WO2009030696A2 - Procédé de préparation de composites polymères thermoconducteurs - Google Patents

Procédé de préparation de composites polymères thermoconducteurs Download PDF

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Publication number
WO2009030696A2
WO2009030696A2 PCT/EP2008/061593 EP2008061593W WO2009030696A2 WO 2009030696 A2 WO2009030696 A2 WO 2009030696A2 EP 2008061593 W EP2008061593 W EP 2008061593W WO 2009030696 A2 WO2009030696 A2 WO 2009030696A2
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polymer
aqueous dispersion
process according
present
thermally conducting
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PCT/EP2008/061593
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WO2009030696A3 (fr
Inventor
Volker Schaedler
Huaili Qin
Karl Haeberle
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Basf Se
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/18—Suspension polymerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L39/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions of derivatives of such polymers
    • C08L39/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
    • C08L39/06—Homopolymers or copolymers of N-vinyl-pyrrolidones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes

Definitions

  • the present invention relates to a process for the preparation of polymer-composites comprising at least one thermally conducting compound and at least one polymer, comprising providing an aqueous dispersion of at least one thermally conducting compound, addition of at least one polymer or precursors of at least one polymer, and optionally at least one polymerisation initiator, to the aqueous dispersion, optionally po- lymerisation of the precursors of the at least one polymer, and removal of the dispersion medium from the aqueous dispersion.
  • thermal management has become critical in enhancing the performance and reliability of de- vices.
  • polymer materials are attractive candidates for these requirements due to their flexibility, low density and electrical insulating properties.
  • the composite comprising AIN and the dia- mine are obtained as a composite-film or -powder.
  • the incorporation of AIN lead to obvious improvement in thermal conductivity and thermal stability, as well as an increase in the dielectric constant.
  • the thermal conductivity and dielectric constant of the composite were greatly influenced by the loading of AIN and coupling agent, wherein a higher amount of AIN and coupling agent result in an increase of thermal conductivity.
  • the content of the thermal conductive filler in polymer-composites should be below a certain level. It is known that the thermal conductivity of polymer- composites can be increased greatly with the formation of heat paths in polymer matrix.
  • S. Yu et al., Composites: Part A 33 (2002) 289 to 292 disclose the ther- mal conductivity of polystyrene-aluminum nitride composites, being prepared by mixing polystyrene and aluminum nitride at room temperature until the aluminum nitride powder surrounds the polystyrene particles, then the mixture is put into a stainless steel die and is hot pressed at 180 0 C.
  • the particle size of the polystyrene particles is 0.15 mm.
  • Object of the present invention is to improve the thermal conductivity of polymer- composites comprising at least one inorganic filler and at least one polymer, wherein the inorganic filler should be present in low amounts, in order not to disturb the polymeric characteristics of the composites.
  • the uniform and homogeneous dispersion of the polymer and the inorganic filler should be obtained in the polymer- composites.
  • step (B) addition of the at least one polymer or precursors of the at least one polymer to the aqueous dispersion of step (A), in order to obtain an aqueous dispersion comprising at least one thermally conducting compound, at least one polymer in dispersed form or precursors of the at least one polymer and optionally at least one polymerisation initiator,
  • step (C) optionally polymerisation of the precursors of the at least one polymer in aqueous dispersion obtained in step (B), in order to obtain at least one polymer in dispersed form,
  • step (D) removal of the dispersion medium of the aqueous dispersion obtained in step (B) or (C), in order to obtain a polymer-composite.
  • the process according to the present invention is conducted in aqueous dispersion, wherein the at least one polymer which is added or the at least one polymer, which is obtained by polymerization of the precursors, is present in dispersed form, makes it possible to obtain polymer-composites having a totally different morphology compared to polymer-composites, in which polymers and inorganic fillers are compounded in dry or molten state. If a film is obtained from an aqueous dispersion of the polymer-composite, honeycomb-like structures are obtained wherein the fillers are in a continuous phase. Based on this very specific structure of the polymer-composites according to the present invention, a very high thermal conductivity can be obtained.
  • Step (A) of the process according to the present invention comprises providing an aqueous dispersion of at least one thermally conducting compound in the form of particles.
  • the at least one thermally conducting compound can be chosen form organic or inorganic thermally conducting compounds.
  • Preferred thermally conducting compounds are compounds having a thermal conductivity of more than 1 W/m * K.
