CN106010403A - Graphene coated inorganic filler composite resin adhesive material - Google Patents
Graphene coated inorganic filler composite resin adhesive material Download PDFInfo
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- CN106010403A CN106010403A CN201610477779.5A CN201610477779A CN106010403A CN 106010403 A CN106010403 A CN 106010403A CN 201610477779 A CN201610477779 A CN 201610477779A CN 106010403 A CN106010403 A CN 106010403A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
- C09J9/02—Electrically-conducting adhesives
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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
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
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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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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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
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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
- 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
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- Compositions Of Macromolecular Compounds (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention relates to a graphene coated inorganic filler composite resin adhesive material. The material is prepared from, by weight, 20-35 parts of resin matrix, 40-60 parts of graphene coated inorganic filler and 20-30 parts of curing agent. According to the composite resin adhesive, the composite resin matrix, the composite inorganic filler and the composite curing agent are adopted, and a heat-conducting pathway and a conductive network can be effectively formed; the product has an extremely high heat-conducting property and a certain flame-retardant property, and the heat-conducting coefficient of the finally prepared composite resin adhesive is larger than 9.0 W/mK, and the electric conductivity is larger than 37 S/m; the heat-resistant property is good, and a certain anti-corrosion capability is achieved; the graphene coated inorganic filler composite resin adhesive material can be widely applied to the fields of heat-sink devices, electronic packages, electronic equipment, chemical industry energy, automobile industry, aerospace and the like.
Description
Technical field
The invention belongs to field of polymer composite material, be specifically related to a kind of high heat-conductivity conducting graphene coated inorganic filler
Composite resin glue material and preparation method thereof.
Background technology
Graphene (Graphene) is the only one layer of atomic thickness being stripped out from graphite material, being made up of carbon atom
Two dimensional crystal.This giving the hot property that Graphene is unique, existing document report, at normal temperatures by confocal elliptical waveguide light
Spectrum measures, and in the face of single-layer graphene, thermal conductivity has reached the scope of 4800-5300 W/mk.The thinnest, strong as have now been found that
A kind of novel nano-material that degree is maximum, electrical and thermal conductivity performance is the strongest, Graphene is referred to as " dark fund ".Therefore, Graphene by with
In the electrical and thermal conductivity performance strengthening polymer.
High performance electronics uses the material with high thermal conductivity to carry out heat dissipation, to prevent too much heat to electricity
Subsystem damages.But, although polymer has many good qualities compared to for other materials, but individually epoxide-resin glue
Thermal conductivity the lowest, only only have about about 0.2 W/mK.This have impact on epoxide-resin glue on many-sided and field
Application.
High-thermal-conductivity epoxy resin compound adhesive is that one can meet Electronic Packaging, thermal management device and electronic device to material
The thermal interfacial material that heat dispersion requires.Metal, metal-oxide and metal nitride particles are employed as heat filling
In the thermal conductivity improving epoxy resin compound adhesive.But, these high heat fillings are to the heat conductivility of epoxy resin compound adhesive
Promote the most notable.This is caused by several factors, including filling kind, granular size and geometry to heat conduction path
Impact, filler shadow of hot interface resistance between scattered impact and epoxy resin-base and filler in epoxy resin-base
Ring.
The more important thing is, simple epoxy resin-base itself there is also the defect in performance, and resin matrix and filler
The compatibility the biggest on the impact of the thermal conductance conductivity of composite resin glue.Therefore, resin improvement substantially itself and filler this
The improvement of body is critically important for composite resin glue.
Summary of the invention
The technical problem to be solved is, overcomes the defect that current single epoxy resin-base exists, Er Qieyi
Determine under loading, Graphene and the very difficult composite resin glue that is uniformly added to of inorganic filler, thus unmanageable weak point,
There is provided a kind of with low cost, it is easy to the high heat-conductivity conducting of industrialized production, there is again the graphene coated of certain fire resistance
Inorganic filler composite resin glue material and preparation technology thereof.
In the present invention, utilize crystal whisker-shaped or nanometer wire inorganic filler to the basic conducting pathway building in epoxy resin-base
Footpath, the graphene oxide of lamellar is coated on the crystal whisker-shaped by surface modifying agent or nanometer wire inorganic matter to strengthen filling out
Directly contact between material.Then, inorganic matter whisker or the nano wire of graphene oxide cladding is entered by different reduction means
Row reduction joined after (including electronation, ultraviolet reduction and high-temperature process) prepares high heat-conductivity conducting stone in epoxy resin-base
Ink alkene coated inorganic filling epoxy resin compound adhesive.
The technical solution adopted in the present invention is:
A kind of graphene coated inorganic filler composite resin glue material, it is characterised in that include following group according to weight fraction meter
Point: resin matrix 20-35 part, inorganic filler 40-60 part of graphene coated, firming agent 20-30 part.
