CN111135806A - Preparation method of super-hydrophobic sponge material for oil-water separation - Google Patents
Preparation method of super-hydrophobic sponge material for oil-water separation Download PDFInfo
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Abstract
The invention provides a preparation method of a super-hydrophobic sponge material for oil-water separation, which relates to the field of oil-water separation materials and comprises the following steps: mixing polyether organic silicon, polyoxypropylene glycol and toluene, heating, adding isophorone diisocyanate and dibutyltin laurate, reacting for 5-10h, adding gamma-aminopropyl trimethoxy silane into an injection mold, and curing and molding a semi-finished product A by the mold; coarsening the semi-finished product A, and freeze-drying the semi-finished product B; ultraviolet irradiation is carried out on the semi-finished product B, and the semi-finished product B is immersed in a triethyl chlorosilane normal hexane solution to obtain a semi-finished product C; the contact angle between the surface of the sponge material and water is more than 150 degrees, the sponge material has super-hydrophobic performance, the contact angle is only reduced a little after n-hexane is absorbed repeatedly for 10 times, and the adsorption capacity of diesel oil with high viscosity is not reduced basically after the diesel oil is absorbed repeatedly for multiple times.
Description
Technical Field
The invention relates to the field of oil-water separation materials, in particular to a preparation method of a super-hydrophobic sponge material for oil-water separation.
Background
With the development of economy, modern society produces a large amount of water sources polluted by organic matters or oil products, more typically frequent marine transportation petroleum leakage pollution events in recent years, the polluted water sources cause great damage to the ecological environment, and the traditional methods for treating the oil-polluted water sources are mainly divided into physical methods, chemical methods and biological methods. The physical treatment method has low efficiency and is greatly influenced by weather environment, and a certain amount of chemical reagents are required to be added for treatment when the water source polluted by oil is treated by a chemical method and a biological method, so that secondary pollution is easily caused to the water source. Factors such as the geographical environment and the severity of an accident need to be considered when selecting a method for treating the oil-polluted water source, so that the adsorption separation of the polluted water source by using the oil absorption material is the simplest and most effective treatment method. The traditional oil absorption material is weak in oil absorption and water resistance, absorbs a large amount of water while absorbing oil, and influences oil absorption efficiency and separation effect. Therefore, development of a novel environment-friendly oil-water separation functional material with excellent performance is urgently needed.
The special infiltration performance of various animal and plant surfaces in nature has already attracted people's attention. In recent years, the bionic super-hydrophobic interface characteristic is introduced into an oil-water separation material, and because the interfacial tension between oil and water is generally large in difference, the super-hydrophobic material can selectively infiltrate one phase in an oil-water mixture and repel the other phase by utilizing the difference of the wettability of the super-hydrophobic material to different liquids, so that the separation efficiency of the material to the oil-water mixture is improved.
Nguyen and the like implant the graphene nano sheets and polydimethylsiloxane on the sponge by adopting an impregnation method to prepare the sponge with super-hydrophobic and super-lipophilic properties, has good selectivity, can be recycled for multiple times, can absorb oil or solvent by 165 times of the mass of the sponge, can be applied to large-range oil pollution,
huang and the like prepare a fibrous nano-grade filter membrane by using an in-situ polymerization method, are applied to the separation of water-in-oil emulsion, have strong antifouling performance and good thermal stability and mechanical durability, and can be repeatedly used.
Liu and the like attach a layer of SiO2 particles on the surface of cotton fabric, and are modified by octadecyl trichlorosilane, so that the super-hydrophobic super-oleophylic material which has higher oil absorption efficiency and can be repeatedly used is prepared, the oil absorption of the super-hydrophobic super-oleophylic material on oil products and solvents can reach about 50 times of the self-mass, and the oil products and solvents absorbed by vacuum filtration can be easily desorbed without influencing the recycling effect.
Chinese patent CN103601907B discloses a preparation method of a super-hydrophobic particle/chitosan skeleton composite oil absorption sponge, relating to a preparation method of a super-hydrophobic oil absorption sponge. The preparation method of the super-hydrophobic oil-absorption chitosan sponge comprises the following steps: (1) the chitosan three-dimensional network sponge is prepared by adopting a freeze drying method. (2) Synthesis of superhydrophobic PMHOS. (3) And (3) assembling the super-hydrophobic PMHOS powder in the step (2) on the surface of the three-dimensional reticular chitosan to obtain the super-hydrophobic chitosan three-dimensional network sponge. The chitosan three-dimensional network structure prepared by the invention is a three-dimensional reticular sponge with a shape memory function, can be repeatedly compressed and released, and further has a liquid absorption function.
