CN105968822B - Heat-conducting silicon rubber and preparation method thereof, laser projection device - Google Patents
Heat-conducting silicon rubber and preparation method thereof, laser projection device Download PDFInfo
- Publication number
- CN105968822B CN105968822B CN201610474471.5A CN201610474471A CN105968822B CN 105968822 B CN105968822 B CN 105968822B CN 201610474471 A CN201610474471 A CN 201610474471A CN 105968822 B CN105968822 B CN 105968822B
- Authority
- CN
- China
- Prior art keywords
- heat
- silicon rubber
- preparation
- conducting silicon
- silicone rubber
- 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
Classifications
-
- 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
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/14—Peroxides
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03B—APPARATUS OR ARRANGEMENTS FOR TAKING PHOTOGRAPHS OR FOR PROJECTING OR VIEWING THEM; APPARATUS OR ARRANGEMENTS EMPLOYING ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ACCESSORIES THEREFOR
- G03B21/00—Projectors or projection-type viewers; Accessories therefor
- G03B21/14—Details
- G03B21/16—Cooling; Preventing overheating
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
The present invention provides a kind of heat-conducting silicon rubber and preparation method thereof, the laser projection device comprising the heat-conducting silicon rubber.The preparation method of the heat-conducting silicon rubber comprising the steps of: heat filling is dispersed in silicone rubber matrix by step 1；Vulcanizing agent is dispersed in the silicone rubber matrix by step 2；Step 3 makes the vulcanizing agent crosslink to react with silicone rubber matrix and obtain heat-conducting silicon rubber；Wherein, the heat filling is the heat filling that silane quasi polymer and metal powder are combined by solution mixing method.The preparation method of heat-conducting silicon rubber according to the present invention, the heat filling used be in advance by metal powder and silane quasi polymer it is compound obtained from heat filling, by being compounded with the silane quasi polymer of metal powder and the good intermiscibility of silicone rubber matrix, it is uniformly dispersed in silicone rubber matrix that heat filling can be improved.
Description
Technical field
The present invention relates to heat-conducting silicon rubber and preparation method thereof, include the laser projection device of the heat-conducting silicon rubber.
Background technique
The main chain of silicon rubber is made of silicon, oxygen atom, and side chain is carbon-containing group.Since the combination of silicon oxygen bond is closer,
So the heat-resisting of silicon rubber, cold tolerance are good, and have excellent against weather, ozone resistance and good insulating properties,
Therefore silicon rubber can be widely applied in the fields such as medical treatment, life, industry.Specifically, also frequent in electronic assembly field
Use silicon rubber.However in recent years, Electronic Assemblies forward direction densification direction is developed, and the power density of electronic component is caused constantly to rise
Height is easy to cause temperature excessively high in use, therefore for the occasion of application silicon rubber, and high-termal conductivity, which becomes, influences electronics member
An important factor for device reliability and service life.Moreover, in order to reduce the thermal contact resistance between interface, it is desirable that boundary material was both
There is higher thermal coefficient, it is also required to have good processing performance and mechanical property, so as between energy preferably filling interface
Minim gap.The heating conduction of silicon rubber itself is very poor, thermal conductivity usually only 0.13-0.25W/MK or so, can not expire
The thermal conductivity demand being continuously improved brought by the continuous improvement of the power density of sufficient Electronic Assemblies.Therefore the scheme proposed
It is, by adding the filler of high thermal conductivity thereto, the heating conduction of Lai Tigao silicon rubber composite material, therefore with thermally conductive
The raising of performance can bring the optimization of heat dissipation performance.
Currently, by the method that the filler of high thermal conductivity is added into silicone rubber matrix mainly include solution blending, powder mix,
The methods of melting mixing.The heat-conducting silicon rubber that method as above obtains is cheap, easily processed into type, thus be widely used in
The silastic product field of electronic component contact.As an example, Xi'an Technology University Wang Ni is in its paper " thermal conductive silicon rubber
The preparation of glue and performance characterization " in disclose, select graphite, silicon carbide, boron nitride, aluminium nitride to lead as heat filling to prepare
Hot silicon rubber, when wherein Boron nitride is 30 parts, the silicon rubber effect of preparation is best, and thermal coefficient is that 0.647W/MK (is surveyed
Test-object is quasi-: GB/T11205-2009), tensile strength is 2.761MPa (testing standard: GB/T528-92).
It will be appreciated, however, that needing to add a large amount of heat fillings, this can lead to form efficient thermally conductive supply chain network structure
The mechanical properties decrease for causing silicon rubber, is unfavorable for machine-shaping.Moreover, a large amount of heat fillings of addition not can be uniformly dispersed in silicon
In rubber matrix, leads to the interruption of thermally conductive network chain, affect heat dissipation effect.Such as it is disclosed in patent document CN102827480A
A kind of method preparing high-heat-conductingsilicon silicon rubber compound material, core be by heat filling and deionized water, ethyl alcohol, toluene,
Dimethylbenzene, tetrahydrofuran or/and acetone are configured to the dispersion liquid that solid content is 1wt%~20wt%, and in dispersing apparatus,
Normal pressure and under room temperature decentralized processing 1 hour to 48 hours, gained dispersion liquid can be used directly, or filtering gained dispersion liquid,
Gained solid formation is used as heat filling after drying.
Inventors have found that although heat filling and silicon rubber can be improved in the method in above patent document CN102827480A
The contact performance of matrix body, but there are still disperse non-uniform phenomenon.
Summary of the invention
Therefore, technical problem to be solved by the present invention lies in provide a kind of preparation method of heat-conducting silicon rubber, utilize this
The preparation method of heat-conducting silicon rubber can prepare heat filling therein and obtain evenly dispersed heat-conducting silicon rubber.
