CN103951983B - A kind of high heat conduction high temperature resistant polysiloxanes ceramic composite and preparation method thereof and application - Google Patents
A kind of high heat conduction high temperature resistant polysiloxanes ceramic composite and preparation method thereof and application Download PDFInfo
- Publication number
- CN103951983B CN103951983B CN201410156149.9A CN201410156149A CN103951983B CN 103951983 B CN103951983 B CN 103951983B CN 201410156149 A CN201410156149 A CN 201410156149A CN 103951983 B CN103951983 B CN 103951983B
- Authority
- CN
- China
- Prior art keywords
- mass parts
- boron
- composite
- vinyl
- heat conduction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The invention discloses a kind of high heat conduction high temperature resistant polysiloxanes ceramic composite and preparation method thereof and application.Described composite is composed of the following components: 100 mass parts vinyl polysiloxane, 20～100 mass parts vinyl methyl MQ silicones, 0～0.5 mass parts inhibitor, 0.05～0.5 mass parts noble metal organic compound catalyst, 3～30 mass parts boron azine and/or boron azine derivatives, 0～5 mass parts Methyl Hydrogen Polysiloxane Fluid and 50～150 mass parts high heat-conducting ceramic powders.Height heat conduction of the present invention high temperature resistant polysiloxanes ceramic composite thermal conductivity factor is high, good springiness, waterproof and dampproof, insulation, damping；Heat resistant excellent performance, at Aeronautics and Astronautics, electronics, electrically and has broad application prospects in the fields such as illumination that communicate.
Description
Technical field
The invention belongs to Organic silicon nano composite material field, be specifically related to a kind of high heat conduction high temperature resistant polysiloxanes pottery
Composite and preparation method thereof and application.
Background technology
Heat conduction protective materials is widely used in Aeronautics and Astronautics, electronics, electric, communication illumination, weaponry, nuclear reactor
Deng field needs heat radiation and the position of heat transfer, it is alternatively arranged as common Heat Conduction Material and is applied to the process of such as Chemical Manufacture and waste water
The heat exchanger of middle use, solar water heater, battery cooler etc., also act as conveying, close, decorate, the material such as potting
Material, has broad application prospects.Along with integrated, the miniaturization of electronic equipment facility and semi-conducting material and high-power
High speed development, has higher requirement to it, in addition to providing protection against the tide, insulation, anticorrosion, high temperature resistant protective action, in time
Heat-sinking capability becomes the important limiting factor affecting its serviceability.It is a large amount of it was verified that electronic devices and components temperature often raises 2
DEG C, reliability decrease 10%, life-span when 50 DEG C only has 1/6 when 25 DEG C.
The inorganic ceramic base heat conduction protective materials rigidity of high heat conduction is big, be easily cracked, be difficult to constructing operation, the most gradually by heat conduction
Organic polymer composite is replaced.Organic polymer composite has excellent protection against the tide, damping, decay resistance and power
Learning performance, most organic polymers are all insulators, have excellent electrical insulation capability, but their thermal conductivity is the most very
Low, typically in 0.15W/ (m K)～0.25W/ (m K) scope.Organic polymer is filled there is filling out of high thermal conductivity coefficient
Material is the common method preparing thermal-conductive polymer matrix composites.At present, the organic polymer preparing Heat Conduction Material conventional has: sky
So rubber, polyurethane rubber, polyethylene, nitrile rubber, silicon rubber, epoxy resin etc..
Thermal grease conduction is with silicone oil or mineral oil as carrier, adds high heat conduction high-temperature resistant ceramic particles type filler aluminium nitride, nitrogen
Changing the paste that boron, carborundum, silicon nitride etc. grind to form, its thermal conductivity the most also only has 0.6-1.2W/ (m K), is smeared
In heat transfer interface, it is possible to fully infiltrate heat transfer interface, reduce interface resistance.But heat-conducting silicone grease is easily stained with glutinous, clean difficulty, thermal grease conduction
Through long-term storage, it may appear that point oil, thermal resistance is caused to raise.Organic silicon type thermal grease conduction is a kind of non-crosslinked shaped material, and it is the highest makes
Being 150 DEG C by temperature, when temperature is more than 180 DEG C, the silicone oil in thermal grease conduction can acutely volatilize, and produces degradation reaction, thus
It is not suitable for more than 150 DEG C or parts that optical performance requirements is the highest.
Polysiloxane rubber is waterproof and dampproof owing to the particularity of its structure makes it have, high-low temperature resistant, high voltage withstanding, resistance to always
The performances such as change, radiation resistance, weatherability, workability so that it is become the conventional base resin material preparing Heat Conduction Material.Add
The molding liquid silicon rubber as easy as rolling off a log expeling intrapore air of contact interface, crosslinking curing does not has little molecule to release when forming rubber
Putting, Volume Changes is the least, can bear the alternation environment between high/low temperature, and internal stress is little.Heat conducting polysiloxane silastic material has
Excellent waterproof and dampproof, insulation, damping and scattered thermal property, except can keep its physics and electrically under operating condition widely
Outside performance, also can support and be cracked by ozone and ultraviolet, there is good chemical stability so that it is in fields such as electronic devices and components
There is irreplaceable effect.
