High-strength wear-resistant acrylate adhesive and preparation method thereof

Abstract

The invention discloses a high-strength wear-resistant acrylate adhesive and a preparation method thereof, and relates to the technical field of adhesives. The high-strength wear-resistant acrylate adhesive is prepared from the following raw materials in parts by weight: 50 to 60 parts of modified acrylate, 20 to 30 parts of modified elastomer, 5 to 10 parts of plasticizer, 5 to 10 parts of filler, 2 to 6 parts of cross-linking agent, 3 to 5 parts of initiator and 2 to 4 parts of accelerant. By modifying the raw materials of the acrylate adhesive, the prepared adhesive has high strength, wear resistance, low contractibility and self-repairing function, the service life and reliability of the adhesive can be improved, in addition, the adhesive is degradable, the degradable adhesive can be gradually decomposed in the natural environment after being used, the output of garbage is reduced, and the environment pollution is reduced. Moreover, soil and water cannot be polluted, and the ecological environment can be protected.

Description

Technical Field

[0001] The invention relates to the technical field of adhesives, in particular to a high-strength and wear-resistant acrylic adhesive and a preparation method thereof. Background Art

[0002] Adhesives are widely used in modern industry and daily life, from aerospace to the manufacture of daily necessities. Acrylic adhesives, as an important type of adhesive, stand out due to their unique advantages.

[0003] Acrylic adhesives offer fast curing properties, rapidly completing the curing process at room or low temperatures, significantly improving production efficiency and offering significant advantages in large-scale industrial production. They exhibit excellent bonding properties to a wide range of materials, including metals, plastics, and glass, and have a wide range of applications. Furthermore, their high bond strength and excellent chemical resistance meet the needs of diverse applications.

[0004] However, current acrylic adhesives also present some challenges. Their insufficient hardness and toughness make them prone to cracking when subjected to impact or vibration, leading to bond failure. Their limited high-temperature resistance leads to softening and degradation at high temperatures, limiting their use in extreme environments. Furthermore, their high cure shrinkage can cause deformation of adhered objects. Therefore, the development of high-performance acrylic adhesives with improved overall performance is of great practical significance and market demand. Summary of the Invention

[0005] In view of the deficiencies in the prior art, the present invention provides a high-strength and wear-resistant acrylic adhesive and a preparation method thereof, which solves the problems of traditional acrylic adhesives such as low hardness, poor wear resistance and large shrinkage.

[0006] To achieve the above objectives, the present invention is implemented through the following technical solutions: A high-strength and wear-resistant acrylic adhesive comprises the following raw materials in parts by weight: 50-60 parts of modified acrylic ester, 20-30 parts of modified elastomer, 5-10 parts of plasticizer, 5-10 parts of filler, 2-6 parts of crosslinking agent, 3-5 parts of initiator, and 2-4 parts of accelerator.

[0007] Furthermore, the modified acrylate comprises the following raw materials in parts by weight: 40-60 parts of butyl acrylate, 10-20 parts of methyl methacrylate, 2-4 parts of benzoyl peroxide, 6-10 parts of mercaptoethanol, 2-5 parts of benzoin dimethyl ether, 6-8 parts of carbon nanotubes, and 4-8 parts of titanium dioxide.

[0008] The modified acrylate is specifically prepared in the following steps: A1. Butyl acrylate and methyl methacrylate were added to a three-necked flask, nitrogen was introduced for 10-15 minutes, the temperature was raised to 75-85°C, a stirring device was turned on, and stirring was carried out at a speed of 300-500 r / min. Benzoyl peroxide was added dropwise through a dropping funnel at a rate of 1-3 drops / second. After the addition was completed, stirring was continued for 1-2 hours while nitrogen was continuously introduced; A2, when the temperature of the reaction system is cooled to 40-60 ° C, mercaptoethanol is added dropwise to the reaction system through a dropping funnel at a rate of 1-3 drops / second under stirring conditions of 300-500 r / min. After the addition is completed, when the system is cooled to 10-20 ° C, benzoin dimethyl ether is added dropwise at a rate of 1-3 drops / second. After the addition is completed, stirring is continued for 20-40 minutes, and the mixed solution is transferred to a transparent reaction vessel and placed in an ultraviolet irradiation device with a wavelength of 365 nm for 1-3 hours; A3. Pour the above reaction product into a separatory funnel, let it stand for stratification, remove the water layer to obtain the desired substance, add it to a high-speed mixer, stir at 700-900 r / min, add carbon nanotubes, stir for 20-40 minutes, then add titanium dioxide and continue stirring for 30-60 minutes. After stirring, take out the product, wash it with anhydrous ethanol 3-5 times, and then dry it in a drying oven at 60-80°C for 3-4 hours, and then crush it to a particle size of 20-50 μm to obtain a modified acrylate.

