Bi-component epoxy modified SMP elastic adhesive and application thereof

Abstract

The invention relates to the technical field of adhesives, in particular to a bi-component epoxy modified SMP elastic adhesive and application thereof. The bi-component epoxy modified SMP elastic adhesive comprises a component A and a component B, the component A is prepared from the following components in parts by weight: 50 to 80 parts of silane modified polyether resin, 50 to 80 parts of acrylic acid modified SMP resin, 5 to 10 parts of an epoxy curing agent, 1 to 5 parts of a compatilizer, 1 to 5 parts of an adhesion promoter, 1 to 5 parts of a water removal agent, 1 to 5 parts of filler, 0.1 to 2 parts of an antioxidant, 0.1 to 2 parts of a light stabilizer and 0.1 to 2 parts of an ultraviolet light absorber; the component B is prepared from the following components in parts by weight: 50 to 100 parts of epoxy resin, 0.1 to 2 parts of catalyst, 1 to 5 parts of filler and 0.1 to 1 part of deionized water.

Description

Technical Field

[0001] This invention relates to the field of adhesive technology, specifically to a two-component epoxy-modified SMP elastic adhesive and its applications. Background Technology

[0002] Silane-modified polyether adhesive (SMP adhesive) is a polymer material with a high molecular weight polyether backbone and hydrolyzable, condensation-crosslinkable siloxane groups at the end groups. This structure endows SMP adhesive with moisture-curing properties while also providing excellent flexibility, ductility, and hydrolysis resistance. Through the hydrolysis and condensation reaction of siloxanes, SMP adhesive can form a Si-O-Si network structure, exhibiting excellent weather resistance, aging resistance, and hydrolysis resistance. Therefore, SMP adhesive is widely used in industries such as construction and home decoration, rail transportation, new energy, and electronics.

[0003] However, when used as an elastic adhesive or sealant, SMP adhesives have lower mechanical properties compared to polyurethane adhesives. This limits their application in structural bonding applications. Although commercially available epoxy-modified SMP adhesives have improved mechanical properties, their performance in bonding certain plastics is not ideal, posing a risk of bond failure, thus limiting their application as well. Currently, in industrial, automotive, and battery packaging fields, with the widespread use of lightweight materials (such as plastics, aluminum, and composites), conventional epoxy-modified SMP adhesives or SMP adhesives perform poorly in bonding with common plastic materials, often resulting in interface damage and the risk of bond failure.

[0004] Therefore, we propose a two-component epoxy-modified SMP elastic adhesive and its application. Summary of the Invention

[0005] The purpose of this invention is to provide a two-component epoxy-modified SMP elastic adhesive and its application, in order to solve the problems raised in the prior art.

[0006] To achieve the above objectives, the present invention provides the following technical solution: A two-component epoxy-modified SMP elastic adhesive comprises component A and component B. Component A, by weight, consists of the following components: 50-80 parts of silane-modified polyether resin, 50-80 parts of acrylic-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 dehydrating 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. Component B, by weight, consists of the following components: 50-100 parts of epoxy resin, 0.1-2 parts of catalyst, 1-5 parts of filler, and 0.1-1 parts of deionized water.

[0007] Preferably, the mass ratio of component A to component B is (1-3):1.

[0008] Preferably, the silane-modified polyether resin is a silane-modified polyether resin end-capped with methyldimethoxysilane or trimethoxysilane, specifically one of KERILON 350A, KERILON 3900, RISUN 30000T, TUPS 303T, and TUPS400.

[0009] A preferred method for preparing the acrylic-modified SMP resin is as follows: butyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, methyl methacrylate, and silane-modified polyether resin are mixed evenly, an initiator and a chain transfer agent are added, the mixture is vacuumed, and the reaction is carried out at 80-100℃ for 5-7 hours to obtain the acrylic-modified SMP resin.

[0010] Preferably, the acrylic-modified SMP resin is composed of the following components by weight: 8-24 parts butyl acrylate, 8-16 parts hydroxyethyl acrylate, 6-12 parts hydroxypropyl acrylate, 8-16 parts methyl methacrylate, 30-80 parts silane-modified polyether resin, 0.2-4.0 parts initiator, and 10-25 parts chain transfer agent.