In order to solve the above technical problem, the present invention provides technical solutions below:
A kind of preparation method of heat-conducting silicon rubber comprising the steps of:
Heat filling is dispersed in silicone rubber matrix by step 1；
Vulcanizing agent is dispersed in the silicone rubber matrix by step 2；
Step 3 makes the vulcanizing agent crosslink to react with silicone rubber matrix and obtain heat-conducting silicon rubber；
Wherein, the heat filling is the heat filling being prepared as follows；
Step (a): the silane chloride containing at least one double bond, excessive mercaptan compound and photoinitiator is made to exist
It is reacted under conditions of illumination in first organic solvent, obtains the first reactant, then remove the first organic solvent and unreacted
Mercaptan compound obtain the second reactant, the second reactant is dissolved in the second organic solvent, the second reactant is obtained
Solution；
Step (b): being dispersed to metal powder in the solution of second reactant, then removes second reactant
Solution in the second organic solvent；The complex of the metal powder Yu second reactant is obtained, the complex is
For heat filling.
Preferably, the weight average molecular weight of the silicone rubber matrix is 150,000~1,000,000；Ethylene in the silicone rubber matrix
Base molar content is 0.05%~2%；The silicone rubber matrix is type siloxane silicone rubber matrix.
Preferably, the number of the silicone rubber matrix and heat filling is respectively 100 parts and 10~40 parts；The vulcanizing agent
Number be 0.3~5 part.
Preferably, it in the step 1, after heat filling is dispersed in silicone rubber matrix, carries out comprising first
The two-stage mixing that section is kneaded and second segment is kneaded；The condition that the first segment is kneaded is that temperature is 60~70 DEG C, and the time is 5~30
Minute；The condition that the second segment is kneaded is that temperature is 75~85 DEG C, and the time is 5~30 minutes.
Preferably, in the step 2, the vulcanizing agent is 2,5- dimethyl -2,5- bis(t-butylperoxy) hexane；
In step 3, it is 150~170 DEG C that the condition of the cross-linking reaction, which is temperature, and pressure is 10~100MPa, retention time 10
~80 minutes.
Preferably, in the step (a), the silane chloride containing at least one double bond is to have the following structure
Dichlorosilane:
Wherein, R1Or R2It is the group at least one-C=C- double bond；
In the step (a), the mercaptan compound is 3,6- dioxa -1,8- octanedithiol；
In the step (a), the photoinitiator is the double acylphosphine oxides for the formula that has following structure:
In the step (a), the condition of the illumination is to be irradiated in the case where wavelength is 365 nanometers of light；
In the step (a), first organic solvent is tetrahydrofuran；
In the step (a), second organic solvent is ethyl alcohol；
In the step (b), the metal powder is that surface-treated metal powder is carried out using acid.
Preferably, in the step (b), the acid is hydrochloric acid or sulfuric acid；The metal powder be selected from copper powder, iron powder,
Bronze, silver powder, zinc powder or combinations thereof.
Preferably, in the step (b), the partial size of the metal powder is 200 nanometers~20 microns.
Preferably, in the step (b), the mode of the second organic solvent in the solution of second reactant is removed
It is to be dried under inert gas protection；The temperature of the drying is 30~35 DEG C.
In addition, the present invention also provides a kind of heat-conducting silicon rubber, for by any of the above-described heat-conducting silicon rubber preparation method system
For what is obtained.
In addition, the present invention also provides a kind of laser projection device, including above-mentioned heat-conducting silicon rubber as heat transfer component.
The preparation method of heat-conducting silicon rubber according to the present invention, can prepare heat filling therein obtain it is evenly dispersed
Heat-conducting silicon rubber.The heat-conducting silicon rubber that heat filling is dispersed in silicone rubber matrix why can be prepared, be because
Heat filling in the present invention, to use be in advance by metal powder and silane quasi polymer it is compound obtained from thermally conductive fill out
Material, to improve thermally conductive fill out by the good intermiscibility of the silane quasi polymer and silicone rubber matrix that are compounded with metal powder
Expect uniformly dispersed in silicone rubber matrix.In addition, silicon rubber prepared by the preparation method of heat-conducting silicon rubber of the invention,
Processing performance is good, the reason is that, metal powder being evenly distributed in silicon rubber, will not influence because reuniting phenomena such as
Processing performance.
Detailed description of the invention
Fig. 1 is first application mode of silicon rubber prepared by the preparation method using heat-conducting silicon rubber of the invention
Schematic diagram.
Fig. 2 is second application mode of silicon rubber prepared by the preparation method using heat-conducting silicon rubber of the invention
Schematic diagram.
Fig. 3 is the third application mode of silicon rubber prepared by the preparation method using heat-conducting silicon rubber of the invention
Schematic diagram.
Fig. 4 is the 4th application mode of silicon rubber prepared by the preparation method using heat-conducting silicon rubber of the invention
Schematic diagram.
Fig. 5 is the 5th application mode of silicon rubber prepared by the preparation method using heat-conducting silicon rubber of the invention
Schematic diagram.
Description of symbols:
1 printed circuit board
2 metallic supports
3 heat-conducting silicon rubbers
4 radiators
5 fluorescent powder wheel motors
6 structural members
7 total internal reflection prisms
8 lasers
9 liquid cooling heads
Specific embodiment
In order to which those skilled in the art can be more fully understood technical solution of the present invention, below with reference to specific implementation
Mode is illustrated.
A kind of preparation method of heat-conducting silicon rubber comprising the steps of:
Heat filling is dispersed in silicone rubber matrix by step 1；
Vulcanizing agent is dispersed in the silicone rubber matrix by step 2；
Step 3 makes the vulcanizing agent crosslink to react with silicone rubber matrix and obtain heat-conducting silicon rubber；
Wherein, the heat filling is the heat filling being prepared as follows；
Step (a): have the silane chloride containing at least one double bond, excessive mercaptan and photoinitiator first
It is reacted under conditions of illumination in solvent, obtains the first reactant, then remove the first organic solvent and unreacted mercaptan
Compound obtains the second reactant, and the second reactant is dissolved in the second organic solvent, obtains the solution of the second reactant；
Step (b): being dispersed to metal powder in the solution of second reactant, then removes second reactant
Solution in the second organic solvent；The complex of the metal powder Yu second reactant is obtained, the complex is
For heat filling.
