CN103146197B - Method for preparing lyophobic heat conduction material with micro-nano core-shell structure - Google Patents
Method for preparing lyophobic heat conduction material with micro-nano core-shell structure Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 32
- 239000011258 core-shell material Substances 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims abstract description 13
- 239000002245 particle Substances 0.000 claims abstract description 102
- 239000002105 nanoparticle Substances 0.000 claims abstract description 80
- 239000011246 composite particle Substances 0.000 claims abstract description 34
- 239000003822 epoxy resin Substances 0.000 claims abstract description 15
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 15
- 229920005989 resin Polymers 0.000 claims abstract description 5
- 239000011347 resin Substances 0.000 claims abstract description 5
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 87
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 78
- 238000006243 chemical reaction Methods 0.000 claims description 77
- 230000015572 biosynthetic process Effects 0.000 claims description 56
- 238000003786 synthesis reaction Methods 0.000 claims description 54
- 239000000243 solution Substances 0.000 claims description 40
- 238000012986 modification Methods 0.000 claims description 35
- 230000004048 modification Effects 0.000 claims description 35
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- 238000001035 drying Methods 0.000 claims description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 24
- 238000005406 washing Methods 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 238000002360 preparation method Methods 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 19
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 17
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 239000003960 organic solvent Substances 0.000 claims description 14
- 238000007711 solidification Methods 0.000 claims description 14
- 230000008023 solidification Effects 0.000 claims description 14
- 239000000725 suspension Substances 0.000 claims description 14
- 235000007164 Oryza sativa Nutrition 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 13
- 235000009566 rice Nutrition 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 239000002699 waste material Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000005119 centrifugation Methods 0.000 claims description 10
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 9
- 239000013543 active substance Substances 0.000 claims description 9
- 229910000077 silane Inorganic materials 0.000 claims description 9
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 8
- 238000010521 absorption reaction Methods 0.000 claims description 8
- XXZNHVPIQYYRCG-UHFFFAOYSA-N trihydroxy(propoxy)silane Chemical compound CCCO[Si](O)(O)O XXZNHVPIQYYRCG-UHFFFAOYSA-N 0.000 claims description 8
- 239000004809 Teflon Substances 0.000 claims description 7
- 229920006362 Teflon® Polymers 0.000 claims description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 229920002050 silicone resin Polymers 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 238000013019 agitation Methods 0.000 claims description 6
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 6
- 238000010907 mechanical stirring Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 230000001681 protective effect Effects 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 238000010790 dilution Methods 0.000 claims description 3
- 239000012895 dilution Substances 0.000 claims description 3
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical group NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- 125000002462 isocyano group Chemical group *[N+]#[C-] 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000003980 solgel method Methods 0.000 claims description 2
- 229960001124 trientine Drugs 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims 1
- 238000011049 filling Methods 0.000 abstract description 5
- 125000000524 functional group Chemical group 0.000 abstract description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 3
- 239000005022 packaging material Substances 0.000 abstract description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract 1
- 239000011859 microparticle Substances 0.000 abstract 1
- 229910052710 silicon Inorganic materials 0.000 abstract 1
- 239000010703 silicon Substances 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 17
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 15
- 230000003075 superhydrophobic effect Effects 0.000 description 13
- 241000209094 Oryza Species 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 10
- 238000000576 coating method Methods 0.000 description 10
- 239000000377 silicon dioxide Substances 0.000 description 9
- 206010013786 Dry skin Diseases 0.000 description 8
- 240000002853 Nelumbo nucifera Species 0.000 description 8
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 8
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 8
- 235000010215 titanium dioxide Nutrition 0.000 description 8
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 7
- 239000002131 composite material Substances 0.000 description 7
- 239000007822 coupling agent Substances 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- 239000004408 titanium dioxide Substances 0.000 description 7
- 235000012239 silicon dioxide Nutrition 0.000 description 6
- 229960001866 silicon dioxide Drugs 0.000 description 6
- 239000004575 stone Substances 0.000 description 6
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical group [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 5
- 239000002114 nanocomposite Substances 0.000 description 5
- 235000013339 cereals Nutrition 0.000 description 4
- 238000007865 diluting Methods 0.000 description 4
- ONJQDTZCDSESIW-UHFFFAOYSA-N polidocanol Chemical compound CCCCCCCCCCCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO ONJQDTZCDSESIW-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
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- 210000001595 mastoid Anatomy 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000011858 nanopowder Substances 0.000 description 2
- 239000011664 nicotinic acid Substances 0.000 description 2
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- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
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- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a method for preparing a lyophobic heat conduction material with a micro-nano core-shell structure. The method comprises the following steps of: preparing micro-nano particles with different particle sizes by adopting a colloidal sol method at first; utilizing organic matters containing special functional groups to wrap the nano particles on microparticles because nano particle surfaces comprise hydroxyls, and thus obtaining composite particles with core-shell structures; and filling the composite particles into epoxy resin or organic silicon resin so as to prepare a packaging material with high thermal conductivity, super hydrophobicity, good heat resistance and thermal mechanical performance. Compared with a conventional particle filling packaging material or thermal interface material, the material has more excellent performances.
Description
Technical field
The present invention relates to a kind of there is the micro-nano composite particles of nucleocapsid structure synthesis and filling epoxy resin or organosilicon in, prepare the preparation method of the excellent property material of super-hydrophobic, high heat conduction.Belong to chemical material field.
