CN108070232A - A kind of makrolon base high heat conductivity insulation composite and preparation method thereof - Google Patents

A kind of makrolon base high heat conductivity insulation composite and preparation method thereof Download PDF

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Publication number
CN108070232A
CN108070232A CN201611009219.3A CN201611009219A CN108070232A CN 108070232 A CN108070232 A CN 108070232A CN 201611009219 A CN201611009219 A CN 201611009219A CN 108070232 A CN108070232 A CN 108070232A
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parts
composite material
nano
makrolon
heat conductive
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高启新
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Chengdu Chuangside Electromechanical Equipment Co Ltd
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Chengdu Chuangside Electromechanical Equipment Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00Processes of treating or compounding macromolecular substances
    • C08J3/24Crosslinking, e.g. vulcanising, of macromolecules
    • C08J3/246Intercrosslinking of at least two polymers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2369/00Characterised by the use of polycarbonates; Derivatives of polycarbonates
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/04Homopolymers or copolymers of ethene
    • C08J2423/06Polyethene
    • 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
    • C08K2201/00Specific properties of additives
    • C08K2201/002Physical properties
    • C08K2201/003Additives being defined by their diameter
    • 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
    • C08K2201/00Specific properties of additives
    • C08K2201/002Physical properties
    • C08K2201/004Additives being defined by their length
    • 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
    • C08K2201/00Specific properties of additives
    • C08K2201/011Nanostructured additives
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00Applications
    • C08L2203/20Applications use in electrical or conductive gadgets

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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)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention discloses a kind of makrolon base high heat conductivity insulation composites and preparation method thereof, are prepared including following parts by weight raw material:30 60 parts of makrolon, 5 10 parts of butanediol, 10 25 parts of polyethylene, 25 parts of stearic acid, 25 parts of nano chromium oxide, 36 parts of carbon nano-fiber, 25 parts of nano aluminum nitride, 13 parts of coupling agent, 15 parts of crosslinking agent;The present invention is made composite material have the advantages of heat conduction constant is big, high mechanical properties, is promoted application of the heat conductive insulating composite material on rapid cooling electronic device is needed using polymer crosslinking and organic inorganic hybridization principle.

