Corrosion-resistant power-on viscosity-reducing adhesive tape and preparation method thereof

Abstract

The invention belongs to the technical field of adhesives, and particularly relates to a corrosion-resistant power-on viscosity-reducing adhesive tape and a preparation method thereof.The power-on viscosity-reducing adhesive tape comprises an adhesive layer and release layers attached to the two sides of the adhesive layer, and the adhesive layer is prepared by adopting an initiator to initiate a free radical polymerization reaction of soft monomers, hard monomers, functional monomers and the like; the functional monomer can be used as a cross-linking agent, so that the prepared acrylate adhesive has relatively high cross-linking density, further the structure of an adhesive layer is more compact, the permeation of a corrosive medium can be effectively prevented, and in addition, the functional monomer has a triazine-perfluoro alternate connection structure, so that the service life of the adhesive layer is prolonged. Wherein the existence of the triazine ring can enable the adhesive layer to show more excellent high temperature resistance, the existence of the perfluorinated chain segment can enable the molecular chain to show a high hydrophobic effect, and a hydrophobic layer can be formed on the surface of the adhesive layer, so that the corrosion resistance of the power-on viscosity-reducing adhesive tape is greatly improved.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of adhesives, and particularly relates to a corrosion-resistant electrically conductive debonding adhesive tape and a preparation method thereof. BACKGROUND

[0002] As an intelligent functional material, the electrically conductive debonding adhesive tape realizes dynamic control of adhesion through electric field regulation, and has become a core technology for realizing non-destructive disassembly and reuse of devices in the fields of precision electronics, new energy batteries, aerospace, etc. The technical principle is based on the electric response characteristics of high molecular materials: when conductive fillers or ionic electrolytes are embedded in the adhesive tape, the migration of electric charges after electrification causes changes in the microstructure of the adhesive layer, such as the rupture of crosslinked networks and the rearrangement of polar groups caused by ion migration, which in turn causes the adhesive layer to change from a high-adhesion state to a low-adhesion state.

[0003] Although the electrically conductive debonding adhesive tape has achieved a breakthrough in function, it faces severe corrosion challenges in practical applications, especially in strong corrosion environments such as new energy batteries, marine equipment, and chemical pipelines. Corrosion resistance has become a key bottleneck restricting its service life and reliability. Therefore, the development of electrically conductive debonding adhesive tapes with corrosion resistance has gradually become a research hotspot. SUMMARY

[0004] In view of the deficiencies of the prior art, the purpose of the present application is to provide a corrosion-resistant electrically conductive debonding adhesive tape and a preparation method thereof.

[0005] In a first aspect of the present application, a corrosion-resistant electrically conductive debonding adhesive tape is provided, comprising an adhesive layer and a release layer attached to both sides of the adhesive layer. The adhesive layer is made of the following raw materials in parts by weight: Soft monomer 35-50 parts; Hard monomer 10-15 parts; Modified monomer 1-3.5 parts; Ionic liquid monomer 1-2 parts; Initiator 0.3-0.6 parts; Polymerization medium 60-80 parts; Conductive additive 3-5 parts; Lithium metal salt 0.5-1 part.

[0006] As a preferred technical scheme of the present application, the soft monomer is butyl acrylate or isooctyl acrylate; the hard monomer is methyl methacrylate or butyl methacrylate; the ionic liquid monomer is 1-vinyl-3-methyl imidazole dicyan amine salt or 1-allyl-3-vinyl imidazole dicyan amine salt; the initiator is azobisdimethyl isobutyl cyanide or azobisdimethyl isohexyl cyanide; the polymerization medium is ethyl acetate; the conductive additive is carbon nanotube or graphene; and the lithium metal salt is any one of lithium itaconate, lithium tetrafluoroborate or lithium bisoxalate borate.

[0007] As a preferred technical scheme of the present application, the modified monomer is prepared by the following method: 2,4-diamino-6-diallyl amino-1,3,5-triazine and N,N-dimethyl formamide are added into a nitrogen-filled polymerization kettle, stirring is started, after a uniform reaction liquid is formed, a chain extender is added into the polymerization kettle, heating is started, the temperature is controlled at 70-80℃, after the temperature is kept at 70-80℃ for 6-9h, an acid binding agent is added, after the addition is completed, stirring is continued for 8-16h, the solvent is evaporated and removed, the product is collected, and the modified monomer is obtained through a purification treatment process.

