CN106496633A - High heat conductance polystyrene boron nitride composite and preparation method thereof - Google Patents
High heat conductance polystyrene boron nitride composite and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to thermal conductive polymer technical field of composite materials, polystyrene boron nitride composite of specially a kind of high heat conductance and preparation method thereof.The present invention obtains complex microsphere by the self assembly between the electronegative boron nitride nanosheet in the surface of polystyrene microsphere and liquid phase stripping of surface positively charged first, then complex microsphere is carried out being molded near vitrification point and obtains final composite material sheet.The present invention can make material build to form heat conduction network under low filler addition, and therefore when boron nitride content is 13.4 vol%, in the face of material, thermal conductivity reaches 8.0 W/mK.The performance is compared with the similar research work that delivers with prominent unit filler thermal conductivity increment rate.The inventive method, simple to operate, production cost is relatively low, it is easy to mass, large-scale production, with the basic and wide application prospect of good industrialized production.
Description
Technical field
The invention belongs to thermal conductive polymer technical field of composite materials, and in particular to one kind has under low boron nitride content
Polymer composites of high heat conductance and preparation method thereof.
Background technology
All kinds of precise electronics and industrial equipment often produce substantial amounts of heat in use, the heat of these generations
If timely and effectively can not dissipate that the reduction even failure of equipment operating efficiency may be caused.Therefore exploitation has height
The material of heat dissipation ability have extensive demand, and also result in the increasing interest of academia in recent years.Poly-
Compound material is as which is easy to process, lightweight and applied in various kinds of equipment in large quantities as component the characteristics of low cost.But
Be polymer thermal conductivity be typically than relatively low, substantially all between 0.1-0.3 W/mK.Conventional raising polymeric material
The method of thermal conductivity mainly mixes all kinds of fillers with high thermal conductivity coefficient, such as from the aluminum oxide of early stage（Al2O3）, nitridation
Silicon（AlN）And carborundum（SiC）Deng CNT finally（CNTs）, reduced graphene（rGO）And boron nitride（BN）.But
As the filler of material with carbon element class can also cause the increasing of material electric conductivity while polymeric material heat conductivility is improved due to it
Greatly, this limits its application on electronic material to a certain extent.Therefore there is good electrical insulating property there is height simultaneously again
The boron nitride of thermal conductivity is of great interest.
The characteristics of boron nitride heat conductivility one is prominent is that namely the thermal conductivity in its direction in the face will with anisotropy
It is significantly higher than the thermal conductivity in direction in face, such as block boron nitride, its thermal conductivity in direction in the face is 400
W/mK, and direction is only 2-20 W/mK in the vertical plane.The bigger individual layer of radius-thickness ratio is obtained by carrying out peeling off boron nitride
Nanometer sheet (BNNS), in its face, thermal conductivity can further bring up to 2000 W/mK.As boron nitride thermal conductivity is respectively to different
Property the characteristics of, therefore its orientation in polymeric matrix and dispersion can be produced very to the lifting of the thermal conductivity of material unit filler
Big impact.But as Nano filling has high surface energy, therefore it easily reunites in polymeric matrix, so as to shadow
Ring the final performance of material.Therefore how reunion of the effectively solving boron nitride filler in polymeric matrix and taking for it is controlled
To obtain high performance polymer composite significant.
Dispersion of the filler in polymerization mainly has three types.The first is that filler is directly dispersing in single polymers,
Now generally require to add substantial amounts of filler as the reunion of filler will obtain high thermal conductivity, such as《ACS applications material and boundary
Face》Work BNNS being added in polyvinyl alcohol of recent report（ACS appl. Mater. Interfaces, 2016,
8, 13567）；Second is that Fillers selection is dispersed in a certain phase of blend, can so significantly reduce to be formed
Filler addition required for heat conduction network, such as《Composite science and technology》On deliver by CNT-SiC Fillers selections
It is distributed to the PVDF phases of PVDF/PS blends（Composites Science and Technology, 2013, 89,
142）；The third is to position filler to be dispersed at the boundary of blend, so can more greatly reduce filler and be formed
The addition of heat conduction network, such as《Materials chemistry will C》The CNT of middle preparation is selectively dispersed at the boundary of PC/ABS
Material（J. Mater. Chem. C, 2012, 22, 22398）.In above-mentioned three types, position filler and be dispersed in phase
Interface is the most difficult but is also the maximally effective method for reducing filler addition.