[0011] More preferably, the epoxy curing agent is 2,4,6-tris(dimethylaminomethyl)phenol.

[0012] Preferably, the compatibilizer is one or more of 3-aminopropyltrimethoxysilane and N-n-butyl-3-aminopropyltrimethoxysilane.

[0013] Preferably, the adhesion promoter is one or more of KH550, KH792, and 1146.

[0014] Preferably, the dehydrating agent is vinyltrimethoxysilane.

[0015] Preferably, the filler is one or more of hydrophobic fumed silica, kaolin, polyamide wax, and organobentonite.

[0016] Preferably, the epoxy resin is one or more of bisphenol A type epoxy resin, bisphenol F type epoxy resin, and phenolic type epoxy resin.

[0017] Preferably, the catalyst is an organotin compound or a mixture of organotin compounds and alkylamines, and more preferably a hydrolysis-resistant tin catalyst, with brand names Changzhou Kerry KR-24 and KR-225.

[0018] A two-component epoxy-modified SMP elastic adhesive, comprising the following steps: Step 1: Mix silane-modified polyether resin, acrylic-modified SMP resin, epoxy curing agent, compatibilizer, adhesion promoter, dehydrating agent, filler, antioxidant, light stabilizer and ultraviolet absorber evenly to obtain component A; Step 2: Mix epoxy resin, catalyst, filler and deionized water evenly to obtain component B; Step 3: Mix component A and component B at a mass ratio of (1-3):1 to obtain a two-component epoxy-modified SMP elastic adhesive.

[0019] Preferably, the epoxy resin has undergone modification treatment, specifically as follows: Step 1: Mix the terminal epoxy allyl polyether and chloroplatinic acid-isopropanol solution evenly, add boron-containing and hydrogen-containing silicone oil, react at 70-80℃ for 8-10 hours, and obtain the terminal epoxy silicone oil by vacuum distillation. Step 2: Mix amino-terminated hyperbranched polyamide and epoxy-terminated silicone oil evenly and react at 85-95℃ for 3-5 hours to obtain the modifier; Step 3: Under nitrogen protection, epoxy resin and diisocyanate compound are mixed and reacted at 80-100℃ for 2-4 hours with dibutyltin dilaurate as catalyst. Then, modifier is added and reacted at 70-90℃ for 3-5 hours to obtain modified epoxy resin.

[0020] In the above technical solution, terminal epoxy-terminated allyl polyether is subjected to a hydrosilylation reaction with boron-containing and hydrogen-containing silicone oil to obtain terminal epoxy-terminated silicone oil. The introduction of boron, flexible polyether segments, and organosilicon structure effectively improves the heat resistance temperature of the material, enabling the obtained two-component epoxy-modified SMP elastic adhesive to maintain good performance stability under high temperature conditions. Then, the terminal amino-terminated hyperbranched polyamide is reacted with the terminal epoxy-terminated silicone oil to introduce hyperbranched structure and polyamide. At the same time, the generated hydroxyl groups can act as active groups to further promote cross-linking reactions with other components (such as epoxy resin). Finally, a diisocyanate compound is used as a binder to combine the modifier with the epoxy resin, successfully obtaining modified epoxy resin. The terminal amino-terminated hyperbranched polyamide has a reinforcing and toughening effect on the epoxy resin, further enhancing the mechanical properties of the adhesive.

[0021] Preferably, the mass ratio of the terminal epoxy allyl polyether to the boron-containing and hydrogen-containing silicone oil is 1:(1-3).

[0022] Preferredly, the mass of the chloroplatinic acid-isopropanol solution, measured in Pt, is 2-4 ppm of the total mass of the terminal epoxy allyl polyether and the boron- and hydrogen-containing silicone oil.

[0023] Preferably, the boron- and hydrogen-containing silicone oil is prepared according to the method of Example 1 in Chinese Invention Patent CN110078927B.

[0024] Preferably, the molar ratio of amino groups in the amino-terminated hyperbranched polyamide to epoxy groups in the epoxy-terminated silicone oil is 1:(1.0-1.2).

