CN108203543B - Graphene-reinforced polyimide nanocomposite material and preparation method and application thereof - Google Patents
Graphene-reinforced polyimide nanocomposite material and preparation method and application thereof Download PDFInfo
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- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
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Abstract
The invention discloses a graphene reinforced polyimide nano composite material and a preparation method and application thereof. The graphene reinforced polyimide nano composite material is mainly formed by compounding a graphene two-dimensional nano sheet, polyimide, polyaniline nano fiber and/or polyaniline nano particle. The graphene reinforced polyimide nano composite material has excellent mechanical property, high temperature resistance and wear resistance, particularly has low friction coefficient and wear rate, can be applied to the long-time scouring-resistant wear-resistant corrosion-resistant fields of particles, coal dust, smoke and liquid in the industries of aerospace, construction, chemical engineering, petroleum, electric power, metallurgy, ships, light spinning, storage, transportation, aerospace and the like, and is simple in preparation process, wide in raw material source and beneficial to large-scale implementation.
Description
Technical Field
The invention specifically relates to a graphene reinforced polyimide nano composite material and a preparation method and application thereof, and belongs to the field of polymer nano composite materials.
Background
Polyimide (PI) has excellent mechanical properties, excellent thermal stability and a low dielectric constant, and has been widely used in the fields of microelectronics, aerospace engineering, adhesives, fuel cells, and the like. However, polyimide itself has some disadvantages, thus limiting its application. For example, in the aerospace field, the radiation of high-energy particles can cause the charge accumulation of polyimide to form a current tree, the atomic oxygen energy is high, and the PI body is degraded to reduce the mechanical property of the material, so that the material fails. Meanwhile, the environment in the aerospace field is severe, the requirement on the temperature resistance of the material is high, but the temperature resistance of the polyimide cannot meet the requirement; in addition, polyimide has a high friction coefficient, which limits the application of polyimide in the field of insulation and heat conduction.
There are many studies on polyimide composites, but there are few studies on frictional wear properties. At present, the research on tribology modification of polyimide is gradually increased, the traditional method is not single, the improvement effect is limited, and the like, and the mainstream research mainly starts from two aspects of structure modification and composite modification, for example, from the view point of chain segment design, a phenylacetylene end-capping reagent is introduced into the condensation polymerization reaction of a precursor to prepare prepolymers with different molecular weights, and then an end-capping modified polyimide matrix material is prepared through an addition reaction; secondly, from the view point of interface design, the polyimide composite material is prepared by in-situ polymerization or direct blending of different fillers (such as graphene, boron nitride and the like) or different surface-modified fillers or a chemical compounding mode such as graphene oxide/nano polytetrafluoroethylene composite filler. The former has complex reaction, higher cost and poor effect; the latter mainly focuses on surface covalent bond modification of graphene, but the technology can destroy the structure of graphene, and to some extent, affects improvement of composite material performance.
Disclosure of Invention
The invention mainly aims to provide a graphene reinforced polyimide nano composite material, and a preparation method and application thereof, so as to overcome the defects in the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the invention provides a graphene reinforced polyimide nano composite material which comprises a graphene two-dimensional nano sheet, polyimide, polyaniline nano fibers and/or polyaniline nano particles.
Further, the graphene reinforced polyimide nanocomposite is formed by compounding a graphene two-dimensional nanosheet, polyimide and a polyaniline nanofiber or nanoparticle.
The invention also provides a preparation method of the graphene reinforced polyimide nano composite material, which comprises the following steps:
mixing a graphene two-dimensional nanosheet with polyaniline nanofibers and/or polyaniline nanoparticles in a solvent to obtain a dispersion liquid of the graphene two-dimensional nanosheet;
mixing the dispersion liquid of the graphene two-dimensional nanosheet with aromatic diamine and aromatic dianhydride, carrying out in-situ polymerization on the aromatic diamine and the aromatic dianhydride to form a polyamide prepolymer/graphene compound, and then carrying out imidization on the polyamide prepolymer to obtain the graphene-reinforced polyimide nanocomposite.
In some embodiments, the graphene reinforced polyimide nanocomposite may be obtained by imidizing a polyamide prepolymer in a polyamide prepolymer/graphene composite by gradient temperature elevation.