The present invention is just being directed to Reasonable Regulation And Control two dimension boron nitride nanosheet regular arrangement in the base, while making filler
Positioning is distributed at boundary.Using the electronegative boron nitride nanosheet in the surface of liquid phase stripping and gathering that the positive electrification in surface is modified
The self assembly of phenylethylene micro ball obtains complex microsphere.Then under the processing temperature near polystyrene vitrification point, to multiple
Conjunction microballoon carries out molding makes polystyrene microsphere along pressure at right angle direction（Direction in face）Generation is orientated deformation, while making cladding
There is regular arrangement also along direction in face in the boron nitride nanosheet on its surface.As processing temperature is in polystyrene vitrifying
Near temperature, therefore boron nitride nanosheet is mainly dispersed at the bead interface of deformation.The composite material sheet for finally giving is low
Filler addition under（13.4 vol%）High thermal conductivity can be obtained（8.0 W/mK）.
Content of the invention
It is an object of the invention to provide obtaining the polymer composites of high heat conductance under low nitridation Boron addition
And preparation method thereof.
There are under the low nitridation Boron addition that the present invention is provided the polymer composites of high heat conductance, be styrene nitridation
Boron composite, the unilateral interior ordered arrangement of its boron nitride nanometer, what which was prepared are concretely comprised the following steps：
（1）Weigh the commercially available boron nitride of 0.5 ~ 5 g（BN）It is added in 50 ~ 500 ml solvents, then in the Ultrasound Instrument of 100 ~ 500W
Middle normal temperature（That is room temperature）8 ~ 24 h of ultrasound, are then centrifuged 10 ~ 60 min under 1000 ~ 3000 rpm rotating speeds, take upper strata stripping
Boron nitride nanosheet（BNNS）Dispersion liquid is standby, and the concentration of dispersion liquid is 0.5 ~ 2 mg/ml；
（2）Weigh 4 ~ 16 g styrene, 20 ~ 150 mg PVPs, 8-24 ml deionized waters and 100 ~ 300 mg
Ammonium persulfate, is dissolved in 80 ~ 200 ml absolute ethyl alcohols, leads to nitrogen 20-60 min；Then at 50 ~ 90 DEG C back flow reaction 6 ~
24 h, through centrifugation, washing, obtain the monodisperse polystyrene microsphere of some scale；By the polystyrene microsphere for preparing point
It is scattered to diallyl dimethyl ammoniumchloride (PDDA) aqueous solution (0.1 ~ 2 wt%) being pre-configured with, stirring reaction 10-15 h,
Filter, wash, obtain the polystyrene microsphere after the positive electrification modification in surface, be designated as PS PDDA；
（3）Weigh 100 ~ 800 mg PS@PDDA microballoons to be distributed in 20 ~ 150 ml solvents, then progressively drip with vigorous stirring
Plus 20 ~ 200 ml steps（1）The BNNS dispersion liquids of configuration, make between BNNS nanometer sheets and polystyrene microsphere occur self assembly and
Precipitation, then through 1000 ~ 3000 rpm centrifugations, drying, obtain complex microsphere, be designated as PS@BNNS；
（4）Complex microsphere powder after by drying is molded under 80 ~ 160 DEG C and 5 ~ 30 Mpa and obtains composite material sheet, is designated as
PS/BNNS.
Step of the present invention（1）With（3）In solvent used be deionized water, ethanol, N,N-dimethylformamide and isopropyl
One kind in alcohol.
The method that the present invention is provided can be realized obtaining high heat conductivity under low nitridation Boron addition, main
If by using the self assembly shape between the electronegative boron nitride nanosheet of polystyrene microsphere and surface of surface positively charged
Into microballoon is met, then boron nitride direction gage entire row along face is obtained through the molding processing near vitrification point again and arrange and be distributed
Polymer composites in boundary.
In polystyrene/boron nitride composite prepared by the present invention, boron nitride has the orientation of height along in face,
With the increase of filer content, gradually contact with each other to form heat conduction network, obtain by showing under low nitridation Boron addition
High thermal conductivity.
