Graphene-waterborne epoxy high-dispersion system and synthetic method thereof

[0052] Example one

[0053] According to the molar ratio of 1:2.0, take polyethylene glycol diglycidyl ether and triethylenetetramine and mix them uniformly, and carry out addition chain extension reaction at 65℃ for 3h, thereby introducing hydrophilic groups on the primary amino groups to obtain the end Amino hydrophilic polyether segment (see figure 1 ). According to the molar ratio of 2.0:1, take the amino-terminated hydrophilic polyether segment and E51 epoxy resin for addition chain extension reaction at 65℃ for 4h to obtain the amino-terminated long-chain non-ionic self-emulsifying epoxy curing agent (see figure 2 ).

[0054] Using ultrasound-assisted Hummers method to prepare low-oxidation graphene, such as image 3 As shown, the specific steps are as follows: (1) Take 100 parts by weight of 98% concentrated sulfuric acid, 0.8 parts by weight of graphite powder and 0.3 parts by weight of sodium nitrate in the first beaker according to the proportion by weight. After stirring at 4°C for 1 hour, Add 2 parts by weight of potassium permanganate to beaker one, control the temperature to be ≤10℃ and continue to react for 2h; ⑵ move the beaker one to a 38℃ water bath and stir for 0.5h to obtain a mixed solution; ⑶take 100ml, 0℃ to remove Place the ionized water in the second beaker, and slowly add the mixture obtained in step (2) into the second beaker, then place the second beaker in a water bath at 95°C and stir for 0.5h; (4) take out the second beaker from the water bath and add it to the second beaker Add 60ml of deionized water to stop the reaction. After standing for 15 minutes, add 15ml of 20% hydrogen peroxide to the second beaker. After reacting for 15 minutes, add 40ml of 10% hydrochloric acid to the second beaker to obtain the reactant; Centrifuge and wash at low speed to remove excess acid and by-products, then disperse the neutral graphite oxide in water after washing, sonicate for 40 minutes at 180W, and centrifuge at 2500rpm for 30 minutes after the end of the ultrasonic. The resulting supernatant is The graphene oxide suspension is filtered, washed, and dried to obtain graphene with a low degree of oxidation. Low-oxidation graphene is a multilayer graphene, the number of layers is ≤10, and the thickness is within 5nm.

[0055] According to the molar ratio of 2.0:1, take the non-ionic self-emulsifying epoxy curing agent and low-oxidation graphene and mix them uniformly, and carry out the covalent graft modification reaction at 60℃ for 4h to obtain the graphene-waterborne epoxy high dispersion system (see Figure 4 ).

[0056] The graphene-waterborne epoxy high dispersion system synthesized by the above method is used to prepare ultra-high strength concrete. The specific preparation method of ultra-high-strength concrete is as follows: ①According to the mass percentage, take 18% of sand that has passed a 70-mesh sieve, 35% of fine stones with a particle size of less than 25mm, 45% of Portland cement, and 2% of additives to form a solid component; ②According to the mass percentage, take 35% graphene-waterborne epoxy high dispersion system and 65% water to form the liquid component; ③According to the mass ratio of 1:5, take the liquid component and the solid component, mix and stir the two to obtain a super High-strength concrete. The additives are composed of the following mass percentages of raw materials: 50% polycarboxylic acid water reducing agent Q801, 20% mid- and late expansion agent UEA, 10% defoamer BYK024, 20% powder, which can be fly ash, ore Mixtures such as powder and silicon powder.

[0057] The graphene-waterborne epoxy high dispersion system synthesized by the above method is used to prepare a waterborne epoxy anticorrosive coating. The specific preparation method of waterborne epoxy anticorrosive coating is as follows: (a) Take 90% waterborne epoxy resin emulsion with 50% solid content, 5% deionized water and 5% auxiliary agent according to the mass percentage, and react at room temperature after mixing evenly. 5min, get component A; (b) take 85% graphene-waterborne epoxy high dispersion system, 10% deionized water and 5% auxiliary agent 2 according to mass percentage, mix well and react at room temperature for 5min to get component B (C) Zinc powder that has passed through a sieve of 500 mesh or more is used as component C. According to the mass ratio of 3:1:3, mix component A, component B and component C, and stir to obtain a water-based epoxy anticorrosive coating. Among them, the first and second additives are at least one of leveling agent PUR-40, defoaming agent T-4505, and substrate wetting agent BYK346.