Disclosure of Invention
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a preparation method of a super-hydrophobic sponge material for oil-water separation.
(II) technical scheme
In order to achieve the purpose, the invention is realized by the following technical scheme:
a preparation method of a super-hydrophobic sponge material for oil-water separation comprises the following steps:
(1) adding polyether organic silicon, polyoxypropylene glycol and toluene into a reactor, stirring and mixing uniformly, heating to 40-60 ℃, adding isophorone diisocyanate and dibutyltin laurate, continuing to react for 5-10h, adding gamma-aminopropyl trimethoxysilane into the reactor, stirring and mixing rapidly for 1-5min, injecting the mixture into a mold, placing the mold into an oven, heating to 60-80 ℃ for heat preservation for 20-40min for once, heating to 110-120 ℃ for heat preservation for 5-10h for molding, and cooling to room temperature to obtain a semi-finished product A;
(2) dissolving chromium oxide and concentrated sulfuric acid in water to prepare coarsening liquid, heating the coarsening liquid in a water bath, immersing the semi-finished product A in the solution for 1-3min, taking out the semi-finished product A, washing the semi-finished product A to be neutral by a large amount of water, and drying the semi-finished product A at a low temperature of-60 ℃ by using a freeze drying method to obtain a semi-finished product B;
(3) cutting the semi-finished product B into a required shape, sequentially carrying out ultrasonic cleaning and drying by using absolute ethyl alcohol and water, irradiating each surface of the semi-finished product B by using an ultraviolet lamp, finally soaking the semi-finished product B into a triethylchlorosilane normal hexane solution with a certain mass concentration for 30-40min, taking out and drying to obtain a semi-finished product C;
(4) adding ammonia water, ethyl orthosilicate, ethanol and water into a reactor, stirring at room temperature to obtain a milky white solution, immersing the semi-finished product C into the solution, taking out the semi-finished product C after 2-5h, drying in a drying oven at 60-80 ℃, taking out the semi-finished product C after drying, soaking in fresh ethanol for 20-40min, taking out, drying, soaking in fresh ethanol, repeating the steps for multiple times, and finally obtaining the finished product of the super-hydrophobic sponge material.
Further, the preparation method of the polyether organic silicon comprises the following steps:
adding hydrogen-terminated hydrogen-containing polysiloxane and propenyl polyether into a reactor, stirring at room temperature for 5-10min under the protection of nitrogen, heating to 60-80 ℃, dropwise adding a platinum catalyst, stirring after dropwise adding, heating to 100-120 ℃, reacting for 3-5h, and removing low-boiling-point substances through reduced pressure distillation after the reaction is finished to obtain the polyether organic silicon.
Further, the mass ratio of the polyether organic silicon to the polypropylene oxide glycol is 1: 5-10.
Furthermore, the speed of the first temperature rise is 1-3 ℃/min, and the speed of the second temperature rise is 5-8 ℃/min.
Further, the mass ratio of the chromium oxide to the concentrated sulfuric acid to the water is 1: 1: 15-20.
Further, the temperature of the heating of the coarsening liquid in the water bath is 35-40 ℃.
Further, the irradiation time of the ultraviolet lamp on each surface of the semi-finished product B is 20-40 min.
Further, the mass concentration of the triethylchlorosilane n-hexane solution is 3-8%.
Further, the volume ratio of ammonia water, ethyl orthosilicate, ethanol and water is 1: 5: 40: 5.
furthermore, the number of soaking times after soaking and drying by fresh ethanol is 3-5.
