CN105538647A - Low-cost multifunctional high-efficiency polymer-based insulation and heat conduction composite material and preparation method thereof - Google Patents

Low-cost multifunctional high-efficiency polymer-based insulation and heat conduction composite material and preparation method thereof Download PDF

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CN105538647A
CN105538647A CN201510410355.2A CN201510410355A CN105538647A CN 105538647 A CN105538647 A CN 105538647A CN 201510410355 A CN201510410355 A CN 201510410355A CN 105538647 A CN105538647 A CN 105538647A
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conductive
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polymer
heat conduction
heat
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CN105538647B (en
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吴宏
张晓朦
郭少云
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Sichuan University
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25Component parts, details or accessories; Auxiliary operations
    • B29C48/36Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/49Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using two or more extruders to feed one die or nozzle
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/16Articles comprising two or more components, e.g. co-extruded layers
    • B29C48/18Articles comprising two or more components, e.g. co-extruded layers the components being layers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25Component parts, details or accessories; Auxiliary operations
    • B29C48/92Measuring, controlling or regulating
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/02Elements
    • C08K3/04Carbon
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/38Boron-containing compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04Homopolymers or copolymers of ethene
    • C08L23/06Polyethene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/38Boron-containing compounds
    • C08K2003/382Boron-containing compounds and nitrogen
    • C08K2003/385Binary compounds of nitrogen with boron

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)
  • Laminated Bodies (AREA)

Abstract

The invention discloses a low-cost multifunctional high-efficiency polymer-based insulation and heat conduction composite material. The composite material has an alternately assigned special double-percolation structure formed through mutual superposition of an electricity and heat conduction layer and an insulation and heat conduction layer. An electricity and heat conduction filler has higher heat conductivity and lower price than an insulation and heat conduction filler, so compared with traditional insulation and heat conduction materials, the directionally layered-assigned composite material has the advantages of material cost reduction, integral heat conduction performance improvement, and certain antistatic and electromagnetic shielding properties due to introduction of the electricity and heat conduction layer. The low-cost multifunctional high-efficiency polymer-based insulation and heat conduction composite material has the advantages of controllable layer number and thickness, adjustable formula, excellent mechanical performances, simple production method, stable performances, and easy large-scale production, and can be widely applied to produce multifunctional high-heat conduction polymer-based plates, sheets and membranes.

Description

A kind of low cost, multi-functional, efficient polymer-based insulating heat-conductive composite and preparation method
Technical field
The present invention relates to a kind of low cost, multi-functional, efficient polymer-based insulating composite material and preparation method, belong to functional composite material technical field.
Background technology
along with integrated, high speed and the high frequency of electronic devices and components, make its localized heat release phenomenon particularly serious, this not only can reduce its operating efficiency, more can its service life of shortening at double.Therefore, in order to solve this difficult problem, existing many scholars are devoted to the high-efficiency heat conduction composite of development of new.Wherein, due to polymer-based material have that quality is light, corrosion-resistant, low cost and other advantages and being paid close attention to widely.For the consideration of the safety in operation of electronic devices and components, again heat-conductive composite material is proposed to the requirement of high-insulativity, because when the heat-conductive composite material with certain electric conductivity is applied to electronic packaging, easily make its behavior of even leaking electricity that is short-circuited, this also just significantly limit conductive and heat-conductive composite application (MicroelectronicsReliability in this field, 2012,52:595-602).Therefore, how by the heat conductivility high efficiency of composites, become and limit it and develop of paramount importance problem.At present, relating to maximum is the directional profile realizing filler, improves its local