone, ethyl acetate, dithiocarbonic anhydride, chloroform; Dissolve in ethanol, tetracol phenixin; Be insoluble to gasoline and water.Under air and daylight, gradually become grey black, but do not affect protection effect.Inflammable.Antioxidant D is the universal anti-aging agent of natural rubber, synthetic rubber and latex.All there is good protective effect to heat, oxygen, flex crack and general aging action, and be slightly better than antioxidant A.Also have protective effect to the ion of poisonous metal, but comparatively antioxidant A is poor.If with anti-aging agent 4040 or 4010NA and use, heat resistanceheat resistant, oxygen, flex crack and ozone-resistant aging resistance all have remarkable increase.Easily be scattered in water in dry glue.Solubleness in rubber is lower than antioxidant A, is about 1.5%.The meeting bloom when consumption is more than 2 parts, with antioxidant A and with then avoiding.Tool contaminative, is unsuitable for light color article.Amount ranges is generally 0.5 ~ 2 part.This kind of anti-aging agent is easy to get because of raw material, manufactures simple, cheap, therefore also occupies certain status at home at present.
The anti-aging agent that further embodiment of this invention uses is: N-phenyl-N`-cyclohexyl Ursol D.Trade name is antioxidant 4010 (or anti-aging agent CPPD).Antioxidant 4010 is pale powder, and sterling is white powder.Irritant to skin.Proportion is 1.29, and fusing point is lower than 110 DEG C, is very easily dissolved in methyl chloride, is soluble in benzene, ethyl acetate, acetone, is insoluble in industrial naptha, water insoluble.In atmosphere or daylight end deepen look, but protection effect do not subtract.Antioxidant 4010 is one of excellent universal anti-aging agent of natural rubber and synthetic rubber, is particularly useful for natural rubber and styrene-butadiene rubber(SBR).Excellent to aging action protective benefitses such as heat, oxygen, ozone, light, be also the excellent lasting be full of cracks of mechanical stress formation and the inhibitor of flex crack.Also have the solarization of high-energy radiation and cupric ion and necessarily have protective effect.All better than the protection effect of antioxidant A T and antioxidant D, have goodish protective benefits time alone, but with its anti-aging agent as AW, crystallinity and with to ozone-induced cracking and weather aging protective benefits higher.Also can use with antioxidant A, D or other universal anti-aging agent.Antioxidant 4010 easily disperses, and can produce bloom when consumption is more than 1 part, and it is serious that goods meet phototropic.Also can migration stain other sizing material contacted with it or material.General amount ranges 0.15 ~ 1 part.
The anti-aging agent that further embodiment of this invention uses is: N-phenyl-N`-sec.-propyl-Ursol D.Trade name is antioxidant 4010NA (or anti-aging agent IPPD).Antioxidant 4010NA is purple plate crystal.Micro-toxic, allergic anti-hydraulic pressure can be caused.Fusing point is not less than 70 DEG C.Dissolve in oils, benzene, ethyl acetate, tetracol phenixin, methylene dichloride, chloroform, dithiocarbonic anhydride, acetone, ethanol, be insoluble in gasoline, water insoluble.Shelf-stable.Meeting variable color under daylight, but do not affect usefulness.Antioxidant 4010NA is the universal anti-aging agent of natural rubber, synthetic rubber latex glue.Good to ozone-induced cracking, flex crack barrier propterty spy; Also be heat, oxygen, light and generally aging superior protection agent.Also can suppress the solarization of variable valency metal ions, protection natural rubber performance compared with 4010 more comprehensively.Antioxidant 4010NA can be alone, produces with not only reducing consumption but also can improve protective benefits with antioxidant A W or wax.Especially with wax and with staying the anti-static ozone-induced cracking performance of improving the standard.Fusing point is lower, easily disperses, and the solubleness in rubber is larger than 4010, and bloom is less, therefore can improve consumption.Contaminative is large.The goods used under being usually used in the higher condition of dynamic and static state stress.General amount ranges is 1 ~ 4 part.
