A high-toughness epoxy resin adhesive and preparation method thereof

Abstract

The invention discloses a high-toughness epoxy resin adhesive and a preparation method thereof. The epoxy resin adhesive consists of component A and component B, wherein component A comprises the following raw materials in parts by weight: 50-80 parts of bisphenol A epoxy resin and 20-50 parts of a modifying additive, and component B comprises the following raw materials in parts by weight: 1-3 parts of a modified filler and 20-40 parts of 4,4'-diaminodiphenyl sulfone. After component A and component B are blended, the addition of the modifying additive can transform linear molecules into branched structures, and at the same time, the surface of the modified filler contains amino groups, which can participate in the curing process of the epoxy resin, and the modified filler is a core-shell structure, which can improve the mechanical properties of the epoxy resin, and the modified filler contains a cage-type silsesquioxane structure and a large number of long-chain alkyl groups, and the modified additive contains a polyrotaxane structure, which can undergo microscopic movements of rotation, sliding, elongation and twisting, thereby further improving the toughness of the epoxy resin adhesive.

Description

Technical Field

[0001] The invention relates to the technical field of epoxy resin adhesive preparation, and in particular to a high-toughness epoxy resin adhesive and a preparation method thereof. Background Art

[0002] In civil engineering, adhesives are increasingly used in structural connection, assembly reinforcement, emergency repair, etc., and have become important engineering materials in the development of safety, environmental protection, and new technologies and processes. Due to the extension of the service life of buildings or other natural disasters, the bearing capacity of reinforced concrete components is insufficient, and concrete cracking due to stress cracking or vibration damage occurs. Epoxy resin building structural adhesives with strong bonding ability and excellent mechanical properties are usually used for bonding and repair. Epoxy resin adhesives have become an indispensable and important material in construction projects, but pure epoxy resin adhesives have the disadvantages of greater brittleness, poor toughness, and poor fatigue resistance after curing, which causes the problem of falling off after a period of use. Summary of the invention

[0003] The purpose of the present invention is to provide a high-toughness epoxy resin adhesive and a preparation method thereof, so as to solve the problem of poor toughness of the epoxy resin adhesive at present.

[0004] The purpose of the present invention can be achieved through the following technical solutions:

[0005] A method for preparing high-toughness epoxy resin adhesive specifically comprises the following steps:

[0006] Weigh the following raw materials in parts by weight: 8-10 parts of component A and 2.5-3 parts of component B, mix component A and component B evenly, and prepare a high-toughness epoxy resin adhesive;

[0007] Component A comprises the following raw materials by weight: 50-80 parts of bisphenol A epoxy resin and 20-50 parts of modified additives, and component B comprises the following raw materials by weight: 1-3 parts of modified filler and 20-40 parts of 4,4'-diaminodiphenyl sulfone.

[0008] Further, the modified additive is prepared by the following steps:

[0009] Step A1: dodecyltrimethoxysilane, sodium hydroxide, isopropanol and deionized water are mixed evenly, and reacted for 10-15 hours at a speed of 120-150 r / min and a temperature of 85-90° C. to obtain sodium dodecylcyclotetrasiloxane tetrasiloxide, sodium dodecylcyclotetrasiloxane tetrasiloxide, triethylamine and tetrahydrofuran are mixed evenly, nitrogen is introduced for protection, and methyldichlorosilane is added under stirring at a speed of 150-200 r / min and a temperature of 0° C. to react for 3-5 hours, and the temperature is raised to 20-25° C. and reacted for 20-25 hours to obtain a modifier;

[0010] Step A2: polyethylene glycol, acrylic acid, p-toluenesulfonic acid and toluene are mixed evenly, and reacted at a speed of 120-150 r / min and a temperature of 110-120° C. for 5-7 hours to obtain intermediate 1; intermediate 1, β-cyclodextrin, deionized water and DMF are mixed, and stirred for 10-15 hours at a speed of 60-80 r / min and a temperature of 30-40° C. to obtain polyrotaxane; modifier, polyrotaxane, chloroplatinic acid and DMF are mixed evenly, nitrogen protection is introduced, and reaction is carried out at a speed of 60-80 r / min and a temperature of 80-85° C. for 20-25 hours to obtain a reinforcing monomer;

[0011] Step A3: 2-hydroxyethyl acrylate, epichlorohydrin, boron trifluoride etherate and DMF are mixed evenly, reacted at a speed of 120-150 r / min and a temperature of 65-70° C. for 2-3 hours, and then sodium hydroxide solution is added, the temperature is raised to 75-80° C., and the reaction is carried out for 3-5 hours to obtain a functional monomer. The reinforcing monomer, functional monomer, benzophenone and DMF are mixed evenly, and reacted at a speed of 150-200 r / min and 365 nm ultraviolet light for 1-1.5 hours to obtain a modified additive.

