CN104830061B - A kind of heat conductive insulating composite and preparation method thereof - Google Patents
A kind of heat conductive insulating composite and preparation method thereof Download PDFInfo
- Publication number
- CN104830061B CN104830061B CN201510152550.XA CN201510152550A CN104830061B CN 104830061 B CN104830061 B CN 104830061B CN 201510152550 A CN201510152550 A CN 201510152550A CN 104830061 B CN104830061 B CN 104830061B
- Authority
- CN
- China
- Prior art keywords
- polyethersulfone resin
- heat
- composite
- filler
- conductive
- 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
- C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
- C08L81/06—Polysulfones; Polyethersulfones
-
- 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
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention discloses a kind of heat conductive insulating composite and preparation method thereof, the composite is made up of the raw material of 100 parts of polyethersulfone resin powder, 25~40 parts of heat-conductive insulation filling, 1~5 part of processing aid；The polyethersulfone resin has
Description
Technical field
The invention belongs to polymeric material field, more particularly it relates to a kind of heat conductive insulating composite and its
Preparation method.
Background technology
It is insulating heat-conductive adhesive, insulation that the research report of the domestic insulating heat-conductive composite to different field is mostly at present
Heat conductive rubber, insulating heat-conductive Embedding Material, the exploitation to insulating and heat-conducting plastics are relatively fewer.Special engineering plastics all have preferable
Heat resistance, the every field being widely used in national economy and national defense industry.Polysulfones is a kind of amorphous thermoplasticity
Special engineering plastics, mainly there are bisphenol-a polysulfone, polyarylsulfone (PAS), polyether sulfone three types, there is excellent heat resistance, creep resistance
, can be long-term use of at 150 DEG C etc. characteristic, electrical insulation capability is excellent.Since exploitation, precision optical machinery processing, automobile making,
It is used widely in electric and Aero-Space, military equipment.But its thermal conductivity only 0.26Wm-1·K-1, nothing
Method meets the industrial requirements to be radiated in time under high temperature operating conditions, thus limits its application to a certain extent.
The main method for improving high polymer material heat conductivility at present is insulating ceramics filler of the filling with high heat conductance,
Such as aluminum oxide, boron nitride, aluminium nitride, because the structure of engineering plastics is amorphous structure, without the presence of plastic crystal, no
Exist and overlapped between plastic crystal and heat filling particle, it is likely that interrupt heat conduction network, thermal conductivity factor can not be carried effectively
Height, thermal conducting path could be formed by generally requiring the filler loading for reaching very high, improved thermal conductivity, thus will be caused composite wood
The impact strength of material, tensile strength dramatic decrease.To keep the mechanical property of plastics as far as possible, it is necessary to reduce filler addition as far as possible
Amount.Therefore, a kind of filer content of urgent need exploitation is relatively low, and thermal conductivity factor is higher, and can maintain the exhausted of the mechanical property of plastics
Edge highly heat-conductive material, plastic composite high performance and functionalization are realized, meet the practice demand of insulating and heat-conducting plastics.
The content of the invention
Based on this, the defects of in order to overcome above-mentioned prior art, the invention provides a kind of filer content is low, thermal conductivity factor
It is high and heat conductive insulating composite of the mechanical property of plastics and preparation method thereof can be maintained.
In order to realize foregoing invention purpose, this invention takes following technical scheme：
A kind of heat conductive insulating composite, the composite are made up of the raw material including following parts by weight：
100 parts of polyethersulfone resin powder
25~40 parts of heat-conductive insulation filling
1~5 part of processing aid；
The polyethersulfone resin hasStructure, wherein x=1~3,
Y=1~3；The crystallinity of the polyethersulfone resin is 20~40%；The molecular weight of the polyethersulfone resin be 5000~
100000。
In wherein some embodiments, the crystallinity of the polyethersulfone resin is 25~35%.
In wherein some embodiments, the polyethersulfone resin is the polyphenyl with the polyether sulfone of halogen end-blocking and halogen end-blocking
It is prepared for raw material.