[0009] Furthermore, the modified elastomer comprises the following raw materials in parts by weight: 40-60 parts of nitrile rubber, 10-15 parts of alkylbenzene sulfonate, 10-15 parts of styrene, 10-15 parts of potassium persulfate, 2-6 parts of calcium chloride, 5-10 parts of ferric chloride, 5-10 parts of ferrous chloride, 30-40 parts of toluene, 1-3 parts of azobisisobutyronitrile, 10-15 parts of methyl methacrylate, and 10-15 parts of fatty acid ester; The modified elastomer is specifically prepared in the following steps: B1. Add deionized water to the reactor, start stirring, control the speed at 100-200r / min, add the alkylbenzene sulfonate aqueous solution, stir for 5-10 minutes to form a stable emulsified system, then add the nitrile rubber and styrene monomer, and continue stirring for 15-20 minutes. Raise the temperature of the reactor to 50-55°C, slowly add the potassium persulfate aqueous solution through the dropping funnel, and control the addition rate at 1-3 ml per minute. Keep the stirring speed and temperature stable during the reaction, and react for 1-3 hours; after the reaction is completed, transfer the product to a precipitation kettle, add calcium chloride coagulant, and stir evenly to precipitate the copolymer; filter and wash the product with deionized water 3-5 times, then place it in an oven and dry it at 50-60°C to constant weight; B2. In a three-necked flask, dissolve ferric chloride and ferrous chloride in deionized water. Under mechanical stirring, slowly add ammonia water through a constant pressure dropping funnel, adjust the pH value to 10, and react for 30-60 minutes. After the reaction is completed, transfer the solution to a centrifuge, centrifuge at a speed of 2000-3000r / min, wash the precipitate with deionized water 3-5 times to obtain pure Fe3O4 nanoparticles, and disperse them in toluene for later use; take the first modified nitrile rubber, add it to toluene, heat it to 50-60°C in a three-necked flask with a magnetic stirrer, stir at a speed of 200-300r / min, and fully dissolve the rubber; slowly add the toluene solution containing magnetic nanoparticles to the nitrile rubber solution, and turn on the ultrasonic disperser at the same time, control the ultrasonic power at 200-300 watts, and the ultrasonic time for 20-30 minutes; pour the mixed solution into a mold, and naturally evaporate the toluene in a ventilated environment to cure the rubber and magnetic nanoparticles. B3. Dissolve azobisisobutyronitrile initiator in toluene. Dissolve the second modified nitrile rubber in toluene, add the mixture to a reactor, and purge with nitrogen for 30 minutes to displace the air. Add the toluene solution containing the initiator and methyl methacrylate monomer, raise the temperature to 60-70°C, stir at 150-200 rpm, and react for 2-3 hours. Add the initiator and fatty acid ester to the reacted rubber solution, and stir at 300-500 rpm for 15-20 minutes in a high-speed stirrer. Pour the resulting mixture into a rotary evaporator and remove the organic solvent by vacuum distillation at 40-50°C. Extrude the resulting product to obtain the modified nitrile rubber.

[0010] Furthermore, the plasticizer is one of dibutyl phthalate, di(2-ethylhexyl) phthalate, and lauryl acrylate.

[0011] Furthermore, the filler is one of calcium carbonate, silicon dioxide and aluminum hydroxide.

[0012] Furthermore, the cross-linking agent is one of trimethylolpropane triacrylate and pentaerythritol tetraacrylate.

[0013] Furthermore, the initiator is one of benzoyl peroxide, di-tert-butyl peroxide, and azobisisobutyronitrile.

[0014] Furthermore, the accelerator is N,N-dimethyl-p-tolidine.

[0015] A method for preparing a high-strength and wear-resistant acrylic adhesive comprises the following steps: C1. Add toluene solvent and modified acrylic acid ester to a three-necked flask equipped with a stirring device, a thermometer, and a condenser. Turn on the stirring device and control the stirring speed at 200-300 r / min. Slowly add the modified elastomer and heat to 50-80°C. Continue stirring until the modified elastomer is completely dissolved in the modified acrylic acid. After dissolution is complete, turn off the heating device and allow the solution to cool naturally. During the cooling process, maintain the stirring speed at 100-200 r / min until the solution temperature drops to room temperature. Then stop stirring and let the solution stand for 15-30 minutes. While stirring, use a pipette to slowly add the plasticizer to the reactor at a dropping speed of 1-3 drops per second. At the same time, stir at a speed of 100-300 r / min. After the plasticizer is added, continue stirring for 30-40 minutes. C2. Divide the dry filler into several small portions and slowly add them to the reactor at a frequency of adding one portion every 4 minutes. During the addition of the filler, increase the stirring speed to 300-400 r / min. After adding each portion of filler, stir for 15-20 minutes before adding the next portion. After all the fillers have been added, increase the stirring speed to 500-600 r / min and continue stirring for 1-2 hours. C3. Adjust the stirring speed to 200-300 r / min, and slowly add the crosslinker, initiator and accelerator in sequence. Stir for 15-30 minutes after adding each additive. Place the stirred adhesive solution in a vacuum drying oven and degas at a vacuum degree of -0.08-0.1 MPa for 30-60 minutes. Let it stand for 1-2 hours to remove bubbles in the solution to obtain a high-strength and wear-resistant acrylic adhesive.

[0016] The present invention provides a high-strength and wear-resistant acrylic adhesive and a preparation method thereof, which have the following beneficial effects: 1. This high-strength and wear-resistant acrylic adhesive uses acrylic ester as the basic resin and adds nitrile rubber to form a copolymer, which has good flexibility. The adhesive will not easily fail in a low-temperature environment. At the same time, wear-resistant fillers are added to synergistically harden the adhesive, thereby improving the wear resistance of the adhesive.

