CN109971183A - Organic silicon composite with three dimentional heat conduction structure - Google Patents
Organic silicon composite with three dimentional heat conduction structure Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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Abstract
The present invention relates to a kind of heat-conductive silicone composite materials, and it includes organic silicon substrates and the organic network structural body being embedded in the organic silicon substrate, wherein load has conducting filler on the organic network structural body；And further relate to a kind of method for preparing the heat-conductive silicone composite material.Organic silicon composite through the invention improves heating conduction while the additive amount of high thermal conductivity filler is greatly reduced and improves conduction stability and realize controllable conductive structure.In addition, the composite material can also keep the due good processing performance of organic silicon composite and mechanical performance.
Description
Technical field
The invention belongs to composite material preparation and application technical field, be related to a kind of heat-conductive silicone composite material and
The method for preparing this organic silicon composite.
Background technique
As a kind of elastomeric high-molecular organic material, organosilicon material has excellent flexibility, weatherability, resistance to height
The advantages that low temperature properties, fatigue resistance, good abrasion performance, in the neck such as Aeronautics and Astronautics, automobile, building, instrument, electronics, electrical
Domain is all widely used.With the continuous progress of science and technology, the especially exploitation of high power power electronic devices, people are to organic
The heating conduction of silicon materials requires also higher and higher.However, the organosilicon material as high molecular material, itself has very
Low heating conduction, therefore the thermal conductivity for improving organosilicon material is particularly important.Improve the organosilicon material after thermal conductivity
Material has become a kind of critical material in electronic device heat management, is widely used in dissipating for electronic device as thermal interfacial material
Heat.
Improving the major way of organosilicon material thermal conductivity at present is led by adding inorganic height into organic silicon substrate
Conductivity fillers prepare composite material to promote bulk thermal conductivity.Common high thermal conductivity filler have metal and its metal oxide,
The carbon materials such as nitride, carbide and carbon fiber, carbon nanotube, graphene.Such composite material is usually by leading height
Conductivity fillers are blended with organic silicon substrate material and are prepared.The thermal conductivity of prepared composite material depends on organic silicon substrate
The comprehensive function of the molecule chain vibration of body, lattice vibration and inorganic filler lattice vibration is promoted.If inorganic fillers are filled out
Charge is smaller, then filler is in mutually isolated dispersity in organic silicon substrate, and filler does not contact directly between each other
And interaction, therefore the bulk thermal conductivity raising of composite material is very limited.If be added into organosilicon a large amount of inorganic
Filler, then while organosilicon composite wood can be greatly improved by forming chain and netted thermal conducting path in the composite
The thermal conductivity of material, but on the one hand high filler additive amount often sacrifices the good processing performance of organosilicon material and its machine
Tool mechanical property usually has also increased dramatically the preparation cost of composite material.
In addition, used high thermal conductivity filler is on the one hand during preparing composite material by above-mentioned blend method
It usually can be granular material.And on the other hand, under same filler additive amount, according to such as sheet of high length-diameter ratio
Or linear filler, then it can be because of the barrier being easier each other by organosilicon macromolecule material, so as to cause high boundary
Face thermal resistance seriously limits the promotion of composite material overall thermal conductivity energy.In addition, the composite material that preparation is blended is difficult to realize pair
Micro Distribution of the filler in organosilicon material matrix effectively controls, and the heating conduction of the composite material of preparation is caused to have shakiness
The problems such as qualitative.
Summary of the invention
Therefore, the purpose of the present invention is to present in the above-mentioned organic silicon composite of high thermal conductivity in the prior art
Problem and propose a kind of novel heat-conductive silicone composite material and preparation method.It is organic by this kind of novel thermal conductivity
Silicon composite should improve heating conduction while the additive amount of high thermal conductivity filler is greatly reduced and improve thermally conductive stabilization
Property and realize controllable conductive structure, to expand its application in the field of radiating of electronic device.In addition, the composite material
It can also keep the due good processing performance of organic silicon composite and mechanical performance.
The first aspect of the invention is related to a kind of heat-conductive silicone composite material, and it includes organic silicon substrates and embedding
Organic network structural body in the organic silicon substrate, wherein load has conducting filler on the organic network structural body.
In scope, the organic network structural body is a kind of knot of three-dimensional network shape being made of organic material
Structure can form stable microcosmic heat conduction network access.In addition, such organic network structural body should also be able to be easy to height to lead
The load of conductivity fillers.
According to the present invention, such network structure body advantageously has porous structure, and can for example be preferably selected from poly-
Urethane, organosilicon, polystyrene, polyvinyl chloride, polyethylene, phenolic resin are more preferably selected from polyurethane sponge or organosilicon bubble
Foam.
In an advantageous embodiment of the invention, the content of the organic network structural body be 50 weight % with
Under, preferably 40 weight % hereinafter, more preferable 20 weight % or 10 weight % hereinafter, based on entire composite material.