Further, described resin matrix is according to matter by epoxy resin, polysulfones, polyimide resin and furfural resin
The hybrid resin matrix that amount mixes than the ratio for 10:5:2:1；
Described epoxy resin-base is that glycidyl ester epoxy resin and glycidyl amine epoxy resin are according to mass ratio
The mixture mixed for 1:1；Wherein, described glycidyl ester epoxy resin is adipic acid 2-glycidyl ester, institute
The glycidyl amine epoxy resin stated is MDA four glycidyl amine and diglycidyl para-aminophenol
It is that 2:1 mixes according to mass ratio；Described polysulfones is bisphenol-a polysulfone (PSU)；Described polyimide resin is span
Carry out acid imide.
Further, the inorganic filler of described graphene coated is crystal whisker-shaped or the zinc oxide of nanometer wire and copper oxide
And nano silver wire mixes according to the ratio that mass ratio is 3:3:1.
Further, described Graphene is single-layer graphene, or few layer graphene microplate.
Further, described firming agent is thiorubber., polybutylene terephthalate (PBT) (PBT) and flame-proof ethylene base
Resin is according to the composite curing agent that mass ratio is that 20:15:7 mixes.
Present invention also offers the preparation method of a kind of graphene coated inorganic filler composite resin glue material, its feature exists
In: comprise the steps of:
(1) 5g graphite and 5gNaNO3 are put in flask, and add 150ml sulphuric acid, then 15gKMnO4 is added in flask,
Maintain the temperature at 30 oC and be sufficiently stirred for 10 h, after having reacted, 200ml deionized water will be added in flask and make temperature increase
Keep 30 minutes to 90 oC, then after solution is cooled to room temperature, and inject hydrogen peroxide and the 700ml of 30ml30% mass concentration
Deionized water, then after washing and pickling twice, take out product, after being placed in 60 DEG C of dry 3h of vacuum drying oven, obtain oxygen
Functionalized graphene；Described graphene oxide is single-layer graphene, or few layer graphene microplate；
(2) first 20g crystal whisker-shaped or nanometer wire inorganic filler are placed on 130 oC in vacuum drying oven and are dried 2 h, be then placed in
In flask containing 200ml dimethylbenzene, reflux condensate device is installed, surface modifier is added flask, and stirs 4 at 150 oC
H, product through ethanol purge and centrifugal after put into 60 DEG C of dry 3h of vacuum drying oven after, obtain the crystalline substance of surface modifier modified
Must shape or nanometer wire inorganic filler；
(3) take the graphene oxide 1g that step (1) prepares to be dissolved in 200ml ethanol and stirring, the most ultrasonic 1.5
H, adds crystal whisker-shaped or the nanometer wire inorganic filler of surface modifier modified obtained by step (2), at the uniform velocity stirs 5
H, afterwards, puts into tube furnace logical nitrogen under 1000 DEG C of high temperature by the inorganic filler that the above-mentioned graphene oxide stirred is coated with
Make annealing treatment 1 h；Or the inorganic filler of the above-mentioned graphene oxide stirred cladding is added containing reproducibility chemical substance
Heated in water solution reduce to 90 DEG C, after keeping 3 h, filtration drying, finally give graphene oxide cladding inorganic
Filler；
(4) inorganic filler and the firming agent of graphene oxide cladding composite resin matrix, step (3) prepared is used by proportioning
Planetary vacuum stirring deaeration machine adds after stirring 15 min under the rotation rotating speed of 2000 rpm revolution rotating speeds and 1000 rpm
In mould, flat-bed press is heated to 100 oC, solidifies 3 h, then solidify 2 h after temperature is increased to 130 oC, obtain
Graphene coated inorganic filler composite resin glue material.
Further, the surface modifier in described step (2) is titanate coupling agent, calculates according to volume fraction, institute
State addition is described organic solvent dimethylbenzene the 2% of titanate coupling agent.
Further, step (3) described reproducibility chemical substance is hydrazine hydrate, described hydrazine hydrate and the matter of graphene oxide
Amount ratio is 10:7.
Compared to prior art, the present invention has a following beneficial effect:
(1) present invention employs the resin matrix of mixed type, the epoxy resin wherein selected comprises (+)-2,3-Epoxy-1-propanol esters asphalt mixtures modified by epoxy resin
Fat and glycidyl amine epoxy resin, the combination of the epoxy resin of both types makes resin matrix have reactivity
Height, bonding force are higher than general purpose epoxy resin, and solidfied material mechanical property is good, and against weather is good, and has good resistance to ultralow temperature
Property, under condition of ultralow temperature, still there is the adhesion strength higher than other type of epoxy resin.It addition, the bismaleimide selected
Amine has the mobility close with epoxy resin and mouldability especially, and the available conventional method similar with epoxy resin adds
Work molding, the resin of both types has the good compatibility, and BMI has excellent electrical property, this resin
The addition of matrix overcomes the shortcoming that epoxy resin thermostability is relatively low.
