CN108408718B - Arylation graphene film and preparation method thereof, and arylation graphene barrier film and preparation method thereof - Google Patents
Arylation graphene film and preparation method thereof, and arylation graphene barrier film and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the field of films, in particular to an arylation graphene film and a preparation method thereof, and an arylation graphene barrier film and a preparation method thereof. In order to solve the problem of poor hydrophobicity of the existing water-oxygen barrier film, the invention provides an arylation graphene film and a preparation method thereof, and an arylation graphene barrier film and a preparation method thereof. The arylation graphene film comprises graphene, and an aromatic hydrocarbon compound is grafted on the surface of the graphene. The arylated graphene barrier film includes an arylated graphene thin film. The arylation graphene barrier film provided by the invention has good hydrophobicity, and the barrier capability to water vapor is improved. The arylation graphene barrier film provided by the invention has good ultraviolet resistance. The invention solves the problem of poor hydrophobicity and ultraviolet resistance of the existing barrier film by introducing the hydrophobic aromatic compound with ultraviolet absorption capacity.
Description
Technical Field
The invention relates to the field of films, in particular to an arylation graphene film and a preparation method thereof, and an arylation graphene barrier film and a preparation method thereof.
Background
Quantum dots are three-dimensional clusters of nanometer-scale dimensions and are therefore also referred to as nanodots or nanocrystals. With the rapid development of semiconductor quantum dot synthesis, the semiconductor quantum dot has the advantages of low cost, strong stability, high quantum yield, large-scale production and the like, so that the semiconductor quantum dot is considered as a solid foundation for further research on a plurality of leading-edge applications. Especially, the quantum dot shows unique luminescence characteristics due to the fact that the diameter of the quantum dot is approximate to the exciton Bohr radius, so that the quantum dot has good application prospects in the aspects of luminescent materials, displays and the like. However, the quantum dots have poor water vapor and oxygen resistance, so that the quantum dots are easily oxidized by oxygen and water vapor in the air to cause the decrease of fluorescence intensity. At present, long-acting packaging protection of quantum dot materials by adopting a water-oxygen barrier film is a key technology for realizing industrialization in the field of optics.
Graphene has received a great deal of attention since its discovery in its unique structure and excellent properties, including its good application in the barrier field. Firstly, graphene is excellent in thermal and chemical stability, so that it can be used in environments with corrosion and oxidation; secondly, the two-dimensional plane structure of the graphene can well form a physical barrier layer to block permeation of outside gas molecules; and the graphene film is transparent and light, has good optical performance, and ensures normal use in the field of optical films.
However, the use of the graphene barrier film is still limited by certain factors: 1. graphene prepared by the traditional Hummers method contains higher content of oxygen-containing functional groups, and the hydrophilicity of the graphene is not favorable for blocking water vapor; 2. the conjugated plane of the graphene is easy to excite under ultraviolet irradiation, and the graphene barrier film is easy to lose effectiveness after long-time use due to the weak weather resistance of the conjugated plane.
Disclosure of Invention
In order to solve the problem of poor hydrophobicity of the existing water-oxygen barrier film, the invention provides an arylation graphene film and a preparation method thereof, and an arylation graphene barrier film and a preparation method thereof. The arylation graphene barrier film provided by the invention has good hydrophobicity, and the barrier capability to water vapor is improved. The arylation graphene barrier film provided by the invention has good ultraviolet resistance. The invention solves the problem of poor hydrophobicity and ultraviolet resistance of the existing barrier film by introducing the hydrophobic aromatic compound with ultraviolet absorption capacity. The preparation process of the arylation graphene film and the arylation graphene barrier film provided by the invention is simple, strong in controllability and low in cost, and can be used for rapidly realizing large-scale production and customized grade fine application.
In order to solve the technical problems, the invention provides the following technical scheme:
the invention provides an arylation graphene film which comprises graphene, wherein an aromatic hydrocarbon compound is grafted on the surface of the graphene.