Description

A kind of makrolon base high heat conductivity insulation composite and preparation method thereof
Technical field
The present invention relates to field of electronic materials, and in particular to a kind of makrolon base high heat conductivity insulation composite and its system Preparation Method.
Background technology
The circuit design of electronic product becomes increasingly complex at present, in densification, trend toward miniaturization.These electronic and electrical equipments Amount of heat can be generated, if these heats cannot discharge in time, accumulation to a certain extent will certainly be to the component of electronic apparatus And equipment damages in itself.So the waste heat that must be generated is timely, is efficiently transferred in ambient enviroment. Traditional metal material in heat dissipation industry, because the geometry of its product is very limited, and such radiator and electricity Subcomponent surface is there are certain interval, so as to more and more easily be substituted by some thermal interfacial materials.
High molecular material electrical insulation capability is excellent, but thermal conductivity factor is very low, generally 0.2W/m.K, is only metal material 1 percent to one thousandth.Compare at present the application scenario that there should be high heat conduction for some while have insulating properties requirement again More conventional method is inorganic filler (aluminium nitride, oxygen of the addition with high thermal conductivity coefficient and high impedance in polymer-based material Change chromium etc.), the patents such as CN02825187.3, CN200880011625.0 and CN201010194959.5 are all using this side Method.But the material prepared in this way, since a large amount of additions of heat filling receive the mechanical property of composite material Serious damage, while the raising of heat conductivility is not also notable, is generally hardly higher than 2W/m.K.For LED radiator, electric appliance Radiator etc. needs the situation using radiator area flash heat transfer, if the thermal conductivity factor of material is small, in length direction On heat transfer with regard to extremely difficult, heat, which is all concentrated in the region of very little, to spread, and the effective area of radiator is caused not have It makes full use of, affects radiating efficiency.
The content of the invention
It is an object of the invention to overcome thermal conductivity factor existing for existing heat conductive insulating composite material low, poor mechanical property Defect provides a kind of makrolon base high heat conductivity insulation composite and preparation method thereof;The present invention utilizes polymer crosslinking With hybrid inorganic-organic principle, the advantages of thermal conductivity factor is big, and mechanical property is good is made it have, heat-conducting insulation material is promoted and exists Need the application on the electronic device of rapid cooling.
In order to realize foregoing invention purpose, the present invention provides a kind of makrolon base high heat conductivity insulation composite, bags Following parts by weight raw material are included to be prepared:30-60 parts of makrolon, 5-10 parts of butanediol, 10-25 parts of polyethylene, 2-5 parts of stearic acid, 2-5 parts of nano chromium oxide, 3-6 parts of carbon nano-fiber, 2-5 parts of nano aluminum nitride, 1-3 parts of idol Join agent, 1-5 parts of crosslinking agent.
A kind of makrolon base high heat conductivity insulation composite using the polymerization that is cross-linked with each other of gas chromatography, forms knot Structure is stablized, the polymer three-dimensional network structure of excellent in mechanical performance, while the hydridization difference Heat Conduction Material in three-dimensional net structure, Chromium oxide-carbon fiber-aluminium nitride three forms a three-dimensional heat radiating structure, and radiating rate increases, heat conductivility increase;Meanwhile Three-dimensional net structure increases mechanical properties of polymer, operating temperature higher;The heat conductive insulating composite material use scope is more Greatly, the development of electronics industry is conducive to.
Preferably, wherein the polycarbonate polymerization degree is 200-500, the degree of polymerization is too big, and strand is too long, formation It is poor that three-dimensional net structure is stablized, and composite material fusing point reduces;The degree of polymerization is too small, and strand is too short, is unfavorable for the miscellaneous of Heat Conduction Material Change and embedded, Heat Conduction Material disperses irregularly, it is possible to create agglomeration, product heat conductivility reduce.
Preferably, wherein the polyethylene polymerization degree is 40-80, the degree of polymerization is too big, and strand is too long, the three-dimensional of formation It is poor that network structure is stablized, and composite materials property reduces;The degree of polymerization is too small, and strand is too short, is unfavorable for the miscellaneous of Heat Conduction Material Change and embedded, Heat Conduction Material disperses irregularly, it is possible to create agglomeration, product heat conductivility reduce.
Preferably, wherein the grain size of the nano chromium oxide is 20-60 nanometers, grain size is too big, is unfavorable for Heat Conduction Material Hydridization in three-dimensional net structure and insertion, Heat Conduction Material disperse irregularly, it is possible to create agglomeration, product thermal conductivity It can reduce, grain size is too small, difficulties in dispersion, easily reunites.
Preferably, wherein a diameter of 2-5nm of the carbon nano-fiber, length 10-50nm, diameter and length are too Greatly, the hydridization in three-dimensional net structure and insertion, Heat Conduction Material for being unfavorable for Heat Conduction Material are disperseed irregularly, it is possible to create group Poly- phenomenon, product heat conductivility reduce, and a diameter of 2-5nm, length is too small for 10-50nm, difficulties in dispersion, easily reunite, it is difficult to The three-dimensional heat dissipation system of structure.
Preferably, wherein the grain size of the nano aluminum nitride is 20-50 nanometers, grain size is too big, is unfavorable for Heat Conduction Material Hydridization in three-dimensional net structure and insertion, Heat Conduction Material disperse irregularly, it is possible to create agglomeration, product thermal conductivity It can reduce, grain size is too small, difficulties in dispersion, easily reunites.
Preferably, wherein the coupling agent is silane coupling agent, silane coupling agent to the coupling effect of Heat Conduction Material most It is good.
Preferably, a kind of makrolon base high heat conductivity insulation composite is prepared including following parts by weight raw material It forms:40-50 parts of makrolon, 5-8 parts of butanediol, 15-20 parts of polyethylene, 2-3 parts of stearic acid, 2-3 parts receive Rice chromium oxide, 2-3 parts of carbon nano-fiber, 4-6 parts of nano aluminum nitride, 1-2 parts of coupling agent, 2-3 parts of crosslinking agent.
In order to realize foregoing invention purpose, further, the present invention provides a kind of makrolon base high heat conductive insulatings to answer The preparation method of condensation material, comprises the following steps:
