CN106496937A - A kind of fiber heat-conductive composite material and preparation method thereof - Google Patents
A kind of fiber heat-conductive composite material and preparation method thereof Download PDFInfo
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- CN106496937A CN106496937A CN201610917130.0A CN201610917130A CN106496937A CN 106496937 A CN106496937 A CN 106496937A CN 201610917130 A CN201610917130 A CN 201610917130A CN 106496937 A CN106496937 A CN 106496937A
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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 fiber heat-conductive composite material, it is made up of the raw material of following weight parts：Cellulose phosphate 34, casein 0.4 1, Sodium fluoroborate 23, vinyl carboxylate 12,10 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, cyanethyl cellulose 23, diacetone alcohol 23, N-[2-(2-methyl-4-oxopentyl) 0.4 1, nonyl phenol 0.1 0.2, graphite powder 23.Present invention adds cellulose phosphate, cyanethyl cellulose etc., effectively raise the toughness and stability of finished composite material, the combination property of finished product is improved.
Description
Technical field
The present invention relates to Heat Conduction Material technical field, more particularly to a kind of fiber heat-conductive composite material and preparation method thereof.
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,
The fast development that meet microelectric technique and encapsulation technology is difficult to.Therefore, about epoxy resin heat conductivility research
Become the focus that electronics is paid close attention to jointly with subjects such as materials；
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 surface modification must be carried out to nano alumina particles, with
Reduce surface energy, reduce the agglomeration power between nano-particle, improve its dispersibility and dispersion stabilization in the base, reduce 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.
Content of the invention
The object of the invention is exactly the defect in order to make up prior art, there is provided a kind of fiber heat-conductive composite material and its preparation
Method.
The present invention is achieved by the following technical solutions：
A kind of fiber heat-conductive composite material, it is made up of the raw material of following weight parts：
Cellulose phosphate 3-4, casein 0.4-1, Sodium fluoroborate 2-3, vinyl carboxylate 1-2, nano aluminium oxide 10-13,3,
5- diaminobenzoic acid 1-2, pyridine 0.3-0.7, triphenyl phosphite 2-3, 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, cyanoethyl
Cellulose 2-3, diacetone alcohol 2-3, N-[2-(2-methyl-4-oxopentyl) 0.4-1, nonyl phenol 0.1-0.2, graphite powder 2-3.
A kind of preparation method of described fiber heat-conductive composite material, comprises the following steps：
（1）Above-mentioned cyanethyl cellulose is added in the dimethylformamide of its weight 13-20 times, it is 65-70 DEG C to rise high-temperature,
Insulated and stirred 6-10 minute, above-mentioned nonyl phenol is added, is stirred to room temperature, is obtained amide dispersion liquid；
（2）Above-mentioned Sodium fluoroborate is added in the deionized water of its weight 14-20 times, is stirred, liter high-temperature is 70-75
DEG C, insulated and stirred 10-19 minute, above-mentioned N-[2-(2-methyl-4-oxopentyl) being added, is stirred to room temperature, the hydrochloric acid of Deca 3-4mol/l is molten
Liquid, regulation pH are 2-3, add above-mentioned graphite powder, ultrasonic 4-7 minutes, mix with above-mentioned amide dispersion liquid, stir, and filter,
By precipitation washing 2-3 time, 1-2 hours are vacuum dried at 50-60 DEG C, obtain fibre modification graphite powder；
（3）By above-mentioned fibre modification graphite powder, nano aluminium oxide, silane coupler kh560 mixing, compound weight 4- is added to
In 6 times of dehydrated alcohol, send in 110-120 DEG C of oil bath, insulated and stirred 3-5 hour, discharging are filtered, and will be deposited in 120-
1-2 hours are vacuum dried in 130 DEG C of baking oven, silane oxidation aluminum is obtained；
（4）Above-mentioned lithium chloride is added in the methanol of its weight 900-1000 times, is stirred；
（5）Above-mentioned silane oxidation aluminum is added in the N-Methyl pyrrolidone of its weight 47-60 times, is stirred, successively plus
Entering above-mentioned 3,5- diaminobenzoic acids, pyridine, triphenyl phosphite, being passed through nitrogen, 3-4 hours are reacted at 98-100 DEG C, cold
But to room temperature, it is added in the methanol solution of above-mentioned lithium chloride, stands 3-4 hours, add above-mentioned cellulose phosphate, stirring is
Even, filter, by precipitation with being rinsed 3-4 time with DMF and methanol successively respectively, be placed in 87-90 DEG C of baking oven
In, 1-2 hours are vacuum dried, grafting aluminium oxide is obtained；
（6）Above-mentioned acetylacetone,2,4-pentanedione neodymium is added in epoxy resin 6101, is stirred 30-40 minutes at 80-86 DEG C, vacuum takes off
Gas, is cooled to room temperature, obtains epoxy solution；
（7）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；
After aluminum oxide nanoparticle is through coupling processing, granule is transformed into hydrophobicity by hydrophilic, so can significantly improve and epoxy
The compatibility of resin.Also aluminum oxide nanoparticle through during silane coupled process, 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
Matrix and the combination of nano-particle boundary, reduce 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, is therefore effectively improved the heat conductivity of epoxy resin/silane oxidation aluminium composite material；
Alumina nanoparticles good dispersion in the epoxy and the compatibility due to 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, itself is excellent compared with epoxy resin
Heat conductivility can play more preferable conduction of heat in the transmittance process of hot-fluid.