Background technology
The preparation of nucleocapsid structure particle realizes people to the design of material structure, composition, combination and optimization, and be the study hotspot of material science, therefore, nucleocapsid structure microballoon has been subjected to increasing concern always.The shell of nucleocapsid structure not only can improve the physics and chemistry character of core, simultaneously the surface effects of shell nanoparticle, quantum size effect and other various physical influences relevant to size make Core-shell structure material be provided with much special character (such as, the chemistry improved and thermostability, higher specific surface area, different magnetomechanics and optical property).Nanoparticle identical or different for two kinds of character and micron particle are made composite particles, all will effectively avoid the agglomeration traits of single nanoparticle, but also the superiority of nanoparticle can be given full play to, improve its result of use.
From thermal conducting path viewpoint, can in order to try with the carrier of a kind of micron particle of very Large stone for formation thermal conducting path, by nanoparticle by absorption or other physics or chemical mode and Large stone micron particle compound, by Nanocomposites at Large stone particle surface.Form the nanoparticle layers of a high heat conduction on macroparticle surface, macroparticle can be conductive particle, also can be low heat conduction or not heat conduction, certainly preferably can heat conduction.The composite particles with nucleocapsid structure of such formation greatly can be saved and reduce nano-powder consumption, also can give full play to the high heat conductance of nanoparticle, improves heat conductivility.
From super-hydrophobic Bionic Design viewpoint, super hydrophobic surface is owing to having huge practical value and wide application prospect, manually prepare super hydrophobic surface and can be used for automotive window, the glass port of buildings and the antifouling of glass outer wall, the surface super hydrophobicization of material can suppress microorganism in the adhesion of body surface, suppress the blood coagulation phenomenon of polymer surfaces, can liquid resistance etc. be reduced for water delivery, oil transportation tube wall.And the research of super hydrophobic surface relates to the multi-door subjects such as chemistry, phytology, materialogy, engineering mechanics.Lotus leaf result of study that is super-hydrophobic to having of occurring in nature, self-cleaning function shows, the ultra-hydrophobicity of lotus leaf surface has two reasons: the wax of lotus leaf surface and special construction.Lotus leaf surface ordered distribution the mastoid process that mean diameter is 5 ~ 9 μm, and each mastoid process surface arrangement has the fine hair of diameter 124nm.The Multi-scale model of the micro-nano that lotus leaf surface is special and the wax of low surface energy make the static contact angle of lotus leaf surface reach 160 °, and roll angle only has 2 °.At present, the method preparing the coating of similar lotus leaf surface structure has template, photolithography, chemical deposition, self-assembly etc.Therefore, according to work and the super-hydrophobic phenomenon of nature of forefathers, super-hydrophobic automatic cleaning surface is by preparing in conjunction with the roughness of hydrophobic chemical substance with surface.
Many techniques and methods that grown up now prepare nucleocapsid structure microballoon from solution.Pyrolytic decomposition, foaming, dispersion polymerization etc. after such as physics, chemical precipitation, sputtering, sol gel, injection.At present, the method synthetic silica cladding titanium dioxide hollow Core-shell structure material of general employing multistep compound, as Imhof [A.F.Demirors, A.Blaaderen and A.Imhof, Synthesis of Eccentric Titania-Silica Core-Shell and Composite Particles, Chem.Mater., Vol.21, No.6, 2009] report by first synthesis of titanium dioxide microballoon, Core-shell structure material is obtained again at Surface coating silicon-dioxide, then the different of titanium dioxide and silicon-dioxide shrinking percentage are in a heated condition utilized, silicon-dioxide-coated titanium dioxide hollow core-shell structural material is obtained by sintering, Ikeda [S.Ikeda, Y.Ikoma, H.Kobayashi, et.al., Encapsulation of titanium (IV) oxide particles in hollow silica for size-selective photocatalytic reactions, Chem.Commun., 2007,3753-3755] report by being sintered at the first coated one deck of titanium dioxide surface the carbon-coating produced by organism, again at carbon-coating Surface coating silicon dioxide layer, then obtain silicon-dioxide-coated titanium dioxide hollow core-shell structural material by high temperature sintering removing carbon-coating.Chinese patent CN102463105A also discloses a kind of one-step synthesis silicon-dioxide-coated titanium dioxide hollow core-shell structural material.
First the present invention adopts the method for collosol and gel to prepare micro-nano granules.Because its surface is containing hydroxyl, nano particle can be coated on micron particle with the organism containing specific functional groups, obtains the composite particles with nucleocapsid structure.
From domestic and international Patent Publication, although there is the report of the preparation method of micro-nano core-shell structure composite particles, as the people such as Shu Hongji report the patent of invention (CN1284525A) of a kind of high hydrophobicity, high thermal conductivity and high-adhesiveness interface coating, in silicone resin solution, add the solia particle through hydrophobization process and silicone couplet, prepare a kind of high hydrophobicity interface coating for the surface treatment of refrigeration-air-conditioning system finned evaporator.But for the material of moisture-proof and high heat conduction demand, adopt and there is the Synthesis and applications that micro-nano core-shell structure fills organic resin have no relevant report.
Summary of the invention
The object of the present invention is to provide nuclear shell structure micro-nano rice composite particles synthesis a kind of simple and easy to control, respond well, workable, and then filling epoxy resin or silicone resin prepare method that is super-hydrophobic, high-heat-conductive composite material.
