Attapulgite-epoxy resin composite high-strength floor paint and preparation method thereof

Abstract

The invention relates to the technical field of epoxy resin, and discloses an attapulgite-epoxy resin composite high-strength floor paint, which is characterized in that attapulgite reacts with 3-mercaptopropyltriethoxysilane to obtain sulfhydrylated attapulgite, methoxyhydroquinone, 4, 4 '-dihydroxypropyltriethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltriethoxysilane, 4 The preparation method comprises the following steps: carrying out a polymerization reaction on 4, 4 '-difluorodiphenyl sulfone and 4, 4'-sulfonyl bis [2-(2-propenyl)] phenol to obtain allylated polyether sulfone, carrying out a reaction on the sulfhydrylated attapulgite and the allylated polyether sulfone to obtain polyether sulfone modified attapulgite, and mixing the polyether sulfone modified attapulgite with epoxy resin to obtain the attapulgite-epoxy resin composite high-strength floor paint. The attapulgite and the polyethersulfone can enhance the capability of absorbing external stress energy of the composite epoxy resin floor paint, and further hinder generation and expansion of cracks, thereby further enhancing the tensile strength and other mechanical properties of the composite epoxy resin floor paint, and effectively expanding the application range of the composite epoxy resin floor paint.

Description

Technical Field

[0001] The invention relates to the technical field of epoxy resins, in particular to an attapulgite-epoxy resin composite high-strength floor paint and a preparation method thereof. Background Art

[0002] Epoxy resin is one of the most widely used thermosetting resins in high-performance fiber-reinforced composites. It has been widely used in many fields such as adhesives, construction, machinery and coatings. Its excellent chemical stability, high and low temperature resistance and electrical insulation make it a good polymer resin floor paint. However, traditional epoxy resin itself has problems such as brittleness and poor impact toughness, which makes it difficult to meet the requirements of engineering technology, greatly limiting its research and development. Therefore, the toughening and modification of epoxy resin has always been a hot research topic. In recent years, the rapid development of inorganic nanomaterials has brought new ideas to the toughening and modification of epoxy resin. By filling inorganic nanomaterials with excellent performance into the epoxy resin matrix and combining the advantages of inorganic nanomaterials, the problems of brittleness and low impact strength of epoxy resin can be effectively improved, thereby further expanding the application range of epoxy resin floor paint.

[0003] Attapulgite is a clay mineral with a special layered chain structure. Studies have found that when attapulgite is filled into an organic polymer matrix, the resulting composite material will have greatly improved properties in terms of toughness, strength and modulus. Therefore, attapulgite has great application value in the field of polymer filling. Chinese patents such as CN102702688B disclose a feasible method for filling attapulgite into an epoxy resin matrix to form a composite material with excellent gas barrier properties and mechanical properties. However, most of these patents use simple physical mixing methods to fill attapulgite into an organic polymer matrix without considering the poor dispersibility of attapulgite itself in the polymer matrix. In addition, the functionality of attapulgite is not enhanced, resulting in the modification effect of the obtained composite material is not obvious. Therefore, it is necessary to modify the attapulgite to improve its dispersibility while enhancing its functionality, thereby expanding the application range of attapulgite. Summary of the invention

[0004] In view of the deficiencies in the prior art, the present invention provides a attapulgite-epoxy resin composite high-strength floor paint and a preparation method, which improves the phenomenon that the performance of the epoxy resin floor paint, such as the impact strength and the tensile strength, is relatively poor.

