CN110317582A - A kind of imide derivative functionalization graphene/carbon nanotube composite heat-conducting film and preparation method thereof - Google Patents
A kind of imide derivative functionalization graphene/carbon nanotube composite heat-conducting film and preparation method thereof Download PDFInfo
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Abstract
The present invention provides a kind of imide derivative functionalization graphene/carbon nanotube composite heat-conducting films and preparation method thereof.The film is to be put up a bridge to form longitudinal bridging enhancing network by the effect of π-π stacking and one-dimensional multi-walled carbon nanotube by height-oriented lamellar graphite alkene and imide derivative.Preparation method are as follows: (1) be (90~75) by mass ratio: (10~25): the graphene/carbon nano-tube/imide derivative of (0.1~0.3) mixes in deionized water, stirring, ultrasonic wave is uniformly dispersed, and filters film forming；(2) for the film for obtaining step (1) in 8~15MPa of mechanical pressure, the pressing time is to suppress under 5~10min, and the composite heat-conducting film can be obtained.Not only longitudinal thermal coefficient is greatly improved composite heat-conducting film of the invention; and mechanical property is also greatly improved; it is low to overcome existing graphene film longitudinal direction thermal coefficient; the characteristics of poor mechanical property; preparation process is simple simultaneously; it is easy to large-scale production, is with a wide range of applications.
Description
Technical field
The present invention relates to a kind of field of thin film material preparation, more particularly, to a kind of imide derivative function graphite
Alkene/carbon nanotube composite heat-conducting film and preparation method thereof.
Background technique
With the development of integrated technology and microelectronic packaging technology, the overall power density of electronic component constantly increases, and
The physical size of electronic component and electronic equipment is but gradually intended to small-sized, micromation, and generated heat is accumulated rapidly, led
The heat flow density around integrated device is caused also to increase, so, hot environment will influence whether electronic component and equipment
Performance, this just needs more efficient thermal control scheme.Therefore, the heat dissipation problem of electronic component has evolved into as Current electronic
One large focal spot of component and electronic equipment manufacturing.
Graphene is by a kind of tightly packed carbonaceous new material at bi-dimensional cellular shape lattice structure of single layer of carbon atom.Rely on
Its unique structure, so that its carrier mobility is 2 × 105cm2/ Vs, thermal conductivity are 5300W/mK and excellent mechanics
Performance, thus received significant attention by the application of the heat conduction and heat radiation film new material of graphene preparation in thermal management.Report at present
Pure graphene film lateral thermal coefficient with higher, generally 200~2000W/mK, but its longitudinal thermal coefficient is very
It is low, about 0.1~1.28W/mK, and also mechanical property is poor, and preparation process is complicated, its application is caused to be restricted.
Imide derivative is a kind of special condensed-nuclei aromatics class compound, has good chemical inertness, anticorrosive
Performance and photostability, and fluorescence quantum yield is high, is widely used in fluorescence probe, organic semiconductor, organic electroluminescent, divides
The fields such as sub- self assembly.Imide derivative has big phenyl ring conjugate planes structure, same as some other can have altogether
By noncovalent interaction power the effect of π-π stacking occurs for the molecule of yoke structure.
Carbon nanotube has the one-dimensional tracheary element structure of unique standard, has excellent thermally conductive, mechanics and electric conductivity, quilt
It is widely used in electronic device and nanocomposite.Existing patent report is by addition carbon fiber and carbon nanotube in stone at present
Mo Xipian interlayer lap-joint forms thermal conducting path, so that the heat transfer property of heat conducting film and tensile strength can improve.Such as middle promulgated by the State Council
Bright patent " graphene of bionical laminated construction-carbon quantum dot composite heat-conducting film and its preparation " (CN108128768A).But mesh
There are still preparation process complexity, the low problem low with tensile strength of longitudinal thermal coefficient for the graphene heat conducting film of preceding report.
Summary of the invention
A kind of imide derivative is provided the purpose of the invention is to overcome the problems of the above-mentioned prior art
Functionalization graphene/carbon nanotube composite heat-conducting film and preparation method thereof.