In some embodiments, the method of making comprises: and mixing the graphene powder and/or the graphene two-dimensional nanosheets and the polyaniline nanofibers and/or the polyaniline nanoparticles in a solvent to obtain a dispersion liquid of the graphene two-dimensional nanosheets. .
Further, the polyimide includes a condensation polymerization type aromatic polyimide, and is preferably formed by in-situ polymerization of an aromatic diamine and an aromatic dianhydride, for example.
The invention also provides an application of the graphene reinforced polyimide nano composite material, for example, an application of the graphene reinforced polyimide nano composite material in preparing a protective structure at least having corrosion resistance and wear resistance.
Compared with the prior art, the graphene reinforced polyimide nano composite material has excellent mechanical property, high temperature resistance and wear resistance, particularly has low friction coefficient and wear rate, can be applied to the long-time scouring-resistant wear-resistant anticorrosion fields of particles, coal dust, smoke and liquid in the industries of aerospace, construction, chemical industry, petroleum, electric power, metallurgy, ship, light spinning, storage, transportation, aerospace and the like, and is simple in preparation process, wide in raw material source and beneficial to large-scale implementation.
Drawings
FIG. 1 is a graph showing mechanical properties of the graphene reinforced polyimide nanocomposites obtained in examples 1 to 4 and the polyimide material obtained in comparative example 1;
FIG. 2 is a graph showing thermal stability tests of the graphene reinforced polyimide nanocomposites obtained in examples 1-4 and the polyimide material obtained in comparative example 1;
FIG. 3 is a graph showing Vickers hardness test patterns of the graphene reinforced polyimide nanocomposites obtained in examples 1 to 4 and the polyimide material obtained in comparative example 1;
FIG. 4 is a graph showing the analysis of the abrasion resistance of the graphene reinforced polyimide nanocomposites obtained in examples 1 to 4 and the graphene reinforced polyimide nanocomposite obtained in comparative example 1;
FIG. 5 is a SEM analysis of the wear marks of the graphene reinforced polyimide nanocomposites obtained in examples 1-4 and the polyimide material obtained in comparative example 1.
Detailed Description
In order to make the technical solution of the present invention clearer and easier to understand, the present invention is specifically described below with reference to the accompanying drawings and examples. It is to be understood, however, that the examples described herein are for the purpose of illustration and explanation only and are not intended to be limiting.
An aspect of an embodiment of the present invention provides a graphene-reinforced polyimide nanocomposite material including a graphene two-dimensional nanosheet, a polyimide, and a polyaniline nanofiber and/or a polyaniline nanoparticle.
In some embodiments, the graphene-reinforced polyimide nanocomposite is formed by compounding graphene two-dimensional nanoplatelets, polyimide, and polyaniline nanofibers and/or polyaniline nanoparticles.
Furthermore, in the graphene reinforced polyimide nanocomposite, at least part of polyaniline nanofibers and/or polyaniline nanoparticles and graphene two-dimensional nanosheets are physically combined to form a composite.
In some embodiments, the graphene-reinforced polyimide nanocomposite material contains 0.1wt% to 50wt%, preferably 0.25wt% to 10wt%, and particularly preferably 0.25wt% to 1wt% of graphene two-dimensional nanoplatelets.
In some embodiments, the graphene reinforced polyimide nanocomposite comprises 0.1 to 50wt% graphene two-dimensional nanoplatelets, 19.23 to 76.81wt% polyimide, 0.05 to 25wt% polyaniline nanofibers, and/or polyaniline nanoparticles.
In some preferred embodiments, the graphene reinforced polyimide nanocomposite comprises 0.25wt% to 1wt% of graphene two-dimensional nanoplatelets, 65.38wt% to 76.35wt% of polyimide, and 0.25wt% to 1wt% of polyaniline nanofibers and/or polyaniline nanoparticles.
In some preferred embodiments, the mass ratio of the graphene two-dimensional nanoplatelets, polyaniline nanofibers and/or polyaniline nanoparticles to polyimide is 0.15: 76.81-15: 65.38, particularly preferably 0.25: 76.35-1: 71.15.
furthermore, the diameter of the polyaniline nanofiber is preferably 10-300 nm, and particularly preferably 10-100 nm.
Furthermore, the length of the polyaniline nanofiber is preferably 0.5-5 μm, and particularly preferably 0.5-2 μm.
Furthermore, the particle size of the polyaniline nanoparticles is 50-500 nm, preferably 100-200 nm.
Further, the material of the polyaniline nanofibers or polyaniline nanoparticles may be selected from polyaniline or alkyl-substituted polyaniline, such as poly-o-toluidine, poly-o-ethylaniline, poly-o-propylaniline, poly-o-phenylenediamine, polybutylaniline, and the like, but is not limited thereto. These polyanilines or alkyl-substituted polyanilines may all be intrinsic.
Further, the aforementioned polyimide includes a condensation polymerization type aromatic polyimide. Preferably, the polyimide is formed by in-situ polymerization of an aromatic diamine and an aromatic dianhydride. The aromatic diamine includes, but is not limited to, diamines having an aromatic structure such as 4,4 diaminodiphenyl ether, 4 diaminobiphenyl, and 3,4 diaminodiphenyl ether. The aromatic dianhydride includes, but is not limited to, pyromellitic dianhydride, benzophenone dianhydride, biphenyl dianhydride, trimellitic anhydride, and other anhydrides having an aromatic structure.
Another aspect of the embodiments of the present invention provides a method for preparing a graphene-reinforced polyimide nanocomposite material, including:
mixing a graphene two-dimensional nanosheet with polyaniline nanofibers and/or polyaniline nanoparticles in a solvent to obtain a dispersion liquid of the graphene two-dimensional nanosheet;
mixing the dispersion liquid of the graphene two-dimensional nanosheet with aromatic diamine and aromatic dianhydride, carrying out in-situ polymerization on the aromatic diamine and the aromatic dianhydride to form a polyamide prepolymer/graphene compound, and then carrying out imidization on the polyamide prepolymer to obtain the graphene-reinforced polyimide nanocomposite.
In some embodiments, the method of making comprises: and mixing the graphene powder and/or the graphene two-dimensional nanosheets and the polyaniline nanofibers and/or the polyaniline nanoparticles in a solvent to obtain a dispersion liquid of the graphene two-dimensional nanosheets.
Further, in some specific embodiments, the preparation method may also include: mixing the graphene two-dimensional nanosheets and polyaniline nanofibers and/or polyaniline nanoparticles in a solvent, and performing ultrasonic treatment to obtain a dispersion liquid of the graphene two-dimensional nanosheets.
Further, in some specific embodiments, the preparation method may also include: in these embodiments, it is of course necessary to remove the graphene particles and the like existing in the form of precipitates and the like by liquid separation, centrifugation and the like if the amount of the graphene powder is excessive, so as to obtain a uniform graphene two-dimensional nanosheet dispersion.
For example, in an embodiment, the butyl polyaniline nanofibers are dissolved in DMAC, graphene powder is added, and ultrasound is performed for about 1h, so that the graphene two-dimensional nanosheets can be peeled off and uniformly dispersed in the DMAC to form a uniform graphene two-dimensional nanosheet dispersion liquid.
In some embodiments, the graphene reinforced polyimide nanocomposite may be obtained by imidizing a polyamide prepolymer in a polyamide prepolymer/graphene composite by gradient temperature elevation.
Further, in some specific embodiments, the preparation method comprises: heating the polyamide prepolymer/graphene composite at 100-150 ℃ for 1-4 h, and then heating at 200-300 ℃ for 1-4 h to obtain the graphene reinforced polyimide nanocomposite.
Further, in some more specific embodiments, the preparation method may comprise: and sequentially heating the polyamide prepolymer/graphene composite at 100-120 ℃ and 150-170 ℃ for 1-3 h at constant temperature respectively, and then sequentially heating at 200-220 ℃, 250-270 ℃ and 300-320 ℃ for 1-2 h at constant temperature respectively to obtain the graphene reinforced polyimide nanocomposite.
Further, in the foregoing embodiment, the mass ratio of the graphene powder to the polyaniline nanofibers and/or polyaniline nanoparticles is preferably 1: 10-1: 0.1, particularly preferably 1: 1-3: 1.
further, in the foregoing embodiment, the mass ratio of the graphene two-dimensional nanoplatelets to the polyaniline nanofibers and/or polyaniline nanoparticles is preferably 1: 5-2: 1, particularly preferably 1: 1-2: 1.
further, the polyaniline nanofibers or nanoparticles, the aromatic diamine, the aromatic dianhydride, etc. may be as described above, and are not described herein again.
Further, the aforementioned solvent may be selected from organic solvents, particularly preferably high-boiling polar organic solvents, for example, any one or more selected from DMAC, DMF, NMP, and the like, without being limited thereto.
In the foregoing embodiment of the present invention, by virtue of the weak physical interaction between the polyaniline nanofibers or/and the polyaniline rice particles and the graphene two-dimensional nanosheets, the graphene two-dimensional nanosheets can be peeled off from the graphene powder by a liquid phase method, and the obtained graphene two-dimensional nanosheets have good physical/chemical structure and morphology, and are well dispersed in a dispersion medium such as an organic solvent, so as to obtain a uniform and stable graphene two-dimensional nanosheet dispersion liquid. Furthermore, the graphene reinforced polyimide nanocomposite can be prepared by matching the graphene two-dimensional nanosheet dispersion liquid with a polyimide precursor (aromatic diamine, aromatic dianhydride and the like), and the like, and the graphene two-dimensional nanosheets in the graphene reinforced polyimide nanocomposite are uniformly dispersed, so that the charge accumulation in the polyimide composite can be effectively prevented, the mechanical property and the radiation resistance of the polyimide composite are greatly improved, the thermal property (especially the high temperature resistance) and the friction resistance and the like of the polyimide composite can be remarkably improved, and the graphene reinforced polyimide nanocomposite can also have a wide application prospect in the field of wear-resistant self-lubricating materials.
The embodiment of the invention also provides the graphene reinforced polyimide nano composite material prepared by any one of the methods.
The invention also provides application of the graphene reinforced polyimide nano composite material, such as application in preparing a protective structure at least having performances of corrosion resistance, wear resistance and the like.
For example, the uncured polyamide prepolymer graphene nanocomposite can be applied to a substrate surface by casting film, spraying, spin coating, printing, knife coating, and the like, followed by thermal curing or photocuring to form a protective coating.
For example, the graphene-reinforced polyimide nanocomposite material in the form of a sheet, a block, or the like may be used as a protective material.
The technical solution of the present invention will be further described in detail with reference to several embodiments as follows. Polyaniline, poly-o-toluidine, poly-o-propylaniline, poly-o-phenylenediamine, polybutylaniline, etc. used in the following examples can be obtained in a manner known in the art or commercially available.
and (3) synthesis of polybutylaniline nano-fibers: dissolving a butylaniline monomer in 1M hydrochloric acid, adding equimolar ammonium persulfate into the solution, standing for 24 hours at room temperature, filtering and washing to obtain polyaniline nano-fibers with the diameter of 50nm and the length of 5 mu M, adding hydrazine hydrate for hydrolysis and doping, washing for 3 times by using distilled water, and drying to obtain the intrinsic polybutylaniline nano-fibers (called polyaniline nano-fibers for short).
Weighing the polyaniline nanofiber (0.01g), the graphene two-dimensional nanosheet (0.01g) and a solvent N, N-dimethylacetamide (28m L), mixing and ultrasonically treating for one hour, then adding 4, 4-diaminodiphenyl ether (2.00g) and pyromellitic anhydride (2.18g) into the obtained mixed solution, mechanically stirring for 24 hours at normal temperature in a nitrogen atmosphere to obtain a polyamide prepolymer graphene nano composite, placing the polyamide prepolymer graphene nano composite on a constant-temperature heating table, heating for 1 hour at 100 ℃ and 150 ℃ respectively at constant temperature to remove a large amount of solvent DMAC, and then placing the polyamide prepolymer graphene nano composite in a muffle furnace, heating for 1 hour at 200 ℃, 250 ℃ and 300 ℃ respectively at constant temperature to implement complete imidization, thereby obtaining the graphene reinforced polyimide nano composite material.
weighing poly-o-toluidine nanofibers (0.02g, diameter of 50nm and length of 5 μm), graphene two-dimensional nanosheets (0.02g) and solvent N, N-dimethylformamide (28m L), mixing and ultrasonically treating for one hour, adding 4, 4-diaminodiphenyl ether (2.00g) and biphenyl dianhydride (2.18g) into the obtained mixed solution, mechanically stirring for 24 hours at normal temperature in a nitrogen atmosphere to obtain a polyamide prepolymer graphene nanocomposite, placing the polyamide prepolymer graphene nanocomposite on a constant temperature heating table, heating for 1 hour at 100 ℃, 150 ℃ respectively at constant temperature to remove a large amount of solvent DMAC, and then placing the polyamide prepolymer graphene nanocomposite in a muffle furnace, heating for 1 hour at 200 ℃, 250 ℃ and 300 ℃ respectively at constant temperature to realize complete imidization, thereby obtaining the graphene reinforced polyimide nanocomposite.
Embodiment 3 this embodiment relates to a graphene-reinforced polyimide nanocomposite (the graphene content in the composite is 1wt%, abbreviated as 1% G/PI), and the preparation process includes:
weighing poly-o-phenylenediamine nanofibers (0.04g, 80nm in diameter and 5 μm in length), graphene two-dimensional nanosheets (0.04g) and solvent N, N-dimethylacetamide (28m L), mixing and ultrasonically treating for one hour, adding 4, 4-diaminodiphenyl ether (2.00g) and trimellitic anhydride (2.18g) into the obtained mixed solution, mechanically stirring for 24 hours at normal temperature in a nitrogen atmosphere to obtain a polyamide prepolymer graphene nanocomposite, placing the polyamide prepolymer graphene nanocomposite on a constant-temperature heating table, heating for 1 hour at 100 ℃ and 150 ℃ respectively to remove a large amount of solvent DMAC, and then placing the polyamide prepolymer graphene nanocomposite in a muffle furnace, heating for 1 hour at 200 ℃, 250 ℃ and 300 ℃ respectively to realize complete imidization, thereby obtaining the graphene reinforced polyimide nanocomposite.
Embodiment 4 this embodiment relates to a graphene-reinforced polyimide nanocomposite (the graphene content in the composite is 2 wt%, abbreviated as 2% G/PI), and the preparation process includes:
the preparation method comprises the steps of weighing poly-o-propylaniline nanofibers (0.08g, the diameter of 60nm and the length of 2 microns), mixing graphene two-dimensional nanosheets (0.08g) and a solvent of methylpyrrolidone (28m L) for one hour by ultrasonic sound, adding 4, 4-diaminodiphenyl ether (2.00g) and benzophenone dianhydride (2.18g) into the obtained mixed solution, mechanically stirring for 24 hours in a nitrogen atmosphere at normal temperature to obtain a polyamide prepolymer graphene nanocomposite, placing the polyamide prepolymer graphene nanocomposite on a constant-temperature heating table, heating for 1 hour at 100 ℃ and 150 ℃ respectively at constant temperature to remove a large amount of solvent DMAC, and then placing the polyamide prepolymer graphene nanocomposite in a muffle furnace, heating for 1 hour at 200 ℃, 250 ℃ and 300 ℃ respectively at constant temperature to realize complete imidization, thereby obtaining the graphene reinforced polyimide nanocomposite.
weighing poly-o-phenylenediamine nanoparticles (0.08g, the particle size of 200nm), graphene two-dimensional nanosheets (0.08g) and a solvent N, N-dimethylacetamide (28m L), mixing and ultrasonically treating for one hour, adding 4, 4-diaminodiphenyl ether (2.00g) and benzophenone dianhydride (2.18g) into the obtained mixed solution, mechanically stirring for 24 hours at normal temperature in a nitrogen atmosphere to obtain a polyamide prepolymer graphene nanocomposite, placing the polyamide prepolymer graphene nanocomposite on a constant-temperature heating table, heating for 1 hour at 100 ℃ and 150 ℃ respectively at constant temperature to remove a large amount of solvent DMAC, and then placing the polyamide prepolymer graphene nanocomposite in a muffle furnace, heating for 1 hour at 200 ℃, 250 ℃ and 300 ℃ respectively at constant temperature to implement complete imidization, thereby obtaining the graphene reinforced polyimide nanocomposite.
Comparative example 1 the process for preparing a pure polyimide material according to the present comparative example comprises:
4,4 diaminodiphenyl ether (2.00g) and pyromellitic anhydride (2.18g) were placed in a solvent of N, N dimethylacetamide (28m L) to obtain a mixed solution, mechanically stirred at normal temperature under a nitrogen atmosphere for 24 hours to obtain a polyamide prepolymer, the polyamide prepolymer was placed on a constant temperature heating table and heated at 100 ℃ and 150 ℃ for 1 hour at constant temperatures to remove a large amount of DMAC (dimethylacetamide), and then placed in a muffle furnace and heated at 200 ℃, 250 ℃, and 300 ℃ for 1 hour at constant temperatures to complete imidization, thereby obtaining a polyimide material (pure PI).
Further, FIGS. 1a to 1c are graphs showing the data of mechanical properties of the graphene reinforced polyimide nanocomposites obtained in examples 1 to 4 and the polyimide material obtained in comparative example 1. As can be seen, the storage modulus of pure polyimide is about 1480MPa, and the graphene/polyimide composite film exceeds 2100MPa, so that the performance is improved by more than 42%; the loss modulus is similar to the change of the storage modulus, the performance enhancement is probably attributed to the good dispersion of the graphene/polyaniline nanofiber composite in the PI matrix, and the graphene sheet layer with high modulus and high aspect ratio can effectively prevent or inhibit the migration of a high molecular chain segment and transfer partial external stress; the relation curve of mechanical loss and temperature shows that the Tg is reduced after the graphene/polyaniline nanofiber composite is added, and the reason is probably that the added AT influences the structure of PI, so that the composite film locally has relatively low interaction force.
FIGS. 2a to 2b are graphs showing thermal stability data of the graphene reinforced polyimide nanocomposites obtained in examples 1 to 4 and the polyimide material obtained in comparative example 1. It can be seen that the degradation to T is observed in mass fractionD10And TD50In the process, the thermal decomposition temperature of the graphene/polyimide composite film is improved compared with that of pure polyimide, and the thermal stability of the composite material is improved after the graphene/polyaniline nanofiber composite with good thermal stability is added.
Fig. 3 is a hardness value test result of the graphene reinforced polyimide nanocomposites obtained in examples 1 to 4 and the polyimide material obtained in comparative example 1, and it can be seen that the hardness of the material is significantly improved after the graphene/polyaniline nanofiber composite is added.
Fig. 4a to 4b show results of abrasion resistance analysis of the graphene reinforced polyimide nanocomposites obtained in examples 1 to 4 and the polyimide material obtained in comparative example 1, respectively. It can be seen that the average friction coefficient can be obviously reduced by doping a certain amount of graphene/polyaniline nanofiber composite into the PI matrix, wherein the graphene/polyimide composite coating with the content of 1wt% is improved most obviously, and the average friction coefficient is reduced by 37%. With the increase of the content of the added graphene, the wear rate of the composite coating is basically consistent with the change of the average friction coefficient, and when the content is 0.25wt%, the wear rate is reduced by 76%; the graphene/polyaniline nanofiber composite is doped, so that the thermal conductivity of the coating is improved, the heat generated in the friction process is effectively relieved, and the excellent mechanical properties of the coating are kept.
Fig. 5a to 5e show SEM analysis graphs of wear marks of the graphene reinforced polyimide nanocomposites obtained in examples 1 to 4 and the polyimide material obtained in comparative example 1, respectively. It can be seen that the pure polyimide has relatively low rigidity and large wear scar width; the width of a grinding mark is effectively reduced by doping a certain amount of graphene/polyaniline nanofiber composite, and the appearance of the grinding mark shows extrusion deformation, because a transfer film is formed after the graphene is added, plastic deformation occurs, and the wear resistance is favorably improved; the significant improvement in DMA and thermal performance can also be the basis for the increase in abrasion resistance.
As for the graphene reinforced polyimide nanocomposite obtained in example 5, tests show that the mechanical properties, thermal stability, hardness, wear resistance and the like of the graphene reinforced polyimide nanocomposite are close to those of examples 1-4, and are far superior to those of the polyimide material in comparative example 1 and the polyimide graphene oxide composite materials in comparative examples 2-3.
Comparative example 2 the preparation process of a fluorinated graphene reinforced polyimide composite material according to the present comparative example includes:
placing fluoridation-treated graphene (0.04g), 4, 4-diaminodiphenyl ether (2.00g) and pyromellitic dianhydride (2.18g) in a solvent N, N-dimethylacetamide (30m L) to obtain a mixed solution, mechanically stirring for 4 hours in a nitrogen atmosphere under an ice bath condition to obtain a polyamide prepolymer graphene nano-composite, coating the polyamide prepolymer graphene nano-composite on a steel sheet, heating in a vacuum drying oven at 80 ℃ for 6 hours to remove a large amount of solvent, and then heating at 80 ℃, 135 ℃ and 300 ℃ for 2 hours at constant temperature respectively to obtain a fluoridation-treated graphene reinforced polyimide composite coating.
Comparative example 3 a process for preparing a polyimide graphene oxide composite material according to the present comparative example includes:
adding 4, 4-diaminodiphenyl ether (2.00g) and pyromellitic dianhydride (2.16g) into a solvent N, N-dimethylacetamide (40m L) to obtain a mixed solution, mechanically stirring for 24h at normal temperature in a nitrogen atmosphere to obtain a polyamide Prepolymer (PAA), adding PAA (1g) and a graphene oxide dispersion liquid (5mg/m L) into a solvent DMAC (5m L), performing ultrasonic treatment for 6h, mechanically stirring for 12h, and then heating at constant temperature of 80 ℃ for 4h, 120 ℃ and 300 ℃ for 2h respectively to obtain the uniformly dispersed graphene oxide reinforced polyimide composite material.
Tests on the aspects of mechanical property, thermal stability, hardness, wear resistance and the like show that the performance of the material obtained in comparative example 2 is greatly different from that of the materials obtained in examples 1-5, and the reason that the structure of graphene is damaged by chemically modifying and modifying the surface of graphene in the comparative example is probably that the material is inferior to the materials obtained in examples 1-5 in various properties, particularly the improvement on the mechanical property and the friction property. The reason why the performance of the materials obtained in examples 1 to 5 is improved more remarkably than that of the material obtained in comparative example 3 is that in comparative example 3, graphene oxide which is not subjected to modification treatment is directly used as a filler, and graphene oxide cannot be uniformly dispersed in the composite material due to the direct blending method.
The above-mentioned embodiments are only used to help understanding the core idea of the method of the present invention, and the description thereof is specific and detailed, but not to be construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the scope of the patent protection of this invention should be determined not by the examples illustrated herein, but by the appended claims, and is intended to be accorded the scope consistent with the principles and features disclosed herein.
Claims (21)
1. A graphene reinforced polyimide nano composite material is characterized by comprising 0.1-50 wt% of graphene two-dimensional nanosheets, 19.23-76.81 wt% of polyimide, and 0.05-25 wt% of polyaniline nanofibers and/or polyaniline nanoparticles; the polyaniline nano-fibers are 10-300 nm in diameter and 0.5-5 mu m in length, the polyaniline nano-particles are 50-500 nm in particle size, and at least part of the polyaniline nano-fibers and/or the polyaniline nano-particles are physically combined with the graphene two-dimensional nanosheets to form a compound.
2. The graphene reinforced polyimide nanocomposite according to claim 1, wherein: the graphene reinforced polyimide nano composite material is formed by compounding a graphene two-dimensional nano sheet, polyimide, polyaniline nano fiber and/or polyaniline nano particle.
3. The graphene reinforced polyimide nanocomposite according to claim 1, wherein: the content of the graphene two-dimensional nanosheet in the graphene reinforced polyimide nanocomposite is 0.25wt% -10 wt%.
4. The graphene reinforced polyimide nanocomposite according to claim 3, wherein: the content of the graphene two-dimensional nanosheet in the graphene reinforced polyimide nanocomposite is 0.25wt% -1 wt%.
5. The graphene reinforced polyimide nanocomposite according to claim 1, wherein: the graphene reinforced polyimide nano composite material comprises 0.25-1 wt% of graphene two-dimensional nano sheet, 65.38-76.35 wt% of polyimide and 0.25-1 wt% of polyaniline nano fiber and/or polyaniline nano particle.
6. The graphene reinforced polyimide nanocomposite according to claim 1, wherein: the mass ratio of the graphene two-dimensional nanosheets, the polyaniline nanofibers and/or the polyaniline nanoparticles to the polyimide is 0.15: 76.81-15: 65.38.
7. the graphene reinforced polyimide nanocomposite according to claim 6, wherein: the mass ratio of the graphene two-dimensional nanosheets, the polyaniline nanofibers and/or the polyaniline nanoparticles to the polyimide is 0.25: 76.35-1: 71.15.
8. the graphene reinforced polyimide nanocomposite according to claim 1, wherein: the polyaniline nanofiber is 10-100 nm in diameter and 0.5-2 mu m in length.
9. The graphene reinforced polyimide nanocomposite according to claim 1, wherein: the particle size of the polyaniline nanoparticles is 100-200 nm.
10. The graphene reinforced polyimide nanocomposite according to claim 1, wherein: the polyimide includes a condensation type aromatic polyimide.
11. The graphene reinforced polyimide nanocomposite according to claim 10, wherein: the polyimide is formed by in-situ polymerization of aromatic diamine and aromatic dianhydride.
12. The graphene reinforced polyimide nanocomposite according to claim 11, wherein: the aromatic diamine includes 4,4 diaminodiphenyl ether, 4 diaminobiphenyl or 3,4 diaminodiphenyl ether, and the aromatic dianhydride includes pyromellitic dianhydride, benzophenone dianhydride, biphenyl dianhydride or trimellitic anhydride.
13. The method of preparing the graphene-reinforced polyimide nanocomposite material according to any one of claims 1 to 12, comprising:
mixing graphene powder and/or graphene two-dimensional nanosheets and polyaniline nanofibers and/or polyaniline nanoparticles in a solvent to obtain a dispersion liquid of the graphene two-dimensional nanosheets;
mixing the dispersion liquid of the graphene two-dimensional nanosheet with aromatic diamine and aromatic dianhydride, carrying out in-situ polymerization on the aromatic diamine and the aromatic dianhydride to form a polyamide prepolymer/graphene composite, heating the polyamide prepolymer/graphene composite at 100-150 ℃ for 1-4 h, and heating at 200-300 ℃ for 1-4 h to carry out imidization reaction on the polyamide prepolymer, thereby obtaining the graphene-reinforced polyimide nanocomposite.
14. The method according to claim 13, characterized by comprising: mixing graphene powder and/or graphene two-dimensional nanosheets and polyaniline nanofibers and/or polyaniline nanoparticles in a solvent, and performing ultrasonic treatment to obtain a dispersion liquid of the graphene two-dimensional nanosheets.
15. The method of manufacturing according to claim 13, wherein: the mass ratio of the graphene powder to the polyaniline nanofiber and/or polyaniline nanoparticle is 1: 10-1: 0.1.
16. the method of claim 15, wherein: the mass ratio of the graphene powder to the polyaniline nanofiber and/or polyaniline nanoparticle is 1: 1-3: 1.
17. the method of manufacturing according to claim 16, wherein: the mass ratio of the graphene two-dimensional nanosheets to the polyaniline nanofibers and/or polyaniline nanoparticles is 1: 5-2: 1.
18. the method of claim 17, wherein: the mass ratio of the graphene two-dimensional nanosheets to the polyaniline nanofibers and/or polyaniline nanoparticles is 1: 1-2: 1.
19. the method according to claim 13, characterized by comprising: and sequentially heating the polyamide prepolymer/graphene composite at 100-120 ℃ and 150-170 ℃ for 1-3 h at constant temperature respectively, and then sequentially heating at 200-220 ℃, 250-270 ℃ and 300-320 ℃ for 1-2 h at constant temperature respectively to obtain the graphene reinforced polyimide nanocomposite.
20. The method of manufacturing according to claim 13, wherein: the solvent includes a high boiling polar organic solvent.
21. The method of claim 20, wherein: the solvent comprises dimethylformamide, N-methylpyrrolidone or dimethylacetamide.
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| 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 |
| 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 |
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