Bi-component flexible compound epoxy resin adhesive

[0029] Example 1

[0030] After mixing graphene oxide and isocyanate in a mass ratio of 1:5, heating and stirring to react, filtering, washing and vacuum drying, pretreated graphene oxide is obtained; silicon dioxide and 12% hydrochloric acid by mass Mix at a ratio of 1:15, stir and react for 4 hours at a temperature of 120°C and a speed of 400r/min, and then filter to obtain an activated silica blank. The activated silica blank is washed with deionized water until the washing solution is After neutralization, and after drying for 2h at a temperature of 100℃, and then calcining at a temperature of 300℃ for 2h, activated silica is obtained. The activated silica is combined with the silane coupling agent KH-550. The mass ratio of 1:3 was mixed in the flask, and 12 times the mass of activated silica was added to the flask. The reaction was stirred for 3 hours at a temperature of 85°C and a speed of 400r/min, and then at room temperature. After standing for 3 hours, filter to obtain aminated silica blanks. After drying the aminated silica blanks at a temperature of 80°C for 3 hours, aminated silica is obtained. The aminated silica is pressed with methanol. The mass ratio of 1:18 was mixed in a three-necked flask, and 3 times the mass of acrylic acid was added to the three-necked flask. Nitrogen was introduced into the three-necked flask at a rate of 30mL/min. The temperature was 45℃ and the rotation speed was Under the condition of 350r/min, the reaction was stirred for 4 days, and then filtered to obtain the pre-modified silica blank. The pre-modified silica was first extracted with methanol in a Soxhlet extractor at a temperature of 85°C for 8 hours. , And then extracted with tetrahydrofuran at a temperature of 90 ℃ for 10 hours to obtain a purified pre-modified silica blank. After the purified pre-modified silica blank was vacuum dried at a temperature of 110 ℃ for 2 hours, the pre-modified For silica, mix pre-modified silica and ethylenediamine in a four-necked flask at a mass ratio of 1:2, and add methanol with 10 times the mass of pre-modified silica to the four-necked flask. Nitrogen was introduced into the mouth flask at a rate of 30 mL/min. Under the conditions of a temperature of 60°C and a rotation speed of 350 r/min, the reaction was stirred for 5 hours and then filtered to obtain a modified silica blank. In the Soxhlet extractor, it was first extracted with methanol at a temperature of 85°C for 8 hours, and then extracted with tetrahydrofuran at a temperature of 90°C for 10 hours to obtain a purified modified silica blank. The purified modified dioxide After the silicon blank is vacuum-dried for 2 hours at a temperature of 120°C, modified silica is obtained, and the additive is obtained. In parts by weight, weigh in order: 100 parts mixed epoxy resin, 15 parts catalyst, 18 parts ring Oxygen soybean oil, 5 parts of curing accelerator, 8 parts of silane coupling agent, 15 parts of active diluent, 30 parts of additives, and pretreated graphene oxide of 5% by mass of mixed epoxy resin, mixed epoxy resin and catalyst In the mixer, add epoxy soybean oil, curing accelerator, silane coupling agent, reactive diluent, additives and pretreated graphene oxide to the mixer in sequence, at a temperature of 40°C and a rotation speed of 350r/min Under the conditions, after stirring and mixing for 80 minutes, component A is obtained; the component B is a mixed curing agent; the component A and the component B are separately packaged to obtain a two-component flexible composite epoxy resin adhesive. The mixed epoxy resin is mixed epoxy resin E-44 and epoxy resin E-51 in a mass ratio of 2:1 to obtain a mixed epoxy resin. The catalyst is zinc chloride. The reactive diluent is polypropylene glycol diglycidyl ether. The curing accelerator is a mixture of curing accelerator DMP-30 and nonylphenol NP at a mass ratio of 2:1 to obtain a curing accelerator. The silane coupling agent is KH-570. The mixed curing agent mixes ethylenediamine and m-phenylenediamine at a mass ratio of 1:1 to obtain a mixed curing agent.