In the preparation method of heat-conducting silicon rubber of the invention, by using heat filling as described above, it can be improved
Dispersing uniformity of the heat filling in silicone rubber matrix.Therefore, in above-mentioned heat filling, due to metal powder and silane
Quasi polymer it is compound, recycle silane quasi polymer and silicone rubber matrix good intermiscibility, can be improved heat filling
It is uniformly dispersed in silicone rubber matrix.Since above-mentioned rubber matrix is also silane quasi polymer, it is preferable that above-mentioned silane
Quasi polymer and above-mentioned silicone rubber matrix are the polymer of identical type.
Weight average molecular weight about the silicone rubber matrix is not particularly limited, such as can be with 150,000 or more, specifically
It can be 200,000,300,000,400,000,500,000,600,000,700,000 or so, more preferably 150,000~1,000,000.The measurement of weight average molecular weight
The methods of intrinsic viscosity method can be used in method.
In addition, can contain vinyl in the silicone rubber matrix, there is no special for the molar content of vinyl
Restriction.As long as can reinforce being cross-linked to form polymer network.Specifically, the molar content of vinyl is preferably
0.05%~2%.If the molar content of vinyl less than 0.05%, can not sufficiently play crosslinked action；And
If the molar content of vinyl is greater than 2%, the crosslink density of finally formed silicon rubber is possible to excessive, thus right
Elasticity decreases.
About the type of the silicone rubber matrix, it is not particularly limited.General silicon rubber can be used.Specially
Type siloxane silicone rubber matrix.It as silicon rubber, can specifically enumerate: methyl vinyl silicone rubber, dimethyl silicone rubber, methyl
Phenyl vinyl silicon rubber etc..
About the proportion of the silicone rubber matrix and heat filling, it is not particularly limited.The content of heat filling is only
It wants that increased thermal conductivity energy can be played.Such as can preferably the proportion of the silicone rubber matrix and heat filling be respectively
100 parts and 10~40 parts, the proportion of the more preferable silicone rubber matrix and heat filling is respectively 100 parts and 15~35 parts, into
The proportion of the preferably described silicone rubber matrix of one step and heat filling is respectively 100 parts and 20~30 parts.Specifically, the silicon rubber
The proportion of matrix body and heat filling is respectively 100 parts and 25 parts.
About the type of vulcanizing agent, there is no specific limitations, premise is that playing the role of cross-linked silicone rubber.It can be with
Use usual ingredient according to the type of rubber constituent, such as can enumerate: metal oxide (magnesia, zinc oxide etc.) has
Machine peroxide (diacyl peroxide, peroxyester, dialkyl peroxide etc.), sulphur class vulcanizing agent etc..Also, sulphur class sulphur
Agent is common.As sulphur class vulcanizing agent, such as powder sulphur, sedimentation sulphur, colloid sulphur, insoluble sulfur, height can be enumerated
Dispersed sulphur, sulfur chloride (sulfur monochloride, sulfur dichloride) etc..These crosslinking agents can be used alone or two or more combinations make
With.In addition, metal oxide can be applied in combination with other vulcanizing agents (sulphur class vulcanizing agent etc.), metal oxide and/or sulphur class
Vulcanizing agent can be used alone or be applied in combination with vulcanization accelerator.The usage amount of vulcanizing agent can be according to vulcanizing agent and rubber
The type of ingredient is from being to select in the range of 0.3 parts by weight~20 parts by weight relative to 100 parts by weight of rubber constituent, such as preferably
For 0.3 parts by weight~5 parts by weight.
In vulcanization, other than vulcanizing agent, other cross-linking aids or vulcanization accelerator can also be used.It can enumerate
Well known cross-linking aid, such as multifunctional (different) cyanurate is (for example, Triallyl isocyanurate (TAIC), triallyl
Cyanurate (TAC) etc.), polydiene (for example, 1,2- polybutadiene etc.), unsaturated carboxylic acid metal salt (for example, (methyl) third
Olefin(e) acid zinc, (methyl) Magnesium Acrylate Prepared etc.), oximes (for example, quininie dioxime etc.), guanidine (for example, diphenylguanidine etc.), multifunctional (first
Base) acrylate is (for example, ethylene glycol two (methyl) acrylate, butanediol two (methyl) acrylate, trimethylolpropane tris
(methyl) acrylate etc.), bismaleimide amine (aliphatic bismaleimide, for example, N, N ' -1,2- ethylidene span
Come acid imide, 1,6 '-bismaleimide-(2,2,4- trimethyl) hexamethylene etc.；Aromatic hydrocarbons bismaleimide or aromatic series are double
Maleimide, for example, N-N '-meta-phenylene bismaleimide, 4- methyl-1,3- phenylene bismaleimide, 4,4 '-
Bis- [4- (4- maleimidephenoxy) phenyl] propane of diphenyl methane bismaleimide, 2,2-, 4,4 '-diphenyl ethers are double
Bis- (3- maleimidephenoxy) benzene of maleimide, 4,4 '-diphenyl sulfone bismaleimide, 1,3-) etc..These crosslinkings
Auxiliary agent may be used singly or in combination of two or more.In these cross-linking aids, preferably bismaleimide amine (N, N '-
The aromatic hydrocarbons such as phenylene bismaleimide bismaleimide or aromatic series bismaleimide).By adding bismaleimide
Amine can be improved the degree of cross linking, prevent bonding abrasion etc..The ratio of cross-linking aid by solid component conversion in terms of can from relative to
The silicon rubber of 100 parts by weight be such as 0.01 parts by weight~10 parts by weight in the range of select, such as can for 0.1 parts by weight~
5 parts by weight (such as 0.3 parts by weight~4 parts by weight), preferably 0.5 parts by weight~3 parts by weight (such as 0.5 parts by weight~2 weight
Part).
