CN112175586B - UV-cured acrylic acid heat-conducting composition, heat-conducting sheet and preparation method thereof - Google Patents

UV-cured acrylic acid heat-conducting composition, heat-conducting sheet and preparation method thereof Download PDF

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CN112175586B
CN112175586B CN202011041446.0A CN202011041446A CN112175586B CN 112175586 B CN112175586 B CN 112175586B CN 202011041446 A CN202011041446 A CN 202011041446A CN 112175586 B CN112175586 B CN 112175586B
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heat
acrylate
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acrylic
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CN112175586A (en
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金勇斌
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Hangzhou Yingxing New Material Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/08—Materials not undergoing a change of physical state when used
    • C09K5/14—Solid materials, e.g. powdery or granular
    • 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
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1812—C12-(meth)acrylate, e.g. lauryl (meth)acrylate
    • 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
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof

Abstract

The invention belongs to the technical field of heat-conducting compositions, and particularly relates to a UV-cured acrylic acid heat-conducting composition, a heat-conducting sheet and a preparation method thereof. The acrylic acid heat-conducting composition comprises 55-140 parts by weight of heat-conducting filler; 1-15 parts of an acrylic polymer; 1-10 parts of (methyl) acrylic acid monomer; 0.01-0.5 part of polyfunctional (methyl) acrylate; 0.01-1 part of initiator. By the special technical process and the method, the heat-conducting fin with the thickness of 0.2-2mm and the heat-conducting fin with the ultrahigh thickness of 2-4.5mm can be prepared, and the heat-conducting fin is low in cost, zero in VOC, halogen-free, flame-retardant and super-soft, and the application range of the heat-conducting fin is expanded.

Description

UV-cured acrylic acid heat-conducting composition, heat-conducting sheet and preparation method thereof
Technical Field
The invention belongs to the technical field of heat-conducting compositions, and particularly relates to a UV-cured acrylic acid heat-conducting composition, a heat-conducting sheet and a preparation method thereof.
Background
With the rapid development of new energy vehicles, communication and electronics industries and the like, the heat-conducting interface material is required to have the performance characteristics of safety, environmental protection, softness, low stress residue, halogen-free flame retardance and the like so as to meet the requirements of high power, high heating and heat dissipation caused by high energy density of batteries, high integration level of components and parts and the like. In addition, the conventional silicone thermal conductive gel has a disadvantage: the micromolecular silicone oil D3-D20 migrates and separates out to the surface when being in a high-temperature environment for a long time, the silicone oil can not only cause the pollution of an electronic mainboard, but also volatilize and atomize and even influence some important electronic elements, so that the heat-conducting interface material of the acrylic acid non-silicon system does not contain the micromolecular silicone oil D3-D20, does not volatilize the silicone oil, and can solve the problem.
Compared with the conventional 80-120 ℃ thermal polymerization and curing molding process for preparing the acrylic matrix resin and the heat-conducting gasket, the UV process can realize polymerization and curing molding at 25-40 ℃, obviously has low energy consumption and meets the requirements of the current green production process. Domestic and foreign companies such as: patents CN200580019276, CN200580023169 and CN200780039654 of 3M company, and patent CN201580023468 of direhde company, etc. successively disclose preparation methods of UV-cured acrylic thermal conductive pads, and acrylic polymers used in these patents have poor polymerization controllability, explosive polymerization and low production efficiency; meanwhile, the defects of low addition amount of heat-conducting particles, low heat conductivity coefficient, no more than 2mm thickness of the heat-conducting fin and the like exist.
Disclosure of Invention
In order to solve the above technical problems, a first aspect of the present invention provides an acrylic thermal conductive composition comprising 55 to 140 parts by weight of a thermal conductive filler; 1-15 parts of an acrylic polymer; 1-10 parts of (methyl) acrylic acid monomer; 0.01-0.5 part of polyfunctional (methyl) acrylate; 0.01-1 part of initiator.
As a preferred technical scheme, the heat-conducting filler comprises 0-140 parts of modified heat-conducting powder and 0-140 parts of unmodified heat-conducting powder; wherein the modified heat-conducting powder is not 0 weight part.
As a preferable technical scheme, the particle size of the heat-conducting filler is 0.1-90 μm.
As a preferred technical scheme, the preparation method of the modified heat-conducting powder comprises the following steps: modifying the heat-conducting powder under a plasma gas source.
As a preferred embodiment, the viscosity of the acrylic polymer is 200-.
As a preferred embodiment, the method for preparing the acrylic polymer comprises the following steps: according to the mass percentage, 95-99.8 percent of acrylic acid based monomer, 0.01-1 percent of UV initiator and 0.01-1 percent of regulator are evenly mixed and polymerized in a UV continuous pipeline polymerization device to obtain the acrylic polymer.