The anti-aging agent that further embodiment of this invention uses is: N-N`-diphenyl-p-phenylenediamine.Trade name is antioxidant H.(having another name called antioxidant DPPD or anti-aging agent PPD).Antioxidant H is that beige powder is lumped together, and sterling is silvery white plate crystal.Proportion is 1.18 ~ 1.22.Fusing point is not less than 140 DEG C.Dissolve in benzene, toluene, acetone, ether, ethylene dichloride, dithiocarbonic anhydride, be slightly soluble in ethanol and gasoline; Water insoluble.Storage-stable.In atmosphere and easy to change under daylight.Inflammable.Antioxidant H is natural rubber, elastomeric universal anti-aging agent, has excellent flex cracking resistance performance, excellent to the aging protective effect of heat, oxygen, ozone, light, particularly copper, mn ion.Especially natural rubber and elastomeric paralled system is applicable to.But variable color and seriously polluted.Solubleness in rubber is low; In styrene-butadiene rubber(SBR), be up to 0.7%, be 0.35% in natural rubber, in polybutadiene rubber, solubleness is lower.There is bloom phenomenon when exceeding its solubleness in consumption, when with other anti-aging agent as antioxidant A and the used time, its consumption can be reduced and can improve protection effect again.Time alone, amount ranges is generalized to 0.2 ~ 0.3 part.
Embodiment 4: the promotor that the embodiment of the present invention uses is one or more in following product: promotor T, N, the two thiamide of N-tetramethyl-two sulphur, tetramethyl-thiuram disulfide, thiram, vulcanization accelerator TMTD, tetramethyl-dithio thiuram, Vulcanization accelerator TMTD, Vulcanization accelerator TMTD-II, promotor TT, curing two (thiocarbonyl group dimethylamine), tetramethyl TMTD, tetramethyl-sulfo-peroxy dicarbonate diamide, tetramethyl thiuram disulfide, TMTD, rubber accelerator DM, accelerant B Z.
Embodiment 5:
The softening agent that one embodiment of the invention uses is: o-phthalic acid dibutyl ester (DOP).Plasticizer DOP is colourless oil liquid, proportion 0.9861 (20/20), fusing point-55, boiling point 370(normal pressure), water insoluble, be dissolved in ethanol, ether, the most of organic solvent of mineral wet goods.General purpose grade DOP, is widely used in the industry such as plastics, rubber, paint and emulsifying agent.DOP is universal softening agent, be mainly used in the processing of the processing of polyvinyl chloride fat, also the can be used for ground superpolymer such as resin, acetate resin, ABS resin and rubber, also can be used for making paint, dyestuff, dispersion agent etc., the PVC of DOP plasticising can be used for manufacturer's fabricate-leather, agricultural film, wrapping material, cable etc.
The softening agent that another embodiment of the present invention uses is: DEDB.DEDB and polyvinyl chloride and the rare multipolymer of vinyl chloride acetic acid second, the poly-rare good intermiscibility of acetic acid second, also and polyvinyl chloride, polymethyl acrylate, polyvinyl alcohol butyral, Nitrocellulose, N-BUTYL ACETATE Mierocrystalline cellulose and ethyl cellulose etc. mix.DEDB lighter color, plasticizing efficiency are high, intermiscibility good, volatility is low, exudative low, thermally-stabilised index is high, cold-resistant water-fast extraction, not oxidizable and volatilization, excellent electrical properties, weighting agent capacity greatly, goods luminance brightness high.Be widely used in PVC plastic particle, non-filling calendered film, leatheroid, CABLE MATERIALS, sheet material, sheet material, soft or hard tubing, sole material, rubber-plastic strip, foamed material, film, paint, rubber, synthetic glass, printing-ink, plastipaste, acetate emulsion tackiness agent etc.Be the one that softening agent industry price is minimum, can significantly reduce rubber product cost.
