Environment-friendly aging-resistant adhesive and preparation method thereof

Abstract

The application relates to the technical field of epoxy resin adhesives, and particularly discloses an environment-friendly aging-resistant adhesive and a preparation method thereof; the environment-friendly aging-resistant adhesive comprises components A and B; the component A comprises the following raw materials in parts by mass: 10-15 parts of bisphenol A type vinyl ester resin, 45-55 parts of bisphenol A type liquid epoxy resin and 5-10 parts of cashew phenol epoxy resin; the component B comprises the following raw materials in parts by mass: 15-20 parts of an amine curing agent, 12-15 parts of additive A, 3-4 parts of additive B, 0.5-1 part of additive C and 0.01-0.02 part of a photoinitiator; the additive A is a metal organic framework loaded with a curing agent; the additive B is lignin containing amino groups and double bonds; and the additive C is styrene-butadiene-styrene.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of epoxy resin adhesive, and discloses an environment-friendly and aging-resistant adhesive and a preparation method thereof. BACKGROUND

[0002] Epoxy resin has excellent wear resistance, mechanical properties, adhesion, chemical stability, electrical insulation, adhesion and other properties, and is widely used in various fields. The adhesive prepared from epoxy resin has high bonding strength and excellent chemical resistance, but the cured epoxy resin is hard and brittle, has poor toughness and is easy to crack, and has poor heat aging resistance, so the epoxy resin needs to be modified.

[0003] The prior art often adds inorganic fillers, introduces phenolic resin, and introduces heat-resistant structural units in the epoxy resin chain segment to improve the heat aging resistance of the epoxy resin, but these modification methods may reduce the toughness of the epoxy resin, and some cannot meet the environmental protection requirements, and it is difficult to balance the environmental protection, aging resistance and mechanical properties. Therefore, it is of great significance to study an environment-friendly and aging-resistant adhesive with good mechanical properties and a preparation method thereof. SUMMARY

[0004] The present application aims to provide an environment-friendly and aging-resistant adhesive and a preparation method thereof to solve the problems in the prior art.

[0005] To achieve the above-mentioned purpose, the present application provides the following technical scheme: an environment-friendly and aging-resistant adhesive comprises component A and component B; the component A comprises the following raw materials in parts by mass: 10-15 parts of bisphenol A type vinyl ester resin, 45-55 parts of bisphenol A type liquid epoxy resin, and 5-10 parts of cashew phenol epoxy resin.

[0006] The component B comprises the following raw materials in parts by mass: 15-20 parts of amine curing agent, 12-15 parts of additive A, 3-4 parts of additive B, 0.5-1 part of additive C, and 0.01-0.02 part of photoinitiator 1173.

[0007] The additive A is a metal organic framework loaded with a curing agent; the additive B is lignin containing amino groups and double bonds; the additive C is styrene-butadiene-styrene; and the amine curing agent is 4,4-diaminodiphenyl sulfone.

[0008] The bisphenol A type vinyl ester resin has a model number of 854, the bisphenol A type liquid epoxy resin has a model number of E51, and the cashew phenol epoxy resin has a model number of NC-513.

[0009] More preferably, the preparation of the additive A specifically comprises the following steps: S1: take zinc acetate and copper acetate, add water and ultrasonic dispersion, add pyromellitic acid, stir to dissolve, add glacial acetic acid, stir evenly, condense reflux, centrifugal washing, dry the material deposited in the centrifugal tube, add methanol, activate at 95-100℃ for 20-24h, dry, and obtain the intermediate;

[0010] S2: take 2-methylimidazole, add ethanol and ultrasonic dispersion, add the intermediate, stir evenly, and remove ethanol by rotary evaporation to obtain the carboxylated metal-organic framework;

[0011] S3: take the carboxylated metal-organic framework, freeze-dried porous cellulose, hydroxyl-terminated silicone oil, and zinc sulfate, add a mixed solution of water and ethanol (volume ratio of water to ethanol 2:1) and mix evenly, pressurize and heat to 110-120℃ for 8-10h, remove the mixed solvent, and obtain the additive A.

[0012] More preferably, the intermediate comprises the following raw materials, in terms of mass fraction: 3-4 parts of zinc acetate, 2-3 parts of copper acetate, 100-120 parts of water, 4-6 parts of pyromellitic acid, 65-70 parts of glacial acetic acid, and 100-120 parts of methanol.