In wherein some embodiments, the heat-conductive insulation filling is silane coupler modified filler.
In wherein some embodiments, the heat-conductive insulation filling is KH560 Modification on Al2O3。
In wherein some embodiments, the heat-conductive insulation filling is that the KH560 being modified through octaphenyl-POSS is modified
Al2O3。
In wherein some embodiments, the heat-conductive insulation filling is boron nitride, aluminium nitride, one kind in aluminum oxide or several
Kind.
In wherein some embodiments, the particle diameter of the boron nitride is 3~5 microns, the particle diameter of the aluminium nitride for 500~
600 nanometers, the particle diameter of the aluminum oxide is 30~40 microns.
In wherein some embodiments, the heat-conductive insulation filling is that weight ratio is 1:2:2 boron nitride, aluminium nitride and oxygen
Change aluminium.
In wherein some embodiments, the processing aid selects silicone oil series lubricant agent, is mainly so that what is be prepared
Insulation high-heat-conductive composite material has good surface smoothness.
Present invention also offers the preparation method of above-mentioned heat conductive insulating composite, comprise the following steps：
(1), will haveStructure polyethersulfone resin 30~60 DEG C dissolving
In DMF so that the concentration of polyether sulfone is 1~10g/100mL；Instill again in 60~90 DEG C of deionized waters, stir, obtain when being added dropwise
To white precipitate；White precipitate is filtered, washed, is dried, that is, obtains polyethersulfone resin powder；
(2), polyethersulfone resin powder, processing aid and the heat-conductive insulation filling of drying process are dropped in high mixer
Premixing, by double screw extruder melt blending, extrusion, granulation, is produced.
The above-mentioned of the application and other features, aspect and advantage is more readily understood with reference to described further below.
Embodiment
Participate in the election of the detailed description of the invention below for being preferable to carry out method and including embodiment this public affairs can be more easily understood
Open content.A large amount of terms can be referred in description below and claims, these terms are defined as following meanings.
Singulative includes plural number and object is discussed, unless the context clearly dictates otherwise.
" optional " or " optionally " refer to that the item that describes thereafter or event may or may not occur, and this is retouched
State the situation that the situation occurred including event and event do not occur.
Approximate term in specification and claims is used for modifying quantity, and it is specific to represent that the present invention is not limited to this
Quantity, include the part of the amendment of the acceptable change without cause related basic function close to the quantity.Phase
Answer, modify a numerical value with " about ", " about " etc., mean that the invention is not restricted to the exact numerical.It is approximate in some examples
Term likely corresponds to the precision of the instrument of measured value.In present specification and claims, scope limits can be with
Combine and/or exchange, these scopes include all subranges contained therebetween if not stated otherwise.
A kind of heat conductive insulating composite of the present invention, the composite are the raw materials by including following parts by weight
It is prepared：
100 parts of polyethersulfone resin powder
25~40 parts of heat-conductive insulation filling
1~5 part of processing aid；
The polyethersulfone resin hasStructure, wherein x=1~3, y=1
~3；The crystallinity of the polyethersulfone resin is 20~40%；The molecular weight of the polyethersulfone resin is 5000~100000.
In the present invention, used raw material is respectively described below：
Polyethersulfone resin powder
Heretofore described polyethersulfone resin powder hasWherein x=1
~3, y=1~3, i.e., with divalent phenyl group (residue formed by benzene 2 hydrogen atoms being bonded with the phenyl ring of removing) and sulfonyl
(-SO2) repeat unit and divalent phenyl group (residue that forms of 2 hydrogen atoms being bonded with the phenyl ring is removed by benzene) weight
The resin of multiple unit.Relative to the total of whole repeat units, it is preferred that the repeat unit of x=2, y=3 polyethersulfone resin
50~100 moles of % are accounted for, it is highly preferred that the repeat unit of x=2, y=3 polyethersulfone resin accounts for 80~100 moles of %.This hair
Having described in brightThe polyethersulfone resin of structure is poly- by being blocked with halogen
What the polyphenyl of ether sulfone and halogen end-blocking was prepared for raw material.The polyether sulfone of halogen end-blocking and the polyphenyl of halogen end-blocking can lead to
Cross using the alkali metal salt of carbonic acid as alkali, polycondensation is suitably prepared in organic polar solvent
The alkali metal salt of carbonic acid can be the alkali metal carbonate salt as normal salt, the heavy carbonic alkali metal salt as acid salt
(bicarbonate alkali metal salt), or both mixture.As alkali metal carbonate salt, preferably using sodium carbonate, potassium carbonate, as weight
Alkali metal carbonate salt, preferably using sodium bicarbonate, potassium bicarbonate.