[0025] More preferably, the ratio of the molar amount of hydroxyl groups in the epoxy resin, the molar amount of isocyanate groups in the diisocyanate compound, and the molar amount of hydroxyl groups in the modifier is 1:(2.0-2.2):(1.0-1.2).

[0026] Preferably, the diisocyanate compound is one or more of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, or 4,4-dicyclohexylmethane diisocyanate.

[0027] Preferably, the mass of the dibutyltin dilaurate is 0.03-0.05% of the total mass of the epoxy resin and diphenylmethane diisocyanate.

[0028] Compared with the prior art, the beneficial effects of the present invention are: This invention discloses a two-component epoxy-modified SMP elastic adhesive and its application. By modifying the SMP adhesive with epoxy resin to form an island structure, the mechanical properties of the SMP adhesive, such as bonding strength and bulk strength, are improved. Based on the above scheme, the overall performance of the adhesive was improved by modifying the epoxy resin and compounding it with acrylic-modified SMP resin. The polar segments (such as hydroxyl and carboxyl groups) of the acrylic-modified SMP resin form an interpenetrating network structure with the epoxy groups, significantly enhancing cohesive strength; simultaneously, its flexible acrylate segments improve the adhesive's flexibility and impact resistance. The modified epoxy resin, through the introduction of boron and polyamide, significantly improves heat resistance, and the introduction of flexible polyether segments and silicone structures enhances the dispersibility and compatibility of the two components in the SMP resin, further strengthening the adhesive's bonding performance to different substrates. The two-component epoxy-modified SMP elastic adhesive prepared by this invention has moderate viscosity, anti-sagging properties, and rapid curing, enabling rapid assembly on production lines. It requires no primer and exhibits good adhesion to conventional metals, common plastics, and building materials. Furthermore, this product is solvent-free, can operate in high-temperature environments, and has a simple preparation method using a cold process that eliminates the need for high-temperature dehydration. During use, only the A and B components need to be mixed evenly. It can be widely applied in industries such as new energy battery packaging, automobiles, aerospace, and electronics. Detailed Implementation

[0029] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0030] It should be noted that the following quantities are by weight. There are no special restrictions on the manufacturers of the raw materials involved in this invention. Exemplary examples include: silane-modified polyether resin: RISUN 30000T; 1146 coupling agent: Dynasylan® 1146; kaolin: 1250 mesh particle size; catalyst: KR-225, purchased from Changzhou Kerry Chemical Technology Co., Ltd.; boron-containing hydrogen-containing silicone oil prepared according to the method in Example 1 of Chinese Invention Patent CN110078927B; RAFT chain transfer agent: 2-[dodecylthio(thiocarbonyl)thio]-2-methylpropionic acid, CAS number 461642-78-4; hydrophobic fumed silica: WACKER HDK H2000 (Germany); amino-terminated hyperbranched polyamide: HyPer N102 was purchased from Wuhan Hyperbranched Resin Technology Co., Ltd.; terminal epoxy silicone oil: model E875446 was purchased from Shanghai Maclean Biochemical Technology Co., Ltd.

[0031] Unless otherwise specified, all the following quantities are parts by weight.

[0032] Example 1: A preparation process for a two-component epoxy-modified SMP elastic adhesive, comprising the following processes: Step 1: Mix 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, 2 parts of 1146 coupling agent, 3 parts of vinyltrimethoxysilane, 4 parts of kaolin, 1 part of antioxidant 1135, 1 part of light stabilizer 765, and 1 part of ultraviolet absorber 384-2 evenly to obtain component A; Step 2: Mix 65 parts of epoxy resin E51, 2 parts of catalyst, 3 parts of hydrophobic fumed silica and 0.2 parts of deionized water evenly to obtain component B; Step 3: Mix component A and component B at a mass ratio of 2:1 to obtain a two-component epoxy-modified SMP elastic adhesive. The preparation method of acrylic modified SMP resin is as follows: 18 parts of butyl acrylate, 10 parts of hydroxyethyl acrylate, 8 parts of hydroxypropyl acrylate, 12 parts of methyl methacrylate and 60 parts of silane modified polyether resin are mixed evenly, 0.8 parts of benzoyl peroxide and 12 parts of chain transfer agent are added, vacuum is applied and the mixture is reacted at 100℃ for 5 hours to obtain acrylic modified SMP resin.