[0031] Example 2

[0032] Mix silica and 12% hydrochloric acid with a mass ratio of 1:15. Under the conditions of a temperature of 120°C and a speed of 400r/min, the reaction is stirred for 4 hours, and then filtered to obtain an activated silica blank. After the activated silica blank is washed with deionized water until the washing solution is neutral, dried at a temperature of 100°C for 2 hours, and then calcined at a temperature of 300°C for 2 hours to obtain activated silica. Activated silica and silane coupling agent KH-550 were mixed in a flask at a mass ratio of 1:3, and 12 times the mass of activated silica was added to the flask with anhydrous ethanol at a temperature of 85°C and a rotation speed of 400r Stir and react for 3h under the condition of 1/min, and then stand still at room temperature for 3h, and then filter to obtain the aminated silica blank. After the aminated silica blank is dried at a temperature of 80℃ for 3h, the amino group is obtained. Silica, which is the additive, are weighed in parts by weight: 100 parts mixed epoxy resin, 15 parts catalyst, 18 parts epoxy soybean oil, 5 parts curing accelerator, 8 parts silane coupling agent, 15 parts of active diluent and 30 parts of additives, mix the mixed epoxy resin and catalyst in a mixer, and sequentially add epoxy soybean oil, curing accelerator, silane coupling agent, active diluent and additives to the mixer, Under the conditions of 40℃ and 350r/min, stir and mix for 80min to obtain component A; in parts by weight, weigh in sequence: the component B is a mixed curing agent, and the component A and the component B Separately encapsulate to obtain a two-component flexible composite epoxy resin adhesive. The mixed epoxy resin is mixed epoxy resin E-44 and epoxy resin E-51 in a mass ratio of 2:1 to obtain a mixed epoxy resin. The catalyst is zinc chloride. The reactive diluent is polypropylene glycol diglycidyl ether. The curing accelerator is a mixture of curing accelerator DMP-30 and nonylphenol NP at a mass ratio of 2:1 to obtain a curing accelerator. The silane coupling agent is KH-570. The mixed curing agent mixes ethylenediamine and m-phenylenediamine at a mass ratio of 1:1 to obtain a mixed curing agent.

[0033] Example 3

[0034] Mix silica and 12% hydrochloric acid with a mass ratio of 1:15. Under the conditions of a temperature of 120°C and a speed of 400r/min, the reaction is stirred for 4 hours, and then filtered to obtain an activated silica blank. After the activated silica blank is washed with deionized water until the washing solution is neutral, dried at a temperature of 100°C for 2 hours, and then calcined at a temperature of 300°C for 2 hours to obtain activated silica. Activated silica and silane coupling agent KH-550 were mixed in a flask at a mass ratio of 1:3, and 12 times the mass of activated silica was added to the flask with anhydrous ethanol at a temperature of 85°C and a rotation speed of 400r Stir and react for 3h under the condition of 1/min, and then stand still at room temperature for 3h, and then filter to obtain the aminated silica blank. After the aminated silica blank is dried at a temperature of 80℃ for 3h, the amino group is obtained. For silica, mix aminated silica and methanol in a three-necked flask at a mass ratio of 1:18, and add acrylic acid with 3 times the mass of aminated silica to the three-necked flask, and add 30mL/min to the three-necked flask. Nitrogen was introduced at a rate of 45°C and a rotation speed of 350r/min. After stirring for 4 days, the pre-modified silica blank was obtained by filtration. The pre-modified silica was placed in a Soxhlet extractor. Firstly, it was extracted with methanol for 8 hours at a temperature of 85°C, and then extracted with tetrahydrofuran for 10 hours at a temperature of 90°C to obtain a purified pre-modified silica blank. After vacuum drying at 110℃ for 2h, the pre-modified silica is obtained, and the additive is obtained. In parts by weight, weigh in order: 100 parts mixed epoxy resin, 15 parts catalyst, 18 parts epoxy soybean oil , 5 parts of curing accelerator, 8 parts of silane coupling agent, 15 parts of active diluent and 30 parts of additives, mix the mixed epoxy resin and catalyst in a mixer, and add epoxy soybean oil and curing accelerator to the mixer in turn , Silane coupling agent, reactive diluent and additives, at a temperature of 40°C and a rotating speed of 350r/min, after stirring and mixing for 80 minutes, the A component is obtained; the B component is the mixed curing agent, and the A component Separately encapsulate the components and B components to obtain a two-component flexible composite epoxy resin adhesive. The mixed epoxy resin is mixed epoxy resin E-44 and epoxy resin E-51 in a mass ratio of 2:1 to obtain a mixed epoxy resin. The catalyst is zinc chloride. The reactive diluent is polypropylene glycol diglycidyl ether. The curing accelerator is a mixture of curing accelerator DMP-30 and nonylphenol NP at a mass ratio of 2:1 to obtain a curing accelerator. The silane coupling agent is KH-570. The mixed curing agent mixes ethylenediamine and m-phenylenediamine at a mass ratio of 1:1 to obtain a mixed curing agent.