concentration, and then the overall thermal conductivity of reinforcing material can (CompositesScienceandTechnology, 2013,89:142-148).But this method process is loaded down with trivial details, and the directional profile region of filler is uncontrollable, but is in disorganized form, makes the overall performance deviation of material comparatively large and performance is single and be difficult to be promoted.And on design on material structure in the present invention, just effectively can solve an above-mentioned difficult problem by the oriented and ordered distribution of filler, the variation of the heat conductivility making material high efficiency and function more.As added conductive and heat-conductive filler in one deck of its alternating laminated structure, insulating heat-conductive filler is added in addition in one deck, and ensure that thermal insulation layer contacts with electronic devices and components, so both can ensure the integral insulation of material, guarantee the safe operation of electronic devices and components, there is the thermally conductive layer (AppliedThermalEngineering of more high heat conductance simultaneously, 2014, 66:493-498) forward synergy can also played perpendicular on layer direction to thermal insulation layer, improve the thermal conductivity of material monolithic, that is can just can reach higher thermal conductivity factor utilizing the insulating heat-conductive filler of lower content and give the certain antistatic behaviour of material and capability of electromagnetic shielding simultaneously, make it can obtain more broad application in electronics field.In addition, by the adjustment of Thickness ratio, the consumption of the insulating heat-conductive filler of more high price in material can also be effectively reduced, increase the more efficient and cheap application to conductive and heat-conductive filler simultaneously, thus under the prerequisite reducing material monolithic cost, its heat conductivility can be strengthened further.In addition, on the architecture basics of this material, can also a series of adjustment be carried out, strengthen component, toughening element or other function ingredients etc. as added, realizing material high performance and multifunction, to meet applying in association area.
Summary of the invention
For Problems existing in above-mentioned heat conduction functional composite material, the invention provides a kind of method preparing low cost, multi-functional, efficient polymer-based insulating heat-conductive composite, this composite can on the basis reduced costs, improve the heat conductivility of material, and realize the multifunction of material.
know-why of the present invention is the multilayer extrusion equipment utilizing independent research, realize conductive and heat-conductive filler and insulating heat-conductive filler directional profile (outermost end of material in the adjacent layer of stratiform alternative materials respectively, one end is insulating heat-conductive filler packed layer, and the other end is conductive and heat-conductive filler packed layer or insulating packing packed layer).This special structural design and function are selected can ensure material insulating properties in the vertical direction, the electric conductivity of parallel direction, so just make material possess insulating properties, static electricity resistance and electromagnetic wave shielding simultaneously.Moreover, the introducing of the thermally conductive layer of high heat conductance, the cooperative effect of forward can also be played in vertical direction to thermal insulation layer, the heat conductivility of further raising material, suitably can also reduce the consumption of price insulating heat-conductive filler costly simultaneously, reduce the production cost of material monolithic, namely can realize higher insulation heat-conducting property on the basis of lower insulating heat-conductive filler addition.And can also a series of system optimization be carried out on this basis, as expanded the synergy of thermally conductive layer further by modification layer thickness rate; Introduce and strengthen component, toughening element or other function ingredients etc., realize the high performance of material and multifunction etc. further.
the present invention is based on above-mentioned know-why, realizing the technical scheme that its goal of the invention adopts is:
the present invention prepares a kind of method of low cost, multi-functional, efficient polymer-based insulating composite material, is be matrix with thermoplastic, it is characterized in that the method includes the steps of:
(1) utilize high stir machine by polymer with conductive and heat-conductive filler or insulating heat-conductive filler by corresponding weight ratio (conductive and heat-conductive filler>=3wt%, insulating heat-conductive filler>=5wt%) Homogeneous phase mixing, and vacuum drying treatment 8h and more than, stand-by.
(2) said mixture is utilized double-screw extruding pelletizing formed pre-composition, and again carry out drying process 8h and more than.