  • the at least one thermally conducting compound is at least one compound of general formula (I)
  • A is chosen from the group consisting of B, Al, Si, Mg, Ca and mixtures thereof,
  • B is chosen from the group consisting of C, N, O and mixtures thereof and
  • x, y are each independently integers of 1 to 3, wherein x and y are, depending on the oxidation number of A and B, chosen that the compound of general formula (I) is neutrally charged.
  • x and y are each independently from each other chosen from integers of 1 to 3, being 1 , 2 and 3.
  • x and y are chosen so that the compound of general formula (I), depending on the oxidation states of A and B, is neutrally charged. For example, if A is boron, and B is nitrogen, x and y are 1. For another example, if A is aluminum and B is oxygen, x is 2 and y is 3, etc.
  • a person having ordinary skill in the art does know which values x and y need to have in order to obtain neutral compounds of general formula (I).
  • the at least one thermally conducting compound is chosen from the group consisting of BN, AI 2 O3, SiC, AIN, MgO, CaO and mixtures thereof.
  • Thermally conductivities of exemplary thermally conducting compounds are CaO 15 W/m * K, MgO 55 W/m * K, SiC 30 - 50 W/m * K, BN 200 - 300 W/m * K.
  • the compounds according to general formula (I) can be obtained by reactions and processes that are known to a person having ordinary skill in the art. Most thermally conducting compounds, preferably compounds of general formula (I), are commercially available. Thermally conducting compounds can optionally be pre-treated on their surface. The skilled artisan does know how this treatment is conducted.
  • the at least one thermally conducting compound is in the form of particles.
  • the particles of at least one thermally conducting compound have a diameter of 10 to 200 ⁇ m.
  • the at least one thermally conducting compound is present in the aqueous dispersion according to step (A) of the present invention in an amount of 1.0 to 20.0% by weight, particularly preferred 2.0 to 15.0 % by weight, based on the aqueous dispersion ob- tained in step (B) of the present invention.
  • the aqueous dispersion according to step (A) of the process according to the present invention is obtained by introducing the at least one thermally conducting compound into an aqueous dispersion medium.
  • Suitable dispersion media are mixtures of water and optionally at least one further solvent, chosen from the group consisting of alcohols, esters, ethers, carboxylic acids, ketones and mixtures thereof.
  • the dispersion medium, which is used in step (A) of the process according to the present invention has to be able to produce an aqueous dis- persion, in which the at least one thermally conducting compound and the polymer, which are added in step (B) of the process according to the present invention are well dispersed, but are not dissolved. If a precursor of the at least one polymer is added in step (A) of the process according to the present invention, this precursor can be dissolved or dispersed in the reaction medium.
  • the dispersion medium according to step (A) of the process according to the present invention is water.
  • solvents which can be present in addition to water, can be chosen from the group consisting of alcohols, for example methanol, ethanol, propanols, like n- propanol, iso-propanol, butanols, like n-butanol, iso-butanol, tert-butanol, ethers, like diethylether, methyl-tert-butyl-ether, diethylether, esters, ketones like aceton and carboxylic acids, like formic acid, acetic acid, propionic acid and mixtures thereof.
  • alcohols for example methanol, ethanol, propanols, like n- propanol, iso-propanol, butanols, like n-butanol, iso-butanol, tert-butanol, ethers, like diethylether, methyl-tert-butyl-ether, diethylether, esters, ketones like
  • these additional solvents are present in the aqueous dispersion medium in amounts of 0.1 to 20 % by weight, particularly preferred 0.1 to 10 % by weight, based on the aqueous dispersion medium.
  • Step (A) of the process according to the present invention can be conducted at any temperature, at which the dispersion medium is in liquid status.
  • step (A) of the process according to the present invention at least one dispersion agent is added.
  • the at least one dispersion agent is pref- erably added to the aqueous dispersion medium, before the at least one thermally conducting compound is added to the aqueous dispersion medium.
  • the at least one dispersion agent can be chosen from all agents, which are able to help dispersing the compound of general formula (I) in the aqueous dispersion medium.
  • a very preferred dispersion agent is poly(vinylpyrrolidone) (PVP).
  • PVP poly(vinylpyrrolidone)
  • the dispersion agent is added in an amount of 0.5 to 10 % by weight, particularly preferably 0.8 to 5 % by weight, based on the aqueous dispersion medium which is present after step (B) of the process according to the present application.