The softening agent that yet another embodiment of the invention uses is: Octyl adipate.Its chemistry is by name: hexanodioic acid 2121 ethylhexyl, molecular formula is C
22h
42o
4, Octyl adipate is colorless and odorless transparent oily liquid, can be dissolved in most of organic solvents such as ethanol, ether, acetone, acetic acid, be slightly soluble in ethylene glycol, water insoluble.But the volatility of Octyl adipate is large, and there is certain deficiency the aspects such as water tolerance, transport property, insulativity.Octyl adipate is normal and phthalate is composite, is applied to cold-resistant agricultural film, cable coating layer, leatheroid, sheet material, outdoor water pipe and Frozen Food Packaging film etc.Octyl adipate can also as the cold resistant plasticizer of the resins such as the low temperature softening agent of various synthetic rubber and Nitrocellulose, ethyl cellulose, polystyrene, vinylchlorid one acetic acid butylene copolymer.At present, di-n-hexyl adipate is also widely used in polyvinyl butyral resin film.In addition, in many countries, legal its can be used as the softening agent of food, medical packaging plastics.
The softening agent that further embodiment of this invention uses is: di-n-hexyl adipate.Di-n-hexyl adipate is the cold resisting type softening agent that consumption is maximum in the world.N-octyl-n-decyl adipate, colourless transparent liquid is by hexanodioic acid and the n-Octanol of straight chain, the straight chain type binary acid mixed ester of nonylcarbinol lactate synthesis; N-octyl-n-decyl adipate is dissolved in mineral oil, gasoline and most of organic solvent, insoluble or be slightly soluble in glycerine, glycols and some amine, is the straight chain type cold-resistant plasticizer of excellent property.Compared with hexanodioic acid branched-chain alcoho, there is better resistance to low temperature, and volatilization loss, thermotolerance and photostabilization, water-extraction resistance etc. are also excellent compared with side chain alcohol ester.When it and phthalic ester shares time, polyvinyl chloride Vinyl Acetate Copolymer Emulsion performance can be improved, be widely used for the cold resistant plasticizer of polyvinyl acetate (PVA), polystyrene, polymethylmethacrylate, nitrocellulose, ethyl cellulose and rubber.
The softening agent that further embodiment of this invention uses is: butyl benzyl phthalate (Butyl benzylphthalate) molecular weight 312.40.Character: colourless transparent oil liquid.Relative density (25 DEG C/4 DEG C) 1.116 ,-35 DEG C, zero pour, boiling point 370 DEG C. flash-point (opening) 199 DEG C. specific refractory power 1.535. viscosity (25 DEG C) 41.5mPas, is dissolved in organic solvent and hydro carbons.Water insoluble.Flammable.Micro-poison.With most of rubber and resin compatible good. solvation is strong, the softening agent of, oil resistant extractable heat-resisting as water tolerance.
The softening agent that further embodiment of this invention uses is: cold resistant plasticizer DOS.Dioctyl sebacate (DOS), formal name used at school: sebacic acid two (2-ethyl hexyl) ester molecule formula: C
26h
50o
4.Cold resistant plasticizer DOS is colourless or pale yellow transparent oily liquids, zero pour-48 ° of C, boiling point: 256 ° of C (0.67Kpa), point of ignition 257-263 ° C, viscosity 25mPa.s (20 ° of C), refractive index 1.449-1.451 (25 ° of C), can be dissolved in the organic solvents such as hydro carbons, alcohols, ketone, ester class, chlorinated hydrocarbon, be insoluble to di-alcohols and water.Cold resistant plasticizer DOS is the excellent cold resistant plasticizer of a kind of polyvinyl chloride, and plasticizing efficiency is high, and volatility is low, therefore except having excellent low temperature cold tolerance, has again good thermotolerance, can use at a higher temperature.The weathering resistance of this product is better, and electrical insulation properties is also more excellent, normal and phthalate use, is specially adapted to the goods such as cold-resistant electric wire and CABLE MATERIALS, leatheroid, film, sheet material, sheet material.Cold resistant plasticizer DOS can as the cold resistant plasticizer of the resins such as the low temperature softening agent of various synthetic rubber and Nitrocellulose, ethyl cellulose, polymethylmethacrylate, polystyrene, vinyl chloride copolymer.