[0005] To achieve the above object, the present invention provides the following technical solution: a attapulgite-epoxy resin composite high-strength floor paint, and the preparation method of the attapulgite-epoxy resin composite high-strength floor paint comprises the following steps: (1) Add ethanol solvent and attapulgite to the reactor, and after ultrasonic dispersion, continue to add 3-mercaptopropyltriethoxysilane, stir evenly and transfer to an oil bath, raise the temperature to 60-80°C, react for 2-8 hours, centrifuge after the reaction, wash and dry to obtain thiolated attapulgite; (2) Add toluene solvent, N-methylpyrrolidone solvent, methoxyhydroquinone, 4,4'-difluorodiphenyl sulfone, 4,4'-sulfonylbis[2-(2-propenyl)]phenol and potassium carbonate into a reactor, stir and mix evenly, then transfer to an oil bath, fill with nitrogen to remove air, increase the temperature to react, and after the reaction is completed, filter, wash and dry to obtain allylated polyether sulfone; (3) Add N,N-dimethylformamide solvent and thiolated attapulgite into the reactor, and after ultrasonic dispersion for 20-40 minutes, continue to add allylated polyethersulfone and benzoin dimethyl ether, stir until completely dissolved, transfer to an oil bath, irradiate the reaction system with ultraviolet light, react at 20-40°C for 2-6 hours, filter, purify, wash and dry after the reaction to obtain polyethersulfone modified attapulgite; (4) Add epoxy resin emulsion, polyethersulfone modified attapulgite, 25-40% of curing agent polyamide, 1-5% of film-forming aid dodecyl alcohol ester and 0.5-1.5% of defoaming agent polydimethylsiloxane into a high-speed mixer, mix them evenly at high speed and then package them to obtain attapulgite-epoxy resin composite high-strength floor paint.

[0006] Preferably, in step (1), the mass ratio of ethanol solvent, attapulgite and 3-mercaptopropyltriethoxysilane is 300-750:10:1.5-4.

[0007] Preferably, in step (2), the mass ratio of toluene solvent, N-methylpyrrolidone solvent, methoxyhydroquinone, 4,4'-difluorodiphenyl sulfone, 4,4'-sulfonylbis[2-(2-propenyl)]phenol and potassium carbonate is 150-400:200-600:4-10:10:0.6-1.4:3-7.5.

[0008] Preferably, the reaction temperature in step (2) is 140-180° C. and the reaction time is 8-24 h.

[0009] Preferably, in step (3), the mass ratio of N,N-dimethylformamide solvent, thiolated attapulgite, allylated polyethersulfone and benzoin dimethyl ether is 650-2000:10:18-35:0.2-0.6.

[0010] Preferably, in step (4), the mass ratio of the epoxy resin emulsion to the polyethersulfone modified attapulgite is 100:8-20.

[0011] Compared with the prior art, the present invention has the following beneficial technical effects: The present invention discloses an attapulgite-epoxy resin composite high-strength floor paint. The attapulgite surface contains a large number of hydroxyl groups. After being modified by 3-mercaptopropyltriethoxysilane, thiolated attapulgite is obtained. Under the action of a catalyst, potassium carbonate, methoxyhydroquinone, 4,4'-difluorodiphenyl sulfone and 4,4'-sulfonylbis[2-(2-propenyl)]phenol undergo a cross-linking polymerization reaction to obtain allylated polyethersulfone. Under the action of an initiator, benzoin dimethyl ether, the thiol in the thiolated attapulgite can undergo a click reaction with the alkenyl in the allylated polyethersulfone to obtain polyethersulfone-modified attapulgite. Thus, polyethersulfone macromolecules are covalently grafted on the surface of attapulgite nanoclay by chemical connection. By combining the advantages of the polyethersulfone macromolecules, the functionality of the attapulgite is enhanced, and the application range of the attapulgite is effectively expanded.

[0012] The attapulgite-epoxy resin composite high-strength floor paint is prepared by mixing epoxy resin and polyethersulfone modified attapulgite and various additives to finally prepare the attapulgite-epoxy resin composite high-strength floor paint. When the composite floor paint is subjected to external force impact after being cured, the cracks caused by the stress will be hindered by the attapulgite during the extension process, forcing the cracks to extend to the two ends of the attapulgite. At the same time, the attapulgite can disperse part of the stress into the polyethersulfone molecular chain, thereby improving the mechanical properties such as the impact strength of the composite epoxy resin floor paint to a certain extent. Polyethersulfone, as a rigid long chain, can promote the brittle-to-ductile transition of the epoxy resin matrix, and at the same time enhance the ability of the composite epoxy resin floor paint to absorb external stress energy, further hinder the occurrence and expansion of cracks, thereby further enhancing the mechanical properties such as the tensile strength of the composite epoxy resin floor paint, and effectively expanding the application range of the composite epoxy resin floor paint. DETAILED DESCRIPTION