  • the dis- persion agent that is added in step (A) of the process according to the present invention is soluble in water.
  • the dispersion agent preferably PVP, and optionally precursors of the at least one polymer are the only components which are soluble in the dispersion medium.
  • the mo- lecular weight of PVP which is used in step (A) of the process of the present invention, is 1000 to 100.000 g/mol.
  • this mixture is preferably stirred for a time which is long enough to completely dissolve the dis- persion agent in the aqueous dispersion medium. For example, a time of 5 minutes to 2 hours is suitable.
  • the at least one thermally conducting compound can be added to the aqueous dispersion medium.
  • the aqueous dispersion obtained is preferably stirred for a time which is long enough to obtain an aqueous dispersion, in which the at least one thermally conducting compound is well dispersed in the aqueous dispersion medium.
  • a time of 8 to 24 hours, preferably 10 to 20 hours, is suitable.
  • Step (B) of the process according to the present invention comprises the addition of at least one polymer or precursors of the at least one polymer and optionally at least one polymerization initiator to the aqueous dispersion medium, obtained in step (A) of the process according to the present invention.
  • At least one polymer is added in step (B) of the process according to the present invention, in order to obtain an aqueous dispersion comprising at least one thermally conducting compound and at least one polymer in dispersed form.
  • all polymers which are dispersed in the dispersion me- dium at the end of step (B) are suitable to be added in step (B) of the process according to the present invention.
  • suitable polymers that can be added in step (B) of the process according to the present invention are polymers known to the skilled artisan for being dispersed in the dispersion media according to the present invention. Reference can be made to D. Distler, Wassrige Polymerdispersionen, Wiley VCH.
  • suitable polymers are chosen from the group consisting of homo- and copolymers of ethylenically unsaturated, preferably vinylic monomers, for example styrene, (meth)acrylic acid, (meth)acrylic acid esters, unsaturated dicarboxylic acids, for example maleic acid, maleic acid anhydride, fumaric acid, itaconic acid, poly- condensates, like polyamides, polyesters, polycarbonates, polyurethanes and mixtures thereof.
  • Preferred polymers which are added in polymeric form in step (B) of the process according to the present invention are polyurethanes.
  • a very preferred polymer which is added in step (B) in polymeric form is an at least partially aliphatic polyure- thane.
  • the polyurethane is based on a polyester containing adipic acid and butane diol and an isocyanate, which can be aliphatic or aromatic.
  • This polyurethane is preferably added in dispersion having a content of polyurethane of ⁇ 20% by weight.
  • suitable polyurethane dispersions can for example be obtained according to EP 1645578 and EP 259679.
  • the polymers that are added in step (B) of the process according to the present invention are commercially available or can be obtained by processes known to a person having ordinary skill in the art, for example radically induced polymerisation of ethylenically unsaturated, preferably vinylic monomers, polycondensation reaction of for example diamines and dicarboxylic acids, diols and dicarboxylic acids or diols and diisocy- anates. It is also possible that these polymers are cross-linked, which is known to a person having ordinary skill in the art.
  • the polymers which are added in step (B) of the process according to the present invention have in general a molecular weight of > 10000 g/mol, preferably > 50000 g/mol.
  • precursors of the at least one polymer are added in step (B) of the process according to the present invention, which are reacted in order to obtain the at least one polymer in dispersed form which is present in the polymer-composite according to the present invention.
  • step (B) monomers are added in step (B), which are polymerized in step (C) to obtain the at least one polymer in dispersed form.
  • step (B) of the process according to the present invention depends on the polymers which are to be obtained from the polymeriza- tion reaction of these monomers.
  • all kinds of polymers and therefore all kinds of precursors can be added in step (B) of the process according to the present invention as long as the polymers that are obtained from the precursors are present in the dispersion medium in dispersed form.
  • a person having ordinary skill in the art does know which polymers can advantageously be incorporated into the polymer-composite according to the present invention, and which precursors have to be added in order to obtain these polymers.
  • the polymer which is obtained from the precursor that are added in step (B) of the process according to the present invention is preferably chosen from homo- and copolymers of ethylenically unsaturated, preferably vinylic monomers like styrene, (meth)acrylic acid, (meth)acrylic acid esters, unsaturated di- carboxylic acids, for example maleic acid, maleic acid anhydride, fumaric acid, itatonic acid, polycondensates, like polyamides, polyesters, polycarbonates, polyurethanes.