Further, the aromatic hydrocarbon compound is a halogenated aromatic hydrocarbon compound.
The halogenated aromatic hydrocarbon compound is a single halogen substituted aromatic compound. The aromatic compound is an aromatic compound, which is also called aromatic compound, and is called aromatic hydrocarbon for short.
Further, the halogen is selected from one of chlorine, bromine or iodine.
Further, the arene is selected from one or a combination of at least two of benzene, thiophene, pyridine, furan, pyrrole or anthracene.
Further, the halogenated aromatic hydrocarbon compound is selected from one or a combination of at least two of 1-bromobenzene, 1-iodobenzene or 1-chlorobenzene.
Further, the halogenated aromatic hydrocarbon compound is preferably 1-bromobenzene.
Further, the mass ratio of the graphene to the halogenated aromatic hydrocarbon compound is 1: 0.5-50.
Further, the mass ratio of the graphene to the halogenated aromatic compound is preferably 1: 1-3.
Further, the mass ratio of the graphene to the halogenated aromatic compound is preferably 1: 1.
the mass ratio of the graphene to the halogenated aromatic compound can be adjusted according to the requirements of the hydrophilic and hydrophobic properties of the required material.
The invention also provides a method for preparing the arylated graphene film, which comprises the following steps:
(1) growing a graphene film on the metal substrate by using a gas phase deposition method;
(2) and (2) placing the graphene film obtained in the step (1) and a halogenated aromatic compound in ammonia water for heating reaction, and after the reaction is finished, washing, centrifuging, filtering and drying in vacuum to obtain the arylated graphene film.
Further, the graphene film obtained in the step (1) and the halogenated aromatic hydrocarbon compound are placed in ammonia water and sodium dodecyl benzene sulfonate for heating reaction.
Further, the heating reaction temperature in the step (2) is 60-120 ℃, the heating time is 12-72 hours, and the vacuum drying temperature is 60-100 ℃.
Further, the heating reaction temperature in the step (2) is 80-100 ℃, the heating time is 24-36 hours, and the vacuum drying temperature is 80-100 ℃.
Further, the heating reaction temperature in the step (2) is 100 ℃, the heating time is 24 hours, and the vacuum drying temperature is 100 ℃.
Further, the metal substrate is a copper foil or a nickel foil.
Further, the metal substrate is preferably a copper foil.
Further, the thickness of the metal substrate is 10-25 microns.
Further, the thickness of the metal substrate is preferably 15 to 20 μm.
Further, the thickness of the metal substrate is preferably 15 μm.
The thickness of the metal substrate affects the flatness of the arylated graphene film during transfer.
The invention also provides an arylation graphene barrier film, which comprises an arylation graphene film.
Further, the barrier film sequentially comprises an arylation graphene film, a barrier adhesive and a substrate layer.
The invention also provides a method for preparing an arylated graphene barrier film, which comprises the following steps:
(1) flatly attaching the metal substrate deposited with the arylation graphene film and the transfer base material with the thermal stripping glue together, etching the metal substrate with acid, washing, and drying in an oven to obtain a semi-finished product of the transfer base material adhered with the arylation graphene film;
(2) and bonding the arylation graphene film on the semi-finished product and the substrate layer by using barrier glue, carrying out UV curing, carrying out high-temperature oven treatment to enable the hot peeling glue to lose viscosity at high temperature, and tearing off the transfer substrate to obtain the arylation graphene barrier film.
Further, the barrier glue is acrylic UV barrier glue.
Further, the substrate layer is a transparent substrate, and the transparent substrate is selected from one of PET, PMMA, PVA, PP and PE.