[0013] To achieve the above object, the present invention provides the following specific implementation methods and examples: A attapulgite-epoxy resin composite high-strength floor paint, the preparation method of which comprises the following steps: (1) adding ethanol solvent and attapulgite into a reactor, and then adding 3-mercaptopropyltriethoxysilane after ultrasonic dispersion, wherein the mass ratio of ethanol solvent, attapulgite and 3-mercaptopropyltriethoxysilane is 300-750:10:1.5-4, stirring evenly and transferring to an oil bath, raising the temperature to 60-80°C, reacting for 2-8h, centrifuging after the reaction, washing and drying to obtain thiolated attapulgite; (2) Adding toluene solvent, N-methylpyrrolidone solvent, methoxyhydroquinone, 4,4'-difluorodiphenyl sulfone, 4,4'-sulfonylbis[2-(2-propenyl)]phenol and potassium carbonate in a mass ratio of 150-400:200-600:4-10:10:0.6-1.4:3-7.5 into a reactor, stirring and mixing evenly, transferring to an oil bath, filling with nitrogen to remove air, reacting at 140-180° C. for 8-24 hours, and filtering after the reaction, washing and drying to obtain allylated polyether sulfone; (3) Add N,N-dimethylformamide solvent and thiolated attapulgite into the reactor, and after ultrasonic dispersion for 20-40 minutes, continue to add allylated polyethersulfone and benzoin dimethyl ether, wherein the mass ratio of N,N-dimethylformamide solvent, thiolated attapulgite, allylated polyethersulfone and benzoin dimethyl ether is 650-2000:10:18-35:0.2-0.6, stir until completely dissolved, transfer to an oil bath, irradiate the reaction system with ultraviolet light, react at 20-40°C for 2-6 hours, filter, purify, wash and dry after the reaction to obtain polyethersulfone modified attapulgite; (4) Add epoxy resin emulsion and polyethersulfone modified attapulgite in a mass ratio of 100:8-20, as well as 25-40% of curing agent polyamide, 1-5% of film-forming aid dodecyl alcohol ester and 0.5-1.5% of defoaming agent polydimethylsiloxane into a high-speed mixer, mix them evenly at high speed and then package them to obtain attapulgite-epoxy resin composite high-strength floor paint. Example 1

[0014] (1) Add 200 mL of ethanol solvent and 5 g of attapulgite into the reactor, and after ultrasonic dispersion, continue to add 0.75 g of 3-mercaptopropyltriethoxysilane, stir evenly, and transfer to an oil bath pot, raise the temperature to 60 ° C, react for 2 h, centrifuge after the reaction, wash and dry to obtain thiolated attapulgite; (2) Add 90 mL of toluene solvent, 100 mL of N-methylpyrrolidone solvent, 2 g of methoxyhydroquinone, 5 g of 4,4'-difluorodiphenyl sulfone, 0.3 g of 4,4'-sulfonylbis[2-(2-propenyl)]phenol and 1.5 g of potassium carbonate into the reactor, stir and mix evenly, then transfer to an oil bath, fill with nitrogen to remove air, react at 140°C for 8 h, and after the reaction is completed, filter, wash and dry to obtain allylated polyether sulfone; (3) Add 345 mL of N,N-dimethylformamide solvent and 5 g of thiolated attapulgite into the reactor, and after ultrasonic dispersion for 20 min, continue to add 9 g of allylated polyethersulfone and 0.1 g of benzoin dimethyl ether, stir until completely dissolved, transfer to an oil bath, irradiate the reaction system with ultraviolet light, react at 20 ° C for 2 h, filter, purify, wash and dry after the reaction to obtain polyethersulfone modified attapulgite; (4) Add 50 g of epoxy resin emulsion, 4 g of polyethersulfone modified attapulgite, 12.5 g of curing agent polyamide, 0.5 g of film-forming aid dodecyl alcohol ester and 0.25 g of defoaming agent polydimethylsiloxane into a high-speed mixer, mix them evenly at high speed and then package to obtain attapulgite-epoxy resin composite high-strength floor paint. Example 2