[0012] Furthermore, the amount ratio of dodecyltrimethoxysilane, sodium hydroxide, isopropanol and deionized water in step A1 is 30mmol:18mmol:25mL:1mL, and the amount ratio of dodecylcyclotetrasiloxane sodium tetrasiloxide, triethylamine, tetrahydrofuran and methyldichlorosilane is 5g:1.2g:10mL:1g.

[0013] Furthermore, the molar ratio of polyethylene glycol and acrylic acid described in step A2 is 1:2, the amount of p-toluenesulfonic acid is 1% by mass of acrylic acid, the molecular weight of polyethylene glycol is 4000, the amount ratio of intermediate 1, β-cyclodextrin, deionized water and DMF is 0.5mmol:1g:10mL:3mL, the molar ratio of Si-H bonds on the modifier and double bonds on the polyrotaxane is 1:1, and the amount of chloroplatinic acid is 1‰ of the mass of the modifier.

[0014] Furthermore, the amount ratio of 2-hydroxyethyl acrylate, epichlorohydrin, boron trifluoride etherate and sodium hydroxide solution described in step A3 is 10mmol:10mmol:0.9g:20mL, the mass fraction of sodium hydroxide solution is 20%, the mass ratio of reinforcing monomer and functional monomer is 20:1, and the amount of benzophenone is 5‰ of the functional monomer.

[0015] Further, the modified filler is prepared by the following steps:

[0016] Step B1: Tetramethyltetraphenylcyclotetrasiloxane, tetramethylcyclotetrasiloxane, octamethylcyclotetrasiloxane, hexamethyldisiloxane, tetramethylammonium hydroxide and dimethyl sulfoxide are mixed uniformly, nitrogen is introduced for protection, and the reaction is carried out for 3-5 hours at a speed of 120-150 r / min and a temperature of 90-95° C. to obtain hydrogen-containing polysiloxane; graphene oxide, KH570 and ethanol are mixed uniformly, and deionized water is added under stirring at a speed of 120-150 r / min and a temperature of 60-70° C. to react for 3-5 hours to obtain modified graphene;

[0017] Step B2: Disperse the modified graphene in DMF, add hydrogenated polysiloxane and chloroplatinic acid, introduce nitrogen protection, react for 20-25 hours at a speed of 150-200 r / min and a temperature of 80-85°C to obtain a precursor, mix the precursor, diethylenetriamine and formaldehyde aqueous solution evenly, react for 3-5 hours at a speed of 200-300 r / min and a temperature of 80-85°C to obtain a modified filler.

[0018] Further, the molar ratio of tetramethyltetraphenylcyclotetrasiloxane, tetramethylcyclotetrasiloxane, octamethylcyclotetrasiloxane, hexamethyldisiloxane and tetramethylammonium hydroxide described in step B1 is 1.3:1.3:1:3:4.5, the amount of dimethyl sulfoxide is 5‰ of the mass of tetramethyltetraphenylcyclotetrasiloxane, tetramethylcyclotetrasiloxane, octamethylcyclotetrasiloxane and hexamethyldisiloxane, and the amount of KH570 is 3% of the mass of graphene oxide.

[0019] Furthermore, the molar ratio of the double bonds on the modified graphene and the Si-H bonds on the hydrogen-containing polysiloxane described in step B2 is 1:1.2, the amount of chloroplatinic acid used is 1‰ of the mass of the hydrogen-containing polysiloxane, the amount ratio of the precursor, diethylenetriamine and formaldehyde aqueous solution is 1g:5g:15mL, and the mass fraction of the formaldehyde aqueous solution is 37%.