The present invention utilizes the method for collosol and gel to prepare micro-nano granules.Because its surface is containing hydroxyl, nano particle can be coated on micron particle with the organism containing specific functional groups, obtains the composite particles with nucleocapsid structure.Again composite particles is filled in organic resin and prepares a kind of heat interfacial material with good heat resistance, thermal conductivity, hydrophobicity and thermomechanical property, compare with traditional heat interfacial material and there is more excellent performance.
Key point of the present invention is the preparation of micro-nano core-shell structure, prepares the reaction conditions of nanoparticle and micron particle, the reaction conditions of the reaction conditions of the micro-nano composite particles of synthetic kernel shell structure and the preparation of lyophobic heat conduction material carries out adjusting super-hydrophobic, the high-heat-conductive composite material that control to obtain excellent property to sol-gel method.
The present invention is achieved in that
(1) SiO
2nanoparticle or Al
2o
3the synthesis of nanoparticle
SiO
2the synthesis of nanoparticle: put into 80-120mL ethanol, 5-10mL ammoniacal liquor and 1-5mL water in there-necked flask, after mechanical stirring is even, slowly drips tetraethoxy or positive silicic acid propyl ester 3-8mL, continues stirring reaction; After reaction terminates, centrifugation is also washed, and discards upper strata waste liquid, obtains the SiO of white 10nm-200nm particle diameter
2particle, carries out drying for standby;
Al
2o
3the synthesis of nanoparticle: take 6-15g aluminum isopropylate and be dissolved in Virahol, and add suitable quantity of water and 5-15mL concentrated nitric acid, stirring reaction; After reaction terminates, centrifugation is also washed, and discards upper strata waste liquid, obtains the Al of white 10nm-100nm particle diameter
2o
3particle, carries out drying for standby;
(2) modification SiO
2nanoparticle or Modification on Al
2o
3the synthesis of nanoparticle
Modification SiO
2the synthesis of nanoparticle: by the SiO obtained
2nanoparticle joins in the dichloromethane solution containing silane coupling agent, and the volumetric concentration of silane coupling agent dichloromethane solution is 50%, reacts 8-12h, obtain the SiO of modification under the condition stirred
2nanoparticle white suspension, centrifugation is also washed, and obtains white modification SiO
2nanoparticle, drying for standby;
Modification on Al
2o
3the synthesis of nanoparticle: the silane coupler solution adding dilution in 80-150mL alcohol solvent, the volume ratio of silane coupler solution and ethanol is 1: 15-25, and to drip acid-conditioning solution pH be 2-4, after being hydrolyzed 2-4h under room temperature; By nanometer Al
2o
3join in hydrolyzed silane coupling agent solution, filter after reacting by heating 3-8h, organic solvent washing, obtain Modification on Al
2o
3nanoparticle, vacuum-drying is for subsequent use;
(3) SiO
2the synthesis of micron particle
In reaction vessel, add 80-100mL concentration is 2-8mol/L hydrochloric acid and tensio-active agent, after magnetic agitation is even, pour rapidly 5-15mL tetraethoxy or positive silicic acid propyl ester into, stirring reaction 2-50min at 40-80 DEG C, after then stopping stirring standing 2-24h, filters, wash with water, drying, finally under the air atmosphere of 600 DEG C-1000 DEG C, calcining removes the tensio-active agent do not washed off, obtains the SiO of white 1-10 μm particle diameter
2spheroidal particle;
(4) nuclear shell structure micro-nano rice SiO
2/ SiO
2or micro-nano SiO
2/ Al
2o
3the synthesis of composite particles
First by the SiO of 1-10 μm of particle diameter
2spheroidal particle is dried with the moisture removing particle absorption, then in flask, adds the SiO of 1-10 μm of particle diameter
2spheroidal particle and isocyanic ester, pour organic solvent into and drip dibutyl tin laurate, logical nitrogen removing moisture, protective reaction system is carried out in anhydrous conditions, reaction is terminated after stirring heating reaction 1-24h, with organic solvent washing, then the particle dispersion after washing is formed in organic solvent suspension to carry out next step reaction;
The 1-10 μm of particle diameter SiO of isocyano by surface grafting
2spheroidal particle suspension is poured in reaction vessel, adds modification SiO
2nanoparticle or Modification on Al
2o
3nanoparticle, pours organic solvent into and drips catalyzer, under the condition of logical nitrogen, terminate reaction after reacting by heating 6-10h, by reaction product organic solvent washing, to remove unreacted isocyanic ester, filters, dry;
(5) preparation of lyophobic heat conduction material
Silicone resin or bisphenol A type epoxy resin E-51 are mixed with solidifying agent, catalyzer and micro-nano core-shell structure composite particles, be uniformly mixed under normal temperature, vacuum outgas is steeped, then pour into and scribble releasing agent and in preheated Teflon mould, baking oven is put in a mold at 70-90 DEG C of solidification 1-3h after levelling, be warming up to 110-130 DEG C of solidification 1-2h again, cool to room temperature; Wherein, the mass fraction of silicone resin or bisphenol A type epoxy resin E-51 is 100 parts, and the mass fraction of micro-nano core-shell structure composite particles is 40-80 part.
In step (1), temperature of reaction is 25 DEG C-150 DEG C, and the reaction times is 1-24h.
In step (2), silane coupling agent is the mixing of in kh550, kh560, kh570 any two kinds.
In step (3), concentration of hydrochloric acid is 1-10mol/L, and volume is 1-250ml, and tensio-active agent is CTAB and AEO-9, and tetraethoxy or positive silicic acid propyl ester are 1-250ml, and temperature of reaction is 25-150 DEG C.
