Anti-interference graphene aluminum foil and preparation method thereof
By combining modified graphene with aluminum foil, the dispersion and adhesion strength are improved by using the quaternary ammonium salt and benzotriazole structure, the problems of graphene with aluminum foil not being tightly bonded with aluminum foil and poor heat dissipation in the prior art are solved, and efficient anti-interference and heat dissipation performance are achieved.
Patent Information
- Application Number
- CN202510055897.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-01-14
- Publication Date
- 2025-04-25
- Estimated Expiration
- Not applicable · inactive patent
AI Technical Summary
In the prior art, the dispersion between graphene and aluminum foil is poor, the bonding is not tight, which affects use, and the heat dissipation of aluminum foil is poor, which poses a safety hazard.
Through the combination of modified graphene and aluminum foil, the surface of modified graphene contains a quaternary ammonium structure and a benzotriazole structure, which improves dispersion and adhesion strength, and enhances its anti-interference performance through heat treatment technology.
The close combination between modified graphene and aluminum foil is achieved, which improves anti-interference and heat dissipation performance, and reduces safety hazards.
Smart Images
Figure BDA0005241419800000021 
Figure BDA0005241419800000031 
Figure BDA0005241419800000032
Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of coated aluminum foil materials, and specifically relates to an anti-interference graphene aluminum foil and a preparation method thereof. Background Art
[0002] Cables are widely used in daily life, mainly for controlling installation, connecting equipment, transmitting electricity and other multiple functions. Connecting wires are usually used for power and signal transmission of electronic equipment and components. The connecting wire body generally includes a structure combining a conductor, an insulating layer, an aluminum foil layer, a metal braided layer and an outer layer. The aluminum foil layer can shield the interference of the electromagnetic field and ensure the anti-interference performance during data transmission. However, the single aluminum foil method has poor heat dissipation, and the heat generated by the conductor core cannot be dissipated in time, posing a safety hazard.
[0003] As a new type of two-dimensional material, graphene has good electrical conductivity, thermal conductivity, mechanical properties and low resistivity. However, the existing graphene has poor dispersion and no interaction with aluminum foil. It is only combined by the single action of the adhesive, so the combination is not tight, which affects its use. Summary of the invention
[0004] The purpose of the present invention is to overcome the defects of the prior art and provide an anti-interference graphene aluminum foil and a preparation method thereof.
[0005] The purpose of the present invention can be achieved through the following technical solutions:
[0006] A method for preparing an anti-interference graphene aluminum foil comprises the following steps:
[0007] (1) Aluminum foil, phosphoric acid and acetone are added to a dry beaker, heated to 40°C, stirred for reaction for 3 hours, filtered, washed until the filtrate is neutral, and the filter residue is dried at 80°C for 6 hours to obtain a pretreated aluminum foil;
[0008] (2) The modified graphene, the binder and the solvent are fully stirred to form a slurry for later use; the pretreated aluminum foil obtained in step (1) is immersed in the slurry for 0.5 h, taken out and dried at 100-110° C. for 6-12 h to obtain an anti-interference graphene aluminum foil.
[0009] Furthermore, the mass ratio of the aluminum foil to the phosphoric acid in step (1) is 10:(0.01-0.02).
[0010] Furthermore, the mass ratio of the modified graphene, the binder and the solvent in step (2) is (92-95):(5-8):(90-110).