[0020] Beneficial effects of the invention: The high-toughness epoxy resin glue disclosed in the invention comprises component A and component B, wherein component A comprises bisphenol A epoxy resin and a modified additive, and component B comprises a modified filler and 4,4'-diaminodiphenyl sulfone, wherein the modified additive is hydrolyzed and condensed with dodecyltrimethoxysilane as a raw material to obtain sodium dodecylcyclotetrasiloxane tetrasilanol, and sodium dodecylcyclotetrasiloxane tetrasilanol is reacted with methyldichlorosilane so that the sodium silanol on the sodium dodecylcyclotetrasiloxane tetrasilanol reacts with the chlorine atom site on the methyldichlorosilane to obtain a modifier, and polyethylene glycol is reacted with acrylic acid so that the alcohol hydroxyl group on the polyethylene glycol reacts with the acrylic acid. The carboxyl group on the acid is esterified to obtain intermediate 1, intermediate 1 is reacted with β-cyclodextrin, so that β-cyclodextrin is included in the molecular chain of intermediate 1 through non-covalent bond interaction to obtain polyrotaxane, polyrotaxane is reacted with a modifier, so that the double bond on the polyrotaxane reacts with the Si-H bond on the modifier to obtain a reinforcing monomer, 2-hydroxyethyl acrylate is reacted with epichlorohydrin, so that the hydroxyl group on 2-hydroxyethyl acrylate reacts with the epoxy group on epichlorohydrin, and then a new epoxy group is formed under the action of sodium hydroxide to obtain a functional monomer, and the reinforcing monomer and the functional monomer are polymerized under the action of benzophenone to obtain a modified additive.

[0021] The modified filler is prepared by ring-opening tetramethyltetraphenylcyclotetrasiloxane, tetramethylcyclotetrasiloxane and octamethylcyclotetrasiloxane as raw materials, and then polymerizing with hexamethyldisiloxane to form hydrogen-containing polysiloxane. Graphene oxide is treated with KH570 to graft double bonds on the surface of graphene oxide to obtain modified graphene. The modified graphene is reacted with hydrogen-containing polysiloxane to react the double bonds on the surface of the modified graphene with the Si-H bonds on the hydrogen-containing polysiloxane to obtain a precursor. The precursor and diethylenetriamine are subjected to Mannich condensation under the action of formaldehyde aqueous solution to obtain the modified filler.

[0022] The addition of the modified additive after component A and component B are blended can transform the linear molecules into branched structures. At the same time, the surface of the modified filler contains amino groups, which can participate in the curing process of the epoxy resin. The modified filler is a core-shell structure, which can improve the mechanical properties of the epoxy resin. The modified filler contains a cage-type silsesquioxane structure and a large number of long-chain alkyl groups, which can increase the toughness of the epoxy resin. The modified additive contains a polyrotaxane structure. The polyrotaxane structure is a structure composed of a main cyclic molecule ring-pierced on the subject linear molecule, which can undergo microscopic movements of rotation, sliding, elongation and twisting, further improving the toughness of the epoxy resin glue. DETAILED DESCRIPTION

[0023] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention. Example

[0024] A method for preparing high-toughness epoxy resin adhesive specifically comprises the following steps:

[0025] Weigh the following raw materials in parts by weight: 8 parts of component A and 2.5 parts of component B, and mix component A and component B evenly to prepare a high-toughness epoxy resin adhesive;

[0026] Component A includes the following raw materials by weight: 50 parts of bisphenol A epoxy resin and 20 parts of modified additives, and component B includes the following raw materials by weight: 1 part of modified filler and 20 parts of 4,4'-diaminodiphenyl sulfone.

[0027] The model of the bisphenol A epoxy resin is EP-51.

[0028] The modified additive is prepared by the following steps:

[0029] Step A1: dodecyltrimethoxysilane, sodium hydroxide, isopropanol and deionized water are mixed evenly, and reacted for 10 hours at a speed of 120 r / min and a temperature of 85° C. to obtain sodium dodecylcyclotetrasiloxane tetrasiloxide. Sodium dodecylcyclotetrasiloxane tetrasiloxide, triethylamine and tetrahydrofuran are mixed evenly, nitrogen is introduced for protection, methyldichlorosilane is added under stirring at a speed of 150 r / min and a temperature of 0° C., and the mixture is reacted for 3 hours, the temperature is raised to 20° C., and the mixture is reacted for 20 hours to obtain a modifier;

[0030] Step A2: polyethylene glycol, acrylic acid, p-toluenesulfonic acid and toluene are mixed evenly, and reacted at a speed of 120 r / min and a temperature of 110° C. for 5 h to obtain intermediate 1; intermediate 1, β-cyclodextrin, deionized water and DMF are mixed, and stirred at a speed of 60 r / min and a temperature of 30° C. for 10 h to obtain polyrotaxane; modifier, polyrotaxane, chloroplatinic acid and DMF are mixed evenly, nitrogen protection is introduced, and reaction is carried out at a speed of 60 r / min and a temperature of 80° C. for 20 h to obtain a reinforcing monomer;