(III) advantageous effects
The invention provides a preparation method of a super-hydrophobic sponge material for oil-water separation, which has the following beneficial effects:
the invention introduces an organosilicon chain segment by adding polyether organosilicon when preparing the polyurethane sponge in the prior period, the organosilicon chain segment can be embedded into a macromolecular chain segment of the polyurethane sponge, the introduction of silicon atoms reduces the free energy of the surface of the polyurethane sponge, and the organosilicon chain segment migrates, enriches and plays a role of super hydrophobicity to the surface of the sponge material, not only so, a coarsening solution prepared by chromium oxide and concentrated sulfuric acid can enable the surface of the sponge material to become uneven and have certain roughness, which is beneficial to the subsequent fixation of nano silicon dioxide, rich active hydroxyl groups are formed on the surface of the sponge material after the irradiation of an ultraviolet lamp, then the sponge material is soaked by a triethylchlorosilane normal hexane solution, triethylchlorosilane is hydrolyzed, chlorine atoms are gradually substituted to generate triethylhydroxysilane which can be combined with the active hydroxyl groups on the surface of the sponge material, the oil-water separation sponge material is closely combined with the oil-water separation sponge material, the sponge material forms a layer of hydrophobic long-chain silane structure, and finally the nano silicon dioxide forms an outermost hydrophobic layer on the surface of the sponge material.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
a preparation method of a super-hydrophobic sponge material for oil-water separation comprises the following steps:
adding polyether organic silicon, polyoxypropylene glycol and toluene into a reactor, wherein the mass ratio of the polyether organic silicon to the polyoxypropylene glycol is 1:8, stirring and mixing uniformly, heating to 45 ℃, adding isophorone diisocyanate and dibutyltin laurate, continuously reacting for 8 hours, adding gamma-aminopropyl trimethoxy silane, quickly stirring and mixing for 3 minutes, injecting the mixture into a mold, placing the mold into an oven, heating to 70 ℃ at the speed of 1 ℃/min, keeping the temperature for 30 minutes, heating to 110 ℃ at the speed of 6 ℃/min, keeping the temperature for 8 hours, forming, cooling to room temperature to obtain a semi-finished product A, dissolving chromium oxide and concentrated sulfuric acid in water to prepare a roughening solution, wherein the mass ratio of the chromium oxide to the concentrated sulfuric acid to the water is 1: 1: 20, heating the coarsening liquid in a water bath at 40 ℃, immersing the semi-finished product A for 1min, taking out, washing a large amount of water to be neutral, drying the semi-finished product A at a low temperature of-60 ℃ by using a freeze drying method to obtain a semi-finished product B, cutting the semi-finished product B into a required shape, sequentially carrying out ultrasonic cleaning and drying by using absolute ethyl alcohol and water, irradiating each surface by using an ultraviolet lamp, wherein the irradiation time of each surface is 20min, immersing the semi-finished product B into a triethylchlorosilane normal hexane solution with the mass concentration of 3-8%, taking out and drying after immersing for 30min to obtain a semi-finished product C, and mixing the raw materials in a volume ratio of 1: 5: 40: 5, adding ammonia water, tetraethoxysilane, ethanol and water into a reactor, stirring at room temperature to obtain a milky white solution, immersing the semi-finished product C into the solution, taking out the semi-finished product C after 4 hours, drying in a 60 ℃ oven, taking out the semi-finished product C after drying, immersing in fresh ethanol for 30min, taking out, drying, immersing in fresh ethanol again, and repeating the steps for 4 times to finally obtain the finished product of the super-hydrophobic sponge material.
The preparation method of the polyether organic silicon comprises the following steps:
adding hydrogen-terminated hydrogen-containing polysiloxane and propenyl polyether into a reactor, stirring at room temperature for 5min under the protection of nitrogen, heating to 60 ℃, dropwise adding a platinum catalyst, stirring after dropwise adding, heating to 110 ℃ for reaction for 5h, and removing low-boiling-point substances through reduced pressure distillation after the reaction is finished to obtain the polyether organic silicon.
Example 2:
a preparation method of a super-hydrophobic sponge material for oil-water separation comprises the following steps:
adding polyether organic silicon, polyoxypropylene glycol and toluene into a reactor, wherein the mass ratio of the polyether organic silicon to the polyoxypropylene glycol is 1:8, stirring and mixing uniformly, heating to 50 ℃, adding isophorone diisocyanate and dibutyltin laurate, continuously reacting for 6h, adding gamma-aminopropyl trimethoxy silane, stirring and mixing rapidly for 2min, injecting the mixture into a mold, placing the mold in an oven, heating to 60 ℃ at the speed of 1 ℃/min, keeping the temperature for 40min, heating to 110 ℃ at the speed of 8 ℃/min, keeping the temperature for 5h, forming, cooling to room temperature to obtain a semi-finished product A, dissolving chromium oxide and concentrated sulfuric acid in water to prepare a roughening solution, wherein the mass ratio of the chromium oxide to the concentrated sulfuric acid to the water is 1: 1: 20, heating the coarsening liquid in a water bath at 40 ℃, immersing the semi-finished product A for 1min, taking out, washing a large amount of water to be neutral, drying the semi-finished product A at a low temperature of-60 ℃ by using a freeze drying method to obtain a semi-finished product B, cutting the semi-finished product B into a required shape, sequentially carrying out ultrasonic cleaning and drying by using absolute ethyl alcohol and water, irradiating each surface by using an ultraviolet lamp, wherein the irradiation time of each surface is 35min, immersing the semi-finished product B into a triethylchlorosilane normal hexane solution with the mass concentration of 3-8%, taking out and drying after immersing for 40min to obtain a semi-finished product C, and mixing the volume ratio of the raw materials to be 1: 5: 40: 5, adding ammonia water, tetraethoxysilane, ethanol and water into a reactor, stirring at room temperature to obtain a milky white solution, immersing the semi-finished product C into the solution, taking out the semi-finished product C after 2 hours, drying in a 60 ℃ oven, taking out the semi-finished product C after drying, immersing in fresh ethanol for 30min, taking out, drying, immersing in fresh ethanol again, and repeating the steps for 4 times to finally obtain the finished product of the super-hydrophobic sponge material.
