Hindered phenol attapulgite modified epoxy resin anti-aging floor paint and preparation method thereof

Abstract

The invention relates to the technical field of epoxy resin, and discloses hindered phenol attapulgite modified epoxy resin anti-aging floor paint, which is prepared by the following steps: reacting epoxidized attapulgite with hydroxyl-terminated polybutadiene to obtain hydroxyl-terminated polybutadiene modified attapulgite, reacting the hydroxyl-terminated polybutadiene modified attapulgite with maleic anhydride to obtain carboxylated polybutadiene modified attapulgite, and further reacting the carboxylated polybutadiene modified attapulgite with 3, 3 '-dihydroxy-terminated polybutadiene to obtain the hindered phenol attapulgite modified epoxy resin anti-aging floor paint. The hindered phenol-based attapulgite modified epoxy resin anti-aging floor paint is prepared by reacting the hindered phenol-based attapulgite and the polybutadiene with 1, 5-di-tert-butyl-4-hydroxybenzylamine to obtain hindered phenol-based attapulgite modified attapulgite, and mixing the hindered phenol-based attapulgite modified attapulgite with the epoxy resin emulsion, and the hindered phenol-based attapulgite modified epoxy resin anti-aging floor paint is prepared finally. The hindered phenol can be combined with free radicals generated in the oxidation process of the epoxy resin to terminate chain growth in the oxidation process of the epoxy resin and finally play a role in delaying oxidation of the composite epoxy resin floor paint, so that the comprehensive properties such as mechanical properties, mechanical properties and oxidation resistance of the composite epoxy resin floor paint are effectively enhanced.

Description

Technical Field

[0001] The invention relates to the technical field of epoxy resins, in particular to a hindered phenol-based attapulgite-modified epoxy resin anti-aging floor paint and a preparation method thereof. Background Art

[0002] Epoxy resin floor paint is a polymer floor paint with excellent properties such as wear resistance, corrosion resistance, and oil resistance. With the continuous improvement of market requirements, epoxy resin floor paint has gradually been given multiple functions such as antibacterial and flame retardant, and is widely used in modern buildings. However, the epoxy resin matrix itself is brittle and prone to stress cracking, and oxidation and other phenomena will occur after long-term use. Therefore, it is necessary to modify the traditional epoxy resin. In modern science, filling modification is the most economical and effective means of modifying polymer materials in all aspects. Whether it is inorganic nanomaterial filling or polymer organic filling, it can have a good modification effect. Combining the two to form a combined filler can further enhance the comprehensive performance of the epoxy resin matrix, which is the current research hotspot.

[0003] With the emergence of nanotechnology, the functions of attapulgite nanoclay have been gradually discovered. Its high strength, good biocompatibility and various excellent properties make it show great application potential in the field of organic polymer material fillers. Chinese patents such as CN102702688B and CN105694653A disclose feasible methods of adding attapulgite into epoxy resin matrix to enhance the mechanical and other comprehensive properties of epoxy resin. However, most of these patents adopt physical blending methods, and no functional modification of attapulgite is performed, which cannot improve the problem of poor dispersibility of attapulgite, and the modification effect is often not significant enough. Therefore, it is necessary to modify the attapulgite, use the hydroxyl groups on its surface, further introduce functional molecules such as hindered phenols and polybutadiene, enhance the functionality of attapulgite, and facilitate the further application of attapulgite.

[0004] 1. Technical issues to be resolved In view of the deficiencies in the prior art, the present invention provides a hindered phenol-based attapulgite-modified epoxy resin anti-aging floor paint and a preparation method thereof, which solves the problems that the epoxy resin floor paint has poor toughness and weak resistance to thermal oxidative aging.