Further, the preparation method of the arylation graphene barrier film comprises the following steps:
(1) the method comprises the following steps of flatly bonding an arylation graphene film with a copper foil and a transfer base material with a thermal stripping adhesive together through rolling, then soaking the composite material in a water tank filled with a hydrochloric acid/hydrogen peroxide mixed solvent for 4-20 hours, taking out the composite material after the copper foil is completely etched, washing the composite material with deionized water and ethanol, and drying the composite material in a drying oven at 60-90 ℃ to obtain a semi-finished product of the transfer base material adhered with the arylation graphene film;
(2) and rolling and laminating the arylation graphene film on the semi-finished product and the target transparent base material by using acrylic UV blocking glue in a slot die mode (slit extrusion coating), carrying out UV curing, carrying out high-temperature oven treatment at 70-120 ℃ to enable the hot stripping glue to lose viscosity at high temperature, and tearing off the transfer base material to obtain the arylation graphene blocking film.
Further, in the preparation of the arylation graphene barrier film, the composite material is soaked in a water tank filled with a hydrochloric acid/hydrogen peroxide mixed solvent for 10-14 hours, dried in an oven at 75-85 ℃ after being washed, and treated in an oven at a high temperature of 100-120 ℃ after being cured by UV.
Further, in the preparation of the arylation graphene barrier film, the composite material is soaked in a water tank filled with a hydrochloric acid/hydrogen peroxide mixed solvent for 12 hours, dried in an oven at 80 ℃ after washing, and subjected to high-temperature oven treatment at 120 ℃ after UV curing.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, graphene is used as a barrier material, a larger two-dimensional plane of the graphene can effectively play a barrier role, and the defect of poor compatibility of a conventional inorganic barrier material and organic glue is avoided; compared with an inorganic barrier material, the transparent graphene film has relatively small influence on the optical performance of the membrane; aromatic compounds are grafted on the surface of the graphene, so that the planar conjugation degree is improved, the ultraviolet absorption capacity is improved, and the weather resistance of the barrier film is effectively improved; the introduction of the aromatic compound with high lipophilicity improves the hydrophobic capacity of the surface of the barrier film and enhances the barrier capacity of the barrier film to water vapor; the introduction of the aromatic compound improves the dyne value of the surface of the barrier film, thereby enhancing the adhesion capability of the barrier film and an application object; the rigidity of the membrane surface can be improved by grafting the rigid aromatic hydrocarbon side chain on the surface of the graphene, and the mechanical property and scratch resistance of the membrane are enhanced; due to the introduction of the aromatic hydrocarbon, the crowding degree of the graphene barrier layer is improved (namely the aromatic hydrocarbon has a volume effect), the diffusion path of molecules is greatly increased, and the barrier capability of the molecules is improved; the design scheme of the invention has simple process and cheap and easily-obtained raw materials, thereby having wider application capability and feasibility of mass production.
Drawings
Fig. 1 is a schematic diagram illustrating the synthesis of an arylated graphene thin film according to the present invention;
fig. 2 is a preparation route diagram of the arylated graphene barrier film provided by the present invention;
fig. 3 is a scanning electron microscope image of the arylated graphene barrier film prepared in example 1 of the present invention;
FIG. 4 is a Fourier infrared spectrum of an arylated graphene film prepared according to example 1 of the present invention;
fig. 5 is a graph of the uv-vis absorption spectrum of the arylated graphene thin film prepared in example 1 of the present invention;
fig. 6 is an optical image of the water contact angle of the arylated graphene barrier film prepared in example 1 of the present invention.
Detailed Description
The following will clearly and completely describe the technical solutions in the embodiments of the present invention, and it is obvious that the described embodiment is only one embodiment of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive step based on the embodiments of the present invention, are within the scope of the present invention.
The preparation method of the arylation graphene film provided by the invention comprises the following steps:
(1) growing a graphene film on the metal substrate by using a gas phase deposition method;
(2) and (2) placing the graphene film obtained in the step (1) and a halogenated aromatic compound in ammonia water for heating reaction, and after the reaction is finished, washing, centrifuging, filtering and drying in vacuum to obtain the arylated graphene film.