  • vinylic monomers like styrene
  • unsaturated di- carboxylic acids for example maleic acid, maleic acid anhydride, fumaric acid, itatonic acid
  • polycondensates like polyamides, polyesters, polycarbonates, polyurethanes.
  • Very preferred polymers which are obtained from the precursors that are added in step (B) of the process according to the present invention, are for example homo- and co- polymers of monomers being chosen from the group consisting of styrene, (meth)acrylic acid, (meth)acrylic acid esters and mixtures thereof.
  • precursors that are added in step (B) of the process according to the present invention preferably monomers are added which after polymerisation give rise to polymers that are present in the polymer composite according to the present invention.
  • Suitable precursor are preferably chosen from the group consisting of styrene, (meth)acrylates, for example butylacrylate, and mixtures thereof.
  • a very preferred polymer which is present in the polymer-composite according to the present invention is polystyrene obtained form polymerisation of styrene as precursors.
  • Another very preferred copolymer which is present in the polymer-composite according to the invention is poly(styrene- butylacrylate), obtained from the copolymerisation reaction of styrene and butylacrylate.
  • cross-linking monomers can be added, for ex- ample monomers having more than one polymerizable functional group which are known to a person having ordinary skill in the art, for example triallylcyanurate, divinyl- benzene, divinylester of dicarboxylic acids like diallyl maleate, diallyl fumarate, diallyl phthalate, allyl acrylate und -methacrylate, dihydrodicyclopentadiene acrylate, di-allyl ether und divinyl ether of bifunctional alcohols like ethylene glycol and 1 ,4-butanediol, diester of polyvalent alcohols and acrylic und methacrylic acid like butanedioldiacrylate, ethyleneglycoldiacrylate, hexanedioldimethacrylate. Amounts that have to be added are known to the skilled artisan.
  • step (B) of the present invention If monomers are added in step (B) of the present invention that have to be polymerized radically, like ethylenically unsaturated, preferably vinylic monomers, for example styrene and/or butylacrylate, at least one suitable polymerisation initiator has to added in step (B) of the process according to the present invention.
  • Polymerisation initiators are preferred that can provide radicals by thermolytic or photolytic cleavage.
  • Suitable polymerisation initiators are chosen from the group consisting of inorganic or organic compounds.
  • inorganic compounds are inorganic peroxides or thi- osulfates.
  • organic polymerisation initiators are azo compounds and organic peroxides.
  • preferred organic polymerisation initiators are azo-bis-iso- butyronitrile that is cleaved into two iso butyronitrile radicals and dibenzoyl peroxide that is cleaved into two benzoyl radicals that provide to phenyl radicals.
  • Radical polym- erization initiators are preferably added in an amount of 0 - 2.0% by weight, particularly preferred 0.1 - 1.0% by weight.
  • the monomers as mentioned above can also be polymerized by all process known to a person having ordinary skill in the art, for example cationically or anionically induced.
  • suitable monomers have to added.
  • Monomers suitable to obtain a polyamide are diamines and dicarboxylic acids, amino acids, lactams and mixtures thereof.
  • Monomers to obtain a polyester are diols and dicarboxylic acids, hydroxy car- boxylic acids, lactones and mixtures thereof.
  • Monomers suitable to obtain a polyure- thane are diisocyanates and diols, being chosen from monomeric and oligomeric diols, and mixtures thereof.
  • Monomers which are added as precursors of the at least one polymer in step (B) of the process according to the present invention are added in an amount of 10 to 50 % by weight, preferably 15 to 40 % by weight, based on the aqueous dispersion which is obtained in step (B).
  • step (B) It is further possible according to the present invention to add precursors of the at least one polymer in step (B) that are not monomers, but which are dimers or oligomers, which have to be further reacted in order to obtain a polymeric material.
  • these precursors are precondensates, for example low molecular polyamides, polyesters or polyetherols which are further reacted to obtain the polycondensates which are present in the polymer-composite.
  • the at least one polymer present in the polymer-composite is a polyester or a polyurethane that oligomeric alcohols, for example obtained by oligomerisation of alkylene oxides and oligomeric dicarboxylic acids are added.
  • Oligomeric precursors are added in step (B) of the process according to the present invention in amounts suitable to obtain polymers having the desired characteristics.
  • step (B) of the process according to the present invention an aqueous dispersion is obtained, having the following composition:
  • the polymer which is added in step (B) of the process is present in the dispersion medium in dispersed form. If precursors of the at least one polymer are added in step (B) of the process according to the present invention, these precursors can be present in the dispersion medium in dissolved or dispersed form.
  • the aqueous dispersion, which is obtained in step (B) is degassed.
  • a person having ordinary skill in the art does know how such an aqueous dispersion can be degassed, for example degassing by an inert gas, chosen from nitrogen, argon, helium and mixtures thereof can be conducted.
  • the aqueous dispersion which is obtained in step (B) is degassed by nitrogen.
  • Optional step (C) of the process according to the present invention comprises polymerization of the precursors of the at least one polymer in aqueous dispersion obtained in step (B), in order to obtain at least one polymer in dispersed form.
  • Step (C) of the process according to the present invention is only necessary if monomers or precondensates have been added as precursors of the at least one polymer, which is present in the polymer-composite obtained by the process according to the present invention. If at least one polymer has been added in step (B) of the process according to the present invention, step (C) is not necessary.
  • the polymerisation reaction in step (C) of the process according to the present invention can be started by all methods known to a person having ordinary skill in the art depending on the type of precursors for the at least one polymer that are present in the reaction medium. Polymerisation reaction can for example be started by heating, addi- tion of polymerisation initiators etc.
  • step (C) is radically initiated.
  • step (B) For example, if ethylenically unsaturated monomers and at least one polymerization initiator have been added in step (B) as precursors of the at least one polymer, polymerization of these monomers can be started by heating the aqueous dispersion obtained in step (B). Heating can be conducted by all methods known to a person having ordinary skill in the art, for example heating by microwaves, or conventional heating by oilbaths or a heating mantle. The skilled artisan does know how the polymerisation reaction can be started in step (C). It is further possible to add an additional polymerisation initiator in step (C) of the process according to the present invention. This additional initiator can be the same as already added in step (B) or can be a different one chosen from the group as mentioned above.
  • the temperature which has to be applied for starting of the polymerization reaction is for example 50 to 200 0 C, preferably 60 to 140 0 C depending on the initiator.
  • the temperature which is applied in step (C) has to be high enough in order to obtain at least one radical from the polymerization initiators which has been added in step (B) of the process according to the present invention. Heating of the aqueous dispersion in step (C) will produce at least one radical from the at least one polymerization initiator, which starts the polymerization of the monomers present in this aqueous dispersion.
  • the reaction time has to be long enough in order to complete the polymerization reaction, for example 2 to 12 hours, preferably 4 to 8 hours.
  • step (B) If polymers chosen from the group of polycondensates are to be obtained for the polymer-composite according to the present invention the polymerization reaction of the respective monomers, which have been added in step (B), has to be started.
  • a polyamide is to be obtained from the polymerization reaction of diamines and dicarboxylic acids, the addition of the catalytical amount of a proton-source, for example a mineral or organic acid, starts the polycondensation reaction.
  • a proton-source for example a mineral or organic acid
  • Radically initiated polymerization reaction of ethylenically unsaturated monomers can also be started by UV-radiation, which can be applied by methods known to a person having ordinary skill in the art.
  • the polymers which are obtained in step (C) of the process according to the present invention have in general a molecular weight of > 10000 g/mol, preferably > 50000 g/mol.
  • step (C) an aqueous dispersion containing the at least one polymer in dispersed form and the at least compound of general formula (I) in dispersed form is obtained.
  • Step (D) of the process according to the present invention comprises the removal of a dispersion medium from the reaction mixture obtained in step (B) or (C) in order to obtain the polymer-composite.
  • the removal of the dispersion medium is conducted by evaporation.
  • evaporation can, for example, be conducted at room temperature.
  • the temperature can be increased in order to speed up the evaporation process.
  • the pressure is lowered to pressures below atmospheric pressure, in order to speed up the evaporation process.
  • step (B) or (C) of the process according to the present invention Another possibility to remove the dispersion medium from the aqueous dispersion obtained in step (B) or (C) of the process according to the present invention is, for exam- pie, filtration and/or centrifugation of the aqueous dispersion, followed by drying of the polymer-composite at ambient temperature or temperatures above.
  • the present invention further relates to polymer-composites which are obtainable by the process according to the present invention.
