Fluorine-containing electrolyte-resistant high-temperature-resistant solvent type acrylate pressure-sensitive adhesive, preparation method thereof and adhesive tape

Abstract

The invention discloses a fluorine-containing electrolyte-resistant high-temperature-resistant solvent type acrylate pressure-sensitive adhesive, a preparation method thereof and an adhesive tape. The pressure-sensitive adhesive is prepared from the following raw material components in parts by weight: 100 to 120 parts of butyl acrylate, 350 to 400 parts of 2-ethylhexyl acrylate, 220 to 250 parts of vinyl acetate, 80 to 100 parts of methyl acrylate, 18 to 22 parts of hydroxypropyl acrylate, 15 to 25 parts of acryloyloxyphenylboronic acid, 40 to 70 parts of fluorine-containing acrylate compounds, 18 to 23 parts of methacrylic acid, 1 to 3g of an initiator, 5 to 40 parts of a curing agent and 400 to 500 parts of a solvent. The dodecafluoroheptyl acrylate and the acryloyloxyphenylboronic acid are introduced into the pressure-sensitive adhesive, and a dual curing system is adopted, so that the comprehensive performance of the pressure-sensitive adhesive is effectively improved; the corrosion resistance and the high temperature resistance are enhanced, and the stability under extreme conditions is ensured.

Description

Technical Field

[0001] The invention relates to the field of adhesive materials, and in particular to a fluorine-containing, electrolyte-resistant, high-temperature-resistant solvent-type acrylic pressure-sensitive adhesive, a preparation method thereof, and an adhesive tape. Background Art

[0002] With the continuous growth of the three major markets of electronic consumption, new energy vehicles and energy storage, lithium-ion batteries have ushered in huge development opportunities, and there is a huge demand for adhesive tapes used in the lithium battery industry. In the PACK process of lithium batteries, one of the processes is to wind the positive electrode sheet, separator and negative electrode sheet into a battery cell and then inject electrolyte. This process requires the use of electrolyte-resistant termination tape. Due to the excellent bonding properties, good chemical corrosion resistance and weather resistance of solvent-based acrylic pressure-sensitive adhesives, as well as the ability to provide stable adhesion on various substrates, most of the termination tapes on the market are acrylic systems.

[0003] However, the performance of traditional acrylic pressure-sensitive adhesives under extreme conditions is not ideal, especially under high temperature and electrolyte (LiPF6) environments. The adhesive is easily soluble in lithium battery electrolytes, and its bonding strength and durability will be significantly reduced or even completely disappear, resulting in battery short circuits, shortening the battery life, and posing serious safety hazards. In addition, the volatile organic compounds released by solvent-based acrylic pressure-sensitive adhesives during production and use have also attracted environmental attention.

[0004] Therefore, it is necessary to improve the existing technology to provide a more reliable solution. Summary of the invention

[0005] The technical problem to be solved by the present invention is to provide a fluorine-containing electrolyte-resistant and high-temperature-resistant solvent-type acrylic pressure-sensitive adhesive, a preparation method thereof, and an adhesive tape in view of the deficiencies in the above-mentioned prior art. The solvent-type acrylic pressure-sensitive adhesive of the present invention significantly improves the high-temperature resistance and chemical corrosion resistance by introducing specific fluorine-containing functional monomers and acryloxyphenylboronic acid, and combining with an optimized polymerization process. The termination tape made of the adhesive will not dissolve or chemically react to lose its viscosity after being immersed in the electrolyte, and can maintain good viscosity.

[0006] To achieve the above object, the technical solution adopted by the present invention is: In the first aspect of the present invention, a fluorine-containing electrolyte-resistant and high-temperature-resistant solvent-type acrylic pressure-sensitive adhesive is provided, comprising the following raw material components in parts by weight:

[0007] Butyl acrylate: 100-120 parts, isooctyl acrylate: 350-400 parts, vinyl acetate: 220-250 parts, methyl acrylate: 80-100 parts, hydroxypropyl acrylate: 18-22 parts, acryloxyphenylboric acid: 15-25 parts, fluorine-containing acrylic acid ester compound: 40-70 parts, methacrylic acid: 18-23 parts, initiator: 1-3g, curing agent: 5-40 parts, solvent: 400-500 parts.

[0008] Preferably, the fluorine-containing acrylic ester compound is at least one of octafluoropentyl acrylate, dodecafluoroheptyl acrylate, and tridecafluorooctyl acrylate.