Further, the heating reaction temperature in the step (2) is 60-120 ℃, the heating time is 12-72 hours, and the vacuum drying temperature is 60-100 ℃.
The preparation method of the arylation graphene barrier film provided by the invention comprises the following steps:
(1) the method comprises the following steps of flatly bonding an arylation graphene film with a copper foil and a transfer base material with a thermal stripping adhesive together through rolling, then soaking the composite material in a water tank filled with a hydrochloric acid/hydrogen peroxide mixed solvent for 4-20 hours, taking out the composite material after the copper foil is completely etched, washing the composite material with deionized water and ethanol, and drying the composite material in a drying oven at 60-90 ℃ to obtain a semi-finished product of the transfer base material adhered with the arylation graphene film;
(2) and rolling and laminating the arylation graphene film on the semi-finished product and the target transparent base material by using acrylic UV blocking glue in a slot die mode (slit extrusion coating), carrying out UV curing, carrying out high-temperature oven treatment at 70-120 ℃ to enable the hot stripping glue to lose viscosity at high temperature, and tearing off the transfer base material to obtain the arylation graphene blocking film.
The materials provided in the examples of the present invention were tested for their relevant performance properties in the following manner, and the results are shown in table 1.
1. Yield of arylated graphene: the mass of each substance before and after the reaction is weighed and calculated to obtain: the yield is (mass of arylated graphene after reaction)/(total mass of halogenated aromatic compound charged for reaction + total mass of graphene charged for reaction).
2. Water contact angle: the arylated graphene barrier film was placed on a contact angle measuring instrument (CA100B), and a drop of deionized water was dropped with a sample injector and its water contact angle was automatically measured. Contact angles greater than 90 ° are hydrophobic, and the greater the contact angle, the more hydrophobic it is.
3. Light transmittance and haze test: a sheet of the arylation graphene barrier film A4 to be tested is placed into a light transmittance haze tester (NDH7000) to be tested, and the light transmittance or haze value of the arylation graphene barrier film is measured.
4. Adhesion force: adopting a hundred-grid test method, wherein the test standard is ASTM D3359-02; a high adhesion level indicates good scratch resistance. The highest rating of adhesion is 5B, which requires: the edges of the cuts were completely smooth without any flaking of the grid edges. The adhesive force refers to the adhesive force between the arylation graphene film and the substrate layer.
5. Hardness: the pencil hardness tester was used, and the test standard was ASTM D3363.
6. Ultraviolet absorbance: the ultraviolet absorption of the diaphragm is measured by an ultraviolet-visible spectrophotometer, and the stronger the peak is at 200-400nm, the stronger the ultraviolet absorption capacity is. The absorbance is not less than 70g/L, which shows that the ultraviolet resistance is excellent; the absorbance of 70g/L is larger than or equal to 60g/L, which indicates that the ultraviolet resistance is general; the absorbance is less than 60g/L, which indicates that the uvioresistant property is poor.
Fig. 1 is a schematic diagram of synthesis of an arylated graphene film provided by the present invention. Fig. 2 is a preparation route diagram of the arylated graphene barrier film provided by the present invention; wherein 1 is the metal substrate, 2 is graphene film, 3 is the hot peeling glue, 4 is the transfer substrate, 5 is the substrate layer, and 6 is the UV separation glue.
Example 1
The invention provides an arylation graphene film which comprises graphene, wherein an aromatic hydrocarbon compound is grafted on the surface of the graphene. The invention further provides an arylation graphene barrier film, which sequentially comprises an arylation graphene film, a barrier adhesive and a substrate layer.
Preparation of arylation graphene film
Growing a graphene film on 100g of copper foil by using a conventional vapor deposition method, then placing graphene/copper foil (the content of graphene is 10g) in an ammonia water tank, adding 10g of 1-bromobenzene, heating at 100 ℃, reacting for 24 hours, filtering, washing with deionized water, acetone, chloroform and ethanol respectively, centrifuging, filtering, and drying in vacuum at 100 ℃ to obtain 19.8g of arylated graphene with copper foil, wherein the yield is 99%. Wherein the thickness of the metal substrate is 15 microns.
Preparation of di-arylation graphene barrier film
And (2) flatly bonding the arylation graphene film with the copper foil and the transfer substrate with the thermal stripping adhesive together by rolling, then soaking the composite material in a water tank filled with a hydrochloric acid/hydrogen peroxide mixed solvent for 12 hours, taking out the composite material after the copper foil is completely etched, washing the composite material with deionized water and ethanol, and drying the composite material in an oven at 80 ℃ to obtain a semi-finished product of the transfer substrate adhered with the arylation graphene film. And rolling and laminating the semi-finished arylation graphene film surface and the target transparent substrate by using acrylic UV blocking glue in a slot die mode, carrying out UV curing, carrying out high-temperature oven treatment at 120 ℃ to enable the hot stripping glue to lose viscosity at high temperature, and tearing off the transfer substrate to obtain the arylation graphene blocking film.
Example 2
Arylated graphene thin films and arylated graphene barrier films as provided in example 1.
Preparation of arylation graphene film
Growing a graphene film on 100g of copper foil by using a conventional vapor deposition method, then placing graphene/copper foil (the content of graphene is 10g) in an ammonia water tank, adding 5g of 1-bromobenzene, heating at 100 ℃, reacting for 24 hours, filtering, washing with deionized water, acetone, chloroform and ethanol respectively, centrifuging, performing suction filtration, and drying in vacuum at 100 ℃ to obtain 13.5g of arylated graphene with copper foil, wherein the yield is 90%. Wherein the thickness of the metal substrate is 15 microns.
Preparation of di-arylation graphene barrier film
And (2) flatly bonding the arylation graphene film with the copper foil and the transfer substrate with the thermal stripping adhesive together by rolling, then soaking the composite material in a water tank filled with a hydrochloric acid/hydrogen peroxide mixed solvent for 12 hours, taking out the composite material after the copper foil is completely etched, washing the composite material with deionized water and ethanol, and drying the composite material in an oven at 80 ℃ to obtain a semi-finished product of the transfer substrate adhered with the arylation graphene film. And rolling and laminating the semi-finished arylation graphene film surface and the target transparent substrate by using acrylic UV blocking glue in a slot die mode, carrying out UV curing, carrying out high-temperature oven treatment at 120 ℃ to enable the hot stripping glue to lose viscosity at high temperature, and tearing off the transfer substrate to obtain the arylation graphene blocking film.
Example 3
Arylated graphene thin films and arylated graphene barrier films as provided in example 1.
Preparation of arylation graphene film
Growing a graphene film on 100g of copper foil by using a conventional vapor deposition method, then placing graphene/copper foil (the content of graphene is 10g) in an ammonia water tank, adding 500g of 1-bromobenzene, heating at 100 ℃, reacting for 24 hours, filtering, washing with deionized water, acetone, chloroform and ethanol respectively, centrifuging, performing suction filtration, and drying in vacuum at 100 ℃ to obtain 448.8g of arylated graphene with copper foil, wherein the yield is 88%. Wherein the thickness of the metal substrate is 15 microns.
Preparation of di-arylation graphene barrier film
And (2) flatly bonding the arylation graphene film with the copper foil and the transfer substrate with the thermal stripping adhesive together by rolling, then soaking the composite material in a water tank filled with a hydrochloric acid/hydrogen peroxide mixed solvent for 12 hours, taking out the composite material after the copper foil is completely etched, washing the composite material with deionized water and ethanol, and drying the composite material in an oven at 80 ℃ to obtain a semi-finished product of the transfer substrate adhered with the arylation graphene film. And rolling and laminating the semi-finished arylation graphene film surface and the target transparent substrate by using acrylic UV blocking glue in a slot die mode, carrying out UV curing, carrying out high-temperature oven treatment at 120 ℃ to enable the hot stripping glue to lose viscosity at high temperature, and tearing off the transfer substrate to obtain the arylation graphene blocking film.