[0017] 2. This modified acrylate uses butyl acrylate as the raw material for modification. Methyl methacrylate is added to react with this butyl acrylate, which has inherent flexibility. The resulting copolymer exhibits high strength and chemical resistance. Mercaptoethanol is added to introduce a dynamic chemical bond, the thiol group. Compounds containing thiol groups are synthesized via a thiol-ene click chemistry reaction with acrylate compounds containing double bonds. Under ultraviolet light, the reaction generates a disulfide-bonded acrylate monomer with self-healing properties that can improve the lifespan and reliability of the adhesive. Carbon nanotubes, inherently strong, synergistically enhance the adhesive's hardness. Graphite also possesses certain electrical and thermal conductivity, making the adhesive antistatic and heat-dissipating.

[0018] 3. This modified elastomer, nitrile rubber itself possesses a certain strength. The copolymerization of styrene and nitrile rubber enhances its rigidity and strength. The inclusion of methyl methacrylate in the reaction also contributes to the overall strength and hardness, making the modified elastomer less susceptible to deformation and damage when subjected to external forces and reducing shrinkage. Acrylate adhesives made from a composite of two magnetic nanoparticles, ferric chloride and ferrous chloride, can be used for bonding magnetic materials and positioning and securing electronic components. Their magnetic properties enable rapid positioning and adsorption, improving production efficiency and assembly accuracy. The addition of fatty acid esters promotes degradation. In environmentally sensitive applications, such as bonding paper packaging in the packaging industry, the adhesive can gradually degrade in the natural environment after the packaging is discarded. DETAILED DESCRIPTION

[0019] The following is a clear and complete description of the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts are within the scope of protection of the present invention.

[0020] Example 1, a high-strength and wear-resistant acrylic adhesive, comprising the following raw materials in parts by weight: 50 parts of modified acrylic ester, 20 parts of modified elastomer, 5 parts of plasticizer, 5 parts of filler, 2 parts of cross-linking agent, 3 parts of initiator, and 2 parts of accelerator.

[0021] A method for preparing a high-strength and wear-resistant acrylic adhesive comprises the following steps: C1. Add toluene solvent and modified acrylic acid ester to a three-necked flask equipped with a stirring device, a thermometer, and a condenser. Turn on the stirring device and control the stirring speed at 200 r / min. Slowly add the modified elastomer and raise the temperature to 50°C. Continue stirring until the modified elastomer is completely dissolved in the modified acrylic acid. After the dissolution is complete, turn off the heating device and allow the solution to cool naturally. During the cooling process, maintain the stirring speed at 100 r / min until the solution temperature drops to room temperature. Then stop stirring and let the solution stand for 15 minutes. While stirring, use a pipette to slowly add dibutyl phthalate to the reactor dropwise at a rate of 1 drop per second while stirring at 100 r / min. After the plasticizer is added, continue stirring for 30 minutes. C2. Divide the dried calcium carbonate into several small portions and slowly add them to the reactor at a frequency of adding one portion every 4 minutes. During the addition of the filler, increase the stirring speed to 300 r / min. After adding each portion of filler, stir for 15 minutes before adding the next portion. After all the fillers have been added, increase the stirring speed to 500 r / min and continue stirring for 1 hour. C3. Adjust the stirring speed to 200 r / min, and slowly add trimethylolpropane triacrylate, benzoyl peroxide and N,N-dimethyl-p-tolidine in sequence. Stir for 15 minutes after adding each additive. Place the stirred adhesive solution in a vacuum drying oven, degas at a vacuum degree of -0.08 MPa for 30 minutes, and let it stand for 1 hour to remove bubbles in the solution to obtain a high-strength and wear-resistant acrylic adhesive.

[0022] The modified acrylate comprises the following raw materials in parts by weight: 40 parts of butyl acrylate, 10 parts of methyl methacrylate, 2 parts of benzoyl peroxide, 6 parts of mercaptoethanol, 2 parts of benzoin dimethyl ether, 6 parts of carbon nanotubes, and 4 parts of titanium dioxide.

[0023] The modified acrylate is specifically prepared in the following steps: A1. Butyl acrylate and methyl methacrylate were added to a three-necked flask, nitrogen was introduced for 10 minutes, the temperature was raised to 75°C, a stirring device was turned on, and stirring was carried out at a speed of 300 r / min. Benzoyl peroxide was added dropwise through a dropping funnel at a rate of 1 drop / second. After the addition was completed, stirring was continued for 1 hour while nitrogen was continuously introduced; A2. When the temperature of the reaction system is cooled to 40°C, mercaptoethanol is added dropwise to the reaction system at a rate of 1 drop / second through a dropping funnel under stirring at 300 r / min. After the addition is completed, benzoin dimethyl ether is added dropwise at a rate of 1 drop / second when the system is cooled to 10°C. After the addition is completed, stirring is continued for 20 minutes. The mixed solution is transferred to a transparent reaction vessel and placed in an ultraviolet irradiation device with a wavelength of 365 nm for 1 hour. A3. The reaction product was poured into a separatory funnel, allowed to stand for stratification, and the water layer was removed to obtain the desired substance. The mixture was added to a high-speed mixer and stirred at 700 r / min. Carbon nanotubes were added and stirred for 20 minutes. Titanium dioxide was then added and stirred for 30 minutes. After stirring, the product was taken out and washed with anhydrous ethanol three times. The product was then dried in a drying oven at 60°C for 3 hours and then crushed to a particle size of 20 μm to obtain a modified acrylate.