[0005] (II) Technical solution To achieve the above object, the present invention provides the following technical solution: a hindered phenol-based attapulgite-modified epoxy resin anti-aging floor paint, and the preparation method of the hindered phenol-based attapulgite-modified epoxy resin anti-aging floor paint comprises the following steps: (1) Add 1-4 g of attapulgite to 200-650 mL of toluene solvent, disperse evenly by ultrasonication, then add 0.05-0.1 g of 3-(2,3-epoxypropoxy)propyltrimethoxysilane, mix evenly and transfer to an oil bath, raise the temperature to 60-80°C, stir and react for 4-12 hours, centrifuge, wash and dry after the reaction is completed to obtain epoxidized attapulgite; (2) adding xylene solvent and epoxidized attapulgite into the reactor, performing ultrasonic dispersion for 20-40 minutes, continuing to add hydroxyl-terminated polybutadiene and a catalyst, and reacting at a constant temperature of 70-90° C. for 2-8 hours. After the reaction is completed, performing reduced pressure distillation, methanol precipitation, washing and drying to obtain hydroxyl-terminated polybutadiene-modified attapulgite; (3) Adding ethyl acetate solvent and hydroxyl-terminated polybutadiene-modified attapulgite to the reactor, performing ultrasonic dispersion until completely dissolved, then continuing to add maleic anhydride and catalyst, mixing evenly and transferring to an oil bath, reacting at 90-110° C. for 4-16 hours, centrifuging after the reaction, washing and drying to obtain carboxyl-terminated polybutadiene-modified attapulgite; (4) adding tetrahydrofuran solvent and carboxyl-terminated polybutadiene-modified attapulgite into a reactor, dispersing them uniformly by ultrasonication, adding 3,5-di-tert-butyl-4-hydroxybenzylamine and a catalyst, mixing them uniformly, and transferring them to an oil bath pot, stirring and reacting at 20-40° C. for 6-24 hours, centrifuging, washing and drying after the reaction is completed, and obtaining hindered phenol-based polybutadiene-modified attapulgite; (5) Add epoxy resin emulsion, hindered phenol-based polybutadiene modified attapulgite, 18-30% of curing agent 4,4-diaminodiphenylmethane, 1-3% of defoaming agent polyoxypropylene glycerol ether and 0.5-2% of leveling agent polydimethylsiloxane into a high-speed mixer, mix well and package to obtain hindered phenol-based attapulgite modified epoxy resin anti-aging floor paint.

[0006] Preferably, in step (2), the mass ratio of xylene, epoxidized attapulgite, hydroxy-terminated polybutadiene and catalyst is 650-2000:10:8-25:0.05-0.16.

[0007] Preferably, the catalyst in step (2) is boron trifluoride etherate complex (BF3-Et2O).

[0008] Preferably, in step (3), the mass ratio of ethyl acetate, hydroxyl-terminated polybutadiene-modified attapulgite, maleic anhydride and catalyst is 200-650:10:0.6-2:0.03-0.06.

[0009] Preferably, the catalyst in step (3) is p-toluenesulfonic acid (PTS).

[0010] Preferably, in step (4), the mass ratio of cyclohexane, ethanol, carboxyl-terminated polybutadiene-modified attapulgite, 3,5-di-tert-butyl-4-hydroxybenzylamine and catalyst is 300-850:100-300:10:0.8-2.5:0.04-0.08.

[0011] Preferably, the catalyst in step (4) is pyridine (Py).

[0012] Preferably, in step (5), the mass ratio of the epoxy resin emulsion to the hindered phenol-based polybutadiene-modified attapulgite is 100:1-6.

[0013] 3. Beneficial technical effects Compared with the prior art, the present invention has the following beneficial technical effects: The hindered phenol-based attapulgite modified epoxy resin anti-aging floor paint comprises a large number of epoxy groups on the surface of the attapulgite modified by 3-(2,3-epoxypropoxy)propyltrimethoxysilane, which can undergo a ring-opening reaction with the terminal hydroxyl group in the terminal hydroxyl polybutadiene under the catalytic action of a catalyst boron trifluoride ether complex to obtain the terminal hydroxyl polybutadiene modified attapulgite, and under the action of a catalyst p-toluenesulfonic acid, the terminal hydroxyl group in the terminal hydroxyl polybutadiene reacts with maleic anhydride to obtain the carboxylated polybutadiene modified attapulgite, and under the catalytic action of a catalyst pyridine, the carboxylated polybutadiene modified attapulgite further undergoes an amidation reaction with the amino group in 3,5-di-tert-butyl-4-hydroxybenzylamine to obtain the hindered phenol-based polybutadiene modified attapulgite, and through chemical connection, polybutadiene toughening macromolecules and hindered phenol antioxidant micromolecules are effectively covalently grafted on the surface of the attapulgite, which is conducive to the further application of the attapulgite.