As vulcanization accelerator, such as thuriam acceserator can be enumerated (for example, tetra methylthiuram list sulfide
(TMTM), tetramethyl thiuram disulfide (TMTD), Thiuram disulphide (TETD), two sulphur of tetrabutyl thiuram
Compound (TBTD), double pentamethylene thiuram tetrasulfides (DPTT), N, N '-dimethyl-N, N '-diphenyl thiuram curing
Object etc.), thiazole accelerator is (for example, the zinc salt of 2-mercaptobenzothiazole, 2-mercaptobenzothiazole, 2-mercaptothiazoline, hexichol
And thiazole disulphide, 2- (4 '-morpholinodithio) benzothiazole etc.), sulfenamide type accelerators is (for example, N- cyclohexyl-
2-[4-morpholinodithio sulfenamide (CBS), N, N '-dicyclohexyl -2-[4-morpholinodithio sulfenamide etc.), bismaleimide amine promote
Into agent (for example, N, N '-meta-phenylene bismaleimide, N, N ' -1,2- ethylenebismaleimide etc.), guanidine (hexichol
Base guanidine, di-o-tolyl guanidine etc.), ureas or Thiourea accelerator (for example, ethylene thiourea etc.), dithiocar-bamate
Class, xanthic acid salt etc..These vulcanization accelerators may be used singly or in combination of two or more.These vulcanization accelerators
In, TMTD, DPTT, CBS etc. is widely used.The ratio of vulcanization accelerator is in terms of solid component conversion relative to 100 parts by weight silicon
Rubber matrix for example can be 0.1 parts by weight~15 parts by weight, preferably 0.3 parts by weight~10 parts by weight, further preferably
0.5 parts by weight~5 parts by weight.
In addition, being not particularly limited for mixing mode of the invention, as long as can play the original of each silicon rubber
Material is kneaded uniform.Such as it can be kneaded by using kneading machines such as mixer, open mills.And the number of segment being kneaded
(or referred to as number) is not particularly limited.It such as can be one section of mixing or two sections of mixings.Preferably, in the step
In rapid 1, two-stage mixing is used.That is, can be carried out mixed comprising first segment after heat filling is dispersed in silicone rubber matrix
The two-stage mixing that refining and second segment are kneaded.For the condition of mixing, and there is no particular limitation.From taking into account melting efficiency and mixed
It sets out in terms of refining uniformity, the condition that the first segment is kneaded is that temperature is 60~70 DEG C, and the time is 5~30 minutes.It can be excellent
The condition for selecting the second segment to be kneaded is that temperature is 75~85 DEG C, and the time is 5~30 minutes.
About the vulcanizing agent used in the step 2, the vulcanizing agent as above enumerated can be used for example.It is preferable to use
2,5- dimethyl -2,5- bis(t-butylperoxy) hexane is as vulcanizing agent.
It about the condition of the cross-linking reaction in step 3, is not particularly limited, as long as being capable of providing enough
Energy to cause cross-linking reaction.Such as preferable temperature is 150~170 DEG C, pressure is
10~100MPa, retention time are 10~80 minutes.
In addition, the silane chloride containing at least one double bond preferably has following knot in the step (a)
The dichlorosilane of structure:
Wherein, R1Or R2For the group at least one-C=C- double bond.R1Or R2It can be same or different.Specifically
Ground, R1Or R2It can be the alkyl or alkenyl with-C=C- a double bond, such as can be the second with-C=C- a double bond
Base, propyl, isopropyl, butyl, isobutyl group, sec-butyl, tert-butyl, amyl, isopentyl, neopentyl, tertiary pentyl, hexyl, dissident
Base, heptyl, octyl, nonyl, decyl etc..
In the step (a), the mercaptan compound can be n-dodecyl mercaptan, ethanethio, butanethiol
Equal straight chain type thiols, but not limited to this.In the present invention, 3,6- dioxa -1,8- octanedithiol can be used as preferably
Example.
In addition, as photoinitiator, such as can be enumerated: benzil, benzoin ether, benzoin in the step (a)
Butyl ether, benzoin propyl ether, benzophenone, 3,3 '-dimethyl -4- methoxy benzophenones, benzoylbenzoic acid, benzophenone first
Carboxylate, the 4- benzoyl -4 '-methyldiphenyl thioether, benzil dimethyl ketal, 2- butoxyethyl group -4- methylamino of acid
Benzoic ether, clopenthixal ketone, methyl thioxanthones, ethyl thioxanthones, isopropyl thioxanthone, dimethyl thioxanthone, diethyl thioxanthene
Ketone, diisopropylthioxanthone, dimethylamino methyl benzoate, 1- (4- dodecylphenyl) -2- hydroxy-2-methyl propane -
1- ketone, 1- hydroxycyclohexyl phenyl ketone, 2- hydroxy-2-methyl -1- phenyl-propane -1- ketone, 1- (4- isopropyl phenyl) -2- hydroxyl
Base-2- methylpropane-1- ketone, methyl benzoylformate, 2- methyl-1-(4- methyl mercapto phenyl)-2- morpholino propane-1- ketone,
2- benzyl -2- dimethylamino -1- (4- morphlinophenyl) -1- butanone, bis- (the trichloromethyl) -6- (4- methoxyphenyl)-of 2,4-
1,3,5- s-triazine, (the trichloromethyl) -1,3,5- of 2,4,6- tri- s-triazine, bis- (trisbromomethyl) -6- (the 4 '-methoxybenzenes of 2,4-
Base) -1,3,5- s-triazine, (the trisbromomethyl) -1,3,5- of 2,4,6- tri- s-triazine, bis- (trichloromethyl) -6- (the 1,3- benzos of 2,4-
Dioxolanes -5- base) -1,3,5- s-triazine, benzophenone, benzoylbenzoic acid, 1- (4- Phenylsulfanylphenyl) butane -1,2- two
Ketone -2- oxime-O- benzoic ether, 1- (4- methyl mercapto phenyl) butane -1,2- diketone -2- oxime-O- acetic acid esters, 1- (4- methylthio phenyl
Base) butane -1- ketoxime-O- acetic acid esters, 4,4 '-bis- (lignocaine) benzophenone, isoamyl p-dimethylaminobenzoate, to two
Methylamino acid ethyl ester, 2,2 '-bis- (O- chlorphenyl) -4,4 ', 5,5 '-tetraphenyl -1,2 '-bisglyoxalines, diazo naphthoquinone class are drawn
Send out agent etc..It is also preferable to use phosphine oxide system photoinitiator.Such as it can it is preferable to use the double acyl groups for the formula that has following structure
Phosphine oxide:
In addition, the condition of the illumination is not particularly limited in the step (a).For specific light-initiated
Agent as described above for double acylphosphine oxides, is preferably irradiated in the case where wavelength is 365 nanometers of light.In addition, described
In step (a), first organic solvent is preferably tetrahydrofuran.In addition, described second is organic molten in the step (a)
Agent is preferably ethyl alcohol.