In addition, being different from the granular filler generallyd use in the prior art, high thermal conductivity filler of the invention should
Be greater than 5, be greater than 10 or preferably greater than 15 or more preferably greater than 25 high length-diameter ratio, such as can be sheet,
Linear, rodlike or irregular shape.In addition, within the scope of the present invention, applicable high thermal conductivity filler is in its longest dimension
Preferably have on direction > 100nm, preferably > 1 micron, more preferably > 5 microns, such as 5-150 microns or 10-100 microns or 10-50
The size of micron.Such non-particulate filler is more likely to form the access of connection, while being also easy to be carried on three-dimensional network knot
Reinforce the effect of thermal conducting path on structure body.
Within the scope of the present invention, conducting filler used there is no special restriction, but advantageous at one
In embodiment, they are preferably selected from metal oxide such as Al2O3, ZnO, CaO, MgO or BeO, nitride such as AlN or BN, carbonization
Object such as SiC or B4C3, metal such as Au, Ag, Cu, carbon material such as carbon fiber, carbon nanotube or graphene；More preferably Ag line or stone
Black alkene.
Due to using novel heat-conducting structure of the invention, so keeping or improving the capacity of heat transmission and machinery and processing
While performance, the load capacity of the conducting filler in organic silicon substrate can decline to a great extent, and for example, be based on entire composite wood
Material meter 80 weight % or less, preferably 50 weight % or less, more preferable 30 weight % or less, most preferably 20 weight % or less.
Another aspect of the present invention relates to a kind of methods for preparing heat-conductive silicone composite material as described above, including
Following steps:
(1) the organic network structural body is contacted with the conducting filler, the conducting filler is made to be supported on institute
It states on organic network structural body,
(2) mix it with the composition of the presoma comprising organic silicon substrate and optional curing agent, and
(3) solidify resulting mixture.
In (1) step according to the method for the present invention, by connecing organic network structural body with the conducting filler
It touches and makes that physics and chemical bonding occur between organic structure network body and conducting filler, so that conducting filler is secured
It is supported on organic network structural body.Such contact can be by being impregnated in network structure body comprising the conducting filler
Solution or dispersion liquid in and carry out, and be preferably dried after immersion, be more preferably repeated as many times and impregnate and dry behaviour
Make.Furthermore, it is possible to by organic network structural body and comprising coupling agent before being contacted with the conducting filler in (1) step
Solution or suspension contact.The active functional group of the coupling agent and it can be compound or oligomer, so as to
It is connect with one side with network structure body, is on the other hand combined with the formation of the filler of high thermal conductivity.In order to facilitate that coupling agent with
The connection of network structure body further has to described preferably before contacting with the solution comprising coupling agent or suspension
Machine network structure body is surface-treated, preferably progress hydrophilicity-imparting treatment, so that its surface generates the hydrophily base of such as-OH
Group.Such surface treatment can using for example selected from plasma clean, ultraviolet lighting and/or the technique of chemical attack into
Row.
A preferred embodiment according to the present invention, the organic network structural body are selected from polyurethane sponge and organic
Silicon foam.
In an advantageous embodiment of the invention, the coupling agent is selected from silane coupling agent or dopamine.It is excellent
Choosing, dopamine can be used.For example, surface treated network structure body can be impregnated in the solution comprising dopamine
In.A large amount of catechol and amino group would generally be contained in dopamine, by can be with using lone pair electrons in these groups
Strong combination is formed between organic three-dimensional net structure body surface face and highly heat-conductive material.
The embodiment of the surface treatment composite material of the present invention of property as an example, will can have organic net first
Network structural body material carries out hydrophilic treated with plasma cleaner.Such as under vacuum conditions, using radio-frequency power supply in a level pressure
The plasma that high-energy is generated under power, it is hydrophilic to generate-OH etc. by the surface of the plasma bombardment network structure material
Group enhances the combination of itself and high thermal conductivity filler and coupling agent.Then, the network structure body after such processing is immersed into packet
Containing coupling agent, as the dopamine of certain ph (such as 8-9) solution in impregnated.Surface treatment is completed as a result,.
In (2) and (3) step of method, the mixture of the presoma comprising organic silicon substrate and curing agent can be poured
Infusing load has on the organic network structural body of high thermal conductivity filler, its solidification is then made to obtain heat-conductive silicone composite wood
Material.
Organic silicon substrate is suitable for the invention to be not particularly limited, refer to containing Si-C key and at least one have
Machine base is the compound for being directly connected with silicon atom or being connected by atoms such as O or S with silicon atom, especially with silicon oxygen bond (-
It Si-O-Si- is) polysiloxanes of skeleton composition.
Advantageous, in the present invention, polysiloxanes basis composition constitutes organic silicon substrate.In the present invention, for poly-
Siloxanes base composition is not particularly limited, and can be solidified into corresponding organosilicon material.It is described according to curing mechanism
Polysiloxanes basis composition can be addition curing, condensation curing and with organic peroxide curing.