[0013] The carboxylated metal-organic framework comprises the following raw materials, in terms of mass fraction: 0.3-0.5 parts of 2-methylimidazole, 100-120 parts of ethanol, and 1-1.5 parts of the intermediate.

[0014] The additive A comprises the following raw materials, in terms of mass fraction: 12-15 parts of the carboxylated metal-organic framework, 3-4 parts of freeze-dried porous cellulose, 4-6 parts of hydroxyl-terminated silicone oil, 0.1-0.2 parts of zinc sulfate, and 50-60 parts of a mixed solution of water and ethanol.

[0015] More preferably, the preparation of the freeze-dried porous cellulose specifically comprises the following steps: take microfibrillated cellulose and water, ultrasonic dispersion, and freeze-drying to obtain the freeze-dried porous cellulose; the mass ratio of microfibrillated cellulose to water is 1: (5-6).

[0016] More preferably, the preparation of the additive B specifically comprises the following steps: Step one: take lignin, add dichloromethane and triethylamine under nitrogen atmosphere protection, stir evenly, ultrasonic for 2-3h, drop in acryloyl chloride, stir at 40-45℃ for 20-24h, add ethanol and stir for 2-3h, water washing, reduced pressure filtration, and drying to obtain modified lignin;

[0017] Step two: take the modified lignin, polyethylene glycol, and NaOH aqueous solution, stir evenly, drop in diethylenetriamine, stir evenly, drop in formaldehyde aqueous solution, react at 90-95℃ for 3-4h, pour the reaction product into water to precipitate, wash, filter, and dry to obtain the additive B.

[0018] More preferably, the modified lignin comprises the following raw materials by mass fraction: 1-2 parts of lignin, 40-60 parts of dichloromethane, 3-6 parts of triethylamine, 10-15 parts of acryloyl chloride, and 10-15 parts of ethanol.

[0019] The additive B comprises the following raw materials by mass fraction: 10-15 parts of modified lignin, 2-3 parts of polyethylene glycol, 3-5 parts of diethylene triamine, and 10-15 parts of a formaldehyde aqueous solution with a formaldehyde concentration of 37wt%; and the NaOH aqueous solution comprises 0.01 parts of NaOH and 12 parts of water.

[0020] More preferably, in the styrene-butadiene-styrene, the ratio of styrene (S) to butadiene (B) is (2-3):(7-8).

[0021] More preferably, the styrene-butadiene-styrene is SBS706 of the Taiwan Yingquan series, and the ratio of S to B is 2:8.

[0022] More preferably, the preparation method of the environment-friendly aging-resistant adhesive comprises the following steps: taking components A and B, stirring for 20-30 minutes, and obtaining the environment-friendly aging-resistant adhesive.

[0023] More preferably, the curing conditions of the environment-friendly aging-resistant adhesive are as follows: irradiation under ultraviolet light (290nm) for 30-60s, curing at 90-100℃ for 2-3h, and curing at 120-140℃ for 3-4h.

[0024] Compared with the prior art, the environment-friendly aging-resistant adhesive has the following beneficial effects: (1) no modified filler or modifier harmful to human body or environment is added, and the environment is friendly;

[0025] (2) Component A comprises a certain proportion of bisphenol A type vinyl ester resin, bisphenol A type liquid epoxy resin, and cashew phenol epoxy resin; wherein, the vinyl ester resin can form an interpenetrating network with the epoxy resin during curing, promotes stable combination, optimizes complementary performance, and improves comprehensive performance, but the addition amount should not be too much, otherwise the performance will be reduced due to poor compatibility; the cashew phenol epoxy resin as a diluent not only plays a dilution role, but also provides excellent water resistance and improves toughness due to the aliphatic side chain on the molecule.

