CN106543645A - A kind of CNT heat-conductive composite material and preparation method thereof - Google Patents
A kind of CNT heat-conductive composite material and preparation method thereof Download PDFInfo
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- CN106543645A CN106543645A CN201610917196.XA CN201610917196A CN106543645A CN 106543645 A CN106543645 A CN 106543645A CN 201610917196 A CN201610917196 A CN 201610917196A CN 106543645 A CN106543645 A CN 106543645A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/08—Materials not undergoing a change of physical state when used
- C09K5/14—Solid materials, e.g. powdery or granular
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The invention discloses a kind of CNT heat-conductive composite material, it is made up of the raw material of following weight parts：Myristic acid soda soap 0.7 1,10 13,3,5 diaminobenzoic acid 12 of nano aluminium oxide, pyridine 0.3 0.7, triphenyl phosphite 23, lithium chloride 0.1 0.2, silane coupler kh5600.6 1, acetylacetone,2,4-pentanedione neodymium 0.7 1, methylhexahydrophthalic anhydride 1.6 2, epoxy resin 6101 80 90, polyvinylbenzenesulfonic acid 12, hexamethyl cyclotrisiloxane 0.4 1, abienol 35, HMPA 0.3 1, CNT 56,2 mercapto benzimidazoles 0.3 1.Present invention adds CNT etc. can effectively improve the heat conductivility of finished composite material.
Description
Technical field
The present invention relates to Heat Conduction Material technical field, more particularly to a kind of CNT heat-conductive composite material and its preparation side
Method.
Background technology
Epoxy resin has excellent mechanical property, electrical property, adhesive property and thermally-stabilised, is widely used to aviation boat
My god, the field such as electric.Epoxy resin is various in style, and what this work was selected is cycloaliphatic epoxy resin, due to aliphatic ring
Epoxide group in oxygen resinous molecular structure is not from expoxy propane, and epoxy radicals are connected directly between on alicyclic ring, so alicyclic
Epoxy resin compared with bisphenol-A type epoxy resin, with good heat stability, excellent electrical insulation capability and weathering
Many advantages, such as property, high safety.But the heat conductivity of epoxy resin relatively low (0.23 W/m K), heat dispersion is poor,
It is difficult to meet the fast development of microelectric technique and encapsulation technology.Therefore, about epoxy resin heat conductivility research
Become the focus that the subjects such as electronics and material are paid close attention to jointly；
The approach for improving the heat conductivity of polymer mainly has two kinds of Intrinsical and filled-type.Former approach difficulty is big, cost compared with
Height, studies less.The latter's method is simple, is widely used.At present, relevant filled-type thermally conductive epoxy resin composite wood
The research of material is much reported.In heat filling, nano aluminium oxide has higher heat conductivity (30 W/m K), excellent
Different heat stability and resistance to chemical corrosion, good electrical insulating property, and cheap and wide material sources and obtain extensively should
With.But as nano oxidized aluminium particle size is little, surface energy is high, in thermodynamics unsteady state, easily assemble agglomerating, so as to
Have impact on the practical application effect of nano alumina particles.So must nano alumina particles be carried out with surface be modified, with
Surface energy is reduced, reduces the agglomeration power between nano-particle, improve its dispersibility and dispersion stabilization in the base, reduced biphase
Interfacial tension, the wettability, adhesion and the compatibility between raising nano alumina particles and matrix resin are multiple so as to improve
The combination property of condensation material.
The content of the invention
The object of the invention is exactly for the defect for making up prior art, there is provided a kind of CNT heat-conductive composite material and its
Preparation method.
The present invention is achieved by the following technical solutions：
A kind of CNT heat-conductive composite material, it is made up of the raw material of following weight parts：
Myristic acid soda soap 0.7-1, nano aluminium oxide 10-13,3,5- diaminobenzoic acid 1-2, pyridine 0.3-0.7, phosphorous acid
Triphenylmethyl methacrylate 2-3, lithium chloride 0.1-0.2, silane coupler kh5600.6-1, acetylacetone,2,4-pentanedione neodymium 0.7-1, methyl hexahydro O-phthalic
Anhydride 1.6-2, epoxy resin 6101 80-90, polyvinylbenzenesulfonic acid 1-2, hexamethyl cyclotrisiloxane 0.4-1, abienol 3-5,
HMPA 0.3-1, CNT 5-6,2- mercapto benzimidazole 0.3-1.