As a preferred embodiment, the method for preparing the acrylic polymer comprises the following steps: according to the mass percentage, 95 to 99.8 percent of acrylic acid based monomer, 0.01 to 1 percent of UV initiator and 0.01 to 1 percent of regulator are evenly mixed and polymerized in a UV continuous pipeline polymerization device, the flow rate of a pipeline is 1 to 3kg/min, the light intensity is 200-600mW/cm2The length of the pipeline polymerizer is 400-800mm, and the polymerization is carried out after the polymerization is finishedStirring for 20-40min to obtain the acrylic polymer.
The second aspect of the present invention provides a thermally conductive sheet obtained by subjecting the acrylic thermally conductive composition to calendar forming and UV forming.
As a preferable technical solution, the heat conductive sheet is formed by subjecting the acrylic heat conductive composition to calender molding to form a belt-shaped sheet having a thickness of 0.2 to 4.5mm, and then continuously passing through a UV molding zone: the illumination intensity is 0.1-10mW/cm2Time is 30-100 s; UV forming two areas: the UV illumination intensity is 10-100mW/cm2Time 30-100s, UV forming three zones: the illumination intensity is 100-600mW/cm2Time 100-.
As a preferable technical scheme, the UV light source adopts a long-wave type LED cold light source, and the wavelength is 400-600 nm.
Has the advantages that: by the special technical process and the method, the heat-conducting fin with the thickness of 0.2-2mm and the heat-conducting fin with the ultrahigh thickness of 2-4.5mm can be prepared, and the heat-conducting fin is low in cost, zero in VOC and ultra-soft, and the application range of the heat-conducting fin is expanded. The preparation method of the acrylic acid heat-conducting composition is a continuous production, energy-saving and emission-reducing green production process, and has remarkable process innovation. The composition and the heat conducting sheet thereof do not contain additives such as solvent, halogen-free flame retardant and the like, realize zero VOC emission and V0-grade flame retardance, have the characteristics of no toxicity, no harm, safety, environmental protection and the like, and meet the requirements of European and American laws and regulations. According to various embodiments, the performance parameters are as follows: coefficient of thermal conductivity: 1.0-4.0W/mK, hardness: 30-80Shore OO; compression ratio: 20-60% @2MPa @60 mm/min; flame retardancy: UL-94V0, halogen-free; temperature resistance: -40 to 120 ℃.
Drawings
FIG. 1 is a schematic view of a UV continuous line polymerization apparatus;
fig. 2 is a schematic view of a device for calendering and UV-molding a thermally conductive sheet.
Detailed Description
In order to solve the above problems, the present invention provides an acrylic thermal conductive composition comprising, by weight, 55 to 140 parts of a thermal conductive filler; 1-15 parts of an acrylic polymer; 1-10 parts of (methyl) acrylic acid monomer; 0.01-0.5 part of polyfunctional (methyl) acrylate; 0.01-1 part of initiator.
In some embodiments, the thermally conductive filler comprises 0 to 140 parts of modified thermally conductive powder and 0 to 140 parts of unmodified thermally conductive powder; wherein the modified heat-conducting powder is not 0 weight part. Preferably, the heat conducting filler comprises 5-50 parts of modified heat conducting powder and 40-90 parts of unmodified heat conducting powder.
The particle size of the heat-conducting filler is 0.1-90 μm. The heat-conducting filler refers to a material added in the matrix to increase the heat conductivity of the matrix, and includes but is not limited to ceramic materials, metals, metal oxides, metal hydroxides, and carbon materials; examples of the ceramic material include boron nitride, aluminum nitride, silicon carbide, and silicon dioxide; examples of the metal include nickel, copper, aluminum, titanium, gold, and silver; examples of the metal oxide include magnesium oxide, aluminum oxide, titanium oxide, iron oxide, and zirconium oxide; examples of the carbon material include graphene, carbon fiber, carbon nanotube, and carbon nanofoam; examples of the metal hydroxide include aluminum hydroxide and magnesium hydroxide.
In some embodiments, the preparation method of the modified heat-conducting powder comprises the following steps: modifying the heat-conducting powder under a plasma gas source. Preferably, the modification condition is 800-. Preferably, the particle size of the heat-conducting powder for modification is 0.3-50 μm. Further preferably, the particle size of the thermal conductive powder for modification is 0.3 to 50 μm. More preferably, the particle size of the thermal conductive powder for modification is 0.3-10 μm. More preferably, the particle size of the thermal conductive powder for modification is 0.3-5 μm.
The plasma gas source comprises at least one of (meth) acrylic acid, alkyl (meth) acrylate, and siloxane. Preferably, the plasma gas source comprises at least one of acrylic acid, methacrylic acid, hydroxyethyl acrylate, hydroxypropyl acrylate, vinylsilyltrimethoxysilane, vinylmethyldimethoxysilane, vinyldimethylmonomethoxysilane, vinylsilyltriethoxysilane, vinylmethyldiethoxysilane and vinyldimethylmonoethoxysilane, preferably acrylic acid, hydroxyethyl acrylate and vinylmethyldimethoxysilane.