Embodiment 6: the inorganic active agent that raw materials comprises is one or more in following compounds (or mixture): MgO, Al
2o
3, Si
3n
4, BN, high purity carbon dust, AlN, ZnO, KAl (SO
4)
212H
2o(alum), Al
2o
3-2SiO
2-2H
2o(kaolin).
Embodiment 7: the MgO that the embodiment of the present invention uses is nano-MgO particle.
Nano-powder material industrialized producing technology requires that preparation method is simple, and production cost is suitable for, and reproducible, powder granularity is even, product purity is high, reunion degree is low.Method about nano magnesia synthesis in prior art is a lot, but in fact can be applied to industrial less.One is because problems such as equipment, cost, raw material, scale, investments; Two is that some technique is still in the laboratory study stage, and realize suitability for industrialized production and have any problem, even some may not realize suitability for industrialized production.
The present embodiment adopts indoor temperature solid phase method to prepare MgO particle.
Solid-phase reaction of the present invention overcomes conventional wet and prepares the agglomeration traits that magnesium oxide nanoparticle exists, and has reaction without the need to solvent, the advantage such as productive rate is high, reaction conditions is easy; And overcome that the efficiency existed in original solid-phase reaction is low, the shortcoming of the oxidizable distortion of particle.
The concrete grammar that the present embodiment indoor temperature solid phase method prepares MgO particle is: by MgCI solution and Na
2cO
3(raw material mass mixture ratio 1:1.2) solution, with PVA solution (polyvinyl alcohol solution) for properties-correcting agent, reaction produces precipitation MgCO
3precipitation, then under 75 ~ 85 DEG C of constant temperature, the mode transformed by precipitation obtains alkali formula carbon formula magnesium presoma.50 ~ 60 DEG C of standing alkali formula carbon formula magnesium presoma precipitation 24-30 hour.Finally pass at Ar air-flow, temperature is calcination under the condition of 600 ~ 650 DEG C, obtains nano-MgO particle.Adopt PVA as polymeric surface active agent, control the reunion of particle, obtained nano-MgO particle dispersion is better, and be cubic structure, substantially spherical in shape, its particle diameter is 25-35nm.
Embodiment 8-1: the Si that the embodiment of the present invention uses
3n
4for nano silicon nitride silicon grain, meet following index:
Embodiment 8-2: the Si that the embodiment of the present invention uses
3n
4it can also be highly heat-conductive silicon nitride.Common silicon nitride has randomly-oriented sintering structure.Highly heat-conductive silicon nitride adds kind of crystal grain (diameter 1um, long 3-4um) at material powder (below particle diameter 1um), makes the sub-orientations of this all crystal grain, forms the fibrous silicon nitride structure reaching 100um with orientation.Due to the formation of filamentary structure, thermal conductivity presents each diversity, and on oriented structure direction, thermal conductivity is 120w/ (mK), is 3 times of common silicon nitride, is equivalent to the thermal conductivity of steel.
Embodiment 9: the BN that the embodiment of the present invention uses is nano silicon nitride boron particles, meets following index:
Embodiment 10: the embodiment of the present invention use high purity carbon dust be: Dongguan pull together produce 10000 high-purity carbon dusts.Performance index are:
| Fixed carbon: | 99.99% | Specification: | 10000 orders |
| The trade mark: | 18925457433 | Moisture: | 0.015% |
| Turgidity: | 1-2 doubly | Screen overflow granularity: | 0.0006% |
| Ash content: | 0.85 | Volatile matter: | 0.01％ |
| Screen underflow granularity: | 0.0005% |
Embodiment 11: the AlN filler that the embodiment of the present invention uses is: AlN whisker and AlN particle do filler.In the embodiment of the present invention, using ABS as matrix, AlN whisker and AlN particle (below 6um) are filled, and obtain the matrix material of the highest thermal conductivity 28.2W/ (m.K), AlN whisker and AlN particle ratio (mass ratio) are l:40 ~ 60.Invention further contemplates the confounding effect of filler and coupling agent to the impact of matrix material heat conductivility.By AlN whisker and the AlN mix particles of adequate rate, give matrix material higher heat-conductivity and lower thermal expansivity than independent whisker and particle.By using coupling agent silane treatment, the thermal conductivity of the ABS composite material of AlN particulate reinforcement improves 98%, and thermal conductivity raising is due to the interface by improving matrix and particle, and the contact resistance of filler-matrix reduces.