Example 4
Arylated graphene thin films and arylated graphene barrier films as provided in example 1.
Preparation of arylation graphene film
Growing a graphene film on 100g of copper foil by using a conventional vapor deposition method, then placing graphene/copper foil (the content of graphene is 10g) in an ammonia water tank, adding 500g of 1-iodobenzene, heating at 100 ℃, reacting for 24 hours, filtering, washing with deionized water, acetone, chloroform and ethanol respectively, centrifuging, performing suction filtration, and drying in vacuum at 100 ℃ to obtain 443.7g of arylated graphene with copper foil, wherein the yield is 87%. Wherein the thickness of the metal substrate is 10 μm.
Preparation of di-arylation graphene barrier film
And (2) flatly bonding the arylation graphene film with the copper foil and the transfer substrate with the thermal stripping adhesive together by rolling, then soaking the composite material in a water tank filled with a hydrochloric acid/hydrogen peroxide mixed solvent for 4 hours, taking out the composite material after the copper foil is completely etched, washing the composite material with deionized water and ethanol, and drying the composite material in an oven at 80 ℃ to obtain a semi-finished product of the transfer substrate adhered with the arylation graphene film. And rolling and laminating the semi-finished arylation graphene film surface and the target transparent substrate by using acrylic UV blocking glue in a slot die mode, carrying out UV curing, carrying out high-temperature oven treatment at 120 ℃ to enable the hot stripping glue to lose viscosity at high temperature, and tearing off the transfer substrate to obtain the arylation graphene blocking film.
Example 5
Arylated graphene thin films and arylated graphene barrier films as provided in example 1.
Preparation of arylation graphene film
Growing a graphene film on 100g of copper foil by using a conventional vapor deposition method, then placing graphene/copper foil (the content of graphene is 10g) in an ammonia water tank, adding 500g of 1-chlorobenzene, heating at 100 ℃, reacting for 24 hours, filtering, washing with deionized water, acetone, chloroform and ethanol respectively, centrifuging, performing suction filtration, and drying in vacuum at 100 ℃ to obtain 453.9g of arylated graphene with copper foil, wherein the yield is 89%. Wherein the thickness of the metal substrate is 25 microns.
Preparation of di-arylation graphene barrier film
And (2) flatly bonding the arylation graphene film with the copper foil and the transfer substrate with the thermal stripping adhesive together by rolling, then soaking the composite material in a water tank filled with a hydrochloric acid/hydrogen peroxide mixed solvent for 20 hours, taking out the composite material after the copper foil is completely etched, washing the composite material with deionized water and ethanol, and drying the composite material in an oven at 80 ℃ to obtain a semi-finished product of the transfer substrate adhered with the arylation graphene film. And rolling and laminating the semi-finished arylation graphene film surface and the target transparent substrate by using acrylic UV blocking glue in a slot die mode, carrying out UV curing, carrying out high-temperature oven treatment at 120 ℃ to enable the hot stripping glue to lose viscosity at high temperature, and tearing off the transfer substrate to obtain the arylation graphene blocking film.
Example 6
Arylated graphene thin films and arylated graphene barrier films as provided in example 1.
Wherein the adding amount of the 1-bromobenzene in the preparation of the arylation graphene film is 20g, the arylation graphene film is filtered after being heated and reacted for 36 hours at 80 ℃, and the arylation graphene film is dried in vacuum at 80 ℃, wherein the thickness of the metal substrate is 20 microns.
In the preparation of the arylation graphene barrier film, the composite material is soaked in a water tank filled with a hydrochloric acid/hydrogen peroxide mixed solvent for 10 hours, dried in a 75 ℃ oven after washing, and subjected to high-temperature oven treatment at 100 ℃ after UV curing.
Example 7
Arylated graphene thin films and arylated graphene barrier films as provided in example 1.
Wherein the adding amount of the 1-bromobenzene in the preparation of the arylation graphene film is 30g, the film is filtered after being heated and reacted for 30 hours at 90 ℃, and the film is dried in vacuum at 90 ℃, wherein the thickness of the metal substrate is 20 microns.
In the preparation of the arylation graphene barrier film, the composite material is soaked in a water tank filled with a hydrochloric acid/hydrogen peroxide mixed solvent for 14 hours, dried in an oven at 85 ℃ after being washed, and subjected to high-temperature oven treatment at 110 ℃ after being UV cured.
Example 8
Arylated graphene thin films and arylated graphene barrier films as provided in example 1.
Wherein the halogenated aromatic hydrocarbon compound in the preparation of the arylation graphene film is 1-iodobenzene, and the aromatic hydrocarbon compound is filtered after being heated and reacted for 72 hours at the temperature of 60 ℃ and is dried in vacuum at the temperature of 60 ℃.
In the preparation of the arylation graphene barrier film, the arylation graphene barrier film is washed and dried in a 60 ℃ oven, and is subjected to UV curing and then is treated in a 120 ℃ high-temperature oven.
Example 9
Arylated graphene thin films and arylated graphene barrier films as provided in example 1.
Wherein the halogenated aromatic hydrocarbon compound in the preparation of the arylation graphene film is 1-chlorobenzene, the mixture is heated to react for 12 hours at 120 ℃, filtered and dried in vacuum at 70 ℃.
In the preparation of the arylation graphene barrier film, the arylation graphene barrier film is washed and dried in a 90 ℃ oven, and is subjected to high-temperature oven treatment at 70 ℃ after UV curing.
Comparative example 1
Preparation of arylation graphene film
Growing a graphene film on 100g of copper foil by using a conventional vapor deposition method, then placing graphene/copper foil (the content of graphene is 10g) in an ammonia water tank, adding 800g of 1-bromobenzene, heating for reaction for 24 hours, filtering, washing with deionized water, acetone, chloroform and ethanol respectively, centrifuging, filtering, and drying in vacuum at 100 ℃ to obtain 413.1g of arylated graphene with copper foil, wherein the yield is 51%. Wherein the thickness of the metal substrate is 15 microns.
Preparation of di-arylation graphene barrier film
And (2) flatly bonding the arylation graphene film with the copper foil and the transfer substrate with the thermal stripping adhesive together by rolling, then soaking the composite material in a water tank filled with a hydrochloric acid/hydrogen peroxide mixed solvent for 12 hours, taking out the composite material after the copper foil is completely etched, washing the composite material with deionized water and ethanol, and drying the composite material in an oven at 80 ℃ to obtain a semi-finished product of the transfer substrate adhered with the arylation graphene film. And rolling and laminating the semi-finished arylation graphene film surface and the target transparent substrate by using acrylic UV blocking glue in a slot die mode, carrying out UV curing, carrying out high-temperature oven treatment at 120 ℃ to enable the hot stripping glue to lose viscosity at high temperature, and tearing off the transfer substrate to obtain the arylation graphene blocking film.
The mass ratio of the graphene and the halogenated aromatic hydrocarbon compound provided in comparative example 1 is 1: 80.
comparative example 2
Preparation of arylation graphene film
A graphene film grows on 100g of copper foil by using a conventional vapor deposition method, then graphene/copper foil (the content of graphene is 10g) is placed in an ammonia water tank, 1g of 1-bromobenzene is added, the mixture is heated and reacted for 24 hours, then the mixture is filtered, and 10.5g of arylation graphene with the copper foil is obtained after washing, centrifugation and suction filtration respectively by using deionized water, acetone, chloroform and ethanol, and vacuum drying is carried out at 100 ℃, and the yield is 95%. Wherein the thickness of the metal substrate is 15 microns.
Preparation of di-arylation graphene barrier film
And (2) flatly bonding the arylation graphene film with the copper foil and the transfer substrate with the thermal stripping adhesive together by rolling, then soaking the composite material in a water tank filled with a hydrochloric acid/hydrogen peroxide mixed solvent for 12 hours, taking out the composite material after the copper foil is completely etched, washing the composite material with deionized water and ethanol, and drying the composite material in an oven at 80 ℃ to obtain a semi-finished product of the transfer substrate adhered with the arylation graphene film. And rolling and laminating the semi-finished arylation graphene film surface and the target transparent substrate by using acrylic UV blocking glue in a slot die mode, carrying out UV curing, carrying out high-temperature oven treatment at 120 ℃ to enable the hot stripping glue to lose viscosity at high temperature, and tearing off the transfer substrate to obtain the arylation graphene blocking film.
The mass ratio of the graphene to the halogenated aromatic compound provided in comparative example 2 was 1: 0.1.
the samples obtained in example 1 were subjected to the relevant structural characterization tests, the results of which are as follows:
fig. 3 is a scanning electron microscope image of the arylated graphene barrier film prepared in example 1, and a test result shows that the obtained material is a graphene barrier film with a smooth surface.
FIG. 4 is a Fourier infrared spectrum of arylated graphene in the arylated graphene barrier film prepared in example 1, wherein the Fourier infrared spectrum is 1280-1630 cm-1And 710-850 cm-1Vibration absorption peaks appearing in the areas indicate that a benzene ring structure exists in the prepared material; 2710-2980 cm-1The vibration absorption peak appeared in the area indicates that the carbon-carbon single bond peak exists in the prepared material. These results indicate that the chemical structure of the prepared arylated graphene is consistent with theoretical expectations.
Fig. 5 is an ultraviolet-visible absorption spectrum of the arylated graphene in the arylated graphene barrier film prepared in example 1, and it can be seen from the ultraviolet-visible absorption spectrum that an obvious absorption peak is present at 200-400nm, which indicates that the arylated graphene can effectively absorb ultraviolet rays.
Fig. 6 is an optical image of the water contact angle of the arylated graphene barrier film provided in example 1 of the present invention. As can be seen from the figure, the water drop does not spread substantially on the surface of the arylated graphene barrier film, and the contact angle is measured to be 137 °, which indicates that the obtained arylated graphene barrier film has strong hydrophobicity.
Table 1 performance test results of the arylated graphene thin films and arylated graphene barrier films provided in examples 1 to 9 and comparative examples 1 to 2
The arylation graphene film provided by the invention has higher yield. The arylation graphene barrier film provided by the invention has good adhesive force, hardness, light transmittance and haze, and good hydrophobicity and ultraviolet resistance. Wherein, the yield of the arylated graphene in the arylated graphene thin films provided by the embodiments 1 and 6 to 7 is 93 to 99 percent; the adhesion force of the arylated graphene barrier film is 5B, the hardness is 2H, the light transmittance is 94.89-98.34%, the haze is 85.62%, the water contact angle is 132-137 DEG, and the ultraviolet resistance is excellent. In particular, the yield of the arylated graphene in the arylated graphene thin film provided in example 1 is 99%; the arylated graphene barrier film has the advantages of 5B adhesion, 2H hardness, 98.34% light transmittance, 85.62% haze, 137% water contact angle and excellent ultraviolet resistance.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (2)
1. An arylated graphene barrier film, wherein the arylated graphene barrier film comprises an arylated graphene thin film;
the arylation graphene film comprises graphene, wherein 1-bromobenzene is grafted on the surface of the graphene, and the mass ratio of the graphene to the 1-bromobenzene is 1: 1.
2. the arylated graphene barrier film according to claim 1, wherein the barrier film comprises an arylated graphene film, a barrier glue and a substrate layer in this order.
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