[0008] As a preferred technical scheme of the present application, the molar ratio of the 2,4-diamino-6-diallyl amino-1,3,5-triazine and the chain extender is 1:1.

[0009] As a preferred technical scheme of the present application, the chain extender is prepared by the following method: Perfluorodiol compound and tetrahydrofuran are added into a reaction kettle, nitrogen is introduced for protection, stirring is started, after mixing is uniform, the reaction kettle is placed in an ice bath environment, halogenated modification reagent and pyridine are added into the reaction kettle, after the addition is completed, the ice bath is removed, stirring is continued at a temperature of 30-40℃ for 3-6h, the solvent is evaporated and removed, the product is collected, and the chain extender is obtained through a purification treatment process.

[0010] As a preferred technical scheme of the present application, the perfluorodiol compound is any one of 1H,1H,2H,3H,3H-perfluorononane-1,2-diol, 1H,1H,9H,9H-perfluoro-1,9-nonanediol or hexadecafluoro-1,10-decanediol.

[0011] As a preferred technical scheme of the present application, the halogenated modification reagent is any one of chloroacetyl chloride, bromoacetyl bromide or 4-bromobutyryl chloride.

[0012] As a preferred technical scheme of the present application, the molar ratio of the perfluorodiol compound and the halogenated modification reagent is 1:2.

[0013] As a preferred technical scheme of the present application, the acid-binding agent is a sodium hydroxide aqueous solution with a mass fraction of 10-20%.

[0014] It should be noted that, in the above technical scheme, first, the perfluorodiol compound is halogenated and modified by using a halogenated modification reagent, a condensation reaction of active acyl halide groups and hydroxyl substituents in the structures is utilized, and the amount ratio of the two is controlled to obtain a perfluoro derivative containing two active halogen substituents in the structure, i.e., a chain extension agent, then, under the action of an acid-binding agent, the two active halogen substituents in the structure successively replace the amino substituents in the structure of 2,4-diamino-6-diallyl amino-1,3,5-triazine, thereby obtaining a modified monomer with a triazine-perfluoro alternating connection structure.

[0015] In a second aspect of the present application, a preparation method of a corrosion-resistant power-conducting adhesion-reducing tape is provided, comprising the following steps: In a first step, each raw material is weighed according to the weight fraction and prepared for use; In a second step, the soft monomer, the hard monomer, the ionic liquid monomer, the modified monomer, and the initiator are added to the polymerization medium, stirring is started, and after uniform mixing, heating is started, the temperature is maintained at 70-75 DEG C, and after 6-12 h of incubation and stirring, the temperature is reduced to 30-40 DEG C, then the lithium metal salt and the conductive additive are added, and stirring is continued for 20-30 min to obtain the adhesive layer precursor; In a third step, the adhesive layer precursor is uniformly coated on one side of the release film, after coating is completed, it is placed in a temperature environment of 70-80 DEG C for 5-10 min to form the adhesive layer, then another layer of release film is attached to the coated surface, and the power-conducting adhesion-reducing tape is obtained.

[0016] It should be noted that, under the action of the initiator, the unsaturated alkenyl functional groups in the structures of the soft monomer, the hard monomer, the ionic liquid monomer, and the modified monomer can undergo free radical polymerization, and since the modified monomer structure contains a large number of unsaturated alkenyl functional groups, it can act as a crosslinking agent, and a highly crosslinked acrylate adhesive can be prepared.

[0017] Compared with the prior art, the present application has the following beneficial effects: The present application, by preparing a functional monomer as one of raw materials of the acrylate adhesive, firstly, since a large amount of unsaturated alkenyl groups contained in the structure can produce crosslinking effect in the process of free radical polymerization reaction, the prepared acrylate adhesive has higher crosslinking density, and the increase of the crosslinking density of the molecular chain can make the structure of the adhesive layer more compact, thereby effectively preventing the penetration of corrosive medium into the adhesive layer, in addition, the functional monomer has a triazine-perfluoro alternating connection structure, the presence of the triazine ring can improve the stability of the adhesive molecular chain, and the presence of the perfluoro chain segment can make the molecular chain have high hydrophobic effect, and can form a hydrophobic layer on the surface of the adhesive layer, further preventing the residence and penetration of corrosive medium, thereby greatly improving the corrosion resistance of the power-on adhesion-reducing tape. BRIEF DESCRIPTION OF DRAWINGS

[0018] In order to more clearly illustrate the technical solutions of the embodiments of the present application, the following will briefly introduce the drawings needed to be used in the description of the embodiments. Obviously, the drawings in the following description are only some embodiments of the present application, and other drawings can also be obtained by those skilled in the art without creative labor.