[0015] (1) Add 260 mL of ethanol solvent and 5 g of attapulgite into the reactor, and after ultrasonic dispersion, continue to add 1 g of 3-mercaptopropyltriethoxysilane, stir evenly, and transfer to an oil bath pot, raise the temperature to 65 ° C, and react for 3 hours. After the reaction is completed, centrifuge, wash and dry to obtain thiolated attapulgite; (2) Add 120 mL of toluene solvent, 150 mL of N-methylpyrrolidone solvent, 2.8 g of methoxyhydroquinone, 5 g of 4,4'-difluorodiphenyl sulfone, 0.6 g of 4,4'-sulfonylbis[2-(2-propenyl)]phenol and 2 g of potassium carbonate into the reactor, stir and mix evenly, then transfer to an oil bath, fill with nitrogen to remove air, react at 150°C for 12 h, and after the reaction is completed, filter, wash and dry to obtain allylated polyether sulfone; (3) Add 500 mL of N,N-dimethylformamide solvent and 5 g of thiolated attapulgite into the reactor, and after ultrasonic dispersion for 25 min, continue to add 11 g of allylated polyethersulfone and 0.15 g of benzoin dimethyl ether, stir until completely dissolved, transfer to an oil bath, irradiate the reaction system with ultraviolet light, react at 25 ° C for 3 h, filter, purify, wash and dry after the reaction to obtain polyethersulfone modified attapulgite; (4) Add 50 g of epoxy resin emulsion, 5.5 g of polyethersulfone modified attapulgite, 14 g of curing agent polyamide, 1 g of film-forming aid dodecyl alcohol ester and 0.4 g of defoaming agent polydimethylsiloxane into a high-speed mixer, mix them evenly at high speed and then package to obtain attapulgite-epoxy resin composite high-strength floor paint. Example 3

[0016] (1) Add 350 mL of ethanol solvent and 5 g of attapulgite into the reactor, and after ultrasonic dispersion, continue to add 1.3 g of 3-mercaptopropyltriethoxysilane, stir evenly, and transfer to an oil bath pot, raise the temperature to 70 ° C, and react for 4 hours. After the reaction is completed, centrifuge, wash and dry to obtain thiolated attapulgite; (2) Add 160 mL of toluene solvent, 200 mL of N-methylpyrrolidone solvent, 3.4 g of methoxyhydroquinone, 5 g of 4,4'-difluorodiphenyl sulfone, 0.9 g of 4,4'-sulfonylbis[2-(2-propenyl)]phenol and 2.5 g of potassium carbonate into the reactor, stir and mix evenly, then transfer to an oil bath, fill with nitrogen to remove air, react at 160°C for 16 h, filter after the reaction, wash and dry to obtain allylated polyether sulfone; (3) Add 700 mL of N,N-dimethylformamide solvent and 5 g of thiolated attapulgite into the reactor, and after ultrasonic dispersion for 30 min, continue to add 13 g of allylated polyethersulfone and 0.2 g of benzoin dimethyl ether, stir until completely dissolved, transfer to an oil bath, irradiate the reaction system with ultraviolet light, react at 30 ° C for 4 h, filter, purify, wash and dry after the reaction to obtain polyethersulfone modified attapulgite; (4) Add 50 g of epoxy resin emulsion, 7 g of polyethersulfone modified attapulgite, 16 g of curing agent polyamide, 1.5 g of film-forming aid dodecyl alcohol ester and 0.5 g of defoaming agent polydimethylsiloxane into a high-speed mixer, mix them evenly at high speed and then package to obtain attapulgite-epoxy resin composite high-strength floor paint. Example 4