Present invention adds cellulose phosphate, cyanethyl cellulose etc., effectively raise the toughness of finished composite material
And stability, improve the combination property of finished product.
Specific embodiment
A kind of fiber heat-conductive composite material, it is made up of the raw material of following weight parts：
Cellulose phosphate 3, casein 0.4, Sodium fluoroborate 2, vinyl carboxylate 1,10,3,5 diaminobenzene first of nano aluminium oxide
Acid 1, pyridine 0.3, triphenyl phosphite 2, lithium chloride 0.1, silane coupler kh5600.6, acetylacetone,2,4-pentanedione neodymium 0.7, methyl hexahydro
Phthalic anhydride 1.6, epoxy resin 6101 80, cyanethyl cellulose 2, diacetone alcohol 2, N-[2-(2-methyl-4-oxopentyl) 0.4, nonyl
Phenol 0.1, graphite powder 2.
A kind of preparation method of described fiber heat-conductive composite material, comprises the following steps：
（1）Above-mentioned cyanethyl cellulose is added in the dimethylformamide of 13 times of its weight, it is 65 DEG C to rise high-temperature, and insulation is stirred
Mix 6 minutes, add above-mentioned nonyl phenol, stir to room temperature, obtain amide dispersion liquid；
（2）Above-mentioned Sodium fluoroborate is added in the deionized water of 14 times of its weight, is stirred, it is 70 DEG C to rise high-temperature, protects
Temperature stirring 10 minutes, adds above-mentioned N-[2-(2-methyl-4-oxopentyl), stirs to room temperature, the hydrochloric acid solution of Deca 3mol/l, adjusts pH and is
2, add above-mentioned graphite powder, ultrasound 4 minutes to mix with above-mentioned amide dispersion liquid, stir, filter, by precipitation washing 2 times,
It is vacuum dried 1 hour at 50 DEG C, obtains fibre modification graphite powder；
（3）By above-mentioned fibre modification graphite powder, nano aluminium oxide, silane coupler kh560 mixing, compound weight 4 is added to
In dehydrated alcohol again, send in 110 DEG C of oil bath, insulated and stirred 3 hours, discharging are filtered, and will be deposited in 120 DEG C of baking oven
Vacuum drying 1 hour, obtains silane oxidation aluminum；
（4）Above-mentioned lithium chloride is added in the methanol of 900 times of its weight, is stirred；
（5）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 is 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, add above-mentioned cellulose phosphate, stir, filter, will precipitation
With being rinsed successively 3 times with DMF and methanol respectively, it is placed in 87 DEG C of baking oven, is vacuum dried 1 hour, must connect
Branch aluminium oxide；
（6）Above-mentioned acetylacetone,2,4-pentanedione neodymium is added in epoxy resin 6101, is stirred 30 minutes at 80 DEG C, vacuum outgass, cooling
To room temperature, epoxy solution is obtained；
（7）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 0.336W/mK.