(3) above-mentioned polymer/conductive and heat-conductive filler pre-composition, polymer/insulating heat-conductive filler pre-composition are melt extruded by extruder A, B respectively, again through the microbedding co-extruder that the junction station (C), layer multiplier (D), the chill roll that are connected with two extruders are formed, be prepared into totally 2 (n+1) special two Chongqing that the thermally conductive layer of layer and thermal insulation layer replace arrange themselves oozes the composite or 2 of structure (n+1) + 1 layer of thermally conductive layer, thermal insulation layer alternately arrangement and outermost end are the composite of thermal insulation layer.
polymer in said method can select in polyolefin, polyamide-based, the thermoplastic such as polyesters or polyethers one or both.
conductive and heat-conductive filler selected in (1) step of said method can be graphite, carbon black, Graphene, CNT, one or more in copper, silver, gold, aluminium, nickel.Insulating heat-conductive filler can be one or more in carborundum, boron carbide, titanium carbide, zirconium carbide, chromium carbide, tungsten carbide, silicon nitride, boron nitride, aluminium nitride, beryllium oxide, aluminium oxide and zinc oxide.
vacuum drying condition in above-mentioned (1) step and (2) step is pressure-0.5 ~-1MPa, temperature 80 ~ 120 DEG C, time 8h and more than.
in above-mentioned (2) step, the temperature of the charge door of double screw extruder, transportation section, melt zone, homogenizing zone, mouth mould is respectively 100 ~ 160 DEG C, 180 ~ 290 DEG C, 190 ~ 290 DEG C, 190 ~ 290 DEG C, 190 ~ 290 DEG C.
in above-mentioned (3) step, the temperature of the charge door of single screw extrusion machine, transportation section, melt zone, homogenizing zone, mouth mould, junction station, layer multiplier is respectively 100 ~ 160 DEG C, 180 ~ 290 DEG C, 190 ~ 290 DEG C, 190 ~ 290 DEG C, 190 ~ 290 DEG C, 200 ~ 290 DEG C, 200 ~ 290 DEG C.
in above-mentioned (3) step, total number of plies of obtained alternately stratified material regulates and controls by superpositing unit number.And the thickness of thermally conductive layer and thermal insulation layer can be regulated by the screw speed of two ends extruder.
patent of the present invention has the following advantages:
(1) composite of the present invention is superimposed by thermally conductive layer and thermal insulation layer and forms, realize the forward synergy of material monolithic heat conductivility, achieve the multifunction of material simultaneously, namely can meet the diversity requirements such as static electricity resistance and electromagnetic wave shielding needed for current electronics field.Specifically, compared to the 0.91w/ (m × k) of independent thermal insulation layer (identical filer content), multilayer materials thermal conductivity containing thermally conductive layer is up to 1.43w/ (m × k), capability of electromagnetic shielding has also brought up at most 45dB from 23dB, and parallel direction resistivity is equally from 1.5 × 10 10 (Ω × cm) has been reduced to 1.05 × 10 4 (Ω × cm), and vertical direction resistivity can all the time 1.5 × 10 10 more than (Ω × cm) (maximum range of equipment equals or exceeds this value and illustrates to be absolute insulator).
(2) composite of the present invention is owing to being the segmentation, superimposed realized in this special structure of layer multiplier, namely realizes under melt state, thus the bonding situation at bed boundary place very well, very firm, can not the mechanical property etc. of damaged material.On the contrary due to two-layer complementation, mechanical property increases.
(3) the preparation method of the present invention one-shot forming technique preparation method technique that adopts lamellar composite to extrude is simple, convenient operation and control; Extrude rotating ratio by regulation and control two extruders, the thickness of thermally conductive layer and thermal insulation layer can be adjusted, by controlling the quantity of increase and decrease layer multiplier, thickness in monolayer and the overall number of plies can be regulated, thus the regulation and control of performance and function can be realized.Specifically, when expanding the Thickness Ratio of thermally conductive layer and thermal insulation layer, can realize significantly reducing thermal insulation layer filer content, reduce costs and significantly improve material monolithic thermal conductivity, parallel conductive electrically and electromagnetic wave shielding, realize high performance and the multifunction of material further.
(4) the present invention also regulates and controls overall performance parameter by changing the recipe ingredient of material, strengthens component and toughening element to regulate the mechanical property of material as added; Add ceramic-like component to regulate the hot property of material; Add ferromagnetic material to increase its magnetic induction performance etc.Namely function combination and the performance optimization of material can be realized in very wide scope.
as can be seen here, in composite of the present invention, polymer and filler are without the need to carrying out specially treated, and preparation method's technique is simple, and convenient operation and control, production efficiency is high, and production cost is low, has wide industrialization and market prospects.
Accompanying drawing explanation
the present invention is further illustrated below in conjunction with accompanying drawing.
fig. 1 is the structural representation of microbedding co-extruder involved in the present invention.In the drawings, A, B: extruder, C: distributor, D: layer multiplier.
fig. 2 be the present invention prepare a kind of low cost, multi-functional, efficient polymer-based insulating heat-conductive composite structure enlarged diagram.In the drawings, E: thermal insulation layer, F: thermally conductive layer.
specific implementation method
be necessary to herein means out, the following examples just further illustrate of the present invention, can not be interpreted as limiting the scope of the invention, and person skilled in art can carry out some nonessential improvement and adjustment according to the invention described above content to the present invention.
embodiment 1
(1) select high density polyethylene (HDPE) (5000s, Yanshan Petrochemical Co., Ltd produces), melt index (MI) is 1g/10min(190 DEG C, 2.16kg); Hexagonal boron nitride (RH-N, Dandong Science and Technology Ltd.), main content 99%, diboron trioxide≤0.5%, moisture content≤0.5%, granularity is 10 μm; Graphite (325 orders, Qingdao Xing Yuan aquadag Co., Ltd), granularity is about 44 μm.High density polyethylene (HDPE) and boron nitride stir in machine at height by weight the ratio of 4:1 and mix, and high density polyethylene (HDPE) and graphite mix by weight the ratio of 3:2 stirring in machine at height, are being placed in 80 DEG C of dry 12h of vacuum drying oven after scattered.
(2) by dried mixture, utilize double screw extruder mixing granulation respectively, form diameter and be about 1mm, length is about the cylinder premixed particle of 3mm, back is respectively referred to as conductive and heat-conductive pre-composition and insulating heat-conductive pre-composition, and wherein the temperature of twin-screw charge door, transportation section, melt zone, homogenizing zone, mouth mould is respectively 155 DEG C, 195 DEG C, 195 DEG C, 195 DEG C, 190 DEG C.The particle got togather by premix is placed in 80 DEG C of vacuum drying ovens, dry 12h.
(3) dried conductive and heat-conductive pre-composition obtained above and insulating heat-conductive pre-composition are dropped in disclosed in Chinese patent CN101439576A respectively by extruder A, B, distributor C, in the extruder A of the microbedding co-extruder that layer multiplier D is formed and extruder B (see Fig. 1), the rotating ratio regulating thermally conductive layer and thermal insulation layer extruder is 1:1, when after the material melts plasticizing in extruder, make two strands of melts superimposed in distributor C, after 0 layer multiplier, again through the compacting of tri-roll press machine and the traction of hauling machine, the wide 40mm of 2 layers of thermally conductive layer extruding and thermal insulation layer alternately arrangement can be obtained, the composite (see Fig. 2) of thick 2mm, wherein, extruder A, B charge door, transportation section, melt zone, homogenizing zone, mouth mould, junction station, the temperature of layer multiplier is respectively 100 ~ 160 DEG C, 180 ~ 250 DEG C, 190 ~ 250 DEG C, 190 ~ 250 DEG C, 190 ~ 250 DEG C, 200 ~ 250 DEG C, 200 ~ 250 DEG C.
after testing, the thermal conductivity that this thermally conductive layer, thermal insulation layer replace two-layer composite is that 0.96w/ (m × k) (utilizes HotDisk thermal constant analyzer to measure, thermal insulation layer directly and probe contacts), parallel direction resistivity is 1 × 10 4 (Ω × cm) (sample length 10cm, width 1cm, thickness 2mm utilize the Keithley6487 type resistance instrument of Keithley instrument company of the U.S. to measure), vertical direction resistivity>=1.5 × 10 10 (Ω × cm) (sample length 2cm, width 2cm, thickness 2mm, the Keithley6487 type resistance instrument of Keithley instrument company of the U.S. is utilized to measure), capability of electromagnetic shielding peak value is 37.5dB, and mechanical property is 26.9MPa (sample is dumbbell shaped standard specimen).
