CN111333890A - High-wear-resistance modified SiO2Polyurethane super-hydrophobic film and preparation method thereof - Google Patents

High-wear-resistance modified SiO2Polyurethane super-hydrophobic film and preparation method thereof Download PDF

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CN111333890A
CN111333890A CN202010333148.2A CN202010333148A CN111333890A CN 111333890 A CN111333890 A CN 111333890A CN 202010333148 A CN202010333148 A CN 202010333148A CN 111333890 A CN111333890 A CN 111333890A
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叶李兄
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    • C08J2433/14—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
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Abstract

The invention relates to the technical field of polyurethane, and discloses high-wear-resistance modified SiO2The polyurethane super-hydrophobic film comprises the following formula raw materials and components: modified porous hollow SiO2Polyether polyol, dodecyl benzene-2, 4-diisocyanate, 1, 4-butanediol, initiator, catalyst and tridecyl methacrylateOctyl fluoride and triethanolamine. The high-wear-resistance modified SiO2Polyurethane super-hydrophobic film, porous nano SiO of hollow structure2Reacts with sodium hydroxide to ensure that the surface is rich in a large amount of active hydroxyl, is easy to react with heptadecafluorodecyltriethoxysilane, and improves the nano SiO2The dispersibility and the compatibility in the polyurethane film enhance the toughness and the wear resistance of the polyurethane film, the dodecyl benzene-2, 4-diisocyanate is taken as a monomer, the tridecafluorooctyl methacrylate is grafted with a polyurethane molecular chain and the nano SiO2The heptadecafluorodecyl long alkyl chain on the surface endows the polyurethane film with excellent super-hydrophobic property.

Description

High-wear-resistance modified SiO2Polyurethane super-hydrophobic film and preparation method thereof
Technical Field
The invention relates to the technical field of polyurethane, in particular to high-wear-resistance modified SiO2Polyurethane super-hydrophobic film and its preparation method.
Background
The lotus effect in nature causes research on a super-hydrophobic surface, the surface of a super-hydrophobic material has self-cleaning capacity, strong anti-icing and anti-frosting capacity, excellent corrosion resistance, higher resistance reduction function and high bearing capacity, the super-hydrophobic material has wide application prospects in the fields of communication, military, environment, energy and the like, the contact angle of the super-hydrophobic material is required to be larger than 150 degrees, and the self-cleaning principle is that when water drops fall on the surface of the super-hydrophobic material, dust scattered on the surface can be adsorbed or dissolved by the water drops, the water drops can not wet the solid surface, the water drops can easily slide off from the surface of the super-hydrophobic material even if the water drops have a tiny inclination angle, so that the attached dust is taken away, and the self-cleaning effect is achieved.
Polyurethane is a high molecular compound, the polyurethane material mainly comprises polyurethane plastic, polyurethane fiber and polyurethane elastomer, has good chemical resistance, rebound resilience and mechanical property, can be prepared into products such as coating, adhesive, leather and shoe resin and the like, and has wide application in the household appliance industry, the building industry, the shoe and leather manufacturing industry and the transportation industry, but the prior polyurethane material has low hydrophobic property, and can be endowed with super-hydrophobic property by physical modification and chemical modification methods, and nano SiO2Has three-dimensional network structure, large specific surface area and high activity, can be used as a filler to improve the mechanical properties of coatings, adhesives, plastics and rubber materials, but has nanometer SiO2The compatibility with polyurethane is poor, and the polyurethane is easy to agglomerate and agglomerate, so that the mechanical properties of the polyurethane material, such as toughness, wear resistance and the like, are influenced.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a modified SiO with high wear resistance2The polyurethane super-hydrophobic film and the preparation method thereof solve the problem that the polyurethane film does not have super-hydrophobic performance and simultaneously solve the problem of nano SiO2Poor dispersibility and compatibility in polyurethane materials.
(II) technical scheme
To achieve the above object, the present invention provides the following technical meansA scheme: high-wear-resistance modified SiO2The polyurethane super-hydrophobic film comprises the following formula raw materials in parts by weight: 3-6 parts of modified porous hollow SiO240-57 parts of polyether polyol, 32-36 parts of dodecyl benzene-2, 4-diisocyanate, 1-2 parts of 1, 4-butanediol, 1-3 parts of initiator, 1-2 parts of catalyst, 3-7 parts of tridecyl octyl methacrylate and 2-4 parts of triethanolamine.
Preferably, the catalyst is dibutyltin dilaurate.
Preferably, the initiator is dibenzoyl peroxide.
Preferably, the modified porous hollow SiO2The preparation method comprises the following steps:
(1) adding 0.3-0.8% by mass of sodium carbonate solution and silk into a reaction bottle, placing the reaction bottle in an oil bath pot, heating to 100-, and (3) removing the solvent by centrifugal separation, placing the solid in distilled water, performing ultrasonic dispersion uniformly, and removing the solvent by freeze drying to prepare the silk fibroin microsphere.