The present invention is easy to operate, and preparation condition is simple, and low production cost, it is easy to mass, large-scale production, with good
The basic and wide application prospect of industrialized production.
Description of the drawings
Fig. 1. the transmission electron microscope figure of the boron nitride nanosheet that isopropanol liquid phase is peeled off.
Fig. 2. the scanning electron microscope diagram of the polystyrene microsphere that suspension polymerisation is obtained.
Fig. 3. the polystyrene, the BNNS for peeling off and polystyrene and BNNS after (a) polystyrene, PDDA are modified is multiple
The zeta current potentials of the PS@BNNS after conjunction；B the isopropanol dispersion liquid of () BNNS is before the polystyrene microsphere for adding PDDA modifications
Photo afterwards.
Fig. 4. the scanning electron microscope diagram of PS BNNS complex microspheres when BNNS contents are 13.4 vol%.
Fig. 5. the transmission electron microscope figure of PS BNNS complex microspheres when BNNS contents are 13.4 vol%.
Fig. 6. BNNS contents are the crisp sectional drawing of the PS/BNNS composites of 13.4 vol%.
Fig. 7. the composite of the BNNS distribution of orientations under different filler additions and the composite wood of BNNS random distributions
Thermal conductivity figure in the face of material.
Fig. 8. pure polystyrene microsphere through molding after brittle failure Surface scan electron microscope picture.
Fig. 9. the PS BNNS complex microspheres and PS/BNNS composites brittle failure face when BNNS contents are 5.9 vol%
Scanning electron microscope diagram.
Figure 10. the PS BNNS complex microspheres and PS/BNNS composites brittle failure face when BNNS contents are 8.5 vol%
Scanning electron microscope diagram.
Figure 11. the PS BNNS complex microspheres and PS/BNNS composites brittle failure face when BNNS contents are 11.1 vol%
Scanning electron microscope diagram.
Specific embodiment
The polymer composite of of the present invention boron nitride nanosheet regular arrangement is further described by the following examples
The preparation method of material and its heat conductivility, the embodiment are merely possible to provide explanation rather than limit the present invention.
Embodiment 1
（1）Weigh the commercially available boron nitride of 2 g（BN）It is added in 200 ml certain solvent, then normal temperature in the Ultrasound Instrument of 250 W
18 h of ultrasound, are then centrifuged 20 min under 1000 rpm rotating speeds, take the boron nitride nanosheet of upper strata stripping（BNNS）Dispersion liquid
Standby, the concentration of dispersion liquid is（1.0 mg/ml）；
（2）Weigh the dissolving of 12 g styrene, 90 mg PVPs, 18 ml deionized waters and 225 mg ammonium persulfates
In 150 ml absolute ethyl alcohols.30 min of logical nitrogen.Then 12 h of back flow reaction at 70 DEG C, obtains a scale through centrifuge washing
The monodisperse polystyrene microsphere of degree.The polystyrene microsphere for preparing is distributed to the polydiene dimethylamine being pre-configured with
Ammonium chloride (PDDA) aqueous solution (0.5 wt%), 12 h of stirring reaction, filtration washing obtain the polyphenyl after the positive electrification modification in surface
Ethene microballoon（PS@PDDA）；
（3）Weigh 320 mg PS@PDDA microballoons to be distributed in 60 ml certain solvent, be then progressively added dropwise with vigorous stirring
100 ml（1）The BNNS dispersion liquids of middle configuration, make self assembly, 1000 rpm between BNNS nanometer sheets and polystyrene microsphere
Complex microsphere is obtained after centrifugation, drying（PS@BNNS）；
（4）Complex microsphere powder after by drying is molded under 120 DEG C and 10 Mpa and obtains composite material sheet, is designated as PS/
BNNS-13.4.