[0033] Example 2: A preparation process for a two-component epoxy-modified SMP elastic adhesive, comprising the following processes: Step 1: Mix 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, 1.5 parts of 1146 coupling agent, 3 parts of vinyltrimethoxysilane, 2 parts of kaolin, 1 part of antioxidant 1135, 1 part of light stabilizer 765, and 1 part of ultraviolet absorber 384-2 evenly to obtain component A; Step 2: Mix 65 parts of epoxy resin E51, 1.5 parts of catalyst, 5 parts of hydrophobic fumed silica and 0.5 parts of deionized water evenly to obtain component B; Step 3: Mix component A and component B at a mass ratio of 2:1 to obtain a two-component epoxy-modified SMP elastic adhesive. The preparation method of acrylic modified SMP resin is as follows: 16 parts of butyl acrylate, 12 parts of hydroxyethyl acrylate, 8 parts of hydroxypropyl acrylate, 8 parts of methyl methacrylate and 40 parts of silane modified polyether resin are mixed evenly, 1 part of benzoyl peroxide and 16 parts of chain transfer agent are added, vacuum is applied and the mixture is reacted at 100℃ for 5 hours to obtain acrylic modified SMP resin.

[0034] Example 3: A preparation process for a two-component epoxy-modified SMP elastic adhesive, comprising the following processes: Step 1: Mix 50 parts of silane-modified polyether resin, 50 parts of acrylic acid-modified SMP resin, 5 parts of 2,4,6-tris(dimethylaminomethyl)phenol, 1 part of N-n-butyl-3-aminopropyltrimethoxysilane, 1 part of 1146 coupling agent, 1 part of vinyltrimethoxysilane, 1 part of kaolin, 0.1 part of antioxidant 1135, 0.1 part of light stabilizer 765, and 0.1 part of ultraviolet absorber 384-2 evenly to obtain component A; Step 2: Mix 50 parts of epoxy resin E51, 0.1 parts of catalyst, 1 part of hydrophobic fumed silica and 0.1 parts of deionized water evenly to obtain component B; Step 3: Mix component A and component B at a mass ratio of 1:1 to obtain a two-component epoxy-modified SMP elastic adhesive. The preparation method of acrylic modified SMP resin is as follows: 8 parts butyl acrylate, 8 parts hydroxyethyl acrylate, 6 parts hydroxypropyl acrylate, 8 parts methyl methacrylate and 30 parts silane modified polyether resin are mixed evenly, 0.2 parts benzoyl peroxide and 10 parts chain transfer agent are added, vacuum is applied and the mixture is reacted at 80℃ for 5 hours to obtain acrylic modified SMP resin. The epoxy resin undergoes modification treatment, and the specific process is as follows: Step 1: Mix 10 parts of terminal epoxy allyl polyether and chloroplatinic acid-isopropanol solution evenly, add 10 parts of boron-containing hydrogen silicone oil, react at 70°C for 8 hours, and obtain terminal epoxy silicone oil by vacuum distillation; the mass of chloroplatinic acid-isopropanol solution is 2 ppm of the total mass of terminal epoxy allyl polyether and boron-containing hydrogen silicone oil according to Pt. Step 2: Mix amino-terminated hyperbranched polyamide and epoxy-terminated silicone oil evenly and react at 85°C for 3 hours to obtain the modifier; the molar ratio of amino groups in amino-terminated hyperbranched polyamide to epoxy groups in epoxy-terminated silicone oil is 1:1. Step 3: Under nitrogen protection, epoxy resin and isophorone diisocyanate are mixed and reacted at 80°C for 2 hours with dibutyltin dilaurate as a catalyst. Then, a modifier is added and the mixture is reacted at 70°C for 3 hours to obtain modified epoxy resin. The ratio of the molar amount of hydroxyl groups in epoxy resin, the molar amount of isocyanate groups in isophorone diisocyanate, and the molar amount of hydroxyl groups in modifier is 1:2:1. The mass of dibutyltin dilaurate is 0.03% of the total mass of epoxy resin and diphenylmethane diisocyanate.