[0014] The hindered phenol-based attapulgite modified epoxy resin anti-aging floor paint is prepared by mixing epoxy resin emulsion, hindered phenol-based polybutadiene modified attapulgite and various additives. When the composite floor paint is subjected to external force, cracks will be generated in the epoxy resin matrix. During the extension process, the cracks will meet the hindered phenol-based polybutadiene modified attapulgite and become stress concentration points, thereby causing a large number of silver streaks and shear bands. The shear bands can effectively inhibit the growth of silver streaks and the extension of cracks, thereby forming a good toughening effect on the epoxy resin matrix, and the attapulgite As a high-strength nanoparticle, attapulgite can absorb a large amount of stress and transfer the stress to the polybutadiene molecular chain, further enhancing the mechanical and mechanical properties of the composite epoxy resin floor paint. The phenolic hydroxyl groups in the hindered phenol groups grafted on the surface of attapulgite lose hydrogen atoms and become phenoloxy free radicals, which combine with the free radicals generated during the oxidation of epoxy resin, consume a large number of free radicals, and then terminate the chain growth during the oxidation of epoxy resin, and finally delay the oxidation of the composite epoxy resin floor paint, thereby effectively enhancing the comprehensive properties of the composite epoxy resin floor paint such as mechanics, mechanical and anti-oxidation. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] Figure 1 Schematic diagram of the reaction between epoxidized attapulgite and hydroxy-terminated polybutadiene.

[0016] Figure 2 Schematic diagram of the reaction between hydroxy-terminated polybutadiene-modified attapulgite and maleic anhydride.

[0017] Figure 3 It is a schematic diagram of the reaction of carboxyl-terminated polybutadiene-modified attapulgite and 3,5-di-tert-butyl-4-hydroxybenzylamine. DETAILED DESCRIPTION

[0018] To achieve the above object, the present invention provides the following specific implementation methods and examples: A hindered phenol-based attapulgite-modified epoxy resin anti-aging floor paint, the preparation method of which comprises the following steps: (1) Add 1-4 g of attapulgite to 200-650 mL of toluene solvent, disperse evenly by ultrasonication, then add 0.05-0.1 g of 3-(2,3-epoxypropoxy)propyltrimethoxysilane, mix evenly and transfer to an oil bath, raise the temperature to 60-80°C, stir and react for 4-12 hours, centrifuge, wash and dry after the reaction is completed to obtain epoxidized attapulgite; (2) Adding xylene solvent and epoxidized attapulgite into a reactor, ultrasonically dispersing for 20-40 minutes, continuing to add terminal hydroxyl polybutadiene and boron trifluoride ether complex, wherein the mass ratio of xylene, epoxidized attapulgite, terminal hydroxyl polybutadiene and boron trifluoride ether complex is 650-2000:10:8-25:0.05-0.16, and reacting at a constant temperature of 70-90°C for 2-8 hours. After the reaction is completed, vacuum distillation, methanol precipitation, washing and drying are performed to obtain terminal hydroxyl polybutadiene modified attapulgite; (3) Adding ethyl acetate solvent and hydroxyl-terminated polybutadiene-modified attapulgite into the reactor, ultrasonically dispersing until completely dissolved, and then continuing to add maleic anhydride and p-toluenesulfonic acid, wherein the mass ratio of ethyl acetate, hydroxyl-terminated polybutadiene-modified attapulgite, maleic anhydride and p-toluenesulfonic acid is 200-650:10:0.6-2:0.03-0.06, mixing evenly and transferring to an oil bath pot, reacting at 90-110°C for 4-16h, centrifuging after the reaction, washing and drying to obtain carboxyl-terminated polybutadiene-modified attapulgite; (4) Add tetrahydrofuran solvent and carboxyl-terminated polybutadiene-modified attapulgite into the reactor, disperse them uniformly by ultrasonication, and continue to add 3,5-di-tert-butyl-4-hydroxybenzylamine and pyridine, wherein the mass ratio of cyclohexane, ethanol, isocyanate-based polybutadiene-modified attapulgite, 3,5-di-tert-butyl-4-hydroxybenzylamine and pyridine is 300-850:100-300:10:0.8-2.5:0.04-0.08, mix them uniformly and transfer them to an oil bath, stir and react at 20-40°C for 6-24h, centrifuge after the reaction, wash and dry to obtain hindered phenol-based polybutadiene-modified attapulgite; (5) Add epoxy resin emulsion, hindered phenol-based polybutadiene modified attapulgite, 18-30% of curing agent 4,4-diaminodiphenylmethane, 1-3% of defoaming agent polyoxypropylene glycerol ether and 0.5-2% of leveling agent polydimethylsiloxane in a mass ratio of 100:1-6 into a high-speed mixer, mix well and package to obtain hindered phenol-based attapulgite modified epoxy resin anti-aging floor paint.