embodiment 2
(1) select high density polyethylene (HDPE) (5000s, Yanshan Petrochemical Co., Ltd produces), melt index (MI) is 1g/10min(190 DEG C, 2.16kg); Hexagonal boron nitride (RH-N, Dandong Science and Technology Ltd.), main content 99%, diboron trioxide≤0.5%, moisture content≤0.5%, granularity is 10 μm; Graphite (325 orders, Qingdao Xing Yuan aquadag Co., Ltd), granularity is about 44 μm.High density polyethylene (HDPE) and boron nitride stir in machine at height by weight the ratio of 4:1 and mix, and high density polyethylene (HDPE) and graphite mix by weight the ratio of 3:2 stirring in machine at height, are being placed in 80 DEG C of dry 12h of vacuum drying oven after scattered.
(2) by dried mixture, utilize double screw extruder mixing granulation respectively, form diameter and be about 1mm, length is about the cylinder pre-composition of 3mm, and wherein the temperature of twin-screw charge door, transportation section, melt zone, homogenizing zone, mouth mould is respectively 155 DEG C, 195 DEG C, 195 DEG C, 195 DEG C, 190 DEG C.The particle got togather by premix is placed in 80 DEG C of vacuum drying ovens, dry 12h.
(3) dried conductive and heat-conductive pre-composition obtained above and insulating heat-conductive pre-composition are dropped in disclosed in Chinese patent CN101439576A respectively by extruder A, B, distributor C, in the extruder A of the microbedding co-extruder that layer multiplier D is formed and extruder B (see Fig. 1), the rotating ratio regulating thermally conductive layer and thermal insulation layer extruder is 1:1, when after the material melts plasticizing in extruder, make two strands of melts superimposed in distributor C, after 2 layer multipliers, again through the compacting of tri-roll press machine and the traction of hauling machine, the width 40mm that 8 layers of thermally conductive layer extruding and thermal insulation layer replace can be obtained, the stratified material (see Fig. 2) of thickness 2mm, wherein, extruder A, B charge door, transportation section, melt zone, homogenizing zone, mouth mould, junction station, the temperature of layer multiplier is respectively 100 ~ 160 DEG C, 180 ~ 250 DEG C, 190 ~ 250 DEG C, 190 ~ 250 DEG C, 190 ~ 250 DEG C, 200 ~ 250 DEG C, 200 ~ 250 DEG C.
after testing, the thermal conductivity that this thermally conductive layer, thermal insulation layer replace 8 layers of composite is that 1.28w/ (m × k) (utilizes HotDisk thermal constant analyzer to measure, thermal insulation layer directly and probe contacts), parallel direction resistivity is 2.3 × 10 4 (Ω × cm) (sample length 10cm, width 1cm, thickness 2mm utilize the Keithley6487 type resistance instrument of Keithley instrument company of the U.S. to measure), vertical direction resistivity>=1.5 × 10 10 (Ω × cm) (sample length 2cm, width 2cm, thickness 2mm, the Keithley6487 type resistance instrument of Keithley instrument company of the U.S. is utilized to measure), capability of electromagnetic shielding peak value is 38dB, and mechanical property is 25.8MPa (sample is dumbbell shaped standard specimen).
embodiment 3
(1) select high density polyethylene (HDPE) (5000s, Yanshan Petrochemical Co., Ltd produces), melt index (MI) is 1g/10min(190 DEG C, 2.16kg); Hexagonal boron nitride (RH-N, Dandong Science and Technology Ltd.), main content 99%, diboron trioxide≤0.5%, moisture content≤0.5%, granularity is 10 μm; Graphite (325 orders, Qingdao Xing Yuan aquadag Co., Ltd), granularity is about 44 μm.High density polyethylene (HDPE) and boron nitride stir in machine at height by weight the ratio of 4:1 and mix, and high density polyethylene (HDPE) and graphite mix by weight the ratio of 3:2 stirring in machine at height, are being placed in 80 DEG C of dry 12h of vacuum drying oven after scattered.