Organic solvent in step (4) is dry toluene, and isocyanic ester is the one in TDI or MDI.
In step (4), oil bath reacting by heating temperature is 25-150 DEG C.
In step (5), solidifying agent is triethylene tetramine or polyetheramine, and mass fraction is 10-15 part, and catalyzer is dibutyl tin laurate, and mass fraction is 0.02-7.
In the present invention, the volumetric concentration of ammoniacal liquor is 29-35%, and the mass concentration of the silane coupler solution of dilution is 10-25%.
The present invention adopts bionics principle to design and preparation micro-nano core-shell structure composite particles, filled high polymer material, with a kind of micron particle of Large stone for forming the carrier of thermal conducting path, by the nanoparticle of high heat conductance by absorption or other physics or chemical mode and Large stone micron particle compound, micro-nano core-shell structure composite particles is formed at Large stone particle surface by Nanocomposites, filled high polymer material makes it have efficient passage of heat, and makes matrix material have the super-drainage structure of similar lotus leaf surface.
Relative to the filler simply mixed by particle, the composite particles of nucleocapsid structure can reduce the total amount of nano-powder greatly, cost-saving, can also give full play to the high heat conductance of nanoparticle, improves heat conductivility.The material of micro-nano core-shell structure composite particles potting resin is except improving heat conductivility, and mechanical property, thermotolerance all improve, and has super-hydrophobic (moisture-proof is moistureproof) function.Preparation forms microelectronic packaging material or the heat interfacial material of super-hydrophobic, high heat conduction.Bionic coating when nuclear shell structure micro-nano rice corpuscles content reaches 50% and the static contact angle of water reach 156 °, have super-hydrophobic effect; Thermal conductivity improves 1.62 times that reach pure epoxy resin; And excellent thermomechanical property.
Accompanying drawing explanation
Fig. 1. (a) and (b) is respectively nuclear shell structure micro-nano rice corpuscles SiO
2/ SiO
2, SiO
2/ Al
2o
3infrared spectra (FTIR) figure
Fig. 2. the scanning electron microscope (SEM) photograph (SEM) of nuclear shell structure micro-nano rice corpuscles
Wherein (a) 1-10 μm SiO
2particle; The 100nm SiO of (b) modified
2particle; (c) SiO
2/ SiO
2nuclear shell structure micro-nano rice composite particles; The scanning electron microscope of the larger multiple of (d) composite particles; (e) SiO
2/ Al
2o
3scanning electron microscope (SEM) constitutional diagram of nuclear shell structure micro-nano rice composite particles
Fig. 3. epoxy resin/nuclear shell structure micro-nano rice SiO
2the DSC curve of particle coating
Fig. 4. the coating layer touch angular curve of two kinds of particle different contents
Fig. 5. epoxy resin/SiO
2particle composite material is the storage modulus of 140 DEG C
Embodiment
Embodiment one:
(1) SiO
2nanoparticle or Al
2o
3the synthesis of nanoparticle
SiO
2the synthesis of nanoparticle: put into 80mL ethanol, 5mL ammoniacal liquor and 1mL water in flask, after mechanical stirring is even, slowly drips the TEOS of 3mL, reacts 12h under room temperature; After reaction terminates, the centrifugal and washing of reaction solution for several times, discards upper strata waste liquid, obtains white Nano-meter SiO_2
2particle, drying for standby at 40 ~ 50 DEG C;
Al
2o
3the synthesis of nanoparticle: get 6g aluminum isopropylate and be dissolved in Virahol, and transfer in flask by solution, adds suitable quantity of water and 5mL concentrated nitric acid, reacts 24h at normal temperatures in flask; After reaction terminates, the centrifugal and washing of reaction solution for several times, discards upper strata waste liquid, obtains the Al of white about 100nm
2o
3particle, drying for standby at 80 DEG C.
(2) modification SiO
2nanoparticle or Modification on Al
2o
3the synthesis of nanoparticle
Modification SiO
2the synthesis of nanoparticle: by SiO
2nanoparticle adds in the dichloromethane solution containing silane coupling agent 40%, and the conditioned response 8h stirred, finally obtains the SiO modified
2nanoparticle white suspension, centrifugation is also washed for several times, obtains white SiO
2particle, drying for standby at 40 ~ 50 DEG C;
Modification on Al
2o
3the synthesis of nanoparticle: add coupling agent diluting soln in 80ml alcohol solvent, the volume ratio of silane coupler solution and ethanol is 1: 15, drips acid-conditioning solution pH=2, is hydrolyzed 2h under room temperature; By nanometer Al
2o
3join in hydrolysis coupling agent solution, heating in water bath to 70 DEG C, filter, by toluene wash, in 80 DEG C of vacuum-drying 24h after reaction 3h.
(3) micron SiO
2the synthesis of particle
In flask, add 80mL concentration is 2mol/L hydrochloric acid, 1.6g CTAB and 1.5gAEO-9, after magnetic agitation is even, pour rapidly 5mL tetraethoxy into, stirring reaction 2 minutes at 40 DEG C, after then stopping stirring standing 2h, filters, wash with water for several times, 80 DEG C of dryings, finally under the air atmosphere of 600 DEG C, calcining removes the tensio-active agent do not washed off, obtains the SiO of white 1-10 μm particle diameter
2spheroidal particle.