As organic polar solvent, for example, dimethyl sulfoxide (DMSO), 1-Methyl-2-Pyrrolidone, sulfolane (1,1-
Dithiolanes), 1,3- dimethyl-2-imidazolinones, 1,3- diethyl -2- imidazolones, dimethyl sulfone, diethyl sulfone, two
Isopropyl sulfone and diphenyl sulfone.
Polyethersulfone resin of the present invention is to be prepared using the polyphenyl of the polyether sulfone of halogen end-blocking and halogen end-blocking as raw material
Obtained by.Its specific preparation process is：
1), using HO-Ph-SO2- Ph-OH (Ph represents phenylene) and excessive X1-Ph-SO2-Ph-X2(X1And X2Each solely
Halogen atom is on the spot represented, Ph represents phenylene) polyether sulfone is prepared(X1And X2Table independently of one another
Show halogen atom)；
2), (HO) is used2-B-Ph-B-(HO)2(Ph represents phenylene) and excessive X3-Ph-X4(X3And X4Independently of one another
Halogen atom is represented, Ph represents phenylene) polyphenyl is prepared(X3And X4Represent that halogen is former independently of one another
Son)；
3), with polyether sulfoneAnd polyphenylIt is prepared for raw material
In above step (1) and (2), the term " excess " represents to mean：That excessive reaction raw materials with it is another
A kind of mol ratio of raw material is at least above 1.2:1, preferably greater than 2:1.So make it that the resin of step (1) and (2) can be with halogen
Base blocks.
In above step (3), the mol ratio of polyether sulfone and polyphenyl is 0.95~1.05:1, preferably 1:1.So cause poly-
Ether sulfone and polyphenyl can polymerize completely.
The dosage of the alkali metal salt of carbonic acid, it is usually 95~115 to rub with alkali metal relative to the hydroxyl in raw material
You are %, preferably 100~110 moles of %.If hypothesis does not produce side reaction, the dosage of the alkali metal salt of carbonic acid is more, then makees
For the purpose of polycondensation more promptly carry out, therefore the degree of polymerization of the polyethersulfone resin of gained and polyphenylene resin increase.The result is that
The trend that reduced viscosity uprises, Mn increases, Mw/Mn reduces be present.But the dosage of the actually alkali metal salt of carbonic acid is more,
Side reaction similar to the above is more also easy to produce, due to this side reaction, the polyethersulfone resin of gained and the degree of polymerization of polyphenylene resin
Reduce.Therefore, it is necessary to which degree in view of this side reaction, the dosage for adjusting the alkali metal salt of carbonic acid is 95~115 moles of %,
To obtain having defined reduced viscosity, MnAnd Mw/MnPolyethersulfone resin and polyphenylene resin.
In the preparation method of typical polyethersulfone resin and polyphenylene resin, as the first stage, two kinds of dissolution of raw material are existed
In organic polar solvent, as second stage, the alkali metal salt of carbonic acid is added in the solution obtained into the first stage, makes two kinds
Raw material carries out polycondensation, and as the phase III, by the reactant mixture obtained in second stage, the alkali for removing unreacted carbonic acid is golden
Belong to salt, caused accessory substance alkali halide and organic polar solvent, obtain polyethersulfone resin and polyphenylene resin.