In a specific embodiment, polysiloxanes basis composition can be addition curing, that is, pass through
Contain vinyl polysiloxane and the hydrogen containing siloxane crosslinking curing under platinum metal catalysts effect in system.
A kind of polysiloxanes basis composition of the addition-curable of illustration includes:
(a1) at least one per molecule contains at least two the polysiloxanes of bonded vinyl on the silicon atoms,
(b1) there is at least one per molecule at least one to be connected to the hydrogeneous of the hydrogen atom on identical or different silicon atom
Polysiloxanes, on condition that the component has at least two hydrogen atoms being connected on identical or different silicon atom in total, and
(c1) catalyst of at least one platinum group metal.
For the polysiloxanes (a1) containing vinyl, the vinyl can be in any position in the polysiloxane backbone
It sets, such as in the end of strand or centre or both ends and centre.
Preferably, the polysiloxanes (a1) containing vinyl includes:
(i) siloxy units of formula (I-1)
R1 aZbSiO[4-(a+b)]/2 (I-1)
Wherein
R1Indicate C2-12, preferably C2-6Alkenyl, most preferably vinyl or allyl,
Z can indicate the univalence hydrocarbyl with 1 to 30, preferably 1 to 12 carbon atom identical or differently, preferred to select
From C1-8Alkyl, including the alkyl optionally replaced by least one halogen atom, and further preferably selected from aryl, particularly
C6-20Aryl,
A is 1 or 2, and b is that the summation of 0,1 or 2 and a+b is 1,2 or 3,
Other siloxy units of (ii) optionally formula (I-2)
Wherein
Z has meaning as described above and c is 0,1,2 or 3.
In one preferred embodiment, Z can be selected from methyl, ethyl, propyl, 3,3,3- trifluoropropyl groups, benzene
Base, xylyl and tolyl etc..Preferably, the group Z of at least 60mol% (or in quantitative terms) is methyl.
The polysiloxanes (a1) containing vinyl can have at least equal to 50mPa.s and preferably smaller than 2,000,
The viscosity of 000mPa.s is also possible to the bigger glue of viscosity.In this application, what all viscosity was directed to is dynamic viscosity
Numerical value and Brookfield apparatus measures can be for example used at 20 DEG C in known manner, if viscosity is very big and uncomfortable
Preferably then measured using the method such as needle penetration with Brookfield instrument.
Polysiloxanes (a1) containing vinyl can be formed only by the unit of formula (I-1) or or additionally include formula
(I-2) unit.The polysiloxanes (a1) containing vinyl is straight chain, branch or cricoid, is not destroying mesh of the present invention
Under the premise of can also contain network-like structure in strand.
The example of the siloxy units of formula (I-1) is vinyidimethylsiloxy groups, vinyl phenylmethyl
Siloxy, vinyl methyl siloxy and vinyl silane oxygroup unit.
The example of the siloxy units of formula (I-2) is SiO4/2Unit, dimethyl silane oxygroup, aminomethyl phenyl first
Siloxy, diphenyl silicon oxygroup, methyl silicane oxygroup and phenylsilane oxygroup.
The example of the polysiloxanes containing vinyl includes straight chain or cricoid compound, such as dimethyl polysiloxane
(with dimethylvinylsilyl end group), (methyl ethylene) (dimethyl) polysiloxane copolymer (have trimethyl
It is silyl-terminated), (methyl ethylene) (dimethyl) polysiloxane copolymer (have dimethylvinylsilyl end
Base) and cricoid methylvinyl-polysiloxane.
In polysiloxanes basis composition of the invention, hydrogen containing siloxane component (b1) must have at least two keys
The hydrogen atom on identical or different silicon atom is connect, to carry out cross-linking reaction with the vinyl polysiloxane of component (a1).Therefore,
At least one per molecule can be used as hydrogen containing siloxane component (b1) and be connected to identical or different silicon at least two
The hydrogen containing siloxane of hydrogen atom on atom or can be used at least two per molecules at least one be connected to it is identical
Or the mixture of the hydrogen containing siloxane of the hydrogen atom on different silicon atoms.
In component according to the present invention (b1) or in the mixture of hydrogen containing siloxane or hydrogen containing siloxane, silicon hydrogen
Group can any position in polysiloxane backbone, such as in the end of strand or centre or both ends and intermediate.
The hydrogen containing siloxane with SiH group can be crosslinked with component (a1) to react, i.e., by making the component
In SiH group reacted with the vinyl in component (a1) and form solidfied material.Preferably, as component (b1), using at least
A kind of each molecule has the hydrogen containing siloxane of two, three or more SiH group.