(4) nuclear shell structure micro-nano rice SiO
2/ SiO
2, SiO
2/ Al
2o
3the synthesis of composite particles
First by micron SiO
2particle oven dry a few hours remove SiO
2the moisture of particle absorption.Then, in flask, a micron SiO is added
2the TDI of particle and 0.1g; pour dry toluene into and drip several dibutyl tin laurates; logical nitrogen removing moisture; protective reaction system is carried out in anhydrous conditions; open mechanical stirrer 200rpm; reaction is terminated, with dry toluene washing several, to carry out next step reaction in redispersion to dry toluene after reacting 1h under room temperature.
By micron SiO
2the dry toluene suspension of particle surface grafting TDI is poured in flask, adds the Nano-meter SiO_2 that surface coupling agent has been modified
2or Al
2o
3particle, pours dry toluene into and drips several triethylamines, and terminate reaction after reacting 6h under room temperature under the condition of logical nitrogen, shift out from oil bath pan, washing removes unreacted TDI for several times, filters, 60 DEG C of dryings.
(5) preparation of lyophobic heat conduction material
By mass fraction by bisphenol A type epoxy resin DGEBA (E-51) 100 parts, 10 parts, solidifying agent, catalyzer 0.02 part, SiO
2micro-nano composite particles 40 parts mixing, be uniformly mixed under normal temperature, vacuum sloughs bubble, then pour into and scribble releasing agent and in preheated Teflon mould, put into 80 DEG C, baking oven solidification 2h in a mold after levelling, then be warmed up to 120 DEG C of solidification 2h, cool to room temperature.
Embodiment two:
(1) SiO
2nanoparticle or Al
2o
3the synthesis of nanoparticle
SiO
2the synthesis of nanoparticle: put into 120mL ethanol, 10mL ammoniacal liquor and 5mL water in flask, after mechanical stirring is even, slowly drips 8mL tetraethoxy, reacts 10h at 40 DEG C; After reaction terminates, the centrifugal and washing of reaction solution for several times, discards upper strata waste liquid, obtains white Nano-meter SiO_2
2particle, drying for standby at 40 ~ 50 DEG C.
100nm Al
2o
3the synthesis of particle: get aluminum isopropylate and be dissolved in Virahol, and solution is transferred in flask, in flask, add water and 15mL concentrated nitric acid, at 40 DEG C, react 16h; After reaction terminates, the centrifugal and washing of reaction solution for several times, discards upper strata waste liquid, obtains the Al of white about 80nm
2o
3particle, drying for standby at 80 DEG C.
(2) modification SiO
2nanoparticle or Modification on Al
2o
3the synthesis of nanoparticle
Modification SiO
2the synthesis of nanoparticle: by the Nano-meter SiO_2 obtained
2particle is added in the dichloromethane solution containing silane coupling agent 60%, and the conditioned response 10h stirred, finally obtains the SiO modified
2nanoparticle white suspension, centrifugation is also washed for several times, obtains white SiO
2particle, drying for standby at 40 ~ 50 DEG C.
Modification on Al
2o
3the synthesis of nanoparticle: add silane coupling agent diluting soln in 150mL alcohol solvent, the volume ratio of silane coupler solution and ethanol is 1: 25, drips acid and regulates aqueous solution pH=4, be hydrolyzed 4h under room temperature; By nanometer Al
2o
3join in hydrolysis coupling agent solution, heating in water bath to 80 DEG C, filter, by toluene wash, in 80 DEG C of vacuum-drying 24h after reaction 4h.
(3) micron SiO
2the synthesis of particle
In flask, add 100mL concentration is 8mol/L hydrochloric acid, 1.8g CTAB and 1.6g AEO-9, after magnetic agitation is even, pour rapidly 15mL tetraethoxy into, stirring reaction 50 minutes at 80 DEG C, after then stopping stirring standing 24h, filters, wash with water for several times, 80 DEG C of dryings, finally under the air atmosphere of 1000 DEG C, calcining removes the tensio-active agent do not washed off, obtains the SiO of white 1-10 μm particle diameter
2spheroidal particle.
(4) nuclear shell structure micro-nano rice SiO
2/ SiO
2or micro-nano SiO
2/ Al
2o
3the synthesis first micron SiO of composite particles
2particle oven dry a few hours remove SiO
2the moisture of particle absorption.Then, in flask, a micron SiO is added
2particle and TDI; pour dry toluene into and drip several dibutyl tin laurates; logical nitrogen removing moisture protective reaction system is carried out in anhydrous conditions; open mechanical stirrer 300rpm; reaction is terminated after being heated to 40 DEG C of reaction 24h; with dry toluene washing several, to carry out next step reaction in redispersion to dry toluene.
By micron SiO
2the dry toluene suspension of particle surface grafting TDI is poured in flask, adds the Nano-meter SiO_2 that surface coupling agent has been modified
2or nanometer Al
2o
3particle, pours dry toluene into and drips several triethylamines, and terminate reaction after being heated to 60 DEG C of reaction 10h under the condition of logical nitrogen, shift out from oil bath pan, washing removes unreacted TDI for several times, filters, 60 DEG C of dryings.
(5) preparation of lyophobic heat conduction material
By mass fraction by bisphenol A type epoxy resin DGEBA (E-51) 100 parts, 15 parts, solidifying agent, catalyzer 7 parts, micro-nano SiO
2composite particles 40 parts mixing, be uniformly mixed under normal temperature, vacuum sloughs bubble, then pour into and scribble releasing agent and in preheated Teflon mould, put into 80 DEG C, baking oven solidification 1h in a mold after levelling, then be warmed up to 120 DEG C of solidification 3h, cool to room temperature.