About above-mentioned steps (b), the metal powder is preferably that surface-treated metal powder is carried out using acid.For
The acid is not restricted, such as can be inorganic acid or organic acid.As long as the spot of metal powder surface can be removed i.e.
It can.It as inorganic acid, can enumerate: hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, boric acid etc..It as organic acid, can enumerate: formic acid, second
Acid, propionic acid, butyric acid, gallic acid, succinic acid etc..Wherein, preferably hydrochloric acid or sulfuric acid.Not about the concentration of hydrochloric acid or sulfuric acid
There is special restriction, but with a premise, that is, when metal powder there can be reactivity with acid, such as metal powder is iron
When powder, iron powder can be reacted with acid generates hydrogen, then the requirement to acid is that concentration cannot be excessively high at this time.Such as hydrochloric acid
Dilute hydrochloric acid or dilute sulfuric acid can be used, such as concentration is no more than 1% dilute hydrochloric acid or dilute sulfuric acid.It is described in the step (b)
Metal powder is preferably selected from copper powder, iron powder, bronze, silver powder, zinc powder or combinations thereof.For the metal in the step (b)
The partial size of powder is not particularly limited, and preferably 200 nanometers~20 microns.If the partial size of metal powder is received less than 200
Rice, then it is very easy to reunite, to influence operability, nor is easy to be dispersed in above-mentioned acid.If metal powder
Partial size is more than 20 microns, then is easy to happen sedimentation phenomenon, and causes dispersion uneven.Furthermore it is preferred that in the step (b),
The mode for removing the second organic solvent in the solution of second reactant is to be dried under inert gas protection.It is preferred that
Ground, the temperature of the drying are 30~35 DEG C.
Hereinafter, technical solution of the present invention is described in detail by specific embodiment.
Test method:
The test method of thermal conductivity uses american standard of testing material: ASTM D5470
The test method of tensile strength uses american standard of testing material: ASTM D638
Chemical sources are as shown in table 1 below:
Table 1
It should be noted that in embodiment of the present invention (including embodiment), if " part " refers to without specified otherwise
Be " parts by weight ".
Embodiment 1
Step 1, by 80 parts of raw-silastic continuouslies (that is, silicone rubber matrix), 20 parts of silicone oil, 10 parts of heat filling (heat fillings
Preparation method it is as described later) at 60 DEG C carry out first segment be kneaded 30 minutes；After be warming up to 75 DEG C of progress second segments and be kneaded 30
Minute；
0.3 part of 2,5- dimethyl -2,5- bis(t-butylperoxy) hexane is added into the raw material after mixing for step 2；
Step 3, at 150 DEG C, pressure 10MPa hot-forming 80 minutes to get arrive heat-conducting silicon rubber.
The preparation of heat filling
Heat filling in the present embodiment the preparation method is as follows:
78 parts of dichlorosilanes, 1 part of 3,6- dioxa -1,8- octanedithiol, 1 part of BAPO are added sequentially to by step (a)
It in tetrahydrofuran solution, is stirred at room temperature, after reactant is completely dissolved, is kept stirring state and is received in illumination wavelength for 365
It is reacted 1 hour under the illumination of rice.Tetrahydrofuran is removed in vacuum after completion of the reaction, reaction product is precipitated in n-hexane three times,
It is dialysed in aqueous solution using bag filter three days and removes unreacted mercaptan compound, be dried under vacuum to after constant weight that be dissolved in ethyl alcohol molten
It in liquid, and is deaerated 30 minutes with bubbling argon, obtains modified dichlorosilane solution.
The Fe powder that 1 part of partial size is 20 microns is dissolved in the hydrochloric acid solution that concentration is 2% by step (b), after stirring 15 minutes
Filtering, is flushed three times with isopropanol, after dry at 35 DEG C in argon atmosphere, is added to modified made from step (a)
Dichlorosilane solution in, it is dry at 35 DEG C after being stirred at room temperature 1 hour, obtain heat filling.
Embodiment 2
Step 1, by 100 parts of raw-silastic continuouslies (that is, silicone rubber matrix), 40 parts of heat filling (preparation sides of heat filling
Method is as described later) first segment mixing 5 minutes is carried out at 70 DEG C；After be warming up to 85 DEG C of progress second segments and be kneaded 5 minutes；
5 parts of 2,5- dimethyl -2,5- bis(t-butylperoxy) hexanes are added into the raw material after mixing for step 2；
Step 3, at 170 DEG C, pressure 100MPa hot-forming 80 minutes to get arrive heat-conducting silicon rubber.