The purpose of the present invention can be achieved through the following technical solutions:
It is an object of the present invention to propose a kind of imide derivative functionalization graphene/carbon nanotube composite guide
Hot film does not carry out the effect of π-π stacking merely with imide derivative and graphene, improves graphene in THIN COMPOSITE membrane material
Dispersibility, mechanical property and heating conduction in material, and composite membrane is further connected by the carbon nanotube of addition functionalization
Bridging is connect, longitudinal bridging enhancing network is formd.The present invention can be achieved through the following technical solutions:
The second object of the present invention is to propose a kind of imide derivative functionalization graphene/carbon nanotube composite guide
The preparation method of hot film, comprising the following steps:
(1) be (90~75) by mass ratio: (10~25): the graphene/carbon nano-tube/acid imide of (0.1~0.3) spreads out
Biology mixes in deionized water, stirs, and ultrasonic wave is uniformly dispersed, and filters film forming；
(2) film for obtaining step (1) is 8~15MPa in mechanical pressure, and the pressing time is to suppress under 5~10min,
Imide derivative functionalization graphene/carbon nanotube thermally conductive film can be obtained.
As a preferred embodiment of the above technical solution, in step (1) imide derivative by acid anhydride and polyethylene polyamine two
Toluene is made under solvent, synthesizes to obtain by amidation process.
As a preferred embodiment of the above technical solution, raw material used in amidation process is polyethylene polyamine, second in step (1)
Diamines, two sub- ethylene triamines, the one or more combination of triethylene tetramine or tetraethylenepentamine.
As a preferred embodiment of the above technical solution, specific preparation process is as follows for imide derivative in step (1):
Acid anhydride is that 1:10 reacts with polyethylene polyamine in molar ratio, the solvent xylene of 40~60mL is added, in N2Protection
Under, in 80~100 DEG C of 6~12h of reaction.To after reaction, filter, filtrate is precipitated in 50~70mL methanol, then will filter
Cake is repeatedly washed with distilled water until filtrate is in neutrality, and is dried overnight in 60 DEG C of vacuum ovens, it is derivative to obtain acid imide
Object (APBI).
As a preferred embodiment of the above technical solution, carbon nanotube described in step (1) be functionalized multi-wall carbonnanotubes or
Person's silane coupledization carboxyl multi-walled carbon nanotube.
As a preferred embodiment of the above technical solution, carbon nanotube described in step (1) is functionalized multi-wall carbonnanotubes,
Preparation step is as follows: in the 250mL three-necked flask with reflux unit, being added 0.8g multi-walled carbon nanotube (MWCNTs), so
After be slowly added to 120mL concentrated nitric acid and the 40mL concentrated sulfuric acid, be stirred to react 12 at 50~70 DEG C~for 24 hours.It will mix after reaction
Liquid filtering is closed, is separated repeatedly with deionized water centrifuge washing to neutrality, functionalized multi-wall carbonnanotubes (c- can be obtained
MWCNTs)。
As a preferred embodiment of the above technical solution, carbon nanotube described in step (1) is silane coupled carboxylated multi wall
Carbon nanotube, preparation step are as follows: 2g KH550 being added dropwise in 200mL dehydrated alcohol, 1h is stirred, it is above-mentioned that 0.2g is added
Functionalized multi-wall carbonnanotubes into above-mentioned mixed liquor, then mixed liquor is heated to 70 DEG C by high-speed stirred 5min, stirring is anti-
Answer 3h.Mixed liquor is filtered after reaction, is washed repeatedly with deionized water to neutrality, filter cake is dried into 12h at 60 DEG C, i.e.,
Silane coupledization carboxyl multi-walled carbon nanotube (s-MWCNTs) can be obtained.
As a preferred embodiment of the above technical solution, imide derivative functionalization graphene/carbon nanometer described in step (2)
Pipe thermally conductive film is with a thickness of 20~30 μm.
Detailed description of the invention
Fig. 1 is imide derivative functionalization graphene/carboxylated multi wall that the specific embodiment of the invention 1 is prepared
Carbon nanotube composite heat conduction film.
Fig. 2 is imide derivative functionalization graphene/carboxylated multi wall that the specific embodiment of the invention 1 is prepared
The stereoscan photograph in carbon nanotube composite heat conduction film section.
Specific embodiment
Primary raw material used in example is as follows: acid anhydride (technical grade), graphene slurry (technical grade), polyethylene polyamine (work
Industry grade), multi-walled carbon nanotube (technical grade), dimethylbenzene (technical grade).It below will be to the technical solution in case study on implementation of the present invention
It is described in detail.