Embodiment three:
(1) SiO
2nanoparticle or Al
2o
3the synthesis of nanoparticle
10nm-200nm SiO
2the synthesis of nanoparticle: put into 100mL ethanol, 8mL ammoniacal liquor and 3mL water in flask, after mechanical stirring is even, slowly drips 5mL tetraethoxy, reacts 8h at 80 DEG C; After reaction terminates, the centrifugal and washing of reaction solution for several times, discards upper strata waste liquid, obtains white Nano-meter SiO_2
2particle, drying for standby at 40 ~ 50 DEG C.
10-100nmAl
2o
3the synthesis of particle: get 10g aluminum isopropylate and be dissolved in Virahol, and transfer in flask by solution, adds water and 10mL concentrated nitric acid, at 80 DEG C, reacts 10h in flask; After reaction terminates, the centrifugal and washing of reaction solution for several times, discards upper strata waste liquid, obtains white nanometer Al
2o
3particle, drying for standby at 80 DEG C.
(2) modification SiO
2nanoparticle or Modification on Al
2o
3the synthesis of nanoparticle
Modification SiO
2the synthesis of nanoparticle: by SiO
2nanoparticle joins in the dichloromethane solution containing silane coupling agent 50% (volumetric concentration), under the condition stirred, react 8h, finally obtains the SiO modified
2nanoparticle white suspension, centrifugation is also washed for several times, obtains white SiO
2particle, drying for standby at 40 ~ 50 DEG C.
Modification on Al
2o
3the synthesis of nanoparticle: add silane coupling agent diluting soln in 100mL alcohol solvent, the volume ratio of silane coupler solution and ethanol is 1: 20, drips acid and regulates aqueous solution pH=3, be hydrolyzed 3h under room temperature; By nanometer Al
2o
3join in hydrolyzed silane coupling agent solution, heating in water bath to 90 DEG C, filter, by toluene wash, in 80 DEG C of vacuum-drying 24h after reaction 3h.
(3) SiO
2the synthesis of micron particle
90mL4mol/L hydrochloric acid, 1.6g CTAB and 1.5g AEO-9 is added in flask, after magnetic agitation is even, pour rapidly the positive silicic acid propyl ester of 10mL into, stirring reaction number minute at 80 DEG C, then after stopping stirring standing 24h, filter, wash with water for several times, 80 DEG C of dryings, the final tensio-active agent that calcining removing is not washed off under the air atmosphere of 1000 DEG C, obtains white 2-6 μm of particle diameter SiO
2spheroidal particle.
(4) nuclear shell structure micro-nano rice SiO
2/ SiO
2or micro-nano SiO
2/ Al
2o
3the synthesis of composite particles
First micron SiO
2particle oven dry a few hours remove SiO
2the moisture of particle absorption.Then, in flask, a micron SiO is added
2the MDI of particle and 0.11g; pour dry toluene into and drip several dibutyl tin laurates; logical nitrogen removing moisture protective reaction system is carried out in anhydrous conditions; open mechanical stirrer 300rpm; reaction is terminated after being heated to 60 DEG C of reaction 6h; with dry toluene washing several, to carry out next step reaction in redispersion to dry toluene.
By micron SiO
2the dry toluene suspension of particle surface grafting MDI is poured in flask, adds the Nano-meter SiO_2 that surface coupling agent has been modified
2or Al
2o
3particle, pours dry toluene into and drips several triethylamines, and terminate reaction after being heated to 80 DEG C of reaction 6h under the condition of logical nitrogen, shift out from oil bath pan, washing removes unreacted MDI for several times, filters, 60 DEG C of dryings.
(5) preparation of lyophobic heat conduction material
By mass fraction by bisphenol A type epoxy resin DGEBA (E-51) 100 parts, 12 parts, solidifying agent, catalyzer 3 parts, micro-nano core-shell structure SiO
2composite particles 60 parts mixing, be uniformly mixed under normal temperature, vacuum sloughs bubble, then pour into and scribble releasing agent and in preheated Teflon mould, put into 80 DEG C, baking oven solidification 3h in a mold after levelling, then be warmed up to 120 DEG C of solidification 1h, cool to room temperature.
Embodiment four:
(1) SiO
2nanoparticle or Al
2o
3the synthesis of nanoparticle
SiO
2the synthesis of nanoparticle: put into 90mL ethanol, 6mL ammoniacal liquor and 2mL water in flask, after mechanical stirring is even, slowly drips the positive silicic acid propyl ester of 6mL, reacts 12h under room temperature; After reaction terminates, the centrifugal and washing of reaction solution for several times, discards upper strata waste liquid, obtains the SiO of white 10-200nm
2particle, drying for standby at 40 ~ 50 DEG C.
10-100nm Al
2o
3the synthesis of particle: get 8g aluminum isopropylate and be dissolved in Virahol, and solution is transferred in flask, add water in flask, 10mL concentrated nitric acid, stirring reaction, react 12h at 80 DEG C; After reaction terminates, the centrifugal and washing of reaction solution for several times, discards upper strata waste liquid, obtains white nanometer Al
2o
3particle, drying for standby at 80 DEG C.
(2) modification SiO
2nanoparticle or Modification on Al
2o
3the synthesis of nanoparticle
Modification SiO
2the synthesis of nanoparticle: by SiO
2nanoparticle joins in the dichloromethane solution containing silane coupling agent 55% (volumetric concentration), under the condition stirred, react 12h, finally obtains the SiO modified
2nanoparticle white suspension, centrifugation is also washed for several times, obtains white modification SiO
2nanoparticle, drying for standby at 40 ~ 50 DEG C.