Polysulfones itself is the thermoplastic resin in molecular backbone containing chain link, the bisphenol-a polysulfone selected by the present invention
(PSU) first, excellent in mechanical performance, high intensity, impact resistance, and there is good dimensional stability and prominent creep resistant
Property, molding shrinkage is little, can do accurate product, but easily stress cracking.Secondly, chemically from the point of view of performance, PSU is to general nothing
Machine acid, alkali, salt and aliphatic hydrocarbon, alcohols and oils are the most stable；The hot strength of the 3rd, PSU mechanical property and bending strength
It is better than equal general engineering plastic；And PSU has good heatproof oxidation performance, when 150 degree through the thermo-oxidative ageing of 2 years, draw
Stretch intensity and heat distortion temperature does not drop and increases on the contrary, there is good electric property simultaneously.The most comprehensive performance
The most excellent resin.
Furfural resin refers to that a kind of furane resins obtained for primary raw material by polycondensation or copolymerization with furfuryl alcohol or furfural are gathered
Compound.Furfuryl alcohol or furfural are initially formed line polymer under acid catalysis, then proceed to occur in presence of an acid double-bond polymerization, are formed
Cross-linking agent insoluble, insoluble.Furfural resin is high temperature resistant, chemical proofing and electrical insulating property excellent, but single furfural tree
Fat glue bond is poor, property is crisp, his application of this characteristic strong influence, and utilizes furfural resin and epoxy resin and gather
Imide resin and polysulfones are used in combination, and overcome and have fallen the problem that the caking property of furfural resin own is poor and property is crisp, the biggest
Improve greatly the temperature applicable range of composite resin, and improve the various mechanics such as resin entirety shock resistance, wet and heat ageing resistant
Performance.
(2) present invention method by chemical modification, is coated with graphene oxide on crystal whisker-shaped or nanometer wire inorganic matter
Or after Graphene basis, add resin matrix and can be obtained by the composite resin heat-conductivity conducting glue of high electrical conductivity, preparation method letter
Single, the large-scale production of filler and composite resin can be realized.
(3) present invention has selected compound inorganic filler, and the zinc oxide of the one-dimentional structure of crystal whisker-shaped or nanometer wire has
Unique electron transport ability and good electric property；The copper dioxide of one-dimentional structure aboundresources especially, with low cost, ring
Border is friendly, has more preferable electric property by providing more high-specific surface area and shorter diffusion length.Nano silver wire
Belong to pure metal class nano wire, there is optimal performance electrically and thermally, nano silver wire in addition to there is the excellent electric conductivity of silver,
Due to the dimensional effect of Nano grade, also there is the light transmission of excellence, flexible resistance.Make it at the aspect such as conducting resinl, heat-conducting glue
Application in also there is prominent advantage.From performance, from the point of view of cost etc. is comprehensive, what the present invention used compound inorganic fills out
Material can be greatly improved the electric property of composite resin glue of the present invention.
(4) firming agent that graphene coated inorganic filler composite resin glue material of the present invention is selected is thiorubber., poly-right
Benzene dicarboxylic acid butanediol ester (PBT) and flame-proof ethylene base resin are the composite curing agent that 20:15:7 mixes according to mass ratio.
The selection of this firming agent has fabulous solidification effect for the resin system of the present invention.
Thiorubber. is a kind of low-molecular weight polymer, and it has the excellences such as low-temperature flexibility, solvent resistance, stress relaxation
Performance.After thiorubber. mixes with epoxy resin, the mercapto of end and epoxy resin generation chemical reaction, hence into solid
In epoxy resin structural after change, impart the good pliability of the epoxy resin after crosslinking, high shear strength and peel off strong
Degree.
Polybutylene terephthalate (PBT) PBT main chain is to be rigidity phenyl ring by each repetitive and flexible fatty alcohol connects
The saturated linear molecular composition got up, it is strong that the height geometrical regularity of molecule and rigid element make polymer have high machinery
Degree, prominent chemical reagent resistance, thermostability and excellent electrical property；Molecule does not has side chain, symmetrical configuration, meets compact reactor
The requirement built, so that this polymer has crystalline and the high-melting-point of height, the structures shape of molecule PBT has good
Combination property.The more important thing is, due to the excellent system energy of PBT itself, they can be with polysulfones, polyamide, epoxy resin etc.
Plastics are used in combination jointly, various mechanical performances and the electric property of material can be greatly improved, can make again material
There is higher chemical stability.Flame-proof ethylene base resin has higher heat stability.After resin solidification, crosslink density is big.