Claims (2)
1. a kind of fiber heat-conductive composite material, it is characterised in that it is made up of the raw material of following weight parts：
Cellulose phosphate 3-4, casein 0.4-1, Sodium fluoroborate 2-3, vinyl carboxylate 1-2, nano aluminium oxide 10-13,3,
5- diaminobenzoic acid 1-2, pyridine 0.3-0.7, triphenyl phosphite 2-3, 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, cyanoethyl
Cellulose 2-3, diacetone alcohol 2-3, N-[2-(2-methyl-4-oxopentyl) 0.4-1, nonyl phenol 0.1-0.2, graphite powder 2-3.
2. a kind of preparation method of fiber heat-conductive composite material as claimed in claim 1, it is characterised in that including following step
Suddenly：
（1）Above-mentioned cyanethyl cellulose is added in the dimethylformamide of its weight 13-20 times, it is 65-70 DEG C to rise high-temperature,
Insulated and stirred 6-10 minute, above-mentioned nonyl phenol is added, is stirred to room temperature, is obtained amide dispersion liquid；
（2）Above-mentioned Sodium fluoroborate is added in the deionized water of its weight 14-20 times, is stirred, liter high-temperature is 70-75
DEG C, insulated and stirred 10-19 minute, above-mentioned N-[2-(2-methyl-4-oxopentyl) being added, is stirred to room temperature, the hydrochloric acid of Deca 3-4mol/l is molten
Liquid, regulation pH are 2-3, add above-mentioned graphite powder, ultrasonic 4-7 minutes, mix with above-mentioned amide dispersion liquid, stir, and filter,
By precipitation washing 2-3 time, 1-2 hours are vacuum dried at 50-60 DEG C, obtain fibre modification graphite powder；
（3）By above-mentioned fibre modification graphite powder, nano aluminium oxide, silane coupler kh560 mixing, compound weight 4- is added to
In 6 times of dehydrated alcohol, send in 110-120 DEG C of oil bath, insulated and stirred 3-5 hour, discharging are filtered, and will be deposited in 120-
1-2 hours are vacuum dried in 130 DEG C of baking oven, silane oxidation aluminum is obtained；
（4）Above-mentioned lithium chloride is added in the methanol of its weight 900-1000 times, is stirred；
（5）Above-mentioned silane oxidation aluminum is added in the N-Methyl pyrrolidone of its weight 47-60 times, is stirred, successively plus
Entering above-mentioned 3,5- diaminobenzoic acids, pyridine, triphenyl phosphite, being passed through nitrogen, 3-4 hours are reacted at 98-100 DEG C, cold
But to room temperature, it is added in the methanol solution of above-mentioned lithium chloride, stands 3-4 hours, add above-mentioned cellulose phosphate, stirring is
Even, filter, by precipitation with being rinsed 3-4 time with DMF and methanol successively respectively, be placed in 87-90 DEG C of baking oven
In, 1-2 hours are vacuum dried, grafting aluminium oxide is obtained；
（6）Above-mentioned acetylacetone,2,4-pentanedione neodymium is added in epoxy resin 6101, is stirred 30-40 minutes at 80-86 DEG C, vacuum takes off
Gas, is cooled to room temperature, obtains epoxy solution；
（7）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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| CN201610917130.0A CN106496937A (en) | 2016-10-21 | 2016-10-21 | A kind of fiber heat-conductive composite material and preparation method thereof |
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| CN201610917130.0A CN106496937A (en) | 2016-10-21 | 2016-10-21 | A kind of fiber heat-conductive composite material and preparation method thereof |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105694032A (en) * | 2016-03-18 | 2016-06-22 | 赵守彬 | Fiber-modified magnetic composite material and preparation method thereof |
| CN105754297A (en) * | 2016-05-06 | 2016-07-13 | 陈昌 | Heat-conducting electronic packaging composite and preparation method thereof |
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- 2016-10-21 CN CN201610917130.0A patent/CN106496937A/en not_active Withdrawn
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105694032A (en) * | 2016-03-18 | 2016-06-22 | 赵守彬 | Fiber-modified magnetic composite material and preparation method thereof |
| CN105754297A (en) * | 2016-05-06 | 2016-07-13 | 陈昌 | Heat-conducting electronic packaging composite and preparation method thereof |
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Application publication date: 20170315 |