In some embodiments, the acrylic polymer has a viscosity of 200-20000 cP. The test temperature was 25 ℃. Preferably, the viscosity of the acrylic polymer is 2000-10000 cP; in some preferred embodiments, the acrylic polymers include those having viscosities of 3000-5000cP and those having viscosities of 9000-10000 cP. In some preferred embodiments, the viscosity of the acrylic polymer is 2000-5000 cP.
The preparation method of the acrylic polymer comprises the following steps: according to the mass percentage, 95-99.8 percent of acrylic acid based monomer, 0.01-1 percent of UV initiator and 0.01-1 percent of regulator are evenly mixed and polymerized in a UV continuous pipeline polymerization device to obtain the acrylic polymer.
Preferably, the preparation method of the acrylic polymer comprises the following steps: according to the mass percentage, 95 to 99.8 percent of acrylic acid based monomer, 0.01 to 1 percent of UV initiator and 0.01 to 1 percent of regulator are evenly mixed and polymerized in a UV continuous pipeline polymerization device, the flow rate of a pipeline is 1 to 3kg/min, the light intensity is 200-600mW/cm2The length of the pipeline polymerizer is 400-800mm, and the acrylic polymer is obtained after the polymerization is finished and the stirring is carried out for 20-40 min.
The acrylic-based monomer includes at least one of monofunctional alkyl (meth) acrylate, a (meth) acryl monomer, and a vinyl ether (meth) acrylate monomer. Wherein the alkyl (meth) acrylate includes methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, isobutyl (meth) acrylate, n-pentyl (meth) acrylate, isoamyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl acrylate, n-heptyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, n-dodecyl (meth) acrylate, isomyristyl (meth) acrylate, iso-decyl (meth) acrylate, n-dodecyl (meth) acrylate, iso-decyl (meth) acrylate, iso-butyl (meth) acrylate, iso-pentyl (meth) acrylate, iso-hexyl (meth) acrylate, iso-octyl (meth) acrylate, iso-decyl (meth) acrylate, iso-octyl (meth) acrylate, iso-decyl acrylate, iso-octyl (meth) acrylate, iso-dodecyl (meth) acrylate, iso-butyl acrylate, iso-octyl (meth) acrylate, iso-dodecyl (meth) acrylate, iso-butyl acrylate, iso-butyl acrylate, iso-butyl acrylate, iso-butyl acrylate, iso, At least one of n-tridecyl (meth) acrylate, n-tetradecyl (meth) acrylate, n-stearyl (meth) acrylate, isostearyl (meth) acrylate, and n-lauryl (meth) acrylate; the vinyl ether (meth) acrylate monomer comprises 2- (2-ethyleneoxyethoxy) ethyl (meth) acrylate, 2-ethyleneoxyethyl (meth) acrylate, 3-ethyleneoxyethyl (meth) acrylate, 2-ethyleneoxypropyl (meth) acrylate, 1-methyl-2-ethyleneoxyethyl (meth) acrylate, 4-ethyleneoxybutyl (meth) acrylate, at least one of 6-vinyloxyhexyl (meth) acrylate, 4-vinyloxycyclohexyl (meth) acrylate, 4-vinyloxymethylcyclohexyl methyl (meth) acrylate, 2- (2-vinyloxyisopropoxy) propyl (meth) acrylate, and 2- {2- (2-vinyloxyethoxy) ethoxy } ethyl (meth) acrylate.
In the present application, the flexibility of the polymer can be improved by selecting C5-C18 alkyl (meth) acrylates, which may be branched or linear, C5-C18 alkyl.
The UV initiator is not particularly limited, and may be any initiator that can generate radicals under the action of UV light to initiate polymerization of monomers without affecting the object of the present invention; for example, benzophenone series, benzoin alkyl ether series, benzildimethyl ketal series, α -hydroxy ketone series, acylphosphine oxide series; the UV initiator may BE either self-made or commercially available, and commercially available commercial models include, but are not limited to, 100, 127, 150, 184, 250, 369, 500, 651, 754, 784, 819DW, 907, 1173, 1490, 1700, 1800, 1850, 2000, 2959, 4265, BE, BMS, DBK, MBF, TPO, DEAP, DMPA, DMBK, TEPO, TPO-L; preferably, the UV initiator is selected from at least one of 819, 907(CAS number: 71868-10-5), 651.
In some embodiments, the modifier comprises at least one of a thiol compound, a thioester compound, an alkene compound; the thiol compound comprises at least one of 1-dodecanethiol, ethyl hexanol 3-mercaptopropionate (EHMPP), 2-dimethylpropane-1, 3-dithiol, pentaerythritol tetrakis (3-mercaptobutyrate); the thioester compound comprises at least one of trimethylolpropane trithiopropionate, dipentaerythritol pentathioglycolate and dipentaerythritol hexathioglycolate; the alkene compound comprises at least one of alpha-methyl styrene linear dimer and 2, 4-diphenyl-4-methyl-1-pentene; preferably, the regulator is 3-mercaptopropionic acid ethyl hexanol ester or alpha-methyl styrene linear dimer.