Embodiment 12: the ZnO that the embodiment of the present invention uses is: nano granular of zinc oxide.Its performance index are:
The embodiment of the present invention use nano zine oxide, for above-mentioned: 1 class nano-ZnO, 2 class nano-ZnOs, 3 class nano-ZnOs, in one.
Embodiment 13: performance test and characterization experiments contrast.
Experimental installation
This experiment adopts flash of light heat transfer analysis instrument LFA447N ano flashTM to measure thermal diffusivity.This conductometer uses xenon lamp as heating source heated sample surface, uses infrared eye to read sample temperature rise, decreases potential surface resistance of heat transfer.
Experimental principle
Under certain design temperature T (constant temperature), light beam pulse is being launched instantaneously by laser source (or photoflash lamp), uniform irradiation is at sample lower surface, use the corresponding temperature rise process in infrared detector measurement sample upper surface centre, obtain the relation curve of temperature rising to the time.By half heating-up time (sample upper surface temperature is elevated to the time needed for the half of maximum value after receiving optical pulse irradiation) t50 (or claiming t1/2), by following formula:
α＝01388×d
2/t
50(1)
The thermal diffusivity α of sample under temperature T can be obtained.In formula, d is the thickness of sample.Thermal conductivity λ is tried to achieve by following formula:
λ＝α×C
p×ρ (2)
In formula, Cp is the specific heat of rubber; ρ is the density of rubber.Specific heat to be compared with reference sample by sample tries to achieve.Density is recorded by micro computer specific gravity material balance.
Prepared by sample
Sizing material is cut into the thin rounded flakes that diameter is 12.5 ~ 12.7mm during test, and ensures that sample upper and lower surface is smooth, smooth.
Experimental procedure
(1) half an hour before experiment, in instrument, pour appropriate liquid nitrogen into, regulate external recirculated water controller, set temperature makes it higher than room temperature 2 ~ 3 degrees Celsius, preheater apparatus.
(2) by precision be 0.02mm vernier callipers to the thickness of test specimen carry out three times measure, get the thickness of its mean value as sample.
(3) with alcohol by sample wiped clean, dry.Uniform graphite coating is carried out in the upper and lower surface of sample.
(4) sample is put into sample well, open Survey Software, parameters, start test.
A liquid nitrogen is filled with every 3.5h in experimentation.Experiment terminates all power supplys of rear closedown.
Various formula heat conductivility and mechanical property
Filler 1: terpolymer EP rubber 150 parts, anti-aging agent [6-oxyethyl group-2,2,4-trimethylammonium-1,2-dihyaroquinoline] 2 parts, carbon black 40 parts, 1 part, sulphur, promotor [N, the two thiamide of N-tetramethyl-two sulphur] 1 part, 6 parts, softening agent [o-phthalic acid dibutyl ester], paraffin oil 40 parts, organic active agent [PEG4000] 3-8 part, inorganic active agent [MgO, Al
2o
3, (high thermal conductivity) Si
3n
4, BN, AlN, (1 class nanometer) ZnO] each 1 part, dispersion agent [triethyl hexyl phosphoric acid] 1 part.
Filler 2: terpolymer EP rubber 160 parts, 2 parts, anti-aging agent [2-dihyaroquinoline], carbon black 50 parts, 2 parts, sulphur, promotor [tetramethyl-thiuram disulfide] 2 parts, 7 parts, softening agent [DEDB], paraffin oil 50 parts, organic active agent [PEG4000] 4 parts, inorganic active agent [MgO2 part, Al
2o
31 part, (nano particle) Si
3n
41 part, BN1 part, AlN1 part, (2 class nanometer) ZnO1 part, KAl (SO
4)
212H
2o1 part], dispersion agent [sodium lauryl sulphate] 2 parts.