(2) Adding ethanol solvent into a reaction bottle, adding ammonia water to adjust the pH value of the solution to 8-10, adding silk fibroin microspheres, adding tetraethoxysilane after ultrasonic dispersion is uniform, stirring at a constant speed for reaction for 10-15h, drying the solution in vacuum to remove the solvent, washing a solid product by using distilled water and ethanol, fully drying, placing the solid product in a resistance furnace, heating at a rate of 2-5 ℃/min, and carrying out heat preservation treatment at the temperature of 550-580 ℃ for 2-5h to prepare the porous nano hollow SiO2。
(3) Into a reaction flaskAdding 5-15% sodium hydroxide solution, and adding porous nanometer hollow SiO2Uniformly dispersing by ultrasonic, heating the solution to 70-90 ℃, uniformly stirring for reaction for 2-4h, cooling the solution, filtering to remove the solvent, washing the solid product by using distilled water and ethanol, and fully drying to prepare the hydroxylated porous hollow SiO2。
(4) Adding distilled water and ethanol solvent into a reaction bottle, wherein the volume ratio of the distilled water to the ethanol solvent is 15-20:1, and then adding hydroxylated porous hollow SiO2After ultrasonic dispersion is uniform, adding a silane coupling agent, heating to 40-80 ℃, stirring at a constant speed for reaction for 3-8h, filtering the solution to remove the solvent, washing the solid product with distilled water and ethanol, and fully drying to prepare the modified porous hollow SiO2。
Preferably, the cryostat of step (1) includes refrigerator, refrigerator below and nitrogen chamber fixed connection, and the below fixedly connected with vacuum heat preservation layer of nitrogen chamber, the inside of vacuum heat preservation layer are provided with the refrigeration aircraft nose, the refrigeration aircraft nose outside is provided with the refrigeration protective layer, and the outside swing joint that the outside of vacuum heat preservation layer is a transparent glass piece, transparent glass piece has the removal apron, and one side swing joint that removes the apron has the gyro wheel, removes the opposite side fixedly connected with supporting shoe of apron.
Preferably, the mass ratio of the silk fibroin microspheres to the tetraethoxysilane in the step (2) is 1: 3-6.
Preferably, the silane coupling in step (4) is heptadecafluorodecyltriethoxysilane, with SiO2The mass ratio of (A) to (B) is 1: 12-18.
Preferably, the high-wear-resistance modified SiO2The preparation method of the polyurethane super-hydrophobic film comprises the following steps:
(1) adding 3-6 parts of modified porous hollow SiO into a reaction bottle240-57 parts of polyether polyol and 32-36 parts of dodecylbenzene-2, 4-diisocyanate, placing a reaction bottle in a constant-temperature water bath kettle, heating to 75-85 ℃, uniformly stirring for reaction for 3-4h, adding a toluene solvent for dilution, reducing the temperature by 50-60 ℃, adding 1-2 parts of catalyst dibutyltin dilaurate and 1-2 parts of 1, 4-butanediol, uniformly stirring for reaction for 3-5h, heating, and reactingAdding 3-7 parts of tridecyl methacrylate and 2-4 parts of triethanolamine at 75-90 ℃, adding 1-3 parts of initiator dibenzoyl peroxide, stirring at a constant speed for reaction for 2-4 hours, pouring the solution into a film forming die, naturally casting to form a film, and fully drying to prepare the high-wear-resistance modified SiO2Polyurethane superhydrophobic films.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
the high-wear-resistance modified SiO2The polyurethane super-hydrophobic film is prepared by taking silk fibroin microspheres prepared from cheap and easily-obtained degummed silk as a sacrificial template, and removing the sacrificial template through in-situ polymerization and thermal cracking to obtain porous nano SiO with a hollow structure2Compared with common nano SiO2Porous nano hollow SiO2The particle size is smaller, the specific surface area is much larger, and the obtained product is subjected to hydroxylation reaction with sodium hydroxide, so that the surface of the product is rich in active hydroxyl groups and is also better than that of common nano SiO2Many more hydroxyl groups can easily react with the heptadecafluorodecyltriethoxysilane, the grafting rate of the heptadecafluorodecyltriethoxysilane is greatly improved, and the porous nano hollow SiO2The surface is rich in a large amount of long branched chain fluorinated alkyl chains, so that the porous nano hollow SiO is greatly improved2Dispersibility and compatibility in polyurethane film, and uniformly dispersed porous nano hollow SiO2As the crosslinking neutrality, the crosslinking degree of polyurethane can be enhanced, and the mechanical properties such as toughness, wear resistance and the like of the polyurethane film material are obviously improved.
The high-wear-resistance modified SiO2The polyurethane super-hydrophobic film takes dodecyl benzene-2, 4-diisocyanate containing a hydrophobic long alkyl chain as a monomer, and the tridecyl methacrylate reacts with a polyurethane molecular chain under the action of an initiator dibenzoyl peroxide to ensure that the fluorinated alkyl chain with strong hydrophobicity is grafted with the polyurethane molecular chain, and meanwhile, the porous nano hollow SiO is adopted2The surface of the polyurethane film is provided with a heptadecafluorodecyl long alkyl chain, and the polyurethane film is endowed with excellent super-hydrophobic performance under the synergistic effect of the heptadecafluorodecyl long alkyl chain, the heptadecafluorodecyl long alkyl chain and the heptadecafluorodecyl long alkyl chain.
Drawings
FIG. 1 is a schematic front view of a cryostat;
fig. 2 is a schematic view of the movable cover plate.
1. A refrigerator; 2. a nitrogen chamber; 3. a vacuum heat-insulating layer; 4. a refrigerating machine head; 5. a refrigeration protective layer; 6. a transparent glass sheet; 7. moving the cover plate; 8. a roller; 9. and (7) a supporting block.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: high-wear-resistance modified SiO2The polyurethane super-hydrophobic film comprises the following formula raw materials in parts by weight: 3-6 parts of modified porous hollow SiO240-57 parts of polyether polyol, 32-36 parts of dodecyl benzene-2, 4-diisocyanate, 1-2 parts of 1, 4-butanediol, 1-3 parts of initiator, 1-2 parts of catalyst, 3-7 parts of tridecyl octyl methacrylate and 2-4 parts of triethanolamine, wherein the catalyst is dibutyltin dilaurate, and the initiator is dibenzoyl peroxide.