The (meth) acrylic monomer includes at least one of monofunctional alkyl (meth) acrylate, a (meth) acryl monomer, and a vinyl ether (meth) acrylate monomer. Wherein the alkyl (meth) acrylate includes methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, isobutyl (meth) acrylate, n-pentyl (meth) acrylate, isoamyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl acrylate, n-heptyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, n-dodecyl (meth) acrylate, isomyristyl (meth) acrylate, iso-decyl (meth) acrylate, n-dodecyl (meth) acrylate, iso-decyl (meth) acrylate, iso-butyl (meth) acrylate, iso-pentyl (meth) acrylate, iso-hexyl (meth) acrylate, iso-octyl (meth) acrylate, iso-decyl (meth) acrylate, iso-octyl (meth) acrylate, iso-decyl acrylate, iso-octyl (meth) acrylate, iso-dodecyl (meth) acrylate, iso-butyl acrylate, iso-octyl (meth) acrylate, iso-dodecyl (meth) acrylate, iso-butyl acrylate, iso-butyl acrylate, iso-butyl acrylate, iso-butyl acrylate, iso, At least one of n-tridecyl (meth) acrylate, n-tetradecyl (meth) acrylate, n-stearyl (meth) acrylate, isostearyl (meth) acrylate, and n-lauryl (meth) acrylate; the vinyl ether (meth) acrylate monomer comprises 2- (2-ethyleneoxyethoxy) ethyl (meth) acrylate, 2-ethyleneoxyethyl (meth) acrylate, 3-ethyleneoxyethyl (meth) acrylate, 2-ethyleneoxypropyl (meth) acrylate, 1-methyl-2-ethyleneoxyethyl (meth) acrylate, 4-ethyleneoxybutyl (meth) acrylate, at least one of 6-vinyloxyhexyl (meth) acrylate, 4-vinyloxycyclohexyl (meth) acrylate, 4-vinyloxymethylcyclohexyl methyl (meth) acrylate, 2- (2-vinyloxyisopropoxy) propyl (meth) acrylate, and 2- {2- (2-vinyloxyethoxy) ethoxy } ethyl (meth) acrylate.
The multifunctional (meth) acrylate comprises at least one of multifunctional alkyl (meth) acrylate, multifunctional (meth) acryloxy isocyanurate and multifunctional (meth) acrylate phosphate; as the polyfunctional alkyl (meth) acrylate, there may be mentioned ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 1, 3-butanediol di (meth) acrylate, 1, 4-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, 1, 9-nonanediol di (meth) acrylate; trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate; as the polyfunctional (meth) acryloyloxy isocyanurate, tris (acryloyloxyethyl) isocyanurate; as the multifunctional (meth) acrylic acid phosphate, 2-hydroxyethyl methacrylate phosphate, ethylene glycol methacrylate phosphate and dodecyl acrylate phosphate can be exemplified. Preferably, the multifunctional (meth) acrylate is at least one selected from the group consisting of polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, and multifunctional (meth) acrylate phosphate.
The initiator is not particularly limited, and may be one capable of generating radicals under the action of UV light to initiate polymerization of the monomer without affecting the object of the present invention; for example, benzophenone series, benzoin alkyl ether series, benzildimethyl ketal series, α -hydroxy ketone series, acylphosphine oxide series; the initiator may BE either self-made or commercially available, and commercially available commercial models include, but are not limited to, 100, 127, 150, 184, 250, 369, 500, 651, 754, 784, 819DW, 907, 1173, 1490, 1700, 1800, 1850, 2000, 2959, 4265, BE, BMS, DBK, MBF, TPO, DEAP, DMPA, DMBK, TEPO, TPO-L; preferably, the initiator is selected from at least one of 819, 907, 651.
As a preferred embodiment, the acrylic thermal conductive composition further comprises 0.1 to 10 parts by weight of a functional additive. The functional auxiliary agent comprises at least one of a dispersant, a halogen-free flame retardant, an antioxidant, a plasticizer, a stabilizer and a toughening agent; the functional auxiliary agent can be prepared by self or purchased; for example, the vendors of dispersants include, but are not limited to, BYK, TEGO, EFKA, luobu, courtesy; the commercial models of the dispersing agent can be exemplified by BYK-111, BYK-9076, Tego 740W, Solsperse 27000, EFKA4010 and FA-196; preferably, the dispersant is at least one of BYK-111, BYK-9076 and FA-196.
The halogen-free flame retardant comprises at least one of liquid phosphate flame retardant and nitrogen flame retardant; the phosphate-based flame retardant includes, but is not limited to, at least one of trimethyl phosphate (TMP), triethyl phosphate (TEP), tributyl phosphate (TBP), trioctyl phosphate (TOP), tributoxyethyl phosphate (TBEPP), triphenyl phosphate (TPP), tricresyl phosphate (TCP), cresyldiphenyl phosphate (CDP), trixylenyl phosphate (TXP), triisopropylphenyl phosphate (IPPP), diphenylisodecyl phosphate (DPDP), diphenylisooctyl phosphate (DPOP), phenol phosphate derivatives (e.g., BDP, RDP, XDP), phosphorus nitrogen derivatives (HPTCP), red phosphorus, albino red phosphorus, ammonium polyphosphate (APP), melamine resin (MF), phosphaphenanthrene-based Derivatives (DOPO); the nitrogen-based flame retardant includes, but is not limited to, triazine and its derivatives, melamine.