The solution temperature of first stage is usually 40~180 DEG C, in addition, the condensation temperature of second stage be usually 180~
400℃.If hypothesis does not produce side reaction, condensation temperature is higher, and the polycondensation as purpose is more promptly carried out, therefore resulting
The degree of polymerization of resin uprise.The result is that exist reduced viscosity uprise, MnIncrease, Mw/MnThe trend of reduction.But actually
Condensation temperature is higher, then is more also easy to produce side reaction similar to the above, and due to this side reaction, the degree of polymerization of the resin of gained drops
It is low.Therefore it is defined to obtain having, it is necessary to which degree in view of this side reaction, adjustment condensation temperature are 180~400 DEG C
Reduced viscosity, MnAnd Mw/MnResin.
In addition, the polycondensation of second stage, the water for being used as accessory substance can be generally removed by one side, is slowly risen on one side
Temperature, after the reflux temperature for reaching organic polar solvent, further generally insulation 1~50 hour, preferably 10~30 hours is carried out.
If hypothesis does not produce side reaction, the polycondensation time is longer, carries out the polycondensation as purpose, therefore resulting resin is poly-
It is right to uprise.The result is that reduced viscosity increase, M be presentnIncrease, Mw/MnThe trend of reduction.But actually the polycondensation time gets over
It is long, side reaction similar to the above is also carried out, due to this side reaction, causes the degree of polymerization of the resin of gained to reduce.Cause
This is, it is necessary to which degree in view of this side reaction, adjustment polycondensation time are 1~50 hour, to obtain having defined contrast viscous
Degree, MnAnd Mw/MnResin.
In phase III, removed not in the reactant mixture obtained first with filtering, centrifugation etc. from second stage
The alkali metal salt of the carbonic acid of reaction and the alkali halide as accessory substance, it is hereby achieved that resin be dissolved in it is organic
The solution formed in polar solvent.Then organic polar solvent is removed by the solution, it is hereby achieved that resin.Polar organic is molten
The removing of agent can be carried out by directly evaporating organic polar solvent from above-mentioned solution, can also be by above-mentioned solution and resin
Poor solvent mixing, separate out resin, using filtering, the separation such as centrifuge and carry out., can as the poor solvent of resin
To enumerate methanol, ethanol, isopropanol, hexane, heptane, water, from the viewpoint of removing is easy to, preferably methanol.
To haveThe polyethersulfone resin of structure is dissolved in DMF at 30~60 DEG C, makes
The concentration for obtaining polyether sulfone is 1~10g/100mL；Instill again in 60~90 DEG C of deionized waters, stirred when being added dropwise, it is heavy to obtain white
Form sediment；White precipitate is filtered, washed, is dried, that is, obtains polyethersulfone resin powder；The volume average particle size of above-mentioned powder, preferably
For 200~2000 μm, more preferably 250~1500 μm, more preferably 300~1000 μm.
As the preferred embodiment of the present invention, the crystallinity of the polyethersulfone resin is 25~35%.
Heat-conductive insulation filling
Heat-conductive insulation filling of the present invention is the one or more in boron nitride, aluminium nitride, aluminum oxide.Wherein, institute
The particle diameter for stating boron nitride is 3~5 microns, and the particle diameter of the aluminium nitride is 500~600 nanometers, and the particle diameter of the aluminum oxide is 30
~40 microns.Preferably, the filler is that weight ratio is 1:2:2 boron nitride, aluminium nitride and aluminum oxide.
Most polymers are saturation systems, and no free electron is present, and molecular motion is difficult, and heat transfer relies primarily on lattice
Vibration, phonon is main heat energy load person.Macromolecular chain randomly tangles each other has larger relative molecular weight simultaneously, causes
Its crystallinity is not high, contains many amorphous fractions；And the polydispersity of molecular weight, lead to not to form perfect crystal；In addition divide
Subchain vibrates the scattering to phonon, and all these cause polymer thermal conductivity very low.