Filler 3: terpolymer EP rubber 170 parts, 3 parts, anti-aging agent [2,2,4-trimethylammonium 1], carbon black 60 parts, 3 parts, sulphur, promotor [thiram] 3 parts, 8 parts, softening agent [sebacic acid two (2-ethyl hexyl) ester], paraffin oil 60 parts, organic active agent [PEG4000], 5 parts, inorganic active agent [MgO, Al
2o
3, BN, AlN, Al
2o
3-2SiO
2-2H
2o] each 2 parts, dispersion agent [methyl amyl alcohol] 3 parts.
Filler 4: terpolymer EP rubber 180 parts, 4 parts, anti-aging agent [N-phenyl-N`-cyclohexyl Ursol D], carbon black 70 parts, 3 parts, sulphur, promotor [vulcanization accelerator TMTD] 3 parts, 9 parts, softening agent [butyl benzyl phthalate], paraffin oil 70 parts, organic active agent [PEG4000], 6 parts, inorganic active agent [MgO, Al
2o
3, (nano particle) Si
3n
4, KAl (SO
4)
212H
2o, Al
2o
3-2SiO
2-2H
2o] each 2 parts, dispersion agent [derivatived cellulose] 4 parts.
Filler 5: terpolymer EP rubber 190 parts, 4 parts, anti-aging agent [N-phenyl-N`-cyclohexyl Ursol D], carbon black 80 parts, 3 parts, sulphur, promotor [vulcanization accelerator TMTD] 3 parts, 10 parts, softening agent [butyl benzyl phthalate], paraffin oil 80 parts, organic active agent [PEG4000] 7 parts, inorganic active agent [Al
2o
3, (high thermal conductivity) Si
3n
4, BN, AlN, (2 class nanometer) ZnO, KAl (SO
4)
212H
2o, Al
2o
3-2SiO
2-2H
2o] each 1 part, dispersion agent [polyacrylamide] 4 parts.
Filler 6: terpolymer EP rubber 200 parts, 4 parts, anti-aging agent [N-phenyl-N`-sec.-propyl-Ursol D], carbon black 80 parts, 3 parts, sulphur, promotor [Vulcanization accelerator TMTD] 3 parts, 10 parts, softening agent [sebacic acid two (2-ethyl hexyl) ester], paraffin oil 80 parts, organic active agent [PEG4000] 8 parts, inorganic active agent [MgO, Si
3n
4(nano particle), BN, AlN, (1 class nanometer) ZnO, KAl (SO
4)
212H
2o, Al
2o
3-2SiO
2-2H
2o] each 1.5 parts, dispersion agent [fatty acid polyglycol ester] 4 parts.
Filler 7: terpolymer EP rubber 200 parts, anti-aging agent [6-oxyethyl group-2,2,4-trimethylammonium-1,2-dihyaroquinoline; N-N`-diphenyl-p-phenylenediamine] each 2 parts, carbon black 60 parts, 2 parts, sulphur, promotor [Vulcanization accelerator TMTD-II; Altax; Accelerant B Z] each 1 part, softening agent [Octyl adipate; Di-n-hexyl adipate; Butyl benzyl phthalate; Sebacic acid two (2-ethyl hexyl) ester] each 1 part, paraffin oil 40 parts, organic active agent [PEG4000] 3 parts, inorganic active agent [MgO, Al
2o
3, Si
3n
4(nano particle), BN, AlN, (1 class nanometer) ZnO ,] each 2 parts, each 1 part of dispersion agent [triethyl hexyl phosphoric acid, sodium lauryl sulphate, methyl amyl alcohol].