A kind of preparation method of described CNT heat-conductive composite material, comprises the following steps：
（1）Above-mentioned 2- mercaptos benzimidazole is added in the dehydrated alcohol of its weight 10-14 times, is stirred, rise high temperature
Spend for 63-70 DEG C, add above-mentioned CNT, ultrasonic 4-8 minutes, obtain CNT alcohol dispersion liquid；
（2）Above-mentioned HMPA is added in the deionized water of its weight 13-20 times, is stirred, rise high-temperature
For 54-60 DEG C, insulated and stirred 6-10 minute, above-mentioned nano aluminium oxide is added, ultrasonic 2-3 minutes, alumina fluid dispersion is obtained；
（3）Above-mentioned CNT alcohol dispersion liquid, alumina fluid dispersion are mixed, above-mentioned hexamethyl cyclotrisiloxane, ultrasound is added
10-13 minutes, filter, 1-2 hours will be vacuum dried at 50-60 DEG C will be deposited in, composite alumina is obtained；
（4）Above-mentioned composite alumina, silane coupler kh560 are mixed, the dehydrated alcohol of compound weight 4-6 times is added to
In, to send in 110-120 DEG C of oil bath, insulated and stirred 3-5 hour, discharging are filtered, and will be deposited in 120-130 DEG C of baking oven true
Sky is dried 1-2 hours, obtains silane oxidation aluminum；
（5）Above-mentioned lithium chloride is added in the methanol of its weight 900-1000 times, is stirred；
（6）Above-mentioned silane oxidation aluminum is added in the N-Methyl pyrrolidone of its weight 47-60 times, is stirred, successively plus
Enter above-mentioned 3,5- diaminobenzoic acids, pyridine, triphenyl phosphite, be passed through nitrogen, 3-4 hours are reacted at 98-100 DEG C, it is cold
But to room temperature, it is added in the methanol solution of above-mentioned lithium chloride, stands 3-4 hours, filter, by precipitation with respectively with N, N- diformazans
Base Methanamide and methanol are rinsed 3-4 time successively, are placed in 87-90 DEG C of baking oven, are vacuum dried 1-2 hours, are obtained grafting aluminium oxide；
（7）Above-mentioned acetylacetone,2,4-pentanedione neodymium, abienol are mixed, is added in above-mentioned epoxy resin 6101, stirred at 80-86 DEG C
30-40 minutes, above-mentioned myristic acid soda soap is added, is stirred, vacuum outgass are cooled to room temperature, obtain epoxy solution；
（8）Above-mentioned grafting aluminium oxide is taken, is added in the acetone of its weight 4-6 times, is stirred, add above-mentioned epoxy solution,
Ultrasonic 20-30 minutes, it is sent in 68-70 DEG C of constant temperature oil bath, is incubated 10-12 hours, adds above-mentioned methyl hexahydro neighbour benzene two
Formic anhydride, stirs, vacuum outgass 30-40 minutes, adds remaining each raw material, first preheats 100-120 point at 130-140 DEG C
Clock, it is 160-170 DEG C to rise high-temperature, solidifies 10-15 hours, is cooled to room temperature, obtains heat-conductive composite material.
It is an advantage of the invention that：Hyperbranched Aromatic Polyamides are grafted to nano alumina particles table using two-step method by the present invention
Face:Nano-particle carries out silane coupler first and processes grafting over-expense on introducing amino group, then nanoparticle after modification
Fluidized polymer；
Jing after coupling processing, granule is transformed into hydrophobicity by hydrophilic to aluminum oxide nanoparticle, so can significantly improve and epoxy
The compatibility of resin.During the silane coupled process of also aluminum oxide nanoparticle Jing, silane coupler one end and aluminium oxide nano
Granule is combined with chemical bond, and other end of amido functional group occurs chemical reaction with epoxy resin, enhances epoxy resin
The combination of matrix and nano-particle boundary, reduces interface void and defect, so as to be conducive to the raising of heat conductivity；
Secondly as the skin effect of nanoparticle, silane oxidation aluminum nanoparticles are with very big specific surface area, Er Qiejing
Nanoparticle after silane treatment preferably can be distributed in epoxy resin-base, at this moment silane oxidation aluminum nanoparticles and epoxy
The chemical bond that chemical reaction between resin is formed just serves more and more important effect.One nano-particle can be used as three
A heat conduction node in dimension network, increasing for this heat conduction node not only reduce further interface resistance, but also formed
The bridged bond of polymer network, therefore it is effectively improved the heat conductivity of epoxy resin/silane oxidation aluminium composite material；
Due to alumina nanoparticles good dispersion in the epoxy and the compatibility of grafted by super branched polymer;Its
The secondary alumina nanoparticles surface due to Hyperbranched Aromatic Polyamides grafting has more ammonia than silane oxidation aluminum nanoparticles
Base functional group, can form more chemical bonds, heat conductivity of this heat conduction node in composite between epoxy resin-base
In serve mastery reaction;It is rigid main chain due to Nomex that last point is, compared with epoxy resin, itself is excellent
Heat conductivility can play more preferable conduction of heat in the transmittance process of hot-fluid.