The antioxidant can delay or inhibit the polymer oxidation process, thereby preventing the aging of the polymer and prolonging the service life of the polymer; the antioxidant comprises peroxide decomposition type antioxidant, free radical scavenging type antioxidant and metal deactivation type antioxidant; such as zinc dialkyldithiophosphate, zinc dialkyldithiocarbamate, N-phenyl-alpha-naphthylamine, alkylphenothiazine, benzotriazole derivatives, mercaptobenzothiazole derivatives. In some embodiments, the commodity model number includes at least one of 1010, 168, 1520, 1726, 126, 245, 1076, B255. Antioxidant 168 is referred to herein as tris [ 2.4-di-tert-butylphenyl ] phosphite.
The plasticizer can weaken the secondary valence bonds among resin molecules, increase the mobility of the resin molecular bonds, reduce the crystallinity of the resin molecules, increase the plasticity of the resin molecules and enhance the flexibility of the resin molecules; the plasticizer comprises at least one of aliphatic dibasic acid ester, fatty acid ester, benzene polyacid ester, polyol ester, epoxy hydrocarbon, alkyl sulfonate and poly alpha-olefin resin.
The preparation method of the acrylic acid heat-conducting composition comprises the following steps: stirring and kneading the heat-conducting filler, the acrylic polymer, (methyl) acrylic acid monomer, polyfunctional group (methyl) acrylate and the initiator.
The invention provides a heat-conducting fin which is obtained by carrying out calendaring molding and UV molding on an acrylic heat-conducting composition.
Preferably, the heat conductive sheet is formed by subjecting the acrylic heat conductive composition to calender molding to form a strip-shaped sheet having a thickness of 0.2 to 4.5mm, and then continuously passing through a UV molding zone: the illumination intensity is 0.1-10mW/cm2Time is 30-100 s; UV forming two areas: the UV illumination intensity is 10-100mW/cm2Time 30-100s, UV forming three zones: the illumination intensity is 100-600mW/cm2Time 100-.
Preferably, the UV light source adopts a long-wave type LED cold light source, and the wavelength is 400-600 nm.
Preferably, the UV light sources of the first UV forming area, the second UV forming area and the third UV forming area are distributed in a vertically symmetrical mode.
The obtained heat conducting sheet is die-cut into heat conducting gaskets with different dimensions according to the requirement.
The method has the advantages that a new chemical group is formed through the interaction of the plasma gas source and the surface of the heat-conducting powder, and the wetting degree of the surface of the heat-conducting powder is improved; meanwhile, gaps are easy to generate when the heat-conducting powder with larger grain diameter is filled in an acrylic resin matrix, and the addition of the heat-conducting powder with smaller grain diameter and the modified heat-conducting powder can play a role in filling the gaps for many times, so that a high-degree heat-conducting network chain is promoted to be formed, and the heat-conducting coefficient reaches 1-4W/(m K); however, the mechanical properties of the acrylic acid heat-conducting composition can be affected due to the excessive heat-conducting filler, and a plurality of physically adsorbed interface weak layers can be formed on the surface of the modified heat-conducting powder; the heat conducting powder modified by a specific method and the UV light source with the wavelength of 400-600nm are added, so that the compression rate of the obtained heat conducting sheet is 20-60%, the heat conducting sheet can be tightly attached between the heating element and the radiator even if the heating element is rough or bent, and air is limited from entering a gap.
The present invention will be specifically described below by way of examples. It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and that the insubstantial modifications and adaptations of the present invention by those skilled in the art based on the above disclosure are still within the scope of the present invention.
In addition, the starting materials used are all commercially available, unless otherwise specified.
Examples
1. Preparation of acrylic acid polymers
Preparation of acrylic Polymer (designated PA-1): 100kg of isooctyl acrylate, 10kg of acrylic acid, 9070.2 kg of UV initiator and 0.1kg of regulator 3-ethyl hexyl mercaptopropionate are uniformly stirred in a premixing kettle at 100rpm for 30min, and then polymerized in a UV continuous pipeline polymerization device (shown in figure 1), a metering pump is started to adjust the flow rate of a pipeline to be 2kg/min, and the light intensity is 300mW/cm2The length of the pipeline polymerizer is 600mm, stirring and cooling are continued for 30min after the polymerization is finished, and the viscosity of the acrylic polymer PA-1 is tested to be 4000cP +/-500 cP.
Preparation of acrylic Polymer (designated PA-2): 100kg of isooctyl acrylate, 10kg of acrylic acid, 9070.2 kg of UV initiator and 0.1kg of regulator 3-ethyl hexyl mercaptopropionate are uniformly stirred in a premixing kettle at 100rpm for 30min, and then polymerized in a UV continuous pipeline polymerization device, a metering pump is started to adjust the flow rate of a pipeline to be 2kg/min, and the light intensity is 600mW/cm2The length of the pipeline polymerizer is 600mm, stirring and cooling are continued for 30min after the polymerization is finished, and the viscosity of the acrylic polymer PA-2 is tested to be 10000cP +/-500 cP.
