CN106366658A - Polyimide graphene nanobelt composite material and preparation method thereof - Google Patents
Polyimide graphene nanobelt composite material and preparation method thereof Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
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- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
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- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
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Abstract
The invention relates to a polyimide graphene nanobelt composite material and a preparation method thereof. The method comprises the following steps that (1) a carbon nanotube is subjected to pyrolysis by a hydrothermal method; an obtained product is dried to obtain a graphene nanobelt; (2) the graphene nanobelt obtained in the first step is added into a mixed solution used for preparing a soluble polyimide film; soluble polyimide is obtained through preparation; meanwhile, the obtained polyimide and the graphene nanobelt are mixed and stirred for reaction; further, the polyimide/graphene nanobelt composite material is formed. The method belongs to a simple, convenient and efficient mixing stirring synthesis method; the graphene nanobelt in the prepared composite material can be uniformly dispersed on the polyimide film, so that the electrical property, the mechanical property, the thermal property and the like can be improved.
Description
Technical field
The present invention relates to polymer based nanocomposites, particularly a kind of polyimides graphene nano belt composite
And preparation method thereof.
Background technology
Polyimides (pi) as a kind of special engineered material, because it has fabulous thermostability, corrosion resistance, mechanics
Property and the advantage such as molding shrinkage is little, it has also become the advanced aircraft such as cruise missile of new generation, high orbit satellite is essential
Mechanism's material.It is also the functional material of objective demand on satellite, manned spaceship and deep space probe simultaneously.But due to polyamides
The imines strand rigidity of itself, and intermolecular strong interaction, common polyimides are neither molten in decomposition temperature
Melt, also do not dissolve, this just makes them be difficult to molding, badly influences its using value.Therefore to existing polyimides
It is modified synthesizing new nano composite material, and keep or even improve its excellent performance.
Graphene has mechanical strength, thermal conductivity and the conductivity of superelevation.And when Graphene width be less than 10nm when
Wait and be commonly referred to as graphene nanobelt, and graphene nanobelt, in addition to inheriting some good natures of Graphene, also has
There is the property of uniqueness.Graphene has the big π key of conjugation and complete structure, so generally its reactivity is not high.And stone
The edge of black alkene nano belt generally has some undersaturated dangling bonds, in addition modified by some oxy radicals it is easy to
Other atoms or radical reaction, improve its activity in chemical reaction.
Based on this, the preparation meaning of polyimides/graphene nano belt composite is: solves the flight of longtime running
The problems such as communication disruption that on device, Kapton surface heat ageing, electric charge accumulation effect and its electrostatic breakdown lead to.Graphite
Alkene nano belt and its derivant (as stannic oxide/graphene nano band and functional modification Graphene) have excellent light, electricity, mechanics
Etc. performance, thus there is and polymer between very strong complementarity.Polyimides/graphene nano belt composite energy storage,
The fields such as capacitor, fuel cell, solar energy and electronic display unit have also obtained very high concern.
Generally first prepare polyamic acid, then polyimides can be obtained by hot imidization or chemical imidization.Hot imines
Change is to carry out under high temperature more than 300 DEG C, and in the course of reaction of its dehydration imidization, polyimides are easy to strand
Between chemical crosslinking, the polyimides therefore prepared can not be dissolved.Chemical imidization have carry out at normal temperatures, be not accompanied by hand over
The advantage of the side reaction such as connection and degraded.
Content of the invention
Present invention is primarily targeted at overcoming the deficiencies in the prior art, provide a kind of polyimides graphene nanobelt multiple
Condensation material and preparation method thereof, in synthetic composite material in a straightforward manner, and the composite being obtained, graphene nanobelt can
To be uniformly dispersed on Kapton, improve the performances such as its electricity, mechanics and calorifics.
For achieving the above object, the present invention employs the following technical solutions:
A kind of polyimides graphene nanobelt composite material and preparation method thereof, comprises the steps:
(1) CNT is cracked by hydro-thermal method, the product of gained is dried, obtains graphene nanobelt；
(2) graphene nanobelt obtaining step (1) is added to the mixed solution preparing soluble polyimide thin film
In, prepare soluble polyimide, the polyimides obtaining reacted with graphene nanobelt mix and blend simultaneously,
And then form polyimides/graphene nano belt composite.
Further:
The described mixed solution preparing soluble polyimide thin film contains in polyamic acid and poly amic acid ester at least
A kind of.
By dibasic acid anhydride and diamine, polycondensation forms described polyamic acid in organic solvent.
Described dibasic acid anhydride includes 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydride, 2,3,3 ', 4 '-oxydiphthalic, 3,
3 ', 4,4- oxydiphthalic, 3,3 ', 4,4 '-triphen diether tetracarboxylic dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride,
One or more of pyromellitic acid dianhydride or double (3,4- dicarboxyphenyi) the hexafluoro propanoic acid dianhydride of 2,2- mixture.
Described diamine include m-diaminobenzene., p-phenylenediamine, 3,3 '-diaminodiphenyl ether, 3,4 '-diaminodiphenyl ether,
4,4 '-diaminodiphenyl ether (oda), 2,3 diamino toluene, 3,3 '-diamidogen diphenyl sulphone (DPS), 3,4 '-diaminodiphenyl ether, 4,4 '-
Diamidogen diphenyl sulphone (DPS) or diaminourea benzoyl are for the mixture of one or more of aniline.
Described organic solvent includes n- methyl pyrrolidone, n, n- dimethyl acetylamide (dmac), n, n- dimethyl formyl
Amine (dmf), one of sulfolane, dimethyl sulfoxide, diethylene glycol dimethyl ether.
The described mixed solution preparing soluble polyimide thin film also contains phosphamide compound and catalyst.
Described phosphamide compound is 2,3- dihydro-sulfur -3- phenylpropyl alcohol oxazolyl phosphate ester (dbop)；Described catalyst is
Tertiary amine compound, preferably triethylamine.
The mol ratio of polyamic acid, phosphamide compound, catalyst and graphene nanobelt is 1:3:3:1～1:4:3:1,
And solvent quality fraction is 85%, stirring reaction temperature is 10 DEG C～50 DEG C, the time is 12-48 hour.
A kind of polyimides graphene nano belt composite, is the polyimides stone being obtained by described manufacture method
Black alkene nanometer belt composite.
The beneficial effect that prior art of the present invention is compared:
The present invention, using the method that is combined graphene nanobelt with the polyimides of solubility, is one kind not only simplicity but also have
Effect mix and blend synthetic method, in prepared composite, graphene nanobelt can be uniformly dispersed on Kapton,
The performances such as its electricity, mechanics and calorifics are made all to be improved.The present invention stirs mixed for the graphene nanobelt preparing
Mix and reacted, the Kapton composite of more high thermal stability can be obtained, and improve the effective of its processing characteristics
Approach.The present invention does not need when preparing Graphene to use a large amount of stimulation sex pill such as concentrated sulphuric acids, nitric acid etc., the graphite of the present invention
Alkene is nano belt preparation technology clean and be readily obtained.The invention has the advantages that the synthetic method of composite is simply effective, that is,
The graphene nanobelt preparing is put in initial mixed solution, with the formation of water-soluble poly imide solution, stone
Black alkene nano belt then can successfully load on polyimides, forms answering of required soluble polyimide/graphene nanobelt
Condensation material.
The present invention prepares graphene nanobelt using multi-walled carbon nano-tubes as initiation material, with CNT for raw material system
Standby graphene nanobelt is easily obtained that size range is narrow, edge-smoothing high-quality graphene nano belt, and can be by control
Make the size initiateing CNT and the number of plies to control size and the number of plies of graphene nanobelt, this preparation method is simple is easy
OK.
In preferred technical scheme, the condition first passing through optimum prepares the graphene nanobelt of high-quality height ratio,
Such that it is able to make up some shortcomings of Graphene, and nano belt is made to have certain band gap width.The electric conductivity of Graphene is
Unordered, it is a perfect conductor, electronics arbitrarily can move freely on its surface.And graphene nanobelt is had due to its width
Certain confinement, can force electronics to pass through to vertically move, control the movement of electronics by the width of graphene nanobelt
Direction.
Because semi-conductor nano particles are because particle diameter is little, surface energy is high, easily reunite, thus limiting its being used alone property.This
Bright it is combined with polymer phase, polymer can play carrier function, not only can prevent from reuniting, and can control particle
Size and distribution and improve stability it is often more important that, the property of nanoparticle is put to apply with material forms,
It is combined and assembling with body phase material phase, make polymer have good processing characteristics and optical transparence so as in compound and group
Dress semi-conductor nano particles aspect is advantageous compared with other materials.Using the photoelectric characteristic of semi-conductor nano particles, can be by complex
It is prepared into practical novel non-linearity optical material, electroluminescent material, laser amplifier material etc., significantly widen it and apply model
Enclose.
When forming composite with polyimides, its composite can be controlled by controlling graphene nano to bring
Electronics moving direction is so as to have certain characteristic of semiconductor.Prepare soluble polyimide by chemical imidization, choose
Some optimum ratios are debugged, and select preferred plan proportioning, using easy mix and blend method, the polyamides of solubility is sub-
Amine is combined with graphene nanobelt, forms the composite with certain potentiality.And the present invention is compared with the prior art, have
The effect of benefit is to make polyimides have good dissolubility first, and processability increases considerably.Reducing strand
Bulk density while, also increase intermolecular distance, be conducive to infiltration and the dissolving of small molecule solvent, be more beneficial for nanometer multiple
The absorption of condensation material and further deep processing.Bi-material simple synthetic method is it is easy to operate, and can obtain high-quality simultaneously
The composite of amount.Therefore there is important using value in high-tech areas such as modern microelectronic, photoelectrons.
Specific embodiment
Hereinafter embodiments of the present invention are elaborated.It is emphasized that what the description below was merely exemplary,
Rather than in order to limit the scope of the present invention and its application.
A kind of preparation method of polyimides graphene nano belt composite, comprises the following steps:
(1) preparation of graphene nanobelt: put in ptfe autoclave for raw material using CNT, add and steam
Distilled water.Reactor is put in baking oven constant temperature 15h at a certain temperature, using hydro-thermal method, makes CNT in vapor
Open along longitudinally cracking under etching, the product obtaining is dried, you can obtain the graphene nanobelt of required even width.
(2) preparation of polyimides/graphene nano belt composite: the graphene nanobelt preparing is added to system
In the mixed solution of standby polyimides, carry out mix and blend reaction, and then it is multiple to form required polyimides/graphene nanobelt
Condensation material.Wherein polyimides are prepared by chemical imidization method.Preferably pass through following component synthesis of soluble in preparation process
Property polyimides: at least one in polyamic acid and poly amic acid ester；Phosphamide compound；Catalyst.
In a preferred embodiment, the CNT in step (1) is high-purity multilamellar (3-5 layer) CNT；Obtain
The width of graphene nanobelt is less than 10nm.
In a preferred embodiment, described polyamic acid by dibasic acid anhydride and diamine in organic solvent polycondensation and
Become.
In a preferred embodiment, described phosphamide compound is 2,3- dihydro-sulfur -3- phenylpropyl alcohol oxazolyl phosphate ester
(dbop)；Described catalyst is tertiary amine compound, most preferably triethylamine.
In a preferred embodiment, described dibasic acid anhydride is 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydride, 2,3,3 ', 4 '-two
Phenylate tetracarboxylic dianhydride, 3,3 ', 4,4- oxydiphthalic, 3,3 ', 4,4 '-triphen diether tetracarboxylic dianhydride, 3,3 ', 4,4 '-two
One of double (3,4- dicarboxyphenyi) hexafluoro propanoic acid dianhydride of benzophenone tetracarboxylic dianhydride, pyromellitic acid dianhydride or 2,2- or several
The mixture planted.
In a preferred embodiment, described diamine be m-diaminobenzene., p-phenylenediamine, 3,3 '-diaminodiphenyl ether, 3,
4 '-diaminodiphenyl ether, 4,4 '-diaminodiphenyl ether (oda), 2,3 diamino toluene, 3,3 '-diamidogen diphenyl sulphone (DPS), 3,4 '-two
Amino-diphenylethers, 4,4 '-diamidogen diphenyl sulphone (DPS) or diaminourea benzoyl are for one or more of aniline mixture.
In a preferred embodiment, described organic solvent is n- methyl pyrrolidone, n, n- dimethyl acetylamide
(dmac), n, n- dimethylformamide (dmf), one of sulfolane, dimethyl sulfoxide, diethylene glycol dimethyl ether.
In a preferred embodiment, polyimide solution component (polyamic acid, phosphinylidyne amination in described mix and blend reaction
Compound, catalyst) it is 1:3:3:1 with the mol ratio of graphene nanobelt；Stirring reaction temperature is 10 DEG C -50 DEG C, time 12-48
Hour.Solvent quality fraction is 85%.Preferably, phosphamide compound and the mol ratio of catalyst are 1:1-4:3, the temperature of reaction
Spend for 20 DEG C～30 DEG C, period will add Polyvinylpyrrolidone surfactant (pvp) in mixed liquor, carries out mix and blend one
The section time, graphene nanobelt is made to be uniformly dispersed in the polyimides of solubility.
In various embodiments of the invention, there is provided one kind is simply mixed stirring and prepares soluble polyimide/Graphene
The preparation method of the composite of nano belt, and prepare soluble polyimide with reference to chemical imidization method, in conjunction with cleaning hydro-thermal
Method prepares graphene nanobelt.The most prominent is with easy mix and blend method synthetic composite material.Soluble polyimide is then
Prepared by chemical imidization.Raw material can use high-purity multilayer carbon nanotube (3-5 layer), polyamic acid, phosphinylidyne amine compounds
Thing, catalyst.Collocation method using being added to the conjunction carrying out polyamic acid in reaction solution by the graphene nanobelt preparing
Become, and then the thin composite of soluble polyimide/graphene nanobelt is prepared by mix and blend.The heat of gained thin film is steady
Qualitative, mechanical property and electric conductivity obtain enhanced effect, obtain thering is electric conductivity, the new type polyimide composite wood of the transparency
Material.
Embodiment 1
In order to prepare preferable graphene nanobelt, raw material multi-walled carbon nano-tubes is selected, selected layer as far as possible
The raw material of number less (3-5 layer), so during reaction, to being easier to, that is, cracking degree compares vapor etching phase
Thoroughly, high-quality graphene nanobelt can be obtained.
Select the optimal condition preparing graphene nanobelt by some different experiment proportionings, different by changing
Reaction temperature, starting material quality, the volume of the distilled water of addition, and response time in an oven, determine optimum
Proportioning, can obtain high-quality, the graphene nanobelt of high yield.Take the multi-walled carbon nano-tubes of 20mg, add the steaming of 0.4ml
Distilled water, puts into 200 DEG C of holding 20h of baking oven, you can obtain required product.
The synthesis step optimizing is as follows: the there-necked flask being dried in the 250ml being furnished with nitrogen inlet and mechanical stirring device
Middle addition 2g 3,3 ' 4.4 '-oxydiphthalic (odpa), 2g 4,4 '-diaminodiphenyl ether (oda), 33ml n- methyl
Ketopyrrolidine (nmp), adds the graphene nanobelt that 77mg has prepared in mixed solution simultaneously.Under nitrogen protection, room
Warming middle-JIAO, by solution stirring 18h, is subsequently added 10mlnmp, 2g triethylamine, is slowly added to 8.1g dbop, continues to make solution at 20 DEG C
Lower stirring 20 hours, with 40ml nmp dilution, subsequently precipitates in 1000ml methanol.The polymer filtration of the composite generating
Cleaned with methanol 3 times afterwards, vacuum drying under the conditions of 50 DEG C obtains required product soluble polyimide/Graphene for 20 hours and receives
Rice belt composite.Obtain high-quality soluble polyimide/graphene nanobelt with this kind of simple and convenient mixing synthetic method multiple
Condensation material.
Embodiment 2
Reaction temperature in the preparation of graphene nanobelt and example 1, starting material quality, the volume of the distilled water of addition, with
And the response time in an oven is consistent, the product obtaining is also consistent with the product in example 1.
Double (the 3,4- dicarboxyl of 4g 2,2- is added in being furnished with the 250ml there-necked flask of nitrogen inlet and mechanical stirring device
Phenyl) hexafluoro propanoic acid dianhydride (6fda), 1.8g 4,4 '-diaminodiphenyl ether (oda), 50ml nmp, and same in mixed solution
When add the graphene nanobelt that prepared of 108mg.It is passed through nitrogen, by solution stirring 20 hours at 25 DEG C, be subsequently added
2.37g triethylamine, is slow added into 11.38g dbop, and solution stirs 24h at 25 DEG C, is diluted with 40ml nmp, subsequently again
Precipitate in 1000ml methanol.Cleaned 3 times with methanol after the polymer filtration generating, be dried under the conditions of 50 DEG C in vacuum drying oven
Obtain within 20 hours final soluble polyimide/graphene nanobelt product.Meanwhile, with this kind of simple and convenient mixing synthetic method
High-quality soluble polyimide/graphene nano belt composite can be obtained.
Graphene nanobelt/soluble polyimide the composite of various embodiments of the present invention preparation, its graphene nano
Band transverse width is less than 10nm, has certain confinement, will electronics along free to move longitudinally, this also makes insulator polyamides
Imines becomes the composite having similar to semiconductor property, and this has larger meaning to the application expanding polyimides
Justice.The mechanical property of polyimides/graphene nanobelt composite membrane has also obtained great lifting simultaneously, through analysis, composite wood
The maximum Young's moduluss of material and tensile strength are respectively 16.5gpa and 138mpa, increased respectively than simple polyimides
610% and 74%.Simultaneously as being doped with graphene nanobelt, its composite is provided with certain electric conductivity.And in polyamides
In imines/graphene nano belt composite, the content of graphene nanobelt is higher, and the thermal conductivity of composite is higher.Can
Dissolubility polyimides/graphene nano belt composite can improve device and circuit as novel semi-conductor type composite
Speed, is widely used in optic communication, mobile communication, microwave communication field, is simultaneously applicable to the high temperature hostile ring such as Aero-Space
In border.So, present invention uses the method for simplicity makes graphene nanobelt and polyimides form composite, apply more
Among many prospects.
Above content is to further describe it is impossible to recognize with reference to concrete/preferred embodiment made for the present invention
Determine the present invention be embodied as be confined to these explanations.For general technical staff of the technical field of the invention,
Without departing from the inventive concept of the premise, it can also make some replacements or modification to the embodiment that these have described that,
And these substitute or variant all should be considered as belonging to protection scope of the present invention.
Claims (10)
1. a kind of polyimides graphene nanobelt composite material and preparation method thereof it is characterised in that: comprise the steps:
(1) CNT is cracked by hydro-thermal method, the product of gained is dried, obtains graphene nanobelt；
(2) graphene nanobelt obtaining step (1) is added in the mixed solution preparing soluble polyimide thin film, system
For obtaining soluble polyimide, the polyimides obtaining are reacted with graphene nanobelt mix and blend simultaneously, and then
Form polyimides/graphene nano belt composite.
2. preparation method according to claim 1 it is characterised in that: the described mixing preparing soluble polyimide thin film
Solution contains at least one in polyamic acid and poly amic acid ester.
3. preparation method according to claim 2 it is characterised in that: described polyamic acid is existed by dibasic acid anhydride and diamine
In organic solvent, polycondensation forms.
4. preparation method according to claim 3 it is characterised in that: described dibasic acid anhydride includes 3,3 ', 4,4 '-biphenyl four
Formic acid dianhydride, 2,3,3 ', 4 '-oxydiphthalic, 3,3 ', 4,4- oxydiphthalic, 3,3 ', 4,4 '-triphen diether
Double (3,4- dicarboxyphenyi) hexafluoro of tetracarboxylic dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, pyromellitic acid dianhydride or 2,2-
One or more of propanoic acid dianhydride mixture.
5. preparation method according to claim 3 it is characterised in that: described diamine include m-diaminobenzene., p-phenylenediamine,
3,3 '-diaminodiphenyl ether, 3,4 '-diaminodiphenyl ether, 4,4 '-diaminodiphenyl ether (oda), 2,3 diamino toluene, 3,
3 '-diamidogen diphenyl sulphone (DPS), 3,4 '-diaminodiphenyl ether, 4,4 '-diamidogen diphenyl sulphone (DPS) or diaminourea benzoyl are for one of aniline or several
The mixture planted.
6. preparation method according to claim 3 it is characterised in that: described organic solvent includes n- methyl pyrrolidone,
N, n- dimethyl acetylamide (dmac), n, n- dimethylformamide (dmf), in sulfolane, dimethyl sulfoxide, diethylene glycol dimethyl ether
One kind.
7. the preparation method according to claim 2 to 6 it is characterised in that: the described soluble polyimide thin film prepared
Mixed solution also contains phosphamide compound and catalyst.
8. preparation method according to claim 7 it is characterised in that: described phosphamide compound be 2,3- dihydro-sulfur-
3- phenylpropyl alcohol oxazolyl phosphate ester (dbop)；Described catalyst is tertiary amine compound, preferably triethylamine.
9. preparation method according to claim 7 it is characterised in that: polyamic acid, phosphamide compound, catalyst and stone
The mol ratio of black alkene nano belt is 1:3:3:1～1:4:3:1, and solvent quality fraction is 85%, and stirring reaction temperature is 10
DEG C～50 DEG C, the time be 12-48 hour.
10. a kind of polyimides graphene nano belt composite it is characterised in that: be by arbitrary according to claim 1 to 9
The polyimides graphene nano belt composite that manufacture method described in obtains.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108440753A (en) * | 2018-04-20 | 2018-08-24 | 武汉科技大学 | Carbon nano-tube/poly aniline/graphene composite and flexible film and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102616770A (en) * | 2012-03-28 | 2012-08-01 | 福州大学 | Method for preparing grapheme nano belts by etching carbon nano tubes through water vapor |
| CN102911360A (en) * | 2012-11-01 | 2013-02-06 | 南京航空航天大学 | Graphene modified polyimide-based composite and preparation method thereof |
| CN104448824A (en) * | 2015-01-05 | 2015-03-25 | 福州大学 | Polyimide-based composite film with optical limiting performance |
-
2016
- 2016-08-29 CN CN201610753477.6A patent/CN106366658A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102616770A (en) * | 2012-03-28 | 2012-08-01 | 福州大学 | Method for preparing grapheme nano belts by etching carbon nano tubes through water vapor |
| CN102911360A (en) * | 2012-11-01 | 2013-02-06 | 南京航空航天大学 | Graphene modified polyimide-based composite and preparation method thereof |
| CN104448824A (en) * | 2015-01-05 | 2015-03-25 | 福州大学 | Polyimide-based composite film with optical limiting performance |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108440753A (en) * | 2018-04-20 | 2018-08-24 | 武汉科技大学 | Carbon nano-tube/poly aniline/graphene composite and flexible film and preparation method thereof |
| CN108440753B (en) * | 2018-04-20 | 2019-02-26 | 武汉科技大学 | Carbon nano-tube/poly aniline/graphene composite and flexible film and preparation method thereof |
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