In one preferred embodiment, the hydrogen containing siloxane includes
(i) siloxy units of formula (I-3):
HdR2 eSiO[4-(d+e)]/2 (I-3)
Wherein
R2Univalence hydrocarbyl can be indicated identical or differently, be preferably selected from C1-8Alkyl, including optionally by least one
The alkyl that a halogen atom replaces, and further preferably it is selected from aryl, particularly C6-20Aryl,
D is 1 or 2, and e is that the summation of 0,1 or 2 and d+e is 1,2 or 3,
Optionally other units of (ii) at least one formula (I-4)
R3 fSiO(4-f)/2 (I-4)
Wherein
R3With meaning as described above and f is 0,1,2 or 3.
In a preferred embodiment, R3Methyl, ethyl, propyl, 3,3,3- trifluoro propyl, benzene can be selected from
Base, xylyl and tolyl etc..
The dynamic viscosity of or mixtures thereof the component (b1) or hydrogen containing siloxane is at least 1mPa.s and preferably
3 between 1000mPa.s, more preferable 5-100mPa.s.
The hydrogen containing siloxane can be formed only by the unit of formula (I-3) or or additionally include formula (I-4)
Unit.The hydrogen containing siloxane can have straight chain, branch or cricoid structure, in the premise for not destroying the object of the invention
Under can also contain network-like structure in strand.
The example of formula (I-3) unit is H (CH3)2SiO1/2,HCH3SiO2/2With H (C6H5)SiO2/2。
The example of formula (I-4) unit then can be identical as example those of is provided for formula (I-2) unit above.
The example of available hydrogen containing siloxane includes straight chain or cricoid compound, as dimethyl polysiloxane (has
Hydrogenate dimetylsilyl end group), copolymer with (dimethyl) (hydrogen methyl) polysiloxane unit is (with trimethyl first
Silylation end group), copolymer with (dimethyl) (hydrogen methyl) polysiloxane unit (there is hydrogenation dimetylsilyl end
Base), the hydrogenating methyl polysiloxanes with trimethylsilyl end groups and cricoid hydrogenating methyl polysiloxanes.
In one embodiment, hydrogen containing siloxane can be the dimethyl comprising hydrogenation dimetylsilyl end group
The mixture of polysiloxanes and the organopolysiloxane comprising at least three hydrosilyls.
The catalyst of at least one platinum group metal can be made of the metal of at least one platinum group or compound, and dosage is answered
It is enough to promote the silicon hydrogen in alkenyl and component (b1) in component (a1) that addition reaction occurs and solidifies.In an advantageous implementation
In mode, the dosage of the catalyst be can be with metal weight in the range of 0.1-1,000ppm, preferably 1-
50ppm。
The catalyst of at least one platinum group metal is known in field of organic silicon and has been commercialized available.Platinum group gold
Category further includes ruthenium, rhodium, palladium, osmium and iridium other than platinum.The catalyst can be composed of the following components: platinum metal or its compound
Or combinations thereof.Such catalyst for example but is not limited only to: platinum black, chloroplatinic acid, platinous chloride, chloroplatinic acid unitary alcohol reactant.
It is preferable to use the compounds of platinum and rhodium.Generally preferable catalyst is platinum.
The complex compound and compound of applicable some platinum be recorded in such as patent US3159601A, US3159602A,
In US3220972A, EP0057459A, EP0188978A and EP0190530A, and it especially can be used and be recorded in such as patent
The complex compound of platinum and vinylic organosiloxane in US3419593A, US3715334A, US3377432A and US3814730A.
Being incorporated by these documents in this specification as reference by reference herein.
In addition to said components (a1) to (c1), it can also press down containing polymerization reaction in the composition of the polysiloxanes basis
Preparation.
Inhibitor common for addition type polysiloxane system be alkyne inhibitor or vinyl-based inhibitor or this
The mixture of the special ratios of two kinds of inhibitor.These inhibitor are disclosed in for example following patent: EP0794217A1,
US20140004359, CN102277128A, CN103554924A and CN103655212A.Here, same by quoting these
Patent is incorporated by present specification.
The example of vinyl-based inhibitor may is that tetramethyl divinyl silane, multi-vinyl silicone oil, tetramethyl tetrem
Alkenyl cyclotetrasiloxane.
The example of alkyne inhibitor may is that 3- butyne-2-alcohol, 1- pentyne -3- alcohol, 1- hexin -3- alcohol, 1- heptyne -
3- alcohol, 5- methyl-1-hexin-3- alcohol, 3,5- dimethyl-1- hexin-3- alcohol, 1- acetenyl-1- cyclopentanol, 1- acetenyl-1-
Cyclohexanol, 1- acetenyl -1- suberol, 3- ethyl -1- hexin -3- alcohol, 3- ethyl -1- heptyne -3- alcohol, 3- isobutyl group -5- first
Base-1- hexin-3- alcohol, 3,4,4- trimethyl-1- pentyne-3- alcohol, 3- ethyl-5- methyl-1-heptyne-3- alcohol, 4- ethyl-1- are pungent
Alkynes-3- alcohol, 3,7,11- trimethyl-1- dodecyne-3- alcohol, 1- acetenyl-1- Lotka-Volterra circle system, 3- methyl-1-butine-3- alcohol, 3- first
Base-1- pentyne-3- alcohol, 3- methyl-1-hexin-3- alcohol, 3- methyl-1-heptyne-3- alcohol, 3- methyl-1-octyne-3- alcohol, 3- first
Base-1- nonyl-3- alcohol, 3- methyl-1-decine-3- alcohol, 3- methyl-1-dodecyne-3- alcohol, 3- ethyl-1- pentyne-3- alcohol, 2,
4,7,9- tetramethyl -5- decine -4,7- glycol.The preferred 2,4,7,9- tetramethyl -5- last of the ten Heavenly stems here is considered from realization the object of the invention
Alkynes -4,7- glycol.
