CN107760028A - A kind of light promotes graphene composite material film and its preparation method and application - Google Patents
A kind of light promotes graphene composite material film and its preparation method and application Download PDFInfo
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- CN107760028A CN107760028A CN201711138996.2A CN201711138996A CN107760028A CN 107760028 A CN107760028 A CN 107760028A CN 201711138996 A CN201711138996 A CN 201711138996A CN 107760028 A CN107760028 A CN 107760028A
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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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
- C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
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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
- 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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- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
Abstract
The present invention relates to a kind of light to promote graphene composite material film and its preparation method and application, belongs to polyimide material light Push Technology field.The graphene composite polyimide material prepared in the present invention has following characteristics：Material has high conduction performance；Material has high intensity, high thermal stability；Material has optical drive performance, can be driven under the irradiation of visible ray, and light source is laser, short arc xenon etc. or simulation daylight, sunshine；The form of driving is promoted under the irradiation of light source, is picked up for the sample of composite.
Description
Technical field
The present invention relates to a kind of light to promote graphene composite material film and its preparation method and application, belongs to polyimides
Material light Push Technology field.
Background technology
Spacecraft is the important tool of mankind's exploration of the universe, and power source problem is tied down always, the mankind can not walk
It is farther.Almost all of Aeronautics and Astronautics flight obtains driving force using the chemical substance by spray combustion at present, fortune
Carry device to be sent into predetermined space track and realize spacecraft technology in orbit, mainly liquid and Solid-state Chemistry promote.With people
Class utilizes to be expanded significantly with the scope in exploration of the universe space and depth, and the mankind have started a new round using survey of deep space as mark again
Space probation upsurge, and traditional chemical propulsion can not meet the needs of future space.Mainly energy density is low, utilizes
Chemical propulsion needs to carry substantial amounts of fuel, and liquid and the fuel entrained by solid propellant rocket will account for gross weight at present
More than 90%, and the features such as payload only accounts for 1-1.5%, and chemical propulsion efficiency is low, reliability is relatively low, consume a large amount of fuel and
Spacecraft can not be accelerated to enough speed, this is can not to meet survey of deep space requirement.Compared with traditional chemical propulsion, stone
It is that need not carry fuel that black alkene light, which promotes the advantages of most prominent, and spacecraft utilizes the photograph of sunshine when atmosphere is in flight
Penetrate, it is possible to drive aircraft.A kind of grapheme material that the experts such as Nankai University professor Chen Yongsheng develop, in its macroscopical material
Expect under special appearance structure and the collective effect of the special electronic structure of graphene itself, can be various including sunshine
The lower effectively driving flight of light source irradiation, its driving force obtained are more than 1000 times of traditional optical pressure.
Present solar sail thin-film material is typically using plastic sheeting as matrix, and reflecting surface is covered with aluminium lamination, the surface of emission is covered with layers of chrome.
Because the light propulsive efficiency of most plastic film material is low, it is smaller to obtain driving force, it is therefore desirable to which its overall dimensions is huge, sail face
Product can reach hundreds if not thousands of square metres so that Solar sail spacecraft often has huge rotary inertia, it has not been convenient to launches
And Spacecraft Attitude Control.Because the CD-ROM drive dynamic pressure of grapheme material is big, film sail material is done using it, greatly improves driving
Power, reduce sail area, beneficial to transmitting and Spacecraft Attitude Control.The present invention is prepared a kind of using graphene, binary acid anhydride, diamine
Optical drive graphene polyimide film material solves the problems such as film sail CD-ROM drive power is small, and area is big, controls spacecraft attitude.
The content of the invention
The technology of the present invention solves problem：Overcome the deficiencies in the prior art, propose that a kind of light promotes graphene composite wood
Expect film and its preparation method and application.
The present invention technical solution be：
A kind of light promotes graphene composite material film, and the composition of the composite material film includes graphene and polyamides is sub-
Amine, the quality of graphene and the mass ratio of polyimides are：10~50：100.
A kind of light promotes the preparation method of graphene composite material film, includes the step of this method：
1) by modified graphene it is agitated, be ultrasonically treated after it is dispersed in organic solvent, obtain the organic of graphene
Dispersion liquid；
2) under conditions of 40~60 DEG C, by pyromellitic acid anhydride and 4,4 '-diaminodiphenyl ether is placed in dimethyl second
Polymerisation is carried out in amide solvent, obtains polyamic acid glue A of the solid content in 15wt%~30wt%；
3) under conditions of 40~60 DEG C, by 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride and p-phenylenediamine are placed in diformazan
Polymerisation is carried out in yl acetamide solvent, obtains polyamic acid glue liquid B of the solid content in 15wt%-30wt%；
4) the polyamic acid glue A and step 3) that the organic dispersions for the graphene for obtaining step 1), step 2) obtain
Obtained polyamic acid glue liquid B is mixed, and obtains polyamic acid composite glue solution；Wherein, graphene content accounts for polyamic acid and answered
10wt%~30wt% of total solid in rubber alloy liquid；
5) under conditions of 40-60 DEG C, pyromellitic acid anhydride is added in the polyamic acid composite glue solution that step 4) obtains,
The viscosity for making polyamic acid composite glue solution is 300~350pa.s；
6) the polyamic acid composite glue solution for obtaining step 5) carries out defoaming treatment, then answers the polyamic acid after defoaming
Film is made by salivating moulding process in rubber alloy liquid, finally will film be sent into imidization stove in carry out biaxial tension, imidization and
Heat treatment, obtain light and promote graphene Kapton.
In described step 1), the preparation method of modified graphene is：
I is scattered in ethanol by the graphene oxide prepared using Hummers methods, agitated, supersound process so that oxidation
Graphene is fully dispersed, obtains the graphene oxide ethanol solution that concentration is 1~2mg/ml；
The graphene oxide ethanol solution that step i is obtained is added in hot high pressure reactor by ii, is sealed reactor, is put into
Preheat in 180~200 DEG C of baking ovens, carry out high-temperature solvent thermal response, hour in reaction time 16-20, stop reaction, be cooled to room
Wen Hou, the grapheme material full of ethanol is taken out, is placed in container；
Solvent in the grapheme material full of ethanol that iii obtains step ii is replaced into deionized water, is full of
The grapheme material of deionized water；
The grapheme material full of deionized water that iv obtains step iii carries out cold at a temperature of -50 DEG C~-60 DEG C
It is lyophilized dry；
V is by the grapheme material after step iv freeze-drying process 800~1000 DEG C in inert atmosphere or vacuum environment
High-temperature calcination 1~2 hour is carried out, grapheme material is made；
The obtained grapheme materials of step v are put into pH=8 2mg/ml aqueous dopamine solutions by vi, in graphenic surface
A strata dopamine thin layer is formd, filtering, vacuum drying obtain modified graphene.
In described step 1), organic solvent is DMF, dimethyl acetamide or N- crassitudes
Ketone；
In described step 1), 1~2mg/ml of relationship between quality of modified graphene and organic solvent；
In described step 2), pyromellitic acid anhydride and 4, the mol ratio of 4 '-diaminodiphenyl ether is 1:1.006~
1.015；
In described step 3), 3,3 ', 4, the mol ratio of 4 '-benzophenone tetracarboxylic dianhydride and p-phenylenediamine is 1:
1.006~1.015；
In described step 3), 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride can also be phthalic anhydride, inclined benzene
Front three acid anhydrides or tetrabromo phthalate anhydride；
In described step 4), the mass ratio of the organic dispersions of graphene, polyamic acid glue A and amic acid glue liquid B
For：1~5:1：1~3；
In described step 6), the temperature of biaxial tension processing is 150~200 DEG C, the drawing of cross directional stretch and longitudinal stretching
Stretch than being 1.10~1.25, the temperature of imidization processing is 360~400 DEG C, and the time of imidization processing is 3~4 minutes, fixed
The temperature of type processing is 180~250 DEG C, and the time of heat treatment is 2~3 minutes.
Beneficial effect
1) technical problem to be solved is to provide the preparation method that a kind of light promotes graphene composite material film, passes through
The light that this method prepares gained promotes graphene composite material film to have high intensity, high stability, high electric strength and CD-ROM drive
The performance advantage such as dynamic.This technology be graphene light Push Technology in the upgrading of spacecraft propulsion system, lift in-orbit space flight
The life-span of device and performance, the cost of existing spacecraft is reduced, create significant economic benefit.
2) the graphene composite polyimide material for preparing of the present invention have high intensity, high stability, high electric strength and
Optical drive performance.
3) the graphene composite polyimide material prepared in the present invention has following characteristics：Material has high conductivity
Energy；Material has high intensity, high thermal stability；Material has optical drive performance, can be driven under the irradiation of visible ray, light
Source is laser, short arc xenon etc. or simulation daylight, sunshine；The form of driving for composite sample under the irradiation of light source quilt
Promote, be picked up.
4) material should be positioned over vacuum environment by the operation of the optical drive, and light source is positioned among vacuum environment, or
Increase optical transmission window structure on device, use quartzy light transmissive material in the part of vacuum plant, so as to which light introducing be able to
Irradiation；
5) the graphene Kapton for preparing gained has the performances such as high intensity, high thermal stability and optical drive excellent
Gesture, described optical drive graphene polyimide material are used for conductive material, space craft and optical drive device or device, too
Positive sail material.
6) preparation method of graphene/polyimide composite material film of the present invention, comprises the following steps：By equal benzene tetramethyl
Acid dianhydride and 4,4 '-diaminodiphenyl ether, which is placed in dimethylacetamide solvent, carries out polymerisation, obtains polyamic acid glue
A, by 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (or phthalic anhydride, trimellitic anhydride, tetrabromo phthalic acid
Acid anhydride) and p-phenylenediamine be placed in dimethylacetamide solvent and carry out polymerisation, polyamic acid glue liquid B is obtained, by polyamic acid
Glue A and the mixing of polyamic acid glue liquid B, prepare graphene dispersing solution, graphene dispersing solution are well-dispersed in into polynary polyamide
In sour glue, polyamic acid composite glue solution is obtained, film is made by salivating moulding process in polyamic acid composite glue solution, finally
Film is sent into imidization stove and handled, produces the Kapton.As the present invention prepare obtained by graphene/
Composite polyimide material film has the performance advantages such as high intensity, high stability, high conductivity and optical drive.
Brief description of the drawings
Fig. 1 is photic driving phenomenon figure of the graphene composite polyimide material under laser action；
The solar sail modelling that Fig. 2 graphenes composite polyimide material makes.
Embodiment
A kind of light promotes graphene composite material film, described graphene/polyimide composite material film by acid anhydrides,
4,4 '-diaminodiphenyl ether, p-phenylenediamine, the organic dispersions of graphene, which are placed in dimethylacetamide solvent, polymerize instead
Should, wherein graphene content accounts for 10~30wt% of total solid in polyamic acid composite glue solution, it is preferred that described graphite
The mass ratio of alkene and polyamic acid glue is 10~30:100.
Described acid anhydrides be pyromellitic acid anhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, phthalic anhydride,
One or more mixtures of trimellitic anhydride, tetrabromo phthalate anhydride.
The method that the light described in claim 1 promotes graphene composite material film is prepared, is comprised the following steps：
(1) it is modified graphene is scattered in organic solvent, agitated, supersound process, it has been dispersed in graphene uniform
Solvent, obtain the organic dispersions of graphene；
(2) under conditions of 40~60 DEG C, by pyromellitic acid anhydride, 4,4 '-diaminodiphenyl ether is placed in dimethyl second
Polymerisation is carried out in amide solvent, pyromellitic acid anhydride and 4, the mol ratio of 4 '-diaminodiphenyl ether is 1:1.006~
1.015, obtain polyamic acid glue A of the solid content in 15~30wt%；
(3) under conditions of 40~60 DEG C, by 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (or phthalic acid
Acid anhydride, trimellitic anhydride, tetrabromo phthalate anhydride) and p-phenylenediamine be placed in dimethylacetamide solvent and carry out polymerisation,
The mol ratio of 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride and p-phenylenediamine is 1:1.006~1.015, solid content is obtained 15
~30wt% polyamic acid glue liquid B；
(4) by modified graphene organic dispersion, polyamic acid glue A, polyamic acid glue liquid B by weight 1~5:
1：1~3 ratio mixes, and obtains polyamic acid composite glue solution, and wherein graphene content accounts for polyamic acid composite glue solution
10~30wt% of middle total solid, finally under conditions of 60 DEG C, by adding pyromellitic acid anhydride by polyamic acid
The viscosity of composite glue solution is controlled in 300~350pa.s；
(5) defoaming treatment is carried out to polyamic acid composite glue solution, be then molded polyamic acid composite glue solution by salivating
Film is made in technique, it is characterised in that：The temperature of biaxial tension processing is 150~200 DEG C, the drawing of cross directional stretch and longitudinal stretching
Stretch than being 1.10~1.25, the temperature of imidization processing is 360~400 DEG C, and the time is 3~4 minutes, the temperature of heat treatment
For 180~250 DEG C, the time is 2~3 minutes, produces the light and promotes graphene Kapton.
Light propulsion graphene composite material film, the preparation method of described graphene are as follows：
(1) it is the graphene oxide prepared using Hummers methods is scattered in ethanol, agitated, supersound process so that oxygen
Graphite alkene is fully dispersed, and it is 1-2mg/ml graphene oxide ethanol solutions to obtain concentration；
(2) above-mentioned dispersion liquid is poured into hot high pressure reactor, seals reactor, be put into 180 DEG C of baking ovens of preheating,
High-temperature solvent thermal response is carried out, hour in reaction time 16-20, stops reaction, after being cooled to room temperature, is taken out full of reaction dissolvent
Grapheme material, it is placed in container；
(3) reaction dissolvent in above-mentioned grapheme material is replaced into deionized water；
(4) the above-mentioned grapheme material full of deionized water is freeze-dried in the case where temperature is -55 DEG C；
(5) grapheme material after above-mentioned freeze-drying process is subjected to height for 1000 DEG C in inert atmosphere or vacuum environment
Temperature calcining 1 hour, is made grapheme material；
(6) the prepared grapheme material that obtains is subjected to surface modification, utilizes 2g/ml aqueous dopamine solution modified graphite
Alkene, a strata dopamine thin layer is formd in graphenic surface, filtering, vacuum drying obtain modified graphene.
Described graphene/polyimide composite material film has high intensity, high stability, high conductivity and optical drive
Etc. performance.The graphene/polyimide composite material film is positioned over vacuum environment, and light source is placed in vacuum environment or device
On set up optical transmission window introduction, in the presence of light, there is provided enough motive forces, be used as the propulsion plant of spacecraft.
The invention will now be further described with reference to specific embodiments, advantages of the present invention and feature will be with description and
It is apparent.But embodiment is only exemplary, does not form any restrictions to the scope of the present invention.Those skilled in the art should
It should be appreciated that the details and form of technical solution of the present invention can be repaiied without departing from the spirit and scope of the invention
Change or replace, but these modifications and replacement are each fallen within protection scope of the present invention.
Embodiment 1
The preparation method of functionalization graphene：
1) it is the graphene oxide prepared using Hummers methods is scattered in ethanol, agitated, supersound process so that oxygen
Graphite alkene is fully dispersed, and it is 1mg/ml graphene oxide ethanol solutions to obtain concentration；
2) above-mentioned dispersion liquid is poured into hot high pressure reactor, seals reactor, be put into 180 DEG C of baking ovens of preheating,
High-temperature solvent thermal response is carried out, in 18 hours reaction time, stops reaction, after being cooled to room temperature, takes out the stone full of reaction dissolvent
Black alkene material, is placed in container；
3) reaction dissolvent in above-mentioned grapheme material is replaced into deionized water；
4) the above-mentioned grapheme material full of deionized water is freeze-dried in the case where temperature is -55 DEG C；
5) grapheme material after above-mentioned freeze-drying process is subjected to height for 1000 DEG C in inert atmosphere or vacuum environment
Temperature calcining 1 hour, light is made and promotes grapheme material；
6) preparation-obtained grapheme material is evenly spread in pH=8 2mg/ml aqueous dopamine solutions, formed
One strata dopamine thin layer, filtering, vacuum drying obtain modified graphene, standby.
Light promotes the preparation method of graphene composite polyimide material, comprises the following steps：
1) graphene dispersion for being modified above-mentioned gained is in dimethylacetamide solvent, agitated, supersound process, fully
It is scattered in dimethylacetamide solvent, obtains the organic dispersions that concentration is 1mg/ml graphenes；
2) 4,4 '-diaminodiphenyl ether is first dissolved in diformazan under the condition of normal pressure full of nitrogen in 45 DEG C of kettle
In base formamide solvent, add pyromellitic acid anhydride and carry out polymerisation, 4 hours reaction time, pyromellitic acid anhydride
Mol ratio with 4,4 '-diaminodiphenyl ether is 1:1.008, obtain polyamic acid glue A (full response mistake of the solid content 17%
Journey speed of agitator 100r/min)；
3) it is molten that p-phenylenediamine is first dissolved in dimethylformamide under the condition of normal pressure full of nitrogen in 55 DEG C of kettle
In agent, 3,3 ', 4 are added, 4 '-benzophenone tetracarboxylic dianhydride carries out polymerisation, 4.5 hours reaction time, and 3,3 ', 4,
The mol ratio of 4 '-benzophenone tetracarboxylic dianhydride and p-phenylenediamine is 1.008, obtains polyamic acid glue of the solid content in 23wt%
Liquid B (full response process speed of agitator 100r/min)；
4) by the organic dispersions of graphene, polyamic acid glue A and polyamic acid glue liquid B by weight 2：1：2.5
Ratio mixes, and obtains the polynary polyamic acid glue of graphene (speed of agitator 200r/min, time 1h)；Wherein graphene
Content accounts for the 15wt% of total solid in polyamic acid composite glue solution, finally under conditions of 45 DEG C, by adding equal benzene four
Formic acid dianhydride controls the viscosity of polyamic acid composite glue solution in 300pa.s；
5) defoaming treatment is carried out to polyamic acid composite glue solution, polyamic acid composite glue solution is then molded work by salivating
Film is made in skill, and the solid content of film controls in 43wt%, finally film is sent into imidization stove and carries out biaxial tension, imines
Change and heat treatment, the Kapton is produced, the temperature of biaxial tension processing is 175 DEG C, cross directional stretch and longitudinal direction drawing
The draw ratio stretched is 1.10 (cross directional stretch after first longitudinal stretching), and the temperature of imidization processing is 360 DEG C, and the time is 4 minutes,
The temperature of heat treatment is 210 DEG C, and the time is 2.5 minutes.
Embodiment 2
1) modified graphene is prepared according to the identical method of embodiment 1, it is standby.
2) light promotes the preparation method of graphene composite polyimide material, comprises the following steps：
The graphene dispersion that above-mentioned gained is modified by i is in dimethylacetamide solvent, agitated, supersound process, fully
It is scattered in dimethylacetamide solvent, obtains the organic dispersions that concentration is 1mg/ml graphenes；
4,4 '-diaminodiphenyl ether under the condition of normal pressure full of nitrogen, is first dissolved in diformazan by ii in 50 DEG C of kettle
In base formamide solvent, add pyromellitic acid anhydride and carry out polymerisation, 4 hours reaction time, pyromellitic acid anhydride
Mol ratio with 4,4 '-diaminodiphenyl ether is 1:1.007, obtain polyamic acid glue A (full response mistake of the solid content 17%
Journey speed of agitator 100r/min)；
P-phenylenediamine under the condition of normal pressure full of nitrogen, is first dissolved in dimethylformamide by iii in 55 DEG C of kettle
In solvent, add phthalic anhydride and carry out polymerisation, 4.5 hours reaction time, phthalic anhydride and p-phenylenediamine
Mol ratio be 1.007, obtain polyamic acid glue liquid B (full response process speed of agitator 100r/ of the solid content in 23wt%
min)；
Iv is by the organic dispersions of graphene, polyamic acid glue A and polyamic acid glue liquid B by weight 3：1：2.5
Ratio mixes, and obtains the polynary polyamic acid glue of graphene (speed of agitator 200r/min, time 1h)；Wherein graphene
Content accounts for the 20wt% of total solid in polyamic acid composite glue solution, finally under conditions of 45 DEG C, by adding equal benzene four
Formic acid dianhydride controls the viscosity of polyamic acid composite glue solution in 300pa.s；
V carries out defoaming treatment to polyamic acid composite glue solution, and polyamic acid composite glue solution then is molded into work by salivating
Film is made in skill, and the solid content of film controls in 43wt%, finally film is sent into imidization stove and carries out biaxial tension, imines
Change and heat treatment, the Kapton is produced, the temperature of biaxial tension processing is 175 DEG C, cross directional stretch and longitudinal direction drawing
The draw ratio stretched is 1.10 (cross directional stretch after first longitudinal stretching), and the temperature of imidization processing is 350 DEG C, and the time is 4 minutes,
The temperature of heat treatment is 200 DEG C, and the time is 2.5 minutes.
Embodiment 3
1) modified graphene is prepared according to the identical method of embodiment 1, it is standby.
2) light promotes the preparation method of graphene composite polyimide material, comprises the following steps：
The graphene dispersion that above-mentioned gained is modified by i is in dimethylacetamide solvent, agitated, supersound process, fully
It is scattered in dimethylacetamide solvent, obtains the organic dispersions that concentration is 1mg/ml graphenes；
4,4 '-diaminodiphenyl ether under the condition of normal pressure full of nitrogen, is first dissolved in diformazan by ii in 40 DEG C of kettle
In base formamide solvent, add pyromellitic acid anhydride and carry out polymerisation, 4 hours reaction time, pyromellitic acid anhydride
Mol ratio with 4,4 '-diaminodiphenyl ether is 1:1.010, obtain polyamic acid glue A (full response mistake of the solid content 17%
Journey speed of agitator 100r/min)；
P-phenylenediamine under the condition of normal pressure full of nitrogen, is first dissolved in dimethylformamide by iii in 50 DEG C of kettle
In solvent, add tetrabromo phthalate anhydride and carry out polymerisation, 4.5 hours reaction time, tetrabromo phthalate anhydride and to benzene
The mol ratio of diamines is 1.010, obtains polyamic acid glue liquid B (full response process speed of agitator 100r/ of the solid content in 23wt%
min)；
Iv is by the organic dispersions of graphene, polyamic acid glue A and polyamic acid glue liquid B by weight 4：1：2.5
Ratio mixes, and obtains the polynary polyamic acid glue of graphene (speed of agitator 200r/min, time 1h)；Wherein graphene
Content accounts for the 30wt% of total solid in polyamic acid composite glue solution, finally under conditions of 45 DEG C, by adding equal benzene four
Formic acid dianhydride controls the viscosity of polyamic acid composite glue solution in 300pa.s；
V carries out defoaming treatment to polyamic acid composite glue solution, and polyamic acid composite glue solution then is molded into work by salivating
Film is made in skill, and the solid content of film controls in 40wt%, finally film is sent into imidization stove and carries out biaxial tension, imines
Change and heat treatment, the Kapton is produced, the temperature of biaxial tension processing is 180 DEG C, cross directional stretch and longitudinal direction drawing
The draw ratio stretched is 1.10 (cross directional stretch after first longitudinal stretching), and the temperature of imidization processing is 360 DEG C, and the time is 4 minutes,
The temperature of heat treatment is 210 DEG C, and the time is 3.0 minutes.
Control implements 1
The preparation method of composite polyimide material, comprises the following steps：
4,4 '-diaminodiphenyl ether under the condition of normal pressure full of nitrogen, is first dissolved in dimethyl by i in 40 DEG C of kettle
In formamide solvent, add pyromellitic acid anhydride carry out polymerisation, 4 hours reaction time, pyromellitic acid anhydride and
The mol ratio of 4,4 '-diaminodiphenyl ether is 1:1.008, obtain polyamic acid glue A (full response process of the solid content 17%
Speed of agitator 100r/min)；
Under the condition of normal pressure full of nitrogen, it is molten to be first dissolved in dimethylformamide in 50 DEG C of kettle by ii for p-phenylenediamine
In agent, add tetrabromo phthalate anhydride and carry out polymerisation, 4.5 hours reaction time, tetrabromo phthalate anhydride and to benzene two
The mol ratio of amine is 1.008, obtains polyamic acid glue liquid B (full response process speed of agitator 100r/ of the solid content in 23wt%
min)；
Iii is by polyamic acid glue A and polyamic acid glue liquid B by weight 1：2.5 ratio mixes, and obtains more
First polyamic acid glue (speed of agitator 200r/min, time 1h)；Finally under conditions of 45 DEG C, by adding Pyromellitic Acid
Dianhydride controls the viscosity of polyamic acid composite glue solution in 300pa.s；
Iv carries out defoaming treatment to polyamic acid composite glue solution, and polyamic acid composite glue solution then is molded into work by salivating
Film is made in skill, and the solid content of film controls in 40wt%, finally film is sent into imidization stove and carries out biaxial tension, imines
Change and heat treatment, the Kapton is produced, the temperature of biaxial tension processing is 180 DEG C, cross directional stretch and longitudinal direction drawing
The draw ratio stretched is 1.10 (cross directional stretch after first longitudinal stretching), and the temperature of imidization processing is 360 DEG C, and the time is 4 minutes,
The temperature of heat treatment is 210 DEG C, and the time is 3.0 minutes.
" fully dispersed " step in the various embodiments described above is used first with high speed dispersor (1800~2500r/min) point
Dissipate, then the technique for disperseing 100~180s with ultrasonic assistant.
Implementing the graphene composite polyimide material obtained by 1-3 has light propulsive performance.Under the irradiation of different light sources,
The material has fast and effectively light propulsive performance.
As shown in figure 1, the operating method that described light promotes：One piece of graphene composite material is taken, it is not high to put vacuum into
In 10Pa, light source is placed in outside vacuum environment, increases optical transmission window structure on device, is able to irradiate material so as to which optics be introduced
Material.
Phenomenon is promoted based on this light, making should can be spent based on graphene composite polyimide material has CD-ROM drive
The solar sail of dynamic performance, a kind of prototype such as Fig. 2 of solar sail.
By according to graphene/Kapton made from embodiment 1 to 3 with compareing 1, conventional polyamides in the market
Imines film carries out performance comparision, as a result such as table 1 below：
1 graphene of table/Kapton performance
| Performance | Implement 1 | Implement 2 | Implement 3 | Control 1 |
| Modulus GPa) | 4.0 | 3.8 | 3.7 | 2.5 |
| Tensile strength MPa) | 299 | 315 | 290 | 200 |
| 5%Td/ DEG C of heat endurance | 530 | 540 | 510 | 550 |
| Electric conductivity (s) | 5.89*10-6 | 8.0*10-6 | 5.89*10-6 | - |
| Whether light propulsive performance | It is | It is | It is | It is no |
It is as can be seen that thin compared to existing conventional polyimide by graphene/Kapton obtained by the present invention
Film has an advantages such as high intensity, high thermal stability, high conductivity and light propulsive performance, and the graphene obtained by the present invention/
The pliability of Kapton is good, good with the adhesive property of copper foil.
It should be understood that example as described herein and embodiment can be made only for explanation, those skilled in the art according to it
Various modifications or change, in the case where not departing from spirit of the invention, belong to protection scope of the present invention.
Claims (10)
1. a kind of light promotes graphene composite material film, it is characterised in that：The composition of the composite material film includes graphene
And polyimides, the quality of graphene and the mass ratio of polyimides are：10~50：100.
2. a kind of light promotes the preparation method of graphene composite material film, it is characterised in that includes the step of this method：
1) by modified graphene it is agitated, be ultrasonically treated after it is dispersed in organic solvent, obtain the organic scattered of graphene
Liquid；
2) under conditions of 40~60 DEG C, by pyromellitic acid anhydride and 4,4 '-diaminodiphenyl ether is placed in dimethyl acetamide
Polymerisation is carried out in solvent, obtains polyamic acid glue A of the solid content in 15wt%~30wt%；
3) under conditions of 40~60 DEG C, by 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride and p-phenylenediamine are placed in dimethyl second
Polymerisation is carried out in amide solvent, obtains polyamic acid glue liquid B of the solid content in 15wt%-30wt%；
4) the polyamic acid glue A and step 3) that the organic dispersions for the graphene for obtaining step 1), step 2) obtain are obtained
Polyamic acid glue liquid B mixed, obtain polyamic acid composite glue solution；Wherein, graphene content accounts for polyamic acid compound adhesive
10wt%~30wt% of total solid in liquid；
5) under conditions of 40-60 DEG C, pyromellitic acid anhydride is added in the polyamic acid composite glue solution that step 4) obtains, makes to gather
The viscosity of amic acid composite glue solution is 300~350pa.s；
6) the polyamic acid composite glue solution that step 5) obtains is prepared into film, obtains light and promote graphene Kapton.
3. a kind of light according to claim 2 promotes the preparation method of graphene composite material film, it is characterised in that：Institute
In the step 6) stated, the method that polyamic acid composite glue solution is prepared into film is：Polyamic acid composite glue solution is carried out first
Defoaming treatment, film then is made by salivating moulding process in the polyamic acid composite glue solution after defoaming, finally send film
Enter and biaxial tension, imidization and heat treatment are carried out in imidization stove, obtain light and promote graphene Kapton.
4. a kind of light according to claim 2 promotes the preparation method of graphene composite material film, it is characterised in that：Institute
In the step 1) stated, the preparation method of modified graphene is：
I is scattered in ethanol by the graphene oxide prepared using Hummers methods, agitated, supersound process so that graphite oxide
Alkene is fully dispersed, obtains the graphene oxide ethanol solution that concentration is 1~2mg/ml；
The graphene oxide ethanol solution that step i is obtained is added in hot high pressure reactor by ii, is sealed reactor, is put into pre-add
In hot 180~200 DEG C of baking ovens, high-temperature solvent thermal response is carried out, hour in reaction time 16-20, stops reaction, is cooled to room temperature
Afterwards, the grapheme material full of ethanol is taken out, is placed in container；
Solvent in the grapheme material full of ethanol that iii obtains step ii is replaced into deionized water, obtain full of go from
The grapheme material of sub- water；
It is dry that the grapheme material full of deionized water that iv obtains step iii carries out freezing at a temperature of -50 DEG C~-60 DEG C
It is dry；
V 800~1000 DEG C of progress in inert atmosphere or vacuum environment by the grapheme material after step iv freeze-drying process
High-temperature calcination 1~2 hour, grapheme material is made；
The obtained grapheme materials of step v are put into pH=8 2mg/ml aqueous dopamine solutions by vi, are formed in graphenic surface
One strata dopamine thin layer, filtering, vacuum drying obtain modified graphene.
5. a kind of light according to claim 2 promotes the preparation method of graphene composite material film, it is characterised in that：Institute
In the step 1) stated, organic solvent is DMF, dimethyl acetamide or 1-METHYLPYRROLIDONE；
In described step 1), the relation of modified graphene and organic solvent is 1~2mg/ml.
6. a kind of light according to claim 2 promotes the preparation method of graphene composite material film, it is characterised in that：Institute
In the step 2) stated, pyromellitic acid anhydride and 4, the mol ratio of 4 '-diaminodiphenyl ether is 1:1.006~1.015.
7. a kind of light according to claim 2 promotes the preparation method of graphene composite material film, it is characterised in that：Institute
In the step 3) stated, 3,3 ', 4, the mol ratio of 4 '-benzophenone tetracarboxylic dianhydride and p-phenylenediamine is 1:1.006~1.015.
8. a kind of light according to claim 2 promotes the preparation method of graphene composite material film, it is characterised in that：Institute
In the step 3) stated, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride can also be phthalic anhydride, trimellitic anhydride or
Tetrabromo phthalate anhydride.
9. a kind of light according to claim 2 promotes the preparation method of graphene composite material film, it is characterised in that：Institute
In the step 4) stated, the mass ratio of the organic dispersions of graphene, polyamic acid glue A and amic acid glue liquid B is：1~5:1：1
~3.
10. a kind of light according to claim 3 promotes the preparation method of graphene composite material film, it is characterised in that：
The temperature of described biaxial tension processing is 150~200 DEG C, the draw ratio of cross directional stretch and longitudinal stretching is 1.10~
1.25, the temperature of imidization processing is 360~400 DEG C, and the time of imidization processing is 3~4 minutes, and the temperature of heat treatment is
180~250 DEG C, the time of heat treatment is 2~3 minutes.
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| CN103665866A (en) * | 2013-12-16 | 2014-03-26 | 宁波今山电子材料有限公司 | Preparation method for graphene-polyimide composite film |
| CN105111476A (en) * | 2015-09-16 | 2015-12-02 | 安徽鑫柏格电子股份有限公司 | Preparation method for polyimide film |
| CN105254916A (en) * | 2015-09-30 | 2016-01-20 | 西南交通大学 | Preparation method for oxidized graphene-poly-dopamine composite aerogel |
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| CN103665866A (en) * | 2013-12-16 | 2014-03-26 | 宁波今山电子材料有限公司 | Preparation method for graphene-polyimide composite film |
| CN105111476A (en) * | 2015-09-16 | 2015-12-02 | 安徽鑫柏格电子股份有限公司 | Preparation method for polyimide film |
| CN105254916A (en) * | 2015-09-30 | 2016-01-20 | 西南交通大学 | Preparation method for oxidized graphene-poly-dopamine composite aerogel |
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| CN110894292A (en) * | 2019-10-31 | 2020-03-20 | 安徽国风塑业股份有限公司 | Fluorescent polyimide film and preparation method thereof |
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