Filler 8: terpolymer EP rubber 180 parts, anti-aging agent [2,2,4-trimethylammonium 1,2-dihydro quinoline polymer; N-phenyl-N`-sec.-propyl-Ursol D] each 1 part, carbon black 50 parts, 2 parts, sulphur, promotor [promotor T tetramethyl-dithio thiuram; Vulcanization accelerator TMTD; ] each 1 part, softening agent [di-n-hexyl adipate; Butyl benzyl phthalate; Sebacic acid two (2-ethyl hexyl) ester] each 3 parts, paraffin oil 50 parts, organic active agent [PEG4000] 6 parts, inorganic active agent [MgO, Al
2o
3, Si
3n
4(nano particle), BN, AlN, (2 class nanometer) ZnO, KAl (SO
4)
212H
2o, Al
2o
3-2SiO
2-2H
2o] each 1 part, each 1 part of dispersion agent [derivatived cellulose, polyacrylamide, guar gum, fatty acid polyglycol ester].
Filler 9: terpolymer EP rubber 170 parts, anti-aging agent [6-oxyethyl group-2,2,4-trimethylammonium-1,2-dihyaroquinoline; N-N`-diphenyl-p-phenylenediamine] each 1 part, carbon black 70 parts, 3 parts, sulphur, promotor [promotor T; Vulcanization accelerator TMTD; Vulcanization accelerator TMTD-II; ] each 1 part, softening agent [di-n-hexyl adipate; Butyl benzyl phthalate] each 4 parts, paraffin oil 70 parts, organic active agent [PEG4000] 4 parts, inorganic active agent [MgO, Al
2o
3, Si
3n
4(high thermal conductivity), BN, AlN, (1 class nanometer) ZnO, KAl (SO
4)
212H
2o, Al
2o
3-2SiO
2-2H
2o] each 1 part, each 1 part of dispersion agent [triethyl hexyl phosphoric acid, methyl amyl alcohol, polyacrylamide].
Filler 10: terpolymer EP rubber 160 parts, anti-aging agent [N-phenyl-N`-cyclohexyl Ursol D; N-phenyl-N`-sec.-propyl-Ursol D.; N-N`-diphenyl-p-phenylenediamine] each 1 part, carbon black 40 parts, 3 parts, sulphur, promotor [TMTD; Altax] each 1 part, softening agent [o-phthalic acid dibutyl ester; Octyl adipate; Butyl benzyl phthalate] each 3 parts, paraffin oil 80 parts, organic active agent [PEG4000] 3 parts, inorganic active agent [MgO, Al
2o
3, Si
3n
4(nano particle), BN, AlN, ZnO ,] each 2 parts, each 1 part of dispersion agent [triethyl hexyl phosphoric acid, methyl amyl alcohol, derivatived cellulose, guar gum].
Filler 11: terpolymer EP rubber 200 parts, anti-aging agent [N-phenyl-α-aniline; N-Phenyl beta naphthylamine; N-phenyl-N`-sec.-propyl-Ursol D] each 1 part, carbon black 40 parts, 1 part, sulphur, promotor [Vulcanization accelerator TMTD; Promotor TT; Tetramethyl TMTD] each 1 part, softening agent [butyl benzyl phthalate; Sebacic acid two (2-ethyl hexyl) ester] each 5 parts, paraffin oil 80 parts, organic active agent [PEG4000] 4 parts, inorganic active agent [MgO, Al
2o
3, Si
3n
4(high thermal conductivity), BN, AlN, (2 class nanometer) ZnO, KAl (SO
4)
212H
2o, Al
2o
3-2SiO
2-2H
2o] each 1 part, dispersion agent [fatty acid polyglycol ester] 2 parts.
Filler 12: terpolymer EP rubber 150 parts, anti-aging agent [N-phenyl-N`-sec.-propyl-Ursol D; N-N`-diphenyl-p-phenylenediamine] each 1 part, carbon black 50 parts, 2 parts, sulphur, promotor [promotor T; ] 2 parts, 9 parts, softening agent [sebacic acid two (2-ethyl hexyl) ester], paraffin oil 70 parts, organic active agent [PEG4000] 6 parts, inorganic active agent [MgO, Si
3n
4(high thermal conductivity), AlN, (1 class nanometer) ZnO, Al
2o
3-2SiO
2-2H
2o] each 2 parts, each 1 part of dispersion agent [sodium lauryl sulphate, derivatived cellulose, fatty acid polyglycol ester].