Modified porous hollow SiO2The preparation method comprises the following steps:
(1) adding 0.3-0.8% by mass of sodium carbonate solution and silk into a reaction bottle, placing the reaction bottle in an oil bath pot, heating to 100-, the method comprises the following steps of fixedly connecting a vacuum heat-insulating layer below a nitrogen chamber, arranging a refrigerating machine head inside the vacuum heat-insulating layer, arranging a refrigerating protective layer outside the refrigerating machine head, arranging a transparent glass sheet outside the vacuum heat-insulating layer, movably connecting a movable cover plate outside the transparent glass sheet, movably connecting a roller on one side of the movable cover plate, fixedly connecting a supporting block on the other side of the movable cover plate, freezing at the temperature of minus 10-minus 20 ℃ for 20-30 hours, unfreezing a freezing solution at room temperature, centrifugally separating to remove a solvent, placing the solid in distilled water, ultrasonically dispersing uniformly, and removing the solvent through freeze drying to prepare the silk fibroin microspheres.
(2) Adding ethanol solvent into a reaction bottle, adding ammonia water to adjust the pH value of the solution to 8-10, adding silk fibroin microspheres, adding ethyl orthosilicate with the mass ratio of 1:3-6 after ultrasonic dispersion is uniform, stirring at a constant speed for reaction for 10-15h, drying the solution in vacuum to remove the solvent, washing a solid product with distilled water and ethanol, fully drying, placing the solid product in a resistance furnace with the heating rate of 2-5 ℃/min, and carrying out heat preservation treatment at 550-580 ℃ for 2-5h to prepare the porous nano hollow SiO2。
(3) Adding 5-15% sodium hydroxide solution into a reaction bottle, and adding porous nano hollow SiO2Uniformly dispersing by ultrasonic, heating the solution to 70-90 ℃, uniformly stirring for reaction for 2-4h, cooling the solution, filtering to remove the solvent, washing the solid product by using distilled water and ethanol, and fully drying to prepare the hydroxylated porous hollow SiO2。
(4) Adding distilled water and ethanol solvent into a reaction bottle, wherein the volume ratio of the distilled water to the ethanol solvent is 15-20:1, and then adding hydroxylated porous hollow SiO2After the ultrasonic dispersion is uniform, adding a silane coupling agent heptadecafluorodecyltriethoxysilane and SiO2The mass ratio of the components is 1:12-18, the mixture is heated to 40-80 ℃, stirred at a constant speed and reacted for 3-8h, the solution is filtered to remove the solvent, the solid product is washed by distilled water and ethanol and fully dried to prepare the modified porous hollow SiO2。
High-wear-resistance modified SiO2The preparation method of the polyurethane super-hydrophobic film comprises the following steps:
(1) adding 3-6 parts of modified porous hollow SiO into a reaction bottle240-57 parts of polyether polyol and 32-36 parts of dodecyl benzene-2, 4-diisocyanate, placing a reaction bottle in a constant-temperature water bath kettle, heating to 75-85 ℃, uniformly stirring for reaction for 3-4h, adding a toluene solvent for dilutionReducing the temperature by 50-60 ℃, adding 1-2 parts of dibutyltin dilaurate serving as a catalyst and 1-2 parts of 1, 4-butanediol, stirring at a constant speed for reacting for 3-5h, heating to 75-90 ℃, adding 3-7 parts of tridecyl methacrylate and 2-4 parts of triethanolamine, adding 1-3 parts of dibenzoyl peroxide serving as an initiator, stirring at a constant speed for reacting for 2-4h, pouring the solution into a film forming mold, naturally casting to form a film, and fully drying to prepare the high-wear-resistance modified SiO2Polyurethane superhydrophobic films.
Example 1
(1) Preparing a silk fibroin microsphere component 1: adding 0.3 mass percent of sodium carbonate solution and silk into a reaction bottle, placing the reaction bottle in an oil bath pot, heating to 100 ℃, stirring at a constant speed for 1h, degumming, filtering the solution to remove the solvent, washing the solid product with distilled water, placing the solid product in 40 mass percent of lithium bromide solution, heating to 40 ℃, stirring at a constant speed for 2h, filtering to remove the solid, placing the filtrate in a dialysis bag, adding distilled water to carry out dialysis impurity removal to obtain degummed silk, adding a mixed solvent of distilled water and ethanol into the reaction bottle, wherein the volume ratio of the two is 5:1, adding the degummed silk, stirring at a constant speed uniformly, placing the solution in a low-temperature thermostat, wherein the low-temperature thermostat comprises a refrigerator, the lower part of the refrigerator is fixedly connected with a nitrogen chamber, the lower part of the nitrogen chamber is fixedly connected with a vacuum heat-insulation layer, and a refrigerating machine head is arranged inside the vacuum heat-, The method comprises the following steps of arranging a refrigeration protective layer outside a refrigerator head, arranging a transparent glass sheet outside a vacuum heat-insulating layer, movably connecting the transparent glass sheet with a movable cover plate, movably connecting one side of the movable cover plate with a roller, fixedly connecting the other side of the movable cover plate with a supporting block, freezing for 20 hours at-10 ℃, unfreezing a refrigerating fluid at room temperature, centrifugally separating to remove a solvent, placing a solid in distilled water for uniform ultrasonic dispersion, and removing the solvent through freeze drying to prepare the silk fibroin microsphere component 1.