Nano MQ silicon resin is to be closed chain link R by simple function group (M group) organosiloxane3SiO1/2(all methyl of R
It it is then methyl MQ silicones；In R, sub-fraction is vinyl, and other is vinyl methyl MQ silicon tree for the product that methyl is prepared
Fat) and four-functional group (Q group) organosiloxane chain link SiO2Special nano-scale has to be hydrolyzed the performance being condensed
Machine silicone material, for the tight orbicule of double-decker, wherein core is that Si-O chain connects, and density is higher, the degree of polymerization be 15～
Caged SiO of 502, spherical shell is the R that density is relatively low3SiO1/2Layer, its molal weight is generally 1000～8000g/mol.
Summary of the invention
In place of shortcoming and defect for solution prior art, the primary and foremost purpose of the present invention is to provide a kind of resistance to height of high heat conduction
Temperature polysiloxanes ceramic composite.
Another object of the present invention is to provide the preparation side of above-mentioned high heat conduction high temperature resistant polysiloxanes ceramic composite
Method.
It is still another object of the present invention to provide the application of above-mentioned high heat conduction high temperature resistant polysiloxanes ceramic composite.
For achieving the above object, the present invention adopts the following technical scheme that
A kind of high heat conduction high temperature resistant polysiloxanes ceramic composite, described composite is by the component of following mass fraction
Composition:
Preferably, described vinyl polysiloxane (also referred to as vinyl silicone oil) be end-vinyl dimethyl silicone polymer (also
Claim end-vinyl methyl-silicone oil), side vinyldimethicone (also referred to as side vinyl methyl silicone oil) or simultaneously containing end second
At least one in the dimethyl silicone polymer of thiazolinyl and side vinyl；Its viscosity is 1000～80000mPa s.
It is furthermore preferred that the viscosity of described vinyl polysiloxane is 3000～50000mPa s.
Preferably, the contents of ethylene of described vinyl methyl MQ silicones is 1.0～4.0wt%, M group and Q group
Mol ratio be 0.6～1.5.
Preferably, described inhibitor is ethynylcyclohexanol.
Preferably, described noble metal organic compound catalyst is three (triphenylphosphine) carbonyl hydrogenation Rh (I), or three
(triphenylphosphine) carbonyl hydrogenation Rh (I) and the mixture of the complex solution of the divinyl tetramethyl disiloxane of platinum, mix
In thing, metal rhodium is 100:0.5～100 with the mass ratio of platinum.
Noble metal catalyst at room temperature forms complex compound, the π in ethynylcyclohexanol with inhibitor ethynylcyclohexanol
Electronics and the unoccupied orbital pairing in noble metal, metal active is suppressed.Prolongation and temperature over time raise, metal catalytic
Activity is gradually released, and catalytic reaction is carried out, and under high temperature, reaction is accelerated.
Preferably, described boron azine derivatives includes replacing boron azine, boron azine dimer, boron azine oligomer, boron a word used for translation
At least one in piperazine polymer or replacement borazine polymer；Described boron azine and boron azine derivatives the most at least contain one
Individual B-H key.
The structural formula of described boron azine and boron azine derivatives respectively as shown in formula 1-5, wherein solid borazine polymer,
The grain diameter replacing borazine polymer is 10～100 μm.
In above-mentioned formula 1-5, R1-R6For H, alkyl or silylation.
Preferably, in described Methyl Hydrogen Polysiloxane Fluid in activated silica hydrogen bond (Si-H) percentage composition of hydrogen be 0.36～
1.00wt%, its viscosity is 50～1000mPa s.
Preferably, described high heat-conducting ceramic powder is at least one in boron nitride, aluminium nitride, carborundum or silicon nitride,
Powder granule average grain diameter is 1～50 μm.
The preparation method of above-mentioned high heat conduction high temperature resistant polysiloxanes ceramic composite, specifically comprises the following steps that 100 mass
Part vinyl polysiloxane, 20～100 mass parts vinyl methyl MQ silicones, 0～0.5 mass parts inhibitor, 0.05～0.5
Mass parts noble metal organic compound catalyst, 3～30 mass parts boron azine and/or boron azine derivatives, 0～5 mass parts first
After base containing hydrogen silicone oil and 50～150 mass parts high heat-conducting ceramic powders mix in proportion, 50～150 DEG C of solidifications obtain described height and lead
The high temperature resistant polysiloxanes ceramic composite of heat.
Preferably, described solidification refers to solidify 2～5h at 50～150 DEG C；Or first solidify before 50～80 DEG C 0.5～
1h, then at 120～150 DEG C carry out after solidify.