Modification on Al
2o
3the synthesis of nanoparticle: add silane coupling agent diluting soln in 120mL alcohol solvent, the volume ratio of silane coupler solution and ethanol is 1: 18, drips acid and regulates aqueous solution pH=3, be hydrolyzed 4h under room temperature; By nanometer Al
2o
3join in hydrolyzed silane coupling agent solution, heating in water bath to 90 DEG C, filter, by toluene wash, in 80 DEG C of vacuum-drying 24h after reaction 8h.
(3) SiO
2the synthesis of micron particle
In flask, add 85mL concentration is 6mol/L hydrochloric acid, 1.6g CTAB and 1.5g AEO-9, after magnetic agitation is even, pour rapidly the positive silicic acid propyl ester of 7mL into, stirring reaction number minute at 50 DEG C, after then stopping stirring standing 24h, filters, wash with water for several times, 80 DEG C of dryings, finally under the air atmosphere of 1000 DEG C, calcining removes the tensio-active agent do not washed off, obtains the SiO of about 10 μm of white particle diameters
2spheroidal particle.
(4) nuclear shell structure micro-nano rice SiO
2/ SiO
2or micro-nano SiO
2/ Al
2o
3the synthesis of composite particles
First micron SiO
2particle oven dry a few hours remove SiO
2the moisture of particle absorption.Then, in flask, a micron SiO is added
2the MDI of particle and 0.11g; pour dry toluene into and drip several dibutyl tin laurates; logical nitrogen removing moisture protective reaction system is carried out in anhydrous conditions; open mechanical stirrer 300rpm; reaction is terminated after being heated to 60 DEG C of reaction 24h; with dry toluene washing several, to carry out next step reaction in redispersion to dry toluene.
By micron SiO
2the dry toluene suspension of particle surface grafting MDI is poured in flask, adds the Nano-meter SiO_2 that surface coupling agent has been modified
2or Al
2o
3or particle, pour dry toluene into and drip several triethylamines, under the condition of logical nitrogen, oil bath terminates reaction after being heated to 80 DEG C of reaction 6h, and shift out from oil bath pan, washing removes unreacted MDI for several times, filters, 60 DEG C of dryings.
(5) preparation of lyophobic heat conduction material
By mass fraction by silicone resin 100 parts, 10 parts, solidifying agent, catalyzer 7 parts, micro-nano core-shell structure SiO
2composite particles 80 parts mixing, be uniformly mixed under normal temperature, vacuum sloughs bubble, then pour into and scribble releasing agent and in preheated Teflon mould, put into 80 DEG C, baking oven solidification 2h in a mold after levelling, then be warmed up to 120 DEG C of solidification 2h, cool to room temperature.
Comparative example:
The preparation of common composite grain filling epoxy resin material
By bisphenol A type epoxy resin DGEBA (E-51), solidifying agent, catalyzer, common Al
2o
3and SiO
2composite grain proportionally mix, be uniformly mixed under normal temperature, vacuum sloughs bubble, then pour into and scribble releasing agent and in preheated Teflon mould, put into 80 DEG C, baking oven solidification 2h in a mold after levelling, then be warmed up to 120 DEG C of solidification 2h, cool to room temperature.
The present invention test nucleocapsid structure composite particles and common composite grain in lyophobic heat conduction material, account for 50% (wt%) under Determination of conductive coefficients report:
Table 1. nucleocapsid structure composite particles or composite grain account for total mass content be 50wt% under the Determination of conductive coefficients result of system
Claims (5)
1. there is a preparation method for the lyophobic heat conduction material of micro-nano core-shell structure, it is characterized in that: adopt the micro-nano SiO of sol-gel method synthetic kernel shell structure
2/ Al
2o
3or micro-nano SiO
2/ SiO
2composite particles, then this composite particles is filled organic resin and obtains lyophobic heat conduction material, the method comprises the following steps:
(1) SiO
2nanoparticle or Al
2o
3the synthesis of nanoparticle
SiO
2the synthesis of nanoparticle: put into 80-120mL ethanol, 5-10mL ammoniacal liquor and 1-5mL water in there-necked flask, after mechanical stirring is even, slowly drips tetraethoxy or positive silicic acid propyl ester 3-8mL, continues stirring reaction; After reaction terminates, centrifugation is also washed, and discards upper strata waste liquid, obtains the SiO of white 10nm-200nm particle diameter
2particle, carries out drying for standby;
Al
2o
3the synthesis of nanoparticle: take 6-15g aluminum isopropylate and be dissolved in Virahol, and add suitable quantity of water and 5-15mL concentrated nitric acid, stirring reaction; After reaction terminates, centrifugation is also washed, and discards upper strata waste liquid, obtains the Al of white 10nm-100nm particle diameter
2o
3particle, carries out drying for standby;
(2) modification SiO
2nanoparticle or Modification on Al
2o
3the synthesis of nanoparticle
Modification SiO
2the synthesis of nanoparticle: by the SiO obtained
2nanoparticle joins in the dichloromethane solution containing silane coupling agent, and the volumetric concentration of silane coupling agent dichloromethane solution is 50%, reacts 8-12h, obtain the SiO of modification under the condition stirred
2nanoparticle white suspension, centrifugation is also washed, and obtains white modification SiO
2nanoparticle, drying for standby;
Modification on Al
2o