Its heat distortion temperature reaches 120-135 DEG C, can extend the service life of final material and have excellent corrosion resistance, and resistance
Combustion performance.PBT is also a kind of fire proofing simultaneously, owing to performance affine with fire retardant is good, so with the flame-proof ethylene base added
Resin has more preferable associativity, it is possible to preferably play the flame retardant effect of material.In general, the composite solid that the present invention selects
Agent can effectively save the time of curing reaction, simultaneously can for composite resin system realize optimal solidification effect with
And flame retardant effect.
(5) product of the present invention has high heat conductivility, and high thermal conductivity coefficient is more than 9.0 W/mK, high conductivity
More than 37 S/m；Heat resistance is good, and has certain corrosion resistance, can use under acid or alkaline conditions.
(6) low raw-material cost that the present invention selects, environmental protection, simple operation, it is easy to industrialized production, is a kind of excellent
Thermal interfacial material, can extensively apply radiating element, electronic equipment, the chemical industry energy, the field such as auto industry and Aero-Space.
Detailed description of the invention
The invention discloses a kind of graphene coated inorganic filler composite resin glue material and preparation method thereof, below by
The present invention is specifically described by several embodiments.
Embodiment 1
(1) 5g graphite and 5gNaNO3 are put in flask, and add 150ml sulphuric acid, then 15gKMnO4 is added in flask,
Maintain the temperature at 30 DEG C and be sufficiently stirred for 10 h, after having reacted, 200ml deionized water will be added in flask and make temperature rise to
90 DEG C keep 30 minutes, then after solution is cooled to room temperature, and inject the hydrogen peroxide of 30ml30% mass concentration and 700ml goes
Ionized water, then after washing and pickling twice, take out product, after being placed in 60 DEG C of dry 3h of vacuum drying oven, aoxidized
Graphene；Graphene is single-layer graphene, or few layer graphene microplate.
(2) first 20g crystal whisker-shaped or nanometer wire inorganic filler are placed on 130 oC in vacuum drying oven and are dried 2 h, then
Put in the flask containing 200ml dimethylbenzene, reflux condensate device is installed, by 4ml titanate coupling agent addition flask, and
150 DEG C of stirring 4 h, product through ethanol purge and centrifugal after put into 60 DEG C of dry 3h of vacuum drying oven after, obtain surface modification
The crystal whisker-shaped of agent modified or nanometer wire inorganic filler；The inorganic filler of graphene coated is crystal whisker-shaped or the two of nanometer wire
Zinc oxide and copper oxide and nano silver wire mix according to the ratio that mass ratio is 3:3:1.
(3) take the graphene oxide 1g that step (1) prepares to be dissolved in 200ml ethanol and stirring, then surpass
Sound 1.5 h, adds crystal whisker-shaped or the nanometer wire inorganic filler of surface modifier modified obtained by step (2), at the uniform velocity
Stir 5 h, afterwards, the inorganic filler that the above-mentioned graphene oxide stirred is coated with is put into tube furnace under 1000 DEG C of high temperature
Logical n 2 annealing processes 1 h；Or the inorganic filler of the above-mentioned graphene oxide stirred cladding is added containing reproducibility
The heated in water solution learning material is reduced to 90 DEG C, after keeping 3 h, and filtration drying, finally give graphene oxide cladding
Inorganic filler；Wherein, reproducibility chemical substance is hydrazine hydrate, and hydrazine hydrate is 10:7 with the mass ratio of graphene oxide.
(4) the inorganic filler 60g graphene oxide that composite resin matrix 35g, step (3) prepare being coated with and firming agent
30g uses planetary vacuum stirring deaeration machine to stir under the rotation rotating speed of 2000 rpm revolution rotating speeds and 1000 rpm by proportioning
Add in mould after 15 min, flat-bed press is heated to 100 DEG C, solidify 3 h, more solid after temperature is increased to 130 DEG C
Change 2 h, obtain graphene coated inorganic filler composite resin glue material.
Wherein, described resin matrix is according to mass ratio by epoxy resin, polysulfones, polyimide resin and furfural resin
The hybrid resin matrix mixed for the ratio of 10:5:2:1；
Described epoxy resin-base is that glycidyl ester epoxy resin and glycidyl amine epoxy resin are according to mass ratio
The mixture mixed for 1:1；Wherein, described glycidyl ester epoxy resin is adipic acid 2-glycidyl ester, institute
The glycidyl amine epoxy resin stated is MDA four glycidyl amine and diglycidyl para-aminophenol
It is that 2:1 mixes according to mass ratio；Described polysulfones is bisphenol-a polysulfone (PSU)；Described polyimide resin is span
Carry out acid imide.