[0024] The modified elastomer comprises the following raw materials in parts by weight: 40 parts of nitrile rubber, 10 parts of alkylbenzene sulfonate, 10 parts of styrene, 10 parts of potassium persulfate, 2 parts of calcium chloride, 5 parts of ferric chloride, 5 parts of ferrous chloride, 30 parts of toluene, 1 part of azobisisobutyronitrile, 10 parts of methyl methacrylate, and 10 parts of fatty acid ester; The modified elastomer is specifically prepared in the following steps: B1. Add deionized water to the reactor, start stirring, control the speed at 100r / min, add the alkylbenzene sulfonate aqueous solution, stir for 5 minutes to form a stable emulsified system, then add the nitrile rubber and styrene monomer, and continue stirring for 15 minutes. Raise the temperature of the reactor to 50°C, slowly add the potassium persulfate aqueous solution through the dropping funnel, and control the addition rate at 1 ml per minute. Keep the stirring speed and temperature stable during the reaction, and react for 1 hour; after the reaction is completed, transfer the product to a precipitation kettle, add calcium chloride coagulant, and stir evenly to precipitate the copolymer; filter and wash the product with deionized water 3 times, then place it in an oven and dry it at 50°C to constant weight; B2. In a three-necked flask, ferric chloride and ferrous chloride were dissolved in deionized water. Under mechanical stirring, ammonia water was slowly added dropwise through a constant pressure dropping funnel, the pH value was adjusted to 10, and the reaction was carried out for 30 minutes. After the reaction, the solution was transferred to a centrifuge, centrifuged at a speed of 2000r / min, and the precipitate was washed 3 times with deionized water to obtain pure Fe3O4 nanoparticles, which were dispersed in toluene for standby use; the nitrile rubber after the first modification was taken, added to toluene, and heated to 50°C in a three-necked flask with a magnetic stirrer, with a stirring speed of 200r / min to fully dissolve the rubber; the toluene solution containing magnetic nanoparticles was slowly added to the nitrile rubber solution, and the ultrasonic disperser was turned on at the same time, the ultrasonic power was controlled at 200 watts, and the ultrasonic time was 20 minutes; the mixed solution was poured into a mold, and the toluene was naturally volatilized under ventilation to cure the rubber and magnetic nanoparticles; B3: Dissolve azobisisobutyronitrile initiator in toluene. Dissolve the second modified nitrile rubber in toluene, add the mixture to a reactor, and replace the air with nitrogen for 30 minutes. Add the initiator-containing toluene solution and methyl methacrylate monomer, heat to 60°C, stir at 150 rpm, and react for 2 hours. Grind the mixture to a particle size of 20 μm and add it to the reacted rubber solution along with the fatty acid ester. Stir at 300 rpm for 15 minutes using a high-speed stirrer. Pour the mixed solution into a rotary evaporator, remove the organic solvent by vacuum distillation at 40°C, and extrude the resulting product to obtain a modified nitrile rubber.

[0025] Example 2, a high-strength and wear-resistant acrylic adhesive, comprising the following raw materials in parts by weight: 60 parts of modified acrylic ester, 30 parts of modified elastomer, 10 parts of plasticizer, 10 parts of filler, 6 parts of cross-linking agent, 5 parts of initiator, and 4 parts of accelerator.

[0026] A method for preparing a high-strength and wear-resistant acrylic adhesive comprises the following steps: C1. Add toluene solvent and modified acrylic acid ester to a three-necked flask equipped with a stirring device, a thermometer, and a condenser. Turn on the stirring device and control the stirring speed at 300 r / min. Slowly add the modified elastomer and raise the temperature to 80°C. Continue stirring until the modified elastomer is completely dissolved in the modified acrylic acid. After dissolution is complete, turn off the heating device and allow the solution to cool naturally. During the cooling process, maintain the stirring speed at 200 r / min until the solution temperature drops to room temperature. Then stop stirring and let the solution stand for 30 minutes. While stirring, use a pipette to slowly add di(2-ethylhexyl) phthalate to the reactor at a dropping speed of 3 drops per second. Stir at the same time at a speed of 300 r / min. After the plasticizer is added, continue stirring for 40 minutes. C2. Divide the dried silica into several small portions and slowly add them to the reactor at a frequency of adding one portion every 4 minutes. During the addition of filler, increase the stirring speed to 400 r / min. After adding each portion of filler, stir for 20 minutes before adding the next portion. After all the fillers have been added, increase the stirring speed to 600 r / min and continue stirring for 2 hours. C3. Adjust the stirring speed to 300 r / min, and slowly add pentaerythritol tetraacrylate, di-tert-butyl peroxide, and N,N-dimethyl-p-tolidine in sequence. Stir for 30 minutes after adding each additive. Place the stirred adhesive solution in a vacuum drying oven, degas at a vacuum degree of -0.1 MPa for 60 minutes, and let it stand for 2 hours to remove bubbles in the solution to obtain a high-strength and wear-resistant acrylic adhesive.

[0027] The modified acrylate comprises the following raw materials in parts by weight: 60 parts of butyl acrylate, 20 parts of methyl methacrylate, 4 parts of benzoyl peroxide, 10 parts of mercaptoethanol, 5 parts of benzoin dimethyl ether, 8 parts of carbon nanotubes, and 8 parts of titanium dioxide.