[0019] Example 1

[0020] (1) Add 1 g of attapulgite to 200 mL of toluene solvent, disperse evenly by ultrasonication, then add 0.05 g of 3-(2,3-epoxypropoxy)propyltrimethoxysilane, mix evenly and transfer to an oil bath, raise the temperature to 60 °C, stir and react for 4 h, centrifuge after the reaction, wash and dry to obtain epoxidized attapulgite; (2) Add 380 mL of xylene solvent and 5 g of epoxidized attapulgite into the reactor, perform ultrasonic dispersion for 20 min, continue to add 4 g of terminal hydroxyl polybutadiene and 0.025 g of boron trifluoride ether complex, and react at 70 ° C for 2 h. After the reaction, perform vacuum distillation, methanol precipitation, washing and drying to obtain terminal hydroxyl polybutadiene modified attapulgite; (3) Add 115 mL of ethyl acetate solvent and 5 g of terminal hydroxyl polybutadiene modified attapulgite into the reactor, disperse by ultrasonic until completely dissolved, then continue to add 0.3 g of maleic anhydride and 0.015 g of p-toluenesulfonic acid, mix well and transfer to an oil bath, react at 90 °C for 4 h, centrifuge after the reaction, wash and dry to obtain terminal carboxyl polybutadiene modified attapulgite; (4) Add 270 mL of tetrahydrofuran solvent and 5 g of carboxyl-terminated polybutadiene-modified attapulgite into the reactor, disperse them evenly by ultrasonication, continue to add 0.4 g of 3,5-di-tert-butyl-4-hydroxybenzylamine and 0.02 g of pyridine, mix evenly and transfer to an oil bath, stir and react at 20°C for 6 h, centrifuge, wash and dry after the reaction to obtain hindered phenol-based polybutadiene-modified attapulgite; (5) Add 50 g of epoxy resin emulsion, 0.5 g of hindered phenol-based polybutadiene-modified attapulgite, 18% of curing agent 4,4-diaminodiphenylmethane, 1% of defoaming agent polyoxypropylene glycerol ether and 0.5% of leveling agent polydimethylsiloxane into a high-speed mixer, mix well and package to obtain hindered phenol-based attapulgite-modified epoxy resin anti-aging floor paint.

[0021] Example 2

[0022] (1) Add 2 g of attapulgite to 300 mL of toluene solvent, disperse evenly by ultrasonication, then add 0.06 g of 3-(2,3-epoxypropoxy)propyltrimethoxysilane, mix evenly and transfer to an oil bath, raise the temperature to 65 °C, stir and react for 6 h, centrifuge, wash and dry after the reaction to obtain epoxidized attapulgite; (2) Add 450 mL of xylene solvent and 5 g of epoxidized attapulgite into the reactor, perform ultrasonic dispersion for 25 min, continue to add 6 g of terminal hydroxyl polybutadiene and 0.035 g of boron trifluoride ether complex, and react at 75 °C for 3 h. After the reaction, perform vacuum distillation, methanol precipitation, washing and drying to obtain terminal hydroxyl polybutadiene modified attapulgite; (3) Add 200 mL of ethyl acetate solvent and 5 g of terminal hydroxyl polybutadiene modified attapulgite into the reactor, disperse by ultrasonic until completely dissolved, then continue to add 0.45 g of maleic anhydride and 0.02 g of p-toluenesulfonic acid, mix well and transfer to an oil bath, react at 95 °C for 6 h, centrifuge after the reaction, wash and dry to obtain terminal carboxyl polybutadiene modified attapulgite; (4) Add 300 mL of tetrahydrofuran solvent and 5 g of terminal carboxyl polybutadiene modified attapulgite into the reactor, disperse them evenly by ultrasonication, continue to add 0.6 g of 3,5-di-tert-butyl-4-hydroxybenzylamine and 0.025 g of pyridine, mix evenly and transfer to an oil bath, stir and react at 25 °C for 8 h, centrifuge after the reaction, wash and dry to obtain hindered phenol-based polybutadiene modified attapulgite; (5) Add 50 g of epoxy resin emulsion, 1.5 g of hindered phenol-based polybutadiene-modified attapulgite, 20% of curing agent 4,4-diaminodiphenylmethane, 1.5% of defoaming agent polyoxypropylene glycerol ether and 0.8% of leveling agent polydimethylsiloxane into a high-speed mixer, mix well and package to obtain hindered phenol-based attapulgite-modified epoxy resin anti-aging floor paint.