Firming agent is that thiorubber., polybutylene terephthalate (PBT) (PBT) and flame-proof ethylene base resin are according to mass ratio
The composite curing agent mixed for 20:15:7.
Through test, the thermal conductivity of the final composite resin glue prepared is 9.5W/mK, and electrical conductivity is 38S/m.
Embodiment 2
(1) 5g graphite and 5gNaNO3 are put in flask, and add 150ml sulphuric acid, then 15gKMnO4 is added in flask,
Maintain the temperature at 30 DEG C and be sufficiently stirred for 10 h, after having reacted, 200ml deionized water will be added in flask and make temperature rise to
90 DEG C keep 30 minutes, then after solution is cooled to room temperature, and inject the hydrogen peroxide of 30ml30% mass concentration and 700ml goes
Ionized water, then after washing and pickling twice, take out product, after being placed in 60 DEG C of dry 3h of vacuum drying oven, aoxidized
Graphene；Graphene is single-layer graphene, or few layer graphene microplate.
(2) first 20g crystal whisker-shaped or nanometer wire inorganic filler are placed on 130 oC in vacuum drying oven and are dried 2 h, then
Put in the flask containing 200ml dimethylbenzene, reflux condensate device is installed, by 4ml titanate coupling agent addition flask, and
150 DEG C of stirring 4 h, product through ethanol purge and centrifugal after put into 60 DEG C of dry 3h of vacuum drying oven after, obtain surface modification
The crystal whisker-shaped of agent modified or nanometer wire inorganic filler；The inorganic filler of graphene coated is crystal whisker-shaped or the two of nanometer wire
Zinc oxide and copper oxide and nano silver wire mix according to the ratio that mass ratio is 3:3:1.
(3) take the graphene oxide 1g that step (1) prepares to be dissolved in 200ml ethanol and stirring, then surpass
Sound 1.5 h, adds crystal whisker-shaped or the nanometer wire inorganic filler of surface modifier modified obtained by step (2), at the uniform velocity
Stir 5 h, afterwards, the inorganic filler that the above-mentioned graphene oxide stirred is coated with is put into tube furnace under 1000 DEG C of high temperature
Logical n 2 annealing processes 1 h；Or the inorganic filler of the above-mentioned graphene oxide stirred cladding is added containing reproducibility
The heated in water solution learning material is reduced to 90 DEG C, after keeping 3 h, and filtration drying, finally give graphene oxide cladding
Inorganic filler；Wherein, reproducibility chemical substance is hydrazine hydrate, and hydrazine hydrate is 10:7 with the mass ratio of graphene oxide.
(4) the inorganic filler 40g graphene oxide that composite resin matrix 20g, step (3) prepare being coated with and firming agent
20g uses planetary vacuum stirring deaeration machine to stir under the rotation rotating speed of 2000 rpm revolution rotating speeds and 1000 rpm by proportioning
Add in mould after 15 min, flat-bed press is heated to 100 DEG C, solidify 3 h, more solid after temperature is increased to 130 DEG C
Change 2 h, obtain graphene coated inorganic filler composite resin glue material.
Wherein, described resin matrix is according to mass ratio by epoxy resin, polysulfones, polyimide resin and furfural resin
The hybrid resin matrix mixed for the ratio of 10:5:2:1；
Described epoxy resin-base is that glycidyl ester epoxy resin and glycidyl amine epoxy resin are according to mass ratio
The mixture mixed for 1:1；Wherein, described glycidyl ester epoxy resin is adipic acid 2-glycidyl ester, institute
The glycidyl amine epoxy resin stated is MDA four glycidyl amine and diglycidyl para-aminophenol
It is that 2:1 mixes according to mass ratio；Described polysulfones is bisphenol-a polysulfone (PSU)；Described polyimide resin is span
Carry out acid imide.
Firming agent is that thiorubber., polybutylene terephthalate (PBT) (PBT) and flame-proof ethylene base resin are according to mass ratio
The composite curing agent mixed for 20:15:7.
Through test, the thermal conductivity of the final composite resin glue prepared is 9.3W/mK, and electrical conductivity is 39S/m.
Embodiment 3
(1) 5g graphite and 5gNaNO3 are put in flask, and add 150ml sulphuric acid, then 15gKMnO4 is added in flask,
Maintain the temperature at 30 DEG C and be sufficiently stirred for 10 h, after having reacted, 200ml deionized water will be added in flask and make temperature rise to
90 DEG C keep 30 minutes, then after solution is cooled to room temperature, and inject the hydrogen peroxide of 30ml30% mass concentration and 700ml goes
Ionized water, then after washing and pickling twice, take out product, after being placed in 60 DEG C of dry 3h of vacuum drying oven, aoxidized
Graphene；Graphene is single-layer graphene, or few layer graphene microplate.