[0011] Furthermore, the modified graphene is prepared by the following steps:
[0012] S1. Under nitrogen protection, 3-dimethylamino-1-propanol, triethylamine and diethyl ether were added to a dry three-necked flask, mixed evenly and heated to 60°C, and then hexadecane bromide was slowly added. After the addition was completed, the mixture was stirred at 60°C for 4 hours. After the reaction was completed, the mixture was cooled to room temperature and distilled under reduced pressure to obtain intermediate 1; the dosage ratio of 3-dimethylamino-1-propanol, hexadecane bromide, triethylamine and diethyl ether was 11.8 mL: 33.2 mL: 16.7 mL: 180 mL;
[0013] Triethylamine is used as an acid binding agent, and the molar ratio of 3-dimethylamino-1-propanol and hexadecane bromide is controlled to be 1:1.05-1.1. Then, 3-dimethylamino-1-propanol and hexadecane bromide undergo a nucleophilic substitution reaction under heating. The reaction process is as follows:
[0014]
[0015] S2, nitrogen blowing dry three-necked flask for 30min to expel air and moisture in the flask, then add intermediate 1, 10wt% sodium hydroxide solution and chloroform, stir evenly and heat to 60°C, then slowly add epichlorohydrin in the constant pressure dropping funnel to the three-necked flask, keep warm at 60°C for 5h after adding, cool to room temperature after the reaction, distill under reduced pressure, purify by column chromatography (eluent is a mixed solution of benzene and acetone, the volume ratio of benzene and acetone is 9:1), distill under reduced pressure to obtain intermediate 2; the amount ratio of intermediate 1 to epichlorohydrin is 38.8g:5.9mL;
[0016] The molar ratio of intermediate 1 to epichlorohydrin is controlled to be 1.2-1.3:1, and intermediate 1 and epichlorohydrin undergo a ring-opening reaction under heating and base catalysis. The reaction process is as follows:
[0017]
[0018] S3. Add intermediate 2, triethylamine and DMF (N,N-dimethylformamide) to a dry three-necked flask under nitrogen protection, mix well and heat to 70°C, then slowly add a mixed solution of benzotriazole and DMF, stir and react at 70°C for 4h after the addition is complete, cool to room temperature after the reaction is completed, and then distill under reduced pressure to obtain intermediate 3; the amount ratio of intermediate 2, benzotriazole, triethylamine and DMF is 40.1g:10.2g:13.3mL:240mL;
[0019] Triethylamine is used as an acid-binding agent to control the molar ratio of intermediate 2 to benzotriazole to be 1:1.05-1.1. The -Cl of intermediate 2 and the -NH of benzotriazole undergo a nucleophilic substitution reaction under heating. The reaction process is as follows:
[0020]
[0021] S4. Add intermediate 3, succinic anhydride, DMAP (4-dimethylaminopyridine) and DMF to a three-necked flask under nitrogen protection, heat to 50°C with stirring, and keep warm for 12 hours. After the reaction is completed, remove the precipitate by suction filtration, wash the filtrate with saturated brine, quickly dry with anhydrous magnesium sulfate, and concentrate to obtain intermediate 4; the amount ratio of intermediate 3, succinic anhydride, DMAP and DMF is 35g:6.4g:0.65g:220mL;
[0022] The molar ratio of intermediate 3 to succinic anhydride is controlled to be 1:1.0-1.1, and then intermediate 3 and succinic anhydride undergo esterification reaction under the catalysis of DMAP. The reaction process is as follows:
[0023]
[0024] S5. Add graphene, intermediate 4 and DMF into a dry three-necked flask, stir evenly and then slowly add concentrated sulfuric acid. After the addition is complete, heat to 100°C and stir to react for 5 hours. After the reaction is completed, cool to room temperature, filter and wash with deionized water until the filtrate is neutral. Dry the filter residue at 110°C for 12 hours to obtain modified graphene. The usage ratio of graphene, intermediate 4, concentrated sulfuric acid and DMF is 16g:3.2g:0.09g:180mL.
[0025] Under the catalytic action of heating and concentrated sulfuric acid, the carboxyl group of intermediate 4 and the hydroxyl group on the graphene surface undergo esterification reaction. The reaction process is as follows:
[0026]
[0027] The modified graphene surface of the present invention contains a quaternary ammonium salt structure (with 16 carbon atoms in the side chain), which can improve the dispersion of the modified graphene in the slurry as a dispersant, and the dispersion effect is more stable and lasting than the dispersant that is simply physically mixed with the graphene. Therefore, the modified graphene of the present invention can be highly dispersed on the surface of the aluminum foil to protect the aluminum foil.
[0028] The surface of the modified graphene also contains a benzotriazole structure, which can anchor aluminum and provide protection for it. The triazole group and the benzene ring in the benzotriazole structure molecule can form a chemical bond and adsorption with the surface of the aluminum foil, which not only makes the modified graphene and the aluminum foil more tightly combined due to the chemical reaction, but also protects the aluminum foil and inhibits the dissolution behavior of the aluminum foil in an acidic environment. Therefore, the modified graphene of the present invention can be firmly combined with the surface of the aluminum foil, and the graphene aluminum foil prepared can effectively shield the interference of the electromagnetic field and ensure the anti-interference performance during data transmission, while dissipating heat in time to reduce safety hazards.