Present invention adds CNT etc. can effectively improve the heat conductivility of finished composite material.
Specific embodiment
A kind of CNT heat-conductive composite material, it is made up of the raw material of following weight parts：
Myristic acid soda soap 0.7,10,3,5 diaminobenzoic acid 1 of nano aluminium oxide, pyridine 0.3, triphenyl phosphite 2, chlorination
Lithium 0.1, silane coupler kh5600.6, acetylacetone,2,4-pentanedione neodymium 0.7, methylhexahydrophthalic anhydride 1.6, epoxy resin
610180th, polyvinylbenzenesulfonic acid 1, hexamethyl cyclotrisiloxane 0.4, abienol 3, HMPA 0.3, CNT 5,
2 mercapto benzimidazoles 0.3.
A kind of preparation method of described CNT heat-conductive composite material, comprises the following steps：
（1）Above-mentioned 2 mercapto benzimidazole is added in the dehydrated alcohol of 10 times of its weight, is stirred, rising high-temperature is
63 DEG C, above-mentioned CNT, ultrasound 4 minutes is added to obtain CNT alcohol dispersion liquid；
（2）Above-mentioned HMPA is added in the deionized water of 13 times of its weight, is stirred, it is 54 to rise high-temperature
DEG C, insulated and stirred 6 minutes adds above-mentioned nano aluminium oxide, ultrasound 2 minutes to obtain alumina fluid dispersion；
（3）Above-mentioned CNT alcohol dispersion liquid, alumina fluid dispersion are mixed, above-mentioned hexamethyl cyclotrisiloxane, ultrasound is added
10 minutes, filter, will be deposited at 50 DEG C and be vacuum dried 1 hour, and obtain composite alumina；
（4）Above-mentioned composite alumina, silane coupler kh560 are mixed, are added in the dehydrated alcohol of 4 times of compound weight,
Send in 110 DEG C of oil bath, insulated and stirred 3 hours, discharging are filtered, will be deposited in 120 DEG C of baking oven and be vacuum dried 1 hour,
Obtain silane oxidation aluminum；
（5）Above-mentioned lithium chloride is added in the methanol of 900 times of its weight, is stirred；
（6）Above-mentioned silane oxidation aluminum is added in the N methyl pyrrolidones of 47 times of its weight, is stirred, is sequentially added
3,5 diaminobenzoic acids, pyridine, triphenyl phosphite are stated, nitrogen is passed through, is reacted 3 hours at 98 DEG C, is cooled to room temperature, plus
Enter in the methanol solution of above-mentioned lithium chloride, stand 3 hours, filter, by precipitation with respectively with DMF and methanol
Rinse 3 times successively, be placed in 87 DEG C of baking oven, be vacuum dried 1 hour, obtain grafting aluminium oxide；
（7）Above-mentioned acetylacetone,2,4-pentanedione neodymium, abienol are mixed, is added in above-mentioned epoxy resin 6101,30 points are stirred at 80 DEG C
Clock, adds above-mentioned myristic acid soda soap, stirs, and vacuum outgass are cooled to room temperature, obtain epoxy solution；
（8）Above-mentioned grafting aluminium oxide is taken, is added in the acetone of 4 times of its weight, is stirred, add above-mentioned epoxy solution, surpassed
Sound 20 minutes, is sent in 68 DEG C of constant temperature oil bath, is incubated 10 hours, adds above-mentioned methylhexahydrophthalic anhydride, stirring
Uniformly, vacuum outgass 30 minutes, add remaining each raw material, first preheat 100 minutes at 130 DEG C, and it is 160 DEG C to rise high-temperature, Gu
Change 10 hours, be cooled to room temperature, obtain heat-conductive composite material.
The heat conductivity of material of the present invention is 0.325W/mK.
Claims (2)
1. a kind of CNT heat-conductive composite material, it is characterised in that it is made up of the raw material of following weight parts：
Myristic acid soda soap 0.7-1, nano aluminium oxide 10-13,3,5- diaminobenzoic acid 1-2, pyridine 0.3-0.7, phosphorous acid
Triphenylmethyl methacrylate 2-3, lithium chloride 0.1-0.2, silane coupler kh5600.6-1, acetylacetone,2,4-pentanedione neodymium 0.7-1, methyl hexahydro O-phthalic
Anhydride 1.6-2, epoxy resin 6101 80-90, polyvinylbenzenesulfonic acid 1-2, hexamethyl cyclotrisiloxane 0.4-1, abienol 3-5,
HMPA 0.3-1, CNT 5-6,2- mercapto benzimidazole 0.3-1.