(2) Preparation of porous nano hollow SiO2Component 1: adding ethanol solvent into a reaction bottle, adding ammonia water to adjust the pH of the solution to 8, adding the silk fibroin microsphere component 1, ultrasonically dispersing uniformly, adding ethyl orthosilicate with the mass ratio of 1:3, stirring at constant speed, and reactingDrying the solution in vacuum for 10h to remove the solvent, washing the solid product with distilled water and ethanol, fully drying, placing the solid product in a resistance furnace, heating at a rate of 2 ℃/min, and carrying out heat preservation treatment at 550 ℃ for 2h to prepare the porous nano hollow SiO2And (3) component 1.
(3) Preparation of hydroxylated porous hollow SiO2Component 1: adding a sodium hydroxide solution with the mass fraction of 5% into a reaction bottle, and then adding porous nano hollow SiO2Uniformly dispersing the component 1 by ultrasonic, heating the solution to 70 ℃, uniformly stirring and reacting for 2 hours, cooling the solution, filtering to remove the solvent, washing the solid product by using distilled water and ethanol, and fully drying to prepare the hydroxylated porous hollow SiO2And (3) component 1.
(4) Preparation of modified porous hollow SiO2Component 1: adding distilled water and ethanol solvent into a reaction bottle, wherein the volume ratio of the distilled water to the ethanol solvent is 15:1, and then adding hydroxylated porous hollow SiO2After the component 1 is dispersed evenly by ultrasonic, adding a silane coupling agent heptadecafluorodecyltriethoxysilane and SiO2The mass ratio of the components is 1:12, the mixture is heated to 40 ℃, stirred at a constant speed and reacted for 3 hours, the solution is filtered to remove the solvent, the solid product is washed by distilled water and ethanol and fully dried to prepare the modified porous hollow SiO2And (3) component 1.
(5) Preparation of high-wear-resistance modified SiO2Polyurethane superhydrophobic film material 1: adding 3 parts of modified porous hollow SiO into a reaction bottle2Putting a reaction bottle in a constant-temperature water bath kettle, heating to 75 ℃, uniformly stirring and reacting for 3 hours, adding a toluene solvent for diluting, reducing the temperature by 50 ℃, adding 1 part of catalyst dibutyltin dilaurate and 1 part of 1, 4-butanediol, uniformly stirring and reacting for 3 hours, heating to 75 ℃, adding 3 parts of tridecyl methacrylate and 2 parts of triethanolamine, adding 1 part of initiator dibenzoyl peroxide, uniformly stirring and reacting for 2 hours, pouring the solution into a film forming mold, naturally casting to form a film, and fully drying to prepare the high-wear-resistance modified SiO2A polyurethane superhydrophobic film material 1.
Example 2
(1) Preparing a silk fibroin microsphere component 2: adding 0.8 mass percent of sodium carbonate solution and silk into a reaction bottle, placing the reaction bottle in an oil bath pot, heating to 100 ℃, stirring at a constant speed for 1h, degumming, filtering the solution to remove the solvent, washing the solid product with distilled water, placing the solid product in 50 mass percent of lithium bromide solution, heating to 40 ℃, stirring at a constant speed for 4h, filtering to remove the solid, placing the filtrate in a dialysis bag, adding distilled water to carry out dialysis impurity removal to obtain degummed silk, adding a mixed solvent of distilled water and ethanol into the reaction bottle, wherein the volume ratio of the two is 12:1, adding the degummed silk, stirring at a constant speed uniformly, placing the solution in a low-temperature thermostat, wherein the low-temperature thermostat comprises a refrigerator, the lower part of the refrigerator is fixedly connected with a nitrogen chamber, the lower part of the nitrogen chamber is fixedly connected with a vacuum heat-insulation layer, and a refrigerating machine head is arranged inside the vacuum heat-, The refrigerating machine head is externally provided with a refrigerating protective layer, a transparent glass sheet is arranged outside the vacuum heat-insulating layer, a movable cover plate is movably connected outside the transparent glass sheet, one side of the movable cover plate is movably connected with a roller, the other side of the movable cover plate is fixedly connected with a supporting block, the movable cover plate is frozen for 20 hours at the temperature of minus 20 ℃, a refrigerating fluid is unfrozen at room temperature, a solvent is removed by centrifugal separation, and after solids are uniformly dispersed in distilled water by ultrasonic, the solvent is removed by freeze drying, so that the silk fibroin microsphere component 2 is prepared.
(2) Preparation of porous nano hollow SiO2And (2) component: adding ethanol solvent into a reaction bottle, adding ammonia water to adjust the pH value of the solution to 10, adding the silk fibroin microsphere component 2, adding ethyl orthosilicate with the mass ratio of 1:6 after uniform ultrasonic dispersion, stirring at a constant speed for 10 hours, drying the solution in vacuum to remove the solvent, washing the solid product with distilled water and ethanol, fully drying, placing the solid product in a resistance furnace, heating at the rate of 5 ℃/min, and carrying out heat preservation treatment at 550 ℃ for 5 hours to obtain the porous nano hollow SiO2And (3) component 2.
(3) Preparation of hydroxylated porous hollow SiO2And (2) component: adding 15 percent sodium hydroxide solution by mass into a reaction bottle, and then adding porous nano hollow SiO2Component 2, ultrasonic dispersing evenly, heating the solution toStirring at constant speed at 90 deg.C for 2 hr, cooling the solution, filtering to remove solvent, washing the solid product with distilled water and ethanol, and drying to obtain hydroxylated porous hollow SiO2And (3) component 2.
(4) Preparation of modified porous hollow SiO2And (2) component: adding distilled water and ethanol solvent into a reaction bottle, wherein the volume ratio of the distilled water to the ethanol solvent is 20:1, and then adding hydroxylated porous hollow SiO2After the component 2 is dispersed evenly by ultrasonic, adding a silane coupling agent heptadecafluorodecyltriethoxysilane and SiO2The mass ratio of the components is 1:12, the mixture is heated to 40 ℃, stirred at a constant speed and reacted for 8 hours, the solution is filtered to remove the solvent, distilled water and ethanol are used for washing a solid product, and the solid product is fully dried to prepare the modified porous hollow SiO2And (3) component 2.