[0031] Step A3: 2-hydroxyethyl acrylate, epichlorohydrin, boron trifluoride etherate and DMF are mixed evenly, reacted at a speed of 120 r / min and a temperature of 65° C. for 2 hours, and then sodium hydroxide solution is added, the temperature is raised to 75° C., and the reaction is carried out for 3 hours to obtain a functional monomer. The reinforcing monomer, functional monomer, benzophenone and DMF are mixed evenly, and reacted at a speed of 150 r / min and 365 nm ultraviolet light for 1 hour to obtain a modified additive.

[0032] The amount ratio of dodecyltrimethoxysilane, sodium hydroxide, isopropanol and deionized water described in step A1 is 30mmol:18mmol:25mL:1mL, and the amount ratio of dodecylcyclotetrasiloxane sodium tetrasiloxide, triethylamine, tetrahydrofuran and methyldichlorosilane is 5g:1.2g:10mL:1g.

[0033] The molar ratio of polyethylene glycol and acrylic acid described in step A2 is 1:2, the amount of p-toluenesulfonic acid is 1% by mass of acrylic acid, the molecular weight of polyethylene glycol is 4000, the amount ratio of intermediate 1, β-cyclodextrin, deionized water and DMF is 0.5mmol:1g:10mL:3mL, the molar ratio of Si-H bonds on the modifier and double bonds on the polyrotaxane is 1:1, and the amount of chloroplatinic acid is 1‰ of the mass of the modifier.

[0034] The amount ratio of 2-hydroxyethyl acrylate, epichlorohydrin, boron trifluoride etherate and sodium hydroxide solution described in step A3 is 10mmol:10mmol:0.9g:20mL, the mass fraction of sodium hydroxide solution is 20%, the mass ratio of reinforcing monomer and functional monomer is 20:1, and the amount of benzophenone is 5‰ of the functional monomer.

[0035] The modified filler is prepared by the following steps:

[0036] Step B1: Tetramethyltetraphenylcyclotetrasiloxane, tetramethylcyclotetrasiloxane, octamethylcyclotetrasiloxane, hexamethyldisiloxane, tetramethylammonium hydroxide and dimethyl sulfoxide are mixed uniformly, nitrogen is introduced for protection, and the mixture is reacted for 3 hours at a speed of 120 r / min and a temperature of 90° C. to obtain hydrogen-containing polysiloxane; graphene oxide, KH570 and ethanol are mixed uniformly, and deionized water is added under stirring at a speed of 120 r / min and a temperature of 60° C. to obtain modified graphene;

[0037] Step B2: Disperse the modified graphene in DMF, add hydrogenated polysiloxane and chloroplatinic acid, introduce nitrogen protection, react for 20 hours at a speed of 150 r / min and a temperature of 80°C to obtain a precursor, mix the precursor, diethylenetriamine and formaldehyde aqueous solution evenly, react for 3 hours at a speed of 200 r / min and a temperature of 80°C to obtain a modified filler.

[0038] The molar ratio of tetramethyltetraphenylcyclotetrasiloxane, tetramethylcyclotetrasiloxane, octamethylcyclotetrasiloxane, hexamethyldisiloxane and tetramethylammonium hydroxide described in step B1 is 1.3:1.3:1:3:4.5, the amount of dimethyl sulfoxide is tetramethyltetraphenylcyclotetrasiloxane, tetramethylcyclotetrasiloxane, octamethylcyclotetrasiloxane and hexamethyldisiloxane by mass and 5‰, and the amount of KH570 is 3% of the mass of graphene oxide.

[0039] The molar ratio of the double bonds on the modified graphene and the Si-H bonds on the hydrogen-containing polysiloxane described in step B2 is 1:1.2, the amount of chloroplatinic acid used is 1‰ of the mass of the hydrogen-containing polysiloxane, the amount ratio of the precursor, diethylenetriamine and formaldehyde aqueous solution is 1g:5g:15mL, and the mass fraction of the formaldehyde aqueous solution is 37%. Example

[0040] A method for preparing high-toughness epoxy resin adhesive specifically comprises the following steps:

[0041] Weigh the following raw materials in parts by weight: 9 parts of component A and 2.8 parts of component B, and mix component A and component B evenly to prepare a high-toughness epoxy resin adhesive;

[0042] Component A includes the following raw materials by weight: 65 parts of bisphenol A epoxy resin and 35 parts of modified additives, and component B includes the following raw materials by weight: 2 parts of modified filler and 30 parts of 4,4'-diaminodiphenyl sulfone.

[0043] The model of the bisphenol A epoxy resin is EP-51.

[0044] The modified additive is prepared by the following steps:

[0045] Step A1: dodecyltrimethoxysilane, sodium hydroxide, isopropanol and deionized water are mixed evenly, and reacted for 10 hours at a speed of 120 r / min and a temperature of 90° C. to obtain sodium dodecylcyclotetrasiloxane tetrasiloxide. Sodium dodecylcyclotetrasiloxane tetrasiloxide, triethylamine and tetrahydrofuran are mixed evenly, nitrogen is introduced for protection, and methyldichlorosilane is added under stirring at a speed of 200 r / min and a temperature of 0° C. to react for 4 hours, and the temperature is raised to 20° C. and reacted for 25 hours to obtain a modifier;

[0046] Step A2: polyethylene glycol, acrylic acid, p-toluenesulfonic acid and toluene are mixed evenly, and reacted at a speed of 120 r / min and a temperature of 115° C. for 6 hours to obtain intermediate 1; intermediate 1, β-cyclodextrin, deionized water and DMF are mixed, and stirred at a speed of 60 r / min and a temperature of 35° C. for 15 hours to obtain polyrotaxane; modifier, polyrotaxane, chloroplatinic acid and DMF are mixed evenly, nitrogen protection is introduced, and reaction is carried out at a speed of 60 r / min and a temperature of 85° C. for 20 hours to obtain a reinforcing monomer;

[0047] Step A3: 2-hydroxyethyl acrylate, epichlorohydrin, boron trifluoride etherate and DMF are mixed evenly, reacted at a speed of 150 r / min and a temperature of 65° C. for 3 hours, and then sodium hydroxide solution is added, the temperature is raised to 75° C., and the reaction is carried out for 4 hours to obtain a functional monomer. The reinforcing monomer, functional monomer, benzophenone and DMF are mixed evenly, and reacted at a speed of 150 r / min and 365 nm ultraviolet light for 1.5 hours to obtain a modified additive.

[0048] The amount ratio of dodecyltrimethoxysilane, sodium hydroxide, isopropanol and deionized water described in step A1 is 30mmol:18mmol:25mL:1mL, and the amount ratio of dodecylcyclotetrasiloxane sodium tetrasiloxide, triethylamine, tetrahydrofuran and methyldichlorosilane is 5g:1.2g:10mL:1g.

[0049] The molar ratio of polyethylene glycol and acrylic acid described in step A2 is 1:2, the amount of p-toluenesulfonic acid is 1% by mass of acrylic acid, the molecular weight of polyethylene glycol is 4000, the amount ratio of intermediate 1, β-cyclodextrin, deionized water and DMF is 0.5mmol:1g:10mL:3mL, the molar ratio of Si-H bonds on the modifier and double bonds on the polyrotaxane is 1:1, and the amount of chloroplatinic acid is 1‰ of the mass of the modifier.

[0050] The amount ratio of 2-hydroxyethyl acrylate, epichlorohydrin, boron trifluoride etherate and sodium hydroxide solution described in step A3 is 10mmol:10mmol:0.9g:20mL, the mass fraction of sodium hydroxide solution is 20%, the mass ratio of reinforcing monomer and functional monomer is 20:1, and the amount of benzophenone is 5‰ of the functional monomer.

[0051] The modified filler is prepared by the following steps:

[0052] Step B1: Tetramethyltetraphenylcyclotetrasiloxane, tetramethylcyclotetrasiloxane, octamethylcyclotetrasiloxane, hexamethyldisiloxane, tetramethylammonium hydroxide and dimethyl sulfoxide are mixed uniformly, nitrogen is introduced for protection, and the mixture is reacted for 4 hours at a speed of 120 r / min and a temperature of 95° C. to obtain hydrogen-containing polysiloxane; graphene oxide, KH570 and ethanol are mixed uniformly, and deionized water is added under stirring at a speed of 120 r / min and a temperature of 65° C. to obtain modified graphene;

[0053] Step B2: Disperse the modified graphene in DMF, add hydrogenated polysiloxane and chloroplatinic acid, introduce nitrogen protection, react for 25 hours at a speed of 200 r / min and a temperature of 80°C to obtain a precursor, mix the precursor, diethylenetriamine and formaldehyde aqueous solution evenly, react for 4 hours at a speed of 200 r / min and a temperature of 85°C to obtain a modified filler.

[0054] The molar ratio of tetramethyltetraphenylcyclotetrasiloxane, tetramethylcyclotetrasiloxane, octamethylcyclotetrasiloxane, hexamethyldisiloxane and tetramethylammonium hydroxide described in step B1 is 1.3:1.3:1:3:4.5, the amount of dimethyl sulfoxide is tetramethyltetraphenylcyclotetrasiloxane, tetramethylcyclotetrasiloxane, octamethylcyclotetrasiloxane and hexamethyldisiloxane by mass and 5‰, and the amount of KH570 is 3% of the mass of graphene oxide.

[0055] The molar ratio of the double bonds on the modified graphene and the Si-H bonds on the hydrogen-containing polysiloxane described in step B2 is 1:1.2, the amount of chloroplatinic acid used is 1‰ of the mass of the hydrogen-containing polysiloxane, the amount ratio of the precursor, diethylenetriamine and formaldehyde aqueous solution is 1g:5g:15mL, and the mass fraction of the formaldehyde aqueous solution is 37%. Example

[0056] A method for preparing high-toughness epoxy resin adhesive specifically comprises the following steps:

[0057] Weigh the following raw materials in parts by weight: 10 parts of component A and 3 parts of component B, and mix component A and component B evenly to prepare a high-toughness epoxy resin adhesive;

[0058] Component A includes the following raw materials by weight: 80 parts of bisphenol A epoxy resin and 50 parts of modified additives, and component B includes the following raw materials by weight: 3 parts of modified filler and 40 parts of 4,4'-diaminodiphenyl sulfone.

[0059] The model of the bisphenol A epoxy resin is EP-51.

[0060] The modified additive is prepared by the following steps:

[0061] Step A1: dodecyltrimethoxysilane, sodium hydroxide, isopropanol and deionized water are mixed evenly, and reacted for 15 hours at a speed of 150 r / min and a temperature of 90° C. to obtain sodium dodecylcyclotetrasiloxane tetrasiloxide. Sodium dodecylcyclotetrasiloxane tetrasiloxide, triethylamine and tetrahydrofuran are mixed evenly, nitrogen is introduced for protection, and methyldichlorosilane is added under stirring at a speed of 200 r / min and a temperature of 0° C. to react for 5 hours, and the temperature is raised to 25° C. and reacted for 25 hours to obtain a modifier;

[0062] Step A2: polyethylene glycol, acrylic acid, p-toluenesulfonic acid and toluene are mixed evenly, and reacted at a speed of 150 r / min and a temperature of 120° C. for 7 hours to obtain intermediate 1; intermediate 1, β-cyclodextrin, deionized water and DMF are mixed, and stirred at a speed of 80 r / min and a temperature of 40° C. for 15 hours to obtain polyrotaxane; modifier, polyrotaxane, chloroplatinic acid and DMF are mixed evenly, nitrogen protection is introduced, and reaction is carried out at a speed of 80 r / min and a temperature of 85° C. for 25 hours to obtain a reinforcing monomer;

[0063] Step A3: 2-hydroxyethyl acrylate, epichlorohydrin, boron trifluoride etherate and DMF are mixed evenly, reacted at a speed of 150 r / min and a temperature of 70°C for 3 hours, and then sodium hydroxide solution is added, the temperature is raised to 80°C, and the reaction is carried out for 5 hours to obtain a functional monomer. The reinforcing monomer, functional monomer, benzophenone and DMF are mixed evenly, and reacted at a speed of 200 r / min and 365 nm ultraviolet light for 1.5 hours to obtain a modified additive.

[0064] The amount ratio of dodecyltrimethoxysilane, sodium hydroxide, isopropanol and deionized water described in step A1 is 30mmol:18mmol:25mL:1mL, and the amount ratio of dodecylcyclotetrasiloxane sodium tetrasiloxide, triethylamine, tetrahydrofuran and methyldichlorosilane is 5g:1.2g:10mL:1g.