(2) first 20g crystal whisker-shaped or nanometer wire inorganic filler are placed on 130 oC in vacuum drying oven and are dried 2 h, then
Put in the flask containing 200ml dimethylbenzene, reflux condensate device is installed, by 4ml titanate coupling agent addition flask, and
150 DEG C of stirring 4 h, product through ethanol purge and centrifugal after put into 60 DEG C of dry 3h of vacuum drying oven after, obtain surface modification
The crystal whisker-shaped of agent modified or nanometer wire inorganic filler；The inorganic filler of graphene coated is crystal whisker-shaped or the two of nanometer wire
Zinc oxide and copper oxide and nano silver wire mix according to the ratio that mass ratio is 3:3:1.
(3) take the graphene oxide 1g that step (1) prepares to be dissolved in 200ml ethanol and stirring, then surpass
Sound 1.5 h, adds crystal whisker-shaped or the nanometer wire inorganic filler of surface modifier modified obtained by step (2), at the uniform velocity
Stir 5 h, afterwards, the inorganic filler that the above-mentioned graphene oxide stirred is coated with is put into tube furnace under 1000 DEG C of high temperature
Logical n 2 annealing processes 1 h；Or the inorganic filler of the above-mentioned graphene oxide stirred cladding is added containing reproducibility
The heated in water solution learning material is reduced to 90 DEG C, after keeping 3 h, and filtration drying, finally give graphene oxide cladding
Inorganic filler；Wherein, reproducibility chemical substance is hydrazine hydrate, and hydrazine hydrate is 10:7 with the mass ratio of graphene oxide.
(4) the inorganic filler 50g graphene oxide that composite resin matrix 30g, step (3) prepare being coated with and firming agent
25g uses planetary vacuum stirring deaeration machine to stir under the rotation rotating speed of 2000 rpm revolution rotating speeds and 1000 rpm by proportioning
Add in mould after 15 min, flat-bed press is heated to 100 DEG C, solidify 3 h, more solid after temperature is increased to 130 DEG C
Change 2 h, obtain graphene coated inorganic filler composite resin glue material.
Wherein, described resin matrix is according to mass ratio by epoxy resin, polysulfones, polyimide resin and furfural resin
The hybrid resin matrix mixed for the ratio of 10:5:2:1；
Described epoxy resin-base is that glycidyl ester epoxy resin and glycidyl amine epoxy resin are according to mass ratio
The mixture mixed for 1:1；Wherein, described glycidyl ester epoxy resin is adipic acid 2-glycidyl ester, institute
The glycidyl amine epoxy resin stated is MDA four glycidyl amine and diglycidyl para-aminophenol
It is that 2:1 mixes according to mass ratio；Described polysulfones is bisphenol-a polysulfone (PSU)；Described polyimide resin is span
Carry out acid imide.
Firming agent is that thiorubber., polybutylene terephthalate (PBT) (PBT) and flame-proof ethylene base resin are according to mass ratio
The composite curing agent mixed for 20:15:7.
Through test, the thermal conductivity of the final composite resin glue prepared is 9.7W/mK, and electrical conductivity is 39S/m.
The composite resin glue that the present invention prepares has the characteristic of high heat conduction and high connductivity.By specific embodiment 1-3,
Can illustrate to add the inorganic filler by Surface coating Graphene in composite resin matrix can be with the heat-conductivity conducting of effective constitution
Network path, is greatly improved thermal conductivity and the conductivity of compound adhesive, and heat conductivity and the heat conductivity of material are significantly improved.
Graphene improves the contact area between filler, enhances original thermal conducting path.Meanwhile, define along filler and effectively lead
Electric network, greatly improves electrical conductivity.
Present invention employs the resin matrix of mixed type, the epoxy resin wherein selected comprises (+)-2,3-Epoxy-1-propanol esters asphalt mixtures modified by epoxy resin
Fat and glycidyl amine epoxy resin, the combination of the epoxy resin of both types makes resin matrix have reactivity
Height, bonding force are higher than general purpose epoxy resin, and solidfied material mechanical property is good, and against weather is good, and has good resistance to ultralow temperature
Property, under condition of ultralow temperature, still there is the adhesion strength higher than other type of epoxy resin.It addition, the bismaleimide selected
Amine has the mobility close with epoxy resin and mouldability especially, and the available conventional method similar with epoxy resin adds
Work molding, the resin of both types has the good compatibility, and BMI has excellent electrical property, this resin
The addition of matrix overcomes the shortcoming that epoxy resin thermostability is relatively low.