(5) Preparation of high-wear-resistance modified SiO2Polyurethane superhydrophobic film material 2: adding 3.5 parts of modified porous hollow SiO into a reaction bottle2Putting a reaction bottle in a constant-temperature water bath kettle, heating to 75 ℃, uniformly stirring and reacting for 4 hours, adding a toluene solvent for diluting, reducing the temperature by 60 ℃, adding 1.2 parts of catalyst dibutyltin dilaurate and 1.3 parts of 1, 4-butanediol, uniformly stirring and reacting for 3 hours, heating to 90 ℃, adding 4 parts of tridecyl methacrylate and 2.5 parts of triethanolamine, adding 1.5 parts of initiator dibenzoyl peroxide, uniformly stirring and reacting for 4 hours, pouring the solution into a film forming mold, naturally casting to form a film, fully drying to prepare the high-wear-resistance modified SiO2A polyurethane superhydrophobic film material 2.
Example 3
(1) Preparing a silk fibroin microsphere component 3: adding 0.5 mass percent of sodium carbonate solution and silk into a reaction bottle, placing the reaction bottle in an oil bath pot, heating to 110 ℃, stirring at a constant speed for 1.5 hours, degumming, filtering the solution to remove the solvent, washing the solid product with distilled water, placing the solid product in 45 mass percent of lithium bromide solution, heating to 45 ℃, stirring at a constant speed for 3 hours, filtering to remove the solid, placing the filtrate in a dialysis bag, adding distilled water for dialysis impurity removal to obtain degummed silk, adding a mixed solvent of distilled water and ethanol into the reaction bottle, wherein the volume ratio of the distilled water to the mixed solvent of ethanol is 8:1, adding the degummed silk, stirring at a constant speed uniformly, placing the solution in a low-temperature thermostat, wherein the low-temperature thermostat comprises a refrigerator, the lower part of the refrigerator is fixedly connected with a nitrogen chamber, the lower part of the nitrogen chamber is fixedly connected with a vacuum heat-insulating layer, and a refrigerating machine head is arranged, The refrigeration machine head is externally provided with a refrigeration protective layer, a transparent glass sheet is arranged outside the vacuum heat-insulating layer, a movable cover plate is movably connected outside the transparent glass sheet, one side of the movable cover plate is movably connected with a roller, the other side of the movable cover plate is fixedly connected with a supporting block, the movable cover plate is frozen for 25 hours at the temperature of-15 ℃, a refrigerating fluid is unfrozen at room temperature, a solvent is removed by centrifugal separation, and after solids are uniformly dispersed in distilled water by ultrasonic, the solvent is removed by freeze drying, so that the silk fibroin microsphere component 3 is prepared.
(2) Preparation of porous nano hollow SiO2And (3) component: adding ethanol solvent into a reaction bottle, adding ammonia water to adjust the pH value of the solution to 9, adding the fibroin protein microsphere component 3, adding ethyl orthosilicate after uniform ultrasonic dispersion, wherein the mass ratio of the ethyl orthosilicate to the ammonia water is 1:4.5, stirring at a constant speed for reaction for 12 hours, drying the solution in vacuum to remove the solvent, washing a solid product by using distilled water and ethanol, fully drying, placing the solid product in a resistance furnace, heating at the rate of 3 ℃/min, and carrying out heat preservation treatment at 565 ℃ for 4 hours to prepare the porous nano hollow SiO solid2And (3) component.
(3) Preparation of hydroxylated porous hollow SiO2And (3) component: adding 10 percent sodium hydroxide solution by mass into a reaction bottle, and then adding porous nano hollow SiO2Uniformly dispersing the component 3 by ultrasonic, heating the solution to 80 ℃, uniformly stirring and reacting for 3 hours, cooling the solution, filtering to remove the solvent, washing the solid product by using distilled water and ethanol, and fully drying to prepare the hydroxylated porous hollow SiO2And (3) component.
(4) Preparation of modified porous hollow SiO2And (3) component: adding distilled water and ethanol solvent into a reaction bottle in a volume ratio of 18:1, and adding hydroxylated porous hollow SiO2After the component 3 is dispersed evenly by ultrasonic, adding a silane coupling agent heptadecafluorodecyl triethoxysilaneWith SiO2The mass ratio of the components is 1:15, the mixture is heated to 60 ℃, stirred at a constant speed and reacted for 5 hours, the solution is filtered to remove the solvent, the solid product is washed by distilled water and ethanol and fully dried to prepare the modified porous hollow SiO2And (3) component.
(5) Preparation of high-wear-resistance modified SiO2Polyurethane superhydrophobic film material 3: adding 4.5 parts of modified porous hollow SiO into a reaction bottle2Putting a reaction bottle in a constant-temperature water bath kettle, heating to 80 ℃, uniformly stirring and reacting for 3.5h, adding a toluene solvent for diluting, reducing the temperature by 55 ℃, adding 1.5 parts of catalyst dibutyltin dilaurate and 1.5 parts of 1, 4-butanediol, uniformly stirring and reacting for 4h, heating to 80 ℃, adding 5 parts of tridecyl methacrylate and 3 parts of triethanolamine, adding 2 parts of initiator dibenzoyl peroxide, uniformly stirring and reacting for 3h, pouring the solution into a film forming die, naturally casting to form a film, and fully drying to prepare the high-wear-resistance modified SiO2A polyurethane superhydrophobic film material 3.