The stripping to sheet boron nitride is mutually successfully realized as can see from Figure 1 with isopropyl alcohol liquid, stripping is obtained
The thickness of nanometer sheet is probably between 5-10 layers.Fig. 2 is shown that the electricity of the monodisperse polystyrene microsphere that suspension polymerisation is obtained
Mirror figure, it can be seen that polystyrene microsphere highly uniform, diameter is probably at 1.4 μm.Fig. 3 shows that original polystyrene is micro-
Ball surface current potential is negative value, after modifying through PDDA, it is achieved that the positive electrification of surface potential.And its surface of BNNS that isopropanol is peeled off
Current potential is negative, so that take xenogenesis electric charge between polystyrene microsphere and BNNS, and after they are mixed, both may occur from
Assemble and precipitate flocculation.Fig. 4 and Fig. 5 obtain PS@BNNS complex microspheres when being shown that BNNS additions are 13.4 vol% respectively
Scanning electron microscopy and transmission electron microscopy figure, it can be observed that PS microsphere surfaces have successfully adsorbed substantial amounts of BNNS nanometers
Piece.Fig. 6 is shown that the crisp of the sheet material for obtaining the PS@BNNS complex microspheres of preparation after the molding near vitrification point
From crisp sectional drawing, sectional drawing, can see that BNNS nanometer sheets are dispersedly highly uniform in polymeric matrix, and mainly be distributed
Interface in the PS microballoons of deformation.In addition it can also be seen that BNNS nanometer sheets have the orientation row of height along direction in face
Row, and there occurs that mutually overlap joint constitutes filler network, this filler network can be effective as the path of heat transfer.Fig. 7 shows
Show that the composite compared to BNNS random dispersions in polymeric matrix, filler are uniformly directed the composite wood of distribution in the base
The thermal conductivity of material in the range of whole filler is intended to seem bigger.Further it has also been found that being uniformly directed distribution for BNNS
Composite, when filler addition is more than 8.5 vol%, in face, thermal conductivity there occurs quickly growth, be 13.4 in filer content
Vol% reaches 8.0 W/mK of maximum of thermal conductivity.Illustrate the method by the distribution of orientations to BNNS in the base, Ke Yiyou
Effect is realized under low filler addition, make composite obtain high thermal conductivity.
Embodiment 2
（1）Weigh the dissolving of 12 g styrene, 90 mg PVPs, 18 ml deionized waters and 225 mg ammonium persulfates
In 150 ml absolute ethyl alcohols.30 min of logical nitrogen.Then 12 h of back flow reaction at 70 DEG C, obtains a scale through centrifuge washing
The monodisperse polystyrene microsphere of degree；
（4）Polystyrene microsphere powder after by drying is molded under 120 DEG C and 10 Mpa and obtains composite material sheet.
Fig. 8 is shown that the crisp sectional drawing of sheet material made after compression by pure PS microballoons, it can be seen that under compression force,
There is orientation deformation along direction in face in PS microballoons, but interface is still more clear between microballoon.
Embodiment 3
（1）Weigh the commercially available boron nitride of 2 g（BN）It is added in 200 ml certain solvent, then normal temperature in the Ultrasound Instrument of 250 W
18 h of ultrasound, are then centrifuged 20 min under 1000 rpm rotating speeds, take the boron nitride nanosheet of upper strata stripping（BNNS）Dispersion liquid
Standby, the concentration of dispersion liquid is（1 mg/ml）；
（2）Weigh the dissolving of 12 g styrene, 90 mg PVPs, 18 ml deionized waters and 225 mg ammonium persulfates
In 150 ml absolute ethyl alcohols.30 min of logical nitrogen.Then 12 h of back flow reaction at 70 DEG C, obtains a scale through centrifuge washing
The monodisperse polystyrene microsphere of degree.The polystyrene microsphere for preparing is distributed to the polydiene dimethylamine being pre-configured with
Ammonium chloride (PDDA) aqueous solution (0.5 wt%), 12 h of stirring reaction, filtration washing obtain the polyphenyl after the positive electrification modification in surface
Ethene microballoon（PS@PDDA）；
（3）Weigh 320 mg PS@PDDA microballoons to be distributed in 60 ml certain solvent, be then progressively added dropwise 40 with vigorous stirring
ml（1）The BNNS dispersion liquids of middle configuration, make between BNNS nanometer sheets and polystyrene microsphere occur self assembly, 1000 rpm from
Complex microsphere is obtained after the heart, drying（PS@BNNS）；
（4）Complex microsphere powder after by drying is molded under 120 DEG C and 10 Mpa and obtains composite material sheet, is designated as PS/
BNNS-5.9.
Fig. 9 is shown that the PS@BNNS complex microspheres that BNNS contents are obtained when being 5.9 vol% are obtained with corresponding compression
PS/BNNS-5.9 composites brittle failure face electron microscope picture, it can be seen that under the BNNS additions, BNNS nanometer sheets
Although still height-oriented evenly along direction in face in polymeric matrix, be distributed comparatively sparse, filler it
Between isolate relatively.
Embodiment 4
（1）Weigh the commercially available boron nitride of 2 g（BN）It is added in 200 ml certain solvent, then normal temperature in the Ultrasound Instrument of 250 W
18 h of ultrasound, are then centrifuged 20 min under 1000 rpm rotating speeds, take the boron nitride nanosheet of upper strata stripping（BNNS）Dispersion liquid
Standby, the concentration of dispersion liquid is（1 mg/ml）；
（2）Weigh the dissolving of 12 g styrene, 90 mg PVPs, 18 ml deionized waters and 225 mg ammonium persulfates
In 150 ml absolute ethyl alcohols.30 min of logical nitrogen.Then 12 h of back flow reaction at 70 DEG C, obtains a scale through centrifuge washing
The monodisperse polystyrene microsphere of degree.The polystyrene microsphere for preparing is distributed to the polydiene dimethylamine being pre-configured with
Ammonium chloride (PDDA) aqueous solution (0.5 wt%), 12 h of stirring reaction, filtration washing obtain the polyphenyl after the positive electrification modification in surface
Ethene microballoon（PS@PDDA）；
（3）Weigh 320 mg PS@PDDA microballoons to be distributed in 60 ml certain solvent, be then progressively added dropwise 60 with vigorous stirring
ml（1）The BNNS dispersion liquids of middle configuration, make between BNNS nanometer sheets and polystyrene microsphere occur self assembly, 1000 rpm from
Complex microsphere is obtained after the heart, drying（PS@BNNS）；
（4）Complex microsphere powder after by drying is molded under 120 DEG C and 10 Mpa and obtains composite material sheet, is designated as PS/
BNNS-8.5.
Can be seen by Figure 10, BNNS additions obtain the filler presence office being orientated in polymeric material when being 8.5 vol%
The phenomenon that portion contacts with each other.
Embodiment 5
（1）Weigh the commercially available boron nitride of 2 g（BN）It is added in 200 ml certain solvent, then normal temperature in the Ultrasound Instrument of 250 W
18 h of ultrasound, are then centrifuged 20 min under 1000 rpm rotating speeds, take the boron nitride nanosheet of upper strata stripping（BNNS）Dispersion liquid
Standby, the concentration of dispersion liquid is（1 mg/ml）；
（2）Weigh the dissolving of 12 g styrene, 90 mg PVPs, 18 ml deionized waters and 225 mg ammonium persulfates
In 150 ml absolute ethyl alcohols.30 min of logical nitrogen.Then 12 h of back flow reaction at 70 DEG C, obtains a scale through centrifuge washing
The monodisperse polystyrene microsphere of degree.The polystyrene microsphere for preparing is distributed to the polydiene dimethylamine being pre-configured with
Ammonium chloride (PDDA) aqueous solution (0.5 wt%), 12 h of stirring reaction, filtration washing obtain the polyphenyl after the positive electrification modification in surface
Ethene microballoon（PS@PDDA）；
（3）Weigh 320 mg PS@PDDA microballoons to be distributed in 60 ml certain solvent, be then progressively added dropwise 80 with vigorous stirring
ml（1）The BNNS dispersion liquids of middle configuration, make between BNNS nanometer sheets and polystyrene microsphere occur self assembly, 1000 rpm from
Complex microsphere is obtained after the heart, drying（PS@BNNS）；
（4）Complex microsphere powder after by drying is molded under 120 DEG C and 10 Mpa and obtains composite material sheet, is designated as PS/
BNNS-11.1.
Figure 11 is the PS@BNNS complex microsphere and PS/BNNS-11.1 that filler addition is prepared when being 11.1 vol%
The electron microscope picture of composite.Can see under the content, the BNNS nanometer sheet contents of PS microsphere surfaces absorption are further
Increase.Can see from the crisp sectional drawing of composite and exist between BNNS the part filler network that mutually overlap joint is formed.
Claims (4)
1. a kind of preparation method of high heat conductance polystyrene boron nitride composite, it is characterised in that concretely comprise the following steps：
（1）Weigh 0.5 ~ 5 g boron nitride to be added in 50 ~ 500 ml solvents, in the Ultrasound Instrument of 100 ~ 500W normal temperature ultrasound 8 ~
24 h, are then centrifuged 10 ~ 60 min under 1000 ~ 3000 rpm rotating speeds, and the boron nitride nanosheet dispersion liquid for taking upper strata stripping is standby
With the concentration of dispersion liquid is 0.5 ~ 2 mg/ml；
（2）Weigh 4 ~ 16 g styrene, 20 ~ 150 mg PVPs, 8-24 ml deionized waters and 100 ~ 300 mg
Ammonium persulfate, is dissolved in 80 ~ 200 ml absolute ethyl alcohols, leads to nitrogen 20-60 min；Then at 50 ~ 90 DEG C back flow reaction 6 ~
24 h, through centrifugation, washing, obtain monodisperse polystyrene microsphere；The polystyrene microsphere for preparing is distributed to and is matched somebody with somebody in advance
During the concentration that puts is for the diallyl dimethyl ammoniumchloride aqueous solution of 0.1 ~ 2 wt%, stirring reaction 12-15 h is filtered, is washed
Wash, obtain the polystyrene microsphere of the positive electrification modification in surface, be designated as PS PDDA；
（3）Weigh 100 ~ 800 mg PS@PDDA microballoons to be distributed in 20 ~ 150 ml solvents, be then progressively added dropwise 20 under agitation
~ 200 ml steps（1）The boron nitride nanosheet dispersion liquid of configuration, makes, between boron nitride nanosheet and polystyrene microsphere, oneself occurs
Assemble and precipitate, then after 1000 ~ 3000 rpm centrifugations, drying, obtain complex microsphere, be designated as PS@BNNS；
（4）Complex microsphere powder after by drying is molded under 80 ~ 160 DEG C and 5 ~ 30 Mpa and obtains composite material sheet, is designated as
PS/BNNS.
2. preparation method according to claim 1, it is characterised in that step（1）And step（3）In used solvent for going
One kind in ionized water, ethanol, N,N-dimethylformamide and isopropanol.
3. a kind of high heat conductance polystyrene boron nitride composite prepared by one of claim 1-2 preparation method.
4. high heat conductance styrene boron nitride composite as claimed in claim 3 on polymer bond's composite should
With.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110892489A (en) * | 2017-06-30 | 2020-03-17 | 沙特基础工业全球技术公司 | Thermally conductive, electrically insulating coating for wire |
| WO2024093718A1 (en) * | 2022-11-01 | 2024-05-10 | 黄晓 | Hollow microsphere composite thermally-conductive filler coated with low-dimensional nanometer high-thermal-conductivity material, preparation method therefor, and use thereof |
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| US20040018945A1 (en) * | 2000-09-14 | 2004-01-29 | Aos Thermal Compounds | Dry thermal interface material |
| CN103183889A (en) * | 2013-03-21 | 2013-07-03 | 上海交通大学 | High-thermal-conductivity and insulating polymer composite material and preparation method thereof |
| CN103203462A (en) * | 2013-03-21 | 2013-07-17 | 上海大学 | Preparation method of boron nitride nanosheet-silver nanoparticle composite material |
| US20160280980A1 (en) * | 2015-03-23 | 2016-09-29 | Empire Technology Development Llc | Functionalized boron nitride materials and methods for their preparation and use |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110892489A (en) * | 2017-06-30 | 2020-03-17 | 沙特基础工业全球技术公司 | Thermally conductive, electrically insulating coating for wire |
| WO2024093718A1 (en) * | 2022-11-01 | 2024-05-10 | 黄晓 | Hollow microsphere composite thermally-conductive filler coated with low-dimensional nanometer high-thermal-conductivity material, preparation method therefor, and use thereof |
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| CN106496633B (en) | 2018-12-11 |
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