Embodiment 1
(1) 0.5g acid anhydride, 5.5g polyethylene polyamine are added in three-necked flask, 40mL dimethylbenzene is condensed back, in N2It protects
80 DEG C are warming up under shield, after reacting 10h, solution precipitates in 40mL methanol, then filter cake is repeatedly washed with distilled water until filter
Liquid is in neutrality, and is dried overnight at 60 DEG C in a vacuum drying oven, is obtained imide derivative (APBI).
(2) it in the 250mL three-necked flask with reflux unit, is added 0.8g multi-walled carbon nanotube (MWCNTs), then
It is slowly added to 120mL concentrated nitric acid and the 40mL concentrated sulfuric acid, is stirred to react 12h at 50 DEG C.To which mixed liquor is filtered after reaction,
It is separated repeatedly with deionized water centrifuge washing to neutrality, functionalized multi-wall carbonnanotubes (c-MWCNTs) can be obtained.
(3) take solid content be 0.05g graphene slurry 1.0g, be added 150mL deionized water ultrasound 30min, then plus
Enter the APBI of 0.5mg step (1) synthesis, after continuing ultrasonic disperse 1h, the c-MWCNTs in 0.5mg step (2) is added, continues to surpass
Dispersion liquid is finally filtered and is formed a film by sound 1h, after dry at 80 DEG C, uses mechanical pressure for 10MPa, pressing time 5min,
It obtains that imide derivative functionalization graphene/functionalized multi-wall carbonnanotubes composite heat-conducting can be obtained with a thickness of 20 μm
Film (APBI-GNS/c-MWCNTs).Measuring lateral thermal coefficient is 303.5W/mK, and longitudinal thermal coefficient is 1.79W/mK,
Tensile strength is 35MPa.
Embodiment 2
(1) 1.0g acid anhydride, 11g polyethylene polyamine are added in three-necked flask, 40mL dimethylbenzene is condensed back, in N2It protects
80 DEG C are warming up under shield, after reacting 12h, solution precipitates in 50mL methanol, then filter cake is repeatedly washed with distilled water until filter
Liquid is in neutrality, and is dried overnight at 60 DEG C in a vacuum drying oven, is obtained imide derivative (APBI).
(2) it in the 250mL three-necked flask with reflux unit, is added 0.8g multi-walled carbon nanotube (MWCNTs), then
It is slowly added to 120mL concentrated nitric acid and the 40mL concentrated sulfuric acid, is stirred to react 12h at 50 DEG C.To which mixed liquor is filtered after reaction,
It is separated repeatedly with deionized water centrifuge washing to neutrality, functionalized multi-wall carbonnanotubes (c-MWCNTs) can be obtained.
(3) take solid content be 0.05g graphene slurry 1.0g, be added 150mL deionized water ultrasound 30min, then plus
Enter the APBI of 1.0mg step (1) synthesis, after continuing ultrasonic disperse 1h, the c-MWCNTs in 0.5mg step (2) is added, continues to surpass
Dispersion liquid is finally filtered and is formed a film by sound 1h, after dry at 80 DEG C, uses mechanical pressure for 10MPa, pressing time 5min,
It obtains that imide derivative functionalization graphene/functionalized multi-wall carbonnanotubes composite heat-conducting can be obtained with a thickness of 20 μm
Film (APBI-GNS/c-MWCNTs).Measuring lateral thermal coefficient is 287.7W/mK, and longitudinal thermal coefficient is 2.36W/mK,
Tensile strength is 44MPa.
Embodiment 3
(1) 1.0g acid anhydride, 11g polyethylene polyamine are added in three-necked flask, 40mL dimethylbenzene is condensed back, in N2It protects
80 DEG C are warming up under shield, after reacting 12h, solution precipitates in 50mL methanol, then filter cake is repeatedly washed with distilled water until filter
Liquid is in neutrality, and is dried overnight at 60 DEG C in a vacuum drying oven, is obtained imide derivative (APBI).