[0035] Example 4: A preparation process for a two-component epoxy-modified SMP elastic adhesive, comprising the following processes: Step 1: Mix 60 parts of silane-modified polyether resin, 60 parts of acrylic acid-modified SMP resin, 8 parts of 2,4,6-tris(dimethylaminomethyl)phenol, 3 parts of N-n-butyl-3-aminopropyltrimethoxysilane, 3 parts of 1146 coupling agent, 3 parts of vinyltrimethoxysilane, 3 parts of kaolin, 1 part of antioxidant 1135, 1 part of light stabilizer 765, and 1 part of ultraviolet absorber 384-2 evenly to obtain component A; Step 2: Mix 60 parts of epoxy resin E51, 1 part of catalyst, 3 parts of hydrophobic fumed silica and 0.5 parts of deionized water evenly to obtain component B; Step 3: Mix component A and component B at a mass ratio of 2:1 to obtain a two-component epoxy-modified SMP elastic adhesive. The preparation method of acrylic modified SMP resin is as follows: 20 parts of butyl acrylate, 12 parts of hydroxyethyl acrylate, 10 parts of hydroxypropyl acrylate, 10 parts of methyl methacrylate and 50 parts of silane modified polyether resin are mixed evenly, 1.5 parts of benzoyl peroxide and 12 parts of chain transfer agent are added, vacuum is applied and the mixture is reacted at 90°C for 6 hours to obtain acrylic modified SMP resin. The epoxy resin undergoes modification treatment, and the specific process is as follows: Step 1: Mix 20 parts of terminal epoxy allyl polyether and chloroplatinic acid-isopropanol solution evenly, add 40 parts of boron-containing hydrogen silicone oil, react at 75°C for 9 hours, and obtain terminal epoxy silicone oil by vacuum distillation; the mass of chloroplatinic acid-isopropanol solution is 3 ppm of the total mass of terminal epoxy allyl polyether and boron-containing hydrogen silicone oil according to Pt. Step 2: Mix amino-terminated hyperbranched polyamide and epoxy-terminated silicone oil evenly and react at 90°C for 4 hours to obtain the modifier; the molar ratio of amino groups in amino-terminated hyperbranched polyamide to epoxy groups in epoxy-terminated silicone oil is 1:1.1. Step 3: Under nitrogen protection, epoxy resin and isophorone diisocyanate are mixed and reacted at 90°C for 3 hours with dibutyltin dilaurate as a catalyst. Then, a modifier is added and the mixture is reacted at 80°C for 4 hours to obtain modified epoxy resin. The ratio of the molar amount of hydroxyl groups in epoxy resin, the molar amount of isocyanate groups in isophorone diisocyanate, and the molar amount of hydroxyl groups in modifier is 1:2.1:1.1. The mass of dibutyltin dilaurate is 0.04% of the total mass of epoxy resin and diphenylmethane diisocyanate.