Heat filling is blended into polyethersulfone resin powder of the present invention, replaces part high with inorganic heat filling
Molecule, its result will cause the heat conductivility of whole system to improve comprehensively.Because of the present invention haveThe polyethersulfone resin powder of structure compared with common polyethersulfone resin, its have 20~
40% or so crystallinity, except the thermal conducting path that the overlap joint between filler grain is formed, it is brilliant with plastics also to there is filler grain
The thermal conducting path that overlap joint between body is formed, accordingly, it is capable to form more thermal conducting paths.Secondly, the heat conduction for different-grain diameter
Filler is added in polymeric matrix, can be because the difference of heat filling particle diameter, heat conductivility have obvious difference.The present invention
The heat conduction network that is formed of composite include the network that is formed between heat filling and heat filling, further comprises heat conduction and fill out
The heat conduction network that material-crystal-heat filling is formed, heat conduction is caused by the interaction and synergy of above-mentioned a variety of heat conduction networks
The addition of filler is fewer, and the thermal conductivity factor of composite can but be improved significantly.
As one of preferred embodiment of the present invention, the heat-conductive insulation filling is filled out to be silane coupler modified
Material.It is highly preferred that the heat-conductive insulation filling is KH560 (technical pure, Nanjing dawn Chemical Co., Ltd.) Modification on Al2O3(particle diameter
50~100nm, specific surface area 150m2/g)。
KH560 Modification on Al2O3Preparation method it is as follows：Silane coupler KH560 is pre-processed before using through hydrolysis, formic acid control
Hydrolyzate pH value processed is between 4.0~4.5.Al2O35 hours are dried in vacuo at 120 DEG C to remove the moisture of Adsorption on Surface,
By 20g Al2O3, 10g hydrolyzes pretreated KH560 and 150ml dispersants and is placed in ultrasonic disperse in 500ml four-hole boiling flask
Half an hour, then be heated to reflux mixture mechanical agitation and under nitrogen protection 10 hours.Question response is cooled to room temperature after terminating,
Product is filtered, and repeatedly washed with ethanol, is extracted 12 hours with Soxhlet extractor after filter residue is dried, ethanol is solvent, is removed
Remove non-grafted KH560, the KH560 aluminium oxide particles (KH560-g-Al that has been bonded after extract product is dried2O3)。
Using the Vector-22 type infrared spectrometers of Bruker companies to KH560-g-Al2O3Particle carries out infrared light stave
Sign, sample are made using pellet technique.Using NETZSCH TG-209 thermogravimetric analyzers to KH560-g-Al2O3Particle enters
Row thermogravimetric analysis, characterizes the grafting rate of nanoparticle surface, and test condition is：N2Atmosphere, air-flow velocity 40ml/min, heating
Speed is 20 DEG C/min.With the weightless Mass Calculation Al between 100~500 DEG C2O3The KH560 grafting rates of particle surface, do not connect
The Al of branch coupling agent2O3Weightlessness between 100~500 DEG C is 2.45%.KH560-g-Al of the present invention2O3Particle is red
External spectrum, which characterizes, can determine that the epoxy bond with polarity is incorporated into a nanometer Al by KH560 surface treatments2O3Surface, grafting rate is
14.2%.
In heat-conductive composite material, the use of coupling agent can improve the deployment conditions of filler in the polymer so as to improve again
The thermal conductivity factor of condensation material, but coupling agent heat conductivility itself is bad, excessive coupling agent, which is coated on filler surface, to be increased
Thermal resistance during heat transfer, it is unfavorable for the raising of polymer bond's performance.Simultaneously because itself there is condensation after the hydrolysis of KH560 alkoxies
Ability, as the excessive KH560 of presence, it understands self-condensation and the webbed material of shape is coated with inorganic particulate, to grafting
KH560 epoxy bond plays shielding action, and then hinders Modification on Al2O3With the interaction of polymeric matrix.Therefore, it is of the invention
Described KH560-g-Al2O3Particle can improve the thermal conductivity factor of composite well.