Example 4
(1) Preparing a silk fibroin microsphere component 4: adding 0.8 mass percent of sodium carbonate solution and silk into a reaction bottle, placing the reaction bottle in an oil bath pot, heating to 120 ℃, stirring at a constant speed for 1h, carrying out degumming treatment, filtering the solution to remove the solvent, washing the solid product with distilled water, placing the solid product in 50 mass percent of lithium bromide solution, heating to 50 ℃, stirring at a constant speed for 2h, filtering to remove the solid, placing the filtrate in a dialysis bag, adding distilled water to carry out dialysis impurity removal to obtain degummed silk, adding a mixed solvent of distilled water and ethanol into the reaction bottle, wherein the volume ratio of the distilled water to the mixed solvent of ethanol is 5:1, adding the degummed silk, stirring at a constant speed uniformly, placing the solution in a low-temperature thermostat, wherein the low-temperature thermostat comprises a refrigerator, the lower part of the refrigerator is fixedly connected with a nitrogen chamber, the lower part of the nitrogen chamber is fixedly connected with a vacuum heat-insulation layer, and a, The refrigeration machine head is externally provided with a refrigeration protective layer, a transparent glass sheet is arranged outside the vacuum heat-insulating layer, a movable cover plate is movably connected outside the transparent glass sheet, one side of the movable cover plate is movably connected with a roller, the other side of the movable cover plate is fixedly connected with a supporting block, the movable cover plate is frozen for 30 hours at the temperature of minus 20 ℃, a refrigerating fluid is unfrozen at room temperature, a solvent is removed by centrifugal separation, and after solids are uniformly dispersed in distilled water by ultrasonic, the solvent is removed by freeze drying, so that the silk fibroin microsphere component 4 is prepared.
(2) Preparation of porous nano hollow SiO2And (4) component: adding ethanol solvent into a reaction bottle, adding ammonia water to adjust the pH value of the solution to 8, adding a silk fibroin microsphere component 4, adding ethyl orthosilicate after uniform ultrasonic dispersion, wherein the mass ratio of the ethyl orthosilicate to the ammonia water is 1:6, stirring at a constant speed for reaction for 10 hours, drying the solution in vacuum to remove the solvent, washing a solid product with distilled water and ethanol, fully drying, placing the solid product in a resistance furnace, heating at the rate of 5 ℃/min, and carrying out heat preservation treatment at 550 ℃ for 5 hours to prepare the porous nano hollow SiO2And (4) component.
(3) Preparation of hydroxylated porous hollow SiO2And (4) component: adding 15 percent sodium hydroxide solution by mass into a reaction bottle, and then adding porous nano hollow SiO2Uniformly dispersing the component 4 by ultrasonic, heating the solution to 90 ℃, uniformly stirring and reacting for 2 hours, cooling the solution, filtering to remove the solvent, washing the solid product by using distilled water and ethanol, and fully drying to prepare the hydroxylated porous hollow SiO2And (4) component.
(4) Preparation of modified porous hollow SiO2And (4) component: adding distilled water and ethanol solvent into a reaction bottle, wherein the volume ratio of the distilled water to the ethanol solvent is 15:1, and then adding hydroxylated porous hollow SiO2After the component 4 is dispersed evenly by ultrasonic, adding a silane coupling agent heptadecafluorodecyltriethoxysilane and SiO2The mass ratio of the components is 1:12, the mixture is heated to 80 ℃, stirred at a constant speed and reacted for 8 hours, the solution is filtered to remove the solvent, distilled water and ethanol are used for washing a solid product, and the solid product is fully dried to prepare the modified porous hollow SiO2And (4) component.
(5) Preparation of high-wear-resistance modified SiO2Polyurethane superhydrophobic film material 4: adding 5 parts of modified porous hollow SiO into a reaction bottle 24, 44 portions of polyether polyol and 35 portions of dodecyl benzene-2, 4-diisocyanate, and a reaction bottlePlacing the mixture into a constant-temperature water bath kettle, heating the mixture to 75 ℃, uniformly stirring the mixture for reaction for 4 hours, adding a toluene solvent for dilution, reducing the temperature by 50 ℃, adding 1.8 parts of dibutyltin dilaurate catalyst and 1.7 parts of 1, 4-butanediol, uniformly stirring the mixture for reaction for 5 hours, heating the mixture to 75 ℃, adding 6 parts of tridecyl methacrylate and 3.5 parts of triethanolamine, adding 2.5 parts of dibenzoyl peroxide initiator, uniformly stirring the mixture for reaction for 4 hours, pouring the solution into a film forming die, naturally casting the solution into a film, and fully drying the film to prepare the high-wear-resistance modified SiO2A polyurethane superhydrophobic film material 4.
Example 5
(1) Preparing a silk fibroin microsphere component 5: adding 0.8 mass percent of sodium carbonate solution and silk into a reaction bottle, placing the reaction bottle in an oil bath pot, heating to 120 ℃, stirring at a constant speed for 2 hours, degumming, filtering the solution to remove the solvent, washing the solid product with distilled water, placing the solid product in 50 mass percent of lithium bromide solution, heating to 50 ℃, stirring at a constant speed for 4 hours, filtering to remove the solid, placing the filtrate in a dialysis bag, adding distilled water to carry out dialysis impurity removal to obtain degummed silk, adding a mixed solvent of distilled water and ethanol into the reaction bottle, wherein the volume ratio of the two is 12:1, adding the degummed silk, stirring at a constant speed uniformly, placing the solution in a low-temperature thermostat, wherein the low-temperature thermostat comprises a refrigerator, the lower part of the refrigerator is fixedly connected with a nitrogen chamber, the lower part of the nitrogen chamber is fixedly connected with a vacuum heat-insulation layer, and a refrigerating machine head is arranged inside the vacuum heat-, The refrigeration machine head is externally provided with a refrigeration protective layer, a transparent glass sheet is arranged outside the vacuum heat-insulating layer, a movable cover plate is movably connected outside the transparent glass sheet, one side of the movable cover plate is movably connected with a roller, the other side of the movable cover plate is fixedly connected with a supporting block, the movable cover plate is frozen for 30 hours at the temperature of minus 20 ℃, a refrigerating fluid is unfrozen at room temperature, a solvent is removed by centrifugal separation, and after solids are uniformly dispersed in distilled water by ultrasonic, the solvent is removed by freeze drying, so that the silk fibroin microsphere component 5 is prepared.
(2) Preparation of porous nano hollow SiO2And (5) component: adding ethanol solvent into a reaction bottle, adding ammonia water to adjust the pH of the solution to 10, adding the silk fibroin microsphere component 5,after ultrasonic dispersion is uniform, adding tetraethoxysilane with the mass ratio of 1:6, stirring at a constant speed for reaction for 15 hours, drying the solution in vacuum to remove the solvent, washing the solid product with distilled water and ethanol, fully drying, placing the solid product in a resistance furnace with the heating rate of 5 ℃/min, carrying out heat preservation treatment for 5 hours at the temperature of 580 ℃, and preparing the porous nano hollow SiO2And (5) component.
(3) Preparation of hydroxylated porous hollow SiO2And (5) component: adding 15 percent sodium hydroxide solution by mass into a reaction bottle, and then adding porous nano hollow SiO2Uniformly dispersing the component 5 by ultrasonic, heating the solution to 90 ℃, uniformly stirring and reacting for 4 hours, cooling the solution, filtering to remove the solvent, washing the solid product by using distilled water and ethanol, and fully drying to prepare the hydroxylated porous hollow SiO2And (5) component.
(4) Preparation of modified porous hollow SiO2And (5) component: adding distilled water and ethanol solvent into a reaction bottle, wherein the volume ratio of the distilled water to the ethanol solvent is 20:1, and then adding hydroxylated porous hollow SiO2After the component 5 is dispersed evenly by ultrasonic, adding a silane coupling agent heptadecafluorodecyltriethoxysilane and SiO2The mass ratio of the components is 1:18, the mixture is heated to 80 ℃, stirred at a constant speed and reacted for 8 hours, the solution is filtered to remove the solvent, the solid product is washed by distilled water and ethanol and fully dried to prepare the modified porous hollow SiO2And (5) component.
(5) Preparation of high-wear-resistance modified SiO2Polyurethane superhydrophobic film material 5: adding 6 parts of modified porous hollow SiO into a reaction bottle2Placing a reaction bottle in a constant-temperature water bath kettle, heating to 85 ℃, uniformly stirring and reacting for 4 hours, adding a toluene solvent for diluting, reducing the temperature by 60 ℃, adding 2 parts of catalyst dibutyltin dilaurate and 2 parts of 1, 4-butanediol, uniformly stirring and reacting for 5 hours, heating to 90 ℃, adding 7 parts of tridecyl methacrylate and 4 parts of triethanolamine, adding 3 parts of initiator dibenzoyl peroxide, uniformly stirring and reacting for 4 hours, pouring the solution into a film forming mold, naturally casting to form a film, and fully drying to prepare the high-wear-resistance modified SiO2 Polyurethane superhydrophobic filmsMaterial 5.
Examples Example 1 Example 2 Example 3 Example 4 Example 5
Hydrophobic angle 151.6 152.6 151.0 150.1 150.6
In summary, the high-wear-resistance modified SiO2The polyurethane super-hydrophobic film is prepared by taking silk fibroin microspheres prepared from cheap and easily-obtained degummed silk as a sacrificial template, and removing the sacrificial template through in-situ polymerization and thermal cracking to obtain porous nano SiO with a hollow structure2Compared with common nano SiO2Porous nano hollow SiO2The particle size is smaller, the specific surface area is much larger, and the obtained product is subjected to hydroxylation reaction with sodium hydroxide, so that the surface of the product is rich in active hydroxyl groups and is also better than that of common nano SiO2Many more hydroxyl groups can easily react with the heptadecafluorodecyltriethoxysilane, the grafting rate of the heptadecafluorodecyltriethoxysilane is greatly improved, and the porous nano hollow SiO2The surface is rich in a large amount of long branched chain fluorinated alkyl chains, so that the porous nano hollow SiO is greatly improved2Dispersibility and compatibility in polyurethane film, and uniformly dispersed porous nano hollow SiO2As the crosslinking neutrality, the crosslinking degree of polyurethane can be enhanced, and the mechanical properties such as toughness, wear resistance and the like of the polyurethane film material are obviously improved.
Dodecyl benzene-2, 4-diisocyanate containing hydrophobic long alkyl chain is taken as a monomer, and tridecyl octyl methacrylate reacts with a polyurethane molecular chain under the action of an initiator dibenzoyl peroxide, so that the polyurethane molecular chain is grafted by the highly hydrophobic fluorinated alkyl chain, and meanwhile, the porous nano hollow SiO is adopted2The surface of the polyurethane film is provided with a heptadecafluorodecyl long alkyl chain, and the polyurethane film is endowed with excellent super-hydrophobic performance under the synergistic effect of the heptadecafluorodecyl long alkyl chain, the heptadecafluorodecyl long alkyl chain and the heptadecafluorodecyl long alkyl chain.