[0036] Example 5: A preparation process for a two-component epoxy-modified SMP elastic adhesive, comprising the following processes: Step 1: Mix 80 parts of silane-modified polyether resin, 80 parts of acrylic acid-modified SMP resin, 10 parts of 2,4,6-tris(dimethylaminomethyl)phenol, 5 parts of N-n-butyl-3-aminopropyltrimethoxysilane, 5 parts of 1146 coupling agent, 5 parts of vinyltrimethoxysilane, 5 parts of kaolin, 2 parts of antioxidant 1135, 2 parts of light stabilizer 765, and 2 parts of ultraviolet absorber 384-2 evenly to obtain component A; Step 2: Mix 100 parts of epoxy resin E51, 2 parts of catalyst, 5 parts of hydrophobic fumed silica and 1 part of deionized water evenly to obtain component B. Step 3: Mix component A and component B at a mass ratio of 3:1 to obtain a two-component epoxy-modified SMP elastic adhesive. The preparation method of acrylic modified SMP resin is as follows: 24 parts of butyl acrylate, 16 parts of hydroxyethyl acrylate, 12 parts of hydroxypropyl acrylate, 16 parts of methyl methacrylate and 80 parts of silane modified polyether resin are mixed evenly, 4 parts of benzoyl peroxide and 25 parts of chain transfer agent are added, vacuum is drawn and reacted at 100℃ for 7h to obtain acrylic modified SMP resin. The epoxy resin undergoes modification treatment, and the specific process is as follows: Step 1: Mix 20 parts of terminal epoxy allyl polyether and chloroplatinic acid-isopropanol solution evenly, add 60 parts of boron-containing hydrogen silicone oil, react at 80℃ for 10 h, and obtain terminal epoxy silicone oil by vacuum distillation; the mass of chloroplatinic acid-isopropanol solution is 4 ppm of the total mass of terminal epoxy allyl polyether and boron-containing hydrogen silicone oil according to Pt. Step 2: Mix amino-terminated hyperbranched polyamide and epoxy-terminated silicone oil evenly and react at 95°C for 5 hours to obtain the modifier; the molar ratio of amino groups in amino-terminated hyperbranched polyamide to epoxy groups in epoxy-terminated silicone oil is 1:1.2. Step 3: Under nitrogen protection, epoxy resin and isophorone diisocyanate are mixed and reacted at 100°C for 4 hours with dibutyltin dilaurate as a catalyst. Then, a modifier is added and the mixture is reacted at 90°C for 5 hours to obtain modified epoxy resin. The ratio of the molar amount of hydroxyl groups in epoxy resin, the molar amount of isocyanate groups in isophorone diisocyanate, and the molar amount of hydroxyl groups in modifier is 1:2.2:1.2. The mass of dibutyltin dilaurate is 0.05% of the total mass of epoxy resin and diphenylmethane diisocyanate.

[0037] Comparative Example 1: A preparation process for a two-component epoxy-modified SMP elastic adhesive, comprising the following processes: Compared to Example 4, Comparative Example 1 did not introduce acrylic-modified SMP resin, but the other steps were the same as in Example 4.

[0038] Comparative Example 2: A preparation process for a two-component epoxy-modified SMP elastic adhesive, comprising the following processes: The epoxy resin undergoes modification treatment, and the specific process is as follows: Under nitrogen protection, epoxy resin and isophorone diisocyanate were mixed and reacted at 90°C for 3 hours using dibutyltin dilaurate as a catalyst. Then, amino-terminated hyperbranched polyamide was added, and the reaction was carried out at 80°C for 4 hours to obtain modified epoxy resin. The ratio of the molar amount of hydroxyl groups in the epoxy resin, the molar amount of isocyanate groups in the isophorone diisocyanate, and the molar amount of hydroxyl groups in the modifier was 1:2.1:1.1. The mass of dibutyltin dilaurate was 0.04% of the total mass of the epoxy resin and diphenylmethane diisocyanate. Compared to Example 4, Comparative Example 2 did not introduce terminal epoxy silicone oil, but replaced the modifier with the same mass of terminal amino hyperbranched polyamide; other steps were the same as in Example 4.

[0039] Comparative Example 3: A preparation process for a two-component epoxy-modified SMP elastic adhesive, comprising the following processes: The epoxy resin undergoes modification treatment, and the specific process is as follows: Step 1: Mix 20 parts of terminal epoxy allyl polyether and chloroplatinic acid-isopropanol solution evenly, add 40 parts of boron-containing hydrogen silicone oil, react at 75°C for 9 hours, and obtain terminal epoxy silicone oil by vacuum distillation; the mass of chloroplatinic acid-isopropanol solution is 3 ppm of the total mass of terminal epoxy allyl polyether and boron-containing hydrogen silicone oil according to Pt. Step 2: Under nitrogen protection, epoxy resin and isophorone diisocyanate were mixed and reacted at 90°C for 3 hours using dibutyltin dilaurate as a catalyst. Then, terminal epoxy-based silicone oil was added, and the mixture was reacted at 80°C for 4 hours to obtain modified epoxy resin. The ratio of the molar amount of hydroxyl groups in the epoxy resin, the molar amount of isocyanate groups in the isophorone diisocyanate, and the molar amount of hydroxyl groups in the modifier was 1:2.1:1.1. The mass of dibutyltin dilaurate was 0.04% of the total mass of epoxy resin and diphenylmethane diisocyanate. Compared to Example 4, Comparative Example 3 did not introduce amino-terminated hyperbranched polyamide, but replaced the modifier with the same mass of epoxy-terminated silicone oil; the other steps were the same as in Example 4.