As another embodiment being more highly preferred to of the present invention, the heat-conductive insulation filling is through diamine-POSS
Modified KH560 Modification on Al2O3。
By " diamine POSS synthesis and its study on the modification to polyimide material " (thunder star cutting edge of a knife or a sword etc., aeronautical material
Report, the 1st phase of volume 33) method synthesis diamine-POSS.By diamine-POSS and KH560 Modification on Al2O3(mol ratio 1:
1) using anhydrous DMAc as solvent, after 80 DEG C are stirred reaction 12h, desolventizing is depressurized, produces diamine-POSS modifications
KH560 Modification on Al2O3.The KH560 Modification on Al being modified through diamine-POSS2O3Filler can be substantially improved in resinous polymer
Deployment conditions, so as to greatly improve the thermal conductivity factor of composite.
Processing aid
In order that the insulation high-heat-conductive composite material that must be prepared has good surface smoothness, processing aid is selected
Silicone oil series lubricant agent.
Present invention also offers the preparation method of above-mentioned heat conductive insulating composite, comprise the following steps：
(1), will haveThe polyethersulfone resin of structure is dissolved in DMF at 30~60 DEG C,
So that the concentration of polyether sulfone is 1~10g/100mL；Instill again in 60~90 DEG C of deionized waters, stirred when being added dropwise, obtain white
Precipitation；White precipitate is filtered, washed, is dried, that is, obtains polyethersulfone resin powder；
(2), polyethersulfone resin powder, processing aid and the filler of drying process are dropped in high mixer and are pre-mixed,
By double screw extruder melt blending, extrusion, granulation, produce.The charge door of above-mentioned double screw extruder, transportation section, melting
Section, homogenizing zone, the temperature of mouth mold are respectively 100~150 DEG C, 170~180 DEG C, 170~180 DEG C, 170~180 DEG C, 170~
180 DEG C, then it is water cooled but, after pelletizing in convection oven dry, that is, obtain insulate high-heat-conductive composite material.
Hereinafter, the present invention is explained in more detail by embodiment, it should be appreciated that these embodiments are only
Example and it is nonrestrictive.If without other explanations, raw materials used is all commercially available.
The present invention is described in detail referring to several examples.
The formula of embodiment 1~7 is as shown in table 1.In following examples, polyethersulfone resin of the invention hasStructure, wherein x=2, the repeat unit of y=3 polyethersulfone resin account for 100 moles of %,
Molecular weight is 10000~50000；Common polyether sulphone resin hasStructure, molecular weight be 5000~
10000。
The formula of the composite of the embodiment 1~7 of table 1
The preparation method of embodiment 1~7 is as follows：
(1) polyethersulfone resin, is dissolved in DMF at 30~60 DEG C so that the concentration of polyether sulfone is 1~10g/100mL；Again
Instill in 60~90 DEG C of deionized waters, stirred when being added dropwise, obtain white precipitate；White precipitate is filtered, washed, is dried, i.e.,
Obtain polyethersulfone resin powder；
(2), polyethersulfone resin powder, processing aid and the filler of drying process are dropped in high mixer and are pre-mixed,
By double screw extruder melt blending, extrusion, granulation, produce.The charge door of above-mentioned double screw extruder, transportation section, melting
Section, homogenizing zone, the temperature of mouth mold are respectively 150 DEG C, 180 DEG C, 180 DEG C, 180 DEG C, 180 DEG C, then it is water cooled but, after pelletizing in drum
Dried in wind baking oven, that is, obtain the high-heat-conductive composite material that insulate.
The thermal conductivity factor of heat conductive insulating composite prepared by the various embodiments described above is according to transient state planar process principle, using adding
Put on airs C-Therm technology companys C-ThermTCiTM types Conduction Coefficient Detector Basing measure；Resistivity foundation GB/T1410-2006,
Determined using EST121 type numeral ultra-high resistance micro currents instrument.Properties test data is listed in Table 2 below.