Polysulfones itself is the thermoplastic resin in molecular backbone containing chain link, the bisphenol-a polysulfone selected by the present invention
(PSU) first, excellent in mechanical performance, high intensity, impact resistance, and there is good dimensional stability and prominent creep resistant
Property, molding shrinkage is little, can do accurate product, but easily stress cracking.Secondly, chemically from the point of view of performance, PSU is to general nothing
Machine acid, alkali, salt and aliphatic hydrocarbon, alcohols and oils are the most stable；The hot strength of the 3rd, PSU mechanical property and bending strength
It is better than equal general engineering plastic；And PSU has good heatproof oxidation performance, when 150 degree through the thermo-oxidative ageing of 2 years, draw
Stretch intensity and heat distortion temperature does not drop and increases on the contrary, there is good electric property simultaneously.The most comprehensive performance
The most excellent resin.
Furfural resin refers to that a kind of furane resins obtained for primary raw material by polycondensation or copolymerization with furfuryl alcohol or furfural are gathered
Compound.Furfuryl alcohol or furfural are initially formed line polymer under acid catalysis, then proceed to occur in presence of an acid double-bond polymerization, are formed
Cross-linking agent insoluble, insoluble.Furfural resin is high temperature resistant, chemical proofing and electrical insulating property excellent, but single furfural tree
Fat glue bond is poor, property is crisp, his application of this characteristic strong influence, and utilizes furfural resin and epoxy resin and gather
Imide resin and polysulfones are used in combination, and overcome and have fallen the problem that the caking property of furfural resin own is poor and property is crisp, the biggest
Improve greatly the temperature applicable range of composite resin, and improve the various mechanics such as resin entirety shock resistance, wet and heat ageing resistant
Performance.
The present invention method by chemical modification, is coated with graphene oxide or stone on crystal whisker-shaped or nanometer wire inorganic matter
After ink alkene basis, adding resin matrix and can be obtained by the composite resin heat-conductivity conducting glue of high electrical conductivity, preparation method is simple, energy
Realize the large-scale production of filler and composite resin.
The present invention has selected compound inorganic filler, and the zinc oxide of the one-dimentional structure of crystal whisker-shaped or nanometer wire has uniqueness
Electron transport ability and good electric property；The copper dioxide of one-dimentional structure aboundresources especially, with low cost, environment is friendly
Good, by providing more high-specific surface area and shorter diffusion length, there is more preferable electric property.Nano silver wire belongs to
Pure metal class nano wire, has optimal performance electrically and thermally, nano silver wire in addition to there is the excellent electric conductivity of silver, due to
The dimensional effect of Nano grade, also has the light transmission of excellence, flexible resistance.Make its answering at the aspect such as conducting resinl, heat-conducting glue
Also there is in prominent advantage.From performance, from the point of view of cost etc. is comprehensive, the compound inorganic filler energy that the present invention uses
Enough it is greatly improved the electric property of composite resin glue of the present invention.
The firming agent that graphene coated inorganic filler composite resin glue material of the present invention is selected is thiorubber., gathers benzene two
Formic acid butanediol ester (PBT) and flame-proof ethylene base resin are the composite curing agent that 20:15:7 mixes according to mass ratio.This is solid
The selection of agent has fabulous solidification effect for the resin system of the present invention.
Thiorubber. is a kind of low-molecular weight polymer, and it has the excellences such as low-temperature flexibility, solvent resistance, stress relaxation
Performance.After thiorubber. mixes with epoxy resin, the mercapto of end and epoxy resin generation chemical reaction, hence into solid
In epoxy resin structural after change, impart the good pliability of the epoxy resin after crosslinking, high shear strength and peel off strong
Degree.
Polybutylene terephthalate (PBT) PBT main chain is to be rigidity phenyl ring by each repetitive and flexible fatty alcohol connects
The saturated linear molecular composition got up, it is strong that the height geometrical regularity of molecule and rigid element make polymer have high machinery
Degree, prominent chemical reagent resistance, thermostability and excellent electrical property；Molecule does not has side chain, symmetrical configuration, meets compact reactor
The requirement built, so that this polymer has crystalline and the high-melting-point of height, the structures shape of molecule PBT has good
Combination property.The more important thing is, due to the excellent system energy of PBT itself, they can be with polysulfones, polyamide, epoxy resin etc.
Plastics are used in combination jointly, various mechanical performances and the electric property of material can be greatly improved, can make again material
There is higher chemical stability.Flame-proof ethylene base resin has higher heat stability.After resin solidification, crosslink density is big.
Its heat distortion temperature reaches 120-135 DEG C, can extend the service life of final material and have excellent corrosion resistance, and resistance
Combustion performance.PBT is also a kind of fire proofing simultaneously, owing to performance affine with fire retardant is good, so with the flame-proof ethylene base added
Resin has more preferable associativity, it is possible to preferably play the flame retardant effect of material.In general, the composite solid that the present invention selects
Agent can effectively save the time of curing reaction, simultaneously can for composite resin system realize optimal solidification effect with
And flame retardant effect.