[0023] Example 3

[0024] (1) Add 2.5 g of attapulgite to 400 mL of toluene solvent, disperse evenly by ultrasonication, then add 0.08 g of 3-(2,3-epoxypropoxy)propyltrimethoxysilane, mix evenly and transfer to an oil bath, raise the temperature to 70 °C, stir and react for 8 h, centrifuge, wash and dry after the reaction to obtain epoxidized attapulgite; (2) Add 600 mL of xylene solvent and 5 g of epoxidized attapulgite into the reactor, perform ultrasonic dispersion for 30 min, continue to add 8 g of terminal hydroxyl polybutadiene and 0.05 g of boron trifluoride ether complex, and react at 80 °C for 4 h. After the reaction, perform vacuum distillation, methanol precipitation, washing and drying to obtain terminal hydroxyl polybutadiene modified attapulgite; (3) Add 250 mL of ethyl acetate solvent and 5 g of terminal hydroxyl polybutadiene modified attapulgite into the reactor, disperse by ultrasonic until completely dissolved, then continue to add 0.6 g of maleic anhydride and 0.024 g of p-toluenesulfonic acid, mix well and transfer to an oil bath, react at 100 °C for 8 h, centrifuge after the reaction, wash and dry to obtain terminal carboxyl polybutadiene modified attapulgite; (4) Add 350 mL of tetrahydrofuran solvent and 5 g of terminal carboxyl polybutadiene modified attapulgite into the reactor, disperse them evenly by ultrasonication, continue to add 0.8 g of 3,5-di-tert-butyl-4-hydroxybenzylamine and 0.03 g of pyridine, mix evenly and transfer to an oil bath, stir and react at 30°C for 12 h, centrifuge after the reaction, wash and dry to obtain hindered phenol-based polybutadiene modified attapulgite; (5) Add 50 g of epoxy resin emulsion, 2 g of hindered phenol-based polybutadiene-modified attapulgite, 24% of curing agent 4,4-diaminodiphenylmethane, 2% of defoaming agent polyoxypropylene glycerol ether and 1.2% of leveling agent polydimethylsiloxane into a high-speed mixer, mix well and package to obtain hindered phenol-based attapulgite-modified epoxy resin anti-aging floor paint.

[0025] Example 4

[0026] (1) Add 3 g of attapulgite to 500 mL of toluene solvent, disperse evenly by ultrasonication, then add 0.09 g of 3-(2,3-epoxypropoxy)propyltrimethoxysilane, mix evenly and transfer to an oil bath, raise the temperature to 75 °C, stir and react for 9 h, centrifuge, wash and dry after the reaction is completed to obtain epoxidized attapulgite; (2) Add 800 mL of xylene solvent and 5 g of epoxidized attapulgite into the reactor, perform ultrasonic dispersion for 35 min, continue to add 10 g of terminal hydroxyl polybutadiene and 0.06 g of boron trifluoride ether complex, and react at 85 °C for 6 h. After the reaction, perform vacuum distillation, methanol precipitation, washing and drying to obtain terminal hydroxyl polybutadiene modified attapulgite; (3) Add 360 mL of ethyl acetate solvent and 5 g of terminal hydroxyl polybutadiene modified attapulgite into the reactor, and then add 0.8 g of maleic anhydride and 0.028 g of p-toluenesulfonic acid to the reactor. After mixing evenly, transfer the mixture to an oil bath and react at 105 °C for 12 h. After the reaction is completed, centrifuge, wash and dry the mixture to obtain terminal carboxyl polybutadiene modified attapulgite. (4) Add 400 mL of tetrahydrofuran solvent and 5 g of terminal carboxyl polybutadiene modified attapulgite into the reactor, disperse them evenly by ultrasonication, continue to add 1 g of 3,5-di-tert-butyl-4-hydroxybenzylamine and 0.035 g of pyridine, mix evenly and transfer to an oil bath, stir and react at 35°C for 18 h, centrifuge after the reaction, wash and dry to obtain hindered phenol-based polybutadiene modified attapulgite; (5) Add 50 g of epoxy resin emulsion, 2.5 g of hindered phenol-based polybutadiene-modified attapulgite, 25% of curing agent 4,4-diaminodiphenylmethane, 2.5% of defoaming agent polyoxypropylene glycerol ether and 1.6% of leveling agent polydimethylsiloxane into a high-speed mixer, mix well and package to obtain hindered phenol-based attapulgite-modified epoxy resin anti-aging floor paint.