[0009] Preferably, the fluorine-containing acrylic ester compound is dodecafluoroheptyl acrylate.

[0010] Preferably, the curing agent is a mixture of an isocyanate curing agent and an epoxy curing agent.

[0011] Preferably, the isocyanate curing agent is at least one of toluene diisocyanate, diphenylmethane diisocyanate and hexamethylene diisocyanate.

[0012] Preferably, the epoxy curing agent is bisphenol A epoxy resin or methyltetrahydrophthalic anhydride.

[0013] Preferably, the initiator is an acyl peroxide or an azo compound, and the solvent is ethyl acetate.

[0014] Preferably, the fluorine-containing electrolyte-resistant and high-temperature-resistant solvent-type acrylic pressure-sensitive adhesive comprises the following raw material components in parts by weight:

[0015] Butyl acrylate: 120 parts, isooctyl acrylate: 360 parts, vinyl acetate: 240 parts, methyl acrylate: 90 parts, hydroxypropyl acrylate: 20 parts, acryloxyphenylboric acid: 20 parts, fluorine-containing acrylic acid ester compound: 50 parts, methacrylic acid: 20 parts, initiator: 2 parts, isocyanate curing agent: 10 parts, epoxy curing agent: 10 parts, ethyl acetate: 450 parts.

[0016] The second aspect of the present invention provides a method for preparing the fluorine-containing electrolyte-resistant and high-temperature-resistant solvent-type acrylic pressure-sensitive adhesive as described above, comprising the following steps:

[0017] S1, take the raw materials of the formula weight parts for use, wherein the initiator, isocyanate curing agent and epoxy curing agent are all diluted with part of ethyl acetate for use;

[0018] S2, pouring the remaining portion of ethyl acetate into the reaction vessel so that it accounts for 40-60% of the total volume of the reaction vessel;

[0019] S3, filling the reaction vessel with nitrogen to allow the reaction to proceed under an inert atmosphere;

[0020] S4, adding all butyl acrylate, isooctyl acrylate, vinyl acetate, methyl acrylate, and fluorine-containing acrylate compounds into a reaction container;

[0021] S5, stirring evenly at 60-70 rpm;

[0022] S6. Heat to 80-82°C, maintain this temperature and continue stirring for 15-30 minutes;

[0023] S7, dropwise add 1 / 2 mass of the initiator in ethyl acetate solution, keep the reaction temperature stable at 80-82°C, and complete the dropwise addition within 1-2 hours;

[0024] S8, premixing hydroxypropyl acrylate, acryloxyphenylboronic acid and methacrylic acid, and adding the resulting mixture and the remaining initiator dropwise into the reaction vessel within 1-2 hours, maintaining the temperature at 80-82° C. and stirring;

[0025] S9, heating to 84-86°C, stirring continuously, and reacting for 3-5 hours;

[0026] S10, after the completion of the heating, the mixture is cooled to room temperature, an ethyl acetate solution of an isocyanate curing agent and an ethyl acetate solution of an epoxy curing agent are added, and the mixture is stirred at a speed of 1500-2000 rpm for 15-20 minutes to obtain the fluorine-containing electrolyte-resistant and high-temperature-resistant solvent-type acrylic pressure-sensitive adhesive.

[0027] Preferably, in step S1, the initiator, isocyanate curing agent and epoxy curing agent are all diluted with 5-20 times the mass of ethyl acetate for standby use.

[0028] The third aspect of the present invention provides a fluorine-containing electrolyte-resistant and high-temperature solvent-resistant acrylate pressure-sensitive adhesive tape, which is prepared by the following method: the fluorine-containing electrolyte-resistant and high-temperature solvent-resistant acrylate pressure-sensitive adhesive as described above is evenly coated on a base film, dried at 110-130°C for 1.5-6 minutes, and a release film is attached to the adhesive layer to obtain a fluorine-containing electrolyte-resistant and high-temperature solvent-resistant acrylate pressure-sensitive adhesive tape.

[0029] The beneficial effects of the present invention are:

[0030] The present invention provides a fluorine-containing electrolyte-resistant and high-temperature-resistant solvent-type acrylic pressure-sensitive adhesive, a preparation method thereof, and an adhesive tape product based on the pressure-sensitive adhesive. The pressure-sensitive adhesive of the present invention effectively improves the comprehensive performance of the pressure-sensitive adhesive by introducing dodecafluoroheptyl acrylate and acryloxyphenylboric acid and adopting a dual curing system; the compound use of dodecafluoroheptyl acrylate and acryloxyphenylboric acid not only significantly improves the corrosion resistance of the pressure-sensitive adhesive in an electrolyte environment, but also enhances its high-temperature resistance and ensures stability under extreme conditions. In addition, the reasonable monomer ratio and the optimization of the curing system enable the pressure-sensitive adhesive to have high performance while still maintaining an excellent bonding effect, meeting the needs of a variety of complex application scenarios. DETAILED DESCRIPTION

[0031] The present invention is further described in detail below in conjunction with embodiments so that those skilled in the art can implement the invention with reference to the description.

[0032] It should be understood that the terms such as “having”, “including” and “comprising” used herein do not exclude the existence or addition of one or more other elements or combinations thereof.

[0033] The test methods used in the following examples are conventional methods unless otherwise specified. The materials and reagents used in the following examples are all commercially available unless otherwise specified. In the following examples, if no specific conditions are specified, the experiments were carried out under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used, if the manufacturer is not specified, are all conventional products that can be purchased commercially.

[0034] The present invention provides a fluorine-containing electrolyte-resistant and high-temperature-resistant solvent-type acrylic pressure-sensitive adhesive, comprising the following raw material components in parts by weight:

[0035] Butyl acrylate: 100-120 parts, isooctyl acrylate: 350-400 parts, vinyl acetate: 220-250 parts, methyl acrylate: 80-100 parts, hydroxypropyl acrylate: 18-22 parts, acryloxyphenylboric acid: 15-25 parts, fluorine-containing acrylic acid ester compound: 40-70 parts, methacrylic acid: 18-23 parts, initiator: 1-3g, curing agent: 5-40 parts, solvent: 400-500 parts.

[0036] In a preferred embodiment, the fluorine-containing acrylic ester compound is at least one of octafluoropentyl acrylate, dodecafluoroheptyl acrylate, and tridecafluorooctyl acrylate.

[0037] In a preferred embodiment, the fluorine-containing acrylate compound is dodecafluoroheptyl acrylate.

[0038] In a preferred embodiment, the curing agent is a mixture of an isocyanate curing agent and an epoxy curing agent.

[0039] In a preferred embodiment, the isocyanate curing agent is at least one of toluene diisocyanate, diphenylmethane diisocyanate, and hexamethylene diisocyanate, and more preferably toluene diisocyanate.

[0040] In a preferred embodiment, the epoxy curing agent is bisphenol A epoxy resin or methyltetrahydrophthalic anhydride, more preferably bisphenol A epoxy resin.

[0041] In a preferred embodiment, the initiator is an acyl peroxide or an azo compound, more preferably benzoyl peroxide.

[0042] In a preferred embodiment, the solvent is ethyl acetate.

[0043] In a preferred embodiment, the fluorine-containing electrolyte-resistant and high-temperature-resistant solvent-type acrylic pressure-sensitive adhesive comprises the following raw material components in parts by weight:

[0044] Butyl acrylate: 120 parts, isooctyl acrylate: 360 parts, vinyl acetate: 240 parts, methyl acrylate: 90 parts, hydroxypropyl acrylate: 20 parts, acryloxyphenylboric acid: 20 parts, fluorine-containing acrylic acid ester compound: 50 parts, methacrylic acid: 20 parts, initiator: 2 parts, isocyanate curing agent: 10 parts, epoxy curing agent: 10 parts, ethyl acetate: 450 parts.

[0045] The present invention also provides a method for preparing the above fluorine-containing electrolyte-resistant and high-temperature-resistant solvent-type acrylic pressure-sensitive adhesive, comprising the following steps:

[0046] S1, take the raw materials in parts by weight of the formula for use, wherein the initiator, isocyanate curing agent and epoxy curing agent are all diluted with part of ethyl acetate for use;

[0047] S2, pouring the remaining portion of ethyl acetate into the reaction vessel so that it accounts for 40-60% of the total volume of the reaction vessel;

[0048] S3, filling the reaction vessel with nitrogen to allow the reaction to proceed under an inert atmosphere;

[0049] S4, adding all butyl acrylate, isooctyl acrylate, vinyl acetate, methyl acrylate, and fluorine-containing acrylate compounds into a reaction container;

[0050] S5, stirring evenly at 60-70 rpm;

[0051] S6. Heat to 80-82°C, maintain this temperature and continue stirring for 15-30 minutes;

[0052] S7, dropwise add 1 / 2 mass of the initiator in ethyl acetate solution, keep the reaction temperature stable at 80-82°C, and complete the dropwise addition within 1-2 hours;

[0053] S8, premixing hydroxypropyl acrylate, acryloxyphenylboronic acid and methacrylic acid, and adding the resulting mixture and the remaining initiator dropwise into the reaction vessel within 1-2 hours, maintaining the temperature at 80-82° C. and stirring;

[0054] S9, heating to 84-86°C, stirring continuously, and reacting for 3-5 hours;

[0055] S10, after completion, stop heating, cool to room temperature, add ethyl acetate solution of isocyanate curing agent and ethyl acetate solution of epoxy curing agent, stir at a speed of 1500-2000 rpm for 15-20 minutes, and obtain fluorine-containing electrolyte-resistant and high-temperature-resistant solvent-type acrylic pressure-sensitive adhesive.

[0056] In a preferred embodiment, in step S1, the initiator, isocyanate curing agent and epoxy curing agent are all diluted with 5-20 times the mass of ethyl acetate for later use; more preferably, they are diluted with 10 times the mass of ethyl acetate for later use.

[0057] The present invention also provides a fluorine-containing electrolyte-resistant and high-temperature solvent-resistant acrylic pressure-sensitive adhesive tape, which is prepared by the following method: uniformly coating the above fluorine-containing electrolyte-resistant and high-temperature solvent-resistant acrylic pressure-sensitive adhesive on a base film, drying at 110-130° C. for 1.5-6 minutes, and laminating a release film on the adhesive layer to obtain the fluorine-containing electrolyte-resistant and high-temperature solvent-resistant acrylic pressure-sensitive adhesive tape.

[0058] The pressure-sensitive adhesive formula of the present invention not only significantly improves the electrolyte resistance and high temperature resistance of the pressure-sensitive adhesive by introducing dodecafluoroheptyl acrylate and acryloxyphenylboric acid, but also further enhances the bonding performance and chemical stability of the adhesive. The long-chain fluorocarbon group in dodecafluoroheptyl acrylate gives the material extremely strong chemical inertness, reduces the surface energy of the pressure-sensitive adhesive, can effectively resist the penetration and corrosion of the electrolyte, and ensures the long-term stability of the adhesive in harsh electrochemical environments such as lithium-ion batteries. Acryloxyphenylboronic acid is a functional monomer with special chemical activity. The benzene ring in its structure gives the pressure-sensitive adhesive good rigidity and heat resistance, while the boric acid group can form strong bonds with the hydroxyl group or other reactive groups on the polymer chain, thereby enhancing the cross-linking density and chemical stability of the pressure-sensitive adhesive. The introduction of acryloxyphenylboronic acid as a functional monomer not only helps to improve the bonding strength of the pressure-sensitive adhesive, but also gives the material better chemical corrosion resistance, especially in complex environments containing strong oxidants and acids and alkalis. This monomer forms a network with a unique structure through copolymerization with other acrylate monomers, which enables the pressure-sensitive adhesive to maintain stable performance under harsh conditions.

[0059] At the same time, the present invention combines the use of isocyanate curing agent and epoxy curing agent. These two curing agents form a complementary network structure after chemical reaction. The isocyanate provides good flexibility and initial adhesion, while the epoxy enhances the strength and thermal stability of the material. The two work synergistically to form a highly cross-linked network structure. This cross-linked structure not only improves the mechanical strength and heat resistance of the pressure-sensitive adhesive, but also ensures its bonding stability under high temperature and dynamic stress. The application of this combination enables the pressure-sensitive adhesive to maintain excellent performance under extreme conditions, expanding its application potential in high-demand fields such as automotive electronics, aerospace, etc.

[0060] In addition, the present invention ensures the structural regularity of the polymer and the uniformity of the molecular weight distribution by optimizing the synthesis process, such as step-by-step dripping and precise temperature control. This process improvement improves the stability of the physical and chemical properties of the pressure-sensitive adhesive, significantly reduces the uncertainty in the production process, and reduces the production cost. Moreover, compared with perfluorooctyl methacrylate, which has serious harm to the environment and human body, the use of dodecafluoroheptyl acrylate not only meets the environmental protection requirements of modern industry, but also reduces the negative impact on the environment while maintaining excellent performance, realizing the unity of material innovation and sustainable development. Compared with the prior art, the present invention shows significant advantages in electrolyte resistance, high temperature resistance, bonding performance and environmental protection, and has broad market application prospects.

[0061] The above is the overall concept of the present invention, and detailed embodiments and comparative examples are provided below on the basis of the overall concept of the present invention to further illustrate the present invention.

[0062] Example 1

[0063] A fluorine-containing electrolyte-resistant and high-temperature-resistant solvent-type acrylic pressure-sensitive adhesive, the raw material components of which are as follows:

[0064] Butyl acrylate: 120g, isooctyl acrylate: 360g, vinyl acetate: 240g, methyl acrylate: 90g, hydroxypropyl acrylate: 20g, acryloxyphenylboric acid: 20g, dodecafluoroheptyl acrylate: 50g, methacrylic acid: 20g, initiator: 2g, toluene diisocyanate curing agent: 10g, bisphenol A type epoxy resin curing agent: 10g. (The raw material bisphenol A type epoxy resin curing agent was purchased from Merck, and the other raw materials were purchased from Anaiji Company, the same below)

[0065] S1. Take the raw materials in parts by weight of the formula for use, wherein the initiator and the curing agent are diluted with ethyl acetate in a mass ratio of 1:10 for use;

[0066] S2, prepare a four-mouth reaction kettle equipped with a condensing reflux device, and pour ethyl acetate into the reaction kettle so that it accounts for 50% of the total reaction system volume;

[0067] S3, filling the reactor with nitrogen so that the reaction can be carried out under an inert atmosphere;

[0068] S4, adding all butyl acrylate, isooctyl acrylate, vinyl acetate, methyl acrylate, and fluorinated acrylate compounds into the reaction kettle;

[0069] S5, start the agitator to uniformly stir the reaction mixture at a speed of 70 rpm to ensure that the monomers are evenly distributed in the solvent;

[0070] S6. Gradually increase the temperature of the reactor to 82°C, maintain this temperature and continue stirring for 30 minutes to ensure uniform mixing;

[0071] S7, slowly add 1 / 2 amount of initiator dropwise, keep the reaction temperature stable at 82°C, and continue the dropwise addition step for 2 hours;

[0072] S8, premix hydroxypropyl acrylate, acryloxyphenylboronic acid and methacrylic acid, and slowly add them dropwise to the reactor within 1 hour; at the same time, slowly add the remaining initiator dropwise, keep the temperature at 82°C, and continue stirring to ensure complete reaction;

[0073] S9, after the functional monomers are completely added, the reaction temperature is raised to 86°C and stirring is maintained, and the reaction is continued for 3 hours;

[0074] S10: After the polymerization reaction is completed, the heating device is turned off, and the temperature of the reactor is slowly lowered to room temperature for discharging. During the cooling process, the stirring speed is gradually reduced to avoid bubbles in the colloid;

[0075] After the reactor was cooled to room temperature, isocyanate curing agent and epoxy curing agent were added, and the mixture was stirred at 2000 rpm for 15 minutes by a disperser to ensure that the curing agent was evenly dispersed in the adhesive solution to obtain a fluorine-containing, electrolyte-resistant, and high-temperature-resistant solvent-type acrylic pressure-sensitive adhesive.

[0076] Example 2

[0077] A fluorine-containing electrolyte-resistant and high-temperature-resistant solvent-type acrylic pressure-sensitive adhesive, the raw material components of which are as follows:

[0078] Butyl acrylate: 100g, isooctyl acrylate: 350g, vinyl acetate: 220g, methyl acrylate: 80g, hydroxypropyl acrylate: 18g, acryloxyphenylboronic acid: 20g, dodecafluoroheptyl acrylate: 40g, methacrylic acid: 18g, initiator: 1.5g, toluene diisocyanate curing agent: 10g, bisphenol A epoxy resin curing agent: 10g

[0079] S1. Take the raw materials in parts by weight of the formula for use, wherein the initiator and the curing agent are diluted with ethyl acetate in a mass ratio of 1:10 for use;

[0080] S2, prepare a four-mouth reaction kettle equipped with a condensing reflux device, and pour ethyl acetate into the reaction kettle so that it accounts for 50% of the total reaction system volume;

[0081] S3, filling the reactor with nitrogen so that the reaction can be carried out under an inert atmosphere;

[0082] S4, adding all butyl acrylate, isooctyl acrylate, vinyl acetate, methyl acrylate, and fluorinated acrylate compounds into the reaction kettle;

[0083] S5, start the agitator to uniformly stir the reaction mixture at a speed of 70 rpm to ensure that the monomers are evenly distributed in the solvent;

[0084] S6. Gradually increase the temperature of the reactor to 82°C, maintain this temperature and continue stirring for 30 minutes to ensure uniform mixing;

[0085] S7, slowly add 1 / 2 amount of initiator dropwise, keep the reaction temperature stable at 82°C, and continue the dropwise addition step for 2 hours;

[0086] S8, premix hydroxypropyl acrylate, acryloxyphenylboronic acid and methacrylic acid, and slowly add them dropwise to the reactor within 1 hour; at the same time, slowly add the remaining initiator dropwise, keep the temperature at 82°C, and continue stirring to ensure complete reaction;

[0087] S9, after the functional monomers are completely added, the reaction temperature is raised to 86°C and stirring is maintained, and the reaction is continued for 3 hours;

[0088] S10: After the polymerization reaction is completed, the heating device is turned off, and the temperature of the reactor is slowly lowered to room temperature for discharging. During the cooling process, the stirring speed is gradually reduced to avoid bubbles in the colloid;

[0089] After the reactor was cooled to room temperature, isocyanate curing agent and epoxy curing agent were added, and the mixture was stirred at 2000 rpm for 15 minutes by a disperser to ensure that the curing agent was evenly dispersed in the adhesive solution to obtain a fluorine-containing, electrolyte-resistant, and high-temperature-resistant solvent-type acrylic pressure-sensitive adhesive.

[0090] Example 3

[0091] A fluorine-containing electrolyte-resistant and high-temperature-resistant solvent-type acrylic pressure-sensitive adhesive, the raw material components of which are as follows:

[0092] Butyl acrylate: 120g, isooctyl acrylate: 400g, vinyl acetate: 250g, methyl acrylate: 100g, hydroxypropyl acrylate: 22g, acryloxyphenylboric acid: 25g, dodecafluoroheptyl acrylate: 70g, methacrylic acid: 23g, initiator: 3g, toluene diisocyanate curing agent: 12g, bisphenol A epoxy resin curing agent: 10g.

[0093] S1. Take the raw materials in parts by weight of the formula for use, wherein the initiator and the curing agent are diluted with ethyl acetate in a mass ratio of 1:10 for use;

[0094] S2, prepare a four-mouth reaction kettle equipped with a condensing reflux device, and pour ethyl acetate into the reaction kettle so that it accounts for 50% of the total reaction system volume;

[0095] S3, filling the reactor with nitrogen so that the reaction can be carried out under an inert atmosphere;

[0096] S4, adding all butyl acrylate, isooctyl acrylate, vinyl acetate, methyl acrylate, and fluorinated acrylate compounds into the reaction kettle;

[0097] S5, start the agitator to uniformly stir the reaction mixture at a speed of 70 rpm to ensure that the monomers are evenly distributed in the solvent;

[0098] S6. Gradually increase the temperature of the reactor to 82°C, maintain this temperature and continue stirring for 30 minutes to ensure uniform mixing;

[0099] S7, slowly add 1 / 2 amount of initiator dropwise, keep the reaction temperature stable at 82°C, and continue the dropwise addition step for 2 hours;

[0100] S8, premix hydroxypropyl acrylate, acryloxyphenylboronic acid and methacrylic acid, and slowly add them dropwise to the reactor within 1 hour; at the same time, slowly add the remaining initiator dropwise, keep the temperature at 82°C, and continue stirring to ensure complete reaction;

[0101] S9, after the functional monomers are completely added, the reaction temperature is raised to 86°C and stirring is maintained, and the reaction is continued for 3 hours;

[0102] S10: After the polymerization reaction is completed, the heating device is turned off, and the temperature of the reactor is slowly lowered to room temperature for discharging. During the cooling process, the stirring speed is gradually reduced to avoid bubbles in the colloid;

[0103] After the reactor was cooled to room temperature, isocyanate curing agent and epoxy curing agent were added, and the mixture was stirred at 2000 rpm for 15 minutes by a disperser to ensure that the curing agent was evenly dispersed in the adhesive solution to obtain a fluorine-containing, electrolyte-resistant, and high-temperature-resistant solvent-type acrylic pressure-sensitive adhesive.

[0104] Comparative Example 1

[0105] This example is basically the same as Example 1, except that the formula of this example does not contain dodecafluoroheptyl acrylate.

[0106] Comparative Example 2

[0107] This example is basically the same as Example 1, except that the formula of this example does not contain acryloxyphenylboric acid.

[0108] Comparative Example 3

[0109] This example is basically the same as Example 1, except that the formula of this example does not contain dodecafluoroheptyl acrylate and acryloxyphenylboric acid.

[0110] Test example:

[0111] The fluorine-containing, electrolyte-resistant, and high-temperature-resistant solvent-type acrylic pressure-sensitive adhesive obtained in the above Examples 1-3 is coated on a 25 μm thick PET film layer and dried at 120° C. for 3 minutes to obtain a 25 μm thick adhesive layer. Finally, a 50 μm thick release film is covered on the surface of the adhesive layer to obtain a pressure-sensitive adhesive tape.

[0112] The following performance parameters were obtained by performing electrolyte resistance and peel strength tests on the samples of the above three embodiments after aging (aging temperature was 55° C., time was 24 h). The test items and methods were as follows:

[0113] 180° peeling force test: flat on steel plate, peeling speed is 300mm / min, no residual glue on the steel plate;

[0114] Initial adhesion test: Tested in accordance with GB / T 4852-2002 standard, requirements: initial adhesion rolling ball> 4#;

[0115] Adhesion test: According to GB / T 4851-1998 standard (80℃, 1h), requirement: displacement <0.20mm;

[0116] Electrolyte resistance test: Placed in LiPF6 electrolyte with the same physical properties, immersed at 60℃ for 24h and 85℃ for 4h, there is no residual glue on the steel plate.

[0117] High temperature resistance test: Flatten the steel plate, bake at 130℃ for 1h, cool to room temperature, and peel off. Requirements: no deformation, no shrinkage, and stickiness;

[0118] Insulation performance test: Under 500VDC, 60s conditions, requirements: insulation resistance> 1GΩ;

[0119] High voltage strength test: No breakdown under 1500VDC, 60s condition, requirement: leakage current <2mA.

[0120] The test results are shown in Table 1 below:

[0121] Table 1

[0122]

[0123] It can be seen from the above table that the performance of the embodiments all meet expectations, and the result of Example 1 is relatively optimal. In the embodiments, a fluorinated pressure-sensitive adhesive with electrolyte resistance, high temperature resistance and good bonding performance is successfully developed through formula combination and process optimization, and it shows obvious advantages in environmental protection, process stability and cost control, opening up new possibilities for the future application of high-performance pressure-sensitive adhesives.

[0124] By comparing the test results of the three comparative examples, it can be seen that the lack of different key components will significantly affect the overall performance of the acrylic pressure-sensitive adhesive. After the lack of dodecafluoroheptyl acrylate (Comparative Example 1), the peeling force decreased significantly, and obvious residual glue phenomenon appeared. In high temperature and electrolyte environments, the tolerance of the adhesive layer was significantly reduced. When acryloxyphenylboric acid (Comparative Example 2) was lacking, the peeling force and the holding force decreased, and the electrolyte resistance was weakened, but the adhesive layer still had a certain viscosity and stability. When these two key components were lacking (Comparative Example 3), the tape performance was the worst, the bonding performance of the adhesive layer was greatly reduced, and serious residual glue phenomenon appeared. The high temperature resistance, electrolyte resistance and insulation performance were all significantly deteriorated. This shows that dodecafluoroheptyl acrylate and acryloxyphenylboric acid have a significant synergistic effect in improving the comprehensive performance of pressure-sensitive adhesives, especially in high temperature resistance and electrolyte resistance environments.

[0125] Although the embodiments of the present invention have been disclosed as above, they are not limited to the applications listed in the specification and the implementation modes. They can be fully applied to various fields suitable for the present invention. For those familiar with the art, additional modifications can be easily implemented. Therefore, without departing from the general concept defined by the claims and the scope of equivalents, the present invention is not limited to specific details.

Claims

1. A fluorine-containing electrolyte-resistant and high-temperature-resistant solvent-type acrylic pressure-sensitive adhesive, characterized in that: The invention comprises the following raw material components by weight: Butyl acrylate: 100-120 parts, isooctyl acrylate: 350-400 parts, vinyl acetate: 220-250 parts, methyl acrylate: 80-100 parts, hydroxypropyl acrylate: 18-22 parts, acryloxyphenylboric acid: 15-25 parts, fluorine-containing acrylic acid ester compound: 40-70 parts, methacrylic acid: 18-23 parts, initiator: 1-3g, curing agent: 5-40 parts, solvent: 400-500 parts.

2. The fluorine-containing electrolyte-resistant and high-temperature-resistant solvent-type acrylic pressure-sensitive adhesive according to claim 1, characterized in that: The fluorine-containing acrylic ester compound is at least one of octafluoropentyl acrylate, dodecafluoroheptyl acrylate, and tridecafluorooctyl acrylate.

3. The fluorine-containing electrolyte-resistant and high-temperature-resistant solvent-type acrylic pressure-sensitive adhesive according to claim 2, characterized in that: The fluorine-containing acrylic ester compound is dodecafluoroheptyl acrylate.

4. The fluorine-containing electrolyte-resistant and high-temperature-resistant solvent-type acrylic pressure-sensitive adhesive according to claim 1, characterized in that: The curing agent is a mixture of an isocyanate curing agent and an epoxy curing agent.

5. The fluorine-containing electrolyte-resistant and high-temperature-resistant solvent-type acrylic pressure-sensitive adhesive according to claim 4, characterized in that: The isocyanate curing agent is at least one of toluene diisocyanate, diphenylmethane diisocyanate and hexamethylene diisocyanate.

6. The fluorine-containing electrolyte-resistant and high-temperature-resistant solvent-type acrylic pressure-sensitive adhesive according to claim 4, characterized in that: The epoxy curing agent is bisphenol A epoxy resin or methyltetrahydrophthalic anhydride.

7. The fluorine-containing electrolyte-resistant and high-temperature-resistant solvent-type acrylic pressure-sensitive adhesive according to claim 1, characterized in that: The initiator is an acyl peroxide or an azo compound, and the solvent is ethyl acetate.

8. The fluorine-containing electrolyte-resistant and high-temperature-resistant solvent-type acrylic pressure-sensitive adhesive according to claim 1, characterized in that: The invention comprises the following raw material components by weight: Butyl acrylate: 120 parts, isooctyl acrylate: 360 parts, vinyl acetate: 240 parts, methyl acrylate: 90 parts, hydroxypropyl acrylate: 20 parts, acryloxyphenylboric acid: 20 parts, fluorine-containing acrylic acid ester compound: 50 parts, methacrylic acid: 20 parts, initiator: 2 parts, isocyanate curing agent: 10 parts, epoxy curing agent: 10 parts, ethyl acetate: 450 parts.

9. A method for preparing a fluorine-containing electrolyte-resistant and high-temperature-resistant solvent-type acrylic pressure-sensitive adhesive as claimed in any one of claims 1 to 8, characterized in that: The following steps are involved: S1, take the raw materials in parts by weight of the formula for use, wherein the initiator, isocyanate curing agent and epoxy curing agent are all diluted with part of ethyl acetate for use; S2, pouring the remaining portion of ethyl acetate into the reaction vessel so that it accounts for 40-60% of the total volume of the reaction vessel; S3, filling the reaction vessel with nitrogen to allow the reaction to proceed under an inert atmosphere; S4, adding all butyl acrylate, isooctyl acrylate, vinyl acetate, methyl acrylate, and fluorine-containing acrylate compounds into a reaction container; S5, stirring evenly at 60-70 rpm; S6. Heat to 80-82°C, maintain this temperature and continue stirring for 15-30 minutes; S7, dropwise add 1 / 2 mass of the initiator in ethyl acetate solution, keep the reaction temperature stable at 80-82°C, and complete the dropwise addition within 1-2 hours; S8, premixing hydroxypropyl acrylate, acryloxyphenylboronic acid and methacrylic acid, and adding the resulting mixture and the remaining initiator dropwise into the reaction vessel within 1-2 hours, maintaining the temperature at 80-82° C. and stirring; S9, heating to 84-86°C, stirring continuously, and reacting for 3-5 hours; S10, after the completion of the heating, the mixture is cooled to room temperature, an ethyl acetate solution of an isocyanate curing agent and an ethyl acetate solution of an epoxy curing agent are added, and the mixture is stirred at a speed of 1500-2000 rpm for 15-20 minutes to obtain the fluorine-containing electrolyte-resistant and high-temperature-resistant solvent-type acrylic pressure-sensitive adhesive.

10. A fluorine-containing electrolyte-resistant and high-temperature-resistant solvent-type acrylic pressure-sensitive adhesive tape, characterized in that: The fluorine-containing electrolyte-resistant and high-temperature solvent-resistant acrylate pressure-sensitive adhesive as described in any one of claims 1 to 8 is uniformly coated on a base film, dried at 110-130° C. for 1.5-6 minutes, and affixed a release film on the adhesive layer to obtain a fluorine-containing electrolyte-resistant and high-temperature solvent-resistant acrylate pressure-sensitive adhesive tape.

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