(2) by dried mixture, utilize double screw extruder mixing granulation respectively, form diameter and be about 1mm, length is about the cylinder pre-composition of 3mm, and wherein the temperature of twin-screw charge door, transportation section, melt zone, homogenizing zone, mouth mould is respectively 155 DEG C, 195 DEG C, 195 DEG C, 195 DEG C, 190 DEG C.The particle got togather by premix is placed in 80 DEG C of vacuum drying ovens, dry 12h.
(3) dried conductive and heat-conductive pre-composition obtained above and insulating heat-conductive pre-composition are dropped into disclosed in Chinese patent CN101439576A respectively by extruder A, B, distributor C, in the extruder A of the microbedding co-extruder that layer multiplier D is formed and extruder B (see Fig. 1), the rotating ratio regulating thermally conductive layer and thermal insulation layer extruder is 1:1, when after the material melts plasticizing in extruder, make two strands of melts superimposed in distributor C, after 4 layer multipliers, again through the compacting of tri-roll press machine and the traction of hauling machine, the width 40mm that 32 layers of thermally conductive layer extruding and thermal insulation layer replace can be obtained, the stratified material (see Fig. 2) of thickness 2mm, wherein, extruder A, B charge door, transportation section, melt zone, homogenizing zone, mouth mould, junction station, the temperature of layer multiplier is respectively 100 ~ 160 DEG C, 180 ~ 250 DEG C, 190 ~ 250 DEG C, 190 ~ 250 DEG C, 190 ~ 250 DEG C, 200 ~ 250 DEG C, 200 ~ 250 DEG C.
after testing, the thermal conductivity that this thermally conductive layer, thermal insulation layer replace 32 layers of composite is that 1.43w/ (m × k) (utilizes HotDisk thermal constant analyzer to measure, thermal insulation layer directly and probe contacts), parallel direction resistivity is 5.6 × 10 4 (Ω × cm) (sample length 10cm, width 1cm, thickness 2mm utilize the Keithley6487 type resistance instrument of Keithley instrument company of the U.S. to measure), vertical direction resistivity>=1.5 × 10 10 (Ω × cm) (sample length 2cm, width 2cm, thickness 2mm, the Keithley6487 type resistance instrument of Keithley instrument company of the U.S. is utilized to measure), capability of electromagnetic shielding peak value is 35dB, and mechanical property is 25.5MPa (sample is dumbbell shaped standard specimen).
comparative example 1
(1) by the above-mentioned multi-layer sheet extruded, being cut into volume is probably 4mm 3 granule, be placed in 80 DEG C of dry 12h of vacuum drying oven.Dried material, utilize banbury banburying 10min under the condition of 180 DEG C, 30 revs/min, again by thermoforming trigger squeeze, 190 DEG C, to make length and width under 10MPa pressure be 10 × 10cm, thickness is that the sheet material of 2mm is stand-by, and gained hydridization filler co-mixing system has identical constituent content with alternately Layered Sample.
after testing, the thermal conductivity of this filler hybrid composite material is 1.39w/ (m × k) (utilizing HotDisk thermal constant analyzer to measure), parallel direction resistivity>=1.5 × 10 10 (Ω × cm) (sample length 10cm, width 1cm, thickness 2mm utilize the Keithley6487 type resistance instrument of Keithley instrument company of the U.S. to measure), vertical direction resistivity>=1.5 × 10 10 (Ω × cm) (sample length 2cm, width 2cm, thickness 2mm utilize the Keithley6487 type resistance instrument of Keithley instrument company of the U.S. to measure), capability of electromagnetic shielding peak value is 28dB, and mechanical property is 21.3MPa.