(2) it in the 250mL three-necked flask with reflux unit, is added 0.8g multi-walled carbon nanotube (MWCNTs), then
It is slowly added to 120mL concentrated nitric acid and the 40mL concentrated sulfuric acid, it is stirred to react 12 at 50~70 DEG C~for 24 hours.To mix after reaction
Liquid filtering is closed, is separated repeatedly with deionized water centrifuge washing to neutrality, functionalized multi-wall carbonnanotubes (c- can be obtained
MWCNTs)。
(3) take solid content be 0.05g graphene slurry 1.0g, be added 150mL deionized water ultrasound 30min, then plus
Enter the APBI of 1.5mg step (1) synthesis, after continuing ultrasonic disperse 1.5h, the c-MWCNTs in 0.5mg step (2) is added, continues
Dispersion liquid is finally filtered and is formed a film by ultrasonic 1h, after dry at 80 DEG C, uses mechanical pressure for 12MPa, and the pressing time is
5min is made with a thickness of 24 μm, and it is multiple that imide derivative functionalization graphene/functionalized multi-wall carbonnanotubes can be obtained
It closes heat conducting film (APBI-GNS/c-MWCNTs).Measuring lateral thermal coefficient is 255.6W/mK, and longitudinal thermal coefficient is 3.4W/
MK, tensile strength 56MPa.
Embodiment 4
(1) 1.0g acid anhydride, 11g polyethylene polyamine are added in three-necked flask, 40mL dimethylbenzene is condensed back, in N2It protects
80 DEG C are warming up under shield, after reacting 12h, solution precipitates in 50mL methanol, then filter cake is repeatedly washed with distilled water until filter
Liquid is in neutrality, and dries at 60 DEG C obtain imide derivative (APBI) overnight in a vacuum drying oven.
(2) it in the 250mL three-necked flask with reflux unit, is added 0.8g multi-walled carbon nanotube (MWCNTs), then
It is slowly added to 120mL concentrated nitric acid and the 40mL concentrated sulfuric acid, is stirred to react 12h at 50~70 DEG C.To after reaction by mixed liquor
Filtering, is separated to neutrality with deionized water centrifuge washing repeatedly, functionalized multi-wall carbonnanotubes (c-MWCNTs) can be obtained.
(3) take solid content be 0.05g graphene slurry 1.0g, be added 150mL deionized water ultrasound 30min, then plus
Enter the APBI of 2.0mg step (1) synthesis, after continuing ultrasonic disperse 1.5h, the c-MWCNTs in 0.5mg step (2) is added, continues
Dispersion liquid is finally filtered and is formed a film by ultrasonic 1h, after dry at 80 DEG C, uses mechanical pressure for 12MPa, and the pressing time is
5min is made with a thickness of 26 μm, and it is multiple that imide derivative functionalization graphene/functionalized multi-wall carbonnanotubes can be obtained
It closes heat conducting film (APBI-GNS/c-MWCNTs).Measuring lateral thermal coefficient is 200.3W/mK, and longitudinal thermal coefficient is
4.35W/mK, tensile strength 46.8MPa.
Embodiment 5
(1) 1.0g acid anhydride, 11g polyethylene polyamine are added in three-necked flask, 40mL dimethylbenzene is condensed back, in N2It protects
80 DEG C are warming up under shield, after reacting 12h, solution precipitates in 50mL methanol, then filter cake is repeatedly washed with distilled water until filter
Liquid is in neutrality, and is dried overnight at 60 DEG C in a vacuum drying oven, is obtained imide derivative (APBI).
(2) it in the 250mL three-necked flask with reflux unit, is added 0.8g multi-walled carbon nanotube (MWCNTs), then
It is slowly added to 120mL concentrated nitric acid and the 40mL concentrated sulfuric acid, is stirred to react 12h at 50 DEG C.To which mixed liquor is filtered after reaction,
It is separated repeatedly with deionized water centrifuge washing to neutrality, functionalized multi-wall carbonnanotubes (c-MWCNTs) can be obtained.
(3) 2g KH550 is added dropwise in 200mL dehydrated alcohol, stirs 1h, carboxylic described in 0.2g step (2) is added
Into above-mentioned mixed liquor, then mixed liquor is heated to 70 DEG C, is stirred to react base multi-walled carbon nano-tube by high-speed stirred 5min
3h.It to after reaction filter mixed liquor, is washed repeatedly with deionized water to neutrality, filter cake is dried into 12h at 60 DEG C, i.e.,
Silane coupledization carboxyl multi-walled carbon nanotube (s-MWCNTs) can be obtained.