[0026] (3) Component B includes a certain proportion of additive A, additive B and additive C; additive A includes carboxylated metal organic framework, freeze-dried porous cellulose and hydroxyl-terminated silicone oil; the metal organic framework has a highly ordered porous structure, good dispersibility, can improve the mechanical properties, stability and chemical properties of the epoxy resin, and 2-methyl imidazole is loaded therein to assist curing; the metal organic framework prepared in the application has a carboxyl group on the surface, which can react with the hydroxyl groups of the freeze-dried porous cellulose and the hydroxyl-terminated silicone oil to obtain additive A; cellulose is environmentally friendly and has a toughening effect on the epoxy resin, and after being freeze-dried to obtain a porous structure, the dispersibility is further improved and the adhesion performance is improved; the hydroxyl-terminated silicone oil improves the flexibility and weather resistance of the epoxy resin and reduces cracking problems during use;

[0027] Additive B is lignin containing amino groups and double bonds, the addition of lignin helps to improve the viscosity and improve the tensile properties and heat-oxidative aging resistance of the epoxy resin, and the amino groups and double bonds can participate in curing, thereby improving the dispersibility and crosslinking degree of the adhesive;

[0028] Additive C is SBS with a S:B ratio of (2-3):(7-8), wherein the rigid segment styrene (S) can improve the strength of the material, and the flexible segment butadiene (B) can improve the flexibility of the material;

[0029] (4) In summary, the adhesive has good compatibility between components, good crosslinking degree, good aging resistance and mechanical properties, is not easy to crack during use, and meets environmental protection standards. DETAILED DESCRIPTION

[0030] The technical solutions in the embodiments of the application will be described below in a clear and complete manner. Obviously, the described embodiments are only part of the embodiments of the application, rather than all the embodiments. Based on the embodiments in the application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the application.

[0031] The following parts are mass parts unless otherwise specified;

[0032] Embodiment 1: S1: Take 4 parts of zinc acetate and 2 parts of copper acetate, add 100 parts of water, ultrasonic dispersion, add 6 parts of pyromellitic acid, stir to dissolve, add 70 parts of ice acetic acid, stir uniformly, and condense at 100℃ for 25h; centrifugal washing, drying the material deposited in the centrifugal tube, adding 120 parts of methanol, 100℃ activation treatment for 24h, drying, obtaining an intermediate; take 0.4 parts of 2-methyl imidazole, add 120 parts of ethanol, ultrasonic dispersion, add 1.5 parts of the intermediate, uniform stirring for 48h, rotary evaporation to remove ethanol, obtaining carboxylated metal organic framework;

[0033] S2: Take 10 parts of microfibrillated cellulose, 60 parts of water, ultrasonic dispersion, freeze-drying, get freeze-dried porous cellulose;

[0034] S3: Take 12 parts of carboxylated metal organic framework, 3 parts of freeze-dried porous cellulose, 5 parts of hydroxyl-terminated silicone oil, 0.15 parts of zinc sulfate, add 60 parts of mixed solution of water and ethanol, mix evenly, pressurize in a closed reaction kettle and heat to 110℃, react for 10h, remove the mixed solvent, get additive A;

[0035] S4: Take 2 parts of lignin in a three-necked flask, add 50 parts of dichloromethane, 4 parts of triethylamine under the protection of nitrogen atmosphere, stir evenly, ultrasonic for 3h, add 12 parts of acryloyl chloride dropwise within 1h, stir at 40℃ for 24h, add 15 parts of ethanol, stir for 3h, wash with water, filter under reduced pressure and dry, get modified lignin;

[0036] Take 12 parts of modified lignin, add 3 parts of polyethylene glycol, NaOH aqueous solution, stir evenly, add 4 parts of diethylenetriamine dropwise, stir evenly, add 14 parts of formaldehyde aqueous solution, stir at 95℃ for 4h, pour the reaction product into water to precipitate, wash, filter and dry, get additive B;

[0037] S5: Take 12 parts of bisphenol A type vinyl ester resin, 50 parts of bisphenol A type liquid epoxy resin, 8 parts of cardanol epoxy resin, mix evenly to get component A; take 18 parts of amine curing agent, 13 parts of additive A, 3 parts of additive B, 0.5 parts of additive C, 0.01 parts of photoinitiator, mix evenly to get component B.

[0038] Example 2: S1: Take 3 parts of zinc acetate, 3 parts of copper acetate, add 100 parts of water, ultrasonic dispersion, add 4 parts of pyromellitic acid, stir to dissolve, add 70 parts of glacial acetic acid, stir evenly, condense at 100℃ for 25h; centrifugal washing, dry the material deposited in the centrifugal tube, add 120 parts of methanol, 100℃ activation treatment for 24h, dry, get intermediate; take 0.3 parts of 2-methylimidazole, add 120 parts of ethanol, ultrasonic evenly, add 1 part of intermediate, uniform stirring for 48h, remove ethanol by rotary evaporation, get carboxylated metal organic framework;