[0040] Comparative Example 4: A preparation process for a two-component epoxy-modified SMP elastic adhesive, comprising the following processes: The epoxy resin undergoes modification treatment, and the specific process is as follows: Step 1: Mix 20 parts of terminal epoxy allyl polyether and chloroplatinic acid-isopropanol solution evenly, add 40 parts of boron-containing hydrogen silicone oil, react at 75°C for 9 hours, and obtain terminal epoxy silicone oil by vacuum distillation; the mass of chloroplatinic acid-isopropanol solution is 3 ppm of the total mass of terminal epoxy allyl polyether and boron-containing hydrogen silicone oil according to Pt. Step 2: Mix amino-terminated hyperbranched polyamide and epoxy-terminated silicone oil evenly and react at 90°C for 4 hours to obtain the modifier; the molar ratio of amino groups in amino-terminated hyperbranched polyamide to epoxy groups in epoxy-terminated silicone oil is 1:0.4. Step 3: Under nitrogen protection, epoxy resin and isophorone diisocyanate were mixed and reacted at 90°C for 3 hours using dibutyltin dilaurate as a catalyst. Then, a modifier was added, and the mixture was reacted at 80°C for 4 hours to obtain modified epoxy resin. The ratio of the molar amount of hydroxyl groups in the epoxy resin, the molar amount of isocyanate groups in the isophorone diisocyanate, and the molar amount of hydroxyl groups in the modifier was 1:2.1:1.1. The mass of dibutyltin dilaurate was 0.04% of the total mass of the epoxy resin and diphenylmethane diisocyanate. Compared with Example 4, in Comparative Example 4, the molar ratio of amino groups in the amino-terminated hyperbranched polyamide to epoxy groups in the epoxy-terminated silicone oil was 1:0.4; other steps were the same as in Example 4.

[0041] Experiment: Two-component epoxy-modified SMP elastic adhesives obtained in Examples 1-5 and Comparative Examples 1-4 were used to prepare samples. Their properties were tested and the test results were recorded. Hardness testing was conducted according to GB / T 531.1-2008; tensile strength and elongation at break testing were conducted according to GB / T 528-2009; and heat resistance testing was conducted according to GB / T 7124-2008. The experimental procedure was as follows: After dust and oil removal treatment, two PVC film bonding substrates were horizontally bonded using a two-component epoxy-modified SMP elastic adhesive. The bonding area was 12.5mm × 25mm, and the adhesive thickness was 0.2mm. After bonding, the substrates were cured at 25℃ / 50%RH for 7 days. The shear strength was then measured using an electronic universal testing machine. The substrates were then placed in a 120℃ oven and left to stand for 24 hours. The shear strength was then tested using a 120℃ high and low temperature tensile tester to evaluate their heat resistance.

[0042] The test results are shown in Table 1.

[0043] Table 1. Performance test results of two-component epoxy-modified SMP elastic adhesive

[0044] Based on the data in the table above, the following conclusions can be clearly drawn: Combining Examples 1-5 and Comparative Examples 1-4, it can be seen that by introducing acrylic-modified SMP resin and modified epoxy resin into silane-modified polyether resin, the mechanical properties, bonding strength, and heat resistance of the adhesive can be improved together. Compared with Example 4, Comparative Example 1 did not introduce acrylic-modified SMP resin, and all properties of the material decreased significantly. The modifier in Comparative Example 2 did not introduce terminal epoxy-based silicone oil, resulting in a decrease in both tensile strength and heat resistance of the adhesive. The modifier in Comparative Example 3 did not introduce terminal amino-based hyperbranched polyamide, resulting in a decrease in both tensile strength and heat resistance of the adhesive. In Comparative Example 4, reducing the amount of terminal epoxy-based silicone oil reduced the heat resistance of the material. It can be seen that the performance of the modifier prepared by this invention is affected by the ratio of each reagent in its preparation process. By selecting the molar ratio within the range described above, the prepared modifier has excellent heat resistance, thereby improving the overall performance of the adhesive.