The preparation of heat filling
Heat filling in the present embodiment the preparation method is as follows:
Step (a) sequentially adds 100 parts of dichlorosilanes, 10 parts of 3,6- dioxa -1,8- octanedithiols, 10 parts of BAPO
It into tetrahydrofuran solution, is stirred at room temperature, after reactant is completely dissolved, being kept stirring state in illumination wavelength is 365
It is reacted 24 hours under the illumination of nanometer.Tetrahydrofuran is removed in vacuum after completion of the reaction, reaction product is precipitated three in n-hexane
It is secondary, it is dialysed in aqueous solution using bag filter three days and removes unreacted mercaptan compound, be dissolved in second after being dried under vacuum to constant weight
It in alcoholic solution, and is deaerated 30 minutes with bubbling argon, obtains modified dichlorosilane solution.
The Au powder that 3 parts of partial sizes are 200 nanometers is dissolved in the hydrochloric acid solution that concentration is 2% by step (b), after stirring 15 minutes
Filtering, is flushed three times with isopropanol, after dry at 30 DEG C in argon atmosphere, is added to modified made from step (a)
Dichlorosilane solution in, it is dry at 30 DEG C after being stirred at room temperature 16 hours, obtain heat filling.
Embodiment 3
Step 1, by 90 parts of raw-silastic continuouslies (that is, silicone rubber matrix), 10 parts of silicone oil, 30 parts of heat filling (heat fillings
Preparation method it is as described later) at 65 DEG C carry out first segment be kneaded 20 minutes；After be warming up to 80 DEG C of progress second segments and be kneaded 20
Minute；
3 parts of 2,5- dimethyl -2,5- bis(t-butylperoxy) hexanes are added into the raw material after mixing for step 2；
Step 3, at 160 DEG C, pressure 90MPa hot-forming 60 minutes to get arrive heat-conducting silicon rubber.
The preparation of heat filling
Heat filling in the present embodiment the preparation method is as follows:
90 parts of dichlorosilanes, 6 parts of 3,6- dioxa -1,8- octanedithiols, 6 parts of BAPO are added sequentially to by step (a)
It in tetrahydrofuran solution, is stirred at room temperature, after reactant is completely dissolved, is kept stirring state and is received in illumination wavelength for 365
It is reacted 18 hours under the illumination of rice.Tetrahydrofuran is removed in vacuum after completion of the reaction, reaction product is precipitated in n-hexane three times,
It is dialysed in aqueous solution using bag filter three days and removes unreacted mercaptan compound, be dried under vacuum to after constant weight that be dissolved in ethyl alcohol molten
It in liquid, and is deaerated 30 minutes with bubbling argon, obtains modified dichlorosilane solution.
The Cu powder that 2 parts of partial sizes are 10 microns is dissolved in the hydrochloric acid solution that concentration is 2% by step (b), after stirring 15 minutes
Filtering, is flushed three times with isopropanol, after dry at 30 DEG C in argon atmosphere, is added to modified made from step (a)
Dichlorosilane solution in, it is dry at 30 DEG C after being stirred at room temperature 10 hours, obtain heat filling.
For the heat-conducting silicon rubber being prepared by Examples 1 to 3, according to american standard of testing material: ASTM D5470
With ASTM D638, thermal conductivity and tensile strength are tested respectively.As a result as shown in table 2 below.
Table 2
| Thermal conductivity (W/MK) | Tensile strength (MPa) | |
| Embodiment 1 | 2 | 5 |
| Embodiment 2 | 4 | 8 |
| Embodiment 3 | 3 | 7 |
As can be seen from Table 2, the heat-conducting silicon rubber prepared using preparation method of the invention, not only thermal conductivity is high,
And tensile strength is also high.
Embodiment 4
Preparation method (preparation method of embodiment 1) institute that the present embodiment provides a kind of using heat-conducting silicon rubber of the invention
The first application of the silicon rubber of preparation.Referring to Figure 1.It can be used and lead between printed circuit board 1 and metallic support 2
Hot silicon rubber 3 connects, to can not only guarantee that the heat of printed circuit board 1 is transferred to rapidly metallic support 2, but also can guarantee
Heat-conducting silicon rubber 3 firmly connects printed circuit board 1 and metallic support 2.Such connection type can be adapted for laser projection
Connection between printed circuit board 1 in equipment and metallic support 2.Heat-conducting silicon rubber 3 is considered as one in laser projection device
Heat transfer component.For each component of clear performance in Fig. 1, thus it is shown that printed circuit board 1, metallic support 2 and they between
The decomposition view of heat-conducting silicon rubber 3 is not the view after connection.
Embodiment 5
Preparation method (preparation method of embodiment 1) institute that the present embodiment provides a kind of using heat-conducting silicon rubber of the invention
Second of application of the silicon rubber of preparation.Refer to Fig. 2.It can be used between printed circuit board 1 and radiator 4 thermally conductive
Silicon rubber 3 connects, to can not only guarantee that the heat of printed circuit board 1 is transferred to rapidly radiator 4, but also can guarantee thermally conductive
Silicon rubber 3 forms biggish contact area between printed circuit board 1 and radiator 4, improves heat dissipation effect.Such connection type
It can be adapted for the connection between the printed circuit board 1 in laser projection device and radiator 4.Heat-conducting silicon rubber 3 is considered as laser
A heat transfer component in projection device.For clear each component of performance in Fig. 2, thus it is shown that printed circuit board 1, radiator 4
And the decomposition view of the heat-conducting silicon rubber 3 between them, it is not the view after connection.