[0058] Example two

[0059] According to the molar ratio of 1:2.1, take polyethylene glycol diglycidyl ether and isophorone diamine and mix them uniformly, and carry out addition chain extension reaction at 60°C for 4 hours to introduce hydrophilic groups on the primary amino groups. The amino-terminated hydrophilic polyether segment is obtained. According to the molar ratio of 2.1:1, the amino-terminated hydrophilic polyether segment and E44 epoxy resin were subjected to addition chain extension reaction at 60°C for 3h to obtain an amino-terminated long-chain non-ionic self-emulsifying epoxy curing agent.

[0060] The ultrasonic-assisted Hummers method is used to prepare low-oxidation graphene. The specific steps are as follows: (1) Take 100 parts by weight of 98% concentrated sulfuric acid, 1.0 part by weight of graphite powder and 0.5 part by weight of sodium nitrate in the first beaker according to the weight ratio. After stirring for 1 hour at 2°C, add 4 parts by weight of potassium permanganate to beaker one, control the temperature to be ≤10°C and continue to react for 2 hours; (2) move the beaker to a 40°C water bath and stir for 0.5h to obtain a mixed solution ⑶ Take 100ml, 0 ℃ deionized water into beaker two, and slowly add the mixture obtained in step ⑵ into beaker two, and then place beaker two in a water bath at 90 ℃, stir for 0.5h; ⑷from the water bath Take out beaker 2 from the pot and add 70ml of deionized water to beaker 2 to stop the reaction. After standing for 15 minutes, add 15ml of 20% hydrogen peroxide to beaker 2. After reacting for 15 minutes, add 40ml of 10% hydrochloric acid to beaker 2. Obtain the reactant; (5) Centrifuge and wash the reactant at low speed to remove excess acid and by-products, then disperse the neutral graphite oxide in water after washing, sonicate at 180W for 40min, and rotate at 2500rpm after the end of the ultrasound After centrifugation for 30 minutes, the obtained upper layer is the graphene oxide suspension, which is filtered, washed, and dried to obtain graphene with a low degree of oxidation. Low-oxidation graphene is a multilayer graphene, the number of layers is ≤10, and the thickness is within 5nm.

[0061] According to the molar ratio of 2.1:1, take the non-ionic self-emulsifying epoxy curing agent and low-oxidation graphene and mix them uniformly, and carry out the covalent graft modification reaction at 65℃ for 3h to obtain the graphene-waterborne epoxy high dispersion system .

[0062] The graphene-waterborne epoxy high dispersion system synthesized by the above method is used to prepare ultra-high strength concrete. The specific preparation method of ultra-high-strength concrete is as follows: ①According to the mass percentage, take 20% of sand that has passed through a 75-mesh sieve, 34% of fine stones with a particle size of less than 25mm, 43% of Portland cement, and 3% of additives to form a solid component; ②According to the mass percentage, take 40% graphene-waterborne epoxy high dispersion system and 60% water to form the liquid component; ③According to the mass ratio of 1:7, take the liquid component and the solid component, mix and stir the two to obtain a super High-strength concrete. The additives are composed of the following mass percentages of raw materials: 70% polycarboxylic acid type water reducing agent SJ-PCA, 10% mid- and late expansion agent AEA, 10% defoamer Nopco NXZ, 10% powder, and powder can be Mixtures of fly ash, mineral powder, silica fume, etc.

[0063] The graphene-waterborne epoxy high dispersion system synthesized by the above method is used to prepare a waterborne epoxy anticorrosive coating. The specific preparation method of waterborne epoxy anticorrosive coating is as follows: (a) Take 95% waterborne epoxy resin emulsion with 50% solid content, 2% deionized water and 3% additives according to the mass percentage, and react at room temperature after mixing evenly. 5min, get component A; (b) take 90% graphene-waterborne epoxy high dispersion system, 9% deionized water and 1% auxiliary agent 2 according to mass percentage, mix well and react at room temperature for 5min to get component B (C) Zinc powder that has passed through a sieve of 500 mesh or more is used as component C. According to the mass ratio of 3:1:3, mix component A, component B and component C, and stir to obtain a water-based epoxy anticorrosive coating. Among them, the first and second additives are at least one of leveling agent PUR-40, defoaming agent T-4505, and substrate wetting agent BYK346.