[0045] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above, and that the invention can be implemented in other specific forms without departing from the spirit or essential characteristics of the invention. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description. Thus, it is intended that all variations falling within the meaning and scope of equivalents of the claims be included within the present invention.

Claims

1. A two-component epoxy-modified SMP elastic adhesive, characterized in that: The product comprises component A and component B. Component A, by weight, consists of the following components: 50-80 parts of silane-modified polyether resin, 50-80 parts of acrylic-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 dehydrating 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. Component B, by weight, consists of the following components: 50-100 parts of epoxy resin, 0.1-2 parts of catalyst, 1-5 parts of filler, and 0.1-1 parts of deionized water. The epoxy resin has undergone modification treatment.

2. The two-component epoxy-modified SMP elastic adhesive according to claim 1, characterized in that: The mass ratio of component A to component B is (1-3):

1.

3. The two-component epoxy-modified SMP elastic adhesive according to claim 1, characterized in that: The silane-modified polyether resin is a silane-modified polyether resin end-capped with methyldimethoxysilane or trimethoxysilane.

4. The two-component epoxy-modified SMP elastic adhesive according to claim 1, characterized in that: The preparation method of the acrylic modified SMP resin is as follows: butyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, methyl methacrylate and silane modified polyether resin are mixed evenly, an initiator and a chain transfer agent are added, vacuum is applied, and the mixture is reacted at 80-100℃ for 5-7 hours to obtain the acrylic modified SMP resin.

5. The two-component epoxy-modified SMP elastic adhesive according to claim 4, characterized in that: The acrylic-modified SMP resin is composed of the following components by weight: 8-24 parts butyl acrylate, 8-16 parts hydroxyethyl acrylate, 6-12 parts hydroxypropyl acrylate, 8-16 parts methyl methacrylate, 30-80 parts silane-modified polyether resin, 0.2-4.0 parts initiator, and 10-25 parts chain transfer agent.

6. The two-component epoxy-modified SMP elastic adhesive according to claim 1, characterized in that: The filler is one or more of the following: hydrophobic fumed silica, kaolin, polyamide wax, and organobentonite.

7. The two-component epoxy-modified SMP elastic adhesive according to claim 1, characterized in that: The epoxy resin is one or more of bisphenol A type epoxy resin, bisphenol F type epoxy resin, and phenolic type epoxy resin.

8. A method for preparing a two-component epoxy-modified SMP elastic adhesive according to any one of claims 1-7, characterized in that: Includes the following steps: Step 1: Mix silane-modified polyether resin, acrylic-modified SMP resin, epoxy curing agent, compatibilizer, adhesion promoter, dehydrating agent, filler, antioxidant, light stabilizer and ultraviolet absorber evenly to obtain component A; Step 2: Mix epoxy resin, catalyst, filler and deionized water evenly to obtain component B; Step 3: Mix component A and component B at a mass ratio of (1-3):1 to obtain a two-component epoxy-modified SMP elastic adhesive.

9. The method for preparing a two-component epoxy-modified SMP elastic adhesive according to claim 8, characterized in that: The epoxy resin undergoes modification treatment, the specific process of which is as follows: Step 1: Mix the terminal epoxy allyl polyether and chloroplatinic acid-isopropanol solution evenly, add boron-containing and hydrogen-containing silicone oil, react at 70-80℃ for 8-10 hours, and obtain the terminal epoxy silicone oil by vacuum distillation. Step 2: Mix amino-terminated hyperbranched polyamide and epoxy-terminated silicone oil evenly and react at 85-95℃ for 3-5 hours to obtain the modifier; Step 3: Under nitrogen protection, epoxy resin and diisocyanate compound are mixed and reacted at 80-100℃ for 2-4 hours with dibutyltin dilaurate as catalyst. Then, modifier is added and reacted at 70-90℃ for 3-5 hours to obtain modified epoxy resin.

10. An application of a two-component epoxy-modified SMP elastic adhesive, characterized in that: The two-component epoxy-modified SMP elastic adhesive according to any one of claims 1-7 is used for battery encapsulation.

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