Embodiment 6
Preparation method (preparation method of embodiment 1) institute that the present embodiment provides a kind of using heat-conducting silicon rubber of the invention
The third application of the silicon rubber of preparation.Refer to Fig. 3.Such as on the fluorescent powder wheel motor 5 in laser projection device
Radiator 4 is usually mounted in favor of the heat dissipation of fluorescent powder wheel motor 5.At this point, if connecting fluorescence by heat-conducting silicon rubber 3
Powder wheel motor 5 and radiator 4 then can not only guarantee that the heat of fluorescent powder wheel motor 5 is transferred to rapidly radiator 4, but also can protect
Card heat-conducting silicon rubber 3 forms biggish contact area between fluorescent powder wheel motor 5 and radiator 4, improves heat dissipation effect.It is thermally conductive
Silicon rubber 3 is considered as a heat transfer component in laser projection device.For clear each component of performance in Fig. 3, thus it is shown that fluorescence
The decomposition view of powder wheel motor 5, radiator 4 and the heat-conducting silicon rubber 3 between them is not the view after connection.
Embodiment 7
Preparation method (preparation method of embodiment 1) institute that the present embodiment provides a kind of using heat-conducting silicon rubber of the invention
4th kind of application of the silicon rubber of preparation.Refer to Fig. 4.Such as the structural member 6 in laser projection device and it is complete in it is anti-
It penetrates between prism (Total internal reflection prism, abbreviation TIR) 7 and is provided with heat-conducting silicon rubber 3.Thermal conductive silicon
Rubber 3 can not only guarantee the connection of structural member 6 and total internal reflection prism 7, but also the rapid transmitting of heat may be implemented.The structure
Part 6 is mainly load-carrying member, preferably has strength and stiffness appropriate.Heat-conducting silicon rubber 3 is considered as one in laser projection device
A heat transfer component.For each component of clear performance in Fig. 4, thus it is shown that structural member 6, total internal reflection prism 7 and they between
Heat-conducting silicon rubber 3 decomposition view, be not connection after view.
Embodiment 8
Preparation method (preparation method of embodiment 1) institute that the present embodiment provides a kind of using heat-conducting silicon rubber of the invention
5th kind of application of the silicon rubber of preparation.Refer to Fig. 5.Such as laser 8 and liquid cooling head 9 in laser projection device
Between be provided with heat-conducting silicon rubber 3.Heat-conducting silicon rubber 3 not only can connect laser 8 and liquid cooling head 9, but also can be by 8 institute of laser
The heat of generation is rapidly transferred to liquid cooling head 9, so as to make full use of 9 pairs of lasers 8 of liquid cooling head to cool down, it is ensured that swashs
The operation steady in a long-term of light device 8.Heat-conducting silicon rubber 3 is considered as a heat transfer component in laser projection device.In order to understand table in Fig. 5
Now each component, thus it is shown that the decomposition view of laser 8, liquid cooling head 9 and the heat-conducting silicon rubber 3 between them is not to connect
View after connecing.
Although technical solution of the present invention is illustrated in conjunction with specific embodiment and specific embodiment, for
For those skilled in the art, under the premise of not departing from spirit and principles of the present invention, various modifications and change can also be made
More.Therefore, these modifications and changes should be considered as within protection scope of the present invention.
Claims (11)
1. a kind of preparation method of heat-conducting silicon rubber comprising the steps of:
Heat filling is dispersed in silicone rubber matrix by step 1；
Vulcanizing agent is dispersed in the silicone rubber matrix by step 2；
Step 3 makes the vulcanizing agent crosslink to react with the silicone rubber matrix and obtain heat-conducting silicon rubber；
Wherein, the heat filling is the heat filling being prepared as follows；
Step (a): make the silane chloride containing at least one double bond, excessive mercaptan compound and photoinitiator first
It is reacted under conditions of illumination in organic solvent, obtains the first reactant, then remove the first organic solvent and unreacted sulphur
Alcoholic compound obtains the second reactant, and the second reactant is dissolved in the second organic solvent, obtains the solution of the second reactant；
Step (b): being dispersed to metal powder in the solution of second reactant, then removes the molten of second reactant
The second organic solvent in liquid；The complex of the metal powder Yu second reactant is obtained, the complex is to lead
Hot filler.
2. the preparation method of heat-conducting silicon rubber according to claim 1, which is characterized in that the weight of the silicone rubber matrix is equal
Molecular weight is 150,000~1,000,000；Vinyl molar content in the silicone rubber matrix is 0.05%~2%；The silicon
Rubber matrix is type siloxane silicone rubber matrix.
3. the preparation method of heat-conducting silicon rubber according to claim 1, which is characterized in that the silicone rubber matrix and thermally conductive
The number of filler is respectively 100 parts and 10~40 parts；The number of the vulcanizing agent is 0.3~5 part.
4. the preparation method of heat-conducting silicon rubber according to claim 1, which is characterized in that in the step 1, will lead
After hot filler is dispersed in silicone rubber matrix, the two-stage mixing being kneaded comprising first segment and second segment is kneaded is carried out；Described
The condition of one section of mixing is that temperature is 60~70 DEG C, and the time is 5~30 minutes；The condition that the second segment is kneaded is that temperature is 75
~85 DEG C, the time is 5~30 minutes.
5. the preparation method of heat-conducting silicon rubber according to claim 1, which is characterized in that in the step 2, the sulphur
Agent is 2,5- dimethyl -2,5- bis(t-butylperoxy) hexane；In step 3, the condition of the cross-linking reaction is temperature
It is 150~170 DEG C, pressure is 10~100MPa, and the retention time is 10~80 minutes.
6. the preparation method of heat-conducting silicon rubber according to claim 1, which is characterized in that described in the step (a)
Silane chloride containing at least one double bond is the dichlorosilane having the following structure:
Wherein, R1Or R2It is the group at least one-C=C- double bond；
In the step (a), the mercaptan compound is 3,6- dioxa -1,8- octanedithiol；
In the step (a), the photoinitiator is the double acylphosphine oxides for the formula that has following structure:
In the step (a), the condition of the illumination is to be irradiated in the case where wavelength is 365 nanometers of light；
In the step (a), first organic solvent is tetrahydrofuran；
In the step (a), second organic solvent is ethyl alcohol；
In the step (b), the metal powder is that surface-treated metal powder is carried out using acid.