For the polysiloxanes basis composition of addition-curable, when can satisfy preparation, fortune when being not added with inhibitor
When the requirement of defeated, storage etc., these inhibitor can not be added.
Component (a1) and the amount of (b1) are determined according to silicon hydrogen-based and the molar ratio of vinyl.In an advantageous embodiment
In, component (a1) and (b1) are in the composition of the polysiloxanes basis with amount so use, so that silicon hydrogen-based and vinyl
Molar ratio is in the range of 0.5-5, preferably 0.8-4 and, for example, 1-3.
In another particular embodiment of the invention, polysiloxanes basis composition can be condensation curing, even if
Containing can be condensed or the reactive polysiloxane of hydrolyzable or hydroxyl and optional curing agent are in optional organotin or organic
Solidified under titanium catalyst effect.
A kind of illustration can the polysiloxanes basis composition of condensation curing include:
(a2) at least one to have at least two in addition to OH to be condensed group or hydrolyzable groups or only in each end of the chain
Straight chain reaction polysiloxanes with hydroxyl,
(b2) it is optionally at least one do not have can be condensed or the non-reacted poly- silicon oxygen of the straight chain of hydrolyzable groups or hydroxyl
Alkane,
(c2) optionally at least one crosslinking agents.
Group or hydrolyzable groups or only straight with hydroxyl are condensed in addition to OH at least two in each end of the chain
In chain reaction polysiloxanes, the group being condensed includes amino, amide groups, amino oxygroup, ketimide oxygroup, imino group
Oxygroup, alkenyloxy group, alkoxy, alkoxy-alkenyloxy group, acyloxy and phosphate groups, and the group being condensed includes hydrogen
Atom and halogen atom, and they can in any position of polysiloxane backbone, i.e., both ends, centre or both ends and in
Between.
In a specific embodiment, straight chain reaction polysiloxanes can have following formula:
XgR4 3-gSiO-(SiR2-O-)hSiR4 3-gXg (1)
Wherein, R4Substituted or unsubstituted alkyl is indicated independently of one another identical or differently, preferably indicates there is 1 to 30
A, preferably 1 to 12 carbon atom univalence hydrocarbyl, is more preferably selected from the alkyl or aryl of C1-8, such as methyl, ethyl, propyl, fourth
Base, hexyl and octyl and phenyl.Group R4Can optionally it be replaced by such as halogen or cyano.As substituted group R4
Example can mention 3,3,3- trifluoro propyl, chlorphenyl and beta-cyano ethyl.
X indicates the group (in addition to OH) or hydroxyl of identical or different hydrolyzable or condensation.
The numerical value of h should be enough such that the dynamic viscosity of the straight chain reaction polysiloxanes at 25 DEG C be 1000 to
2000000mPas, preferably 5000 to 80000mPas, such as h are the integers of 30-3000, and g is 1,2 or 3.When X table
G is equal to 1 when showing hydroxyl.
As cell S iR2The example of O- can enumerate (CH3)2SiO、CH3(C6H5)SiO、(C6H5)2SiO、CF3CH2CH2
(CH3)SiO、NC-CH2CH2(CH3)SiO。
It can these preferably following groups as group X: n-butylamino, s-butylamino and Cyclohexylamino, benzene first
Acylamino-, dimethylamino oxygroup, diethylamino oxygroup, dioctylamino oxygroup, diphenyl amino oxygroup are derived from benzene second
Ketoxime, acetoxime, diphenyl-ketoxime, methyl ethyl ketone oxime, the imino group oxygroup and ketone of diisopropyl ketoxime and chlorine cyclohexanone oxime
Imines oxygroup group, with 1 to 8 carbon atom alkoxy for example methoxyl group, propoxyl group, isopropoxy, butoxy, hexyloxy and
Octyloxy, Methoxy-vinyl oxygroup, the acyloxy containing 1 to 8 carbon atom for example formyloxy, acetoxyl group, propionyloxy and
2- ethyl hexanoyl oxygroup is derived from those of dimethyl phosphate, diethyl phosphate and dibutylphosphoric acid ester group phosphate groups, with
And there are also halogen such as chlorine.