Above-mentioned high heat conduction high temperature resistant polysiloxanes ceramic composite is at Aeronautics and Astronautics, electronics, electric or communication illumination neck
Application in territory.
The principle of the present invention is: the present invention, with add-on type vinyl methyl polysiloxanes for base glue, leads with micron order height
Thermal Ceramics powder boron nitride, silicon nitride, aluminium nitride, carborundum etc. are heat filling, with nanoscale vinyl methyl MQ silicones
Boron azine other with molecular level and derivative thereof be activity heat filling, nanoscale vinyl methyl MQ silicones and boron azine and
Its liquid derivative is evenly dispersed in matrix resin and heat filling with classification levels, is catalyzed at noble metal organic compound
Under agent effect, form complete silicon rubber ceramic composite, after addition polymerization by boron hydrogen addition, Si-H addition reaction polymerisation
Boron azacyclo-, MQ silicones molecule enter silicon rubber main chain or side chain, significantly significantly reduce micro-ceramic heat conduction particle,
Replace the interface resistance of borazine polymer solid particle and matrix resin, define good thermal conducting path, substantially increase
The thermal conductivity of composite, significantly improves the resistance to elevated temperatures of composite simultaneously.
Compared with prior art, the present invention has the following advantages and beneficial effect:
(1) thermal conductivity factor is high, good springiness, waterproof and dampproof, insulation, damping；Test result indicate that prepared by the present invention compound
Material thermal conductivity brings up to more than 9.5W/ (m K), far above common heat-conducting silicone grease from the 0.20W/ (m K) of base-material
1.0W/ (m K), improves more than nearly ten times.
(2) heat resistant excellent performance, can the high temperature of the most resistance to 300 DEG C, test result indicate that prepared by the present invention
Composite can use in the environment of 300 DEG C, uses far above in the environment of common heat-conducting silicone grease 150 DEG C.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited to this.
Embodiment 1: raw material prepares
(1) by heat conduction refractory ceramics powder stuffing boron nitride that mean particle size is 1～50 μm, aluminium nitride, carbonization
Silicon, silicon nitride are respectively placed in vacuum drying chamber, vacuumize, and are warmed up to 150 DEG C, keep vacuum (-101.3KPa) 3 little
Time, then cool down taking-up, be positioned in drying box, standby.
(2) preparation of silylation boron azine: take out the boron azine of 40.3g from-5 DEG C of storage rooms of low temperature, pour into one equipped with
In the there-necked flask of the 1000mL of drying device, add the dichloromethane being dried of 200g, the RhH of lower addition 0.4g is stirred at room temperature
(CO)(PPH3)3, it is kept stirring for down being slowly added to vinyl three (trimethylsiloxy group) silane 322g, reaction 8 is stirred at room temperature little
Time, it is subsequently adding ethynylcyclohexanol 0.2g, decompression distillation, removes low boiling point solvent, prepare based on the silicon of disilane base
Boron alkyl azine BZ2, preserves at low temperature-5 DEG C, standby.Preparation reaction is as shown in reaction equation 1.
The preparation of (3) three silylation boron azines: take out the boron azine of 20.1g from-5 DEG C of storage rooms of low temperature, pour a dress into
Have in the there-necked flask of 1000mL of drying device, add the dichloromethane being dried of 200g, the RhH of lower addition 0.3g is stirred at room temperature
(CO)(PPH3)3, it is kept stirring for down being slowly added to vinyl three (trimethylsiloxy group) silane 241.5g, reaction 24 is stirred at room temperature
Hour, decompression distillation, remove low boiling point solvent, prepare three silylation boron azine BZ3, preserve at low temperature-5 DEG C, standby.
Boron azine is also known as borazine, and containing unoccupied orbital on boron (B) atom, adjacent nitrogen (N) atom contains lone pair electrons,
Form pairing each other.Confirm through single-crystal X-ray diffraction analysis, borazine molecule exists conjugatedπbond, its structure and benzene
Similar, it is ring isoelectronic with benzene, there is fragrant.The physical property of boron azine (borazine) is close with benzene, a kind of
Colourless volatile liquid.But owing to boron is different with the electronegativity of nitrogen, the cloud density on nitrogen-atoms is relatively big, on boron atom
Cloud density is less, and therefore nitrogen-atoms remains in that its partial alkaline, boron atom then keep its partially acidic.Institute
With, in boron azine, B-H and N-H is susceptible to addition or polymerisation at a certain temperature.
Boron azine is at complex compound three (triphenylphosphine) carbonyl hydrogenation Rh (I) RhH (the CO) (PPH of Noble Metal Rhodium3)3Under catalysis
Boron hydrogen addition is there is in the vinyl in silane vinyl three (trimethylsiloxy group) silane containing vinyl under B-H key room temperature
Reaction defines silylation boron azine, and under the effect of inhibitor ethynylcyclohexanol, unnecessary B-H key is retained, and is formed
Product silane base boron azine in containing unnecessary B-H key.Because of the sterically hindered effect of silylation, the B-in silylation boron azine
H key is the most stable, can preserve the long period at low temperatures.