[0028] The modified acrylate is specifically prepared in the following steps: A1. Butyl acrylate and methyl methacrylate were added to a three-necked flask, nitrogen was introduced for 15 minutes, the temperature was raised to 85°C, a stirring device was turned on, stirring was carried out at a speed of 500 r / min, and benzoyl peroxide was added dropwise at a rate of 3 drops / second through a dropping funnel. After the addition was completed, stirring was continued for 2 hours while nitrogen was continuously introduced; A2. When the temperature of the reaction system is cooled to 60°C, mercaptoethanol is added dropwise to the reaction system at a rate of 3 drops per second through a dropping funnel under stirring at 300 r / min. After the addition is completed, dimethyl benzoate is added dropwise at a rate of 3 drops per second when the system is cooled to 20°C. After the addition is completed, stirring is continued for 40 minutes. The mixture is transferred to a transparent reaction vessel and placed in an ultraviolet irradiation device with a wavelength of 365 nm for 3 hours. A3. The reaction product was poured into a separatory funnel, allowed to stand for stratification, and the water layer was removed to obtain the desired substance. The mixture was added to a high-speed mixer and stirred at 900 r / min. Carbon nanotubes were added and stirred for 40 minutes. Titanium dioxide was then added and stirred for 60 minutes. After stirring, the product was taken out and washed with anhydrous ethanol five times. The product was then dried in a drying oven at 80°C for 4 hours and then crushed to a particle size of 50 μm to obtain a modified acrylate.

[0029] The modified elastomer comprises the following raw materials in parts by weight: 60 parts of nitrile rubber, 15 parts of alkylbenzene sulfonate, 15 parts of styrene, 15 parts of potassium persulfate, 6 parts of calcium chloride, 10 parts of ferric chloride, 10 parts of ferrous chloride, 40 parts of toluene, 3 parts of azobisisobutyronitrile, 15 parts of methyl methacrylate, and 15 parts of fatty acid ester; The modified elastomer is specifically prepared in the following steps: B1. Add deionized water to the reactor, start stirring, control the speed at 200r / min, add alkylbenzene sulfonate aqueous solution, stir for 10 minutes to form a stable emulsified system, then add nitrile rubber and styrene monomer, and continue stirring for 20 minutes. Raise the temperature of the reactor to 55°C, slowly add potassium persulfate aqueous solution through a dropping funnel, control the addition rate at 3 ml per minute, keep the stirring speed and temperature stable during the reaction, and react for 3 hours; after the reaction is completed, transfer the product to a precipitation kettle, add calcium chloride coagulant, and stir evenly to precipitate the copolymer; filter and wash the product with deionized water 5 times, then place it in an oven and dry it at 60°C to constant weight; B2. In a three-necked flask, ferric chloride and ferrous chloride were dissolved in deionized water. Under mechanical stirring, ammonia water was slowly added dropwise through a constant pressure dropping funnel, the pH value was adjusted to 10, and the reaction was carried out for 60 minutes. After the reaction, the solution was transferred to a centrifuge, centrifuged at a speed of 3000r / min, and the precipitate was washed 5 times with deionized water to obtain pure Fe3O4 nanoparticles, which were dispersed in toluene for standby use; the nitrile rubber after the first modification was taken, added to toluene, and heated to 60°C in a three-necked flask with a magnetic stirrer, with a stirring speed of 300r / min, so that the rubber was fully dissolved; the toluene solution containing magnetic nanoparticles was slowly added to the nitrile rubber solution, and the ultrasonic disperser was turned on at the same time, the ultrasonic power was controlled at 300 watts, and the ultrasonic time was 30 minutes; the mixed solution was poured into a mold, and the toluene was naturally volatilized under ventilation to cure the rubber and magnetic nanoparticles; B3. Dissolve azobisisobutyronitrile initiator in toluene. Dissolve the second modified nitrile rubber in toluene and add to a reactor. Replace the air with nitrogen for 30 minutes. Add the toluene solution containing the initiator and methyl methacrylate monomer. Heat to 70°C, stir at 200 rpm, and react for 3 hours. Grind to a particle size of 80 μm and add it to the reacted rubber solution along with the fatty acid ester. Stir at 500 rpm for 20 minutes in a high-speed stirrer. Pour the mixed solution into a rotary evaporator and remove the organic solvent by vacuum distillation at 50°C. Extrude the resulting product to obtain the modified nitrile rubber.

[0030] Example 3, a high-strength and wear-resistant acrylic adhesive, comprising the following raw materials in parts by weight: 55 parts of modified acrylic ester, 25 parts of modified elastomer, 7 parts of plasticizer, 7 parts of filler, 4 parts of cross-linking agent, 4 parts of initiator, and 3 parts of accelerator.