It is preferable to use straight chain reaction polysiloxanes be general formula (1) α, alpha, omega-dihydroxy diorganopolysiloxaneand,
Wherein X=OH and g=1, and the numerical value of h should be enough to make dynamic viscosity 1000 of the straight chain reaction polysiloxanes at 25 DEG C
To 2000000mPas, preferably 5000 to 80000mPas.
It can be condensed or the non-reacted polysiloxanes of the straight chain of hydrolyzable groups or hydroxyl, can be used following logical for not having
The silicone oil of formula (2):
R4 3SiO-(SiR2-O-)h’SiR4 3 (2)
Wherein group R4It can be identical or differently as defined in general formula (1), and the numerical value of h ' should be enough to make the non-reaction
Property dynamic viscosity of the polysiloxanes at 25 DEG C be 10 to 10000mPas, preferably 30 to 2000mPas.
It should be appreciated that in scope, the hydroxylated reactive polysiloxane of workable general formula (1) be containing
The mixture of the mutually different several hydroxylated polymers of the property of its viscosity number and/or the substituent group being connected with silicon atom.Also
It should be appreciated that the hydroxylated polymer of general formula (1) is SiR in addition to general formula2It, can also optionally content ratio be extremely outside the D unit of O
The SiR of mostly 10% (based on the number of the T unit of every 100 silicon atoms and/or Q unit)3/2And/or SiR4/2List
Member.Same explanation and the non-reacted polysiloxanes for being suitable for formula (2).
In addition, this can also optionally include one or more following formulas in the polysiloxanes basis composition of condensation curing
Silane or part thereof hydrolysate as crosslinking agent c2):
R4 4-zSiXz (3)
Wherein, group R43 or 4 are indicated with definition in X such as general formula (1) and index z.
When reactive polysiloxane is α, when alpha, omega-dihydroxy diorganopolysiloxaneand, crosslinking agent is required, and is worked as
When each end of the chain, which has, can be condensed group or hydrolyzable groups, then the crosslinking agent may not be necessary reactive polysiloxane.
Preferred crosslinking agent is, for example, vinyltrimethoxysilane, vinyltriethoxysilane, 3- (glycidyl
Oxygroup) propyl Ethoxysilane.
In addition, this can also be optionally comprising at least one organic in the polysiloxanes basis composition of condensation curing
Tin or organotitanium or their compositions are as catalytic component d2).
The catalytic component d2) it is mainly selected from organotin or organic titanic compound, such as stannous octoate, dibutyl tin, two
It is two fourth tin of acetic acid, dibutyl tin dilaurate, two (second-thylhexoic acid) dibutyl tins, diisooctyl dibutyitin maleate, new
The third two oxygroup titanium of capric acid stannous, tetrabutyl titanate, isopropyl titanate, iso-butyl titanate, 1,3- is bis- (ethyl acetoacetate).
In another specific embodiment, polysiloxanes basis composition, which can be, uses peroxide cure
's.
A kind of polysiloxanes basis composition of illustrative available peroxide cure includes:
(a3) at least one organo-siloxanes polymer, the ethylene containing 0-4 weight %, preferably 0.01-3 weight %
Base, and
(b3) at least one organic peroxide.
It (such as in 25 DEG C of viscosity is 50000-1000000mPa that these organo-siloxanes polymers, which can be oily,
S), it is also possible to gluey (such as viscosity is higher than 1000000mPas), or the mixture of oil and glue.They are commercially available to obtain
, it method can also be made according to prior art.
These organo-siloxanes polymers can be the diorganopolysiloxanecompositions of straight chain, and main chain is mainly by formula R5 2SiO
Unit is constituted.This chain is in each end formula R5 3Si0.5Unit and/or formula OR6Group end capping.
Group R in above-mentioned formula5C is indicated identical or differently1-C18, preferably C1-C12Alkyl or halohydrocarbyl.The hydrocarbon
Base includes alkyl, alkenyl, aryl, aralkyl, alkaryl, naphthenic base, cycloalkenyl, cyanoalkyl.Preferably, group R5Indicate first
Base, ethyl, propyl, octyl, octadecyl, phenyl, tolyl, xylyl, benzyl, phenethyl, cyclohexyl, suberyl, ring
Hexenyl, vinyl, allyl, cyano ethyl, chloromethyl, 3,3,3- trifluoro propyl, chlorphenyl, dibromo phenyl, trifluoromethyl
Phenyl.
Group R6Indicate hydrogen atom, C1-C4Alkyl or 'beta '-methoxy ethyl.
Preferably, at least 60% group R5Indicate methyl.But along diorganopolysiloxanecompositions chain, there may also be few
Amount is different from R5 2The unit of SiO, such as formula R5Si1.5Unit and/or SiO2Unit, (these % numerical tabulars of ratio most 2%
Show the number of the T and/or Q unit in terms of every 100 silicon atoms).
