CN103589154A - Preparation method for graphene/polyimide composite material - Google Patents
Preparation method for graphene/polyimide composite material Download PDFInfo
- Publication number
- CN103589154A CN103589154A CN201310554749.6A CN201310554749A CN103589154A CN 103589154 A CN103589154 A CN 103589154A CN 201310554749 A CN201310554749 A CN 201310554749A CN 103589154 A CN103589154 A CN 103589154A
- Authority
- CN
- China
- Prior art keywords
- graphene
- preparation
- modified graphene
- modified
- polyimide material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
Abstract
The invention discloses a preparation method of a graphene/polyimide composite material. The preparation method adopts composite materials in percentage by weight and the processes, wherein the composite material comprises the following components in in percentage by weight: 80 to 99.99 percent of polyimide and 20 to 0.01 percent of Si-modified graphene; the preparation method particularly comprises the following steps: (1), preparing graphite oxide; (2), preparing Si-modified graphene: performing ultrasonographic treatment on the obtained graphite oxide powder in an aprotic organic solvent for 0.5 to 2 hours to obtain dispersion liquid with the concentration of 0.5 to 5mg/mL, adding an siloxane modification reagent into the dispersion liquid for reaction for 1 to 24 hours at a temperature of 30 to 180 DEG C, and performing washing and drying to obtain the powder of Si-modified graphene , wherein the mass content of Si is 2 to 13 percent;(3), preparing a precursor of Si-modified graphene/polyimide; (4), preparing the Si-modified graphene/polyimide composite material.
Description
Technical field
The present invention relates to composite polyimide material technology, specifically a kind of preparation method of Graphene/composite polyimide material.This preparation method's principal feature is to have adopted Si modified graphene.
Background technology
Polyimide is widely used in the sophisticated technology fields such as aerospace, microelectronics, communication because it has excellent resistance toheat, dielectric properties, mechanical property etc.But along with the development of modern industry, also more and more higher to the properties requirement of material, not only need resistance to more high temperature, want high strength and high-modulus simultaneously.Tradition polyimide material can not meet the demands.Need to carry out modification to obtain the composite polyimide material with resistance to more high temperature, high strength and modulus performance to polyimide.Graphene is with SP by carbon atom
2the monoatomic layer that hydridization connects forms, and is the thinnest current two-dimensional nano material.Due to unique two-dirnentional structure, Graphene has excellent electricity, calorifics and mechanical property.Its mechanical strength can reach 130GPa, be the highest material of intensity in the world, and can improve the mechanics of materials, resistance toheat etc., so Graphene becomes desirable polymer-filled material at present.
At present, Graphene/composite polyimide material technology of preparing has been reported, for example, Zhang Qinghua, the preparation method > > of a < < graphene/polyimide composite fibers (Chinese patent CN102534858), its principal character comprises: take graphene oxide as filler, after mixing with polyamic acid, carry out wet spinning or dry-spinning Graphene/polyamic acid conjugated fibre, through imidization, process and obtain Graphene/polyimide fiber afterwards.Sungho Lee etc. prepares Graphene/polyimide composite film by situ aggregation method, and after interpolation Graphene, laminated film conductivity significantly improves (J.D.Zhu, C.H.Lee, H.I.Joh, H.C.Kim and S.Lee, Carbon letters, 13, (2012)).Song ?Young Park etc. by solution blending process, prepared Graphene/polyimide composite film, add after Graphene mechanical property, the conductivity of laminated film be all improved (Ha, H.W.; Choudhury, A.; Kamal, T.; Kim, D.H., Park, S.Y.ACS Appl.Mater.Interfaces, 4, (2012) .).But the composite material combination property after the interpolation Graphene of having reported does not reach ideal value, and mechanics and resistance toheat can not be taken into account simultaneously.Trace it to its cause and be: the reunion certainly of Graphene in (1) preparation process, causes its dispersion inhomogeneous; (2) Graphene and polyimide matrix bounding force are poor, cause stress concentration, thereby can not effectively improve the over-all properties of Graphene and composite polyimide material.
Summary of the invention
For the deficiencies in the prior art, the technical problem that quasi-solution of the present invention is determined is that a kind of preparation method of Graphene/composite polyimide material is provided.This preparation method introduces in polyimide matrix by high temperature resistant inorganic Si and Graphene simultaneously, can improve mechanical property, second-order transition temperature and the resistance toheat of Graphene/composite polyimide material simultaneously, have processing method simple, raw material is cheap and easy to get, is convenient to the features such as industrializing implementation.
The technical scheme that the present invention solve the technical problem is, design a kind of Graphene/composite polyimide material preparation method, this preparation method adopts following matrix material mass percent to form and technique: the mass percent of this matrix material forms and comprises: polyimide 80～99.99% and Si modified graphene 20～0.01%;
This preparation method's concrete technology step is:
(1) preparation of graphite oxide
Take natural flake graphite as raw material, adopt and improve Hummer legal system for graphite oxide powder; Graphite is natural flake graphite, is of a size of 8000～50 orders;
(2) preparation of Si modified graphene
The graphite oxide powder of preparation after ultrasonic 0.5～2 hour, is obtained to 0.5～5mg/mL graphene oxide dispersion liquid in aprotic organic solvent; In dispersion liquid, add silicone-modified reagent, at 30～180 ℃, react 1～24 hour; After washing, being dried, obtain Si modified graphene powder, Si mass content is wherein 2～13%; Si modified graphene thickness is 0.8～1.4nm, and particle diameter is 2～60 μ m;
(3) Si modified graphene/polyimide precursor preparation
Si modified graphene, dianhydride and diamines are mixed in described aprotic polar solvent, nitrogen protection He ?home position polymerization reaction 1～36 hour at 10～30 ℃, obtain Si modified graphene/polymeric amide presoma acid solution, its quality solid content is 5～40%;
(4) preparation of Si modified graphene/composite polyimide material
By Si modified graphene/polyamic acid presoma curtain coating of preparation, 30～100 ℃ except desolventizing; Temperature programming to 100 afterwards～450 ℃, and be incubated 1～4 hour, make the Graphene/composite polyimide material of Si modification;
Aprotic organic solvent in described step (2) is N, N ?dimethyl formamide, N, N ?N,N-DIMETHYLACETAMIDE, dimethyl sulfoxide (DMSO) or N ?a kind of in methyl-2-pyrrolidone;
Silicone-modified reagent in described step (2) is: 3 ?aminopropyltriethoxywerene werene, 4 ?aminophenyl triethoxyl silane, 3 ?(2 ?aminoethylamino) propyl group methyl dimethoxysilane, 3 ?(2 ?aminoethyl base) propyl-triethoxysilicane, 4 ?aminophenyl triethoxyl silane, 3 ?aminopropyl diethoxymethyl silane or 3 ?1 in aminopropyl trimethoxysilane ?2 kinds;