(4) preparation of boron azine liquid oligomer: add in the there-necked flask of a 500mL being dried reflux
The boron azine (Cord blood) of 241.5g, is heated to 80 DEG C and is incubated two hours, cooling down the most rapidly, preparing boron azine liquid
Oligomer PBZL2, and it is positioned in the refrigerator of-5 DEG C sealing preservation, standby.Preparation reaction is as shown in reaction equation 2.
B-H key in boron azine is relatively active, at a certain temperature (70～110 DEG C) gradually to send dehydrogenation autohemagglutination anti-
Should, form line style liquid oligomer, prolongation over time during beginning, under oligomer uniform temperature (70～110 DEG C), enter one
Step crosslinking curing, forms solid network polymer.
(5) preparation of boron azine solid polymer: add the boron a word used for translation of 241.5g in the rustless steel container of an airtight 1L
Piperazine, is warming up to 75 DEG C in confined conditions, and is incubated 48 hours, prepares boron azine solid polymer.Then grinding is sampled, respectively
Sieving, prepare 100～80 μm, 20～10 pressed powder PBZS1 of μm, then airtight preservation at low temperature 0 DEG C, standby.Preparation
Reaction is as shown in reaction equation 3.
(6) preparation of boron azine-boron alkyl azine oligomer: in the there-necked flask of a 500mL being dried reflux
Add boron azine (Cord blood) and three silylation boron azine BZ3 (see (3)) of 261.6g of 10.1g, stirring, be heated to 80 DEG C
And it is incubated 4 hours, cool down the most rapidly, prepare the aqueous boron azine containing B-H key-boron alkyl azine oligomer PBZL3, and put
It is placed in the refrigerator of-5 DEG C sealing to preserve, standby.Preparation reaction is as shown in reaction equation 4.
(7) preparation of boron azine-boron alkyl azine solid polymer: add in the rustless steel container of an airtight 1L
The boron azine of 20.1g and disilane base boron azine (see 2-1) of 181.1g, be warming up to 80 DEG C in confined conditions, and be incubated 48
Hour, prepare boron azine-boron alkyl azine solid polymer.Then sample grinding, sieve respectively, prepare 100～80 μm, 20
～10 pressed powder PBZS2 of μm, then airtight preservation at low temperature 0 DEG C, standby.Preparation reaction is as shown in reaction equation 5.
Silylation boron azine, three silylation boron azines, boron azine liquid oligomer, boron azine solid polymerization in the present embodiment
Below the preparation method Primary Reference of thing, boron azine-boron alkyl azine oligomer and boron azine-boron alkyl azine solid polymer
Method described in document:
(1)Fazen P J,Remsen E E,Beck J S,et al.Chem.Mater.,1995,7:1942-1956
(2)Brunner A R,Bujalski D R,Moyer E S,et al.Chem.Mater.,2000,12:2770-
2780
(3)Laubengayer A W,Beachler O T.Jr,in“Boron-Nitrogen Chemistry”,R F
Gould,Ed,Advances in Chemistry Series,No 42,American Chemical Society,
Washington D C,1964,281
Embodiment 2
The preparation method of a kind of high heat conduction high temperature resistant polysiloxanes ceramic composite, specifically comprises the following steps that
By end-vinyl methyl-silicone oil (viscosity 50000mPa s) 100g, vinyl methyl MQ silicones (ethene under room temperature
Base content 4.0wt%, M/Q=1.5) 30g, three (triphenylphosphine) carbonyl hydrogenation Rh (I) RhH (CO) (PPH3)3(containing of metal rhodium
Amount is for 11.2wt%) 0.45g, boron azine 3g and the dried boron nitride ceramics powder (average grain diameter 50 μm) of embodiment 1
After 100g mixes, it is positioned in 50 DEG C of environment insulation 5 hours, obtains described high heat conduction high temperature resistant polysiloxanes Ceramic Composite
Material.
Its shore hardness, thermal conductivity factor and heat resistant performance is measured after composite cooling.Experimental results arranges
In table 1.
Shore hardness is tested: by the hardness of LX-A type shore durometer direct test silicon rubber.
Thermal conductivity factor: directly test by DRL-III heat conduction coefficient tester.
Heat resistant performance test: by liquid silastic composite (the uncured composite wood of the present invention
Feed composition) it is respectively coated on clean metal aluminum sheet and ceramic substrate, solid according to the solidification temperature specified and program curing
Change, weigh and observe the outward appearance of composite, being then placed in 300 DEG C of environment 500 hours carrying out air oven aging test, seeing
Examine the cosmetic variation (including color, be full of cracks situation and bonding plane dropping situations) of silicon rubber composite material, weigh after cooling, calculate
The mass loss of silicon rubber composite material.