The various performance parameters of the composite of the embodiment 1~7 of table 2
As can be known from Table 2, the present invention using with certain crystallinity polyethersulfone resin as composite matrix,
Modified inorganic filler forms filler-filler, filled out as composite heat-conducting filler between the matrix and modified inorganic filler of this crystallization
The heat conduction network of material-polymer crystals-filler, hence it is evident that improve the thermal conductivity factor of composite.
Foregoing example is merely illustrative, some features of the feature for explaining the present invention.Appended claim
It is intended to require the scope as wide as possible being contemplated that, and embodiments as presented herein is only according to all possible embodiment
Combination selection embodiment explanation.Therefore, the purpose of applicant is appended claim not by the explanation present invention
Feature example selectional restriction.And the progress in science and technology will not formed due to the inaccuracy of language performance and not
The possible equivalent or son being presently considered are replaced, and these changes should also be interpreted by appended in the conceived case
Claim covers.
Claims (1)
1. a kind of heat conductive insulating composite, it is characterised in that the composite is made up of the raw material including following parts by weight：
100 parts of polyethersulfone resin powder；
35 parts of heat-conductive insulation filling；
5 parts of processing aid；
The polyethersulfone resin hasStructure, wherein x
=1~3, y=1~3；The crystallinity of the polyethersulfone resin is 28%；The molecular weight of the polyethersulfone resin be 5000~
100000；
The heat-conductive insulation filling is the KH560 Modification on Al being modified through octaphenyl-POSS2O3；
The polyethersulfone resin is to be prepared using the polyphenyl of the polyether sulfone of halogen end-blocking and halogen end-blocking as raw material；
The preparation method of the heat conductive insulating composite, comprises the following steps：
(1), will haveThe polyethersulfone resin of structure exist
30~60 DEG C are dissolved in DMF so that the concentration of polyether sulfone is 1~10g/100mL；Instill again in 60~90 DEG C of deionized waters, side
Side stirring is added dropwise, obtains white precipitate；White precipitate is filtered, washed, is dried, that is, obtains polyethersulfone resin powder；Wherein x=
1~3, y=1~3；The crystallinity of the polyethersulfone resin is 28%；The molecular weight of the polyethersulfone resin be 5000~
100000；
(2), polyethersulfone resin powder, processing aid and the heat-conductive insulation filling of drying process are dropped in high mixer and premixed
Close, by double screw extruder melt blending, extrusion, granulation, produce.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510152550.XA CN104830061B (en) | 2015-03-12 | 2015-03-12 | A kind of heat conductive insulating composite and preparation method thereof |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510107568.8 | 2015-03-12 | ||
| CN201510152550.XA CN104830061B (en) | 2015-03-12 | 2015-03-12 | A kind of heat conductive insulating composite and preparation method thereof |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510107568.8 Division | 2015-03-12 | 2015-03-12 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104830061A CN104830061A (en) | 2015-08-12 |
| CN104830061B true CN104830061B (en) | 2018-01-30 |
Family
ID=53808273
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510152550.XA Active CN104830061B (en) | 2015-03-12 | 2015-03-12 | A kind of heat conductive insulating composite and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104830061B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6902193B2 (en) * | 2016-03-02 | 2021-07-14 | Jnc株式会社 | Manufacture method of composition for heat dissipation member, heat dissipation member, electronic device, heat dissipation member |
| CN112812360A (en) * | 2020-12-31 | 2021-05-18 | 广东安拓普聚合物科技有限公司 | Heat-conducting filler and application thereof |
| CN115073818B (en) * | 2022-06-17 | 2023-12-26 | 山东海科创新研究院有限公司 | Heat-conducting filler, high-heat-conducting polyether sulfone composite material and preparation method thereof |