Claims (8)

1. High-wear-resistance modified SiO2The polyurethane super-hydrophobic film comprises the following formula raw materials and components in parts by weight, and is characterized in that: 3-6 parts of modified porous hollow SiO240-57 parts of polyether polyol, 32-36 parts of dodecyl benzene-2, 4-diisocyanate, 1-2 parts of 1, 4-butanediol, 1-3 parts of initiator, 1-2 parts of catalyst, 3-7 parts of tridecyl octyl methacrylate and 2-4 parts of triethanolamine.
2. The modified SiO with high wear resistance as claimed in claim 12-a polyurethane superhydrophobic film characterized in that: the catalyst is dibutyltin dilaurate.
3. The modified SiO with high wear resistance as claimed in claim 12-a polyurethane superhydrophobic film characterized in that: the initiator is dibenzoyl peroxide.
4. The modified SiO with high wear resistance as claimed in claim 12-a polyurethane superhydrophobic film characterized in that: the modified porous hollow SiO2The preparation method comprises the following steps:
(1) adding silk into 0.3-0.8% sodium carbonate solution, heating to 100-120 deg.C, stirring at constant speed for degumming for 1-2 hr, filtering, washing, adding solid product into 40-50% lithium bromide solution, heating to 40-50 deg.C, stirring at constant speed for 2-4 hr, filtering to remove solid, placing filtrate in dialysis bag, adding distilled water, dialyzing to remove impurities to obtain degummed silk, adding degummed silk into mixed solvent of distilled water and ethanol at volume ratio of 5-12:1, stirring at uniform speed, placing the solution in a low temperature thermostat, freezing at-10 deg.C to-20 deg.C for 20-30h, thawing the frozen solution at room temperature, removing solvent, placing the solid in distilled water, ultrasonically dispersing uniformly, and removing solvent to obtain silk fibroin microsphere;
(2) adding ammonia water into an ethanol solvent to adjust the pH value of the solution to 8-10, adding silk fibroin microspheres, after uniform ultrasonic dispersion, adding tetraethoxysilane, reacting for 10-15h, removing the solvent from the solution, washing and drying, placing a solid product into a resistance furnace, heating at the rate of 2-5 ℃/min, and carrying out heat preservation treatment for 2-5h at the temperature of 550-580 ℃, thereby preparing the porous nano hollow SiO2；
(3) Adding porous nano hollow SiO into sodium hydroxide solution with mass fraction of 5-15%2Uniformly dispersing by ultrasonic, heating the solution to 70-90 ℃, reacting for 2-4h, cooling, filtering, washing and drying the solution to prepare the hydroxylated porous hollow SiO2；
(4) Adding hydroxylated porous hollow SiO into distilled water and ethanol solvent with volume ratio of 15-20:12After ultrasonic dispersion is uniform, adding a silane coupling agent, heating to 40-80 ℃, reacting for 3-8h, filtering, washing and drying the solution to prepare the modified porous hollow SiO2。
5. The modified SiO with high wear resistance as claimed in claim 42-a polyurethane superhydrophobic film characterized in that: the low-temperature thermostat in the step (1) comprises a refrigerator, a refrigerator lower part fixedly connected with a nitrogen chamber, a vacuum heat-insulating layer fixedly connected with the lower part of the nitrogen chamber, a refrigerating machine head arranged in the vacuum heat-insulating layer, and a refrigerating machine head arranged outside the refrigerating machine headThe refrigeration protective layer, the outside of vacuum heat preservation is a transparent glass piece, and the outside swing joint of transparent glass piece has the removal apron, and one side swing joint of removing the apron has the gyro wheel, and the opposite side fixedly connected with supporting shoe of removing the apron.
6. The modified SiO with high wear resistance as claimed in claim 42-a polyurethane superhydrophobic film characterized in that: the mass ratio of the silk fibroin microspheres to the tetraethoxysilane in the step (2) is 1: 3-6.
7. The modified SiO with high wear resistance as claimed in claim 42-a polyurethane superhydrophobic film characterized in that: the silane coupling in the step (4) is heptadecafluorodecyltriethoxysilane and SiO2The mass ratio of (A) to (B) is 1: 12-18.
8. The modified SiO with high wear resistance as claimed in claim 12-a polyurethane superhydrophobic film characterized in that: the high-wear-resistance modified SiO2The preparation method of the polyurethane super-hydrophobic film comprises the following steps:
(1) adding 3-6 parts of modified porous hollow SiO into a reaction bottle240-57 parts of polyether polyol and 32-36 parts of dodecylbenzene-2, 4-diisocyanate, heating the solution to 75-85 ℃, reacting for 3-4h, adding a toluene solvent for dilution, reducing the temperature by 50-60 ℃, adding 1-2 parts of catalyst dibutyltin dilaurate and 1-2 parts of 1, 4-butanediol, reacting for 3-5h, heating to 75-90 ℃, adding 3-7 parts of tridecyl methacrylate and 2-4 parts of triethanolamine, adding 1-3 parts of initiator dibenzoyl peroxide, reacting for 2-4h, pouring the solution into a film forming die, casting to form a film and drying to prepare the high-wear-resistance modified SiO2Polyurethane superhydrophobic films.
CN202010333148.2A 2020-04-24 2020-04-24 High-wear-resistance modified SiO2Polyurethane super-hydrophobic film and preparation method thereof Withdrawn CN111333890A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116023196A (en) * 2022-12-30 2023-04-28 沈阳农业大学 Plant-source polyurethane coated fertilizer and preparation method thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116023196A (en) * 2022-12-30 2023-04-28 沈阳农业大学 Plant-source polyurethane coated fertilizer and preparation method thereof
CN116023196B (en) * 2022-12-30 2024-05-17 沈阳农业大学 Plant-source polyurethane coated fertilizer and preparation method thereof

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