Embodiment 3
The preparation method of a kind of high heat conduction high temperature resistant polysiloxanes ceramic composite, specifically comprises the following steps that
By end-vinyl methyl-silicone oil (viscosity 3000mPa s) 100g, vinyl methyl MQ silicones (ethene under room temperature
Base content 2.4wt%, M/Q=0.75) 100g, ethynylcyclohexanol 0.48g, three (triphenylphosphine) carbonyl hydrogenation Rh (I) RhH
(CO)(PPH3)3(content of metal rhodium is 11.2wt%) 4.3g, disilane base boron azine BZ2 (embodiment 1 prepares gained) 30g
After boron nitride ceramics powder (the average grain diameter 10 μm) 100g dried with embodiment 1 mixes, it is positioned over 150 DEG C of rings
In border 2 hours, obtain described high heat conduction high temperature resistant polysiloxanes ceramic composite.
Measuring its hardness, thermal conductivity factor and heat resistant performance after composite cooling, detection method is with embodiment 1.
Experimental results is shown in Table 1.
Embodiment 4
The preparation method of a kind of high heat conduction high temperature resistant polysiloxanes ceramic composite, specifically comprises the following steps that
By end-vinyl methyl-silicone oil (viscosity 1000mPa s) 100g, vinyl methyl MQ silicones (ethene under room temperature
Base content 1.0wt%, M/Q=0.6) 100g, ethynylcyclohexanol 0.2g, three (triphenylphosphine) carbonyl hydrogenation Rh (I) RhH (CO)
(PPH3)3(content of metal rhodium is 11.2wt%) 0.9g, liquid boron azine oligomer PBZL2 (embodiment 1 prepares gained) 15g,
Borazine polymer pressed powder PBZS1 (embodiment 1 prepares gained) (100～80 μm) 10g and embodiment 1 are dried
After boron nitride ceramics powder (average grain diameter 10 μm) 100g, Silicon Carbide Powder (average grain diameter 5 μm) 50g mix, first
It is positioned in 80 DEG C of environment insulation 0.5 hour, then heats to 150 DEG C and be incubated 1.5 hours, obtaining described high heat conduction high temperature resistant
Polysiloxanes ceramic composite.
Measuring its hardness, thermal conductivity factor and heat resistant performance after composite cooling, detection method is with embodiment 1.
Experimental results is shown in Table 1.
Embodiment 5
The preparation method of a kind of high heat conduction high temperature resistant polysiloxanes ceramic composite, specifically comprises the following steps that
By end-vinyl methyl-silicone oil (viscosity 5000mPa s) 50g, pendant vinyl ylmethyl silicone oil (viscosity under room temperature
80000mPa s) 50g, vinyl methyl MQ silicones (contents of ethylene 2.4wt%, M/Q=0.75) 100g, acetylene basic ring
Hexanol 0.3g, three (triphenylphosphine) carbonyl hydrogenation Rh (I) RhH (CO) (PPH3)3(content of metal rhodium is 11.2wt%) 0.9g,
Boron azine-silylation boron azine oligomer PBZL3 (embodiment 1 prepares gained) 10g, borazine polymer pressed powder PBZS1
((embodiment 1 prepares gained) 20～10 μm) 20g and dried boron nitride ceramics powder (average grain diameter 10 μ of embodiment 1
M), after 50g, silicon nitride ceramics powder (average grain diameter 20 μm) 50g mix, it is positioned in 120 DEG C of environment 4 hours, obtains institute
State high heat conduction high temperature resistant polysiloxanes ceramic composite.
Measuring the hardness of composite, thermal conductivity factor and heat resistant performance after cooling, detection method is with embodiment 1.
Experimental results is shown in Table 1.
Embodiment 6
The preparation method of a kind of high heat conduction high temperature resistant polysiloxanes ceramic composite, specifically comprises the following steps that
By vinyl methyl silicone oil (simultaneously containing end-vinyl and side vinyl, viscosity 10000mPa in molecule under room temperature
S) 100g, vinyl methyl MQ silicones (contents of ethylene 2.4wt%, M/Q=0.75) 20g, ethynylcyclohexanol 0.2g, three
(triphenylphosphine) carbonyl hydrogenation Rh (I) RhH (CO) (PPH3)3(content of metal rhodium is 11.2wt%) 0.9g, boron azine 5g, boron
Azine-silylation borazine polymer pressed powder PBZS2 (20～10 μm) (embodiment 1 prepares gained) 25g and embodiment 1 are dry
After dry boron nitride ceramics powder (the average grain diameter 10 μm) 100g processed mixes, it is positioned in 50 DEG C of environment 1 hour, so
After be warming up to 120 DEG C be incubated 4 hours, obtain described high heat conduction high temperature resistant polysiloxanes ceramic composite.
Measuring its hardness, thermal conductivity factor and heat resistant performance after composite cooling, detection method is with embodiment 1.
Experimental results is shown in Table 1.