(1)Nano chromium oxide, carbon nano-fiber, nano aluminum nitride are dispersed in butanediol and form suspension;
(2)The suspension that step 1 is obtained is esterified with stearic acid, coupling agent, coupling reaction, and it is miscellaneous to obtain stearic acid butanediol ester Change mixture;
(3)The stearic acid butanediol ester hybridized mixed object and makrolon that step 2 is obtained, polyethylene, crosslinking agent mixing are laggard Row cross-linking reaction obtains makrolon base high heat conductivity insulation composite.
A kind of preparation method of makrolon base high heat conductivity insulation composite is first uniform by butanediol by Heat Conduction Material It scatter, esterification and coupling agent is recycled to be coupled the ester of synthesis and Heat Conduction Material, form stearic acid butanediol ester hydridization Mixture so that the arrangement of the uniform rule of Heat Conduction Material is dispersed in three-dimensional net structure, will not reunite, and form oxidation Chromium-carbon fiber-aluminium nitride three-dimensional heat radiating structure, radiating rate increase, heat conductivility increase;Finally by with other macromolecule materials The crosslinking of material forms the makrolon base high heat conductivity insulation composite with three-dimensional net structure, makes polymer mechanical property It can increase, operating temperature higher;The preparation method of the makrolon base high heat conductivity insulation composite is simple, stablizes, is reliable, It is suitble to extensive, the industrialized production of makrolon base high heat conductivity insulation composite.
Preferably, the esterification reaction temperature is 120-150 DEG C, and reaction temperature is excessively high, and reaction is violent, and control is difficult, instead Answer temperature too low, reaction speed is slow, and the production cycle is long.
Preferably, the reaction time of esterification is 2-5h, and the reaction time is long, and the production cycle is long, and efficiency is low, the reaction time Too short, reaction is incomplete, and product heat conductivility reduces.
Preferably, the cross-linking reaction temperature is 180-250 DEG C, and crosslinking temperature is excessively high, is crosslinked transition, the three dimensional network of formation Network irregular structure, properties of product reduce, and crosslinking temperature is too low, and the reaction time is too long, and the production cycle is long.
Preferably, the time of the cross-linking reaction is 1-3h, and the reaction time is long, and the production cycle is long, and efficiency is low, during reaction Between it is too short, reaction is incomplete, and product heat conductivility reduces.
Compared with prior art, beneficial effects of the present invention:
1st, makrolon base high heat conductivity insulation composite of the present invention contains three-dimensional net structure and chromium oxide-carbon fiber-nitridation Aluminium three-dimensional heat radiating structure has higher heat conductivility and mechanical property.
2nd, the preparation method of makrolon base high heat conductivity insulation composite of the present invention first passes through esterification and hydridization, recycles Crosslinking, by Heat Conduction Material Monodispersed in three-dimensional net structure system, parallel into the three-dimensional heat dissipation of chromium oxide-carbon fiber-aluminium nitride Structure, so as to add the radiating rate of composite material.
3rd, the preparation method of makrolon base high heat conductivity insulation composite of the present invention is simple, stablizes, is reliable, is suitble to poly- carbon Extensive, the industrialized production of perester radical high heat conductivity insulation composite.
Specific embodiment
With reference to test example and specific embodiment, the present invention is described in further detail.But this should not be understood Following embodiment is only limitted to for the scope of the above-mentioned theme of the present invention, it is all that this is belonged to based on the technology that present invention is realized The scope of invention.
Embodiment 1
(1)The nano aluminum nitride of the nano chromium oxide of 3 parts by weight, the carbon nano-fiber of 5 parts by weight, 4 parts by weight is dispersed in 10 Solution is formed in the butanediol of parts by weight;
(2)Solution and the stearic acid of 3 parts by weight that step 1 is obtained, the silane coupling agent of 2 parts by weight are under conditions of 120 DEG C It is esterified, coupling reaction 5h, obtains stearic acid butanediol ester hybridized mixed object;
(3)The stearic acid butanediol ester hybridized mixed object and the degree of polymerization of 20 parts by weight that step 2 is obtained are 200 poly- carbonic acid Ester, the degree of polymerization of 5 parts by weight are 40 polyethylene, carry out being crosslinked at a temperature of 180 DEG C after the crosslinking agent mixing of 2 parts by weight anti- 3h is answered, obtains makrolon base high heat conductivity insulation composite.
Embodiment 2
(1)The nano aluminum nitride of the nano chromium oxide of 2 parts by weight, the carbon nano-fiber of 3 parts by weight, 6 parts by weight is dispersed in 5 weights It measures in the butanediol of part and forms solution;
(2)The solution that step 1 obtains and the stearic acid of 2 parts by weight, the coupling agent of 1 parts by weight are carried out at a temperature of 150 DEG C Esterification, coupling reaction 2h, obtain stearic acid butanediol ester hybridized mixed object;
(3)The stearic acid butanediol ester hybridized mixed object and the degree of polymerization of 15 parts by weight that step 2 is obtained are 500 poly- carbonic acid Ester, the degree of polymerization of 10 parts by weight are 80 polyethylene, are crosslinked after the crosslinking agent mixing of 3 parts by weight at a temperature of 250 DEG C 1h is reacted, obtains makrolon base high heat conductivity insulation composite.
Embodiment 3
(1)The nano aluminum nitride of the nano chromium oxide of 2 parts by weight, the carbon nano-fiber of 3 parts by weight, 5 parts by weight is dispersed in 5 weights It measures in the butanediol of part and forms solution;
(2)Solution and the stearic acid of 5 parts by weight, the coupling agent of 1 parts by weight that step 1 is obtained are esterified, coupling reaction, are obtained Stearic acid butanediol ester hybridized mixed object;
(3)The stearic acid butanediol ester hybridized mixed object and the makrolon of 30 parts by weight that step 2 is obtained, 10 parts by weight are gathered Ethylene carries out cross-linking reaction after the crosslinking agent mixing of 1 parts by weight, obtains makrolon base high heat conductivity insulation composite.
Embodiment 4
(1)The nano aluminum nitride of the nano chromium oxide of 5 parts by weight, the carbon nano-fiber of 5 parts by weight, 3 parts by weight is dispersed in 15 Solution is formed in the butanediol of parts by weight;
(2)Solution and the stearic acid of 2 parts by weight, the coupling agent of 3 parts by weight that step 1 is obtained are esterified, coupling reaction, are obtained Stearic acid butanediol ester hybridized mixed object;
(3)The stearic acid butanediol ester hybridized mixed object and the makrolon of 60 parts by weight that step 2 is obtained, 5 parts by weight are gathered Ethylene carries out cross-linking reaction after the crosslinking agent mixing of 1 parts by weight, obtains makrolon base high heat conductivity insulation composite.