[0029] Furthermore, the solvent in step (2) is one or more of dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.
[0030] Furthermore, the binder in step (2) is one or more of polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene copolymer, polyacrylonitrile, and polytetrafluoroethylene.
[0031] The present invention also discloses an anti-interference graphene aluminum foil, which is prepared according to the above-mentioned method for preparing the anti-interference graphene aluminum foil.
[0032] The beneficial effects of the present invention are as follows: the surface of the modified graphene contains a dispersant with a quaternary ammonium salt structure, so the modified graphene can be highly dispersed in the slurry, and then bonded to the surface of the aluminum foil through the binder; at the same time, the surface of the modified graphene contains a benzotriazole structure, so there is a chemical reaction between the modified graphene and the aluminum foil, and then the modified graphene can be firmly present on the surface of the aluminum foil, giving full play to the protective effect, so that the graphene aluminum foil of the present invention can effectively shield the interference of the electromagnetic field and ensure the anti-interference performance during data transmission, and at the same time, timely dissipate heat and reduce safety hazards. DETAILED DESCRIPTION
[0033] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.
[0034] Example 1, preparing modified graphene, the specific steps are as follows:
[0035] S1. Under nitrogen protection, 11.8 mL of 3-dimethylamino-1-propanol, 16.7 mL of triethylamine and 180 mL of ether were added to a 500 mL dry three-necked flask. After mixing evenly, the temperature was raised to 60° C., and then 33.2 mL of hexadecane bromide was slowly added. After the addition was completed, the mixture was stirred at 60° C. for 4 h. After the reaction was completed, the mixture was cooled to room temperature and distilled under reduced pressure to obtain intermediate 1.
[0036] S2, nitrogen was blown into a 500mL dry three-necked flask for 30min to expel the air and moisture in the flask, then 38.8g of intermediate 1, 7mL of 10wt% sodium hydroxide solution and 200mL of chloroform were added, stirred evenly and heated to 60°C, then 5.9mL of epichlorohydrin in a constant pressure dropping funnel was slowly added to the three-necked flask, and after the addition was completed, the mixture was kept at 60°C for 5h. After the reaction was completed, it was cooled to room temperature, distilled under reduced pressure, purified by column chromatography (the eluent was a mixed solution of benzene and acetone, and the volume ratio of benzene and acetone was 9:1), and distilled under reduced pressure to obtain intermediate 2;
[0037] S3, under nitrogen protection, add 40.1 g of intermediate 2, 13.3 mL of triethylamine and 200 mL of DMF to a 500 mL dry three-necked flask, mix well and heat to 70°C, then slowly add 10.2 g of benzotriazole and 40 mL of DMF, stir and react at 70°C for 4 h after the addition is complete, cool to room temperature after the reaction is completed, and then distill under reduced pressure to obtain intermediate 3;
[0038] S4, under nitrogen protection, add 35g of intermediate 3, 6.4g of succinic anhydride, 0.65g of DMAP and 220mL of DMF into a 500mL three-necked flask, stir and heat to 50°C, keep warm for 12h, after the reaction is completed, filter out the precipitate, wash the filtrate with saturated brine, quickly dry with anhydrous magnesium sulfate, and concentrate to obtain intermediate 4;
[0039] S5. Add 16 g of graphene, 3.2 g of intermediate 4 and 180 mL of DMF into a 500 mL dry three-necked flask, stir evenly and then slowly add 0.09 g of concentrated sulfuric acid. After the addition is complete, heat to 100 °C and stir to react for 5 h. After the reaction is completed, cool to room temperature, filter and wash with deionized water until the filtrate is neutral, and dry the residue at 110 °C for 12 h to obtain modified graphene.
[0040] Example 2, preparing anti-interference graphene aluminum foil, the specific steps are as follows:
[0041] (1) Aluminum foil, phosphoric acid and 200 mL of acetone were added to a dry beaker (the mass ratio of aluminum foil, phosphoric acid and acetone was 10:0.01), heated to 40°C, stirred for reaction for 3 hours, filtered, washed until the filtrate was neutral, and dried the residue at 80°C for 6 hours to obtain a pretreated aluminum foil;
[0042] (2) The modified graphene, polyvinylidene fluoride and dimethyl sulfoxide prepared in Example 1 are fully stirred (the mass ratio of modified graphene, polyvinylidene fluoride and dimethyl sulfoxide is 92:5:90) to form a slurry for standby use; the pretreated aluminum foil obtained in step (1) is immersed in the slurry for 0.5 h, taken out and dried at 100° C. for 12 h to obtain an anti-interference graphene aluminum foil.
[0043] Example 3, preparing anti-interference graphene aluminum foil, the specific steps are as follows:
[0044] (1) Aluminum foil, phosphoric acid and 200 mL of acetone were added to a dry beaker (the mass ratio of aluminum foil, phosphoric acid and acetone was 10:0.015), heated to 40°C, stirred for reaction for 3 hours, filtered, washed until the filtrate was neutral, and dried the residue at 80°C for 6 hours to obtain a pretreated aluminum foil;
[0045] (2) The modified graphene, polyvinylidene fluoride-hexafluoropropylene copolymer, polyacrylonitrile and N,N-dimethylformamide prepared in Example 1 are fully stirred (the mass ratio of modified graphene, polyvinylidene fluoride-hexafluoropropylene copolymer, polyacrylonitrile and N,N-dimethylformamide is 94:3:3:100) to form a slurry for standby use; the pretreated aluminum foil obtained in step (1) is soaked in the slurry for 0.5 h, taken out and dried at 105° C. for 8 h to obtain an anti-interference graphene aluminum foil.
[0046] Example 4, preparing anti-interference graphene aluminum foil, the specific steps are as follows:
[0047] (1) Aluminum foil, phosphoric acid and 200 mL of acetone were added to a dry beaker (the mass ratio of aluminum foil, phosphoric acid and acetone was 10:0.02), heated to 40°C, stirred for reaction for 3 hours, filtered, washed until the filtrate was neutral, and dried the residue at 80°C for 6 hours to obtain a pretreated aluminum foil;
[0048] (2) The modified graphene, polyvinylidene fluoride, polytetrafluoroethylene and N-methylpyrrolidone prepared in Example 1 are fully stirred (the mass ratio of modified graphene, polyvinylidene fluoride, polytetrafluoroethylene and N-methylpyrrolidone is 95:4:4:110) to form a slurry for standby use; the pretreated aluminum foil obtained in step (1) is immersed in the slurry for 0.5 h, taken out and dried at 110° C. for 6 h to obtain an anti-interference graphene aluminum foil.
[0049] Comparative Example 1: preparing graphene aluminum foil, the specific steps are as follows:
[0050] The remaining steps remain unchanged, except that the modified graphene in step (2) of Example 2 is replaced by graphene without any treatment to prepare graphene aluminum foil.
[0051] Comparative Example 2: preparing graphene aluminum foil, the specific steps are as follows:
[0052] The remaining steps remain unchanged, only the modified graphene in step (2) in Example 2 is replaced by untreated graphene, hexadecyltrimethylammonium bromide and benzotriazole, wherein the mass ratio of untreated graphene, hexadecyltrimethylammonium bromide and benzotriazole is 76:8:8, and graphene aluminum foil is prepared.
[0053] Performance Testing
[0054] Peel strength test: The graphene aluminum foils prepared in Examples 2-4 and Comparative Examples 1-2 were cut into small pieces of 4×10 cm and subjected to a peel strength test on a peel strength tester;
[0055] Warpage test: The graphene aluminum foils prepared in Examples 2-4 and Comparative Examples 1-2 were cut into small pieces of 50×50 mm, and the warpage of the four corners was measured and the average value was calculated. The evaluation was performed according to the following criteria: A: warpage is less than 0-3 mm; B: warpage is greater than 3 mm and less than 7 mm; C: warpage is greater than 7 mm;
[0056] The test results of all items are shown in Table 1 below:
[0057] Table 1
[0058]
[0059] From the test results in Table 1 above, it can be seen that the peel strength of the graphene aluminum foil prepared in Examples 2-4 of the present invention is high, and the warpage grade is A, which indicates that the modified graphene prepared by grafting quaternary ammonium salt structure and benzotriazole on graphene and the aluminum foil have excellent adhesion strength. Therefore, the graphene aluminum foil of the present invention can effectively shield the interference of electromagnetic fields and ensure the anti-interference performance during data transmission, while dissipating heat in time to reduce safety hazards.
[0060] In the description of the specification, the description with reference to the terms "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representation of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.
[0061] The above contents are merely examples and explanations of the present invention. Those skilled in the art may make various modifications or additions to the specific embodiments described or replace them in a similar manner. As long as they do not deviate from the invention or exceed the scope defined by the claims, they shall all fall within the protection scope of the present invention.
Claims
1. A method for preparing an anti-interference graphene aluminum foil, characterized in that: The following steps are involved: (1) adding aluminum foil, phosphoric acid and acetone into a beaker, heating to 40°C, reacting for 3 hours, filtering, washing, and drying the residue at 80°C for 6 hours to obtain a pretreated aluminum foil; (2) fully stirring the modified graphene, the binder and the solvent to form a slurry for standby use; soaking the pretreated aluminum foil obtained in step (1) in the slurry for 0.5 h, taking it out and drying it at 100-110° C. for 6-12 h to obtain an anti-interference graphene aluminum foil; Wherein, the modified graphene is prepared by the following steps: S1. Add 3-dimethylamino-1-propanol, triethylamine and diethyl ether into a flask under nitrogen protection, mix, heat to 60° C., add hexadecane bromide, react for 4 h, cool, and distill under reduced pressure to obtain intermediate 1; S2, after nitrogen blowing into the flask, add intermediate 1, 10wt% sodium hydroxide solution and chloroform, stir and heat to 60°C, add epichlorohydrin, react for 5h, cool, distill under reduced pressure, purify by column chromatography, and distill under reduced pressure to obtain intermediate 2; S3, under nitrogen protection, add intermediate 2, triethylamine and DMF into a flask, mix, heat to 70°C, add benzotriazole and DMF, react for 4h, cool, and distill under reduced pressure to obtain intermediate 3; S4. Add intermediate 3, succinic anhydride, DMAP and DMF into a flask under nitrogen protection, stir and heat to 50°C, react for 12 hours, filter, wash the filtrate with saturated brine, dry and concentrate to obtain intermediate 4; S5. Add graphene, intermediate 4 and DMF into a flask, stir, add concentrated sulfuric acid, heat to 100° C. and react for 5 h, cool, filter, wash and dry to obtain modified graphene.
2. The method for preparing an anti-interference graphene aluminum foil according to claim 1, characterized in that: The usage ratio of 3-dimethylamino-1-propanol, hexadecane bromide, triethylamine and diethyl ether in step S1 is 11.8 mL: 33.2 mL: 16.7 mL: 180 mL.
3. The method for preparing an anti-interference graphene aluminum foil according to claim 1, characterized in that: The usage ratio of the intermediate 1 and epichlorohydrin in step S2 is 38.8 g:5.9 mL.
4. The method for preparing an anti-interference graphene aluminum foil according to claim 1, characterized in that: The usage ratio of the intermediate 2, benzotriazole, triethylamine and DMF in step S3 is 40.1 g:10.2 g:13.3 mL:240 mL.
5. The method for preparing an anti-interference graphene aluminum foil according to claim 1, characterized in that: The usage ratio of the intermediate 3, succinic anhydride, DMAP and DMF in step S4 is 35 g:6.4 g:0.65 g:220 mL.
6. The method for preparing an anti-interference graphene aluminum foil according to claim 1, characterized in that: The amount ratio of graphene, intermediate 4, concentrated sulfuric acid and DMF in step S5 is 16g:3.2g:0.09g:180mL.
7. The method for preparing an anti-interference graphene aluminum foil according to claim 1, characterized in that: The mass ratio of the aluminum foil to the phosphoric acid in the step (1) is 10:(0.01-0.02).
8. The method for preparing an anti-interference graphene aluminum foil according to claim 1, characterized in that: The mass ratio of the modified graphene, the binder and the solvent in the step (2) is (92-95):(5-8):(90-110).
9. The method for preparing an anti-interference graphene aluminum foil according to claim 1, characterized in that: The solvent of step (2) is one or more of dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; the binder of step (2) is one or more of polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene copolymer, polyacrylonitrile, and polytetrafluoroethylene.
10. An anti-interference graphene aluminum foil, characterized in that: The anti-interference graphene aluminum foil is prepared according to the preparation method of any one of claims 1-9.