Preparation of acrylic Polymer (designated PA-3): 100kg of isooctyl acrylate, 10kg of acrylic acid and a UV initiator9070.2 kg and 0.1kg of ethyl hexanol 3-mercaptopropionate as a regulator are uniformly stirred in a premixing kettle at 100rpm for 30min, and then polymerized in a UV continuous pipeline polymerization device, a metering pump is started to adjust the flow rate of a pipeline to be 1kg/min, and the light intensity is 300mW/cm2The length of the pipeline polymerizer is 600mm, stirring and cooling are continued for 30min after the polymerization is finished, and the viscosity of the acrylic polymer PA-3 is tested to be 9000cP +/-500 cP.
Preparation of acrylic Polymer (designated PA-4): 100kg of lauryl acrylate, 10kg of acrylic acid, 9070.2 kg of UV initiator and 0.1kg of regulator 3-ethyl hexyl mercaptopropionate are uniformly stirred in a premixing kettle at 100rpm for 30min, and then polymerized in a UV continuous pipeline polymerization device, a metering pump is started to adjust the flow rate of a pipeline to be 2kg/min, and the light intensity is 300mW/cm2The length of the pipeline polymerizer is 600mm, stirring and cooling are continued for 30min after the polymerization is finished, and the viscosity of the acrylic polymer PA-4 is tested to be 2500cP +/-500 cP.
Preparation of acrylic Polymer (designated PA-5): 50kg of isooctyl acrylate, 50kg of lauryl acrylate, 10kg of acrylic acid, 9070.2 kg of UV initiator and 0.1kg of regulator 3-ethyl hexyl mercaptopropionate are uniformly stirred in a premixing kettle at 100rpm for 30min, and then polymerized in a UV continuous pipeline polymerization device, a metering pump is started to regulate the flow rate of a pipeline to be 2kg/min, and the light intensity is 300mW/cm2The length of the pipeline polymerizer is 600mm, stirring and cooling are continued for 30min after the polymerization is finished, and the viscosity of the acrylic polymer PA-5 is tested to be 3000cP +/-500 cP.
Preparation of acrylic Polymer (designated PA-6): 50kg of isooctyl acrylate, 50kg of lauryl acrylate, 10kg of acrylic acid, 9070.2 kg of UV initiator and 0.1kg of regulator 3-ethyl hexyl mercaptopropionate are uniformly stirred in a premixing kettle at 100rpm for 30min, and then polymerized in a UV continuous pipeline polymerization device, a metering pump is started to adjust the flow rate of a pipeline to be 1.7kg/min, and the light intensity is 850mW/cm2The length of the pipeline polymerizer is 600mm, stirring and cooling are continued for 30min after the polymerization is finished, and the viscosity of the acrylic polymer PA-5 is tested to be 25000cP +/-500 cP.
2. Preparation of modified heat-conducting powder
Preparing acrylic acid modified aluminum nitride heat-conducting powder: 10kg of aluminum nitride heat-conducting powder is modified under the condition of a plasma gas source acrylic acid, wherein the modification condition is that the power is 1000W, the vacuum degree is 10bar, and the treatment time is 20 min.
The specific implementation mode of the preparation of the acrylic acid modified aluminum oxide heat-conducting powder is the same as that of the acrylic acid modified aluminum nitride heat-conducting powder.
Preparation of vinylmethyldimethoxysilane modified aluminum nitride heat-conducting powder: 10kg of aluminum nitride heat-conducting powder is modified under the condition of a plasma gas source vinyl methyl dimethoxy silane, wherein the modification condition is that the power is 1000W, the vacuum degree is 10bar, and the treatment time is 20 min.
The specific implementation mode of preparing the vinylmethyldimethoxysilane modified aluminum oxide heat-conducting powder is the same as that of preparing the vinylmethyldimethoxysilane modified aluminum nitride heat-conducting powder.
Preparing hydroxyethyl acrylate modified aluminum nitride heat-conducting powder: modifying 10kg of aluminum nitride heat-conducting powder under the condition of a plasma gas source hydroxyethyl acrylate, wherein the modification condition is that the power is 1000W, the vacuum degree is 10bar, and the treatment time is 20 min.
The specific implementation mode of preparing the hydroxyethyl acrylate modified aluminum oxide heat-conducting powder is the same as that of preparing the hydroxyethyl acrylate modified aluminum nitride heat-conducting powder.
3. Preparation of acrylic acid heat-conducting composition and heat-conducting sheet
Example 1
Acrylic polymer PA-19 kg, acrylic polymer PA-24 kg, isooctyl acrylate 5kg, BYK-1110.5 kg, 2-hydroxyethyl methacrylate phosphate (HEMAP)0.3kg, antioxidant 1680.2 kg, flame retardant TCP 2kg, plasticizer DOZ (manufacturer: American Avient)3kg, 1 μm acrylic modified aluminum nitride 5kg, 5 μm acrylic modified alumina 30kg, 10 μm boron nitride 5kg, 10 μm aluminum hydroxide 36kg, initiator 9070.05 kg, and strongly stirring and kneading for 60min in a planetary stirrer under vacuum to obtain the acrylic heat-conducting composition.