Embodiment 7
The preparation method of a kind of high heat conduction high temperature resistant polysiloxanes ceramic composite, specifically comprises the following steps that
By end-vinyl methyl-silicone oil (viscosity 5000mPa s) 100g, vinyl methyl MQ silicones (ethene under room temperature
Base content 1.0wt%, M/Q=0.6) 50g, ethynylcyclohexanol 0.2g, three (triphenylphosphine) carbonyl hydrogenation Rh (I) RhH (CO)
(PPH3)3(content of rhodium is 11.2wt%) 0.9g, divinyl tetramethyl disiloxane (vinyl double-seal head) complex compound of platinum
Solution (2000ppm) 0.5g (content of metal platinum is 0.5*0.2%=0.001g), liquid boron azine oligomer PBZL2 (implement
Example 1 prepares gained) 10g, borazine polymer pressed powder PBZS1 (embodiment 1 prepares gained) (100～80 μm) 20g, methyl
Containing hydrogen silicone oil (reactive hydrogen 0.36wt%, viscosity 1000mPa s) 5g and the dried boron nitride ceramics powder of embodiment 1
After (average grain diameter 10 μm) 50g, Silicon Carbide Powder (average grain diameter 5 μm) 50g mix, it is positioned in 120 DEG C of environment
It is incubated 5 hours, obtains described high heat conduction high temperature resistant polysiloxanes ceramic composite.
Measuring its hardness, thermal conductivity factor and heat resistant performance after composite cooling, detection method is with embodiment 1.
Experimental results is shown in Table 1.
Embodiment 8
The preparation method of a kind of high heat conduction high temperature resistant polysiloxanes ceramic composite, specifically comprises the following steps that
By end-vinyl methyl-silicone oil (viscosity 5000mPa s) 80g, pendant vinyl ylmethyl silicone oil (viscosity under room temperature
80000mPa s) 20g, vinyl methyl MQ silicones (contents of ethylene 1.0wt%, M/Q=0.6) 80g, acetenyl hexamethylene
Alcohol 0.2g, three (triphenylphosphine) carbonyl hydrogenation Rh (I) RhH (CO) (PPH3)3(content of rhodium is 11.2wt%) 0.9g, the two of platinum
(content of metal platinum is 0.3* to vinyl tetramethyl disiloxane (vinyl double-seal head) complex solution (2000ppm) 0.3g
0.2%=0.0006g.), boron azine 3g, boron azine-boron alkyl azine polymer solids powder PBZS2 (100～80 μm) (real
Executing example 1 and prepare gained) 10g, Methyl Hydrogen Polysiloxane Fluid (reactive hydrogen 1.0wt%, viscosity 50mPa s) 3g and embodiment 1 be dried and process
Boron nitride ceramics powder (the average grain diameter 10 μm) 50g, silicon nitride ceramics powder (the average grain diameter 20 μm) 50g that cross mix
After, first it is positioned in 50 DEG C of environment insulation 1 hour, then heats to 130 DEG C and be incubated 2 hours, obtaining the described resistance to height of high heat conduction
Temperature polysiloxanes ceramic composite.
Measuring its hardness, thermal conductivity factor and heat resistant performance after composite cooling, detection method is with embodiment 1.
Experimental results is shown in Table 1.
Embodiment 9
The preparation method of a kind of high heat conduction high temperature resistant polysiloxanes ceramic composite, specifically comprises the following steps that
By vinyl methyl silicone oil (simultaneously containing end-vinyl and side vinyl, viscosity 10000mPa in molecule under room temperature
S) 30g, end-vinyl methyl-silicone oil (viscosity 5000mPa s) 70g, vinyl methyl MQ silicones (contents of ethylene
2.4wt%, M/Q=0.75) 100g, ethynylcyclohexanol 0.1g, three (triphenylphosphine) carbonyl hydrogenation Rh (I) RhH (CO)
(PPH3)3(content of rhodium is 11.2wt%) 0.45g, divinyl tetramethyl disiloxane (vinyl double-seal head) complexing of platinum
Thing solution (20000ppm) 2.5g (content of metal platinum is 2.5*2%=0.05g), boron azine-silylation boron azine oligomer
PBZL3 (embodiment 1 prepares gained) 30g, Methyl Hydrogen Polysiloxane Fluid (reactive hydrogen 0.75wt%, viscosity 200mPa s) 4g and enforcement
Boron nitride ceramics powder (average grain diameter 3 μm) 40g, aluminum nitride ceramic powder (the average grain diameter 1 μm) 10g that example 1 is dried
After mixing, it is positioned in 100 DEG C of environment insulation 5 hours, obtains described high heat conduction high temperature resistant polysiloxanes Ceramic Composite material
Material.
Measuring its hardness, thermal conductivity factor and heat resistant performance after composite cooling, detection method is with embodiment 1.
Experimental results is shown in Table 1.