2. a kind of preparation method of CNT heat-conductive composite material as claimed in claim 1, it is characterised in that including following
Step：
（1）Above-mentioned 2- mercaptos benzimidazole is added in the dehydrated alcohol of its weight 10-14 times, is stirred, rise high temperature
Spend for 63-70 DEG C, add above-mentioned CNT, ultrasonic 4-8 minutes, obtain CNT alcohol dispersion liquid；
（2）Above-mentioned HMPA is added in the deionized water of its weight 13-20 times, is stirred, rise high-temperature
For 54-60 DEG C, insulated and stirred 6-10 minute, above-mentioned nano aluminium oxide is added, ultrasonic 2-3 minutes, alumina fluid dispersion is obtained；
（3）Above-mentioned CNT alcohol dispersion liquid, alumina fluid dispersion are mixed, above-mentioned hexamethyl cyclotrisiloxane, ultrasound is added
10-13 minutes, filter, 1-2 hours will be vacuum dried at 50-60 DEG C will be deposited in, composite alumina is obtained；
（4）Above-mentioned composite alumina, silane coupler kh560 are mixed, the dehydrated alcohol of compound weight 4-6 times is added to
In, to send in 110-120 DEG C of oil bath, insulated and stirred 3-5 hour, discharging are filtered, and will be deposited in 120-130 DEG C of baking oven true
Sky is dried 1-2 hours, obtains silane oxidation aluminum；
（5）Above-mentioned lithium chloride is added in the methanol of its weight 900-1000 times, is stirred；
（6）Above-mentioned silane oxidation aluminum is added in the N-Methyl pyrrolidone of its weight 47-60 times, is stirred, successively plus
Enter above-mentioned 3,5- diaminobenzoic acids, pyridine, triphenyl phosphite, be passed through nitrogen, 3-4 hours are reacted at 98-100 DEG C, it is cold
But to room temperature, it is added in the methanol solution of above-mentioned lithium chloride, stands 3-4 hours, filter, by precipitation with respectively with N, N- diformazans
Base Methanamide and methanol are rinsed 3-4 time successively, are placed in 87-90 DEG C of baking oven, are vacuum dried 1-2 hours, are obtained grafting aluminium oxide；
（7）Above-mentioned acetylacetone,2,4-pentanedione neodymium, abienol are mixed, is added in above-mentioned epoxy resin 6101, stirred at 80-86 DEG C
30-40 minutes, above-mentioned myristic acid soda soap is added, is stirred, vacuum outgass are cooled to room temperature, obtain epoxy solution；
（8）Above-mentioned grafting aluminium oxide is taken, is added in the acetone of its weight 4-6 times, is stirred, add above-mentioned epoxy solution,
Ultrasonic 20-30 minutes, it is sent in 68-70 DEG C of constant temperature oil bath, is incubated 10-12 hours, adds above-mentioned methyl hexahydro neighbour benzene two
Formic anhydride, stirs, vacuum outgass 30-40 minutes, adds remaining each raw material, first preheats 100-120 point at 130-140 DEG C
Clock, it is 160-170 DEG C to rise high-temperature, solidifies 10-15 hours, is cooled to room temperature, obtains heat-conductive composite material.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103172973A (en) * | 2013-03-26 | 2013-06-26 | 上海交通大学 | High thermal-conductivity polymer composite material and preparation method thereof |
| CN103951985A (en) * | 2014-05-08 | 2014-07-30 | 南京新伟仑材料科技有限公司 | High-molecular heat-conducting composite material and preparation method thereof |
| CN104277420A (en) * | 2014-09-18 | 2015-01-14 | 华侨大学 | Polymeric composite material and preparation method thereof |
| CN105968763A (en) * | 2016-06-12 | 2016-09-28 | 安徽广燕新材料科技有限责任公司 | Preparation method of artificial stone material with good heat stability, high hardness and good toughness |
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2016
- 2016-10-21 CN CN201610917196.XA patent/CN106543645A/en not_active Withdrawn
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103172973A (en) * | 2013-03-26 | 2013-06-26 | 上海交通大学 | High thermal-conductivity polymer composite material and preparation method thereof |
| CN103951985A (en) * | 2014-05-08 | 2014-07-30 | 南京新伟仑材料科技有限公司 | High-molecular heat-conducting composite material and preparation method thereof |
| CN104277420A (en) * | 2014-09-18 | 2015-01-14 | 华侨大学 | Polymeric composite material and preparation method thereof |
| CN105968763A (en) * | 2016-06-12 | 2016-09-28 | 安徽广燕新材料科技有限责任公司 | Preparation method of artificial stone material with good heat stability, high hardness and good toughness |
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Application publication date: 20170329 |