[0027] Example 5

[0028] (1) Add 4 g of attapulgite to 650 mL of toluene solvent, disperse evenly by ultrasonication, then add 0.1 g of 3-(2,3-epoxypropoxy)propyltrimethoxysilane, mix evenly and transfer to an oil bath, raise the temperature to 80 °C, stir and react for 12 h, centrifuge, wash and dry after the reaction to obtain epoxidized attapulgite; (2) Add 1150 mL of xylene solvent and 5 g of epoxidized attapulgite into the reactor, perform ultrasonic dispersion for 40 min, continue to add 12.5 g of terminal hydroxyl polybutadiene and 0.08 g of boron trifluoride ether complex, and react at 90 ° C for 8 h. After the reaction is completed, vacuum distillation, methanol precipitation, washing and drying are performed to obtain terminal hydroxyl polybutadiene modified attapulgite; (3) Add 360 mL of ethyl acetate solvent and 5 g of terminal hydroxyl polybutadiene modified attapulgite into the reactor, disperse by ultrasonic until completely dissolved, then continue to add 1 g of maleic anhydride and 0.03 g of p-toluenesulfonic acid, mix well and transfer to an oil bath, react at 110 ° C for 16 h, centrifuge after the reaction, wash and dry to obtain terminal carboxyl polybutadiene modified attapulgite; (4) Add 470 mL of tetrahydrofuran solvent and 5 g of carboxyl-terminated polybutadiene-modified attapulgite into the reactor, disperse them evenly by ultrasonication, continue to add 1.25 g of 3,5-di-tert-butyl-4-hydroxybenzylamine and 0.04 g of pyridine, mix evenly and transfer to an oil bath, stir and react at 40 °C for 24 h, centrifuge after the reaction, wash and dry to obtain hindered phenol-based polybutadiene-modified attapulgite; (5) Add 50 g of epoxy resin emulsion, 3 g of hindered phenol-based polybutadiene-modified attapulgite, 30% of curing agent 4,4-diaminodiphenylmethane, 3% of defoaming agent polyoxypropylene glycerol ether and 2% of leveling agent polydimethylsiloxane into a high-speed mixer, mix well and package to obtain hindered phenol-based attapulgite-modified epoxy resin anti-aging floor paint.

[0029] Comparative Example 1 (1) Add 1.5 g of attapulgite to 240 mL of toluene solvent, disperse evenly by ultrasonication, then add 0.06 g of 3-(2,3-epoxypropoxy)propyltrimethoxysilane, mix evenly and transfer to an oil bath, raise the temperature to 65 °C, stir and react for 5 h, centrifuge, wash and dry after the reaction to obtain epoxidized attapulgite; (2) Add 400 mL of xylene solvent and 5 g of epoxidized attapulgite into the reactor, perform ultrasonic dispersion for 25 min, continue to add 5 g of terminal hydroxyl polybutadiene and 0.03 g of boron trifluoride ether complex, and react at 75 °C for 3 h. After the reaction, perform vacuum distillation, methanol precipitation, washing and drying to obtain terminal hydroxyl polybutadiene modified attapulgite; (3) Add 50 g of epoxy resin emulsion, 0.8 g of terminal hydroxyl polybutadiene modified attapulgite, 20% of curing agent 4,4-diaminodiphenylmethane, 1.2% of defoaming agent polyoxypropylene glycerol ether and 1% of leveling agent polydimethylsiloxane into a high-speed mixer, mix well and package to obtain attapulgite modified epoxy resin floor paint.

[0030] The composite floor paints in the examples and comparative examples were placed in a mold for curing and prepared into samples with a size of 4 cm×4 cm. The impact strength of the composite floor paints was tested using a TS-XB-A impact strength tester.