7. the preparation method of heat-conducting silicon rubber according to claim 6, which is characterized in that described in the step (b)
Acid is hydrochloric acid or sulfuric acid；The metal powder is selected from copper powder, iron powder, bronze, silver powder, zinc powder or combinations thereof.
8. the preparation method of heat-conducting silicon rubber according to claim 1, which is characterized in that described in the step (b)
The partial size of metal powder is 200 nanometers~20 microns.
9. the preparation method of heat-conducting silicon rubber according to claim 1, which is characterized in that in the step (b), remove
The mode of the second organic solvent in the solution of second reactant is to be dried under inert gas protection；The drying
Temperature be 30~35 DEG C.
10. a kind of heat-conducting silicon rubber, to be prepared by heat-conducting silicon rubber preparation method according to any one of claims 1 to 9
It obtains.
11. a kind of laser projection device, which is characterized in that including heat-conducting silicon rubber described in any one of claim 10 as heat transfer part
Part.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610474471.5A CN105968822B (en) | 2016-06-24 | 2016-06-24 | Heat-conducting silicon rubber and preparation method thereof, laser projection device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610474471.5A CN105968822B (en) | 2016-06-24 | 2016-06-24 | Heat-conducting silicon rubber and preparation method thereof, laser projection device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105968822A CN105968822A (en) | 2016-09-28 |
| CN105968822B true CN105968822B (en) | 2019-03-01 |
Family
ID=57019066
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610474471.5A Active CN105968822B (en) | 2016-06-24 | 2016-06-24 | Heat-conducting silicon rubber and preparation method thereof, laser projection device |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105968822B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107365456A (en) * | 2017-09-15 | 2017-11-21 | 厦门万新橡胶有限公司 | A kind of novel graphite alkene is modified heat conductive rubber |
| CN111174966A (en) * | 2020-01-06 | 2020-05-19 | 中国科学院微电子研究所 | Heat radiation structure and capacitive pressure sensor |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101597430B (en) * | 2009-07-03 | 2011-05-11 | 广东信力特种橡胶制品有限公司 | Preparation method of filled-type thermally conductive silicone rubber composite material |
| CN102827480A (en) * | 2012-09-03 | 2012-12-19 | 华东理工大学 | Method for preparing high-heat-conducting silicon rubber compound material |
| CN104262971A (en) * | 2014-08-28 | 2015-01-07 | 华南理工大学 | High heat conductive thermally-vulcanized silicone rubber composite material and preparation method thereof |
-
2016
- 2016-06-24 CN CN201610474471.5A patent/CN105968822B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101597430B (en) * | 2009-07-03 | 2011-05-11 | 广东信力特种橡胶制品有限公司 | Preparation method of filled-type thermally conductive silicone rubber composite material |
| CN102827480A (en) * | 2012-09-03 | 2012-12-19 | 华东理工大学 | Method for preparing high-heat-conducting silicon rubber compound material |
| CN104262971A (en) * | 2014-08-28 | 2015-01-07 | 华南理工大学 | High heat conductive thermally-vulcanized silicone rubber composite material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105968822A (en) | 2016-09-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101936713B1 (en) | Composite for heat-radiating elastic body and heat-radiating elastic body formed therefrom | |
| KR101491188B1 (en) | Process for producing resin varnish containing semi-ipn composite thermosetting resin and, resin varnish for printed wiring board, prepreg and metal-clad laminate provided using the same | |
| TWI568791B (en) | Molded body with suppressed bleed-out and manufacturing method thereof | |
| CN105968822B (en) | Heat-conducting silicon rubber and preparation method thereof, laser projection device | |
| WO2017028383A1 (en) | Organic silicone resin aluminum base copper clad laminate and preparation method thereof | |
| JP6348700B2 (en) | Thermosetting resin composition for semiconductor bonding and semiconductor device using the same | |
| JP2015110732A (en) | Polyphenylene sulfide resin composition | |
| JP2010232535A (en) | Heat-resistant heat dissipation sheet | |
| CN111647231A (en) | Functional ethylene propylene diene monomer rubber and preparation method thereof | |
| JP2011529511A5 (en) | Rubber vulcanizing agent using polyorganosiloxane, masterbatch and mixture, and method for vulcanizing rubber | |
| CN106117921B (en) | Heat conduction fluorubber and preparation method thereof, laser projection device | |
| WO2022181446A1 (en) | Composition containing (meth)acrylamide compound and compound having polyoxyalkylene chain | |
| CN111909519A (en) | Flexible heat-conducting silicon rubber and preparation method and application thereof | |
| US20080166552A1 (en) | Silicone based compositions for thermal interface materials | |
| JP2018065965A (en) | Polyarylene sulfide resin composition, molded article and production method | |
| CN110591174A (en) | High-mechanical-property, high-conductivity and light-weight rubber composition and preparation method thereof | |
| WO2024045226A1 (en) | Graphene-modified chloroprene rubber and high-performance rubber v belt prepared from same | |
| WO2017170042A1 (en) | Acrylic polymer composition | |
| JP2023062580A (en) | Composition containing compound with polyoxyalkylene chain and thermally conductive filler | |
| CN106117926A (en) | By poly-1,2 butadiene rubber crosslinking and the methods of reinforcement 4 third fluorubber | |
| WO2017170043A1 (en) | Acrylic polymer composition | |
| KR102665653B1 (en) | Thermoplastic vulcanizate comprising fluorosilicone rubber and method for preparing the same | |
| JP7288660B2 (en) | Flame-retardant rubber composition and flame-retardant fuel hose | |
| WO2017170041A1 (en) | Acrylic polymer composition | |
| CN116554620A (en) | Preparation and process of high-weather-resistance fluororubber damping material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |