Epoxy perylene bisimide, preparation method and application thereof, and aqueous graphene dispersion liquid

Abstract

The invention provides epoxy perylene bisimide, a preparation method and application thereof and water-based graphene dispersion liquid, and belongs to the technical field of graphene composite materials. According to the epoxy perylene bisimide provided by the invention, through the pi-pi action of the perylene bisimide and graphene and the hydrophilicity and electrostatic repulsion of a quaternary ammonium salt group, the graphene is uniformly dispersed in a solvent without agglomeration, the stability of a water-based dispersion liquid is kept, and the effective dispersion of the graphene in water is promoted; and the epoxy group of the perylene bisimide derivative (epoxy perylene bisimide) has the effect of changing the rheological property of the aqueous dispersion liquid, such as increasing the viscosity, and after the aqueous dispersion liquid is coated on the surface of a metal material, cross-linking occurs through heat treatment (150-300 DEG C, 1-5 min), so that the adsorption of graphene to the surface of the metal material is increased, and the metal material surface is further improved. And the metal-based composite material with excellent conductivity and corrosion resistance is formed.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of graphene composite materials, and particularly relates to an epoxy-based perylene imide, a preparation method and application thereof, and a water-based graphene dispersion liquid. BACKGROUND

[0002] Graphene is a two-dimensional carbon nanomaterial, and is currently known as a material with the highest carrier mobility. Graphene / metal-based composite material is a composite material in which graphene with excellent electrical conductivity and mechanical properties is used as a reinforcing phase in a metal matrix. In terms of carrier concentration and mobility of the material, graphene and metal (copper, etc.) are two types of obviously different but complementary conductor materials. Therefore, through the compounding of graphene / metal, it is expected to obtain a new material with super-high electrical conductivity and corrosion resistance by means of the compounding effect and synergistic effect.

[0003] Graphene is difficult to be processed by means of dissolution or melting, and is usually configured into a dispersion liquid for use. Common dispersion solvents are organic solvents (N-methyl pyrrolidone, ethylene glycol, etc.) and water. Among them, water as a solvent has the characteristics of green environmental protection and easy removal. Current research and technical development mostly select a surfactant to be added to water, so as to reduce the water surface tension, overcome the van der Waals force between graphene layers, and promote the dispersion of graphene. For example, a surfactant is selected to be one of sodium dodecyl benzene sulfonate (SDBS), sodium dodecyl sulfonate (SDS), dodecyl trimethyl ammonium chloride (DTAC), octadecyl trimethyl ammonium chloride (NOT), polyvinyl pyrrolidone (PVP), and polyaspartic acid sodium (PASP-Na), and a ball milling method is used for the dispersion of graphene; different types of quaternary ammonium salt surfactants are used as graphene dispersants, graphene is prepared by ultrasonic exfoliation of graphite, and the dispersibility of graphene in an aqueous solution is studied; perylene-3,4,9,10-tetracarboxylic dianhydride is used as a raw material, a series of polyethylene polyamines are refluxed in toluene, and formic acid is acidified to obtain a graphene dispersant, which can play a role in stably dispersing graphene in water, but there are problems of large amount of dispersant and low graphene concentration. The excessive amount of dispersant and the low graphene concentration are both unfavorable factors for the construction of a composite material. SUMMARY

[0004] In view of this, the present application aims to provide an epoxy-based perylene imide, a preparation method and application thereof, and a water-based graphene dispersion liquid. The epoxy-based perylene imide provided by the present application can promote the effective dispersion of graphene in water and improve the graphene concentration.

[0005] In order to achieve the above-mentioned application purposes, the present application provides the following technical solutions: The present application provides an epoxy-based perylene imide, which has a structure shown in formula I or II. Formula I, Formula II; n in Formula I is 2-16; X in Formulae I and II is chloride ion, bromide ion or iodide ion.

[0006] Preferably, the epoxy perylene imide is bis-epoxy-N,N'-bis[3-(dimethylamino)ethyl]perylene-3,4,9,10-tetracarboxylic diimide, bis-epoxy-N,N'-bis[3-(dimethylamino)propyl]perylene-3,4,9,10-tetracarboxylic diimide or bis-epoxy-N,N'-bis(4-(dimethylamino)phenyl)-3,4,9,10-perylenetetracarboxylic diimide.

[0007] The present application also provides a preparation method of the epoxy perylene imide according to the technical solution described above, comprising the following steps: mixing perylene-3,4,9,10-tetracarboxylic dianhydride and N,N-dialkyl diamine to perform a condensation reaction to obtain a condensation product; mixing the condensation product with an epoxy halogenated hydrocarbon to perform a quaternary ammonium reaction to obtain the epoxy perylene imide.

[0008] Preferably, the N,N-dialkyl diamine comprises one or more of N,N-dialkyl dialkylamine, N,N-dialkyl diphenylamine and N,N-dialkyl dinaphthylamine.

[0009] Preferably, the N,N-dialkyl dialkylamine comprises one or more of N,N-dimethylethylenediamine, N,N-dimethylpropylenediamine, N,N-dimethylbutylenediamine, N,N-diethylethylenediamine, N,N-diethylpropylenediamine and N,N-diethylbutylenediamine.

[0010] Preferably, the epoxy halogenated hydrocarbon comprises one or more of epoxy fluoropropane, epoxy chloropropane, epoxy bromopropane, epoxy iodopropane, 2-(2-bromoethyl)oxirane, 2-(3-bromopropyl)oxirane, 2-(4-chlorobutyl)oxirane, 2,2-bis(chloromethyl)oxirane, 2-(chloromethyl)-1,2-epoxybutane and 2-(chloromethyl)-1,2-epoxypropane.

[0011] Preferably, the condensation reaction is performed at a temperature of 120-180℃ for 4-10h.

[0012] The present application also provides application of the epoxy perylene imide according to the technical solution described above in the field of dispersion.

[0013] The present application also provides an aqueous graphene dispersion liquid comprising the epoxy perylene imide according to the technical solution described above, graphene and water.

[0014] Preferably, the aqueous graphene dispersion contains 0.5% to 10% graphene by mass and 0.5% to 5% epoxy perylene imide by mass.

[0015] Compared with the prior art, the beneficial effects of the present invention are as follows: This invention provides an epoxy perylene imide. Through the π-π interaction between perylene imide and graphene, as well as the hydrophilicity and electrostatic repulsion of the quaternary ammonium salt group, graphene is uniformly dispersed in a solvent without agglomeration, maintaining the stability of the aqueous dispersion and promoting effective dispersion of graphene in water. Furthermore, the epoxy group of the perylene imide derivative (epoxy perylene imide) alters the rheological properties of the aqueous dispersion, such as increasing viscosity. After being coated onto the surface of a metal material, crosslinking occurs through heat treatment (150~300℃, 1~5min), increasing the adsorption of graphene on the metal surface and forming a metal-based composite material with excellent conductivity and corrosion resistance.

[0016] The present invention also provides a method for preparing the epoxy perylene imide described in the above technical solution. The preparation method of the present invention is simple to operate and easy to implement for industrial application.

[0017] This invention also provides an aqueous graphene dispersion. By adjusting the structure of the epoxy perylene imide and its proportion in the aqueous graphene dispersion, graphene exhibits good dispersibility in water, with no agglomeration, stratification, or sedimentation, thus better utilizing the excellent properties of graphene. Furthermore, the preparation process is simple, with high production efficiency and low cost, enabling the development of a large-scale, continuous, and low-cost metal surface coating composite material production process at room temperature. Data from the examples show that the aqueous graphene dispersion prepared by this invention shows no precipitation even after standing for one month, demonstrating extremely high stability. Attached Figure Description

[0018] Figure 1 The images show the fresh aqueous graphene dispersion of Example 1 and the actual product after standing for three weeks. Detailed Implementation

[0019] This invention provides an epoxy perylene imide having the structure shown in Formula I or II: Formula I, Formula II; In Equation I, n ranges from 2 to 16; In Formulas I and II, X represents chloride ions, bromide ions, or iodide ions.

[0020] In this invention, n can specifically be 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 14 or 16.

[0021] In this invention, the epoxy perylene imide is preferably a diepoxy-N,N'-bis[3-(dimethylamino)ethyl]peryl-3,4,9,10-tetracarboxylic acid diimide (i.e., n is 2 and X is bromide ion in Formula I), a diepoxy-N,N'-bis[3-(dimethylamino)propyl]peryl-3,4,9,10-tetracarboxylic acid diimide (i.e., n is 3 and X is bromide ion in Formula I), or a diepoxy-N,N'-bis(4-(dimethylamino)phenyl)-3,4,9,10-perylenetetracarboxylic acid diimide (i.e., X is bromide ion in Formula II).

[0022] The function of the epoxy perylene imide dispersant described in this invention is to uniformly disperse graphene in the solvent through the π-π interaction between perylene imide and graphene, as well as the hydrophilicity and electrostatic repulsion of the quaternary ammonium salt group, preventing agglomeration and maintaining the stability of the aqueous dispersion. The epoxy group of the epoxy perylene imide (perylene imide derivative) changes the rheological properties of the aqueous dispersion, such as increasing the viscosity, so that it can crosslink after heat treatment after being coated onto the surface of the metal material, thereby increasing the adsorption of graphene on the surface of the metal material.

[0023] This invention also provides a method for preparing the epoxy perylene imide described in the above technical solution, comprising the following steps: Perylene-3,4,9,10-tetracarboxylic acid dianhydride and N,N-dialkyldiamine were mixed and subjected to a condensation reaction to obtain the condensation product; The condensation product is mixed with an epoxy haloalkane and subjected to a quaternization reaction to obtain the epoxy perylene imide.

[0024] Unless otherwise specified, all raw materials used in this invention are commercially available products in the field.

[0025] In this invention, perylene-3,4,9,10-tetracarboxylic dianhydride and N,N-dialkyldiamine are mixed and subjected to a condensation reaction to obtain a condensation product.

[0026] In this invention, the N,N-dialkyldiamine preferably includes one or more of N,N-dialkyldialkylamine, N,N-dialkyldiphenylamine and N,N-dialkyldinaphthylamine.

[0027] In this invention, the N,N-dialkyldialkylamine preferably includes one or more of N,N-dimethylethylenediamine, N,N-dimethylpropylenediamine, N,N-dimethylbutyldiamine, N,N-diethylethylenediamine, N,N-diethylpropylenediamine, and N,N-diethylbutyldiamine. One end of the N,N-dialkyldiamine is a primary amine group, which can react with perylene-3,4,9,10-tetracarboxylic acid dianhydride to generate perylene imide. The other end of the amine group is disubstituted, which can form a quaternary ammonium salt structure with epoxy haloalkanes, which is beneficial to the solubility of perylene imide derivatives in water.

[0028] In this invention, the molar ratio of perylene-3,4,9,10-tetracarboxylic dianhydride and N,N-dialkyldiamine is preferably 1:2.0~2.5, specifically 1:2.1~2.3.

[0029] In this invention, the preferred temperature for the condensation reaction is 120~180℃, specifically 120, 140, 160 or 180℃, and the preferred time is 4~10h, specifically 4, 6, 8 or 10h. The condensation reaction uses dimethyl sulfoxide containing 10 vol% imidazole as a solvent. After the reaction, the material is cooled to room temperature and then poured into 10 times its volume of water containing dimethyl sulfoxide. The precipitated solid is filtered and washed with ethanol to obtain the condensation product.

[0030] After obtaining the condensation product, the present invention mixes the condensation product with an epoxy haloalkane and carries out a quaternization reaction to obtain the epoxy perylene imide.

[0031] In this invention, the epoxy halide preferably includes one or more of epifluoropropane, epichlorohydrin, epibromopropane, epiiodopropane, 2-(2-bromoethyl)ethylene oxide, 2-(3-bromopropyl)ethylene oxide, 2-(4-chlorobutyl)ethylene oxide, 2,2-bis(chloromethyl)ethylene oxide, 2-(chloromethyl)-1,2-epoxybutane, and 2-(chloromethyl)-1,2-epoxypropane, wherein the epoxy halide contains an epoxy group and a halogenated hydrocarbon group.

[0032] In this invention, the molar ratio of the condensation product to the epoxide haloalkane is preferably 1:2.0~2.5, specifically 1:2.05~2.1.

[0033] In this invention, the quaternization reaction is preferably carried out at room temperature, i.e., no additional heating or cooling is required, and the reaction time is preferably 2-4 hours, specifically 2, 3, or 4 hours. Water is used as the solvent in the quaternization reaction. As the reaction proceeds, the quaternary ammonium salt product dissolves in the water, and any unreacted material is preferably removed by extraction with ethyl acetate.

[0034] The present invention also provides the application of the epoxy perylene imide described in the above technical solution in the field of dispersion.

[0035] The present invention also provides an aqueous graphene dispersion comprising the epoxy perylene imide, graphene and water described in the above technical solution.

[0036] In this invention, the mass percentage of graphene in the aqueous graphene dispersion is preferably 0.5% to 10%, specifically 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, or 10%.

[0037] In this invention, the graphene preferably includes physically processed graphene and / or chemically reduced graphene oxide.

[0038] In this invention, the mass fraction of epoxy perylene imide in the aqueous graphene dispersion is preferably 0.5% to 5%, specifically 0.5%, 0.8%, 1%, 2%, 3%, 4% or 5%.

[0039] The present invention also provides a method for preparing the aqueous graphene dispersion described in the above technical solution, comprising the following steps: subjecting the epoxy perylene imide, graphene and water to magnetic stirring and ultrasonic treatment in sequence to obtain the aqueous graphene dispersion.

[0040] In this invention, the epoxy perylene imide and water are first mixed to obtain a mixture, and then the graphene is added to the mixture to obtain the aqueous graphene dispersion.

[0041] In this invention, the solid-liquid concentration of the graphene and the mixture is preferably 5~50 mg / mL, specifically 5, 10, 20, 30, 40 or 50 mg / mL.

[0042] This invention adjusts the structure of epoxy perylene imide and its proportion in an aqueous graphene dispersion to achieve good dispersibility of graphene in water, preventing agglomeration, stratification, or sedimentation, thus better utilizing the excellent properties of graphene. Moreover, the preparation process is simple, efficient, and low-cost, enabling the development of a large-scale, continuous, and low-cost metal surface coating composite material production process at room temperature.

[0043] The present invention does not have any special limitations on the specific parameters of the magnetic stirring and ultrasonic treatment. The graphene can be dispersed evenly by means well known to those skilled in the art. Specifically, the total time of the magnetic stirring and ultrasonic treatment is preferably 4 to 24 hours, and more preferably 6 to 12 hours.

[0044] The present invention also provides the application of the aqueous graphene dispersion described in the above technical solution. Preferably, the aqueous graphene dispersion is used to form a graphene coating on the surface of a metal material. The epoxy groups in the epoxy perylene imide undergo cross-linking after being heat-treated after being coated onto the surface of the metal material, which increases the adsorption with the surface of the metal material and forms a metal matrix composite material with excellent conductivity and corrosion resistance.

[0045] In this invention, the metal preferably includes copper.

[0046] In this invention, the heat treatment temperature is preferably 150~300℃, specifically 150, 200, 250 or 300℃, and the time is preferably 1~5min, specifically 1, 2, 3, 4 or 5min.

[0047] The technical solutions of this invention will be clearly and completely described below with reference to the embodiments thereof. Obviously, the described embodiments are only a part of the embodiments of this invention, and not all of them. All other embodiments obtained by those skilled in the art based on the embodiments of this invention without creative effort are within the scope of protection of this invention.

[0048] Example 1 The preparation of bis(epoxy)-N,N'-bis[3-(dimethylamino)ethyl]perylene-3,4,9,10-tetracarboxylic acid diimide includes the following steps: The raw materials are weighed according to a molar ratio of perylene-3,4,9,10-tetracarboxylic acid dianhydride and N,N-dimethylethylenediamine of 1:2.1. Using dimethyl sulfoxide containing 10 vol% imidazole as solvent, the mixture is heated in an oil bath to 140°C and reacted for 6 h. After cooling to room temperature, the mixture is poured into 10 times its volume of water containing dimethyl sulfoxide. The precipitated solid is filtered and washed with ethanol to obtain N,N'-bis[3-(dimethylamino)ethyl]perylene-3,4,9,10-tetracarboxylic acid diimide with a yield of 90%. The raw material was weighed according to the molar ratio of the product to epoxybromopropane of 1:2.05, placed in an aqueous solution, and magnetically stirred at room temperature for 3 hours. As the reaction proceeded, the quaternary ammonium salt product dissolved in the water, and the unreacted material was removed by extraction with ethyl acetate. Finally, diepoxy-N,N'-bis[3-(dimethylamino)ethyl]perylene-3,4,9,10-tetracarboxylic acid diimide was obtained dissolved in water with a yield of 95%.

[0049] 1H NMR(400MHz, D2O): δ 2.84-2.94 [12H, 2.89 (s), 2.89 (s), 2.89 (s),2.89 (s), 2.89 (s), 2.89 (s)], 3.02-3.15 [4H, 3.08 (dd, J = 8.1, 4.3 Hz),3.08 (dd, J = 8.1, 4.3 Hz), 3.09 (dd, J = 7.7, 4.3 Hz), 3.09 (dd, J = 7.7,4.3Hz)], 3.23-3.34 [4H, 3.29 (t, J = 7.4 Hz), 3.29 (t, J = 7.4 Hz), 3.29 (t,J = 7.4 Hz), 3.29 (t, J = 7.4 Hz)], 3.46-3.58 [4H, 3.52 (d, J = 5.4 Hz), 3.52(d, J = 5.4 Hz), 3.52 (d, J = 5.4 Hz)], 3.68-3.83 [2H, 3.75 (ddt, J = 8.1,7.7, 5.4 Hz), 3.76 (ddt, J = 8.1, 7.7, 5.4 Hz)], 4.07-4.19 [4H, 4.13 (t, J =7.4 Hz), 4.13 (t, J = 7.4 Hz), 4.13 (t, J = 7.4 Hz)], 8.33-8.45 [4H, 8.39 (d,J = 5.4 Hz), 8.39 (d, J = 5.4 Hz), 8.39 (d, J = 5.4 Hz), 8.39 (d, J = 5.4Hz)], 8.55-8.67 [4H, 8.61 (dd, J = 5.4, 0.5 Hz), 8.61 (dd, J = 5.4, 0.5 Hz),8.61 (dd, J = 5.4, 0.5 Hz), 8.61 (dd, J = 5.4, 0.5 Hz)]. 13C NMR,D2O: δ 39.0(2C, s), 46.1 (2C, s), 50.3 (2C, s), 50.7 (2C, s), 50.8 (4C, s), 63.6 (2C,s), 115.6 (4C, s), 120.7-120.8 [4C, 120.8 (s), 120.8 (s)], 126.5 (4C, s), 127.8 (4C, s), 132.4 (4C, s), 161.2 (4C, s). 20 mg of physically extracted graphene was dispersed in 4 mL of an aqueous solution containing 1 wt% of diepoxy-N,N'-bis[3-(dimethylamino)ethyl]perylene-3,4,9,10-tetracarboxylic acid diimide. The solution was stirred at room temperature for 3 h and then ultrasonically dispersed for 6 h to prepare an aqueous graphene dispersion with a solid-liquid concentration of 5 mg / mL. After standing for two weeks, the aqueous graphene dispersion showed no obvious aggregation or sedimentation.

[0050] Figure 1 The images show the fresh aqueous graphene dispersion of Example 1 and the actual product after standing for three weeks. It can be seen that there is no obvious aggregation or sedimentation after standing for three weeks.

[0051] Example 2 The preparation of bis(epoxy)-N,N'-bis[3-(dimethylamino)propyl]perylene-3,4,9,10-tetracarboxylic acid diimide includes the following steps: The raw materials are weighed according to a molar ratio of perylene-3,4,9,10-tetracarboxylic acid dianhydride and N,N-dimethylpropanediamine of 1:2.1. Using dimethyl sulfoxide containing 10 vol% imidazole as solvent, the mixture is heated in an oil bath to 140°C and reacted for 6 h. After cooling to room temperature, the mixture is poured into 10 times its volume of water containing dimethyl sulfoxide. The precipitated solid is filtered and washed with ethanol to obtain N,N'-bis[3-(dimethylamino)propyl]perylene-3,4,9,10-tetracarboxylic acid diimide with a yield of 91%. The raw material was weighed according to the molar ratio of the product to epoxypropane 1:2.1, placed in an aqueous solution, and magnetically stirred at room temperature for 3 hours. As the reaction proceeded, the quaternary ammonium salt product dissolved in the water, and the unreacted material was removed by extraction with ethyl acetate. Finally, diepoxy-N,N'-bis[3-(dimethylamino)propyl]perylene-3,4,9,10-tetracarboxylic acid diimide was obtained dissolved in water with a yield of 95%.

[0052] 1H NMR (400MHz, D2O): δ 2.09-2.23 [4H, 2.16 (tt, J = 7.3, 7.1 Hz), 2.16(tt, J = 7.3, 7.1 Hz)], 2.83-2.93 [12H, 2.88 (s), 2.88 (s)], 3.02-3.17 [8H,3.08 (dd, J = 7.9, 4.3 Hz), 3.09 (dd, J = 7.9, 4.3 Hz), 3.11 (t, J = 7.3 Hz),3.11 (t, J = 7.3 Hz)], 3.46-3.57 [4H, 3.51 (d, J = 5.4 Hz), 3.51 (d, J = 5.4Hz)], 3.69-3.92 [6H, 3.75 (tt, J = 7.9, 5.4 Hz), 3.86 (t, J = 7.1 Hz), 3.86(t, J = 7.1 Hz)], 8.37 (4H, d, J = 5.5 Hz), 8.59 (4H, dd, J = 5.5, 0.5 Hz). 13 CNMR,D2O: δ 29.4 (2C, s), 39.0 (2C, s), 41.1 (2C, s), 46.1 (2C, s), 50.7 (2C,s), 50.8 (4C, s), 63.6 (2C, s), 115.6 (4C, s), 120.7-120.8 [4C, 120.8 (s),120.8 (s)], 126.5 (4C, s), 127.8 (4C, s), 132.4 (4C, s), 161.2 (4C, s). 40 mg of reduced graphene was dispersed in 4 mL of an aqueous solution containing 2 wt% diepoxy-N,N'-bis[3-(dimethylamino)propyl]perylene-3,4,9,10-tetracarboxylic acid diimide. The solution was stirred at room temperature for 4 h and then ultrasonically dispersed for 8 h to prepare an aqueous graphene dispersion with a solid-liquid concentration of 10 mg / mL. After standing for three weeks, no obvious aggregation or sedimentation was observed in the aqueous graphene dispersion.

[0053] Example 3 The preparation of bis(dimethylamino)phenyl)-3,4,9,10-perylenetetracarboxylic diimide includes the following steps: The raw materials are weighed according to a molar ratio of perylene-3,4,9,10-tetracarboxylic dianhydride and N,N-dimethyl-p-phenylenediamine of 1:2.1. Using dimethyl sulfoxide containing 10 vol% imidazole as solvent, the mixture is heated in an oil bath to 160°C and reacted for 6 h. After cooling to room temperature, the mixture is poured into 10 times its volume of water containing dimethyl sulfoxide. The precipitated solid is filtered and washed with ethanol to obtain N,N'-bis[3-(dimethylamino)phenyl]perylene-3,4,9,10-tetracarboxylic diimide with a yield of 85%. The raw material was weighed according to the molar ratio of the product to epoxypropane 1:2.1, placed in an aqueous solution, and magnetically stirred at room temperature for 3 hours. As the reaction proceeded, the quaternary ammonium salt product dissolved in the water, and the unreacted material was removed by extraction with ethyl acetate. Finally, diepoxy-N,N'-bis[3-(dimethylamino)phenyl]perylene-3,4,9,10-tetracarboxylic acid diimide was obtained dissolved in water with a yield of 90%.

[0054] 1 H NMR (400MHz, D2O): δ 2.80-2.90 [12H, 2.85 (s), 2.85 (s)], 3.03-3.22[4H, 3.10 (dd, J = 7.9, 4.3 Hz), 3.15 (dd, J = 7.9, 4.3 Hz)], 3.50-3.61 [4H,3.56 (d, J = 5.4 Hz), 3.56 (d, J = 5.4 Hz)], 3.83 (2H, tt, J = 7.9, 5.4 Hz), 7.63 (4H, ddd, J = 8.7, 1.8, 0.4 Hz), 8.16 (4H, ddd, J = 8.7, 2.2, 0.4 Hz), 8.38 (4H, d, J = 5.5 Hz), 8.59 (4H, dd, J = 5.5, 0.5 Hz). 13C NMR,D2O: δ 39.0(2C, s), 46.1 (2C, s), 50.7 (2C, s), 53.6 (4C, s), 115.6 (4C, s), 117.7 (4C,s), 120.7-120.8 [4C, 120.8 (s), 120.8 (s)], 126.5 (4C, s), 127.8 (4C, s), 132.4 (4C, s), 133.4 (4C, s), 135.4 (2C, s), 144.6 (2C, s), 161.5 (4C, s). 80 mg of reduced graphene was dispersed in 4 mL of an aqueous solution containing 3 wt% diepoxy-N,N'-bis(4-(dimethylamino)phenyl)-3,4,9,10-perylenetetracarboxydiimide. The solution was stirred at room temperature for 5 h and then ultrasonically dispersed for 10 h to prepare an aqueous graphene dispersion with a solid-liquid concentration of 20 mg / mL. After standing for three weeks, no obvious aggregation or sedimentation was observed in the aqueous graphene dispersion.

[0055] Comparative Example Using perylene-3,4,9,10-tetracarboxylic acid dianhydride (PTCDA) as a raw material, graphene dispersant HAPBI-3 was obtained by reflux reaction with triethylenetetramine in toluene and acidification with formic acid. The amount of this dispersant was 1 / 3 of the mass of graphene powder (XF 001W), resulting in an aqueous graphene dispersion with a solid-liquid concentration of 2 mg / mL.

[0056] The aqueous graphene dispersions prepared in the examples and comparative examples were sprayed onto copper substrates and then heated at 150°C for 5 minutes to obtain metal matrix composites.

[0057] The conductivity of the graphene copper-based composite material obtained in the examples is 105-107% IACS (International Annealed Copper Standard), which is higher than that of single-crystal copper (101% IACS); the conductivity of the graphene aluminum-based composite material obtained in the examples is 62-65% IACS (International Annealed Copper Standard), which is higher than that of pure aluminum (61% IACS).

[0058] As can be seen from the above, the aqueous graphene dispersion based on epoxy perylene imide provided by the present invention is composed of graphene, epoxy perylene imide dispersant and deionized water. Magnetic stirring and ultrasonic treatment make the dispersion uniform. It can be used to form a graphene coating on the surface of metal materials. After being coated onto the surface of metal materials, the epoxy groups undergo cross-linking after heat treatment, which increases the adsorption with the surface of metal materials and forms a metal matrix composite material with excellent conductivity and corrosion resistance. This enables the development of a large-scale, continuous and low-cost composite material production process at room temperature.

[0059] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. It should be noted that those skilled in the art can make various improvements and modifications without departing from the principles of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. An epoxy-based perylene imide having a structure shown in Formula I or II: Formula I wherein n is 2-16; and Formula I and II wherein X is chloride ion, bromide ion, or iodide ion. Formula I, Formula II; The epoxy-based perylene imide is bis-epoxy-N,N'-bis[3-(dimethylamino)ethyl]perylene-3,4,9,10-tetracarboxylic diimide, bis-epoxy-N,N'-bis[3-(dimethylamino)propyl]perylene-3,4,9,10-tetracarboxylic diimide, or bis-epoxy-N,N'-bis(4-(dimethylamino)phenyl)-3,4,9,10-perylenetetracarboxylic diimide. comprising the steps of:

2. The epoxy-based perylene imide according to claim 1, characterized in that, mixing perylene-3,4,9,10-tetracarboxylic dianhydride and N,N-dialkyl diamine to perform a condensation reaction to obtain a condensation product; 3. The method of preparing an epoxy perylenimide according to claim 1 or 2, characterized in that, mixing the condensation product and an epoxy halogenated hydrocarbon to perform a quaternary ammonium reaction to obtain the epoxy-based perylene imide. The N,N-dialkyl diamine includes one or more of N,N-dialkyl dialkyl amine, N,N-dialkyl diphenyl amine, and N,N-dialkyl dinaphthyl amine. The N,N-dialkyl dialkyl amine includes one or more of N,N-dimethyl ethylenediamine, N,N-dimethyl propylenediamine, N,N-dimethyl butylenediamine, N,N-diethyl ethylenediamine, N,N-diethyl propylenediamine, and N,N-diethyl butylenediamine.

4. The production method according to claim 3, characterized by, The epoxy halogenated hydrocarbon includes one or more of epoxy fluoropropane, epoxy chloropropane, epoxy bromopropane, epoxy iodopropane, 2-(2-bromoethyl)oxirane, 2-(3-bromopropyl)oxirane, 2-(4-chlorobutyl)oxirane, 2,2-bis(chloromethyl)oxirane, 2-(chloromethyl)-1,2-epoxybutane, and 2-(chloromethyl)-1,2-epoxypropane.

5. The preparation method according to claim 3, characterized in that, The condensation reaction has a temperature of 120-180 °C and a time of 4-10 h.

6. The preparation method according to claim 3, characterized in that, 8. Use of the epoxy-based perylene imide of claim 1 or 2 in the field of dispersion.

7. The preparation method according to claim 3, characterized in that, comprising the epoxy-based perylene imide of claim 1 or 2, graphene, and water. The aqueous graphene dispersion has a mass percentage of graphene of 0.5%-10% and a mass percentage of the epoxy-based perylene imide of 0.5%-5%.

9. An aqueous graphene dispersion, characterized in that, ​ 10. The aqueous graphene dispersion of claim 9, wherein, ​

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