[0064] Example three

[0065] According to the molar ratio of 1:2.05, take triethylene glycol diglycidyl ether and p-xylylenediamine and mix them uniformly, and carry out addition chain extension reaction at 63℃ for 3.5h, thereby introducing hydrophilic groups on the primary amino groups. The amino-terminated hydrophilic polyether segment is obtained. According to the molar ratio of 2.05:1, the amino-terminated hydrophilic polyether segment and the E20 epoxy resin were subjected to addition chain extension reaction at 63° C. for 3.5 hours to obtain an amino-terminated long-chain non-ionic self-emulsifying epoxy curing agent.

[0066] The ultrasonic-assisted Hummers method is used to prepare low-oxidation graphene. The specific steps are as follows: (1) Take 100 parts by weight of 98% concentrated sulfuric acid, 1.2 parts by weight of graphite powder, and 0.7 parts by weight of sodium nitrate in the first beaker. After stirring for 1 hour at 0°C, add 6 parts by weight of potassium permanganate to beaker one, control the temperature to ≤10°C and continue the reaction for 2 hours; (2) move the beaker to a 35°C water bath and stir for 0.5h to obtain a mixed solution ⑶ Take 100ml, 0 ℃ deionized water into beaker two, and slowly add the mixture obtained in step ⑵ into beaker two, then put the beaker two in a 93 ℃ water bath, stirring for 0.5h; ⑷from the water bath Take out beaker 2 from the pot and add 80ml of deionized water to beaker 2 to stop the reaction. After standing for 15 minutes, add 15ml of 20% hydrogen peroxide to beaker 2. After reacting for 15 minutes, add 40ml of 10% hydrochloric acid to beaker 2. Obtain the reactant; (5) Centrifuge and wash the reactant at low speed to remove excess acid and by-products, then disperse the neutral graphite oxide in water after washing, sonicate at 180W for 40min, and rotate at 2500rpm after the end of the ultrasound After centrifugation for 30 minutes, the obtained upper layer is the graphene oxide suspension, which is filtered, washed, and dried to obtain graphene with a low degree of oxidation. Low-oxidation graphene is a multilayer graphene, the number of layers is ≤10, and the thickness is within 5nm.

[0067] According to the molar ratio of 2.05:1, take the non-ionic self-emulsifying epoxy curing agent and low-oxidation graphene and mix them uniformly, and carry out the covalent graft modification reaction at 63℃ for 3.5h to obtain graphene-waterborne epoxy high dispersion system.

[0068] The graphene-waterborne epoxy high dispersion system synthesized by the above method is used to prepare ultra-high strength concrete. The specific preparation method of ultra-high-strength concrete is as follows: ①According to the mass percentage, take 23% of the sand that has passed the 80-mesh sieve, 32% of the fine stones with a particle size of less than 25mm, 442% of Portland cement, and 3% of additives to form a solid component; ②According to the mass percentage, take 38% graphene-waterborne epoxy high dispersion system and 62% water to form the liquid component; ③According to the mass ratio of 1:6, take the liquid component and the solid component, mix and stir the two to obtain a super High-strength concrete. The additives are composed of the following mass percentages of raw materials: 60% polycarboxylic acid type water reducing agent Q801, 10% mid-late expansion agent AEA, 15% defoamer Nopco 154, 15% powder, and powder can be pulverized coal Mixtures of ash, mineral powder, silicon powder, etc. The graphene-waterborne epoxy high dispersion system synthesized by the above method is used to prepare a waterborne epoxy anticorrosive coating. The specific preparation method of waterborne epoxy anticorrosive coating is as follows: (a) Take 94% waterborne epoxy resin emulsion with 50% solid content, 5% deionized water and 1% auxiliary agent according to the mass percentage, and mix well and react at room temperature. 5min, get component A; (b) take 88% graphene-waterborne epoxy high dispersion system, 8% deionized water and 4% auxiliary agent 2 according to mass percentage, mix well and react at room temperature for 5min to get component B (C) Zinc powder that has passed through a sieve of 500 mesh or more is used as component C. According to the mass ratio of 3:1:3, mix component A, component B and component C, and stir to obtain a water-based epoxy anticorrosive coating. Among them, the first and second additives are at least one of leveling agent PUR-40, defoaming agent T-4505, and substrate wetting agent BYK346.