Dianhydride in described step (3) is 4, 4 ′ ?diphthalic anhydrides, 3, 3 ', 4, 4 ′ ?benzophenone tetracarboxylic dianhydride, 4, 4 ′ ?the two Tetra hydro Phthalic anhydrides of oxygen, 3, 4 ′ ?the two Tetra hydro Phthalic anhydrides of oxygen, 3, 3 ', 4, 4 ′ ?sulfobenzide tetracarboxylic acid dicarboxylic anhydride, 4, 4 ′ ?(hexafluoro isopropylidene) two anhydride phthalic acids, pyromellitic acid anhydride, 3, 3 ', 4, 4 ′ ?benzophenone tetracarboxylic dianhydride, dicyclo [2.2.2] Xin ?7 ?Xi ?2, 3, 5, 6 ?tetracarboxylic acid dianhydride, 3, 3 ', 4, 4 ′ ?sulfobenzide tetracarboxylic acid dicarboxylic anhydride, 4, 4 ′ ?(hexafluoro isopropylidene) two anhydride phthalic acids, Nai ?1, 4, 5, 8 ?tetracarboxylic dianhydride, 3, 4 ′ ?the two Tetra hydro Phthalic anhydrides or 3 of oxygen, 4, 9, 10 ?1 in perylenetetracarboxylic dianhydride ?2 kinds,
Diamines in described step (3) be 4,4 ′ ?diaminobenzophenone, 1,4 ?phenylenediamine, 4,4 ′ ?diaminodiphenyl-methane, 4,4 ′ ?diaminodiphenyl oxide, two [4 ?(the 4 ?ammonia phenoxy group) phenyl] propane of 2,2 ?, two (4-aminophenyl) sulfone, two (the 4 ?ammonia phenoxy group) benzene of 1,4 ?, α, α ′ ?two (4 ?aminophenyl) ?1,4 ?diisopropyl benzene, 2,2 ′ ?two (trifluoromethyl) benzidines, 4,4 ′ ?benzidine, 4,4 ′ ?diamino octafluoro biphenyl, 3,3 ′ ?dihydroxybiphenyl amine, 3,3 ′ ?diaminodiphenylmethane, 3,4 ′ ?diaminodiphenyl-methane, 4,4 ′ ?Er An Ji ?3,3 ′ ?dimethyl diphenyl methane, 4,4 ′ ?methylene-bis (2 ?chloroaniline), 4,4 ′ ?methylene-bis (2 ?Yi Ji ?6 ?monomethylaniline), 3,3 ′ ?diaminobenzophenone, 1,3 ?two (3 ?amino-benzene oxygen) benzene, two (the 4 ?ammonia phenoxy group) benzene of 1,3 ?, 3,4 ′ ?diaminodiphenyl oxide, two (4 ?aminophenyl) thioether, two (3 ?aminophenyl) sulfone, two [4 ?(3 ?amino-benzene oxygen) phenyl] sulfone, two [4 ?(4 ?amino-benzene oxygen) phenyl] sulfone, 2,2 ?two (3 ?An Ji ?4 ?tolyl) HFC-236fa, 2,2 ?two [4 ?(4 ?amino-benzene oxygen) benzene] HFC-236fa, 2,2 ?two (3 ?An Ji ?4 ?hydroxyphenyl) HFC-236fa or 2,2 ?1 in two (3 ?aminophenyl) HFC-236fa ?2 kinds.
Compared with prior art, preparation method's of the present invention beneficial effect is:
(1) the present invention passes through graphene oxide modification, at Graphene surface grafting can with the group of polyimide matrix generation chemical reaction, introduced again inorganic high-temperature resistant Si element, suppressed the reunion certainly of Graphene, improved the dispersiveness of Graphene in polyimide matrix simultaneously; Chemical bonding between Graphene and polyimide matrix, increases the two bounding force, answers force transmission effect to significantly improve; The introducing of inorganic high-temperature resistant Si element, has also improved the thermostability of composite polyimide material.
(2) in functionalization graphene/composite polyimide material preparation method of the present invention, add a small amount of functionalization graphene and just can reach the effect that improves mechanical property and thermostability simultaneously, there is preparation method easy, raw material is cheap and easy to get, be convenient to the features such as industrializing implementation, also widened the Application Areas of composite polyimide material simultaneously.
(3) functionalization graphene/composite polyimide material of the present invention, the tensile strength of adding 5%Si modified graphene matrix material is increased to 153MPa from 102MPa, with respect to comparative example, improves 50%; Second-order transition temperature is brought up to 401 ℃ from 371 ℃, with respect to comparative example, improves 30 ℃; Resistance toheat is brought up to 542 ℃ from 508 ℃, with respect to comparative example, improves 34 ℃; Performance significantly improves.
Accompanying drawing explanation
Fig. 1 is the transmission electron microscope photo figure of the functionalization graphene in Graphene/composite polyimide material preparation method of the present invention.
Fig. 2 is the X ray electronic energy spectrum of Graphene/composite polyimide material preparation method gained functionalization graphene/composite polyimide material film of the present invention.
Embodiment
By specific embodiment and accompanying drawing thereof, technical scheme of the present invention is further specifically described below.
A kind of Graphene/composite polyimide material preparation method of the present invention's design (being called for short preparation method, referring to Fig. 1,2), this preparation method adopts the mass percent of following Graphene/composite polyimide material to form and concrete technology:
The mass percent of this matrix material forms and comprises: polyimide 80～99.99% and Si modified graphene 20～0.01%.Described Si modified graphene and polyimide mass percent are preferably: polyimide 95%～99.95%, Si modified graphene 5～0.05%.Research experiment shows, in preferred mass percent forms, prepared composite materials property and thermostability are even more ideal.
This preparation method's concrete technology step is:
(1) preparation of graphite oxide
Take natural flake graphite as raw material, adopt and improve Hummer legal system for graphite oxide.The described improvement Hummer method of preparing graphite oxide is prior art;
(2) preparation of Si modified graphene
Graphite oxide powder prepared by step (1) after ultrasonic 0.5～2 hour, obtains 0.5～5mg/mL graphene oxide dispersion liquid in aprotic organic solvent; In dispersion liquid, add silicone-modified reagent, at 30～180 ℃, react 1～24 hour; After washing, being dried, obtain Si modified graphene black powder; The Si modified graphene obtaining through ultimate analysis and X-ray photoelectron spectroscopic analysis, wherein Si mass content is 2～13%.
(3) Si modified graphene/polyimide precursor preparation
Si modified graphene, dianhydride and diamines are mixed in described aprotic polar solvent, under nitrogen protection ， Yu ?at 10～30 ℃, home position polymerization reaction 1～36 hour, obtains Si modified graphene/polyamic acid solution, its quality solid content is 5～40%.For obtaining superpolyamide acid, preferable reaction temperature Wei ?10～15 ℃, the preferred reaction time is 6～12 hours, the quality solid content of presoma is preferably 10～20%.
(4) preparation of Si modified graphene/composite polyimide material
By Si modified graphene/polyamic acid presoma curtain coating of preparation, 30～100 ℃ except desolventizing; Temperature programming to 100 afterwards～450 ℃, and be incubated 1～4 hour, obtain the Graphene/composite polyimide material of Si modification.
In preparation method of the present invention, described graphite is natural flake graphite, is of a size of 8000～50 orders.
In preparation method of the present invention, described Si modified graphene thickness is 0.8～1.4nm, and particle diameter is 2～60 μ m.
In preparation method of the present invention, the aprotic polar solvent in described step (2) is N, N ?dimethyl formamide, N, N ?N,N-DIMETHYLACETAMIDE, dimethyl sulfoxide (DMSO) or N ?a kind of in methyl-2-pyrrolidone.
In preparation method of the present invention, the silicone-modified reagent in described step (2) is: 3 ?aminopropyltriethoxywerene werene, 4 ?aminophenyl triethoxyl silane, 3 ?(2 ?aminoethylamino) propyl group methyl dimethoxysilane, 3 ?(2 ?aminoethyl base) propyl-triethoxysilicane, 4 ?aminophenyl triethoxyl silane, 3 ?aminopropyl diethoxymethyl silane or 3 ?1 in aminopropyl trimethoxysilane ?2 kinds.
In preparation method of the present invention, dianhydride in described step (3) is: 4, 4 ′ ?diphthalic anhydrides, 3, 3 ', 4, 4 ′ ?benzophenone tetracarboxylic dianhydride, 4, 4 ′ ?the two Tetra hydro Phthalic anhydrides of oxygen, 3, 4 ′ ?the two Tetra hydro Phthalic anhydrides of oxygen, 3, 3 ', 4, 4 ′ ?sulfobenzide tetracarboxylic acid dicarboxylic anhydride, 4, 4 ′ ?(hexafluoro isopropylidene) two anhydride phthalic acids, pyromellitic acid anhydride, 3, 3 ', 4, 4 ′ ?benzophenone tetracarboxylic dianhydride, dicyclo [2.2.2] Xin ?7 ?Xi ?2, 3, 5, 6 ?tetracarboxylic acid dianhydride, 3, 3 ', 4, 4 ′ ?sulfobenzide tetracarboxylic acid dicarboxylic anhydride, 4, 4 ′ ?(hexafluoro isopropylidene) two anhydride phthalic acids, Nai ?1, 4, 5, 8 ?tetracarboxylic dianhydride, 3, 4 ′ ?the two Tetra hydro Phthalic anhydrides or 3 of oxygen, 4, 9, 10 ?1 in perylenetetracarboxylic dianhydride ?2 kinds.
In preparation method of the present invention, the diamines in described step (3) is: 4,4 ′ ?diaminobenzophenone, 1,4 ?phenylenediamine, 4,4 ′ ?diaminodiphenyl-methane, 4,4 ′ ?diaminodiphenyl oxide, two [4 ?(the 4 ?ammonia phenoxy group) phenyl] propane of 2,2 ?, two (4 ?aminophenyl) sulfone, two (the 4 ?ammonia phenoxy group) benzene of 1,4 ?, α, α ′ ?two (4 ?aminophenyl) ?1,4 ?diisopropyl benzene, 2,2 ′ ?two (trifluoromethyl) benzidines, 4,4 ′ ?benzidine, 4,4 ′ ?diamino octafluoro biphenyl, 3,3 ′ ?dihydroxybiphenyl amine, 3,3 ′ ?diaminodiphenylmethane, 3,4 ′ ?diaminodiphenyl-methane, 4,4 ′ ?Er An Ji ?3,3 ′ ?dimethyl diphenyl methane, 4,4 ′ ?methylene-bis (2 ?chloroaniline), 4,4 ′ ?methylene-bis (2 ?Yi Ji ?6 ?monomethylaniline), 3,3 ′ ?diaminobenzophenone, 1,3 ?two (3 ?amino-benzene oxygen) benzene, two (the 4 ?ammonia phenoxy group) benzene of 1,3 ?, 3,4 ′ ?diaminodiphenyl oxide, two (4 ?aminophenyl) thioether, two (3 ?aminophenyl) sulfone, two [4 ?(3 ?amino-benzene oxygen) phenyl] sulfone, two [4 ?(4 ?amino-benzene oxygen) phenyl] sulfone, 2,2 ?two (3 ?An Ji ?4 ?tolyl) HFC-236fa, 2,2 ?two [4 ?(4 ?amino-benzene oxygen) benzene] HFC-236fa, 2,2 ?two (3 ?An Ji ?4 ?hydroxyphenyl) HFC-236fa or 2,2 ?1 in two (3 ?aminophenyl) HFC-236fa ?2 kinds.
The preparation method of Graphene/composite polyimide material of the present invention can prepare Graphene/composite polyimide material, when its quality percentage composition is polyimide 95%-99.95%, Si modified graphene 5-0.05%; Tensile strength can reach 153MPa; Second-order transition temperature can reach 401 ℃; Heat resisting temperature can reach 542 ℃, and performance significantly improves.
The present invention does not address part and is applicable to prior art.
Provide specific embodiments of the invention below.These embodiment are only not used in the protection domain of restriction the application claim for the present invention is described.Should be understood that the person skilled in the art of this area can make some nonessential improvement and adjustment to the present invention according to foregoing after having read the content of the present invention's instruction, but these equivalent form of values all should belong to the protection domain of the application's claim.
Embodiment 1
The preparation of step (1) graphene oxide:
The 325 order natural flake graphites of take are raw material, adopt and improve Hummer legal system for graphite oxide powder.
The preparation of step (2) Si modified graphene:
Take graphite oxide powder prepared in a certain amount of step (1), supersound process 1 hour, is distributed in N ?crassitude ketone solvent; Add in proportion properties-correcting agent 3 ?aminopropyl trimethoxysilane, temperature of reaction is 50 ℃, the reaction times is 20 hours, wherein graphene oxide and silicone-modified dose 3 ?the mass ratio of aminopropyltriethoxywerene werene be 1:3; After reaction finishes, by anhydrous methanol repetitive scrubbing reaction product, after filtration, obtain black objects product, in 80 ℃ of vacuum drying ovens, be dried 24 hours, obtain Si modified graphene.Through atomic force microscope, detect, the Si modified graphene thickness obtaining is 0.9nm, and particle diameter is 5～20 μ m.
The preparation of step (3) Si modified graphene/polyimide precursor:
Weigh pyromellitic acid anhydride 2.2g, 4,4 ′ ?diaminodiphenyl oxide 2.0g(mole of metering ratio be: pyromellitic acid anhydride: 4,4 ′ ?diaminodiphenyl oxide=1.01:1), Si modified graphene 4.2mg, wherein Si modified graphene and polyamic acid mass ratio are 0.1:100; First Si modified graphene is joined to 24g N, N ?in dimethyl formamide, supersound process 1 hour; Add afterwards 4,4 ′ ?diaminodiphenyl oxide, in ice-water bath, mechanical stirring 2 hours is to 4,4 ′ ?diaminodiphenyl oxide all dissolve, add pyromellitic acid anhydride in batches again, after reinforced end, continue to stir 12 hours, it is 0 ℃ that this stage keeps temperature of reaction, after reaction finishes, obtain thick precursor solution.
The preparation of step (4) Si modified graphene/composite polyimide material:
By the Si modified graphene/polyamic acid presoma curtain coating described in step (3), in 50 ℃ of baking ovens, dry 12 hours except desolventizing; With 3 ℃/min of temperature rise rates, be warming up to 100,200,300 ℃ afterwards, and each temperature constant temperature 1 hour, make Si modified graphene/composite polyimide material.
After testing, the fundamental property of the present embodiment matrix material is: tensile strength 90MPa, 520 ℃ of thermostabilitys (5% mass loss).
Embodiment 2
The present embodiment as different from Example 1, in step (2) graphene oxide and silicone-modified dose 3 ?the mass ratio of aminopropyltriethoxywerene werene be 1:5, other is identical with embodiment 1.
Embodiment 3
The present embodiment as different from Example 1, in step (2) graphene oxide and silicone-modified dose 3 ?the mass ratio of aminopropyltriethoxywerene werene be 1:10, other is identical with embodiment 1.
Embodiment 4
The present embodiment as different from Example 1, in step (2) graphene oxide and silicone-modified dose 3 ?the mass ratio of aminopropyltriethoxywerene werene be 1:15, other is identical with embodiment 1.
Embodiment 5
The present embodiment as different from Example 1, in step (2) graphene oxide and silicone-modified dose 3 ?the mass ratio of aminopropyltriethoxywerene werene be 1:20, other is identical with embodiment 1.
Embodiment 6
The present embodiment as different from Example 1, in step (2) graphene oxide and silicone-modified dose 3 ?the mass ratio of aminopropyltriethoxywerene werene be 1:25, other is identical with embodiment 1.
After testing, Si modified graphene/composite polyimide material performance of embodiment 1～6 preparation is listed in table 1:
Si modified graphene/composite polyimide material performance table of table 1 embodiment 1～6 preparation
a: the content of Si element in Si modified graphene.
From embodiment 1～6 detected result, can find out, along with the increase of Si constituent content in Si modified graphene, the mechanical property of the Si modified graphene/composite polyimide material of preparation first rises and declines afterwards, and second-order transition temperature and thermostability continue to increase.Comprehensive analysis: in the Si modified graphene described in preparation method of the present invention, Si element mass content is preferably 4.6～10.2%.
Embodiment 7
The present embodiment as different from Example 4 middle temperature of reaction of step (2) is 80 ℃, and other is identical with embodiment 4.
Embodiment 8
The present embodiment as different from Example 4 middle temperature of reaction of step (2) is 100 ℃, and other is identical with embodiment 4.
Embodiment 9
The present embodiment as different from Example 4 middle temperature of reaction of step (2) is 120 ℃, and other is identical with embodiment 4.
Embodiment 10
The present embodiment as different from Example 4 middle temperature of reaction of step (2) is 150 ℃, and other is identical with embodiment 4.
After testing, the prepared Si modified graphene/composite polyimide material performance of embodiment 7～10 is listed in table 2:
Si modified graphene/composite polyimide material performance table of table 2 embodiment 7～10 preparations
a: the content of Si element in Si modified graphene.
From embodiment 7～10 detected results, can find out, along with the rising of temperature of reaction, in Si modified graphene, the mass content of Si element remains unchanged substantially, and mechanical property, second-order transition temperature and thermal characteristics also change not quite.Therefore from save energy and security standpoint, consider, in preparation method's step of the present invention (2), temperature of reaction preferred range is 50～100 ℃.
Embodiment 11
The preparation of step (1) graphene oxide:
The 325 order natural flake graphites of take are raw material, adopt and improve Hummer legal system for graphite oxide.
The preparation of step (2) Si modified graphene:
Take graphite oxide powder prepared in a certain amount of step (1), supersound process is distributed in N ?crassitude ketone solvent for 1 hour.Add in proportion properties-correcting agent 3 ?aminopropyl trimethoxysilane, temperature of reaction is 80 ℃, the reaction times is 20 hours.Wherein graphene oxide and silicone-modified dose 3 ?the mass ratio of aminopropyltriethoxywerene werene be 1:15.After reaction finishes, by anhydrous methanol repetitive scrubbing reaction product, after filtration, obtain black objects product, in 80 ℃ of vacuum drying ovens, be dried 24 hours, obtain Si modified graphene.Through atomic force microscope, detect, the Si modified graphene thickness obtaining is 1.1nm, and particle diameter is 5～20 μ m.
The preparation of step (3) Si modified graphene/polyimide precursor:
In the present embodiment, the preparation method of Si modified graphene/polyamic acid presoma is with step (3) in embodiment 1.
The preparation of step (4) Si modified graphene/composite polyimide material:
In the present embodiment, the preparation method of Si modified graphene/polyimide material is with step (4) in embodiment 1.
Embodiment 12
The present embodiment and embodiment 11 differences are, in the preparation of step (2) Si modified graphene, the reaction times is 5 hours, and other is identical with embodiment 11.
Embodiment 13
The present embodiment and embodiment 11 differences are, in the preparation of step (2) Si modified graphene, the reaction times is 10 hours, and other is identical with embodiment 11.
Embodiment 14
The present embodiment and embodiment 11 differences are, in the preparation of step (2) Si modified graphene, the reaction times is 15 hours, and other is identical with embodiment 11.
Embodiment 15
The present embodiment and embodiment 11 differences are, in the preparation of step (2) Si modified graphene, the reaction times is 24 hours, and other is identical with embodiment 11.
After testing, the prepared Si modified graphene/composite polyimide material performance of embodiment 11～15 is listed in table 3:
Table 3
a: the content of Si element in Si modified graphene.
From embodiment 11～15 detected results, can find out the increase along with the reaction times, in Si modified graphene, Si constituent content is increase trend, consider mechanics, thermal characteristics and economy and the experiment safety of prepared Si modified graphene/composite polyimide material, in the preparation process of step of the present invention (2) Si modified graphene, preferred reaction time range is 10～20 hours.
Embodiment 16
The preparation of step (1) graphene oxide:
The 100 order natural flake graphites of take are raw material, adopt and improve Hummer legal system for graphite oxide.
The preparation of step (2) Si modified graphene:
Take graphite oxide powder prepared in a certain amount of step (1), supersound process is distributed in N ?crassitude ketone solvent for 1 hour.Add in proportion properties-correcting agent 3 ?aminopropyl trimethoxysilane, temperature of reaction is 80 ℃, the reaction times is 20 hours.Wherein graphene oxide and silicone-modified dose 3 ?the mass ratio of aminopropyltriethoxywerene werene be 1:15.After reaction finishes, by anhydrous methanol repetitive scrubbing reaction product, after filtration, obtain black objects product, in 80 ℃ of vacuum drying ovens, be dried 24 hours, obtain Si modified graphene.Through atomic force microscope, detect, the Si modified graphene thickness obtaining is 1.2nm, and particle diameter is 15～30 μ m.
The preparation of step (3) Si modified graphene/polyimide precursor:
Weigh pyromellitic acid anhydride 2.2g, 4,4 ′ ?diaminodiphenyl oxide 2.0g(mole of metering ratio be: pyromellitic acid anhydride: 4,4 ′ ?diaminodiphenyl oxide=1.01:1), Si modified graphene 12.6mg, wherein Si modified graphene and polyamic acid mass ratio are 0.3:100.First Si modified graphene is joined to 24g N, N ?in dimethyl formamide, supersound process 1 hour; Add afterwards 4,4 ′ ?diaminodiphenyl oxide, in ice-water bath mechanical stirring 2 hours to 4,4 ′ ?diaminodiphenyl oxide all dissolve, then add pyromellitic acid anhydride in batches.After reinforced end, continue to stir 12 hours, it is 0 ℃ that this stage keeps temperature of reaction, after reaction finishes, obtains thick precursor solution.
The preparation of step (4) Si modified graphene/composite polyimide material:
By the Si modified graphene/polyamic acid presoma curtain coating film forming described in step (3), in 50 ℃ of baking ovens, dry 12 hours, except desolventizing; With 3 ℃/min of temperature rise rates, be warming up to 100,200,300 ℃ afterwards, and each temperature constant temperature 1 hour, obtain Si modified graphene/composite polyimide material.
Embodiment 17
The present embodiment and embodiment 16 differences are that in the preparation process of step (3) Si modified graphene/polyamic acid presoma, the mass ratio of Si modified graphene and polyamic acid is 0.5:100, and other are identical with embodiment 16.
Embodiment 18
The present embodiment and embodiment 16 differences are that in the preparation process of step (3) Si modified graphene/polyamic acid presoma, the mass ratio of Si modified graphene and polyamic acid is 1:100, and other are identical with embodiment 16.
Embodiment 19
The present embodiment and embodiment 16 differences are that in the preparation process of step (3) Si modified graphene/polyamic acid presoma, the mass ratio of Si modified graphene and polyamic acid is 5:100, and other are identical with embodiment 16.
Embodiment 20
The present embodiment and embodiment 16 differences are that in the preparation process of step (3) Si modified graphene/polyamic acid presoma, the mass ratio of Si modified graphene and polyamic acid is 10:100, and other are identical with embodiment 16.
Embodiment 21
The present embodiment and embodiment 16 differences are that in the preparation process of step (3) Si modified graphene/polyamic acid presoma, the mass ratio of Si modified graphene and polyamic acid is 15:100, and other are identical with embodiment 16.
After testing, the prepared Si modified graphene/composite polyimide material performance of embodiment 16～21 is listed in table 4:
Table 4
a: the content of Si element in Si modified graphene
From embodiment 16～21, detecting data can find out, increase along with Si modified graphene content, the mechanical property of Si modified graphene/composite polyimide material and second-order transition temperature sharply decline after first rising, and this is because Si modified graphene occurs due to serious reunion in polyimide matrix.The preferred Si modified graphene of the present invention and polyimide matrix mass percent are Si modified graphene: 0.05%～5%; Polyimide: 99.95%～95%.
Embodiment 22
The present embodiment as different from Example 1 in step (2) silicone-modified dose be 3 ?aminopropyltriethoxywerene werene and 4 ?aminophenyl triethoxyl silane.Wherein graphene oxide, silicone-modified dose 3 ?aminopropyltriethoxywerene werene and silicone-modified dose 4 ?the mass ratio of aminophenyl triethoxyl silane be 1:3:3, other is identical with embodiment 1.
Embodiment 23
The present embodiment as different from Example 22 in step (2) silicone-modified dose be 3 ?aminopropyltriethoxywerene werene and 4 ?aminophenyl triethoxyl silane.Wherein graphene oxide, silicone-modified dose 3 ?aminopropyltriethoxywerene werene and silicone-modified dose 4 ?the mass ratio of aminophenyl triethoxyl silane be 1:3:6, other is identical with embodiment 22.
Embodiment 24
The present embodiment as different from Example 22 in step (2) silicone-modified dose be 3 ?aminopropyltriethoxywerene werene and 4 ?aminophenyl triethoxyl silane.Wherein graphene oxide, silicone-modified dose 3 ?aminopropyltriethoxywerene werene and silicone-modified dose 4 ?the mass ratio of aminophenyl triethoxyl silane be 1:3:12, other is identical with embodiment 22.
Embodiment 25
The present embodiment as different from Example 22 in step (2) silicone-modified dose be 3 ?aminopropyltriethoxywerene werene and 4 ?aminophenyl triethoxyl silane.Wherein graphene oxide, silicone-modified dose 3 ?aminopropyltriethoxywerene werene and silicone-modified dose 4 ?the mass ratio of aminophenyl triethoxyl silane be 1:3:18, other is identical with embodiment 22.
Embodiment 26
The present embodiment as different from Example 22 in step (2) silicone-modified dose be 3 ?aminopropyltriethoxywerene werene and 4 ?aminophenyl triethoxyl silane.Wherein graphene oxide, silicone-modified dose 3 ?aminopropyltriethoxywerene werene and silicone-modified dose 4 ?the mass ratio of aminophenyl triethoxyl silane be 1:3:24, other is identical with embodiment 22.
After testing, the performance of the prepared Si modified graphene/composite polyimide material of embodiment 22～26 is listed in table 5:
Table 5
a: the content of Si element in Si modified graphene.
From embodiment 22～26, detecting data can find out, the introducing of the second properties-correcting agent, and the mechanical property of Si modified graphene/composite polyimide material, second-order transition temperature and thermal characteristics all improve a lot, and this is relevant with the attribute of properties-correcting agent own.Preferential oxidation Graphene of the present invention and silicone-modified dose 3 ?aminopropyltriethoxywerene werene and silicone-modified dose 4 ?the mass ratio of aminophenyl triethoxyl silane be 1:3:3～18.
Embodiment 27
The preparation of step (1) graphite oxide:
The 100 order natural graphites of take are raw material, adopt and improve Hummer legal system for graphite oxide.
The preparation of step (2) Si modified graphene:
In the present embodiment, the preparation method of Si modified graphene is identical with the preparation method of Si modified graphene in embodiment 4 steps (2).Through atomic force microscope, detect, Si modified graphene thickness is 1.1nm, and particle diameter is 5～20 μ m.
The preparation of step (3) Si modified graphene/polyimide precursor:
Weigh pyromellitic acid anhydride 2.2g, 4,4 ′ ?diaminodiphenyl oxide 1.98g, 4,4 ′ ?diaminobenzophenone 0.02g, mole metering of acid anhydrides and diamines is than being 1.01:1, wherein 4,4 ′ ?diaminodiphenyl oxide and 4,4 ′ ?mole metering ratio of diaminobenzophenone be: 99:1.Si modified graphene 12.6mg, Si modified graphene and polyamic acid mass ratio are 0.3:100.First Si modified graphene is joined to 24g N, N ?in dimethyl formamide, supersound process 1 hour; Add afterwards 4,4 ′ ?diaminodiphenyl oxide and 4,4 ′ ?diaminobenzophenone, in ice-water bath mechanical stirring 2 hours to 4,4 ′ ?diaminodiphenyl oxide and 4,4 ′ ?diaminobenzophenone all dissolve, then add pyromellitic acid anhydride in batches.After reinforced end, continue to stir 12 hours, it is 0 ℃ that this stage keeps temperature of reaction, after reaction finishes, obtains thick precursor solution.
The preparation of step (4) Si modified graphene/composite polyimide material:
In the present embodiment, the preparation method of Si modified graphene/polyimide composite film is identical with the preparation method of Si modified graphene/composite polyimide material in embodiment 4 steps (4).
Embodiment 28
The present embodiment is as different from Example 27 in step (3) Si modified graphene/polyimide precursor preparation process, 4,4 ′ ?diaminodiphenyl oxide and 4,4 ′ ?diaminobenzophenone mole metering than being 97:3, other are identical with embodiment 27.
Embodiment 29
The present embodiment is as different from Example 27 in step (3) Si modified graphene/polyimide precursor preparation process, 4,4 ′ ?diaminodiphenyl oxide and 4,4 ′ ?diaminobenzophenone mole metering than being 95:5, other are identical with embodiment 27.
Embodiment 30
The present embodiment is as different from Example 27 in step (3) Si modified graphene/polyimide precursor preparation process, 4,4 ′ ?diaminodiphenyl oxide and 4,4 ′ ?diaminobenzophenone mole metering than being 85:15, other are identical with embodiment 27.
Embodiment 31
The present embodiment is as different from Example 27 in step (3) Si modified graphene/polyimide precursor preparation process, 4,4 ′ ?diaminodiphenyl oxide and 4,4 ′ ?diaminobenzophenone mole metering than being 80:20, other are identical with embodiment 27.
After testing, the prepared Si modified graphene/composite polyimide material performance of embodiment 27～31 is listed in table 6:
Table 6
a: the content of Si element in Si modified graphene.
Consider mechanics, thermal characteristics and the Financial cost of matrix material, in the present invention preferably 4,4 ′ ?diaminodiphenyl oxide and 4,4 ′ ?diaminobenzophenone mole metering than being 99:1～90:10.
Embodiment 32
The present embodiment is as different from Example 29 in step (3) Si modified graphene/polyimide precursor preparation process, and the mass ratio of Si modified graphene and polyamic acid is 0.5:100, and other are identical with embodiment 29.
Embodiment 33
The present embodiment is as different from Example 29 in step (3) Si modified graphene/polyimide precursor preparation process, and the mass ratio of Si modified graphene and polyamic acid is 1:100, and other are identical with embodiment 29.
Embodiment 34
The present embodiment is as different from Example 29 in step (3) Si modified graphene/polyimide precursor preparation process, and the mass ratio of Si modified graphene and polyamic acid is 5:100, and other are identical with embodiment 29.
Embodiment 35
The present embodiment is as different from Example 29 in step (3) Si modified graphene/polyimide precursor preparation process, and the mass ratio of Si modified graphene and polyamic acid is 10:100, and other are identical with embodiment 29.
Embodiment 36
The present embodiment is as different from Example 29 in step (3) Si modified graphene/polyimide precursor preparation process, and the mass ratio of Si modified graphene and polyamic acid is 20:100, and other are identical with embodiment 29.
After testing, the prepared Si modified graphene/composite polyimide material performance of embodiment 32～36 is listed in table 7:
Table 7
a: the content of Si element in Si modified graphene.
Embodiment 37
The preparation of step (1) graphite oxide:
The 100 order natural graphites of take are raw material, adopt and improve Hummer legal system for graphite oxide.
The preparation of step (2) Si modified graphene:
The preparation method of the present embodiment Si modified graphene is identical with the preparation method of embodiment 22 steps (2) Si modified graphene.Through atomic force microscope, detect, Si modified graphene thickness is 1.2nm, and particle diameter is 5～26 μ m.
The preparation of step (3) Si modified graphene/polyimide precursor:
The preparation method of the present embodiment Si modified graphene/polyimide precursor is identical with embodiment 29 steps (3) Si modified graphene/polyimide precursor preparation method.
The preparation of step (4) Si modified graphene/composite polyimide material:
In the present embodiment, the preparation method of Si modified graphene/polyimide composite film is identical with the preparation method of Si modified graphene/composite polyimide material in embodiment 29 steps (4).
Embodiment 38
The present embodiment is as different from Example 37 in the preparation process of step (2) Si modified graphene, graphene oxide, silicone-modified dose 3 ?aminopropyltriethoxywerene werene and silicone-modified dose 4 ?the mass ratio of aminophenyl triethoxyl silane be 1:3:6, other is identical with embodiment 37.
Embodiment 39
The present embodiment is as different from Example 37 in the preparation process of step (2) Si modified graphene, graphene oxide, silicone-modified dose 3 ?aminopropyltriethoxywerene werene and silicone-modified dose 4 ?the mass ratio of aminophenyl triethoxyl silane be 1:3:12, other is identical with embodiment 37.
Embodiment 40
The present embodiment is as different from Example 37 in the preparation process of step (2) Si modified graphene, graphene oxide, silicone-modified dose 3 ?aminopropyltriethoxywerene werene and silicone-modified dose 4 ?the mass ratio of aminophenyl triethoxyl silane be 1:3:18, other is identical with embodiment 37.
Embodiment 41
The present embodiment is as different from Example 37 in the preparation process of step (2) Si modified graphene, graphene oxide, silicone-modified dose 3 ?aminopropyltriethoxywerene werene and silicone-modified dose 4 ?the mass ratio of aminophenyl triethoxyl silane be 1:3:24, other is identical with embodiment 37.
After testing, the prepared Si modified graphene/composite polyimide material performance of embodiment 37～41 is listed in table 8:
Table 8
a: the content of Si element in Si modified graphene.
Comparative example 1
, its concrete preparation process comprises the synthetic of polyamic acid presoma and later stage hot imidization processing.
The preparation of step (1) polyamic acid presoma:
Take 2.0g4,4 ′ ?diaminodiphenyl oxide join 24g N, N ?in dimethyl formamide, in ice-water bath, mechanical stirring within 2 hours, make 4,4 ′ ?diaminodiphenyl oxide fully dissolve.Add afterwards 2.2g pyromellitic acid anhydride, this elementary reaction system temperature remains on 0 ℃ in batches, continues to stir 12 hours, obtains yellow viscous liquid.
The preparation of step (2) polyimide material:
The thick solution of polyimide precursor described in step (1) is carried out to casting film-forming, in 50 ℃ of baking ovens, dry 12 hours, afterwards with the temperature programming to 100 of 3 ℃/min temperature rise rate, 200,300 ℃, and respectively keep 1 hour, make the abundant imidization of polyimide material.
The fundamental property of this comparative example 1 material: tensile strength 80MPa, second-order transition temperature: 384 ℃, thermostability (5% mass loss): 497.9 ℃.
Comparative example 2
Another kind of polyimide, its concrete preparation process comprises the synthetic of polyamic acid presoma and later stage hot imidization processing.
The preparation of step (1) polyamic acid presoma:
Weigh pyromellitic acid anhydride 2.2g, 4,4 ′ ?diaminodiphenyl oxide 1.9g, 4,4 ′ ?diaminobenzophenone 0.1g, mole metering of acid anhydrides and diamines is than being 1.01:1, wherein 4,4 ′ ?diaminodiphenyl oxide and 4,4 ′ ?mole metering ratio of diaminobenzophenone be: 95:5, join 24g N, N ?in dimethyl formamide, in ice-water bath, mechanical stirring makes 4 in 2 hours, 4 ′ ?diaminodiphenyl oxide and 4,4 ′ ?diaminobenzophenone fully dissolve.Add afterwards 2.2g pyromellitic acid anhydride, this elementary reaction system temperature remains on 0 ℃ in batches, continues to stir 12 hours, obtains yellow viscous liquid.
The preparation of step (2) polyimide material:
The thick solution of polyimide precursor described in step (1) is carried out to casting film-forming, in 50 ℃ of baking ovens, dry 12 hours, afterwards with the temperature programming to 100 of 3 ℃/min temperature rise rate, 200,300 ℃, and respectively keep 1 hour, make the abundant imidization of polyimide material.
The fundamental property of this comparative example 2 materials: tensile strength 102MPa, second-order transition temperature: 371 ℃, thermostability (5% mass loss): 508.4 ℃.
Claims (9)
1. Graphene/composite polyimide material preparation method, this preparation method adopts following matrix material mass percent to form and technique, and the mass percent of this matrix material forms and comprises: polyimide 80-99.99% and Si modified graphene 20-0.01%;
This preparation method's concrete technology step is:
(1) preparation of graphite oxide
Take natural flake graphite as raw material, adopt and improve Hummer legal system for graphite oxide powder; Graphite is natural flake graphite, is of a size of 8000-50 order;
(2) preparation of Si modified graphene
The graphite oxide powder of preparation after ultrasonic 0.5-2 hour, is obtained to 0.5-5mg/mL graphene oxide dispersion liquid in aprotic organic solvent; In dispersion liquid, add silicone-modified reagent, at 30-180 ℃, react 1-24 hour; After washing, being dried, obtain Si modified graphene powder, Si mass content is wherein 2-13%; Si modified graphene thickness is 0.8-1.4nm, and particle diameter is 2-60 μ m;
(3) Si modified graphene/polyimide precursor preparation
Si modified graphene, dianhydride and diamines are mixed in described aprotic polar solvent, nitrogen protection and-10-30 ℃ at home position polymerization reaction 1-36 hour, obtain Si modified graphene/polymeric amide presoma acid solution, its quality solid content is 5-40%;
(4) preparation of Si modified graphene/composite polyimide material
By Si modified graphene/polyamic acid presoma curtain coating of preparation, 30-100 ℃ except desolventizing; Temperature programming is afterwards to 100-450 ℃, and is incubated 1-4 hour, makes the Graphene/composite polyimide material of Si modification;
Aprotic organic solvent in described step (2) is a kind of in DMF, N,N-dimethylacetamide, dimethyl sulfoxide (DMSO) or N-Methyl pyrrolidone;
Silicone-modified reagent in described step (2) is: the 1-2 kind in APTES, 4-aminophenyl triethoxyl silane, 3-(2-aminoethylamino) propyl group methyl dimethoxysilane, 3-(2-aminoethyl base) propyl-triethoxysilicane, 4-aminophenyl triethoxyl silane, 3-aminopropyl diethoxymethyl silane or 3-aminopropyl trimethoxysilane;
Dianhydride in described step (3) is 4, 4'-diphthalic anhydrides, 3, 3', 4, 4'-benzophenone tetracarboxylic dianhydride, 4, the two Tetra hydro Phthalic anhydrides of 4'-oxygen, 3, the two Tetra hydro Phthalic anhydrides of 4'-oxygen, 3, 3', 4, 4'-sulfobenzide tetracarboxylic acid dicarboxylic anhydride, 4, 4'-(hexafluoro isopropylidene) two anhydride phthalic acids, pyromellitic acid anhydride, 3, 3', 4, 4'-benzophenone tetracarboxylic dianhydride, dicyclo [2.2.2] is pungent-7-alkene-2, 3, 5, 6-tetracarboxylic acid dianhydride, 3, 3', 4, 4'-sulfobenzide tetracarboxylic acid dicarboxylic anhydride, 4, 4'-(hexafluoro isopropylidene) two anhydride phthalic acids, naphthalene-1, 4, 5, 8-tetracarboxylic dianhydride, 3, the two Tetra hydro Phthalic anhydrides or 3 of 4'-oxygen, 4, 9, 1-2 kind in 10-perylenetetracarboxylic dianhydride,
Diamines in described step (3) is 4,4'-diaminobenzophenone, Isosorbide-5-Nitrae-phenylenediamine, 4,4'-diaminodiphenyl-methane, 4,4'-diaminodiphenyl oxide, two [4-(the 4-ammonia phenoxy group) phenyl] propane of 2,2-, two (4-aminophenyl) sulfone, Isosorbide-5-Nitrae-bis-(4-ammonia phenoxy group) benzene, α, α '-bis-(4-aminophenyl)-Isosorbide-5-Nitrae-diisopropyl benzene, two (trifluoromethyl) benzidines of 2,2'-, 4,4'-benzidine, 4,4'-diamino octafluoro biphenyl, 3,3'-dihydroxybiphenyl amine, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenyl-methane, 4,4'-diamino-3,3'-dimethyl diphenyl methane, 4,4'-methylene-bis (2-chloroaniline), 4,4'-methylene-bis (2-ethyl-6-monomethylaniline), 3,3'-diaminobenzophenone, two (3-amino-benzene oxygen) benzene of 1,3-, two (the 4-ammonia phenoxy group) benzene of 1,3-, 3,4'-diaminodiphenyl oxide, two (4-aminophenyl) thioether, two (3-aminophenyl) sulfone, two [4-(3-amino-benzene oxygen) phenyl] sulfone, two [4-(4-amino-benzene oxygen) phenyl] sulfone, two (3-amino-4-tolyl) HFC-236fa of 2,2-, two [4-(4-amino-benzene oxygen) benzene] HFC-236fa of 2,2-, 1-2 kind in two (3-amino-4-hydroxyphenyl) HFC-236fa of 2,2-or two (3-aminophenyl) HFC-236fa of 2,2-.
2. the preparation method of Graphene/composite polyimide material according to claim 1, is characterized in that described Si modified graphene and polyimide mass percent are polyimide 95-99.95%, Si modified graphene 5-0.05%.
3. the preparation method of Graphene/composite polyimide material according to claim 1, is characterized in that in described (3) step process, and temperature of reaction is-10-15 ℃, and the reaction times is 6-12 hour, and quality solid content is 10-20%.
4. the preparation method of Graphene/composite polyimide material according to claim 1, is characterized in that in described Si modified graphene, the mass content of Si element is 4.6-10.2%.
5. the preparation method of Graphene/composite polyimide material according to claim 1, is characterized in that the temperature of reaction in described step (2) is 50-100 ℃.
6. the preparation method of Graphene/composite polyimide material according to claim 1, is characterized in that, in the preparation process of described step (2) Si modified graphene, the reaction times is 10-20 hour.
7. the preparation method of Graphene/composite polyimide material according to claim 1, it is characterized in that the silicone-modified reagent adding in described step (2) is APTES and 4-aminophenyl triethoxyl silane, and the mass ratio of graphene oxide and silicone-modified dose of APTES and 4-aminophenyl triethoxyl silane is 1:3:3-18.
8. the preparation method of Graphene/composite polyimide material according to claim 1, it is characterized in that the diamines adding in described step (3) is 4,4'-diaminodiphenyl oxide and 4,4'-diaminobenzophenone, and both mole meterings are than being 99:1-90:10.
9. described in claim 1-8 any one, the preparation method of Graphene/composite polyimide material prepares the Graphene/composite polyimide material of gained, and its quality percentage composition is polyimide 95-99.95%, Si modified graphene 5-0.05%; Tensile strength is 153MPa; Second-order transition temperature is 401 ℃; Heat resisting temperature is 542 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310554749.6A CN103589154A (en) | 2013-11-08 | 2013-11-08 | Preparation method for graphene/polyimide composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310554749.6A CN103589154A (en) | 2013-11-08 | 2013-11-08 | Preparation method for graphene/polyimide composite material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103589154A true CN103589154A (en) | 2014-02-19 |
Family
ID=50079488
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310554749.6A Pending CN103589154A (en) | 2013-11-08 | 2013-11-08 | Preparation method for graphene/polyimide composite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103589154A (en) |
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104177615A (en) * | 2014-08-08 | 2014-12-03 | 合肥工业大学 | Method for preparing imide type bicyclobenzoxazine resin/ graphene oxide composite material |
| CN104788676A (en) * | 2015-04-27 | 2015-07-22 | 重庆大学 | Preparation method for low-dielectric-constant polyimide/multilayer graphene oxide composite film |
| CN105086447A (en) * | 2015-08-26 | 2015-11-25 | 苏州卓伟企业管理咨询有限公司 | Preparation method of modified graphene oxide/PI (polyimide) composite material |
| CN106750295A (en) * | 2017-02-13 | 2017-05-31 | 常州大学 | One class oh type polyimide/graphene nanocomposite material and preparation method thereof |
| CN106807255A (en) * | 2016-12-22 | 2017-06-09 | 浙江工商大学 | Three-dimensional structure TiO2Stannic oxide/graphene nano composite in-situ polymerization doped polyimide film and its preparation |
| CN106928413A (en) * | 2017-03-26 | 2017-07-07 | 天津工业大学 | A kind of method of styrene maleic anhydride copolymer graft modification Graphene |
| CN107033591A (en) * | 2016-10-11 | 2017-08-11 | 陕西科技大学 | A kind of high temperature resistance polyester imine nanometer ultrathin membrane and preparation method thereof |
| CN107556750A (en) * | 2017-07-24 | 2018-01-09 | 四川大学 | High temperature resistant polyetherimide amido composite foam material and preparation method thereof |
| CN107551835A (en) * | 2017-10-09 | 2018-01-09 | 辽宁科技大学 | The preparation method of high flux graphene oxide/polyimides mixed-matrix membrane material |
| CN107417940B (en) * | 2017-06-25 | 2018-08-24 | 远科秦皇岛节能环保科技开发有限公司 | A kind of production technology of graphene nano laminated film |
| CN109437905A (en) * | 2018-11-27 | 2019-03-08 | 宁波今山新材料有限公司 | A kind of preparation method of tear-resistant graphite film |
| CN109546137A (en) * | 2018-12-14 | 2019-03-29 | 中南民族大学 | Carbon-based supporting polyimide array and preparation method thereof and stored energy application |
| CN110218321A (en) * | 2019-06-14 | 2019-09-10 | 吉林大学 | A kind of polyamic acid and preparation method thereof, polyimides thermally conductive film and preparation method thereof |
| CN110304625A (en) * | 2019-06-25 | 2019-10-08 | 浙江福斯特新材料研究院有限公司 | Graphene induces the preparation method of the high thermal conductivity graphite film of orientation of polyimide crystallization |
| CN110903505A (en) * | 2019-11-22 | 2020-03-24 | 桂林电器科学研究院有限公司 | Graphene-enhanced polyimide composite film, preparation method thereof and artificial graphite film |
| CN112735706A (en) * | 2020-12-23 | 2021-04-30 | 晟大科技(南通)有限公司 | Preparation method of heat-conducting mica tape |
| CN113307972A (en) * | 2021-06-15 | 2021-08-27 | 中国科学院长春应用化学研究所 | Polyimide and preparation method thereof, and polyimide sealing ring and preparation method thereof |
| CN113501984A (en) * | 2021-06-25 | 2021-10-15 | 浙江中科玖源新材料有限公司 | Graphene in-situ modified polyimide film and preparation method thereof |
| CN113896470A (en) * | 2021-11-29 | 2022-01-07 | 安徽瑞联节能科技股份有限公司 | Cement-based thin felt for composite board and production process thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102153877A (en) * | 2011-02-22 | 2011-08-17 | 中国科学技术大学 | Graphene composite material and preparation method thereof |
| EP2554568A2 (en) * | 2010-04-02 | 2013-02-06 | Pusan National University Industry-University Cooperation Foundation | Polyimide nanocomposite and method for preparing same |
-
2013
- 2013-11-08 CN CN201310554749.6A patent/CN103589154A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2554568A2 (en) * | 2010-04-02 | 2013-02-06 | Pusan National University Industry-University Cooperation Foundation | Polyimide nanocomposite and method for preparing same |
| CN102153877A (en) * | 2011-02-22 | 2011-08-17 | 中国科学技术大学 | Graphene composite material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 王远: ""有机硅功能化石墨烯及其聚合物复合材料的制备和性能研究"", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104177615B (en) * | 2014-08-08 | 2016-05-11 | 合肥工业大学 | A kind of preparation method of imide-type dicyclo benzoxazine colophony/graphene oxide composite material |
| CN104177615A (en) * | 2014-08-08 | 2014-12-03 | 合肥工业大学 | Method for preparing imide type bicyclobenzoxazine resin/ graphene oxide composite material |
| CN104788676A (en) * | 2015-04-27 | 2015-07-22 | 重庆大学 | Preparation method for low-dielectric-constant polyimide/multilayer graphene oxide composite film |
| CN105086447A (en) * | 2015-08-26 | 2015-11-25 | 苏州卓伟企业管理咨询有限公司 | Preparation method of modified graphene oxide/PI (polyimide) composite material |
| CN107033591A (en) * | 2016-10-11 | 2017-08-11 | 陕西科技大学 | A kind of high temperature resistance polyester imine nanometer ultrathin membrane and preparation method thereof |
| CN106807255A (en) * | 2016-12-22 | 2017-06-09 | 浙江工商大学 | Three-dimensional structure TiO2Stannic oxide/graphene nano composite in-situ polymerization doped polyimide film and its preparation |
| CN106750295A (en) * | 2017-02-13 | 2017-05-31 | 常州大学 | One class oh type polyimide/graphene nanocomposite material and preparation method thereof |
| CN106928413A (en) * | 2017-03-26 | 2017-07-07 | 天津工业大学 | A kind of method of styrene maleic anhydride copolymer graft modification Graphene |
| CN107417940B (en) * | 2017-06-25 | 2018-08-24 | 远科秦皇岛节能环保科技开发有限公司 | A kind of production technology of graphene nano laminated film |
| CN107556750A (en) * | 2017-07-24 | 2018-01-09 | 四川大学 | High temperature resistant polyetherimide amido composite foam material and preparation method thereof |
| CN107551835A (en) * | 2017-10-09 | 2018-01-09 | 辽宁科技大学 | The preparation method of high flux graphene oxide/polyimides mixed-matrix membrane material |
| CN109437905A (en) * | 2018-11-27 | 2019-03-08 | 宁波今山新材料有限公司 | A kind of preparation method of tear-resistant graphite film |
| CN109437905B (en) * | 2018-11-27 | 2021-08-17 | 宁波今山新材料有限公司 | Preparation method of tear-resistant graphite film |
| CN109546137A (en) * | 2018-12-14 | 2019-03-29 | 中南民族大学 | Carbon-based supporting polyimide array and preparation method thereof and stored energy application |
| CN110218321A (en) * | 2019-06-14 | 2019-09-10 | 吉林大学 | A kind of polyamic acid and preparation method thereof, polyimides thermally conductive film and preparation method thereof |
| CN110304625A (en) * | 2019-06-25 | 2019-10-08 | 浙江福斯特新材料研究院有限公司 | Graphene induces the preparation method of the high thermal conductivity graphite film of orientation of polyimide crystallization |
| CN110903505A (en) * | 2019-11-22 | 2020-03-24 | 桂林电器科学研究院有限公司 | Graphene-enhanced polyimide composite film, preparation method thereof and artificial graphite film |
| CN110903505B (en) * | 2019-11-22 | 2022-05-06 | 桂林电器科学研究院有限公司 | Graphene-enhanced polyimide composite film, preparation method thereof and artificial graphite film |
| CN112735706A (en) * | 2020-12-23 | 2021-04-30 | 晟大科技(南通)有限公司 | Preparation method of heat-conducting mica tape |
| CN113307972A (en) * | 2021-06-15 | 2021-08-27 | 中国科学院长春应用化学研究所 | Polyimide and preparation method thereof, and polyimide sealing ring and preparation method thereof |
| CN113307972B (en) * | 2021-06-15 | 2022-06-07 | 中国科学院长春应用化学研究所 | Polyimide and preparation method thereof, and polyimide sealing ring and preparation method thereof |
| CN113501984A (en) * | 2021-06-25 | 2021-10-15 | 浙江中科玖源新材料有限公司 | Graphene in-situ modified polyimide film and preparation method thereof |
| CN113501984B (en) * | 2021-06-25 | 2023-11-21 | 浙江中科玖源新材料有限公司 | Graphene in-situ modified polyimide film and preparation method thereof |
| CN113896470A (en) * | 2021-11-29 | 2022-01-07 | 安徽瑞联节能科技股份有限公司 | Cement-based thin felt for composite board and production process thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103589154A (en) | Preparation method for graphene/polyimide composite material | |
| Singh et al. | Influence of surface modified MWCNTs on the mechanical, electrical and thermal properties of polyimide nanocomposites | |
| CN108276576A (en) | Carbon nanotube and graphene are covalently attached collaboration enhancing composite polyimide material and preparation method thereof | |
| EP2520607B1 (en) | Method for manufacturing a wholly aromatic polyimide powder having an antistatic or conductive property | |
| CN109438703B (en) | Black polyimide microsphere, preparation method thereof and preparation method of film containing black polyimide microsphere | |
| CN101827882B (en) | Polyimide film with improved thermal stability | |
| CN106496614B (en) | Antistatic polyimide film and preparation method thereof | |
| CN104892968A (en) | Preparation method of high-heat-conduction hexagonal boron nitride/polyimide composite material | |
| CN103589152A (en) | Preparation method for polyimide/oxidized graphene nanocomposite film | |
| CN108276577A (en) | Poly-dopamine modified lithium carbon nanotube graphene/polyimide composite material and preparation method thereof | |
| KR101284175B1 (en) | Composition for graphene/polyimide electroconductive composites, method for preparing the composites using the same and the composites prepared thereby | |
| CN109689745B (en) | High-heat-dissipation graphene-polyimide composite film with insulating property and preparation method thereof | |
| CN110172151A (en) | A kind of preparation method of graphene/carbon nano-tube/polyimide composite film | |
| CN109135554A (en) | polyimide varnish and its preparation method and application | |
| Zhang et al. | Mechanically strong polyimide aerogels cross-linked with dopamine-functionalized carbon nanotubes for oil absorption | |
| CN109021233A (en) | The high thermal stability composite polyimide material and preparation method thereof of the material of boron nitride nanometer containing amino functional | |
| Jia et al. | Chemically bonded iron carbonyl for magnetic composites based on phthalonitrile polymers | |
| CN110172170A (en) | A kind of manufacturing method of polyimides and graphene composite film | |
| CN103608392A (en) | Colored polyimide films and methods relating thereto | |
| CN109438735A (en) | A kind of high thermal conductivity polyimides based coextruded film and preparation method thereof | |
| JP2013036021A (en) | Carbon nanotube dispersant including polyamic acid | |
| CN105672025A (en) | Polyimide paper with controllable electrical property and preparation method thereof | |
| CN105542458B (en) | A kind of high-strength and high ductility polyimide resin based composites and preparation method thereof | |
| CN107286651B (en) | A kind of preparation method of Nano diamond/Kapton | |
| US9576698B2 (en) | Methods for forming polyimide-carbon nanotube composite film, and polyimide-carbon nanotube composite films formed thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20140219 |