[0039] S2: Take 10 parts of microfibrillated cellulose, 60 parts of water, ultrasonic dispersion, freeze-drying, get freeze-dried porous cellulose;

[0040] S3: Take 12 parts of carboxylated metal organic framework, 3 parts of freeze-dried porous cellulose, 4 parts of hydroxyl-terminated silicone oil, 0.15 parts of zinc sulfate, add 60 parts of mixed solution of water and ethanol, mix evenly, pressurize in a closed reaction kettle and heat to 110℃, react for 10h, remove the mixed solvent, get additive A;

[0041] S4: Take 1 part of lignin in a three-necked flask, add 40 parts of dichloromethane, 3 parts of triethylamine under the protection of nitrogen atmosphere, stir uniformly, ultrasonic for 3h, add 10 parts of acryloyl chloride dropwise within 1h, stir at 40℃ for 24h, add 15 parts of ethanol, stir for 3h, wash with water, filter under reduced pressure, and dry to obtain modified lignin;

[0042] Take 10 parts of modified lignin, add 2 parts of polyethylene glycol, NaOH aqueous solution, stir uniformly, add 3 parts of diethylenetriamine dropwise, stir uniformly, add 10 parts of formaldehyde aqueous solution, stir at 95℃ for 4h, pour the reaction product into water to precipitate, wash, filter, and dry to obtain additive B;

[0043] S5: Take 10 parts of bisphenol A type vinyl ester resin, 55 parts of bisphenol A type liquid epoxy resin, and 5 parts of cardanol epoxy resin, mix uniformly to obtain component A; take 15 parts of amine curing agent, 15 parts of additive A, 4 parts of additive B, 1 part of additive C, and 0.01 part of photoinitiator, mix uniformly to obtain component B.

[0044] Example 3: S1: Take 4 parts of zinc acetate and 3 parts of copper acetate, add to 100 parts of water, ultrasonic dispersion, add 6 parts of pyromellitic acid, stir to dissolve, add 70 parts of glacial acetic acid, stir uniformly, and condense at 100℃ for 25h; centrifugal washing, dry the material deposited in the centrifugal tube, add 120 parts of methanol, activate at 100℃ for 24h, and dry to obtain an intermediate; take 0.5 parts of 2-methylimidazole, add to 120 parts of ethanol, ultrasonic dispersion, add 1.5 parts of the intermediate, and stir uniformly for 48h; rotary evaporation to remove ethanol to obtain a carboxylated metal organic framework;

[0045] S2: Take 10 parts of microfibrillated cellulose and 60 parts of water, ultrasonic dispersion, and freeze-drying to obtain freeze-dried porous cellulose;

[0046] S3: Take 15 parts of carboxylated metal organic framework, 4 parts of freeze-dried porous cellulose, 6 parts of hydroxyl-terminated silicone oil, and 0.15 parts of zinc sulfate, add to 60 parts of mixed solution of water and ethanol, mix uniformly, pressurize in a sealed reaction kettle, and heat to 110℃, react for 10h, and remove the mixed solvent to obtain additive A;

[0047] S4: Take 2 parts of lignin in a three-necked flask, add 60 parts of dichloromethane and 6 parts of triethylamine under the protection of nitrogen atmosphere, stir uniformly, ultrasonic for 3h, add 15 parts of acryloyl chloride dropwise within 1h, stir at 40℃ for 24h, add 15 parts of ethanol, stir for 3h, wash with water, filter under reduced pressure, and dry to obtain modified lignin;

[0048] Take 15 parts of modified lignin, add 3 parts of polyethylene glycol, NaOH aqueous solution, stir evenly, add 5 parts of diethylene triamine dropwise, stir evenly, add 15 parts of formaldehyde aqueous solution, stir at 95℃ for 4h, pour the reaction product into water to precipitate, wash, filter, dry, get additive B;

[0049] S5: Take 15 parts of bisphenol A type vinyl ester resin, 55 parts of bisphenol A type liquid epoxy resin, 10 parts of cashew phenol epoxy resin, mix evenly to get component A; take 20 parts of amine curing agent, 15 parts of additive A, 4 parts of additive B, 1 part of additive C, 0.01 part of photoinitiator, mix evenly to get component B.