[0031] A method for preparing a high-strength and wear-resistant acrylic adhesive comprises the following steps: C1. Add toluene solvent and modified acrylic acid ester to a three-necked flask equipped with a stirring device, a thermometer, and a condenser. Turn on the stirring device and control the stirring speed at 250 r / min. Slowly add the modified elastomer and raise the temperature to 65°C. Continue stirring until the modified elastomer is completely dissolved in the modified acrylic acid. After the dissolution is complete, turn off the heating device and allow the solution to cool naturally. During the cooling process, maintain the stirring speed at 150 r / min until the solution temperature drops to room temperature. Then stop stirring and let the solution stand for 22 minutes. While stirring, use a pipette to slowly add lauryl acrylate to the reactor at a dropping speed of 2 drops per second. At the same time, stir at a speed of 200 r / min. After the plasticizer is added, continue stirring for 35 minutes. C2. Divide the dried aluminum hydroxide into several small portions and slowly add them to the reactor at a frequency of adding one portion every 4 minutes. During the addition of the filler, increase the stirring speed to 350 r / min. After adding each portion of filler, stir for 17 minutes before adding the next portion. After all the fillers have been added, increase the stirring speed to 550 r / min and continue stirring for 1.5 hours. C3. Adjust the stirring speed to 250 r / min, and slowly add trimethylolpropane triacrylate, azobisisobutyronitrile and N,N-dimethyl-p-tolidine in sequence. Stir for 22 minutes after adding each additive. Place the stirred adhesive solution in a vacuum drying oven, degas at a vacuum degree of -0.09 MPa for 45 minutes, and let it stand for 1.5 hours to remove bubbles in the solution to obtain a high-strength and wear-resistant acrylic adhesive.

[0032] The modified acrylate comprises the following raw materials in parts by weight: 50 parts of butyl acrylate, 15 parts of methyl methacrylate, 3 parts of benzoyl peroxide, 8 parts of mercaptoethanol, 3 parts of benzoin dimethyl ether, 7 parts of carbon nanotubes, and 6 parts of titanium dioxide.

[0033] The modified acrylate is specifically prepared in the following steps: A1. Butyl acrylate and methyl methacrylate were added to a three-necked flask, nitrogen was introduced for 12 minutes, the temperature was raised to 80°C, a stirring device was turned on, and stirring was carried out at a speed of 400 r / min. Benzoyl peroxide was added dropwise through a dropping funnel at a rate of 2 drops / second. After the addition was completed, stirring was continued for 1.5 hours while nitrogen was continuously introduced; A2. When the temperature of the reaction system is cooled to 50°C, mercaptoethanol is added dropwise to the reaction system at a rate of 2 drops per second through a dropping funnel under stirring at 400 r / min. After the addition is completed, benzoin dimethyl ether is added dropwise at a rate of 2 drops per second when the system is cooled to 15°C. After the addition is completed, stirring is continued for 30 minutes. The mixed solution is transferred to a transparent reaction vessel and placed in an ultraviolet irradiation device with a wavelength of 365 nm for 2 hours. A3. The reaction product was poured into a separatory funnel, allowed to stand for stratification, and the water layer was removed to obtain the desired substance. The mixture was added to a high-speed mixer and stirred at 800 r / min. Carbon nanotubes were added and stirred for 30 minutes. Titanium dioxide was then added and stirred for 45 minutes. After stirring, the product was taken out and washed with anhydrous ethanol four times. The product was then dried in a drying oven at 70°C for 3.5 hours and then crushed to a particle size of 35 μm to obtain a modified acrylate.

[0034] The modified elastomer comprises the following raw materials in parts by weight: 50 parts of nitrile rubber, 12 parts of alkylbenzene sulfonate, 12 parts of styrene, 12 parts of potassium persulfate, 4 parts of calcium chloride, 7 parts of ferric chloride, 7 parts of ferrous chloride, 35 parts of toluene, 2 parts of azobisisobutyronitrile, 12 parts of methyl methacrylate, and 12 parts of fatty acid ester; The modified elastomer is specifically prepared in the following steps: B1. Add deionized water to the reactor, start stirring, control the speed at 150r / min, add alkylbenzene sulfonate aqueous solution, stir for 7 minutes to form a stable emulsified system, then add nitrile rubber and styrene monomer, and continue stirring for 17 minutes. Raise the temperature of the reactor to 52°C, slowly add potassium persulfate aqueous solution through a dropping funnel, control the addition rate at 2 ml per minute, keep the stirring speed and temperature stable during the reaction, and react for 2 hours; after the reaction is completed, transfer the product to a precipitation kettle, add calcium chloride coagulant, and stir evenly to precipitate the copolymer; filter and wash the product with deionized water 4 times, then put it in an oven and dry it at 55°C to constant weight; B2. In a three-necked flask, dissolve ferric chloride and ferrous chloride in deionized water. Under mechanical stirring, slowly add ammonia water through a constant pressure dropping funnel, adjust the pH value to 10, and react for 45 minutes. After the reaction is completed, transfer the solution to a centrifuge, centrifuge at a speed of 2500r / min, wash the precipitate with deionized water 4 times to obtain pure Fe3O4 nanoparticles, and disperse them in toluene for standby use; take the first modified nitrile rubber, add it to toluene, heat it to 55°C in a three-necked flask with a magnetic stirrer, stir at a speed of 250r / min, and fully dissolve the rubber; slowly add the toluene solution containing magnetic nanoparticles to the nitrile rubber solution, and turn on the ultrasonic disperser at the same time, control the ultrasonic power at 250 watts, and the ultrasonic time for 25 minutes; pour the mixed solution into a mold, and naturally evaporate the toluene in a ventilated environment to cure the rubber and magnetic nanoparticles. B3. Dissolve azobisisobutyronitrile initiator in toluene. Dissolve the second modified nitrile rubber in toluene and add to a reactor. Replace the air with nitrogen for 30 minutes. Add the toluene solution containing the initiator and methyl methacrylate monomer. Raise the temperature to 65°C, stir at 175 rpm, and react for 2.5 hours. Grind the mixture to a particle size of 50 μm and add it to the reacted rubber solution along with the fatty acid ester. Stir at 400 rpm for 17 minutes in a high-speed stirrer. Pour the mixed solution into a rotary evaporator and remove the organic solvent by vacuum distillation at 45°C. Extrude the resulting product to obtain the modified nitrile rubber.