High heat conducting nano compounded rubber of the present invention is that thermal conductivity can up to the thermoplastic composite resin of 22.25 ~ 35.56w/mK.The technology of the present invention utilizes unique molecular designing, improves the interaction force of molecule between thermoplastic elastomer and filler, and filler high-level efficiency contact each other defines thermal pathways, has increased substantially thermal conductivity.
All above-mentioned this intellecture properties of primary enforcement, not setting restriction this product innovation of other forms of enforcement and/or novel method.Those skilled in the art will utilize this important information, and foregoing is revised, to realize similar implementation status.But all modifications or transformation belong to the right of reservation based on product innovation of the present invention.
The above is only preferred embodiment of the present invention, and be not restriction invention being made to other form, any those skilled in the art may utilize the technology contents of above-mentioned announcement to be changed or be modified as the Equivalent embodiments of equivalent variations.But everyly do not depart from technical solution of the present invention content, any simple modification, equivalent variations and the remodeling done above embodiment according to technical spirit of the present invention, still belong to the protection domain of technical solution of the present invention.
Claims (1)
1. a high heat conducting nano compounded rubber, is characterized in that, its raw material comprises following component: terpolymer EP rubber, anti-aging agent, carbon black, sulphur, promotor, softening agent, paraffin oil, organic active agent PEG4000, inorganic active agent, dispersion agent;
Described material content proportioning is by weight:
Terpolymer EP rubber 150-200 part,
Anti-aging agent 1-4 part,
Carbon black 40-80 part,
Sulphur 1-3 part,
Promotor 1-3 part,
Softening agent 6-10 part,
Paraffin oil 40-80 part,
Organic active agent PEG4000,3-8 part
Inorganic active agent 6-12 part,
Dispersion agent 1-4 part;
Described anti-aging agent is one or more in following reagent: 6-oxyethyl group-2,2,4-trimethylammonium-1,2-dihyaroquinoline; N-phenyl-α-aniline; N-Phenyl beta naphthylamine; N-phenyl-N`-cyclohexyl Ursol D; N-phenyl-N`-sec.-propyl-Ursol D; N, N`-diphenyl-para-phenylene diamine;
Described promotor is one or more in following reagent: promotor T; Altax; Accelerant B Z;
Described softening agent is one or more in following reagent: dioctyl phthalate (DOP); DEDB; Octyl adipate; Di-n-hexyl adipate; Butyl benzyl phthalate; Sebacic acid two (2-ethyl hexyl) ester;
Described dispersion agent is one or more in following reagent: triethyl hexyl phosphoric acid, sodium lauryl sulphate, methyl amyl alcohol, derivatived cellulose, polyacrylamide, guar gum, fatty acid polyglycol ester;
Described inorganic active agent is multiple in following reagent: MgO, Al
2o
3, Si
3n
4, BN, AlN, ZnO, KAl (SO
4)
212H
2o, Al
2o
3-2SiO
2-2H
2o;
Described Si
3n
4for highly heat-conductive silicon nitride, described highly heat-conductive silicon nitride adds diameter 1 μm at particle diameter less than 1 μm material powder, and long 3-4 μm of kind crystal grain, makes the sub-orientations of this all crystal grain, form the fibrous silicon nitride structure reaching 100 μm with orientation;
Described BN is nano silicon nitride boron particles, meets following index:
Described high heat conducting nano compounded rubber, it is prepared by following steps:
The first step, synthetic rubber: by Banbury mixer by described Material synthesis rubber;
Second step, shaping: by mill, synthetic rubber is shaping;
3rd step, sulfuration: mould molded rubber being put into vulcanizer, pressurization scope is 150-210kgf/ ㎝
2, be warmed up to 220-230 DEG C, the time is 80-100 second, carries out sulfuration.
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| JP2017037833A (en) * | 2015-08-06 | 2017-02-16 | 国立大学法人豊橋技術科学大学 | Composite insulation sheet and manufacturing method of composite insulation sheet |
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