The performance test results of Ceramic Composite protective materials after table 1 heat cure
From table, polysiloxanes ceramic composite prepared by the present invention solidify to form tool under heat and catalyst action
There are certain degree of hardness and elastic silicon rubber heat-conductive composite material, not only there is the highest thermal conductivity factor (or claiming thermal conductivity), up to
More than 9.5W/ (m K) (far above the 1.0W/ (m K) of heat-conducting silicone grease) is also multiple under high temperature 300 DEG C is up to 500 hours environment
Condensation material is without coming off, chap and metachromatism, and mass loss is little, has the heat resistant performance of excellence.
Above-described embodiment is the present invention preferably embodiment, but embodiments of the present invention are not by above-described embodiment
Limit, the change made under other any Spirit Essence without departing from the present invention and principle, modify, substitute, combine, simplify,
All should be the substitute mode of equivalence, within being included in protection scope of the present invention.
Claims (10)
1. a high heat conduction high temperature resistant polysiloxanes ceramic composite, it is characterised in that described composite is by following quality
The component composition of number:
The mass fraction of wherein said noble metal organic compound catalyst is in terms of bullion content.
Composite the most according to claim 1, it is characterised in that described vinyl polysiloxane is end-vinyl poly-two
Methylsiloxane, side vinyldimethicone or simultaneously in dimethyl silicone polymer containing end-vinyl and side vinyl
At least one；Its viscosity is 1000～80000mPa s.
Composite the most according to claim 1, it is characterised in that the vinyl of described vinyl methyl MQ silicones contains
Amount is 1.0～4.0wt%, and the mol ratio of M group and Q group is 0.6～1.5；Described inhibitor is ethynylcyclohexanol.
Composite the most according to claim 1, it is characterised in that described noble metal organic compound catalyst is three
(triphenylphosphine) carbonyl hydrogenation Rh (I), or three (triphenylphosphine) carbonyl hydrogenation Rh (I) and divinyl tetramethyl two silicon of platinum
The mixture of the complex solution of oxygen alkane, in mixture, metal rhodium is 100:0.5～100 with the mass ratio of platinum.
Composite the most according to claim 1, it is characterised in that described boron azine derivatives include replace boron azine,
At least one in boron azine dimer, boron azine oligomer, borazine polymer or replacement borazine polymer；Described boron a word used for translation
Piperazine and boron azine derivatives the most at least contain a B-H key.
Composite the most according to claim 1, it is characterised in that hydrogen in activated silica hydrogen bond in described Methyl Hydrogen Polysiloxane Fluid
Percentage composition be 0.36～1.00wt%, its viscosity is 50～1000mPa s.
Composite the most according to claim 1, it is characterised in that described high heat-conducting ceramic powder is boron nitride, nitridation
At least one in aluminium, carborundum or silicon nitride, powder granule average grain diameter is 1～50 μm.
8. the preparation method of high heat conduction high temperature resistant polysiloxanes ceramic composite described in any one of claim 1～7, its feature
Be, specifically comprise the following steps that by 100 mass parts vinyl polysiloxane, 20～100 mass parts vinyl methyl MQ silicones, 0
～0.5 mass parts inhibitor, 0.05～0.5 mass parts noble metal organic compound catalyst, 3～30 mass parts boron azine and/
Or boron azine derivatives, 0～5 mass parts Methyl Hydrogen Polysiloxane Fluid and 50～150 mass parts high heat-conducting ceramic powders mix in proportion
After, 50～150 DEG C of solidifications obtain described high heat conduction high temperature resistant polysiloxanes ceramic composite.
Preparation method the most according to claim 8, it is characterised in that described solidification refer to 50～150 DEG C solidification 2～
5h；Or before 50～80 DEG C, first solidify 0.5～1h, then at 120～150 DEG C carry out after solidify.