| CN114989608B (en) * | 2022-07-01 | 2024-01-30 | 宁夏清研高分子新材料有限公司 | Heat-conducting polysulfone composite material and preparation method thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4532288A (en) * | 1982-03-29 | 1985-07-30 | Union Carbide Corporation | Poly(aryl ether) blends |
| ES2298517T3 (en) * | 2002-04-15 | 2008-05-16 | Solvay Advanced Polymers, Llc | POLY COMPOSITIONS (ARILETER-SULFONA) THAT PRESENT REDUCED LIGHT AND YELLOW TRANSMITANCE PROPERTIES AND ARTICLES OBTAINED FROM THEM. |
| JP5882532B2 (en) * | 2012-03-28 | 2016-03-09 | ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ | Polybiphenyl ether sulfone polymer tubing and connecting parts for gas conduction |
| CN103435805B (en) * | 2013-09-06 | 2015-08-12 | 重庆杰博科技有限公司 | fluorine-containing biphenyl polyether sulfone copolymer and preparation method thereof |
-
2015
- 2015-03-12 CN CN201510152550.XA patent/CN104830061B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN104830061A (en) | 2015-08-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104830061B (en) | A kind of heat conductive insulating composite and preparation method thereof | |
| JP6079930B2 (en) | N-substituted maleimide group-containing polyphenylene ether derivative, and thermosetting resin composition, resin varnish, prepreg, metal-clad laminate, and multilayer printed wiring board using the same | |
| CN106751516B (en) | A kind of toughening, heat-resisting modified epoxy and preparation method thereof | |
| CN103154140B (en) | Method for producing thermoplastic resin composition, thermoplastic resin composition, and molded product | |
| CN105131598A (en) | Low-dielectric resin composition, resin film using same, prepreg and circuit board | |
| CN103159948B (en) | POSS (polyhedral oligomeric silsesquioxane) fluoric polyaryletherketone nano composite material with low dielectric coefficients and preparation method thereof | |
| KR101605174B1 (en) | Ultrafine poly(phenylene ether) particles and compositions derived therefrom | |
| WO2015059950A1 (en) | Polyimide resin composition, and heat-conductive adhesive film produced using same | |
| JP2010095613A (en) | Polyether ether ketone resin composition | |
| KR20140109500A (en) | Prepreg comprising polyphenylene ether particles | |
| JPWO2011093079A1 (en) | Metal resin composite | |
| Xu et al. | Aqueous solution blending route for preparing low dielectric constant films of polyimide hybridized with polytetrafluoroethylene | |
| CN105111475A (en) | Colorless and transparent polyimide nanocomposite membrane and preparation method thereof | |
| JP2008516028A (en) | Sulfone polymer composition | |
| CN110423370A (en) | Prepreg containing quartz glass fibre and the substrate containing quartz glass fibre | |
| CN114391030A (en) | Chemically compatible fluoropolymer blends | |
| JP2019006879A (en) | Resin composition, prepreg, laminate sheet, multilayer printed wiring board and semiconductor package | |
| BR112020025762A2 (en) | fiber-reinforced resin-based material | |
| Zhang et al. | Mesoscopic simulation assistant design of immiscible polyimide/BN blend films with enhanced thermal conductivity | |
| JP2023500518A (en) | Blends of polyaryletherketone copolymers | |
| Zhang et al. | Trisilanolphenyl-POSS nano-hybrid poly (biphenyl dianhydride-p-phenylenediamine) polyimide composite films: miscibility and structure-property relationship | |
| EP3489304B1 (en) | Polyarylene sulfide resin composition, molded article, and production methods | |
| JP2021138849A (en) | Resin composition, prepreg, laminate, resin film, printed wiring board, semiconductor package, and method for producing resin composition | |
| CN109971131A (en) | Polyphenyl ether resin composition and application thereof | |
| CN110204862A (en) | Resin combination, prepreg, laminate, metal-clad laminate and printed wiring board |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| EXSB | Decision made by sipo to initiate substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20190705 Address after: Room 318, 1755 Lane 30, Qibei Highway, Nanxiang Town, Jiading District, Shanghai, 201800 Patentee after: Shanghai Han Pu new Mstar Technology Ltd Address before: Room 3235, 3-storey C District, 36th Building, 1188 Huyi Highway, Jiading District, Shanghai 201802 Patentee before: On tolerate it general Industrial Co., Ltd. |
|
| TR01 | Transfer of patent right |