Preparing a heat conducting sheet: the acrylic heat-conducting composition is subjected to calendaring molding to prepare a strip-shaped sheet with the thickness of 0.2mm, and then the strip-shaped sheet continuously passes through a UV molding area: the illumination intensity is 0.5mW/cm2Time 30 s; UV forming two areas: the UV illumination intensity is 20mW/cm2Time of day30s, UV Forming three-zone: the illumination intensity is 300mW/cm2And time 100 s. The UV light source adopts a long-wave LED cold light source with the wavelength of 460 nm. The UV light sources of the UV forming first area, the UV forming first area and the UV forming first area are distributed in an up-and-down symmetrical mode (see figure 2).
Example 2
Acrylic polymer PA-18 kg, acrylic polymer PA-35 kg, isooctyl acrylate 5kg, BYK-1110.5 kg, 2-hydroxyethyl methacrylate phosphate (HEMAP)0.3kg, antioxidant 1680.2 kg, flame retardant TCP 2kg, toughening agent DOZ 3kg, 1 μm hydroxyethyl acrylate modified aluminum nitride 5kg, 5 μm acrylic acid modified aluminum oxide 30kg, 10 μm boron nitride 5kg, 10 μm aluminum hydroxide 36kg and initiator 9070.5 kg, and strongly stirring and kneading for 60min in a planetary stirrer under vacuum to obtain the acrylic heat-conducting composition.
Preparing a heat conducting sheet: the acrylic heat-conducting composition is subjected to calendaring molding to prepare a strip-shaped sheet with the thickness of 0.2mm, and then the strip-shaped sheet continuously passes through a UV molding area: the illumination intensity is 0.5mW/cm2Time 30 s; UV forming two areas: the UV illumination intensity is 20mW/cm2Time 30s, UV forming three zone: the illumination intensity is 200mW/cm2And time 100 s. The UV light source adopts a long-wave LED cold light source with the wavelength of 460 nm. The UV light sources of the UV forming first area, the UV forming first area and the UV forming first area are distributed in an up-and-down symmetrical mode.
Example 3
Acrylic polymer PA-43 kg, acrylic polymer PA-52 kg, lauryl acrylate 3kg, dispersant BYK-1110.5 kg, 2-hydroxyethyl methacrylate phosphate (HEMAP)0.3kg, antioxidant 1680.2 kg, flame retardant TCP 2kg, toughening agent M (dimethyl terephthalate) 3kg, 1 μ M acrylic modified aluminum nitride 1kg, 3 μ M vinyl methyl dimethoxy silane modified aluminum oxide 20kg, 10 μ M boron nitride 3kg, 30 μ M aluminum hydroxide 24kg, initiator 9070.5 kg, and strongly stirring and kneading for 60min in a planetary stirrer under vacuum to obtain the acrylic heat-conducting composition.
Preparing a heat conducting sheet: the acrylic heat-conducting composition is subjected to calendaring molding to prepare a strip-shaped sheet with the thickness of 4.5mm, and then the strip-shaped sheet continuously passes through a UV molding area:the illumination intensity is 10mW/cm2Time 60 s; UV forming two areas: the UV illumination intensity is 50mW/cm2Time 40s, UV forming three zones: the illumination intensity is 300mW/cm2And time 180 s. The UV light source adopts a long-wave LED cold light source with the wavelength of 460 nm. The UV light sources of the UV forming first area, the UV forming first area and the UV forming first area are distributed in an up-and-down symmetrical mode.
Comparative example 1
A heat conductive acrylic composition and a heat conductive gasket, the embodiment is the same as example 3, except that "1 kg of 1 μm acrylic acid modified aluminum nitride and 20kg of 3 μm vinylmethyldimethoxysilane modified alumina" are replaced with "1 kg of 1 μm aluminum nitride and 20kg of 3 μm alumina".
Comparative example 2
An acrylic heat-conducting composition and a heat-conducting gasket, the specific embodiment is the same as example 3, except that PA-5 is replaced by PA-6.
Comparative example 3
An acrylic thermal conductive composition and a thermal conductive pad, the specific embodiment of which is the same as example 3, except that the wavelength of the UV light source is 300 nm.
Comparative example 4
The specific implementation mode of the acrylic acid heat-conducting composition and the heat-conducting gasket is the same as that in example 3, and the difference is that the preparation of the heat-conducting sheet is as follows: the acrylic heat-conducting composition is subjected to calendaring molding to prepare a strip-shaped sheet with the thickness of 4.5mm, and then the strip-shaped sheet continuously passes through a UV molding second area: the UV illumination intensity is 50mW/cm2Time 40s, UV forming three zones: the illumination intensity is 300mW/cm2And time 180 s. The UV light source adopts a long-wave LED cold light source with the wavelength of 460 nm. And UV light sources of the UV forming second area and the UV forming third area are distributed in an up-and-down symmetrical mode.