(4) take solid content be 0.05g graphene slurry 1.0g, be added 150mL deionized water ultrasound 30min, then plus
Enter the APBI of 0.5mg step (1) synthesis, after continuing ultrasonic disperse 1h, the s-MWCNTs in 0.5mg step (3) is added, continues to surpass
Dispersion liquid is finally filtered and is formed a film by sound 1h, after dry at 80 DEG C, uses mechanical pressure for 12MPa, pressing time 5min,
It is made with a thickness of 24 μm, imide derivative functionalization graphene/functionalized multi-wall carbonnanotubes composite guide can be obtained
Hotting mask (APBI-GNS/s-MWCNTs).Measuring lateral thermal coefficient is 330W/mK, and longitudinal thermal coefficient is 1.22W/mK,
Tensile strength is 32MPa.
Embodiment 6
(1) 1.0g acid anhydride, 11g polyethylene polyamine are added in three-necked flask, 40mL dimethylbenzene is condensed back, in N2It protects
80 DEG C are warming up under shield, after reacting 12h, solution precipitates in 50mL methanol, then filter cake is repeatedly washed with distilled water until filter
Liquid is in neutrality, and is dried overnight at 60 DEG C in a vacuum drying oven, is obtained imide derivative (APBI).
(2) it in the 250mL three-necked flask with reflux unit, is added 0.8g multi-walled carbon nanotube (MWCNTs), then
It is slowly added to 120mL concentrated nitric acid and the 40mL concentrated sulfuric acid, is stirred to react 12h at 60 DEG C.To which mixed liquor is filtered after reaction,
It is separated repeatedly with deionized water centrifuge washing to neutrality, functionalized multi-wall carbonnanotubes (c-MWCNTs) can be obtained.
(3) 2g KH550 is added dropwise in 200mL dehydrated alcohol, stirs 1h, carboxylic described in 0.2g step (2) is added
Into above-mentioned mixed liquor, then mixed liquor is heated to 70 DEG C, is stirred to react base multi-walled carbon nano-tube by high-speed stirred 5min
3h.It to after reaction filter mixed liquor, is washed repeatedly with deionized water to neutrality, filter cake is dried into 12h at 60 DEG C, i.e.,
Silane coupledization carboxyl multi-walled carbon nanotube (s-MWCNTs) can be obtained.
(4) take solid content be 0.05g graphene slurry 1.0g, be added 150mL deionized water ultrasound 30min, then plus
Enter the APBI of 1.0mg step (1) synthesis, after continuing ultrasonic disperse 1h, the s-MWCNTs in 0.5mg step (3) is added, continues to surpass
Dispersion liquid is finally filtered and is formed a film by sound 1h, after dry at 80 DEG C, uses mechanical pressure for 12MPa, pressing time 5min,
It is made with a thickness of 26 μm, imide derivative functionalization graphene/functionalized multi-wall carbonnanotubes composite guide can be obtained
Hotting mask (APBI-GNS/s-MWCNTs).Measuring lateral thermal coefficient is 309W/mK, and longitudinal thermal coefficient is 1.65W/mK,
Tensile strength is 46MPa.
Embodiment 7
(1) 1.0g acid anhydride, 11g polyethylene polyamine are added in three-necked flask, 40mL dimethylbenzene is condensed back, in N2It protects
80 DEG C are warming up under shield, after reacting 12h, solution precipitates in 50mL methanol, then filter cake is repeatedly washed with distilled water until filter
Liquid is in neutrality, and is dried overnight at 60 DEG C in a vacuum drying oven, is obtained imide derivative (APBI).
(2) it in the 250mL three-necked flask with reflux unit, is added 0.8g multi-walled carbon nanotube (MWCNTs), then
It is slowly added to 120mL concentrated nitric acid and the 40mL concentrated sulfuric acid, is stirred to react 12h at 60 DEG C.To which mixed liquor is filtered after reaction,
It is separated repeatedly with deionized water centrifuge washing to neutrality, functionalized multi-wall carbonnanotubes (c-MWCNTs) can be obtained.
(3) 2g KH550 is added dropwise in 200mL dehydrated alcohol, stirs 1h, carboxylic described in 0.2g step (2) is added
Into above-mentioned mixed liquor, then mixed liquor is heated to 70 DEG C, is stirred to react base multi-walled carbon nano-tube by high-speed stirred 5min
3h.Mixed liquor is filtered after reaction, is washed repeatedly with deionized water to neutrality, filter cake is dried into 12h at 60 DEG C
Obtain silane coupledization carboxyl multi-walled carbon nanotube (s-MWCNTs).
(4) take solid content be 0.05g graphene slurry 1.0g, be added 150mL deionized water ultrasound 30min, then plus
Enter the APBI of 1.0mg step (1) synthesis, after continuing ultrasonic disperse 1h, the s-MWCNTs in 0.5mg step (3) is added, continues to surpass
Dispersion liquid is finally filtered and is formed a film by sound 1h, after dry at 80 DEG C, uses mechanical pressure for 12MPa, pressing time 5min,
It is made with a thickness of 26 μm, imide derivative functionalization graphene/functionalized multi-wall carbonnanotubes composite guide can be obtained
Hotting mask (APBI-GNS/s-MWCNTs).Measuring lateral thermal coefficient is 309W/mK, and longitudinal thermal coefficient is 1.65W/mK,
Tensile strength is 46MPa.
Embodiment 8
(1) 1.0g acid anhydride, 11g polyethylene polyamine are added in three-necked flask, 40mL dimethylbenzene is condensed back, in N2It protects
80 DEG C are warming up under shield, after reacting 12h, solution precipitates in 50mL methanol, then filter cake is repeatedly washed with distilled water until filter
Liquid is in neutrality, and is dried overnight at 60 DEG C in a vacuum drying oven, is obtained imide derivative (APBI).
(2) it in the 250mL three-necked flask with reflux unit, is added 0.8g multi-walled carbon nanotube (MWCNTs), then
It is slowly added to 120mL concentrated nitric acid and the 40mL concentrated sulfuric acid, is stirred to react 12h at 60 DEG C.To which mixed liquor is filtered after reaction,
It is separated repeatedly with deionized water centrifuge washing to neutrality, functionalized multi-wall carbonnanotubes (c-MWCNTs) can be obtained.
(3) 2gKH550 is added dropwise in 200mL dehydrated alcohol, stirs 1h, carboxylic described in 0.2g step (2) is added
Into above-mentioned mixed liquor, then mixed liquor is heated to 70 DEG C, is stirred to react base multi-walled carbon nano-tube by high-speed stirred 5min
3h.Mixed liquor is filtered after reaction, is washed repeatedly with deionized water to neutrality, filter cake is dried into 12h at 60 DEG C
Obtain silane coupledization carboxyl multi-walled carbon nanotube (s-MWCNTs).
(4) take solid content be 0.05g graphene slurry 1.0g, be added 150mL deionized water ultrasound 30min, then plus
Enter the APBI of 1.5mg step (1) synthesis, after continuing ultrasonic disperse 1h, the s-MWCNTs in 0.5mg step (3) is added, continues to surpass
Dispersion liquid is finally filtered and is formed a film by sound 1h, after dry at 80 DEG C, uses mechanical pressure for 15MPa, pressing time 8min,
It obtains that imide derivative functionalization graphene/functionalized multi-wall carbonnanotubes composite heat-conducting can be obtained with a thickness of 24 μm
Film (APBI-GNS/s-MWCNTs).Measuring lateral thermal coefficient is 289W/mK, and longitudinal thermal coefficient is 2.3W/mK, is drawn
Stretching intensity is 58MPa.
Embodiment 9
(1) 1.0g acid anhydride, 11g polyethylene polyamine are added in three-necked flask, 40mL dimethylbenzene is condensed back, in N2It protects
80 DEG C are warming up under shield, after reacting 12h, solution precipitates in methyl alcohol, then filter cake is repeatedly washed with distilled water until filtrate is in
Neutrality dries overnight at 60 DEG C in a vacuum drying oven, obtains imide derivative (APBI).
(2) it in the 250mL three-necked flask with reflux unit, is added 0.8g multi-walled carbon nanotube (MWCNTs), then
It is slowly added to 120mL concentrated nitric acid and the 40mL concentrated sulfuric acid, is stirred to react 12h at 60 DEG C.To which mixed liquor is filtered after reaction,
It is separated repeatedly with deionized water centrifuge washing to neutrality, functionalized multi-wall carbonnanotubes (c-MWCNTs) can be obtained.
(3) 2g KH550 is added dropwise in 200mL dehydrated alcohol, stirs 1h, carboxylic described in 0.2g step (2) is added
Into above-mentioned mixed liquor, then mixed liquor is heated to 70 DEG C, is stirred to react base multi-walled carbon nano-tube by high-speed stirred 5min
3h.Mixed liquor is filtered after reaction, is washed repeatedly with deionized water to neutrality, filter cake is dried into 12h at 60 DEG C
Obtain silane coupledization carboxyl multi-walled carbon nanotube (s-MWCNTs).
(4) take solid content be 0.05g graphene slurry 1.0g, be added 150mL deionized water ultrasound 30min, then plus
Enter the APBI of 2.0mg step (1) synthesis, after continuing ultrasonic disperse 1.5h, the s-MWCNTs in 0.5mg step (3) is added, continues
Dispersion liquid is finally filtered and is formed a film by ultrasonic 1h, after dry at 80 DEG C, uses mechanical pressure for 15MPa, and the pressing time is
8min is made with a thickness of 26 μm, and it is multiple that imide derivative functionalization graphene/functionalized multi-wall carbonnanotubes can be obtained
It closes heat conducting film (APBI-GNS/s-MWCNTs).Measuring lateral thermal coefficient is 267W/mK, and longitudinal thermal coefficient is 3.2W/
MK, tensile strength 45MPa.
The above embodiments are a part of the invention, are not intended to restrict the invention, for those skilled in the art
For member, the present invention can have various change.It is all within principle and innovation of the invention, made any modification is equally replaced
It changes, improve, should all be included in the protection scope of the present invention.
Claims (8)
1. a kind of imide derivative functionalization graphene/carbon nanotube thermally conductive film, it is characterised in that the film is by height
The lamellar graphite alkene and imide derivative for spending orientation form the effect of π-π stacking and one-dimensional multi-walled carbon nanotube into one
Step connection bridging, which forms longitudinal bridging, enhances network.
2. imide derivative functionalization graphene/carbon nanotube thermally conductive film according to claim 1, feature exist
In the thermally conductive film with a thickness of 20~30 μm.
3. a kind of prepare imide derivative functionalization graphene/carbon nanotube thermally conductive film according to claim 1
Preparation method, it is characterised in that the following steps are included:
It (1) is (90~75): (10~25): the graphene/carbon nano-tube/imide derivative of (0.1~0.3) by mass ratio
It mixes, stirs in deionized water, ultrasonic wave is uniformly dispersed, and filters film forming；
(2) for the film for obtaining step (1) in 8~15MPa of mechanical pressure, the pressing time is to suppress under 5~10min, can be obtained
To imide derivative functionalization graphene/carbon nanotube thermally conductive film.
4. preparation method according to claim 3, it is characterised in that the imide derivative is by acid anhydride and more
Ethylene polyamine is prepared in the case where dimethylbenzene makees solvent by amidation process.
5. the preparation method according to claim 4, it is characterised in that raw material used in the amidation process is more second
Alkene polyamines, ethylenediamine, two sub- ethylene triamines, the one or more combination of triethylene tetramine or tetraethylenepentamine.
6. preparation method according to claim 3, it is characterised in that the carbon nanotube is carboxylated multi-wall carbon nano-tube
Pipe or silane coupledization carboxyl multi-walled carbon nanotube.
7. preparation method according to claim 6, it is characterised in that the preparation of the functionalized multi-wall carbonnanotubes walks
It is rapid as follows: in the 250mL three-necked flask with reflux unit, to be added 0.8g multi-walled carbon nanotube (MWCNTs), then slowly
120mL concentrated nitric acid and the 40mL concentrated sulfuric acid is added, it is stirred to react 12 at 50~70 DEG C~for 24 hours, to after reaction by mixed liquor
Filtering is washed with deionized centrifuge separation to neutrality repeatedly, functionalized multi-wall carbonnanotubes (c-MWCNTs) can be obtained.
8. preparation method according to claim 6, it is characterised in that the silane coupledization carboxyl multi-walled carbon nanotube
Preparation step it is as follows:
2g KH550 is added dropwise in 200mL dehydrated alcohol, 1h is stirred, carboxylated described in 0.2g claim 5 is added
Into above-mentioned mixed liquor, then mixed liquor is heated to 70 DEG C, is stirred to react 3h multi-walled carbon nanotube by high-speed stirred 5min, to
Mixed liquor is filtered after reaction, is washed repeatedly with deionized water to neutrality, filter cake is dried into 12h at 60 DEG C, can be obtained
To silane coupledization carboxyl multi-walled carbon nanotube (s-MWCNTs).
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