As above-mentioned R5SiO、R5 3SiO0.5Unit and formula OR6Group can there are (CH3)2SiO、CH3(CH2=CH)
SiO、CH3(C6H5)SiO、(C6H5)2SiO、CH3(C2H5)SiO、(CH3CH2CH2)CH3SiO、CH3(n-C3H7)SiO、(CH3)3SiO0.5、(CH3)2(CH2=CH) SiO0.5、CH3(C6H5)SiO0.5、CH3(C6H5)(CH2=CH) SiO0.5、OH、-OCH3、-
OC2H5、-O-n-C3H7、-O-iso-C3H7、-O-n-C4H9With-OCH2CH2OCH3。
Organic peroxide component (b3) used in the embodiment is not particularly limited, as long as it is free to decompose generation
Oxygen radical.It can be used with pure state, and the form being also soluble in organic solvent and silicone oil uses.Organic mistake
Oxide component is made of at least one peroxide, and the peroxide is selected from such as di-t-butyl peroxide, 2,5- diformazan
Base -2,5- di-t-butyl hexane peroxide, benzoyl peroxide, peroxidating 2,4 dichloro benzene formyl, peroxidating monochloro-benzene formyl,
Two perbenzoate of t-butyl peroxy-acetate, dicumyl peroxide and 2,5- dimethylhexane -2,5-.
The dosage of organic peroxide component is the 0.05-15 parts by weight, excellent based on the component (a3) of 100 parts by weight
Select 0.2-8 parts by weight.
Detailed description of the invention
Fig. 1 is silver nanowires scanning electron microscope (SEM) photograph；
Fig. 2 is silver nanowires silicon foams three-dimensional net structure body low power number scanning electron microscope (SEM) photograph；
Fig. 3 is silver nanowires silicon foams three-dimensional net structure body high magnification numbe scanning electron microscope (SEM) photograph；
Fig. 4 is the schematic diagram according to high thermal conductivity flexible silicone composite material produced by the present invention.
Specific embodiment
Below with reference to specific implementation case, using the heat conductive silica gel of the silicon foams of absorption carriage silver nanowires as embodiment
1 is described further.
Embodiment 1
(1) preparation of silver nanowires
The polyvinylpyrrolidone (PVP) that 0.2g molecular weight is about 360000 is taken to be dissolved in 25mL ethylene glycol by recipe requirements molten
Liquid, ultrasonic disperse is uniform, adds 0.25g AgNO3With 3.5g FeCl3, 5h is reacted under the conditions of 130 DEG C after mixing.Instead
Acetone is added after answering and EtOH Sonicate centrifugation washs 2-3 times repeatedly and washes away impurity, finally obtained silver nanowires dispersion
Into ethanol solution.
(2) hydrophilic treated of silicon foams
Silicon foams are cut into the sample of certain size, are fixed on glass slide, are put into plasma cleaner, are taken out
Vacuum opens switch to most high-grade, processing 2 minutes.
180g deionized water is taken, 0.446g tri- (methylol) aminomethane is added, pH to 8-9 is adjusted, it is more to add 0.258g
Bar amine.It takes out, is transferred in baking oven in 40 DEG C of drying 2h after silicon foams are impregnated 24 hours in dopamine solution.
(3) preparation of heat conduction network structural body
The good silicon foams of hydrophilic treated are sufficiently impregnated in silver nanowires ethanol solution, in 70 DEG C of baking ovens after taking-up
Middle drying.It repeats to impregnate drying operation 5-7 times, so that more silver nanowiress is adsorbed on silicon foams surface as far as possible.
(4) casting of silica gel
The presoma and 1g curing agent for taking 10g silica gel are sufficiently stirred, and are uniformly mixed, vacuumize removing bubble, then take appropriate
Mixed solution is poured into heat conduction network structural body obtained.In 75 DEG C of solidification 5h, the thermal conductivity silica gel filled.
(5) laser heat conducting instrument measures thermal diffusion coefficient
The thermal conductivity silica gel of the filling of the thickness of 2mm made from the above method and unfilled pure original silica gel are cut respectively
At the thin slice of 10x 10x 2mm size.Sample is put into the specific position of laser conductometer, is turned on the switch, laser gets to silica gel
The signal received is obtained the thermal diffusion of material by simulation by the lower surface of piece, the hygrosensor in the upper surface of silica gel piece
Coefficient calculates the thermal conductivity for obtaining the heat-conductive silicone composite material containing 5 weight % silver nanowiress by pure organosilicon material
0.2W/mK increases to 0.8W/mK, and sample has preferable flexibility.
Embodiment 2
The preparation method is the same as that of Example 1, repeatedly impregnates and increase the mass fraction of silver wire, and obtaining silver wire mass fraction is 10%
Sample, measuring its thermal conductivity increases to 1.252W/mK, and sample has preferable flexibility.
Embodiment 3
The preparation method is the same as that of Example 1, reduces the mass fraction for impregnating number and changing silver wire, obtains silver wire mass fraction and is
3% sample, measuring its thermal conductivity increases to 0.279W/mK, and sample has preferable flexibility.