Comparative example 5
The specific implementation mode of the acrylic acid heat-conducting composition and the heat-conducting gasket is the same as that in example 3, and the difference is that the preparation of the heat-conducting sheet is as follows: the acrylic heat-conducting composition is subjected to calendaring molding to prepare a strip-shaped sheet with the thickness of 4.5mm, and then the strip-shaped sheet continuously passes through a UV molding area: the illumination intensity is 10mW/cm2When at the same timeFor 60 s; and (4) UV forming three zones: the illumination intensity is 300mW/cm2And time 180 s. The UV light source adopts a long-wave LED cold light source with the wavelength of 460 nm. And UV light sources of the UV forming first area and the UV forming third area are distributed in an up-and-down symmetrical mode.
Performance testing
And (3) testing the heat conductivity coefficient: reference standard ASTM D5470.
And (3) compression ratio testing: the compression rate is 60mm/min, and the compression rate is calculated when the maximum stress reaches 2 MPa.
Figure BDA0002706770550000121
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in other forms, and any person skilled in the art may modify or change the technical content of the above disclosure into equivalent embodiments with equivalent changes, but all those simple modifications, equivalent changes and modifications made to the above embodiments according to the technical spirit of the present invention still belong to the protection scope of the present invention.

Claims (5)

1. A thermally conductive sheet obtained by UV curing an acrylic thermally conductive composition,
the acrylic acid heat-conducting composition comprises 55-140 parts by weight of heat-conducting filler; 1-15 parts of an acrylic polymer; 1-10 parts of (methyl) acrylic acid monomer; 0.01-0.5 part of polyfunctional (methyl) acrylate; 0.01-1 part of initiator;
the acrylic polymer comprises an acrylic polymer with the viscosity of 3000-5000cP and an acrylic polymer with the viscosity of 9000-10000 cP;
the (meth) acrylic monomer comprises at least one of monofunctional alkyl (meth) acrylate, vinyl (meth) acrylate ether-based monomers;
the heat-conducting filler comprises 0-140 parts of modified heat-conducting powder and 0-140 parts of unmodified heat-conducting powder; wherein the modified heat-conducting powder is not 0 weight part; the particle size of the modified heat-conducting powder is 0.3-5 mu m;
the preparation method of the modified heat-conducting powder comprises the following steps: modifying the heat-conducting powder under a plasma gas source; the plasma gas source comprises at least one of (meth) acrylic acid, alkyl (meth) acrylate and siloxane;
the acrylic acid heat-conducting composition is subjected to calendaring molding and UV molding to obtain a heat-conducting sheet; the method comprises the following specific steps: the heat-conducting sheet is manufactured into a strip-shaped sheet with the thickness of 0.2-4.5mm by calendaring the acrylic heat-conducting composition, and then continuously passes through a UV molding area: the illumination intensity is 0.1-10mW/cm2Time is 30-100 s; UV forming two areas: the UV illumination intensity is 10-100mW/cm2Time 30-100s, UV forming three zones: the illumination intensity is 100-600mW/cm2Time 100-;
the UV light source adopts a long-wave LED cold light source, the wavelength is 400-600nm, and the UV light sources of the UV forming first area, the UV forming second area and the UV forming third area are distributed in a vertically symmetrical mode.
2. A thermally conductive sheet obtained by UV-curing the acrylic thermally conductive composition as claimed in claim 1, wherein the thermally conductive filler has a particle size of 0.1 to 90 μm.
3. A thermally conductive sheet obtained by UV curing the acrylic thermally conductive composition as claimed in claim 1, wherein the acrylic polymer is prepared by a method comprising the steps of: according to the mass percentage, 95-99.8 percent of acrylic acid based monomer, 0.01-1 percent of UV initiator and 0.01-1 percent of regulator are evenly mixed and polymerized in a UV continuous pipeline polymerization device to obtain the acrylic polymer.
4. A thermally conductive sheet obtained by UV curing the acrylic thermally conductive composition as claimed in claim 3, wherein the acrylic polymer is prepared by a method comprising the steps of: according to the mass percentage, 95 to 99.8 percent of acrylic acid based monomer, 0.01 to 1 percent of UV initiator and 0.01 to 1 percent of regulator are evenly mixed and polymerized in a UV continuous pipeline polymerization deviceThe flow rate of the pipeline is 1-3kg/min, the light intensity is 200-600mW/cm2The length of the pipeline polymerizer is 400-800mm, and the acrylic polymer is obtained after the polymerization is finished and the stirring is carried out for 20-40 min.
5. A thermally conductive sheet obtained by UV curing the acrylic thermally conductive composition as claimed in claim 1, wherein the multifunctional (meth) acrylate comprises at least one of multifunctional alkyl (meth) acrylate, multifunctional (meth) acryloxyisocyanurate, and multifunctional phosphate (meth) acrylate.
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