10. high heat conduction high temperature resistant polysiloxanes ceramic composite described in any one of claim 1～7 is at Aeronautics and Astronautics, electricity
Son, the electric or application in lighting field that communicates.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410156149.9A CN103951983B (en) | 2014-04-17 | 2014-04-17 | A kind of high heat conduction high temperature resistant polysiloxanes ceramic composite and preparation method thereof and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410156149.9A CN103951983B (en) | 2014-04-17 | 2014-04-17 | A kind of high heat conduction high temperature resistant polysiloxanes ceramic composite and preparation method thereof and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103951983A CN103951983A (en) | 2014-07-30 |
| CN103951983B true CN103951983B (en) | 2016-09-07 |
Family
ID=51329348
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410156149.9A Active CN103951983B (en) | 2014-04-17 | 2014-04-17 | A kind of high heat conduction high temperature resistant polysiloxanes ceramic composite and preparation method thereof and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103951983B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104231918B (en) * | 2014-09-19 | 2016-06-29 | 中科院广州化学有限公司 | The quick-dry type oiliness infiltration nano combined protective agent of film-forming type and preparation method and application |
| CN104650713B (en) * | 2015-01-25 | 2018-06-05 | 河南城建学院 | A kind of modified computer cabinet shell |
| CN105924979B (en) * | 2016-05-27 | 2019-01-08 | 成都硅宝科技股份有限公司 | Ceramic organic silicon rubber |
| CN112292346B (en) * | 2018-06-21 | 2023-10-20 | 株式会社Adeka | Method for producing surface-treated aluminum nitride, resin composition, and cured product |
| WO2022031654A1 (en) * | 2020-08-03 | 2022-02-10 | Henkel IP & Holding GmbH | Hydrosilation curable compositions |
| CN112500031A (en) * | 2020-12-14 | 2021-03-16 | 晟大科技(南通)有限公司 | Ceramic substrate material and preparation method and application thereof |
| CN113881232B (en) * | 2021-11-04 | 2023-03-21 | 广东航迈新材料科技有限公司 | Ceramic organic silica gel material for medium-voltage fire-resistant cable and preparation method thereof |
| CN116218363B (en) * | 2023-03-31 | 2024-03-08 | 无锡兴华衡辉科技有限公司 | Protective slurry and preparation method thereof, protective sleeve containing protective slurry and preparation method thereof and application of protective sleeve in laser welding of stainless steel |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101831181A (en) * | 2010-05-21 | 2010-09-15 | 浙江三元电子科技有限公司 | Addition thermal conductive insulation silicon rubber composite material and preparation method thereof |
| CN103249762A (en) * | 2010-12-09 | 2013-08-14 | 株式会社大赛璐 | Addition-curable metallosiloxane compound |
| CN103254647A (en) * | 2012-02-20 | 2013-08-21 | 深圳德邦界面材料有限公司 | Heat-conductive gap interface material and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030171487A1 (en) * | 2002-03-11 | 2003-09-11 | Tyco Electronics Corporation | Curable silicone gum thermal interface material |
-
2014
- 2014-04-17 CN CN201410156149.9A patent/CN103951983B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101831181A (en) * | 2010-05-21 | 2010-09-15 | 浙江三元电子科技有限公司 | Addition thermal conductive insulation silicon rubber composite material and preparation method thereof |
| CN103249762A (en) * | 2010-12-09 | 2013-08-14 | 株式会社大赛璐 | Addition-curable metallosiloxane compound |
| CN103254647A (en) * | 2012-02-20 | 2013-08-21 | 深圳德邦界面材料有限公司 | Heat-conductive gap interface material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103951983A (en) | 2014-07-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103951983B (en) | A kind of high heat conduction high temperature resistant polysiloxanes ceramic composite and preparation method thereof and application | |
| CN103102689B (en) | Organic-silicon pouring sealant composition with high thermal conductivity and application thereof | |
| CN107001802B (en) | One-pack addition-curable silicone composition, method for storing same, and method for curing same | |
| Kim et al. | Pyrolysis behavior of polysilazane and polysilazane-coated-boron nitride for high thermal conductive composite | |
| CN109890900A (en) | One-part curable type heat conductive silicone grease composition and electronic/electrical pneumatic module | |
| CN105419343B (en) | Printable or dispensing formula heat-conducting pad and preparation method thereof | |
| CN107043541A (en) | Thermal conductive silicon gel combination and preparation method thereof | |
| CN107082651B (en) | A kind of coat of silicon carbide and preparation method thereof | |
| JP6313258B2 (en) | Chemical heat storage material and chemical heat storage material forming composition | |
| CN101831181A (en) | Addition thermal conductive insulation silicon rubber composite material and preparation method thereof | |
| CN107177345A (en) | A kind of heat conduction Silica hydrogel and preparation method | |
| CN101928462A (en) | Acetone-removing silicon rubber and preparation method thereof | |
| CN107793763A (en) | A kind of thermostable heat-conductive silicone grease and preparation method thereof | |
| TW200815531A (en) | Heat conductive silicone grease composition | |
| CN101423745A (en) | Friction braking material and preparation method thereof | |
| CN103589336A (en) | Room-temperature-curing acrylic heteropolysiloxane nano-ceramic protection coating and preparation method thereof | |
| CN104479606B (en) | A kind of high temperature resistance high heat conduction bora organosilicon epoxy casting glue and preparation method thereof and application | |
| CN107078112A (en) | Fin material | |
| CN109467706A (en) | A kind of novel liquid Polycarbosilane and preparation method thereof | |
| CN110982277B (en) | Single-component temperature-resistant heat-conducting silicon mud composition and preparation method thereof | |
| CN103227270A (en) | Light emitting diode device and method of producing the same | |
| CN110157375A (en) | A kind of conductive and heat-conductive Silica hydrogel adhesive and preparation method thereof | |
| CN112694757A (en) | Novel organic silicon surface treating agent composition and preparation method thereof | |
| CN110776745A (en) | Preparation method of thermal interface material | |
| CN107501954A (en) | Heat Conduction Material, battery bag and electric automobile |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |