CN108203543A - Graphene enhancing polyimide nano-composite material and preparation method and application - Google Patents
Graphene enhancing polyimide nano-composite material and preparation method and application Download PDFInfo
- Publication number
- CN108203543A CN108203543A CN201611169406.8A CN201611169406A CN108203543A CN 108203543 A CN108203543 A CN 108203543A CN 201611169406 A CN201611169406 A CN 201611169406A CN 108203543 A CN108203543 A CN 108203543A
- Authority
- CN
- China
- Prior art keywords
- nano
- graphene
- polyaniline
- composite material
- polyimide
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions 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 C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—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
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
The invention discloses a kind of graphene enhancing polyimide nano-composite materials and preparation method and application.The graphene enhancing polyimide nano-composite material is mainly compounded to form by graphene two-dimensional nano piece, polyimides and polyaniline nano fiber and/or Nano particles of polyaniline.The graphene enhancing polyimide nano-composite material of the present invention has excellent mechanical property, high temperature resistance and wear-resisting property; particularly there is low friction coefficient and wear rate; it can be applicable to space flight and aviation; the prolonged resistance to erosion wear-and corrosion-resistant field of particle, coal dust, dust, flue gas, liquid in the industries such as building, chemical industry, oil, electric power, metallurgy, ship, light textile, storage, traffic, space flight; its preparation process is simple simultaneously; raw material sources are extensive, implement conducive to scale.
Description
Technical field
Present invention relates particularly to a kind of graphene enhancing polyimide nano-composite materials and preparation method and application, belong to
In high molecule nano composite material field.
Background technology
Polyimides (PI) has excellent mechanical property, excellent thermal stability and relatively low dielectric constant, wide
It is general to apply in fields such as microelectronics, Aerospace Engineering, adhesive, fuel cells.But there is also one for polyimides itself
It is a little insufficient, therefore limit its application.Such as in space industry, the radiation of high energy particle can tire out polyimides generation charge
Product forms electric current tree, and atom oxygen energy is high, and forming " degrading " to PI ontologies reduces material mechanical performance, makes material failure.Together
When, space industry bad environments are also very high to the heat resistance requirement of material, but the temperature tolerance of polyimides can not reach in this way
Requirement；In addition, polyimides has higher friction coefficient, its application in insulating heat-conductive field is limited.
The current research in relation to composite polyimide material has very much, but the research in terms of friction and wear behavior is less.
Nowadays polyimide friction study on the modification gradually increases, and no longer as former means are single, and improvement is limited etc., mainstream is ground
Study carefully mainly from structurally-modified and composite modified two aspect, for example, from segment design angle, it is anti-in presoma polycondensation
Middle the phenylacetylene-capped dose of performed polymer for being prepared for different molecular weight should be introduced, blocking modification polyamides is prepared for using addition reaction
Imine matrix material；Secondly, from interface angle, with different filler (such as graphene, boron nitride etc.) or difference
The filler of surface modification, or gathered in a manner of chemically composited such as graphene oxide/nanometer polytetrafluoroethylcomposite compounded mix by situ
It closes or the mode that is directly blended prepares composite polyimide material.The former reacts complicated, and cost is higher, ineffective；Afterwards
Person focuses primarily upon the surface covalent bond modification of graphene, but the technology can destroy the structure of graphene, to a certain extent shadow
Ring the raising of composite property.
Invention content
It is a primary object of the present invention to provide a kind of graphene enhancing polyimide nano-composite material and its preparation side
Method and application, to overcome deficiency of the prior art.
To realize aforementioned invention purpose, the technical solution adopted by the present invention includes：
The present invention provides a kind of graphenes to enhance polyimide nano-composite material, including graphene two-dimensional nano
Piece, polyimides and polyaniline nano fiber and/or Nano particles of polyaniline.
Further, the graphene enhancing polyimide nano-composite material is sub- by graphene two-dimensional nano piece, polyamides
Amine and polyaniline nano fiber or Nanocomposites are formed.
The present invention also provides a kind of graphene enhancing polyimide nano-composite material preparation method, including：
Graphene two-dimensional nano piece with polyaniline nano fiber and/or Nano particles of polyaniline is mixed in a solvent, is obtained
Obtain the dispersion liquid of graphene two-dimensional nano piece；
The dispersion liquid of the graphene two-dimensional nano piece is mixed, and make aroma type with aroma type diamines and aroma type dianhydride
Diamines and aroma type dianhydride in-situ polymerization form Polvamide prepolymer/graphene complex, make Polvamide prepolymer later
Imidization, so as to obtain the graphene enhancing polyimide nano-composite material.
In some embodiments, the polyamides in Polvamide prepolymer/graphene complex can be made by gradient increased temperature
The imidization of amine prepolymer and obtain graphene enhancing polyimide nano-composite material.
In some embodiments, the preparation method includes：By graphene powder and/or graphene two-dimensional nano piece
It is mixed in a solvent with polyaniline nano fiber and/or Nano particles of polyaniline, obtains the dispersion of graphene two-dimensional nano piece
Liquid..
Further, aforementioned polyimides include condensation polymer type aromatic polyimide, such as preferably by aroma type diamines with
Aroma type dianhydride in-situ polymerization is formed.
The present invention also provides the application of graphene enhancing polyimide nano-composite material, for example, the graphite
Alkene enhances purposes of the polyimide nano-composite material in the preparation at least safeguard structure with anticorrosion antiwear performance.
Compared with the prior art, graphene of the invention enhancing polyimide nano-composite material has excellent mechanical property
Energy, high temperature resistance and wear-resisting property especially with low friction coefficient and wear rate, can be applicable to space flight and aviation, build,
Particle, coal dust, dust, flue gas, liquid in the industries such as chemical industry, oil, electric power, metallurgy, ship, light textile, storage, traffic, space flight
Prolonged resistance to erosion wear-and corrosion-resistant field, while its preparation process is simple, raw material sources are extensive, implement conducive to scale.
Description of the drawings
Fig. 1 is that embodiment 1-4 obtains graphene enhancing polyimide nano-composite material and comparative example 1 obtains polyimides
Measurement of Material Mechanical Performance figure；
Fig. 2 is that embodiment 1-4 obtains graphene enhancing polyimide nano-composite material and comparative example 1 obtains polyimides
The heat stability testing figure of material；
Fig. 3 is that embodiment 1-4 obtains graphene enhancing polyimide nano-composite material and comparative example 1 obtains polyimides
The vickers hardness test collection of illustrative plates of material；
Fig. 4 is that embodiment 1-4 obtains graphene enhancing polyimide nano-composite material and comparative example 1 obtains polyimides
Material graphene enhances the wear-resisting property analysis chart of polyimide nano-composite material；
Fig. 5 is that embodiment 1-4 obtains graphene enhancing polyimide nano-composite material and comparative example 1 obtains polyimides
The polishing scratch sem analysis figure of material.
Specific embodiment
In order to make technical scheme of the present invention of greater clarity, it is easy to understand, has below in conjunction with the accompanying drawings and with example
Body illustrates the present invention.It is understood, however, that example described herein is merely to illustrate and explain the present invention, it is not used to limit
The fixed present invention.
A kind of graphene enhancing polyimide nano-composite material that the one side of the embodiment of the present invention provides includes stone
Black alkene two-dimensional nano piece, polyimides and polyaniline nano fiber and/or Nano particles of polyaniline.
In some embodiments, the graphene enhances polyimide nano-composite material by graphene two-dimensional nano
Piece, polyimides and polyaniline nano fiber and/or Nano particles of polyaniline are compounded to form.
Further, in the graphene enhances polyimide nano-composite material, at least part Nano fiber polyaniline
Dimension and/or Nano particles of polyaniline are combined to form compound with graphene two-dimensional nano piece by physics mode.
In some embodiments, graphene two-dimensional nano piece in the graphene enhancing polyimide nano-composite material
Content be 0.1wt%~50wt%, especially preferably preferably 0.25wt%~10wt%, 0.25wt%~1wt%.
In some embodiments, graphene enhancing polyimide nano-composite material include 0.1wt%~
50wt% graphenes two-dimensional nano piece, 19.23wt%~76.81wt% polyimides, 0.05wt%~25wt% polyanilines are received
Rice fiber and/or Nano particles of polyaniline.
In some preferred embodiments, graphene enhancing polyimide nano-composite material include 0.25wt%~
1wt% graphenes two-dimensional nano piece, 65.38wt%~76.35wt% polyimides and 0.25wt%~1wt% polyaniline nanos
Fiber and/or Nano particles of polyaniline.
In some preferred embodiments, the graphene two-dimensional nano piece, polyaniline nano fiber and/or polyaniline are received
The mass ratio of rice corpuscles and polyimides is 0.15：76.81~15：65.38 especially preferably 0.25：76.35~1：71.15.
Further, the diameter of the polyaniline nano fiber is preferably 10~300nm, especially preferably 10~100nm.
Further, the length of the polyaniline nano fiber is preferably 0.5~5 μm, especially preferably 0.5~2 μm.
Further, the grain size of the Nano particles of polyaniline is 50~500nm, preferably 100~200nm.
Further, the material of aforementioned polyaniline nano fiber or Nano particles of polyaniline can be selected from polyaniline or alkyl
Substituted polyaniline etc., such as polyortho methylaniline, poly- o ethyl aniline, poly- adjacent propyl aniline, poly-o-phenylenediamine, poly- butyl benzene
Amine etc., and it is without being limited thereto.These polyanilines or alkyl-substituted polyaniline can be eigenstates.
Further, aforementioned polyimides includes condensation polymer type aromatic polyimide.Preferably, the polyimides is by fragrance
Type diamines is formed with aroma type dianhydride in-situ polymerization.Aforementioned fragrance type diamines includes 4,4 diaminodiphenyl ethers, 4,4 diamino join
Benzene, 3,4 diaminodiphenyl ethers etc. have the diamines of aromatic structure, and without being limited thereto.Aforementioned fragrance type dianhydride includes equal benzene tetramethyl
The acid anhydrides containing aromatic structure such as acid anhydrides, benzophenone dianhydride, biphenyl dianhydride, trimellitic anhydride, and it is without being limited thereto.
The system of a kind of graphene enhancing polyimide nano-composite material that the other side of the embodiment of the present invention provides
Preparation Method includes：
Graphene two-dimensional nano piece with polyaniline nano fiber and/or Nano particles of polyaniline is mixed in a solvent, is obtained
Obtain the dispersion liquid of graphene two-dimensional nano piece；
The dispersion liquid of the graphene two-dimensional nano piece is mixed, and make aroma type with aroma type diamines and aroma type dianhydride
Diamines and aroma type dianhydride in-situ polymerization form Polvamide prepolymer/graphene complex, make Polvamide prepolymer later
Imidization, so as to obtain the graphene enhancing polyimide nano-composite material.
In some embodiments, the preparation method includes：By graphene powder and/or graphene two-dimensional nano piece
It is mixed in a solvent with polyaniline nano fiber and/or Nano particles of polyaniline, obtains the dispersion liquid of graphene two-dimensional nano piece.
Further, in some more specific embodiment, the preparation method may also comprise：By graphene two
Dimension nanometer sheet mixes, and be ultrasonically treated in a solvent with polyaniline nano fiber and/or Nano particles of polyaniline, obtains stone
The dispersion liquid of black alkene two-dimensional nano piece.
Further, in some more specific embodiment, the preparation method may also comprise：By stirring,
The physics modes such as ultrasound, oscillation (such as (it is other suitable also to coordinate in some embodiments certainly for mechanical agitation, ultrasound
Non-physical method) by graphene powder and polyaniline nano fiber and/or Nano particles of polyaniline, simple physical is mixed in a solvent
It closes, so as to obtain the dispersion liquid of graphene two-dimensional nano piece.Certainly, in these embodiments, if graphene powder is excessive
, then also need by by graphene particles etc. existing for the forms such as sediment by removing in a manner of liquid separation, centrifugation etc., so as to obtain
Even graphene two-dimensional nano piece dispersion liquid.
For example, in a case study on implementation, butyl polyaniline nano fiber can be dissolved in DMAC, add in Graphene powder
Body, ultrasonic 1h or so, you can separate graphene two-dimensional nano piece, be dispersed in DMAC and form uniform graphene
Two-dimensional nano piece dispersion liquid.
In some embodiments, the polyamides in Polvamide prepolymer/graphene complex can be made by gradient increased temperature
The imidization of amine prepolymer and obtain graphene enhancing polyimide nano-composite material.
Further, in some more specific embodiment, the preparation method includes：By the polyamide prepolymer
Polymers/graphene complex heats 1h~4h in 100 DEG C~150 DEG C, heats 1h~4h at 200 DEG C~300 DEG C later, obtains institute
State graphene enhancing polyimide nano-composite material.
Further, in some more specifically embodiment, the preparation method can include：By the polyamides
Amine prepolymer/graphene complex is successively in 100 DEG C~120 DEG C, 150 DEG C~170 DEG C difference heated at constant temperature 1h~3h, Zhi Houyi
Inferior to 200 DEG C~220 DEG C, 250 DEG C~270 DEG C, 300 DEG C~320 DEG C difference heated at constant temperature 1h~2h, obtain the graphene and increase
Strong polyimide nano-composite material.
Further, in foregoing embodiments, the graphene powder is received with polyaniline nano fiber and/or polyaniline
The mass ratio of rice corpuscles is preferably 1：10~1：0.1, especially preferably 1：1~3：1.
Further, in foregoing embodiments, the graphene two-dimensional nano piece and polyaniline nano fiber and/or poly-
The mass ratio of aniline nano particle is preferably 1：5~2：1, especially preferably 1：1~2：1.
Further, wherein polyaniline nano fiber or nano-particle, aroma type diamines, aroma type dianhydride etc. can be as above
Described, details are not described herein again.
Further, aforementioned solvents can be selected from organic solvent, particularly preferred high boiling point polar organic solvent, such as can be excellent
Any one or more among DMAC, DMF, NMP etc., and it is without being limited thereto.
In previously-described implementation of the present invention, by polyaniline nano fiber or and/or polyaniline rice corpuscles and graphite
Physics weak interaction between alkene two-dimensional nano piece can realize graphene two-dimensional nano piece from the liquid phase on graphene powder
Method is removed, and obtained graphene two-dimensional nano piece is made to have good physical/chemical constitution, pattern, and make graphene two-dimensional nano
Piece fine dispersion in the decentralized media such as organic solvent obtains uniform and stable graphene two-dimensional nano piece dispersion liquid.And then profit
With cooperations such as the precursors of the graphene two-dimensional nano piece dispersion liquid and polyimides (aroma type diamines, aroma type dianhydride etc.), i.e.,
The graphene enhancing polyimide nano-composite material can be made, and enhance polyimide nano composite wood in the graphene
In material, graphene two-dimensional nano piece is in homodisperse state, so as to can not only effectively prevent in composite polyimide material
Middle generation charge accumulation, greatly improves the mechanical property and shielding property of composite polyimide material, and can also significantly carry
Rise thermal property (particularly high temperature resistance) and crocking resistance of composite polyimide material etc., be allowed to can also it is wear-resisting oneself
Lubriation material field generates wide application prospect.
The embodiment of the present invention additionally provides compound by the graphene enhancing polyimide nano of aforementioned any method preparation
Material.
The present invention also provides the purposes of graphene enhancing polyimide nano-composite material, such as preparing at least
Purposes in safeguard structure with performances such as anticorrosion antiwears etc..
For example, can by the uncured Polvamide prepolymer graphene nanometer composite by casting film-forming, spraying,
Spin coating, printing, blade coating etc. mode are applied to substrate surface, and heat cure later or photocuring form protective coating.
For example, also can using in the form of sheets, the graphene of the forms such as bulk enhancing polyimide nano-composite material as
Protective materials uses.
Technical scheme of the present invention will be described in further detail with reference to several embodiments as follows.In following examples
Polyaniline, polyortho methylaniline, poly- adjacent propyl aniline, poly-o-phenylenediamine, poly- butylaniline for using etc. can be used known to industry
Mode produce or bought from commercially available approach.
1 the present embodiment of embodiment, which is related to a kind of graphene, enhances polyimide nano-composite material (in the composite material
Graphene content is 0.25wt%, abbreviation 0.25%G/PI), preparation method includes the following steps：
The synthesis of poly- butylaniline nanofiber：Butylaniline monomer is dissolved in 1M hydrochloric acid, later by equimolar amounts
Ammonium persulfate is added in above-mentioned solution and stands 24 hours at room temperature, a diameter of 50nm is obtained after being filtered, washed, length is
5 μm of polyaniline nano fiber adds in hydration hydrazinolysis doping, is washed with distilled water 3 times, the poly- fourth of eigenstate is obtained after dry later
Base aniline nano-fiber (abbreviation polyaniline nano fiber).
Weigh aforementioned polyaniline nano fiber (0.01g), graphene two-dimensional nano piece (0.01g) and solvent N, N dimethyl
Acetamide (28mL) mixing ultrasound one hour adds in 4,4 diaminodiphenyl ethers (2.00g) and equal in obtained mixed solution later
Benzene tetracarboxylic acid acid anhydride (2.18g), mechanical agitation for 24 hours, obtains Polvamide prepolymer graphene nano and answers in nitrogen atmosphere under room temperature
Object is closed, Polvamide prepolymer graphene nanometer composite is positioned on heated at constant temperature platform at 100 DEG C, 150 DEG C to each constant temperature adds
Hot 1h to remove a large amount of solvent DMAC, is subsequently placed to Muffle furnace each heated at constant temperature 1h at 200 DEG C, 250 DEG C, 300 DEG C, from
And realize fully imidization, obtain graphene enhancing polyimide nano-composite material.
2 the present embodiment of embodiment, which is related to a kind of graphene, enhances polyimide nano-composite material (in the composite material
Graphene content is 0.5wt%, abbreviation 0.5%G/PI), preparation process includes：
Weigh polyortho methylaniline nanofiber (0.02g, a diameter of 50nm, length are 5 μm), graphene two-dimensional nano piece
(0.02g) and solvent n,N dimethylformamide (28mL) mixing ultrasound one hour, adds in 4,4 diaminos in obtained mixed solution
Yl diphenyl ether (2.00g) and biphenyl dianhydride (2.18g), mechanical agitation for 24 hours, obtains polyamide pre-polymerization in nitrogen atmosphere under room temperature
Polvamide prepolymer graphene nanometer composite is positioned on heated at constant temperature platform at 100 DEG C by object graphene nanometer composite,
Each heated at constant temperature 1h at 150 DEG C to remove a large amount of solvent DMAC, is subsequently placed to Muffle furnace at 200 DEG C, 250 DEG C, 300 DEG C
Each heated at constant temperature 1h so as to fulfill fully imidization, obtains graphene enhancing polyimide nano-composite material.
3 the present embodiment of embodiment, which is related to a kind of graphene, enhances polyimide nano-composite material (in the composite material
Graphene content is 1wt%, abbreviation 1%G/PI), preparation process includes：
Weigh poly-o-phenylenediamine nanofiber (0.04g, a diameter of 80nm, length are 5 μm), graphene two-dimensional nano piece
(0.04g) and solvent N, N dimethyl acetamide (28mL) mixing ultrasound one hour, adds in 4,4 diaminos in obtained mixed solution
Yl diphenyl ether (2.00g) and trimellitic anhydride (2.18g), mechanical agitation for 24 hours, obtains polyamide prepolymer in nitrogen atmosphere under room temperature
Polvamide prepolymer graphene nanometer composite is positioned on heated at constant temperature platform at 100 DEG C by polymers graphene nanometer composite,
Each heated at constant temperature 1h at 150 DEG C to remove a large amount of solvent DMAC, is subsequently placed to Muffle furnace at 200 DEG C, 250 DEG C, 300 DEG C
Each heated at constant temperature 1h so as to fulfill fully imidization, obtains graphene enhancing polyimide nano-composite material.
4 the present embodiment of embodiment, which is related to a kind of graphene, enhances polyimide nano-composite material (in the composite material
Graphene content is 2wt%, abbreviation 2%G/PI), preparation process includes：
Weigh poly- adjacent propyl aniline nano-fiber (0.08g, a diameter of 60nm, length are 2 μm), graphene two-dimensional nano piece
(0.08g) and solvent methyl pyrrolidones (28mL) mixing ultrasound one hour, adds in 4,4 diamino two in obtained mixed solution
Phenylate (2.00g) and benzophenone dianhydride (2.18g), mechanical agitation for 24 hours, obtains Polvamide prepolymer in nitrogen atmosphere under room temperature
Polvamide prepolymer graphene nanometer composite is positioned on heated at constant temperature platform at 100 DEG C, 150 by graphene nanometer composite
Each heated at constant temperature 1h at DEG C to remove a large amount of solvent DMAC, is subsequently placed to Muffle furnace each perseverance at 200 DEG C, 250 DEG C, 300 DEG C
Temperature heating 1h so as to fulfill fully imidization, obtains graphene enhancing polyimide nano-composite material.
5 the present embodiment of embodiment, which is related to a kind of graphene, enhances polyimide nano-composite material (in the composite material
Graphene content is 1wt%, abbreviation 1%G/PI), preparation process includes：
Weigh poly-o-phenylenediamine nano-particle (0.08g, grain size 200nm), graphene two-dimensional nano piece (0.08g) and molten
Agent N, N dimethyl acetamide (28mL) mixing ultrasound one hour, adds in 4,4 diaminodiphenyl ethers in obtained mixed solution
(2.00g) and benzophenone dianhydride (2.18g), mechanical agitation for 24 hours, obtains Polvamide prepolymer graphite in nitrogen atmosphere under room temperature
Polvamide prepolymer graphene nanometer composite is positioned on heated at constant temperature platform at 100 DEG C, 150 DEG C by alkene nano-complex
Each heated at constant temperature 1h to remove a large amount of solvent DMAC, is subsequently placed to Muffle furnace each constant temperature at 200 DEG C, 250 DEG C, 300 DEG C and adds
Hot 1h so as to fulfill fully imidization, obtains graphene enhancing polyimide nano-composite material.
The preparation process of a kind of pure polyimide material that 1 comparative example of comparative example is related to includes：
4,4 diaminodiphenyl ethers (2.00g), pyromellitic dianhydride (2.18g) are placed in solvent N, N dimethyl acetamide
Mixed liquor is obtained in (28mL), mechanical agitation for 24 hours, obtains Polvamide prepolymer in nitrogen atmosphere under room temperature, by polyamide
Prepolymer is positioned on heated at constant temperature platform each heated at constant temperature 1h at 100 DEG C, 150 DEG C, to remove a large amount of solvent DMAC, then puts
Each heated at constant temperature 1h at 200 DEG C, 250 DEG C, 300 DEG C is placed in Muffle furnace, so as to fulfill fully imidization, obtains polyamides Asia
Amine material (pure PI).
Further, Fig. 1 a- Fig. 1 c are that embodiment 1-4 obtains graphene enhancing polyimide nano-composite material and compares
Example 1 obtains the mechanical performance data figure of polyimide material.It can be seen that the storage modulus of pure polyimides is about 1480MPa,
And graphene/polyimide composite film, more than 2100MPa, performance improves more than 42%；Loss modulus and storage modulus
Change similar, the enhancing of performance may be attributed to graphene/polyaniline nanofiber composite and obtained in PI matrixes well
Dispersion, the graphene sheet layer that modulus is high and aspect ratio is big can effectively prevent or inhibit polymer segment migration and
Transfer part external carbuncle；Mechanical loss shows to add in after graphene/polyaniline nanofiber composite with temperature curve
Tg decreases, and reason may be that the AT of addition affects the structure of PI so that laminated film locally lies in relatively low phase
Interreaction force.
Fig. 2 a- Fig. 2 b be embodiment 1-4 obtain graphene enhancing polyimide nano-composite material and comparative example 1 obtain it is poly-
The datagram of the thermal stability of acid imide material.It can be seen that it is degraded to T in mass fractionD10And TD50When, graphene/poly-
The heat decomposition temperature of acid imide laminated film is promoted than pure polyimides, shows the graphite for adding in good thermal stability
After alkene/polyaniline nano fiber compound, composite material thermal stability is improved.
Fig. 3 is that embodiment 1-4 obtains graphene enhancing polyimide nano-composite material and comparative example 1 obtains polyamides Asia
The hardness number test result of amine material, it can be seen that add in graphene/polyaniline nanofiber composite after, material it is hard
Degree is obviously improved.
Fig. 4 a- Fig. 4 b respectively illustrate embodiment 1-4 and obtain graphene enhancing polyimide nano-composite material and compare
Example 1 obtains the wear-resisting property analysis result of polyimide material.It can be seen that a certain amount of graphene/polyaniline nanofiber
Compound, which is incorporated into PI matrixes, can be substantially reduced average friction coefficient, and wherein graphene/polyimides of content 1wt% is multiple
Conjunction coating improvement is the most apparent, and average friction coefficient reduces 37%.And with the raising for adding in graphene content, compound painting
The wear rate of layer and average friction coefficient variation are basically identical, and when content is 0.25wt%, wear rate reduces 76%；Graphite
The incorporation of alkene/polyaniline nano fiber compound improves the thermal conductance of coating, effectively alleviates the heat generated in friction process,
Keep the mechanical performance that itself is excellent.
Fig. 5 a- Fig. 5 e respectively illustrate embodiment 1-4 and obtain graphene enhancing polyimide nano-composite material and compare
Example 1 obtains the polishing scratch sem analysis figure of polyimide material.It can be seen that the rigidity of pure polyimides is relatively small, wear scar width
It is larger；The incorporation of a certain amount of graphene/polyaniline nanofiber composite efficiently reduces wear scar width, and grinding defect morphology embodies
Go out crimp, the reason is that foring transfer membrane after adding graphene, plastic deformation occurs, be conducive to improve wearability
Energy；It can also become the increased foundation of wearability from DMA and significantly improving for thermal property.
Polyimide nano-composite material is enhanced for the graphene that embodiment 5 is obtained, test indicate that, mechanical property
Energy, thermal stability, hardness, wear-resisting property etc. are approached with embodiment 1-4, and far superior to the polyimide material of comparative example 1 and
The polyimides graphene oxide composite material of comparative example 2-3.
The preparation process of a kind of fluorination treatment graphene enhancing composite polyimide material that 2 comparative examples of comparative example are related to
Including:
By fluorination treatment graphene (0.04g), 4,4 diaminodiphenyl ethers (2.00g) and pyromellitic dianhydride (2.18g) are put
Obtain mixed liquor in solvent N, N dimethyl acetamide (30mL), under condition of ice bath in nitrogen atmosphere mechanical agitation 4h, obtain
Polvamide prepolymer graphene nanometer composite is coated on steel disc, true by Polvamide prepolymer graphene nanometer composite
80 DEG C of constant temperature 6h are heated in empty drying box, to remove a large amount of solvents, subsequent each heated at constant temperature 2h at 80 DEG C, 135 DEG C, 300 DEG C,
Finally obtain the graphene enhancing polyimides composite coating of fluorination treatment.
The preparation process of a kind of polyimides graphene oxide composite material that 3 comparative examples of comparative example are related to includes：
4,4 diaminodiphenyl ethers (2.00g) and pyromellitic dianhydride (2.16g) are added in into solvent N, N dimethyl acetamide
Mixed liquor is obtained in (40mL), mechanical agitation for 24 hours, obtains Polvamide prepolymer (PAA), takes in nitrogen atmosphere under room temperature
PAA (1g) and graphene oxide dispersion (5mg/mL) are added in solvent DMAC (5mL), and ultrasonic 6h then passes through mechanical agitation
12h, then at 80 DEG C heated at constant temperature 4h, 120 DEG C, each heated at constant temperature 2h obtains homodisperse graphene oxide at 300 DEG C
Enhance composite polyimide material.
Test through mechanical property, thermal stability, hardness, wear-resisting property etc. shows that comparative example 2 obtains the property of material
The performance difference that material can be obtained compared with embodiment 1-5 is larger, may be because being carried out in comparative example to graphene surface
Chemical modification is modified, and destroys the structure of graphene, so as to be allowed in multinomial performance, particularly in mechanical property and frictional behaviour
It is not so good as embodiment 1-5 in terms of improvement.In addition, embodiment 1-5 obtains material obtains material in performance raising compared with comparative example 3
It is also more obvious protrusion, reason may is that, comparative example 3 is the direct graphene oxide work for utilizing and not being modified processing
For filler, and direct blending method is used, graphene oxide can not uniformly disperse in the composite.
Embodiment described above is only used for the core concept that help understands the method for the present invention, and description is more specific and detailed
Carefully, but can not the limitation to the scope of the claims of the present invention therefore be interpreted as.It should be pointed out that the common skill for this field
For art personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to this hair
In bright protection domain.To a variety of modifications of these embodiments for one of skill in the art it is clear that institute herein
The General Principle of definition can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore,
The protection domain of patent of the present invention should be determined by the appended claims, without limitation on these shown in this article examples, but
Meet the range consistent with principles disclosed herein and feature.
Claims (10)
1. a kind of graphene enhances polyimide nano-composite material, it is characterised in that including graphene two-dimensional nano piece, polyamides
Imines and polyaniline nano fiber and/or Nano particles of polyaniline.
2. graphene according to claim 1 enhances polyimide nano-composite material, it is characterised in that：The graphene
Enhance polyimide nano-composite material by graphene two-dimensional nano piece, polyimides and polyaniline nano fiber and/or gather
Aniline nano particle is compounded to form；It is at least partly poly- and/or in the graphene enhances polyimide nano-composite material
Aniline nano-fiber and/or Nano particles of polyaniline are combined to form compound with graphene two-dimensional nano piece by physics mode；
And/or in the graphene enhancing polyimide nano-composite material graphene two-dimensional nano piece content for 0.1wt%~
50wt%, preferably 0.25wt%~10wt%, especially preferably 0.25wt%~1wt%.
3. graphene according to claim 1 enhances polyimide nano-composite material, it is characterised in that：The graphene
Enhance polyimide nano-composite material include 0.1wt%~50wt% graphenes two-dimensional nano piece, 19.23wt%~
76.81wt% polyimides, 0.05wt%~25wt% polyaniline nano fibers and/or Nano particles of polyaniline；Preferably, institute
It states graphene enhancing polyimide nano-composite material and includes 0.25wt%~1wt% graphenes two-dimensional nano piece, 65.38wt%
~76.35wt% polyimides and 0.25wt%~1wt% polyaniline nano fibers and/or Nano particles of polyaniline；Preferably,
The graphene two-dimensional nano piece, polyaniline nano fiber and/or the mass ratio of Nano particles of polyaniline and polyimides are
0.15：76.81~15：65.38 especially preferably 0.25：76.35~1：71.15.
4. graphene according to claim 1 enhances polyimide nano-composite material, it is characterised in that：The polyaniline
A diameter of 10~300nm of nanofiber, preferably 10~100nm；And/or the length of the polyaniline nano fiber is 0.5
~5 μm, preferably 0.5~2 μm；And/or the grain size of the Nano particles of polyaniline be 50~500nm, preferably 100~
200nm；And/or the polyimides includes condensation polymer type aromatic polyimide；Preferably, the polyimides is by aroma type two
Amine is formed with aroma type dianhydride in-situ polymerization；Preferably, the aroma type diamines includes 4,4 diaminodiphenyl ethers, 4,4 diamino
Biphenyl or 3,4 diaminodiphenyl ethers, it is preferred that the aroma type dianhydride includes pyromellitic acid anhydride, benzophenone dianhydride, connection
Benzene dianhydride or trimellitic anhydride.
5. a kind of preparation method of graphene enhancing polyimide nano-composite material, which is characterized in that including：
Graphene two-dimensional nano piece with polyaniline nano fiber and/or Nano particles of polyaniline is mixed in a solvent, obtains stone
The dispersion liquid of black alkene two-dimensional nano piece；
The dispersion liquid of the graphene two-dimensional nano piece with aroma type diamines and aroma type dianhydride is mixed, and makes aroma type diamines
And aroma type dianhydride in-situ polymerization forms Polvamide prepolymer/graphene complex, makes Polvamide prepolymer that imines occur later
Change reaction, so as to obtain the graphene enhancing polyimide nano-composite material.
6. preparation method according to claim 5, which is characterized in that the preparation method includes：By graphene powder
And/or graphene two-dimensional nano piece mixes in a solvent with polyaniline nano fiber and/or Nano particles of polyaniline, obtains graphite
The dispersion liquid of alkene two-dimensional nano piece；Preferably, the preparation method includes：By two wiener of graphene powder and/or graphene
Rice piece mixes, and be ultrasonically treated in a solvent with polyaniline nano fiber and/or Nano particles of polyaniline, obtains graphene
The dispersion liquid of two-dimensional nano piece；Preferably, the graphene powder and the polyaniline nano fiber and/or polyaniline nano grain
The mass ratio of son is 1：10~1：0.1, especially preferably 1：1~3：1；Preferably, the graphene two-dimensional nano piece with it is described
The mass ratio of polyaniline nano fiber and/or Nano particles of polyaniline is 1：5~2：1, especially preferably 1：1~2：1.
7. preparation method according to claim 5, which is characterized in that the preparation method includes：By the polyamide
Prepolymer/graphene complex heats 1h~4h in 100 DEG C~150 DEG C, heats 1h~4h at 200 DEG C~300 DEG C later, obtains
The graphene enhances polyimide nano-composite material；Preferably, the preparation method includes：By the polyamide pre-polymerization
Object/graphene complex successively in 100 DEG C~120 DEG C, 150 DEG C~170 DEG C difference heated at constant temperature 1h~3h, later successively in
It is poly- to obtain the graphene enhancing by 200 DEG C~220 DEG C, 250 DEG C~270 DEG C, 300 DEG C~320 DEG C difference heated at constant temperature 1h~2h
Acid imide nanocomposite.
8. preparation method according to claim 5, it is characterised in that：A diameter of the 10 of the polyaniline nano fiber~
300nm, preferably 10~100nm；And/or the length of the polyaniline nano fiber is 0.5~5 μm, preferably 0.5~2 μ
m；And/or the grain size of the Nano particles of polyaniline is 50~500nm, preferably 100~200nm；And/or the polyamides is sub-
Amine includes condensation polymer type aromatic polyimide；Preferably, the polyimides is by aroma type diamines and aroma type dianhydride in-situ polymerization
It is formed；Preferably, the aroma type diamines includes 4,4 diaminodiphenyl ethers, 4,4 benzidines or 3,4 diamino hexichol
Ether, it is preferred that the aroma type dianhydride includes pyromellitic acid anhydride, benzophenone dianhydride, biphenyl dianhydride or trimellitic anhydride；
And/or the solvent includes high boiling point polar organic solvent；Preferably, the solvent includes dimethylformamide, N- methyl pyrroles
Pyrrolidone or dimethylacetylamide.
9. polyimide nano-composite material is enhanced by graphene prepared by any one of claim 5-8 the methods.
10. the graphene enhancing polyimide nano-composite material described in claim 1,2,3,4 or 9 at least has anti-in preparation
Purposes in the safeguard structure of rotten wear-resisting property.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611169406.8A CN108203543B (en) | 2016-12-16 | 2016-12-16 | Graphene-reinforced polyimide nanocomposite material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611169406.8A CN108203543B (en) | 2016-12-16 | 2016-12-16 | Graphene-reinforced polyimide nanocomposite material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108203543A true CN108203543A (en) | 2018-06-26 |
| CN108203543B CN108203543B (en) | 2020-07-14 |
Family
ID=62601646
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611169406.8A Active CN108203543B (en) | 2016-12-16 | 2016-12-16 | Graphene-reinforced polyimide nanocomposite material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108203543B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113512256A (en) * | 2021-08-18 | 2021-10-19 | 苏州度辰新材料有限公司 | Antistatic polyolefin master batch and preparation method thereof |
| CN113861684A (en) * | 2021-11-20 | 2021-12-31 | 江苏科技大学 | Preparation method and application of nanosheet layer graphene reinforced polyimide composite material |
| CN113881226A (en) * | 2021-09-30 | 2022-01-04 | 浙江中科玖源新材料有限公司 | Polyimide antistatic film and preparation method thereof |
| CN114763428A (en) * | 2021-01-14 | 2022-07-19 | 中国科学院大连化学物理研究所 | Method for preparing polymer and graphene composite material, composite material and base resin obtained by method |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20240038790A (en) * | 2021-08-04 | 2024-03-25 | 룀 게엠베하 | Polymer compositions based on poly(meth)acrylimide for tribological applications |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102268134A (en) * | 2011-04-21 | 2011-12-07 | 扬中市华鑫氟塑电器设备有限公司 | Preparation method for polyimide/graphene nanocomposite material |
| CN102553462A (en) * | 2012-01-11 | 2012-07-11 | 上海理工大学 | Carbon nano tube/polyaniline/polysulfone composite ultra-filtration membrane and preparing method thereof |
| CN102911360A (en) * | 2012-11-01 | 2013-02-06 | 南京航空航天大学 | Graphene modified polyimide-based composite and preparation method thereof |
| CN102961981A (en) * | 2012-12-03 | 2013-03-13 | 浙江大学 | Preparation method of ultrafiltration membrane with enhanced antibacterial property by using modified carbon nanotubes |
| WO2013070691A2 (en) * | 2011-11-07 | 2013-05-16 | University Of Cincinnati | Nano-graphene sheet-filled polyimide composites and methods of making same |
| CN103589152A (en) * | 2013-10-21 | 2014-02-19 | 江苏大学 | Preparation method for polyimide/oxidized graphene nanocomposite film |
| CN104194335A (en) * | 2014-08-27 | 2014-12-10 | 中国科学院宁波材料技术与工程研究所 | Preparation method of polyimide/graphene composite material and product of material |
| CN104211962A (en) * | 2014-09-10 | 2014-12-17 | 北京化工大学常州先进材料研究院 | High dielectric polyimide composite material and preparation method thereof |
-
2016
- 2016-12-16 CN CN201611169406.8A patent/CN108203543B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102268134A (en) * | 2011-04-21 | 2011-12-07 | 扬中市华鑫氟塑电器设备有限公司 | Preparation method for polyimide/graphene nanocomposite material |
| WO2013070691A2 (en) * | 2011-11-07 | 2013-05-16 | University Of Cincinnati | Nano-graphene sheet-filled polyimide composites and methods of making same |
| CN102553462A (en) * | 2012-01-11 | 2012-07-11 | 上海理工大学 | Carbon nano tube/polyaniline/polysulfone composite ultra-filtration membrane and preparing method thereof |
| CN102911360A (en) * | 2012-11-01 | 2013-02-06 | 南京航空航天大学 | Graphene modified polyimide-based composite and preparation method thereof |
| CN102961981A (en) * | 2012-12-03 | 2013-03-13 | 浙江大学 | Preparation method of ultrafiltration membrane with enhanced antibacterial property by using modified carbon nanotubes |
| CN103589152A (en) * | 2013-10-21 | 2014-02-19 | 江苏大学 | Preparation method for polyimide/oxidized graphene nanocomposite film |
| CN104194335A (en) * | 2014-08-27 | 2014-12-10 | 中国科学院宁波材料技术与工程研究所 | Preparation method of polyimide/graphene composite material and product of material |
| CN104211962A (en) * | 2014-09-10 | 2014-12-17 | 北京化工大学常州先进材料研究院 | High dielectric polyimide composite material and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 闵春英等: ""耐高温GO/聚酰亚胺复合材料的制备及摩擦性能"", 《固体火箭技术》 * |
| 魏从杰等: ""聚苯胺纳米纤维/石墨烯复合物的制备及其电化学性能"", 《功能材料》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114763428A (en) * | 2021-01-14 | 2022-07-19 | 中国科学院大连化学物理研究所 | Method for preparing polymer and graphene composite material, composite material and base resin obtained by method |
| CN113512256A (en) * | 2021-08-18 | 2021-10-19 | 苏州度辰新材料有限公司 | Antistatic polyolefin master batch and preparation method thereof |
| CN113881226A (en) * | 2021-09-30 | 2022-01-04 | 浙江中科玖源新材料有限公司 | Polyimide antistatic film and preparation method thereof |
| CN113881226B (en) * | 2021-09-30 | 2023-12-05 | 浙江中科玖源新材料有限公司 | Polyimide antistatic film and preparation method thereof |
| CN113861684A (en) * | 2021-11-20 | 2021-12-31 | 江苏科技大学 | Preparation method and application of nanosheet layer graphene reinforced polyimide composite material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108203543B (en) | 2020-07-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108203543A (en) | Graphene enhancing polyimide nano-composite material and preparation method and application | |
| Ren et al. | Modification on glass fiber surface and their improved properties of fiber-reinforced composites via enhanced interfacial properties | |
| Gu et al. | Facile preparation of water-dispersible graphene sheets stabilized by carboxylated oligoanilines and their anticorrosion coatings | |
| Chen et al. | Polydopamine as an efficient and robust platform to functionalize carbon fiber for high-performance polymer composites | |
| Zhang et al. | Flame-retardant electrical conductive nanopolymers based on bisphenol F epoxy resin reinforced with nano polyanilines | |
| CN107033539B (en) | Epoxy resin boron nitride nm composite material and preparation method thereof | |
| US6479581B1 (en) | Aqueous-based polyamide-amic acid compositions | |
| KR101757084B1 (en) | Electrically conductive coatings containing graphenic carbon particles | |
| CN103108923B (en) | Conducting paint composite and use it to prepare the method for conducting film | |
| Choi et al. | Flexible and high thermal conductivity thin films based on polymer: aminated multi-walled carbon nanotubes/micro-aluminum nitride hybrid composites | |
| CN102532896A (en) | Modified graphene/polyimide resin composite material and preparation method thereof | |
| Wang et al. | New reactive rigid-rod aminated aromatic polyamide for the simultaneous strengthening and toughening of epoxy resin and carbon fiber/epoxy composites | |
| Rout et al. | In-situ generation and application of nanocomposites on steel surface for anti-corrosion coating | |
| Nie et al. | Improved dispersion of the graphene and corrosion resistance of waterborne epoxy–graphene composites by minor cellulose nanowhiskers | |
| CN108117658A (en) | The preparation method of electrostatic prevention suction agglomeration imide membrane | |
| Mohammadkhani et al. | Synthesis and characterization of polyaniline/nanodiamond hybrid nanostructures with various morphologies to enhance the corrosion protection performance of epoxy coating | |
| CN107129573B (en) | Diamond-reinforced polyimide nano composite material and preparation method and application thereof | |
| Wang et al. | Hyperbranched polybenzoxazoles incorporated polybenzoxazoles for high‐performance and low‐K materials | |
| Wang et al. | Fully aminated rigid-rod aramid reinforced high strength epoxy resin and its composite with carbon fibers | |
| Hamciuc et al. | Thermal and electrical properties of nitrile‐containing polyimide/BaTiO3 composite films | |
| Ma et al. | Preparation of self‐emulsifying waterborne polyamide‐imide sizing for carbon fiber and improvement on mechanical performances of carbon fiber reinforced thermoplastic polymer | |
| Cao et al. | A novel self-healing and removable hexagonal boron nitride/epoxy coating with excellent anti-corrosive property based on Diels-Alder reaction | |
| Dash et al. | Structural characterization of fillers of inorganic materials in bismaleimide resins | |
| An et al. | Synthesis and properties of fluorene‐based polyimide adhesives | |
| Ghosh et al. | Water-based layer-by-layer surface chemical modification of biomimetic materials: oil repellency |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |