Epoxy modified SMP elastic adhesive for battery packaging and preparation method thereof

Abstract

The invention relates to the technical field of adhesives, in particular to an epoxy modified SMP elastic adhesive for battery packaging and a preparation method thereof.In the SMP adhesive preparation process, acrylic ester and epoxy resin are used for modifying SMP adhesive, the bonding strength of the SMP adhesive to common plastic materials is improved by means of introduction of chain segments of the acrylic ester, the service life of the SMP adhesive is prolonged, and the service life of the SMP adhesive is prolonged. The boron element and the branched structure are introduced into the epoxy resin, the introduction of the boron element can effectively improve the flame retardant property of the SMP adhesive and improve the safety performance of the SMP adhesive, the epoxy resin with the branched structure can also effectively increase the complexity of a cross-linked network, the SMP adhesive is sealed to form an island structure, the bonding strength, the body strength and the like of the SMP adhesive are improved, and the service life of the SMP adhesive is prolonged. And the viscosity of the SMP adhesive is reduced, so that the SMP adhesive disclosed by the invention can generate good cohesiveness to conventional metal, plastic and other substrates under the conditions of not adding a solvent and not needing a prime coat, and has excellent working performance.

Description

Technical Field

[0001] The invention relates to the technical field of adhesives, and in particular to an epoxy-modified SMP elastic adhesive for battery packaging and a preparation method thereof. Background Art

[0002] Silane-modified polyether adhesive (SMP adhesive) is a macromolecular structural material with polyether as the main chain and reactive alkoxysilane groups at both ends of the molecule. It not only has excellent flexibility and ductility, but also has excellent hydrolysis resistance. During use, alkoxysilane will cross-link through hydrolysis and condensation reactions to form a three-dimensional network structure of Si-O-Si, thereby giving SMP adhesive excellent weather resistance, aging resistance and hydrolysis resistance. These characteristics make SMP adhesive a kind of elastic sealant and adhesive, widely used in building decoration, rail transportation, new energy and electronics. However, its mechanical properties are relatively low, and it will be greatly restricted to application fields that require structural bonding. Therefore, epoxy-modified SMP is often used in the prior art to improve its bonding strength, but epoxy-modified SMP adhesive has poor bonding to common plastics and has the defect of bonding failure. Summary of the invention

[0003] The object of the present invention is to provide an epoxy-modified SMP elastic adhesive for battery packaging and a preparation method thereof, so as to solve the problems raised in the prior art.

[0004] To achieve the above object, the present invention provides the following technical solution: an epoxy-modified SMP elastic adhesive for battery packaging, which is composed of component A and component B mixed in a mass ratio of 2:1; Wherein, the component A is composed of 50-80 parts of silane-modified polyether resin, 50-80 parts of acrylic acid-modified SMP resin, 5-10 parts of epoxy curing agent, 1-5 parts of compatibilizer, 1-5 parts of adhesion promoter, 1-5 parts of dewatering agent, 1-5 parts of filler, 0.1-2 parts of antioxidant, 0.1-2 parts of light stabilizer, and 0.1-2 parts of ultraviolet absorber by weight; The component B comprises 50-100 parts of modified epoxy resin, 0.1-2 parts of catalyst, 1-5 parts of filler and 0.1-1 part of deionized water.

[0005] Furthermore, the silane-modified polyether resin is a polyether resin terminated with methyldimethoxysilane or trimethoxysilane; The epoxy curing agent is 2,4,6-tris(dimethylaminomethyl)phenol; The adhesion promoter is any one or more of KH550, KH792, and 1146; The compatibilizer is any one or more of 3-aminopropyltrimethoxysilane and N-n-butyl-3-aminopropyltrimethoxysilane.

[0006] Furthermore, the filler is any one of hydrophobic fumed silica, kaolin, polyamide wax, and organic bentonite; The antioxidant is any one or more of antioxidant 1010, antioxidant 1035, and antioxidant 1176; The light stabilizer is any one or more of light stabilizer 292, light stabilizer 770, and light stabilizer 944; The ultraviolet absorber is any one or more of UV326, UV327, and UV328; The catalyst is any one of an organotin catalyst or a mixture of organotin and alkylamine.

[0007] Furthermore, the preparation method of the acrylic acid modified SMP resin is: Butyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, methyl methacrylate and silane-modified polyether resin are mixed, an initiator and a chain transfer agent are added thereto, vacuum is evacuated, the temperature is raised to 80-100° C., the reaction is carried out for 3-5 hours, and the material is cooled and discharged to obtain an acrylic acid-modified SMP resin.

[0008] Furthermore, the acrylic modified SMP resin is prepared by reacting 4-12 parts of butyl acrylate, 4-8 parts of hydroxyethyl acrylate, 3-6.5 parts of hydroxypropyl acrylate, 4-8 parts of methyl methacrylate, 15-40 parts of silane modified polyether resin, 0.1-2 parts of initiator and 5-15 parts of chain transfer agent, by weight.

[0009] Furthermore, the preparation method of the modified epoxy resin is: a. After nitrogen was passed through tetrahydrofuran for 30-45min, 1,4-bis(dimethylsilyl)benzene was added thereto, and the mixture was uniformly mixed by ultrasonic stirring to obtain a 1,4-bis(dimethylsilyl)benzene dispersion; Under nitrogen atmosphere protection, 2,4,6-trivinyl boroxine is mixed with clean tetrahydrofuran, and after mixing evenly, boron trifluoride is added thereto, and mixing is continued for 15-20 minutes, and then it is added dropwise to the 1,4-bisdimethylsilylbenzene dispersion, and stirring is continuously performed during the dropping process. After the dropping is completed, the reaction system is heated to 65-68°C, and refluxed and stirred for reaction for 1.5-8 hours, and then the excess solvent is removed by rotary evaporation. The product is washed 1-2 times with deionized water at a temperature of 1-5°C, and then dried to constant weight to obtain a three-arm boron compound terminated with silicon hydrogen; b. Heat DMF to 105-110°C, dry and remove water for 0.5-1h, cool to warm, add the three-arm boron compound terminated with silicon hydrogen, stir and disperse evenly, then add it dropwise to DMF dissolved with 1,6-hexanediisocyanate, after the addition is completed, heat to 105-110°C, stir and react for 2-4h, then add the mixture dropwise to 1,6-hexanediol diglycidyl ether, stir continuously during the addition, heat to 65-75°C after the addition is completed, stir and react for 1.5-4h, then remove excess solvent by rotary evaporation to obtain a boron-modified epoxy resin monomer; c. Mix the boron-modified epoxy resin monomer and bisphenol A epoxy resin, stir evenly, and then perform vacuum degassing to obtain a modified epoxy resin.

[0010] Furthermore, in step a, the mass ratio of 1,4-bisdimethylsilylbenzene, 2,4,6-trivinylcycloboroxine, and boron trifluoride is (2.9-3.7):1:(0.015-0.05).

[0011] Furthermore, in step b, the mass ratio of the silyl-terminated three-arm boron compound, 1,6-hexamethylene diisocyanate, and 1,6-hexanediol diglycidyl ether is 1: (0.58-0.68): (0.89-0.95).

[0012] Furthermore, in step c, the mass ratio of the boron-modified epoxy resin monomer to the bisphenol A epoxy resin is 1:1.

[0013] A method for preparing an epoxy-modified SMP elastic adhesive for battery packaging comprises the following steps: S1. Preparation of component A; Silane-modified polyether resin, acrylic acid-modified SMP resin, epoxy curing agent, compatibilizer and filler are mixed, stirred for 5-10 minutes, and then an adhesion promoter, a water scavenger, an antioxidant, a light stabilizer and an ultraviolet absorber are added thereto. After continuing to mix for 3-5 minutes, vacuum degassing is performed to obtain component A. S2. Preparing component B; The modified epoxy resin, catalyst, filler and deionized water are mixed, stirred for 3-5 minutes, and then vacuum-defoamed to obtain component B; S3. Component A and component B are mixed to obtain an epoxy-modified SMP elastic adhesive for battery encapsulation.

[0014] Compared with the prior art, the present invention has the following beneficial effects: In order to improve the mechanical properties of the SMP glue and its adhesion to the substrate, the present invention uses acrylate and epoxy resin to modify the SMP glue in the process of preparing the SMP glue. The introduction of the acrylate chain segment increases the bonding strength of the SMP glue to common plastic materials, effectively avoiding the defect of too low bonding strength to the plastic material substrate. The present invention also performs a modification treatment on the epoxy resin. The present invention first uses 2,4,6-trivinyl boroxine with a three-arm structure as a raw material, wherein the boroxine has three vinyl groups, and after reacting the boroxine with 1,4-bisdimethylsilylbenzene containing a silicon-hydrogen bond, the silicon-hydrogen bond reacts with the carbon-carbon double bond in the vinyl group to form a silicon-hydrogen terminated three-arm boron compound, and then reacts the boroxine with 1,6-hexanediisocyanate containing an isocyanate group and 1,6-hexanediol diglycidyl ether containing an epoxy group, thereby Finally, a boron-modified epoxy resin with a branched structure was prepared, which contains a large amount of boron and silicon elements, which can effectively improve the flame retardant properties of the SMP glue and improve its safety performance. The epoxy resin with a branched structure can also effectively increase the complexity of the cross-linked network, seal the SMP glue to form an island structure, improve its bonding strength and body strength, etc. The branched structure can also effectively reduce the viscosity of the SMP glue, so that the present invention can have good adhesion to conventional metal, plastic and other substrates without adding solvents and without the need for primers, and has excellent working performance. DETAILED DESCRIPTION

[0015] Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in the field without making any creative work shall fall within the scope of protection of the present invention.

[0016] Example 1. A method for preparing an epoxy-modified SMP elastic adhesive for battery packaging, comprising the following steps: S1. Preparation of component A; 65 parts of silane-modified polyether resin, 65 parts of acrylic acid-modified SMP resin, 6.5 parts of 2,4,6-tris(dimethylaminomethyl)phenol, 2 parts of N-n-butyl-3-aminopropyltrimethoxysilane and 4 parts of kaolin were mixed by weight, and after stirring for 8 minutes, 2 parts of Dynasylan®1146, 3 parts of vinyltrimethoxysilane, 1 part of antioxidant 1135, 1 part of light stabilizer 765 and 1 part of ultraviolet absorber UV326 were added thereto, and after continuing to mix for 5 minutes, vacuum degassing was performed to obtain component A; Wherein, the preparation method of the acrylic acid modified SMP resin is: 9 parts of butyl acrylate, 5 parts of hydroxyethyl acrylate, 4 parts of hydroxypropyl acrylate, 6 parts of methyl methacrylate and 30 parts of silane-modified polyether resin were mixed, 0.5 parts of initiator and 6 parts of chain transfer agent were added thereto, reacted at 100° C. in vacuum for 5 hours, cooled and discharged, to generate acrylic acid-modified silane-modified polyether resin; S2. Preparing component B; 65 parts of modified epoxy resin, 2 parts of catalyst KR-225, 3 parts of hydrophobic fumed silica, and 0.2 parts of deionized water were mixed, stirred for 5 minutes, and vacuum-defoamed to obtain component B; Wherein, the preparation method of the modified epoxy resin is: a. After nitrogen was passed through tetrahydrofuran for 30 min, 2.9 parts of 1,4-bis(dimethylsilyl)benzene were added thereto, and the mixture was uniformly mixed by ultrasonic stirring to obtain a dispersion of 1,4-bis(dimethylsilyl)benzene; Under nitrogen atmosphere protection, 1 part of 2,4,6-trivinyl cycloboroxine was mixed with clean tetrahydrofuran. After mixing evenly, 0.025 parts of boron trifluoride was added thereto. After continuing to mix for 15 minutes, the mixture was added dropwise to the 1,4-bis(dimethylsilyl)benzene dispersion. The mixture was stirred continuously during the addition. After the addition was completed, the reaction system was heated to 65-68°C, refluxed and stirred for 5.5 hours, and then the excess solvent was removed by rotary evaporation. The product was washed once with deionized water at a temperature of 1-5°C, and then dried to constant weight to obtain a three-arm boron compound terminated with silicon hydrogen. b. DMF was heated to 105-110°C, dried and dehydrated for 0.5h, cooled to a temperature rise, 1 part of a three-arm boron compound terminated with silicon hydrogen was added thereto, stirred and dispersed evenly, and then added dropwise to DMF containing 0.58 parts of 1,6-hexanediisocyanate. After the addition was completed, the temperature was raised to 105°C, stirred and reacted for 4h, and the mixture was added dropwise to 0.89 parts of 1,6-hexanediol diglycidyl ether. The mixture was stirred continuously during the addition process. After the addition was completed, the temperature was raised to 68°C, stirred and reacted for 3h, and then the excess solvent was removed by rotary evaporation to obtain a boron-modified epoxy resin monomer; c. The boron-modified epoxy resin monomer and bisphenol A type E51 epoxy resin were mixed in a mass ratio of 1:1, stirred evenly and then vacuum-defoamed to obtain a modified epoxy resin; S3. Component A and component B are mixed in a mass ratio of 2:1 to obtain an epoxy-modified SMP elastic adhesive for battery encapsulation.

[0017] Example 2. A method for preparing an epoxy-modified SMP elastic adhesive for battery packaging, comprising the following steps: Compared with Example 1, the amount of each raw material added when preparing component A in step S1 is changed in this example; S1. Preparation of component A; 75 parts of silane-modified polyether resin, 55 parts of acrylic acid-modified SMP resin, 6.5 parts of 2,4,6-tris(dimethylaminomethyl)phenol, 1.5 parts of N-n-butyl-3-aminopropyltrimethoxysilane and 2 parts of kaolin were mixed by weight, and after stirring for 8 minutes, 1.5 parts of Dynasylan®1146, 3 parts of vinyltrimethoxysilane, 1 part of antioxidant 1135, 1 part of light stabilizer 765 and 1 part of ultraviolet absorber UV326 were added thereto, and after continuing to mix for 5 minutes, vacuum degassing was performed to obtain component A; Wherein, the preparation method of the acrylic acid modified SMP resin is: 8 parts of butyl acrylate, 6 parts of hydroxyethyl acrylate, 4 parts of hydroxypropyl acrylate, 4 parts of methyl methacrylate, and 20 parts of silane-modified polyether resin were mixed, 0.5 parts of initiator and 8 parts of chain transfer agent were added thereto, and the mixture was reacted at 100° C. in vacuum for 5 hours, and the material was cooled and discharged to generate acrylic acid-modified silane-modified polyether resin; S2. Preparing component B; 65 parts of modified epoxy resin, 2 parts of catalyst KR-225, 3 parts of hydrophobic fumed silica, and 0.2 parts of deionized water were mixed, stirred for 5 minutes, and vacuum-defoamed to obtain component B; Wherein, the preparation method of the modified epoxy resin is: a. After nitrogen was passed through tetrahydrofuran for 30 min, 2.9 parts of 1,4-bis(dimethylsilyl)benzene were added thereto, and the mixture was uniformly mixed by ultrasonic stirring to obtain a dispersion of 1,4-bis(dimethylsilyl)benzene; Under nitrogen atmosphere protection, 1 part of 2,4,6-trivinyl cycloboroxine was mixed with clean tetrahydrofuran. After mixing evenly, 0.025 parts of boron trifluoride was added thereto. After continuing to mix for 15 minutes, the mixture was added dropwise to the 1,4-bis(dimethylsilyl)benzene dispersion. The mixture was stirred continuously during the addition. After the addition was completed, the reaction system was heated to 65-68°C, refluxed and stirred for 5.5 hours, and then the excess solvent was removed by rotary evaporation. The product was washed once with deionized water at a temperature of 1-5°C, and then dried to constant weight to obtain a three-arm boron compound terminated with silicon hydrogen. b. DMF was heated to 105-110°C, dried and dehydrated for 0.5h, cooled to a temperature rise, 1 part of a three-arm boron compound terminated with silicon hydrogen was added thereto, stirred and dispersed evenly, and then added dropwise to DMF containing 0.58 parts of 1,6-hexanediisocyanate. After the addition was completed, the temperature was raised to 105°C, stirred and reacted for 4h, and the mixture was added dropwise to 0.89 parts of 1,6-hexanediol diglycidyl ether. The mixture was stirred continuously during the addition process. After the addition was completed, the temperature was raised to 68°C, stirred and reacted for 3h, and then the excess solvent was removed by rotary evaporation to obtain a boron-modified epoxy resin monomer; c. The boron-modified epoxy resin monomer and bisphenol A type E51 epoxy resin were mixed in a mass ratio of 1:1, stirred evenly and then vacuum-defoamed to obtain a modified epoxy resin; S3. Component A and component B are mixed in a mass ratio of 2:1 to obtain an epoxy-modified SMP elastic adhesive for battery encapsulation.

[0018] Example 3. A method for preparing an epoxy-modified SMP elastic adhesive for battery packaging, comprising the following steps: Compared with Example 1, this example increases the amount of 1,4-bisdimethylsilylbenzene added in step a; S1. Preparation of component A; 65 parts of silane-modified polyether resin, 65 parts of acrylic acid-modified SMP resin, 6.5 parts of 2,4,6-tris(dimethylaminomethyl)phenol, 2 parts of N-n-butyl-3-aminopropyltrimethoxysilane and 4 parts of kaolin were mixed by weight, and after stirring for 8 minutes, 2 parts of Dynasylan®1146, 3 parts of vinyltrimethoxysilane, 1 part of antioxidant 1135, 1 part of light stabilizer 765 and 1 part of ultraviolet absorber UV326 were added thereto, and after continuing to mix for 5 minutes, vacuum degassing was performed to obtain component A; Wherein, the preparation method of the acrylic acid modified SMP resin is: 9 parts of butyl acrylate, 5 parts of hydroxyethyl acrylate, 4 parts of hydroxypropyl acrylate, 6 parts of methyl methacrylate and 30 parts of silane-modified polyether resin were mixed, 0.5 parts of initiator and 6 parts of chain transfer agent were added thereto, reacted at 100° C. in vacuum for 5 hours, cooled and discharged, to generate acrylic acid-modified silane-modified polyether resin; S2. Preparing component B; 65 parts of modified epoxy resin, 2 parts of catalyst KR-225, 3 parts of hydrophobic fumed silica, and 0.2 parts of deionized water were mixed, stirred for 5 minutes, and vacuum-defoamed to obtain component B; Wherein, the preparation method of the modified epoxy resin is: a. After nitrogen was passed through tetrahydrofuran for 30 min, 3.7 parts of 1,4-bis(dimethylsilyl)benzene were added thereto, and the mixture was uniformly mixed by ultrasonic stirring to obtain a dispersion of 1,4-bis(dimethylsilyl)benzene; Under nitrogen atmosphere protection, 1 part of 2,4,6-trivinyl cycloboroxine was mixed with clean tetrahydrofuran. After mixing evenly, 0.025 parts of boron trifluoride was added thereto. After continuing to mix for 15 minutes, the mixture was added dropwise to the 1,4-bis(dimethylsilyl)benzene dispersion. The mixture was stirred continuously during the addition. After the addition was completed, the reaction system was heated to 65-68°C, refluxed and stirred for 5.5 hours, and then the excess solvent was removed by rotary evaporation. The product was washed once with deionized water at a temperature of 1-5°C, and then dried to constant weight to obtain a three-arm boron compound terminated with silicon hydrogen. b. DMF was heated to 105-110°C, dried and dehydrated for 0.5h, cooled to a temperature rise, 1 part of a three-arm boron compound terminated with silicon hydrogen was added thereto, stirred and dispersed evenly, and then added dropwise to DMF containing 0.58 parts of 1,6-hexanediisocyanate. After the addition was completed, the temperature was raised to 105°C, stirred and reacted for 4h, and the mixture was added dropwise to 0.89 parts of 1,6-hexanediol diglycidyl ether. The mixture was stirred continuously during the addition process. After the addition was completed, the temperature was raised to 68°C, stirred and reacted for 3h, and then the excess solvent was removed by rotary evaporation to obtain a boron-modified epoxy resin monomer; c. The boron-modified epoxy resin monomer and bisphenol A type E51 epoxy resin were mixed in a mass ratio of 1:1, stirred evenly and then vacuum-defoamed to obtain a modified epoxy resin; S3. Component A and component B are mixed in a mass ratio of 2:1 to obtain an epoxy-modified SMP elastic adhesive for battery encapsulation.

[0019] Example 4. A method for preparing an epoxy-modified SMP elastic adhesive for battery packaging, comprising the following steps: Compared with Example 3, this example increases the amount of 1,6-hexamethylene diisocyanate added in step b; S1. Preparation of component A; 65 parts of silane-modified polyether resin, 65 parts of acrylic acid-modified SMP resin, 6.5 parts of 2,4,6-tris(dimethylaminomethyl)phenol, 2 parts of N-n-butyl-3-aminopropyltrimethoxysilane and 4 parts of kaolin were mixed by weight, and after stirring for 8 minutes, 2 parts of Dynasylan®1146, 3 parts of vinyltrimethoxysilane, 1 part of antioxidant 1135, 1 part of light stabilizer 765 and 1 part of ultraviolet absorber UV326 were added thereto, and after continuing to mix for 5 minutes, vacuum degassing was performed to obtain component A; Wherein, the preparation method of the acrylic acid modified SMP resin is: 9 parts of butyl acrylate, 5 parts of hydroxyethyl acrylate, 4 parts of hydroxypropyl acrylate, 6 parts of methyl methacrylate and 30 parts of silane-modified polyether resin were mixed, 0.5 parts of initiator and 6 parts of chain transfer agent were added thereto, reacted at 100° C. in vacuum for 5 hours, cooled and discharged, to generate acrylic acid-modified silane-modified polyether resin; S2. Preparing component B; 65 parts of modified epoxy resin, 2 parts of catalyst KR-225, 3 parts of hydrophobic fumed silica, and 0.2 parts of deionized water were mixed, stirred for 5 minutes, and vacuum-defoamed to obtain component B; Wherein, the preparation method of the modified epoxy resin is: a. After nitrogen was passed through tetrahydrofuran for 30 min, 3.7 parts of 1,4-bis(dimethylsilyl)benzene were added thereto, and the mixture was uniformly mixed by ultrasonic stirring to obtain a dispersion of 1,4-bis(dimethylsilyl)benzene; Under nitrogen atmosphere protection, 1 part of 2,4,6-trivinyl cycloboroxine was mixed with clean tetrahydrofuran. After mixing evenly, 0.025 parts of boron trifluoride was added thereto. After continuing to mix for 15 minutes, the mixture was added dropwise to the 1,4-bis(dimethylsilyl)benzene dispersion. The mixture was stirred continuously during the addition. After the addition was completed, the reaction system was heated to 65-68°C, refluxed and stirred for 5.5 hours, and then the excess solvent was removed by rotary evaporation. The product was washed once with deionized water at a temperature of 1-5°C, and then dried to constant weight to obtain a three-arm boron compound terminated with silicon hydrogen. b. DMF was heated to 105-110°C, dried and dehydrated for 0.5h, cooled to a temperature rise, 1 part of a three-arm boron compound terminated with silicon hydrogen was added thereto, stirred and dispersed evenly, and then added dropwise to DMF containing 0.68 parts of 1,6-hexanediisocyanate. After the addition was completed, the temperature was raised to 105°C, stirred and reacted for 4h, and the mixture was added dropwise to 0.89 parts of 1,6-hexanediol diglycidyl ether. The mixture was stirred continuously during the addition process. After the addition was completed, the temperature was raised to 68°C, stirred and reacted for 3h, and then the excess solvent was removed by rotary evaporation to obtain a boron-modified epoxy resin monomer; c. The boron-modified epoxy resin monomer and bisphenol A type E51 epoxy resin were mixed in a mass ratio of 1:1, stirred evenly and then vacuum-defoamed to obtain a modified epoxy resin; S3. Component A and component B are mixed in a mass ratio of 2:1 to obtain an epoxy-modified SMP elastic adhesive for battery encapsulation.

[0020] Example 5. A method for preparing an epoxy-modified SMP elastic adhesive for battery packaging, comprising the following steps: Compared with Example 4, this example increases the amount of 1,6-hexanediol diglycidyl ether added in step b; S1. Preparation of component A; 65 parts of silane-modified polyether resin, 65 parts of acrylic acid-modified SMP resin, 6.5 parts of 2,4,6-tris(dimethylaminomethyl)phenol, 2 parts of N-n-butyl-3-aminopropyltrimethoxysilane and 4 parts of kaolin were mixed by weight, and after stirring for 8 minutes, 2 parts of Dynasylan®1146, 3 parts of vinyltrimethoxysilane, 1 part of antioxidant 1135, 1 part of light stabilizer 765 and 1 part of ultraviolet absorber UV326 were added thereto, and after continuing to mix for 5 minutes, vacuum degassing was performed to obtain component A; Wherein, the preparation method of the acrylic acid modified SMP resin is: 9 parts of butyl acrylate, 5 parts of hydroxyethyl acrylate, 4 parts of hydroxypropyl acrylate, 6 parts of methyl methacrylate and 30 parts of silane-modified polyether resin were mixed, 0.5 parts of initiator and 6 parts of chain transfer agent were added thereto, reacted at 100° C. in vacuum for 5 hours, cooled and discharged, to generate acrylic acid-modified silane-modified polyether resin; S2. Preparing component B; 65 parts of modified epoxy resin, 2 parts of catalyst KR-225, 3 parts of hydrophobic fumed silica, and 0.2 parts of deionized water were mixed, stirred for 5 minutes, and vacuum-defoamed to obtain component B; Wherein, the preparation method of the modified epoxy resin is: a. After nitrogen was passed through tetrahydrofuran for 30 min, 3.7 parts of 1,4-bis(dimethylsilyl)benzene were added thereto, and the mixture was uniformly mixed by ultrasonic stirring to obtain a dispersion of 1,4-bis(dimethylsilyl)benzene; Under nitrogen atmosphere protection, 1 part of 2,4,6-trivinyl cycloboroxine was mixed with clean tetrahydrofuran. After mixing evenly, 0.025 parts of boron trifluoride was added thereto. After continuing to mix for 15 minutes, the mixture was added dropwise to the 1,4-bis(dimethylsilyl)benzene dispersion. The mixture was stirred continuously during the addition. After the addition was completed, the reaction system was heated to 65-68°C, refluxed and stirred for 5.5 hours, and then the excess solvent was removed by rotary evaporation. The product was washed once with deionized water at a temperature of 1-5°C, and then dried to constant weight to obtain a three-arm boron compound terminated with silicon hydrogen. b. DMF was heated to 105-110°C, dried and dehydrated for 0.5h, cooled to a temperature rise, 1 part of a three-arm boron compound terminated with silicon hydrogen was added thereto, stirred and dispersed evenly, and then added dropwise to DMF containing 0.68 parts of 1,6-hexanediisocyanate. After the addition was completed, the temperature was raised to 105°C, stirred and reacted for 4h, and the mixture was added dropwise to 0.95 parts of 1,6-hexanediol diglycidyl ether. The mixture was stirred continuously during the addition process. After the addition was completed, the temperature was raised to 68°C, stirred and reacted for 3h, and then the excess solvent was removed by rotary evaporation to obtain a boron-modified epoxy resin monomer; c. The boron-modified epoxy resin monomer and bisphenol A type E51 epoxy resin were mixed in a mass ratio of 1:1, stirred evenly and then vacuum-defoamed to obtain a modified epoxy resin; S3. Component A and component B are mixed in a mass ratio of 2:1 to obtain an epoxy-modified SMP elastic adhesive for battery encapsulation.

[0021] Comparative Example 1. A method for preparing an epoxy-modified SMP elastic adhesive for battery packaging, comprising the following steps: Compared with Example 1, this example does not prepare acrylic acid-modified SMP resin; S1. Preparation of component A; 130 parts of silane-modified polyether resin, 6.5 parts of 2,4,6-tris(dimethylaminomethyl)phenol, 2 parts of N-n-butyl-3-aminopropyltrimethoxysilane and 4 parts of kaolin were mixed by weight, and stirred for 8 minutes. Then, 2 parts of Dynasylan®1146, 3 parts of vinyltrimethoxysilane, 1 part of antioxidant 1135, 1 part of light stabilizer 765 and 1 part of ultraviolet absorber UV326 were added thereto. After continuing to mix for 5 minutes, vacuum degassing was performed to obtain component A. S2. Preparing component B; 65 parts of modified epoxy resin, 2 parts of catalyst KR-225, 3 parts of hydrophobic fumed silica, and 0.2 parts of deionized water were mixed, stirred for 5 minutes, and vacuum-defoamed to obtain component B; Wherein, the preparation method of the modified epoxy resin is: a. After nitrogen was passed through tetrahydrofuran for 30 min, 2.9 parts of 1,4-bis(dimethylsilyl)benzene were added thereto, and the mixture was uniformly mixed by ultrasonic stirring to obtain a dispersion of 1,4-bis(dimethylsilyl)benzene; Under nitrogen atmosphere protection, 1 part of 2,4,6-trivinyl cycloboroxine was mixed with clean tetrahydrofuran. After mixing evenly, 0.025 parts of boron trifluoride was added thereto. After continuing to mix for 15 minutes, the mixture was added dropwise to the 1,4-bis(dimethylsilyl)benzene dispersion. The mixture was stirred continuously during the addition. After the addition was completed, the reaction system was heated to 65-68°C, refluxed and stirred for 5.5 hours, and then the excess solvent was removed by rotary evaporation. The product was washed once with deionized water at a temperature of 1-5°C, and then dried to constant weight to obtain a three-arm boron compound terminated with silicon hydrogen. b. DMF was heated to 105-110°C, dried and dehydrated for 0.5h, cooled to a temperature rise, 1 part of a three-arm boron compound terminated with silicon hydrogen was added thereto, stirred and dispersed evenly, and then added dropwise to DMF containing 0.58 parts of 1,6-hexanediisocyanate. After the addition was completed, the temperature was raised to 105°C, stirred and reacted for 4h, and the mixture was added dropwise to 0.89 parts of 1,6-hexanediol diglycidyl ether. The mixture was stirred continuously during the addition process. After the addition was completed, the temperature was raised to 68°C, stirred and reacted for 3h, and then the excess solvent was removed by rotary evaporation to obtain a boron-modified epoxy resin monomer; c. The boron-modified epoxy resin monomer and bisphenol A type E51 epoxy resin were mixed in a mass ratio of 1:1, stirred evenly and then vacuum-defoamed to obtain a modified epoxy resin; S3. Component A and component B are mixed in a mass ratio of 2:1 to obtain an epoxy-modified SMP elastic adhesive for battery encapsulation.

[0022] Comparative Example 2. A method for preparing an epoxy-modified SMP elastic adhesive for battery packaging, comprising the following steps: Compared with Example 1, this comparative example only used E51 epoxy resin; S1. Preparation of component A; 65 parts of silane-modified polyether resin, 65 parts of acrylic acid-modified SMP resin, 6.5 parts of 2,4,6-tris(dimethylaminomethyl)phenol, 2 parts of N-n-butyl-3-aminopropyltrimethoxysilane and 4 parts of kaolin were mixed by weight, and after stirring for 8 minutes, 2 parts of Dynasylan®1146, 3 parts of vinyltrimethoxysilane, 1 part of antioxidant 1135, 1 part of light stabilizer 765 and 1 part of ultraviolet absorber UV326 were added thereto, and after continuing to mix for 5 minutes, vacuum degassing was performed to obtain component A; Wherein, the preparation method of the acrylic acid modified SMP resin is: 9 parts of butyl acrylate, 5 parts of hydroxyethyl acrylate, 4 parts of hydroxypropyl acrylate, 6 parts of methyl methacrylate and 30 parts of silane-modified polyether resin were mixed, 0.5 parts of initiator and 6 parts of chain transfer agent were added thereto, reacted at 100° C. in vacuum for 5 hours, cooled and discharged, to generate acrylic acid-modified silane-modified polyether resin; S2. Preparing component B; 65 parts of E51 epoxy resin, 2 parts of catalyst KR-225, 3 parts of hydrophobic fumed silica, and 0.2 parts of deionized water were mixed, stirred for 5 minutes, and vacuum-defoamed to obtain component B; S3. Component A and component B are mixed in a mass ratio of 2:1 to obtain an epoxy-modified SMP elastic adhesive for battery encapsulation.

[0023] Detection: According to GB / T 528-2009, the epoxy-modified SMP elastic adhesive for battery encapsulation prepared in Examples 1-5 and Comparative Examples 1-2 was prepared into a test sample shape, the dumbbell-shaped sample shape was type 2, the thickness was 2.0±0.2 mm, and after 7 days of environmental curing at 25°C and 50%RH, the tensile strength and elongation at break were tested; Test the hardness of the test specimen according to GB / T 531.1; Test its vertical flame retardant properties according to GB / T 2408-2008; The test results are shown in Table 1 below; Table 1. According to GB / T 7124-2008, the epoxy-modified SMP elastic adhesive for battery encapsulation prepared in Example 1, Example 2 and Comparative Example 1 was tested for shear strength. During the test, the lap length was 12.5±0.25 mm, the width was 25±0.25 mm, and the lap adhesive thickness was 0.3 mm. Regarding the failure form, MF is mixed failure, AF is adhesion failure, and CF is cohesive failure. The most ideal is CF, followed by MF, and AF represents adhesion failure. The test results are shown in Table 2 below. Table 2. Finally, it should be noted that the above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art can still modify the technical solutions described in the aforementioned embodiments or replace some of the technical features therein by equivalents. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. An epoxy-modified SMP elastic adhesive for battery packaging, characterized in that: The epoxy-modified SMP elastic adhesive for battery encapsulation is composed of component A and component B mixed in a mass ratio of 2:1; Wherein, the component A is composed of 50-80 parts of silane-modified polyether resin, 50-80 parts of acrylic acid-modified SMP resin, 5-10 parts of epoxy curing agent, 1-5 parts of compatibilizer, 1-5 parts of adhesion promoter, 1-5 parts of dewatering agent, 1-5 parts of filler, 0.1-2 parts of antioxidant, 0.1-2 parts of light stabilizer, and 0.1-2 parts of ultraviolet absorber by weight; The component B comprises 50-100 parts of modified epoxy resin, 0.1-2 parts of catalyst, 1-5 parts of filler and 0.1-1 parts of deionized water; The preparation method of the acrylic acid modified SMP resin is: Butyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, methyl methacrylate and silane-modified polyether resin are mixed, an initiator and a chain transfer agent are added thereto, vacuum is evacuated, the temperature is raised to 80-100° C., the reaction is carried out for 3-5 hours, and the material is cooled and discharged to obtain an acrylic acid-modified SMP resin.

2. The epoxy-modified SMP elastic adhesive for battery packaging according to claim 1, characterized in that: The silane-modified polyether resin is a polyether resin terminated with methyldimethoxysilane or trimethoxysilane; The epoxy curing agent is 2,4,6-tris(dimethylaminomethyl)phenol; The adhesion promoter is any one or more of KH550, KH792, and 1146; The compatibilizer is any one or more of 3-aminopropyltrimethoxysilane and N-n-butyl-3-aminopropyltrimethoxysilane.

3. The epoxy-modified SMP elastic adhesive for battery packaging according to claim 1, characterized in that: The filler is any one of hydrophobic fumed silica, kaolin, polyamide wax, and organic bentonite; The antioxidant is any one or more of antioxidant 1010, antioxidant 1035, and antioxidant 1176; The light stabilizer is any one or more of light stabilizer 292, light stabilizer 770, and light stabilizer 944; The ultraviolet absorber is any one or more of UV326, UV327, and UV328; The catalyst is any one of an organotin catalyst or a mixture of organotin and alkylamine.

4. The epoxy-modified SMP elastic adhesive for battery packaging according to claim 1, characterized in that: The acrylic modified SMP resin is prepared by reacting 4-12 parts of butyl acrylate, 4-8 parts of hydroxyethyl acrylate, 3-6.5 parts of hydroxypropyl acrylate, 4-8 parts of methyl methacrylate, 15-40 parts of silane modified polyether resin, 0.1-2 parts of initiator and 5-15 parts of chain transfer agent by weight.

5. The epoxy-modified SMP elastic adhesive for battery packaging according to claim 1, characterized in that: The preparation method of the modified epoxy resin is: a. After nitrogen was passed through tetrahydrofuran for 30-45min, 1,4-bis(dimethylsilyl)benzene was added thereto, and the mixture was uniformly mixed by ultrasonic stirring to obtain a 1,4-bis(dimethylsilyl)benzene dispersion; Under nitrogen atmosphere protection, 2,4,6-trivinyl boroxine is mixed with clean tetrahydrofuran, and after mixing evenly, boron trifluoride is added thereto, and mixing is continued for 15-20 minutes, and then it is added dropwise to the 1,4-bisdimethylsilylbenzene dispersion, and stirring is continuously performed during the dropping process. After the dropping is completed, the reaction system is heated to 65-68°C, and refluxed and stirred for reaction for 1.5-8 hours, and then the excess solvent is removed by rotary evaporation. The product is washed 1-2 times with deionized water at a temperature of 1-5°C, and then dried to constant weight to obtain a three-arm boron compound terminated with silicon hydrogen; b. Heat DMF to 105-110°C, dry and remove water for 0.5-1h, cool to warm, add the three-arm boron compound terminated with silicon hydrogen, stir and disperse evenly, then add it dropwise to DMF dissolved with 1,6-hexanediisocyanate, after the addition is completed, heat to 105-110°C, stir and react for 2-4h, then add the mixture dropwise to 1,6-hexanediol diglycidyl ether, stir continuously during the addition, heat to 65-75°C after the addition is completed, stir and react for 1.5-4h, then remove excess solvent by rotary evaporation to obtain a boron-modified epoxy resin monomer; c. Mix the boron-modified epoxy resin monomer and bisphenol A epoxy resin, stir evenly, and then perform vacuum degassing to obtain a modified epoxy resin.

6. The epoxy-modified SMP elastic adhesive for battery packaging according to claim 5, characterized in that: In step a, the mass ratio of 1,4-bisdimethylsilylbenzene, 2,4,6-trivinylcycloboroxine and boron trifluoride is (2.9-3.7):1:(0.015-0.05).

7. The epoxy-modified SMP elastic adhesive for battery packaging according to claim 5, characterized in that: In step b, the mass ratio of the silyl-terminated three-arm boron compound, 1,6-hexamethylene diisocyanate, and 1,6-hexanediol diglycidyl ether is 1: (0.58-0.68): (0.89-0.95).

8. The epoxy-modified SMP elastic adhesive for battery packaging according to claim 5, characterized in that: In step c, the mass ratio of the boron-modified epoxy resin monomer to the bisphenol A epoxy resin is 1:

1.

9. A method for preparing the epoxy-modified SMP elastic adhesive for battery packaging according to any one of claims 1 to 8, characterized in that: The following steps are involved: S1. Preparation of component A; Silane-modified polyether resin, acrylic acid-modified SMP resin, epoxy curing agent, compatibilizer and filler are mixed, stirred for 5-10 minutes, and then an adhesion promoter, a water scavenger, an antioxidant, a light stabilizer and an ultraviolet absorber are added thereto. After continuing to mix for 3-5 minutes, vacuum degassing is performed to obtain component A. S2. Preparing component B; The modified epoxy resin, catalyst, filler and deionized water are mixed, stirred for 3-5 minutes, and then vacuum-defoamed to obtain component B; S3. Component A and component B are mixed to obtain an epoxy-modified SMP elastic adhesive for battery encapsulation.

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