[0065] The molar ratio of polyethylene glycol and acrylic acid described in step A2 is 1:2, the amount of p-toluenesulfonic acid is 1% by mass of acrylic acid, the molecular weight of polyethylene glycol is 4000, the amount ratio of intermediate 1, β-cyclodextrin, deionized water and DMF is 0.5mmol:1g:10mL:3mL, the molar ratio of Si-H bonds on the modifier and double bonds on the polyrotaxane is 1:1, and the amount of chloroplatinic acid is 1‰ of the mass of the modifier.

[0066] The amount ratio of 2-hydroxyethyl acrylate, epichlorohydrin, boron trifluoride etherate and sodium hydroxide solution described in step A3 is 10mmol:10mmol:0.9g:20mL, the mass fraction of sodium hydroxide solution is 20%, the mass ratio of reinforcing monomer and functional monomer is 20:1, and the amount of benzophenone is 5‰ of the functional monomer.

[0067] The modified filler is prepared by the following steps:

[0068] Step B1: Tetramethyltetraphenylcyclotetrasiloxane, tetramethylcyclotetrasiloxane, octamethylcyclotetrasiloxane, hexamethyldisiloxane, tetramethylammonium hydroxide and dimethyl sulfoxide are mixed uniformly, nitrogen is introduced for protection, and the mixture is reacted for 5 hours at a speed of 150 r / min and a temperature of 95° C. to obtain hydrogen-containing polysiloxane; graphene oxide, KH570 and ethanol are mixed uniformly, and deionized water is added under stirring at a speed of 150 r / min and a temperature of 70° C. to obtain modified graphene;

[0069] Step B2: Disperse the modified graphene in DMF, add hydrogenated polysiloxane and chloroplatinic acid, introduce nitrogen protection, react for 25 hours at a speed of 200 r / min and a temperature of 85°C to obtain a precursor, mix the precursor, diethylenetriamine and formaldehyde aqueous solution evenly, react for 5 hours at a speed of 300 r / min and a temperature of 85°C to obtain a modified filler.

[0070] The molar ratio of tetramethyltetraphenylcyclotetrasiloxane, tetramethylcyclotetrasiloxane, octamethylcyclotetrasiloxane, hexamethyldisiloxane and tetramethylammonium hydroxide described in step B1 is 1.3:1.3:1:3:4.5, the amount of dimethyl sulfoxide is tetramethyltetraphenylcyclotetrasiloxane, tetramethylcyclotetrasiloxane, octamethylcyclotetrasiloxane and hexamethyldisiloxane by mass and 5‰, and the amount of KH570 is 3% of the mass of graphene oxide.

[0071] The molar ratio of the double bonds on the modified graphene and the Si-H bonds on the hydrogen-containing polysiloxane described in step B2 is 1:1.2, the amount of chloroplatinic acid used is 1‰ of the mass of the hydrogen-containing polysiloxane, the amount ratio of the precursor, diethylenetriamine and formaldehyde aqueous solution is 1g:5g:15mL, and the mass fraction of the formaldehyde aqueous solution is 37%.

[0072] Comparative Example 1

[0073] Compared with Example 1, this comparative example uses polyrotaxane instead of the reinforcing monomer, and the remaining steps are the same.

[0074] Comparative Example 2

[0075] Compared with Example 1, β-cyclodextrin was not added in this comparative example, and the remaining steps were the same.

[0076] Comparative Example 3

[0077] Compared with Example 1, this comparative example uses methyltrimethoxysilane instead of dodecyltrimethoxysilane, and the remaining steps are the same.

[0078] Comparative Example 4

[0079] Compared with Example 1, this comparative example uses graphene oxide instead of the modified filler, and the remaining steps are the same.

[0080] The epoxy resin adhesives prepared in Examples 1-3 and Comparative Examples 1-4 were tested for tensile strength and elongation at break at a stretching rate of 10 mm / min according to the standard of GB / T2567-2008. Type I specimens were made and the impact strength was tested. The test results are shown in the following table.

[0081]

[0082] It can be seen from the above table that this application has good toughness.

[0083] The above contents are merely examples and explanations of the concept of the present invention. The technicians in this technical field may make various modifications or additions to the specific embodiments described or replace them in a similar manner. As long as they do not deviate from the concept of the invention or exceed the scope defined by the claims, they should all fall within the protection scope of the present invention.