[0017] (1) Add 400 mL of ethanol solvent and 5 g of attapulgite into the reactor, and after ultrasonic dispersion, continue to add 1.6 g of 3-mercaptopropyltriethoxysilane, stir evenly, and transfer to an oil bath pot, raise the temperature to 75 ° C, and react for 6 hours. After the reaction is completed, centrifuge, wash and dry to obtain thiolated attapulgite; (2) Add 200 mL of toluene solvent, 240 mL of N-methylpyrrolidone solvent, 4.2 g of methoxyhydroquinone, 5 g of 4,4'-difluorodiphenyl sulfone, 1.3 g of 4,4'-sulfonylbis[2-(2-propenyl)]phenol and 3 g of potassium carbonate into the reactor, stir and mix evenly, then transfer to an oil bath, fill with nitrogen to remove air, react at 170°C for 20 h, filter after the reaction, wash and dry to obtain allylated polyether sulfone; (3) Add 850 mL of N,N-dimethylformamide solvent and 5 g of thiolated attapulgite into the reactor, and after ultrasonic dispersion for 35 min, continue to add 15 g of allylated polyethersulfone and 0.25 g of benzoin dimethyl ether, stir until completely dissolved, transfer to an oil bath, irradiate the reaction system with ultraviolet light, react at 35 ° C for 5 h, filter, purify, wash and dry after the reaction to obtain polyethersulfone modified attapulgite; (4) Add 50 g of epoxy resin emulsion, 8.5 g of polyethersulfone modified attapulgite, 18 g of curing agent polyamide, 2 g of film-forming aid dodecyl alcohol ester and 0.6 g of defoaming agent polydimethylsiloxane into a high-speed mixer, mix them evenly at high speed and then package to obtain attapulgite-epoxy resin composite high-strength floor paint. Example 5

[0018] (1) Add 475 mL of ethanol solvent and 5 g of attapulgite into the reactor, and after ultrasonic dispersion, continue to add 2 g of 3-mercaptopropyltriethoxysilane, stir evenly, and transfer to an oil bath pot, raise the temperature to 80 ° C, and react for 8 hours. After the reaction is completed, centrifuge, wash and dry to obtain thiolated attapulgite; (2) Add 230 mL of toluene solvent, 290 mL of N-methylpyrrolidone solvent, 5 g of methoxyhydroquinone, 5 g of 4,4'-difluorodiphenyl sulfone, 1.7 g of 4,4'-sulfonylbis[2-(2-propenyl)]phenol and 3.75 g of potassium carbonate into the reactor, stir and mix evenly, then transfer to an oil bath, fill with nitrogen to remove air, react at 180°C for 24 h, and after the reaction is completed, filter, wash and dry to obtain allylated polyether sulfone; (3) Add 1050 mL of N,N-dimethylformamide solvent and 5 g of thiolated attapulgite into the reactor, and after ultrasonic dispersion for 40 min, continue to add 17.5 g of allylated polyethersulfone and 0.3 g of benzoin dimethyl ether, stir until completely dissolved, transfer to an oil bath, irradiate the reaction system with ultraviolet light, react at 40 ° C for 6 h, filter, purify, wash and dry after the reaction to obtain polyethersulfone modified attapulgite; (4) Add 50 g of epoxy resin emulsion, 10 g of polyethersulfone modified attapulgite, 20 g of curing agent polyamide, 2.5 g of film-forming aid dodecyl alcohol ester and 0.75 g of defoaming agent polydimethylsiloxane into a high-speed mixer, mix them evenly at high speed and then package to obtain attapulgite-epoxy resin composite high-strength floor paint.

[0019] Comparative Example 1 (1) Add 200 mL of ethanol solvent and 5 g of attapulgite into the reactor, and after ultrasonic dispersion, continue to add 0.75 g of 3-mercaptopropyltriethoxysilane, stir evenly, and transfer to an oil bath pot, raise the temperature to 60 ° C, react for 2 h, centrifuge after the reaction, wash and dry to obtain thiolated attapulgite; (2) Add 50 g of epoxy resin emulsion, 4.2 g of mercapto-modified attapulgite, 13 g of curing agent polyamide, 0.6 g of film-forming aid dodecyl alcohol ester and 0.3 g of defoaming agent polydimethylsiloxane into a high-speed mixer, mix them evenly at high speed and then package to obtain attapulgite-epoxy resin composite floor paint.