[0031]

[0032] The composite floor paint in the embodiment and the comparative example was placed in a mold for curing, and prepared into a sample with a specification of 4 cm×4 cm, which was then placed in an oven at 120° C. The peel strength of the composite floor paint before and after baking for 48 hours was tested using an ASR-1025B peel strength tester, and the peel strength retention rate was calculated.

[0033]

Claims

1. A hindered phenol-based attapulgite-modified epoxy resin anti-aging floor paint, characterized in that: The following steps are involved: (1) Add 1-4 g of attapulgite to 200-650 mL of toluene solvent, disperse evenly by ultrasonication, then add 0.05-0.1 g of 3-(2,3-epoxypropoxy)propyltrimethoxysilane, mix evenly and transfer to an oil bath, raise the temperature to 60-80°C, stir and react for 4-12 hours, centrifuge, wash and dry after the reaction is completed to obtain epoxidized attapulgite; (2) Adding epoxidized attapulgite to xylene solvent, ultrasonically dispersing for 20-40 minutes, continuing to add hydroxyl-terminated polybutadiene and a catalyst, and reacting at a constant temperature of 70-90° C. for 2-8 hours. After the reaction is completed, vacuum distillation, methanol precipitation, washing and drying are performed to obtain hydroxyl-terminated polybutadiene-modified attapulgite; (3) Adding the hydroxy-terminated polybutadiene-modified attapulgite to the ethyl acetate solvent, dispersing by ultrasonic until it is completely dissolved, then adding maleic anhydride and a catalyst, mixing evenly, transferring to an oil bath, reacting at 90-110° C. for 4-16 hours, centrifuging after the reaction, washing and drying to obtain the carboxyl-terminated polybutadiene-modified attapulgite; (4) Adding carboxyl-terminated polybutadiene-modified attapulgite to tetrahydrofuran solvent, uniformly dispersing by ultrasonication, continuing to add 3,5-di-tert-butyl-4-hydroxybenzylamine and a catalyst, mixing evenly and transferring to an oil bath, stirring and reacting at 20-40° C. for 6-24 hours, centrifuging after the reaction, washing and drying to obtain hindered phenol-based polybutadiene-modified attapulgite; (5) Add epoxy resin emulsion, hindered phenol-based polybutadiene modified attapulgite, 18-30% of curing agent 4,4-diaminodiphenylmethane, 1-3% of defoaming agent polyoxypropylene glycerol ether and 0.5-2% of leveling agent polydimethylsiloxane into a high-speed mixer, mix well and package to obtain hindered phenol-based attapulgite modified epoxy resin anti-aging floor paint.

2. The hindered phenol-based attapulgite-modified epoxy resin anti-aging floor paint according to claim 1, characterized in that: In the step (2), the mass ratio of xylene, epoxidized attapulgite, hydroxy-terminated polybutadiene and catalyst is 650-2000:10:8-25:0.05-0.

16.

3. The hindered phenol-based attapulgite-modified epoxy resin anti-aging floor paint according to claim 1, characterized in that: The catalyst in step (2) is boron trifluoride etherate complex.

4. The hindered phenol-based attapulgite-modified epoxy resin anti-aging floor paint according to claim 1, characterized in that: In the step (3), the mass ratio of ethyl acetate, hydroxyl-terminated polybutadiene-modified attapulgite, maleic anhydride and catalyst is 200-650:10:0.6-2:0.03-0.

06.

5. The hindered phenol-based attapulgite-modified epoxy resin anti-aging floor paint according to claim 1, characterized in that: The catalyst in step (3) is p-toluenesulfonic acid.

6. The hindered phenol-based attapulgite-modified epoxy resin anti-aging floor paint according to claim 1, characterized in that: In the step (4), the mass ratio of tetrahydrofuran, carboxyl-terminated polybutadiene-modified attapulgite, 3,5-di-tert-butyl-4-hydroxybenzylamine and catalyst is 300-850:10:0.8-2.5:0.04-0.

08.

7. The hindered phenol-based attapulgite-modified epoxy resin anti-aging floor paint according to claim 1, characterized in that: The catalyst in step (4) is pyridine.

8. The hindered phenol-based attapulgite-modified epoxy resin anti-aging floor paint according to claim 1, characterized in that: In the step (5), the mass ratio of the epoxy resin emulsion to the hindered phenol-based polybutadiene-modified attapulgite is 100:1-6.

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