Claims

1. A method for preparing a high-toughness epoxy resin adhesive, characterized in that: The specific steps include: Weigh the following raw materials in parts by weight: 8-10 parts of component A and 2.5-3 parts of component B, mix component A and component B evenly, and prepare a high-toughness epoxy resin adhesive; Component A comprises the following raw materials by weight: 50-80 parts of bisphenol A epoxy resin and 20-50 parts of modified additives, and component B comprises the following raw materials by weight: 1-3 parts of modified filler and 20-40 parts of 4,4'-diaminodiphenyl sulfone; The modified additive is prepared by the following steps: Step A1: dodecyltrimethoxysilane, sodium hydroxide, isopropanol and deionized water are mixed for reaction to obtain sodium dodecylcyclotetrasiloxane tetrasiloxide, sodium dodecylcyclotetrasiloxane tetrasiloxide, triethylamine and tetrahydrofuran are mixed evenly, nitrogen is introduced for protection, methyldichlorosilane is added for stirring and reaction is carried out to obtain a modifier; Step A2: polyethylene glycol, acrylic acid, p-toluenesulfonic acid and toluene are mixed and reacted to obtain intermediate 1, intermediate 1, β-cyclodextrin, deionized water and DMF are mixed and stirred to obtain polyrotaxane, and the modifier, polyrotaxane, chloroplatinic acid and DMF are mixed uniformly, and nitrogen protection is introduced to react to obtain a reinforcing monomer; Step A3: After mixing 2-hydroxyethyl acrylate, epichlorohydrin, boron trifluoride etherate and DMF for reaction, sodium hydroxide solution is added to react to obtain a functional monomer, and the reinforcing monomer, functional monomer, benzophenone and DMF are mixed for reaction to obtain a modified additive; The modified filler is made by the following steps: Step B1: Tetramethyltetraphenylcyclotetrasiloxane, tetramethylcyclotetrasiloxane, octamethylcyclotetrasiloxane, hexamethyldisiloxane, tetramethylammonium hydroxide and dimethyl sulfoxide are uniformly mixed, nitrogen is introduced for protection, and a reaction is carried out to obtain hydrogen-containing polysiloxane; graphene oxide, KH570 and ethanol are mixed and stirred, and deionized water is added to react to obtain modified graphene; Step B2: Disperse the modified graphene in DMF, add hydrogen-containing polysiloxane and chloroplatinic acid, introduce nitrogen protection, react to obtain a precursor, mix the precursor, diethylenetriamine, and formaldehyde aqueous solution to obtain a modified filler.

2. The method for preparing a high-toughness epoxy resin adhesive according to claim 1, characterized in that: The amount ratio of dodecyltrimethoxysilane, sodium hydroxide, isopropanol and deionized water described in step A1 is 30mmol:18mmol:25mL:1mL, and the amount ratio of dodecylcyclotetrasiloxane sodium tetrasiloxide, triethylamine, tetrahydrofuran and methyldichlorosilane is 5g:1.2g:10mL:1g.

3. The method for preparing a high-toughness epoxy resin adhesive according to claim 1, characterized in that: The molar ratio of polyethylene glycol and acrylic acid described in step A2 is 1:2, the amount ratio of intermediate 1, β-cyclodextrin, deionized water and DMF is 0.5mmol:1g:10mL:3mL, and the molar ratio of Si-H bonds on the modifier and double bonds on the polyrotaxane is 1:

1.

4. The method for preparing a high-toughness epoxy resin adhesive according to claim 1, characterized in that: The amount ratio of 2-hydroxyethyl acrylate, epichlorohydrin, boron trifluoride etherate and sodium hydroxide solution in step A3 is 10mmol:10mmol:0.9g:20mL, and the mass ratio of the reinforcing monomer to the functional monomer is 20:

1.

5. The method for preparing a high-toughness epoxy resin adhesive according to claim 1, characterized in that: The molar ratio of tetramethyltetraphenylcyclotetrasiloxane, tetramethylcyclotetrasiloxane, octamethylcyclotetrasiloxane, hexamethyldisiloxane and tetramethylammonium hydroxide described in step B1 is 1.3:1.3:1:3:4.5, and the amount of KH570 used is 3% of the mass of graphene oxide.

6. The method for preparing a high-toughness epoxy resin adhesive according to claim 1, characterized in that: The molar ratio of the double bonds on the modified graphene and the Si-H bonds on the hydrogen-containing polysiloxane described in step B2 is 1:1.2, and the amount ratio of the precursor, diethylenetriamine and formaldehyde aqueous solution is 1g:5g:15mL.

7. A high-toughness epoxy resin adhesive, characterized in that: Prepared according to any one of claims 1 to 6.

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