The product of the present invention has high heat conductivility, and the heat conductivity of the final composite resin glue prepared is more than 9.0
W/mK, electrical conductivity is more than 37 S/m；Heat resistance is good, and has certain corrosion resistance, can be in acid or alkaline condition
Lower use.
Above example has been shown and described the ultimate principle of the present invention and principal character and advantages of the present invention.The industry
Skilled person will appreciate that, the present invention is not restricted to the described embodiments, described in above-described embodiment and description simply
The principle of the present invention is described rather than limits the scope of the present invention by any way, without departing from the scope of the invention,
The present invention also has various changes and modifications, and these changes and improvements both fall within claimed scope.
Claims (5)
1. a graphene coated inorganic filler composite resin glue material, it is characterised in that include following according to weight fraction meter
Component: resin matrix 20-35 part, inorganic filler 40-60 part of graphene coated, firming agent 20-30 part.
Graphene coated inorganic filler composite resin glue material the most according to claim 1, it is characterised in that: described tree
Aliphatic radical body is according to the ratio mixing that mass ratio is 10:5:2:1 by epoxy resin, polysulfones, polyimide resin and furfural resin
Hybrid resin matrix；
Described epoxy resin-base is that glycidyl ester epoxy resin and glycidyl amine epoxy resin are according to mass ratio
The mixture mixed for 1:1；Wherein, described glycidyl ester epoxy resin is adipic acid 2-glycidyl ester, institute
The glycidyl amine epoxy resin stated is MDA four glycidyl amine and diglycidyl para-aminophenol
It is that 2:1 mixes according to mass ratio；Described polysulfones is bisphenol-a polysulfone (PSU)；Described polyimide resin is span
Carry out acid imide.
Graphene coated inorganic filler composite resin glue material the most according to claim 1 and 2, it is characterised in that: described
The inorganic filler of graphene coated is that crystal whisker-shaped or the zinc oxide of nanometer wire and copper oxide and nano silver wire are according to quality
Mix than the ratio for 3:3:1.
4. according to the graphene coated inorganic filler composite resin glue material described in claim 1-3, it is characterised in that: described
Graphene is single-layer graphene, or few layer graphene microplate.
5. according to the graphene coated inorganic filler composite resin glue material described in claim 1,2 or 4, it is characterised in that: institute
The firming agent stated be thiorubber., polybutylene terephthalate (PBT) (PBT) and flame-proof ethylene base resin be 20 according to mass ratio:
The composite curing agent that 15:7 mixes.
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| CN107722904A (en) * | 2017-11-07 | 2018-02-23 | 深圳市傲川科技有限公司 | Epoxy adhesive |
| CN107828211A (en) * | 2017-11-15 | 2018-03-23 | 江苏亚宝绝缘材料股份有限公司 | A kind of polymer of graphene compound polyimide resin and its preparation and application |
| CN109516706A (en) * | 2018-12-20 | 2019-03-26 | 四川聚创石墨烯科技有限公司 | With the production technology of preparing graphene by utilizing solid carbon source cladding cement filler |
| CN114958266A (en) * | 2022-06-02 | 2022-08-30 | 惠州学院 | Single-component waterway epoxy resin modified adhesive and preparation method thereof |
| CN115181520A (en) * | 2022-05-25 | 2022-10-14 | 惠州市杜科新材料有限公司 | High-temperature-resistant single-component epoxy-structure inductor magnetic core bonding adhesive and preparation method thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107722904A (en) * | 2017-11-07 | 2018-02-23 | 深圳市傲川科技有限公司 | Epoxy adhesive |
| CN107828211A (en) * | 2017-11-15 | 2018-03-23 | 江苏亚宝绝缘材料股份有限公司 | A kind of polymer of graphene compound polyimide resin and its preparation and application |
| CN107828211B (en) * | 2017-11-15 | 2020-07-17 | 江苏亚宝绝缘材料股份有限公司 | Polymer of graphene composite polyimide resin and preparation and application thereof |
| CN109516706A (en) * | 2018-12-20 | 2019-03-26 | 四川聚创石墨烯科技有限公司 | With the production technology of preparing graphene by utilizing solid carbon source cladding cement filler |
| CN109516706B (en) * | 2018-12-20 | 2021-03-09 | 四川聚创石墨烯科技有限公司 | Production process for preparing graphene coated cement filler by using solid carbon source |
| CN115181520A (en) * | 2022-05-25 | 2022-10-14 | 惠州市杜科新材料有限公司 | High-temperature-resistant single-component epoxy-structure inductor magnetic core bonding adhesive and preparation method thereof |
| CN114958266A (en) * | 2022-06-02 | 2022-08-30 | 惠州学院 | Single-component waterway epoxy resin modified adhesive and preparation method thereof |
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