[0019] Figure 1 The infrared analysis test diagram of the modified monomer. DETAILED DESCRIPTION

[0020] In order to facilitate the understanding of the present application, the present application lists the following embodiments. It should be understood by those skilled in the art that the embodiments are only to help understand the present application, and should not be regarded as a specific limitation on the present application.

[0021] Embodiment 1:

[0022] The present embodiment provides a kind of corrosion-resistant power-on adhesion-reducing tape, including adhesive layer and the release layer attached to the both sides of adhesive layer; The adhesive layer is made of the following raw materials measured by weight fraction: Butyl acrylate 35 parts; Methyl methacrylate 10 parts; Modified monomer 1 part; 1-ethenyl-3-methyl imidazole dicyan amine salt 1 part; Azobisdimethyl isobutyronitrile 0.3 parts; Ethyl acetate 60 parts; Carbon nanotube 3 parts; Lithium tetrafluoroborate 0.5 parts; The preparation method of the power-on adhesion-reducing tape includes the following steps: First step, each raw material is weighed according to weight fraction, and is ready for use; Second step, butyl acrylate, methyl methacrylate, 1-vinyl-3-methyl imidazole dicyan amine salt, modified monomer and azobisisobutyronitrile are added into ethyl acetate, stirring is started, after mixing, heating is started, the temperature is maintained at 75℃, after 9h of incubation and stirring, the temperature is reduced to 35℃, then lithium tetrafluoroborate and carbon nanotubes are added, stirring is continued for 30min, to obtain the adhesive layer precursor; Third step, the adhesive layer precursor is uniformly coated on one side of the release film, after coating is completed, it is placed in a temperature environment of 75℃ for 10min, to form the adhesive layer, the thickness of the adhesive layer is controlled to be 50μm, then another layer of release film is attached on the coated surface, to obtain the electrification adhesion reduction tape.

[0023] The modified monomer is prepared by the following method: Step one, 0.8g of 1H, 1H, 9H, 9H-perfluoro-1, 9-nonanediol and tetrahydrofuran are added into the reaction kettle, nitrogen protection is started, stirring is started, after mixing, it is placed in an ice bath environment, then 0.44g of chloroacetyl chloride and 0.1g of pyridine are added into the reaction kettle, after addition, the ice bath is removed, stirring is continued at a temperature of 35℃ for 4h, the solvent is evaporated, the product is collected, after purification treatment, the chain extender is obtained; Step two, 0.5g of 2, 4-diamino-6-diallyl amino-1, 3, 5-triazine and N, N-dimethylformamide are added into the nitrogen-filled polymerization kettle, stirring is started, after a uniform reaction liquid is formed, 1.37g of the chain extender is added into the polymerization kettle, after addition, heating is started, the temperature is controlled to be 75℃, after 8h of incubation and stirring at this temperature, 4mL of 10% sodium hydroxide aqueous solution is added, after addition, stirring is continued for 12h, the solvent is evaporated, the product is collected, after purification treatment, the modified monomer is obtained.

[0024] Figure 1 The infrared analysis test diagram of the modified monomer is shown in the figure, the characteristic absorption peaks appearing at 3371cm -1 and 3284cm -1 belong to N-H characteristic absorption peaks, the characteristic absorption peak appearing at 1737cm -1 belongs to the C=O characteristic absorption peak of ester group, the characteristic absorption peak appearing at 1589cm -1 belongs to the C=N characteristic absorption peak of triazine ring, the characteristic absorption peak appearing at 1296cm -1 belongs to the C-F characteristic absorption peak.

[0025] Example 2:

[0026] The present embodiment provides a kind of corrosion-resistant electrification adhesion reduction tape, including adhesive layer and the release layer attached on both sides of adhesive layer; The adhesive layer is made of the following raw materials measured by weight fraction: butyl acrylate 40 parts; methyl methacrylate 12 parts; modified monomer 3 parts; 1-vinyl-3-methyl imidazole dicyan amine salt 1.5 parts; azobis isobutyronitrile 0.5 parts; ethyl acetate 70 parts; carbon nanotube 4 parts; lithium tetrafluoroborate 0.8 parts; The preparation method of the conductive adhesive tape includes the following steps: Step 1, weigh each raw material according to the weight fraction and prepare for use; Step 2, add butyl acrylate, methyl methacrylate, 1-vinyl-3-methyl imidazole dicyan amine salt, modified monomer and azobis isobutyronitrile into ethyl acetate, start stirring, mix evenly, then start heating, maintain the temperature at 75℃, after 9h of incubation and stirring, reduce the temperature to 35℃, then add lithium tetrafluoroborate and carbon nanotube, continue stirring for 30min, to obtain the adhesive layer precursor; Step 3, evenly coat the adhesive layer precursor on one side of the release film, after coating is completed, place it in a temperature environment of 75℃ for 10min, to form the adhesive layer, control the thickness of the adhesive layer to be 50μm, then attach another layer of release film on the coated surface, to obtain the conductive adhesive tape.

[0027] The preparation method of the modified monomer is the same as that of Example 1.

[0028] Example 3:

[0029] The present embodiment provides a corrosion-resistant conductive adhesive tape, which comprises an adhesive layer and release layers attached on both sides of the adhesive layer. The adhesive layer is made of the following raw materials measured by weight fraction: butyl acrylate 50 parts; methyl methacrylate 15 parts; modified monomer 3.5 parts; 1-vinyl-3-methyl imidazole dicyan amine salt 2 parts; azobis isobutyronitrile 0.6 parts; ethyl acetate 80 parts; carbon nanotube 5 parts; lithium tetrafluoroborate 1 part; The preparation method of the conductive adhesive tape includes the following steps: Step 1, weigh each raw material according to the weight fraction and prepare for use; Second step, butyl acrylate, methyl methacrylate, 1-vinyl-3-methyl imidazole dicyan amine salt, modified monomer and azobis isobutyronitrile are added into ethyl acetate, stirring is started, after mixing evenly, heating is started, the temperature is maintained at 75℃, after incubation and stirring for 9h, the temperature is reduced to 35℃, then lithium tetrafluoroborate and carbon nanotubes are added, and stirring is continued for 30min to obtain the adhesive layer precursor; Third step, the adhesive layer precursor is uniformly coated on one side of the release film, after coating is completed, it is placed in a temperature environment of 75℃ for 10min to form an adhesive layer, the thickness of the adhesive layer is controlled to be 50μm, then another layer of release film is attached to the coated surface, and the power-on adhesion reduction tape is obtained.

[0030] The preparation method of the modified monomer is the same as that of Example 1.

[0031] Comparative Example 1 The difference between this comparative example and Example 2 is that the modified monomer is replaced by 2,4-diamino-6-diallyl amino-1,3,5-triazine, and the rest are the same.

[0032] Comparative Example 2 The difference between this comparative example and Example 1 is that no modified monomer is added, and the rest are the same.

[0033] The performance of the power-on adhesion reduction tape provided by the above examples and comparative examples is tested, and the test method is as follows: (1) According to standard GB / T 2792-2014, the adhesive tape sample is attached to a stainless steel plate for bonding performance test; (2) The adhesive tape sample is attached to a stainless steel plate, then placed in an oven at 150℃ for 4h, then the adhesive tape is hot stripped, and the presence or absence of residual glue is observed to evaluate the high temperature resistance of the adhesive tape; (3) The adhesive tape sample is attached to the surface of an aluminum foil, then immersed in lithium battery electrolyte, the temperature is set to 80℃, and after immersion for 24h, it is taken out, the adhesive layer phenomenon is observed, and the corrosion resistance of the adhesive tape is evaluated; The performance test data is shown in Table 1.

[0034] Table 1 Performance test results

[0035] From the above, the electrically conductive adhesion-reducing adhesive tape prepared in the embodiment of the application has good adhesion, high temperature resistance and corrosion resistance. After the modified monomer is replaced by 2,4-diamino-6-diallyl amino-1,3,5-triazine, the adhesive molecular chain does not contain a perfluorinated highly hydrophobic chain, resulting in insufficient hydrophobicity of the adhesive tape surface, and thus the corrosion resistance is reduced. In addition, it can be found that the presence of the crosslinking agent also has a positive effect on the adhesion of the adhesive layer, because the increase in crosslinking density increases the cohesive energy of the adhesive, thereby exhibiting higher adhesion.

[0036] The principles and implementations of the present application are described herein by applying specific examples, and the above description of the examples is only used to help understand the method of the present application and its core idea, including the best mode, and also enables any person skilled in the art to practice the present application, including manufacturing and using any device or system, and implementing any combined method. It should be noted that, for those skilled in the art, without departing from the principles of the present application, several improvements and modifications can be made to the present application, and these improvements and modifications also fall within the scope of protection of the present application.

Claims

1. A corrosion-resistant, electrically-conductive, adhesion-reducing tape, characterized by, The adhesive layer is prepared by using the following raw materials in the amount of parts by weight: The adhesive layer is prepared by using the following raw materials in the amount of parts by weight: The soft monomer is butyl acrylate or isooctyl acrylate; the hard monomer is methyl methacrylate or butyl methacrylate; the ionic liquid monomer is 1-vinyl-3-methyl imidazole dicyanamide salt or 1-allyl-3-vinyl imidazole dicyanamide salt; the initiator is azobisdimethyl isobutyronitrile or azobisdimethyl isohexyl nitrile; the polymerization medium is ethyl acetate; the conductive additive is carbon nanotube or graphene; and the lithium metal salt is any one of lithium itaconate, lithium tetrafluoroborate or lithium bisoxalate borate. The modified monomer is prepared by the following method: The 2,4-diamino-6-diallyl amino-1,3,5-triazine and the chain extender are mixed in a molar ratio of 1:

1. The chain extender is prepared by the following method: The perfluorinated diol compound and tetrahydrofuran are added to a reaction kettle, nitrogen is introduced for protection, stirring is started, and then the mixture is placed in an ice bath environment. Then, the halogenated modification reagent and pyridine are added to the reaction kettle, the ice bath is removed, and stirring is continued at a temperature of 30-40°C for 3-6 hours. The solvent is evaporated and removed, and the product is collected and purified to obtain the chain extender. The perfluorinated diol compound is any one of 1H,1H,2H,3H,3H-perfluorinated nonane-1,2-diol, 1H,1H,9H,9H-perfluoro-1,9-nonane diol or hexadecafluoro-1,10-decanediol. The halogenated modification reagent is any one of chloroacetyl chloride, bromoacetyl bromide or 4-bromobutyryl chloride. The molar ratio of the perfluorinated diol compound to the halogenated modification reagent is 1:

2.

2. The corrosion-resistant, electrically-conductive adhesive tape of claim 1, wherein, The acid-binding agent is a sodium hydroxide aqueous solution with a mass fraction of 10-20%.

3. The corrosion resistant, electrically conductive adhesive tape of claim 1, wherein, The following steps are included: First step, the raw materials are weighed according to the weight fraction and prepared for use; 4. The corrosion-resistant, electrically-conductive adhesive tape of claim 3, wherein, Second step, the soft monomer, hard monomer, ionic liquid monomer, modified monomer and initiator are added to the polymerization medium, stirring is started, and then the temperature is maintained at 70-75°C for 6-12 hours. After the temperature is reduced to 30-40°C, the lithium metal salt and the conductive additive are added, and stirring is continued for 20-30 minutes to obtain the adhesive layer precursor.

5. The corrosion resistant, electrically conductive adhesive tape of claim 3, wherein, ​ ​ 6. The corrosion-resistant, electrically-conductive adhesive tape of claim 5, wherein, ​ 7. The corrosion resistant, electrically conductive adhesive tape of claim 5, wherein, ​ 8. The corrosion resistant, electrically conductive adhesive tape of claim 5, wherein, ​ 9. The corrosion resistant, electrically conductive adhesive tape of claim 3, wherein, ​ 10. A method of producing the corrosion-resistant conductive adhesive tape according to claim 1, characterized by, ​ ​ ​ Third step, the adhesive layer precursor is evenly coated on one side of the release film, after coating, it is placed in a temperature environment of 70-80℃ for 5-10min, forming the adhesive layer, then another layer of release film is attached on the coated surface, and the electrically conductive adhesive tape is obtained.

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