contrast through above-described embodiment 1,2,3 and the blended sample of filler hydridization can be found out, under identical amount of filler, alternate multiple sample has higher parallel direction electrical conductivity, thus make it have higher antistatic property, can also keep perpendicular to the electrical insulating property on stratiform direction simultaneously, and the more common hybrid systems of its heat conductivility is equal to each other, even higher.By the biaxial tension field of force in stratiform multiplier (superpositing unit), filler is possessed higher dispersity and degree of orientation, makes its mechanical property there has also been and significantly improves.In sum, this special alternating laminated structure, can on the basis of high insulating heat-conductive ensureing material monolithic, realize its antistatic property, also can be reduced the addition of the heat fillings such as BN simultaneously by the introducing of graphite linings significantly, thus low cost, multi-functional, efficient polymer-based insulating heat-conductive composite can be prepared.
detailed performance contrast is as shown in the table:
Sample Heat conduction (w/ (m*k)) Vertical resistor (Ω * cm) Parallel resistance (Ω * cm) Electromagnetic shielding (dB) Mechanical property (MPa)
2L 0.96 ≥1.5×10 10 1.05×10 4 37.5 26.9
8L 1.28 ≥1.5×10 10 2.25×10 4 38 25.8
32L 1.43 ≥1.5×10 10 5.63×10 4 35 25.5
Blended sample 1.39 ≥1.5×10 10 ≥1.5×10 10 28 21.3

Claims (6)

1. low cost, multi-functional, an efficient polymer-based insulating heat-conductive composite, it is characterized in that this composite be by following polymer-based/conductive and heat-conductive filler pre-composition, polymer-based/insulating heat-conductive filler pre-composition are superimposed and formed 2 through fusion plastification, n stratiform (n+1)the composite or 2 of structure is oozed in special two Chongqing that layer thermally conductive layer, thermal insulation layer are alternately arranged (n+1)the composite that+1 layer of thermally conductive layer, thermal insulation layer are alternately arranged, wherein the outermost end of material is thermal insulation layer, and the preparation method of this composite comprises following step:
The first step: utilize and highly stir machine by polymer with conductive and heat-conductive filler or insulating heat-conductive filler Homogeneous phase mixing by a certain percentage, and vacuum drying treatment, stand-by;
Second step: utilize double screw extruder to extrude said mixture, granulation formed pre-composition, and again carry out drying process;
3rd step: above-mentioned polymer/conductive and heat-conductive filler pre-composition, polymer/insulating heat-conductive filler pre-composition are melt extruded by extruder A, B respectively, again through the microbedding co-extruder that the junction station (C), layer multiplier (D), the chill roll that are connected with two extruders are formed, be prepared into totally 2 (n+1)layer or 2 (n+1)+ 1 layer of thermally conductive layer, thermal insulation layer replace the composite that structure is oozed in special two Chongqing of arranging.
2. a kind of low cost according to claim 1, multi-functional, efficient polymer-based insulating heat-conductive composite is characterized in that selected high molecular polymer can be one or both in TPO, polyamide-based, the thermoplastic such as polyesters, polyethers.
3. a kind of low cost according to claim 1, multi-functional, efficient polymer-based insulating heat-conductive composite is characterized in that selected conductive and heat-conductive filler can be graphite, carbon black, Graphene, CNT, one or more in copper, silver, gold, aluminium, nickel.
4. a kind of low cost according to claim 1, multi-functional, efficient polymer-based insulating heat-conductive composite is characterized in that selected insulating heat-conductive filler can be one or more in carborundum, boron carbide, titanium carbide, zirconium carbide, chromium carbide, tungsten carbide, silicon nitride, boron nitride, aluminium nitride, beryllium oxide, aluminium oxide and zinc oxide.
5. a kind of low cost according to claim 1,3, multi-functional, efficient polymer-based insulating heat-conductive composite is characterized in that the addition of its conductive and heat-conductive filler is more than or equal to 3wt% with thermally conductive layer total mass ratio.
6. a kind of low cost according to claim 1,4, multi-functional, efficient polymer-based insulating heat-conductive composite is characterized in that the addition of its insulating heat-conductive filler is more than or equal to 5wt% with thermal insulation layer total mass ratio.
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