Claims (10)

1. a kind of heat conductive insulating composite material, which is characterized in that be prepared including following parts by weight raw material:30-60 parts Makrolon, 5-10 parts of butanediol, 10-25 parts of polyethylene, 2-5 parts of stearic acid, 2-5 parts of nano chromium oxide, 3-6 parts Carbon nano-fiber, 2-5 parts of nano aluminum nitride, 1-3 parts of coupling agent, 1-5 parts of crosslinking agent.
2. heat conductive insulating composite material according to claim 1, which is characterized in that the polycarbonate polymerization degree is 200- 500。
3. heat conductive insulating composite material according to claim 1, which is characterized in that the polyethylene polymerization degree is 40-80.
4. heat conductive insulating composite material according to claim 1, which is characterized in that the grain size of the nano chromium oxide is 20-60nm。
5. heat conductive insulating composite material according to claim 1, which is characterized in that a diameter of 2- of the carbon nano-fiber 5nm, length 10-50nm.
6. heat conductive insulating composite material according to claim 1, which is characterized in that the grain size of the aluminium nitride is 20- 50nm。
7. heat conductive insulating composite material according to claim 1, which is characterized in that prepared including following parts by weight raw material It forms:40-50 parts of makrolon, 5-8 parts of butanediol, 15-20 parts of polyethylene, 2-3 parts of stearic acid, 2-3 parts receive Rice chromium oxide, 2-3 parts of carbon nano-fiber, 4-6 parts of nano aluminum nitride, 1-2 parts of coupling agent, 2-3 parts of crosslinking agent.
8. the preparation method of heat conductive insulating composite material described in a kind of claim 1, which is characterized in that comprise the following steps:
(1)Nano chromium oxide, carbon nano-fiber, nano aluminum nitride are dispersed in butanediol and form suspension;
(2)The suspension that step 1 is obtained is esterified with stearic acid, coupling agent, coupling reaction, and it is miscellaneous to obtain stearic acid butanediol ester Change mixture;
(3)The stearic acid butanediol ester hybridized mixed object and makrolon that step 2 is obtained, polyethylene, crosslinking agent mixing are laggard Row cross-linking reaction obtains makrolon base high heat conductivity insulation composite.
9. preparation method according to claim 8, which is characterized in that esterification reaction temperature is 120-150 DEG C in step 2, Time is 2-5h.
10. preparation method according to claim 8, which is characterized in that cross-linking reaction temperature is 180-250 DEG C in step 3, Time is 1-3h.
CN201611009219.3A 2016-11-17 2016-11-17 A kind of makrolon base high heat conductivity insulation composite and preparation method thereof Withdrawn CN108070232A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114805984A (en) * 2022-04-25 2022-07-29 广东中讯通讯设备实业有限公司 High-heat-dissipation HDPE power conduit and preparation method thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114805984A (en) * 2022-04-25 2022-07-29 广东中讯通讯设备实业有限公司 High-heat-dissipation HDPE power conduit and preparation method thereof
CN114805984B (en) * 2022-04-25 2023-02-17 广东中讯通讯设备实业有限公司 High-heat-dissipation HDPE electric power conduit and preparation method thereof

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Application publication date: 20180525