Embodiment 4
Using polyurethane sponge as three-dimensional net structure body, graphene is high thermal conductivity filler, and preparation has three-dimensional network
The heat-conductive silicone composite material of structural body.Specific step is as follows:
(1) preparation of graphene oxide
Graphite powder and sodium nitrate are blended in the concentrated sulfuric acid according to recipe requirements, ice-water bath is to 0 DEG C.Then formula is added to want
The potassium permanganate for the amount of asking, then by container global transfer to 40 DEG C of waters bath with thermostatic control.After water bath with thermostatic control and stirring after 1 hour, add one
Quantitative deionized water dilution, is then added dropwise quantitative hydrogen peroxide dropwise, finally obtained solution after removal of impurities repeatedly from
Heart processing, obtained precipitating are dispersed in inorganic solvent such as deionized water to arrive required graphene oxide solution again.
(2) preparation of three-dimensional net structure body
Commercially available conventional polyurethanes sponge is thinly sliced, is immersed in hydrochloric acid, dopamine and three hydroxyls according to recipe requirements
24 hours in the mixed solution of methylamino methane, it is small to be then immersed in graphene oxide solution made from step (1) 1
When, it after drying, is restored using hydrothermal reduction method, then be placed in constant temperature convection oven and dry.
(3) preparation of high heat conduction organosilicon composite material and performance measurement
The three dimentional heat conduction network structure body that step (2) obtain is immersed in the mixture of organosilane precursor and curing agent
In.After five minutes, composite material is transferred in baking oven, keeps the temperature 1 hour in 120 DEG C, obtains high-termal conductivity organosilicon composite wood
Material.Thermal conductivity test shows: the sample thermal conductivity that filer content is 3 weight % is 0.56W/mK, while sample has preferably
Flexibility.
Claims (14)
1. heat-conductive silicone composite material, it includes organic silicon substrates and the organic network being embedded in the organic silicon substrate
Structural body, wherein load has conducting filler on the organic network structural body.
2. composite material according to claim 1, which is characterized in that the network structure body has porous structure, preferably
With > 60%, > 80% or > 90% percent opening.
3. composite material according to claim 1 or 2, which is characterized in that the network structure body is selected from polyurethane, organic
Silicon, polystyrene, polyvinyl chloride, polyethylene, phenolic resin are more preferably selected from polyurethane sponge or silicon foams.
4. composite material according to any one of claims 1 to 3, which is characterized in that the conducting filler, which has, to be greater than
5,10 draw ratio, preferably sheet, threadiness, rodlike or irregular shape are greater than.
5. the described in any item composite materials of Claims 1-4, which is characterized in that the conducting filler is in its longest dimension
Degree has on direction > 100nm, preferably > 1 micron, more preferably > 5 microns, such as 5-150 microns or 10-100 microns or 10-50 it is micro-
The size of rice.
6. composite material according to any one of claims 1 to 5, which is characterized in that the conducting filler is selected from metal
Oxide such as Al2O3, ZnO, CaO, MgO or BeO, nitride such as AlN or BN, carbide such as SiC or B4C3, metal such as Au, Ag,
Cu, carbon material such as carbon fiber, carbon nanotube or graphene；Preferably Ag line or graphene.
7. composite material according to any one of claims 1 to 6, which is characterized in that the load capacity of the conducting filler
For 80 weight % or less, preferably 50 weight % or less, more preferable 30 weight % or less, most preferably 20 based on entire composite material
Weight % or less.
8. composite material according to any one of claims 1 to 7, which is characterized in that the organic network structural body contains
Amount be 50 weight % hereinafter, it is preferred that 40 weight % hereinafter, more preferable 20 weight % or 10 weight % hereinafter, be based on entire composite wood
Material meter.
9. the method for preparing composite material according to any one of claims 1 to 8, includes the following steps:
(1) the organic network structural body is contacted with the conducting filler, being supported on the conducting filler described has
On machine network structure body,
(2) mix it with the composition of the presoma comprising organic silicon substrate and optional curing agent, and
(3) solidify resulting mixture.
10. method according to claim 9, which is characterized in that the organic network structural body is impregnated in packet in (1) step
In solution or dispersion liquid containing the conducting filler.
11. method according to claim 9 or 10, which is characterized in that contacting it with the conducting filler in (1) step
Before contact the organic network structural body with the solution comprising coupling agent or suspension, the active functional group of coupling agent
Group.
12. method according to claim 11, which is characterized in that the coupling agent is selected from silane coupling agent or dopamine.
13. method according to any one of claims 11 to 12, which is characterized in that with the solution comprising coupling agent
Or before suspension contact, the organic network structural body is surface-treated, preferably carry out hydrophilicity-imparting treatment.
14. method according to claim 13, which is characterized in that the surface treatment is using selected from plasma clean, ultraviolet
The technique of illumination and/or chemical attack carries out.
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