[0035] Comparative Example 1 Compared with Example 2, this comparative example does not add modified acrylate, and the remaining steps are the same.

[0036] Comparative Example 2 Compared with Example 2, this comparative example does not add modified elastomer, and the remaining steps are the same.

[0037] Performance Testing

[0038] Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Repair efficiency 80% 88% 83% 60% 87% Volume resistivity (Ω·cm) 64 52 60 52 124 Self-cleaning efficiency 85% 89% 86% 62% 88% hardness 6H 6H 6H 5H 5H Degradation rate 94% 96% 94% 95% 70% Shrinkage 28% 20% 24% 21% 72% As can be seen from the test results in the table above, when the amounts of various substances added and the operating conditions in Example 2 are at their maximum values, the repair efficiency, self-cleaning efficiency, and degradation rate of the high-strength, wear-resistant acrylic adhesive prepared are improved, and the volume resistivity and shrinkage rate are significantly reduced, compared to the amounts of substances added and the operating conditions in Examples 1 and 3. This shows that the high-strength, wear-resistant acrylic adhesive prepared in Example 2 is the optimal formula. In Comparative Example 1, no modified acrylic ester is added, and its repair efficiency, self-cleaning efficiency, and hardness are far inferior to those of the adhesive with the modified acrylic ester. In Comparative Example 2, the adhesive without the modified elastomer does not have good conductivity, hardness, degradation rate, and shrinkage rate. This shows that the adhesive with the modified acrylic ester and modified elastomer has better performance.

[0039] The above contents are merely examples and explanations of the present invention. Those skilled in the art may make various modifications or additions to the described specific embodiments or replace them in similar ways. As long as they do not deviate from the invention or exceed the scope defined by the claims, they should all fall within the scope of protection of the present invention.

Claims

1. A high-strength and wear-resistant acrylic adhesive, characterized by: The invention comprises the following raw materials in parts by weight: 50-60 parts of modified acrylate, 20-30 parts of modified elastomer, 5-10 parts of plasticizer, 5-10 parts of filler, 2-6 parts of crosslinking agent, 3-5 parts of initiator and 2-4 parts of accelerator.

2. The high-strength and wear-resistant acrylic adhesive according to claim 1, characterized in that: The modified acrylate is characterized by comprising the following raw materials in parts by weight: 40-60 parts of butyl acrylate, 10-20 parts of methyl methacrylate, 2-4 parts of benzoyl peroxide, 6-10 parts of mercaptoethanol, 2-5 parts of benzoin dimethyl ether, 6-8 parts of carbon nanotubes, and 4-8 parts of titanium dioxide; The modified acrylate is specifically prepared in the following steps: A1. Butyl acrylate and methyl methacrylate were added to a three-necked flask, nitrogen was introduced for 10-15 minutes, the temperature was raised to 75-85°C, a stirring device was turned on, and stirring was carried out at a speed of 300-500 r / min. Benzoyl peroxide was added dropwise through a dropping funnel at a rate of 1-3 drops / second. After the addition was completed, stirring was continued for 1-2 hours while nitrogen was continuously introduced; A2, when the temperature of the reaction system is cooled to 40-60 ° C, mercaptoethanol is added dropwise to the reaction system through a dropping funnel at a rate of 1-3 drops / second under stirring conditions of 300-500 r / min. After the addition is completed, when the system is cooled to 10-20 ° C, benzoin dimethyl ether is added dropwise at a rate of 1-3 drops / second. After the addition is completed, stirring is continued for 20-40 minutes, and the mixed solution is transferred to a transparent reaction vessel and placed in an ultraviolet irradiation device with a wavelength of 365 nm for 1-3 hours; A3. Pour the above reaction product into a separatory funnel, let it stand for stratification, remove the water layer to obtain the desired substance, add it to a high-speed mixer, stir at 700-900 r / min, add carbon nanotubes, stir for 20-40 minutes, then add titanium dioxide and continue stirring for 30-60 minutes. After stirring, take out the product, wash it with anhydrous ethanol 3-5 times, and then dry it in a drying oven at 60-80°C for 3-4 hours, and then crush it to a particle size of 20-50 μm to obtain a modified acrylate.

3. The high-strength and wear-resistant acrylic adhesive according to claim 1, characterized in that: The modified elastomer is characterized by comprising the following raw materials in parts by weight: 40-60 parts of nitrile rubber, 10-15 parts of alkylbenzene sulfonate, 10-15 parts of styrene, 10-15 parts of potassium persulfate, 2-6 parts of calcium chloride, 5-10 parts of ferric chloride, 5-10 parts of ferrous chloride, 30-40 parts of toluene, 1-3 parts of azobisisobutyronitrile, 10-15 parts of methyl methacrylate, and 10-15 parts of fatty acid ester; The modified elastomer is specifically prepared in the following steps: B1, deionized water is added to the reactor, stirring is started, the speed is controlled at 100-200r / min, an alkylbenzene sulfonate aqueous solution is added, and a stable emulsion system is formed for 5-10 minutes, then a nitrile rubber and styrene monomer are added, and stirring is continued for 15-20 minutes; the reactor temperature is raised to 50-55°C, and an aqueous solution of potassium persulfate is slowly added dropwise through a dropping funnel at a rate of addition of 1-3 ml per minute. During the reaction, the stirring speed and temperature are kept stable and the reaction is carried out for 1-3 hours; after the reaction is completed, the product is transferred to a precipitation kettle, a calcium chloride coagulant is added, and the copolymer is precipitated by stirring; the product is filtered and washed with deionized water for 3-5 times, then placed in an oven and dried to constant weight at 50-60°C; B2, in a three-necked flask, ferric chloride and ferrous chloride are dissolved in deionized water, under mechanical stirring, ammonia water is slowly added dropwise by constant pressure dropping funnel, pH value is adjusted to 10, react 30-60 minute, after reaction finishes, solution is transferred in centrifuge, with the speed centrifugation of 2000-3000r / min, precipitated 3-5 times with deionized water, obtain pure Fe3O4 nanoparticles, be dispersed in toluene standby; Take the acrylonitrile-butadiene rubber after first modification, join in toluene, in the three-necked flask with magnetic stirrer, be heated to 50-60 ℃, stirring speed 200-300r / min, fully dissolve rubber; Toluene solution containing magnetic nanoparticles is slowly added in the acrylonitrile-butadiene rubber solution, open ultrasonic disperser simultaneously, ultrasonic power is controlled at 200-300 watts, ultrasonic time 20-30 minute; The mixed solution is poured in mould, under ventilation environment, naturally volatilizes toluene, makes rubber and magnetic nanoparticle composite solidification; B3. Take azobisisobutyronitrile initiator, dissolve it in toluene, dissolve the second modified nitrile rubber in toluene, add it to a reactor, and introduce nitrogen to replace the air for 30 minutes; add a toluene solution containing the initiator and methyl methacrylate monomer, raise the temperature to 60-70°C, stir at 150-200r / min, react for 2-3 hours, add it to the reacted rubber solution together with the fatty acid ester, stir at a speed of 300-500r / min for 15-20 minutes with a high-speed stirrer, pour the mixed solution into a rotary evaporator, and remove the organic solvent by reduced pressure distillation at 40-50°C; extrude the obtained product to obtain a modified nitrile rubber.

4. The high-strength and wear-resistant acrylic adhesive according to claim 1, characterized in that: The plasticizer is one of dibutyl phthalate, di(2-ethylhexyl) phthalate, and lauryl acrylate.

5. The high-strength and wear-resistant acrylic adhesive according to claim 1, characterized in that: The filler is one of calcium carbonate, silicon dioxide and aluminum hydroxide.

6. The high-strength and wear-resistant acrylic adhesive according to claim 1, characterized in that: The cross-linking agent is one of trimethylolpropane triacrylate and pentaerythritol tetraacrylate.

7. The high-strength and wear-resistant acrylic adhesive according to claim 1, characterized in that: The initiator is one of benzoyl peroxide, di-tert-butyl peroxide and azobisisobutyronitrile.

8. The high-strength and wear-resistant acrylic adhesive according to claim 1, characterized in that: The accelerator is N,N-dimethyl-p-tolidine.

9. A method for preparing a high-strength and wear-resistant acrylic adhesive, characterized in that: The specific steps include: C1. Add toluene solvent and modified acrylic acid ester to a three-necked flask equipped with a stirring device, a thermometer, and a condenser. Turn on the stirring device and control the stirring speed at 200-300 r / min. Slowly add the modified elastomer and heat to 50-80°C. Continue stirring until the modified elastomer is completely dissolved in the modified acrylic acid. After dissolution is complete, turn off the heating device and allow the solution to cool naturally. During the cooling process, maintain the stirring speed at 100-200 r / min until the solution temperature drops to room temperature. Then stop stirring and let the solution stand for 15-30 minutes. While stirring, use a pipette to slowly add the plasticizer to the reactor at a dropping speed of 1-3 drops per second. At the same time, stir at a speed of 100-300 r / min. After the plasticizer is added, continue stirring for 30-40 minutes. C2. Divide the dry filler into several small portions and slowly add them to the reactor at a frequency of adding one portion every 4 minutes. During the addition of the filler, increase the stirring speed to 300-400 r / min. After adding each portion of filler, stir for 15-20 minutes before adding the next portion. After all the fillers have been added, increase the stirring speed to 500-600 r / min and continue stirring for 1-2 hours. C3. Adjust the stirring speed to 200-300 r / min, and slowly add the crosslinker, initiator and accelerator in sequence. Stir for 15-30 minutes after adding each additive. Place the stirred adhesive solution in a vacuum drying oven and degas at a vacuum degree of -0.08-0.1 MPa for 30-60 minutes. Let it stand for 1-2 hours to remove bubbles in the solution to obtain a high-strength and wear-resistant acrylic adhesive.