[0050] Comparative example 1 (change the amount of additive A, additive B, additive C in component B, the rest of the method steps are consistent with example 1): S1: take 4 parts of zinc acetate, 2 parts of copper acetate, add 100 parts of water, ultrasonic dispersion evenly, add 6 parts of pyromellitic acid, stir to dissolve, add 70 parts of glacial acetic acid, stir evenly, condense reflux at 100℃ for 25h; centrifugal washing, drying the material deposited in the centrifuge tube, add 120 parts of methanol, 100℃ activation treatment for 24h, dry, get intermediate; take 0.4 parts of 2-methylimidazole, add 120 parts of ethanol, ultrasonic evenly, add 1.5 parts of intermediate, uniform stirring for 48h, rotary evaporation to remove ethanol, get carboxylated metal organic framework;

[0051] S2: take 10 parts of microfibrillated cellulose, 60 parts of water, ultrasonic dispersion evenly, freeze-drying, get freeze-dried porous cellulose;

[0052] S3: take 12 parts of carboxylated metal organic framework, 3 parts of freeze-dried porous cellulose, 5 parts of hydroxyl-terminated silicone oil, 0.15 parts of zinc sulfate, add 60 parts of mixed solution of water and ethanol, mix evenly, pressurize in a sealed reaction kettle and heat to 110℃, react for 10h, remove the mixed solvent, get additive A;

[0053] S4: take 2 parts of lignin in a three-necked flask, add 50 parts of dichloromethane, 4 parts of triethylamine under nitrogen atmosphere protection, stir evenly, ultrasonic for 3h, add 12 parts of acryloyl chloride dropwise within 1h, stir at 40℃ for 24h, add 15 parts of ethanol, stir for 3h, wash with water, reduce pressure filtration, dry, get modified lignin;

[0054] Take 12 parts of modified lignin, add 3 parts of polyethylene glycol, NaOH aqueous solution, stir evenly, add 4 parts of diethylene triamine dropwise, stir evenly, add 14 parts of formaldehyde aqueous solution, stir at 95℃ for 4h, pour the reaction product into water to precipitate, wash, filter, dry, get additive B;

[0055] S5: Take 12 parts of bisphenol A type vinyl ester resin, 50 parts of bisphenol A type liquid epoxy resin, 8 parts of cashew phenol epoxy resin, mix evenly to get component A; take 18 parts of amine curing agent, 8 parts of additive A, 5 parts of additive B, 1.5 parts of additive C, 0.01 parts of photoinitiator, mix evenly to get component B.

[0056] Comparative Example 2 (change the amount of additive A, additive B, additive C in component B, the rest of the method steps are consistent with Example 1): S1: Take 4 parts of zinc acetate, 2 parts of copper acetate, add 100 parts of water, ultrasonic dispersion, add 6 parts of pyromellitic acid, stir to dissolve, add 70 parts of glacial acetic acid, stir evenly, condense at 100℃ for 25h; centrifugal washing, drying the material deposited in the centrifuge tube, adding 120 parts of methanol, 100℃ activation treatment for 24h, drying, getting intermediate; take 0.4 parts of 2-methylimidazole, add 120 parts of ethanol, ultrasonic evenly, add 1.5 parts of intermediate, uniform stirring for 48h, rotary evaporation to remove ethanol, get carboxylated metal organic framework;

[0057] S2: Take 10 parts of microfibrillated cellulose, 60 parts of water, ultrasonic dispersion, freeze-drying, get freeze-dried porous cellulose;

[0058] S3: Take 12 parts of carboxylated metal organic framework, 3 parts of freeze-dried porous cellulose, 5 parts of hydroxyl-terminated silicone oil, 0.15 parts of zinc sulfate, add 60 parts of mixed solution of water and ethanol, mix evenly, pressurize in a sealed reaction kettle and heat to 110℃, react for 10h, remove the mixed solvent, get additive A;

[0059] S4: Take 2 parts of lignin in a three-necked flask, add 50 parts of dichloromethane, 4 parts of triethylamine under nitrogen atmosphere protection, stir evenly, ultrasonic for 3h, add 12 parts of acryloyl chloride dropwise within 1h, stir at 40℃ for 24h, add 15 parts of ethanol, stir for 3h, wash with water, reduce pressure filtration, dry, get modified lignin;

[0060] Take 12 parts of modified lignin, add 3 parts of polyethylene glycol, NaOH aqueous solution, stir evenly, add 4 parts of diethylenetriamine dropwise, stir evenly, add 14 parts of formaldehyde aqueous solution dropwise, stir at 95℃ for 4h, pour the reaction product into water to precipitate, wash, filter, dry, get additive B;

[0061] S5: Take 12 parts of bisphenol A type vinyl ester resin, 50 parts of bisphenol A type liquid epoxy resin, 8 parts of cashew phenol epoxy resin, mix evenly to get component A; take 18 parts of amine curing agent, 16 parts of additive A, 1 part of additive B, 0.1 part of additive C, 0.01 part of photoinitiator, mix evenly to get component B.

[0062] Comparative Example 3 (changing the amount of each raw material in component A, and the remaining method steps are consistent with Example 1): S1: Take 4 parts of zinc acetate, 2 parts of copper acetate, add 100 parts of water, ultrasonic dispersion, add 6 parts of pyromellitic acid, stir to dissolve, add 70 parts of glacial acetic acid, stir evenly, and condense at 100°C for 25h; centrifugal washing, drying the material deposited in the centrifugal tube, adding 120 parts of methanol, 100°C activation treatment for 24h, drying, and obtaining the intermediate; Take 0.4 parts of 2-methylimidazole, add 120 parts of ethanol, ultrasonic evenly, add 1.5 parts of intermediate, uniform stirring for 48h, and remove ethanol by rotary evaporation to obtain a carboxylated metal organic framework;

[0063] S2: Take 10 parts of microfibrillated cellulose, 60 parts of water, ultrasonic dispersion, and freeze-drying to obtain freeze-dried porous cellulose;

[0064] S3: Take 12 parts of carboxylated metal organic framework, 3 parts of freeze-dried porous cellulose, 5 parts of hydroxyl-terminated silicone oil, and 0.15 parts of zinc sulfate, add 60 parts of mixed solution of water and ethanol, mix evenly, and heat to 110°C in a sealed reaction kettle for 10h, remove the mixed solvent, and obtain additive A;

[0065] S4: Take 2 parts of lignin in a three-necked flask, add 50 parts of dichloromethane and 4 parts of triethylamine under nitrogen atmosphere, stir evenly, ultrasonic for 3h, add 12 parts of acryloyl chloride dropwise within 1h, stir at 40°C for 24h, add 15 parts of ethanol, stir for 3h, wash with water, filter under reduced pressure, and dry to obtain modified lignin;

[0066] Take 12 parts of modified lignin, add 3 parts of polyethylene glycol and NaOH aqueous solution, stir evenly, add 4 parts of diethylenetriamine dropwise, stir evenly, add 14 parts of formaldehyde aqueous solution, and stir at 95°C for 4h; pour the reaction product into water to precipitate, wash, filter, and dry to obtain additive B;

[0067] S5: Take 20 parts of bisphenol A type vinyl ester resin, 45 parts of bisphenol A type liquid epoxy resin, and 5 parts of cardanol epoxy resin, mix evenly to obtain component A; take 18 parts of amine curing agent, 13 parts of additive A, 3 parts of additive B, 0.5 parts of additive C, and 0.01 parts of photoinitiator, mix evenly to obtain component B.

[0068] Comparative Example 4 (carboxylated metal organic framework as additive A, the rest of the method steps are consistent with Example 1): S1: Take 4 parts of zinc acetate, 2 parts of copper acetate, add 100 parts of water, ultrasonic dispersion, add 6 parts of pyromellitic acid, stir to dissolve, add 70 parts of glacial acetic acid, stir evenly, condense at 100℃ for 25h; centrifugal washing, drying the material deposited in the centrifugal tube, adding 120 parts of methanol, 100℃ activation treatment for 24h, drying, obtaining the intermediate; Take 0.4 parts of 2-methylimidazole, add 120 parts of ethanol, ultrasonic evenly, add 1.5 parts of intermediate, uniform stirring for 48h, remove ethanol by rotary evaporation, obtain additive A;

[0069] S2: Take 2 parts of lignin in a three-necked flask, add 50 parts of dichloromethane, 4 parts of triethylamine under nitrogen atmosphere, stir evenly, ultrasonic for 3h, add 12 parts of acryloyl chloride dropwise within 1h, stir at 40℃ for 24h, add 15 parts of ethanol, stir for 3h, wash with water, reduce pressure filtration, drying, obtaining modified lignin;

[0070] Take 12 parts of modified lignin, add 3 parts of polyethylene glycol, NaOH aqueous solution, stir evenly, add 4 parts of diethylene triamine dropwise, stir evenly, add 14 parts of formaldehyde aqueous solution, stir at 95℃ for 4h, pour the reaction product into water to precipitate, wash, filter, dry, obtaining additive B;

[0071] S3: Take 12 parts of bisphenol A type vinyl ester resin, 50 parts of bisphenol A type liquid epoxy resin, 8 parts of cashew phenol epoxy resin, mix evenly to obtain component A; Take 18 parts of amine curing agent, 13 parts of additive A, 3 parts of additive B, 0.5 parts of additive C, 0.01 parts of photoinitiator, mix evenly to obtain component B.

[0072] The test methods used in the above examples are conventional methods unless otherwise specified. The raw materials used are commercially available unless otherwise specified. The sources of the raw materials are as follows: ethanol (CAS: 64-17-5); photoinitiator (photoinitiator 1173, CAS: 7473-98-5); zinc acetate (S48372, Shanghai Yuan Ye); copper acetate (S42613, Shanghai Yuan Ye); pyromellitic acid (CAS: 89-05-4); glacial acetic acid (CAS: 64-19-7); methanol (CAS: 67-56-1); 2-methylimidazole (CAS: 693-98-1); microfibrillated cellulose (210609145917, Kelamay); hydroxyl-terminated silicone oil (both alcohol hydroxyl silicone oil IOTA2110, Anhui Aiyouta Silicone Co., Ltd.); zinc sulfate (S22124, Shanghai Yuan Ye); lignin (6875, Wuhan Xinxinjiali Biological Technology Co., Ltd.); dichloromethane (CAS: 75-09-2); triethylamine (CAS: 121-44-8); acryloyl chloride (CAS: 814-68-6); polyethylene glycol (polyethylene glycol 400, Shandong Xin Heng Chemical Co., Ltd.); diethylenetriamine (CAS: 111-40-0); bisphenol A type vinyl ester resin 854 (Shanghai Fuchen Chemical Co., Ltd.); bisphenol A type liquid epoxy resin E51 (Jinan Shanhai Chemical Technology Co., Ltd.); cashew phenol epoxy resin NC-513 (Cardolite); 4,4-diaminodiphenyl sulfone (CAS: 80-08-0).

[0073] Experiment: Take components A and B prepared in Examples 1-3 and Comparative Examples 1-4, stir for 25 min to obtain a test sample; (1) used for bonding LY12CZ aluminum test pieces, irradiated under ultraviolet light (290 nm) for 45 s, cured at 100°C for 2 h, cured at 120°C for 4 h, cooled to room temperature, and the shear strength was tested according to the GB / T 7124-2008 standard, with a test speed of 15 mm / min; (2) 177°C high-temperature heat aging for 100 h, cooling to room temperature, and testing the shear strength after heat aging; (3) taking the test sample, irradiating under ultraviolet light (290 nm) for 45 s, curing at 100°C for 2 h, curing at 120°C for 4 h, cooling to room temperature, and testing the elongation at break according to the GB / T 1040.3-2006 standard; the specific data are shown in the following table.

[0074]

[0075] Conclusion: The performance of Comparative Example 1 and Comparative Example 2 is not as good as that of the examples, which indicates that the amount of additive A, additive B and additive C needs to be controlled; the performance of Comparative Example 3 is decreased, which indicates that the amount of bisphenol A type vinyl ester resin, bisphenol A type liquid epoxy resin and cashew phenol epoxy resin is also important; the performance of Comparative Example 4 is obviously decreased, which indicates that the carboxylated metal organic framework is used as additive A, i.e. without adding freeze-dried porous cellulose and hydroxyl-terminated silicone oil; in summary, the prepared component A and component B can be used to prepare an adhesive with good bonding performance, good mechanical performance and good aging resistance, and meet the environmental protection requirements.

[0076] It will be obvious to a person skilled in the art that the application is not limited to the details of the foregoing exemplary embodiments and can be implemented in other concrete forms without departing from the spirit or essential characteristics of the application. The foregoing embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the application being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.

Claims

1. An environmentally friendly aging resistant adhesive, characterized by: The component A comprises the following raw materials in parts by mass: 10-15 parts of bisphenol A type vinyl ester resin, 45-55 parts of bisphenol A type liquid epoxy resin, 5-10 parts of cashew phenol epoxy resin; The component B comprises the following raw materials in parts by mass: 15-20 parts of amine curing agent, 12-15 parts of additive A, 3-4 parts of additive B, 0.5-1 part of additive C, 0.01-0.02 part of photoinitiator; The preparation steps of the additive A are as follows: zinc acetate and copper acetate are taken, uniformly dispersed in water by ultrasonic, uniformity is added to pyromellitic acid, stirred and dissolved, ice acetic acid is added, stirred uniformly, condensed and refluxed, centrifuged and washed, the substance deposited in the centrifuge tube is dried, methanol is added for activation treatment, dried, and an intermediate is obtained; 2-methyl imidazole is taken, uniformly dispersed in ethanol by ultrasonic, the intermediate is added, stirred at a uniform speed, ethanol is removed by rotary evaporation, and a carboxylated metal organic framework is obtained; the carboxylated metal organic framework, freeze-dried porous cellulose, hydroxyl-terminated silicone oil and zinc sulfate are taken, uniformly mixed in a mixed solution of water and ethanol, pressurized and heated to 110-120 DEG C for 8-10 h, and the mixed solvent is removed, and the additive A is obtained; The preparation steps of the additive B are as follows: lignin is taken, dichloromethane and triethylamine are added under the protection of nitrogen atmosphere, stirred uniformly, ultrasonic is applied for 2-3 h, acryloyl chloride is added dropwise, stirred at 40-45 DEG C for 20-24 h, ethanol is added and stirred for 2-3 h, washed with water, filtered under reduced pressure, and dried, and modified lignin is obtained; The modified lignin, polyethylene glycol and NaOH aqueous solution are stirred uniformly, diethylene triamine is added dropwise, stirred uniformly, formaldehyde aqueous solution is added dropwise, and reaction is carried out at 90-95 DEG C for 3-4 h, the reaction product is poured into water to precipitate, washed, filtered and dried, and the additive B is obtained; The additive C is styrene-butadiene-styrene.

2. The environment-friendly aging-resistant adhesive according to claim 1, characterized in that: The intermediate comprises the following raw materials in parts by mass: 3-4 parts of zinc acetate, 2-3 parts of copper acetate, 100-120 parts of water, 4-6 parts of pyromellitic acid, 65-70 parts of ice acetic acid and 100-120 parts of methanol; the carboxylated metal organic framework comprises the following raw materials in parts by mass: 0.3-0.5 parts of 2-methyl imidazole, 100-120 parts of ethanol and 1-1.5 parts of the intermediate; and the additive A comprises the following raw materials in parts by mass: 12-15 parts of the carboxylated metal organic framework, 3-4 parts of freeze-dried porous cellulose, 4-6 parts of hydroxyl-terminated silicone oil, 0.1-0.2 parts of zinc sulfate and 50-60 parts of a mixed solution of water and ethanol.

3. The environment-friendly aging-resistant adhesive according to claim 1, characterized in that: The preparation of the freeze-dried porous cellulose specifically comprises the following steps: microfibrillated cellulose and water are taken, uniformly dispersed by ultrasonic, and freeze-dried, and the freeze-dried porous cellulose is obtained; the mass ratio of the microfibrillated cellulose to water is 1: (5-6).

4. The environment-friendly aging-resistant adhesive according to claim 1, characterized in that: The modified lignin comprises the following raw materials in parts by mass: 1-2 parts of lignin, 40-60 parts of dichloromethane, 3-6 parts of triethylamine, 10-15 parts of acryloyl chloride and 10-15 parts of ethanol; the additive B comprises the following raw materials in parts by mass: 10-15 parts of modified lignin, 2-3 parts of polyethylene glycol, 3-5 parts of diethylenetriamine and 10-15 parts of formaldehyde aqueous solution with a formaldehyde concentration of 37 wt%; and the NaOH aqueous solution comprises 0.01-0.02 parts of NaOH and 10-15 parts of water.

5. The environment-friendly aging-resistant adhesive according to claim 1, characterized in that: In the styrene-butadiene-styrene, the ratio of styrene to butadiene is (2-3):(7-8).

6. The preparation method of the environment-friendly aging-resistant adhesive according to any one of claims 1-5, characterized in that: The method comprises the following steps: Take the A component and the B component, stir for 20-30 min, and obtain the environment-friendly aging-resistant adhesive.

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