3the synthesis of nanoparticle: the silane coupler solution adding dilution in 80-150mL alcohol solvent, the volume ratio of silane coupler solution and ethanol is 1: 15-25, and to drip acid-conditioning solution pH be 2-4, after being hydrolyzed 2-4h under room temperature; By nanometer Al
2o
3join in hydrolyzed silane coupling agent solution, filter after reacting by heating 3-8h, organic solvent washing, obtain Modification on Al
2o
3nanoparticle, vacuum-drying is for subsequent use;
(3) SiO
2the synthesis of micron particle
In reaction vessel, add 80-100mL concentration is 2-8mol/L hydrochloric acid and tensio-active agent, after magnetic agitation is even, pour rapidly 5-15mL tetraethoxy or positive silicic acid propyl ester into, stirring reaction 2-50min at 40-80 DEG C, after then stopping stirring standing 2-24h, filters, wash with water, drying, finally under the air atmosphere of 600 DEG C-1000 DEG C, calcining removes the tensio-active agent do not washed off, obtains the SiO of white 1-10 μm particle diameter
2spheroidal particle;
(4) nuclear shell structure micro-nano rice SiO
2/ SiO
2or micro-nano SiO
2/ Al
2o
3the synthesis of composite particles
First by the SiO of 1-10 μm of particle diameter
2spheroidal particle is dried with the moisture removing particle absorption, then in flask, adds the SiO of 1-10 μm of particle diameter
2spheroidal particle and isocyanic ester, pour organic solvent into and drip dibutyl tin laurate, logical nitrogen removing moisture, protective reaction system is carried out in anhydrous conditions, reaction is terminated after stirring heating reaction 1-24h, with organic solvent washing, then the particle dispersion after washing is formed in organic solvent suspension to carry out next step reaction;
The 1-10 μm of particle diameter SiO of isocyano by surface grafting
2spheroidal particle suspension is poured in reaction vessel, adds modification SiO
2nanoparticle or Modification on Al
2o
3nanoparticle, pours organic solvent into and drips catalyzer, under the condition of logical nitrogen, terminate reaction after reacting by heating 6-10h, by reaction product organic solvent washing, to remove unreacted isocyanic ester, filters, dry;
(5) preparation of lyophobic heat conduction material
Silicone resin or bisphenol A type epoxy resin E-51 are mixed with solidifying agent, catalyzer and micro-nano core-shell structure composite particles, be uniformly mixed under normal temperature, vacuum outgas is steeped, then pour into and scribble releasing agent and in preheated Teflon mould, baking oven is put in a mold at 70-90 DEG C of solidification 1-3h after levelling, be warming up to 110-130 DEG C of solidification 1-2h again, cool to room temperature; Wherein, the mass fraction of silicone resin or bisphenol A type epoxy resin E-51 is 100 parts, and the mass fraction of micro-nano core-shell structure composite particles is 40-80 part.
2. preparation method according to claim 1, is characterized in that: in step (1), temperature of reaction is 25 DEG C-150 DEG C, and the reaction times is 1-24h.
3. preparation method according to claim 2, is characterized in that: in step (2), silane coupling agent is the mixing of in kh550, kh560, kh570 any two kinds.
4. preparation method according to claim 1, is characterized in that: the organic solvent in step (4) is dry toluene, and isocyanic ester is the one in TDI or MDI, and catalyzer is triethylamine.
5. preparation method according to claim 4, is characterized in that: in step (5), solidifying agent is triethylene tetramine or polyetheramine, and mass fraction is 10-15 part, and catalyzer is dibutyl tin laurate, and mass fraction is 0.02-7 part.
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| CN103834127B (en) * | 2014-02-27 | 2016-07-06 | 华南理工大学 | A kind of high heat conduction Micron-nano composites and preparation method thereof |
| EP3169716B1 (en) * | 2014-07-17 | 2018-04-04 | Dow Global Technologies LLC | Epoxy systems employing triethylaminetetraamine and tin catalysts |
| CN104927733A (en) * | 2015-06-24 | 2015-09-23 | 深圳先进技术研究院 | Underfill and preparing method thereof |
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| CN108384284B (en) * | 2018-02-09 | 2020-12-29 | 航天特种材料及工艺技术研究所 | Super-hydrophobic inorganic material powder and preparation method thereof |
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| CN111319109B (en) * | 2020-02-10 | 2021-11-05 | 浙江农林大学 | Preparation method of flexible hydrophobic reversible photochromic wood and wood prepared by same |
| CN111334185B (en) * | 2020-03-17 | 2021-10-01 | 中物院成都科学技术发展中心 | Super-hydrophobic coating with heat conduction and corrosion prevention functions and preparation method thereof |
| CN112011092B (en) * | 2020-09-07 | 2021-11-30 | 中国矿业大学(北京) | White carbon black modification method |
| CN114433041B (en) * | 2020-10-30 | 2024-03-08 | 中国石油化工股份有限公司 | Super macroporous alumina material and preparation method thereof |
| CN113185825B (en) * | 2021-06-05 | 2022-11-29 | 上海经海纬象生物材料有限公司 | Tear-resistant and degradable polylactic acid food packaging film and preparation method thereof |
| CN113604095B (en) * | 2021-06-29 | 2022-06-24 | 东南大学 | Porous powder loaded with super-hydrophobic particles and preparation method and application thereof |
| CN116285564A (en) * | 2022-12-27 | 2023-06-23 | 深圳市鸿合创新信息技术有限责任公司 | Coating, preparation method thereof and electronic device |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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