  • polymer-composites comprise at least on polymer and at least one thermally conducting compound, wherein all definitions and preferred embodiments as mentioned above apply.
  • the at least one thermally conducting compound is preferably present in an amount of 0.5 to 35.0 % by volume.
  • the polymer-composite according to the present invention can be put in all forms and shapes depending on its further use, for example moldings, films, coating etc. A person having ordinary skill in the art does know how the polymer-composite can be put into the desired form or shape.
  • the present invention further relates to polymer-composites, comprising at least one thermally conducting compound, preferably at least one thermally conducting compound of general formula (I) A x B y (I) having the meanings of A, B, x and y as defined above, and at least one polymer, wherein the thermally conductive compound is pre- sent in particles having a diameter of 10 to 200 ⁇ m.
  • the present invention further relates to the use of a polymer-composite according to the present invention for head management in electrical and/or electronical devices, for example removal of thermal energy from electrical and/or electronical devices.
  • polyvinyl pyrrolidone PVP
  • SiC silicon carbide
  • the resulting suspension is transferred to a 500 ml reactor with continuous stirring, wherein the stirrer speed is 400 rpm.
  • 25 parts styrene as monomers and 0.6 parts azobisisobutyronitrile (AIBN) as initiator are degassed with nitrogen and added into the reactor.
  • Reaction temperature is kept at 80 0 C for 6 h, after which polymerization is finished.
  • the reaction dispersion is cooled and kept at low temperature for several hours, in which the polystyrene/SiC composite settles.
  • the final composite is washed, filtered and dried at 80 0 C.
  • the PS/SiC composite can be thermally molded to any polymer-composite articles according to requirements.
  • the heat path network of SiC is fabricated in PS matrix, and the filler content is 2.3 vol.%.
  • polyvinyl pyrrolidone PVP
  • solu- tion is mixed with 4 parts silicon carbide (SiC) for 16 h.
  • SiC silicon carbide
  • the resulting suspension is transferred to a 500 ml reactor with continuous stirring, wherein the stirrer speed is 400 rpm.
  • 10 parts styrene and 15 parts butyl acrylate as monomers and 0.6 parts azobisisobutyronitrile (AIBN) as initiator are degassed with nitrogen and added into the reactor.
  • Reaction temperature is kept at 80°C for 6 h, after which polymerization is fin- ished.
  • the reaction dispersion is transferred into a plastics mold and dried for 24 h under ambient conditions.
  • the resulting composite films have a thickness of 100 microns to 5 mm, and the filler content is 4.5 vol.%.
  • Table 1 lists the thermal conductivities of composite films with various filler content, and the relative Maxwell values are provided for comparison. The thermal conductivity is higher than the relative Maxwell value due the thermal conductive network formed in polymer matrix. Table 1 :
  • polyvinyl pyrrolidone PVP
  • BN boron nitride
  • the resulting suspension is transferred to a 500 ml reactor with continuous stirring, wherein the stirrer speed is 400 rpm. 10 parts styrene and 15 parts butyl acrylate as monomers and 0.6 parts azobisisobuty- ronitrile (AIBN) as initiator are degassed with nitrogen and added into the reactor. Re- action temperature is kept at 80 0 C for 6 h, after which polymerization is finished.
  • the reaction dispersion is transferred into a plastics mold and dried for 24 h under ambient conditions.
  • the resulting composite films have a thickness of 100 microns to 5 mm, and the filler content is 11.6 vol.%.
  • Table 2 lists the thermal conductivities of composite films with various filler content, and the relative Maxwell values are provided for com- parison. The thermal conductivity is higher than the relative Maxwell value due the thermal conductive network formed in polymer matrix.
  • polyvinyl pyrrolidone PVP
  • alumina AI 2 O3
  • the resulting suspension is transferred to a 500 ml reactor with continuous stirring, wherein the stirrer speed is 400 rpm. 10 parts styrene and 15 parts butyl acrylate as monomers and 0.6 parts azobisisobuty- ronitrile (AIBN) as initiator are degassed with nitrogen and added into the reactor. Re- action temperature is kept at 80 0 C for 6 h, after which polymerization is finished.
  • the reaction dispersion is transferred into a plastics mold and dried for 24 h under ambient conditions.
  • the resulting composite films have a thickness of 100 microns to 5 mm, and the filler content is 3.7 vol.%.