[0020] The composite epoxy resin floor paint in the embodiment and the comparative example was placed in a mold for curing, and was injection molded into a square sample block with a specification of 4 mm×4 cm×4 cm using an injection molding machine, and its impact strength was tested using an MZ-2056 impact testing machine.

[0021]

[0022] The composite epoxy resin floor paint in the embodiment and the comparative example was placed in a mold for curing, and was injection molded into a square sample block with a specification of 4 mm×4 cm×4 cm using an injection molding machine. The impact strength thereof was tested using a CS-6003A tensile strength testing machine.

[0023]

Claims

1. A attapulgite-epoxy resin composite high-strength floor paint, characterized in that: The following steps are involved: (1) Add attapulgite to ethanol solvent, disperse it evenly with ultrasonic wave, then add 3-mercaptopropyltriethoxysilane, stir evenly and transfer to an oil bath, raise the temperature to 60-80°C, react for 2-8h, centrifuge after the reaction, wash and dry to obtain thiolated attapulgite; (2) adding methoxyhydroquinone, 4,4'-difluorodiphenyl sulfone, 4,4'-sulfonylbis[2-(2-propenyl)]phenol and potassium carbonate to a mixed solvent of toluene and N-methylpyrrolidone, stirring and mixing the mixture evenly, transferring the mixture to an oil bath, filling the mixture with nitrogen to remove air, raising the temperature to react, and filtering after the reaction, washing and drying the mixture to obtain allylated polyether sulfone; (3) Add thiolated attapulgite to N,N-dimethylformamide solvent, and ultrasonically disperse for 20-40 minutes, then continue to add allylated polyethersulfone and benzoin dimethyl ether, stir until completely dissolved, transfer to an oil bath, irradiate the reaction system with ultraviolet light, react at 20-40°C for 2-6 hours, filter, purify, wash and dry after the reaction to obtain polyethersulfone modified attapulgite; (4) Add epoxy resin emulsion, polyethersulfone modified attapulgite, 25-40% of curing agent polyamide, 1-5% of film-forming aid dodecyl alcohol ester and 0.5-1.5% of defoaming agent polydimethylsiloxane into a high-speed mixer, mix them evenly at high speed and then package them to obtain attapulgite-epoxy resin composite high-strength floor paint.

2. The attapulgite-epoxy resin composite high-strength floor paint according to claim 1, characterized in that: In the step (1), the mass ratio of the ethanol solvent, attapulgite and 3-mercaptopropyltriethoxysilane is 300-750:10:1.5-4.

3. The attapulgite-epoxy resin composite high-strength floor paint according to claim 1, characterized in that: In the step (2), the mass ratio of toluene solvent, N-methylpyrrolidone solvent, methoxyhydroquinone, 4,4'-difluorodiphenyl sulfone, 4,4'-sulfonylbis[2-(2-propenyl)]phenol and potassium carbonate is 150-400:200-600:4-10:10:0.6-1.4:3-7.

5.

4. The attapulgite-epoxy resin composite high-strength floor paint according to claim 1, characterized in that: The reaction temperature in step (2) is 140-180° C. and the reaction time is 8-24 hours.

5. The attapulgite-epoxy resin composite high-strength floor paint according to claim 1, characterized in that: In the step (3), the mass ratio of N,N-dimethylformamide solvent, thiolated attapulgite, allylated polyethersulfone and benzoin dimethyl ether is 650-2000:10:18-35:0.2-0.

6.

6. The attapulgite-epoxy resin composite high-strength floor paint according to claim 1, characterized in that: In the step (4), the mass ratio of the epoxy resin emulsion to the polyethersulfone modified attapulgite is 100:8-20.

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