  • polyvinyl pyrrolidone PVP
  • PVP polyvinyl pyrrolidone
  • the resulting dispersion is mixed with 55 parts polyurethane emulsion, which is obtained according to example 1 of EP 259 679, for 4 h to get homogenous dispersion.
  • the mixed dispersion is transferred into a plastics mold and dried for 24 h under ambient conditions.
  • the resulting composite films have a thickness of 100 microns to 5 mm, and the filler content is 25 vol.%.
  • the mixed dispersion can be used as water based thermal conductive coating.
  • Table 3 lists the thermal conductivities of composite films with various filler content, and the relative Maxwell values are provided for comparison. The thermal conductivity is higher than the relative Maxwell value due the thermal conductive network formed in polymer matrix.
  • the experimental data are obviously greater than the reference data according to prior art.
  • the reference data match the Maxwell value well.
  • the fabrication of heat path network in polymer matrix increases TC greatly.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polymerisation Methods In General (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

L'invention concerne un procédé de préparation de composites polymères thermoconducteurs renfermant au moins un composé thermoconducteur sous la forme de particules et au moins un polymère, lequel procédé consiste à: (A) former une dispersion aqueuse d'au moins un composé thermoconducteur; (B) ajouter le polymère précité ou les précurseurs du polymère précité à la dispersion aqueuse mentionnée sous (A) afin d'obtenir une dispersion aqueuse comprenant au moins un composé thermoconducteur, au moins un polymère sous forme dispersée ou des précurseurs du polymère précité et, facultativement, un initiateur de polymérisation; (C) facultativement, procéder à la polymérisation des précurseurs du polymère précité dans la dispersion aqueuse obtenue à l'étape (B) afin d'obtenir au moins un polymère sous forme dispersée; (D) enlever le milieu de dispersion de la dispersion aqueuse obtenue à l'étape (B) ou (C) afin d'obtenir un composite polymère.
PCT/EP2008/061593 2007-09-04 2008-09-03 Procédé de préparation de composites polymères thermoconducteurs WO2009030696A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP07115643.4 2007-09-04
EP07115643 2007-09-04

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WO2009030696A2 true WO2009030696A2 (fr) 2009-03-12
WO2009030696A3 WO2009030696A3 (fr) 2009-05-07

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5601874A (en) * 1994-12-08 1997-02-11 The Dow Chemical Company Method of making moisture resistant aluminum nitride powder and powder produced thereby
WO2000042098A1 (fr) * 1999-01-11 2000-07-20 Ferro Corporation Thermoplastique thermoconducteur
US6949289B1 (en) * 1998-03-03 2005-09-27 Ppg Industries Ohio, Inc. Impregnated glass fiber strands and products including the same
WO2006023860A2 (fr) * 2004-08-23 2006-03-02 General Electric Company Composition thermoconductrice et son procede de preparation
WO2007108217A1 (fr) * 2006-03-20 2007-09-27 Kotobuki Industries Co., Ltd. Procede de production d'une dispersion de nanoparticules, dispersion de nanoparticules et appareil destine a la production d'une dispersion de nanoparticules

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5601874A (en) * 1994-12-08 1997-02-11 The Dow Chemical Company Method of making moisture resistant aluminum nitride powder and powder produced thereby
US6949289B1 (en) * 1998-03-03 2005-09-27 Ppg Industries Ohio, Inc. Impregnated glass fiber strands and products including the same
WO2000042098A1 (fr) * 1999-01-11 2000-07-20 Ferro Corporation Thermoplastique thermoconducteur
WO2006023860A2 (fr) * 2004-08-23 2006-03-02 General Electric Company Composition thermoconductrice et son procede de preparation
WO2007108217A1 (fr) * 2006-03-20 2007-09-27 Kotobuki Industries Co., Ltd. Procede de production d'une dispersion de nanoparticules, dispersion de nanoparticules et appareil destine a la production d'une dispersion de nanoparticules

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
SHU-HUI XIE, BAO-KU ZHU, JU-BIAO LI, XIU-ZHEN WEI, ZHI-KANG XU: "Preparation and properties of polyimide/aluminum nitride composites" POLYMER TESTING, vol. 23, 2004, pages 797-801, XP002517819 cited in the application *
SUZHU YU, PETER HING, XIAO HU: "Thermal conductivity of polystyrene-aluminum nitride composite" COMPOSITES PART A, vol. 33, 2002, pages 289-292, XP002517818 cited in the application *

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