The preparation method of the polyether organic silicon comprises the following steps:
adding hydrogen-terminated hydrogen-containing polysiloxane and propenyl polyether into a reactor, stirring at room temperature for 5min under the protection of nitrogen, heating to 70 ℃, dropwise adding a platinum catalyst, stirring after dropwise adding, heating to 100 ℃ for reaction for 5h, and removing low-boiling-point substances through reduced pressure distillation after the reaction is finished to obtain the polyether organic silicon.
Example 3:
a preparation method of a super-hydrophobic sponge material for oil-water separation comprises the following steps:
adding polyether organic silicon, polyoxypropylene glycol and toluene into a reactor, wherein the mass ratio of the polyether organic silicon to the polyoxypropylene glycol is 1:8, stirring and mixing uniformly, heating to 55 ℃, adding isophorone diisocyanate and dibutyltin laurate, continuously reacting for 10 hours, adding gamma-aminopropyl trimethoxysilane into the reactor, stirring and mixing rapidly for 2 minutes, injecting the mixture into a mold, placing the mold into an oven, heating to 60 ℃ at the speed of 3 ℃/min, keeping the temperature for 30 minutes, heating to 110 ℃ at the speed of 5 ℃/min, keeping the temperature for 5 hours, forming, cooling to room temperature to obtain a semi-finished product A, dissolving chromium oxide and concentrated sulfuric acid in water to prepare a roughening solution, wherein the mass ratio of the chromium oxide to the concentrated sulfuric acid to the water is 1: 1: 20, heating the coarsening liquid in a water bath at 40 ℃, immersing the semi-finished product A for 1min, taking out, washing a large amount of water to be neutral, drying the semi-finished product A at a low temperature of-60 ℃ by using a freeze drying method to obtain a semi-finished product B, cutting the semi-finished product B into a required shape, sequentially carrying out ultrasonic cleaning and drying by using absolute ethyl alcohol and water, irradiating each surface by using an ultraviolet lamp, wherein the irradiation time of each surface is 20min, immersing the semi-finished product B into a triethylchlorosilane normal hexane solution with the mass concentration of 3-8%, taking out and drying after immersing for 30min to obtain a semi-finished product C, and mixing the raw materials in a volume ratio of 1: 5: 40: 5, adding ammonia water, tetraethoxysilane, ethanol and water into a reactor, stirring at room temperature to obtain a milky white solution, immersing the semi-finished product C into the solution, taking out the semi-finished product C after 5 hours, drying in a 60 ℃ oven, taking out the semi-finished product C after drying, soaking in fresh ethanol for 25min, taking out, drying, soaking in fresh ethanol again, repeating the steps for 5 times, and finally obtaining the finished product of the super-hydrophobic sponge material.
The preparation method of the polyether organic silicon comprises the following steps:
adding hydrogen-terminated hydrogen-containing polysiloxane and propenyl polyether into a reactor, stirring at room temperature for 5min under the protection of nitrogen, heating to 60 ℃, dropwise adding a platinum catalyst, stirring after dropwise adding, heating to 100 ℃ for reaction for 4h, and removing low-boiling-point substances through reduced pressure distillation after the reaction is finished to obtain the polyether organic silicon.
Example 4:
a preparation method of a super-hydrophobic sponge material for oil-water separation comprises the following steps:
adding polyether organic silicon, polyoxypropylene glycol and toluene into a reactor, wherein the mass ratio of the polyether organic silicon to the polyoxypropylene glycol is 1:5, stirring and mixing uniformly, heating to 50 ℃, adding isophorone diisocyanate and dibutyltin laurate, continuously reacting for 5h, adding gamma-aminopropyl trimethoxy silane, stirring and mixing rapidly for 1min, injecting the mixture into a mold, placing the mold in an oven, heating to 80 ℃ at the speed of 2 ℃/min, keeping the temperature for 40min, heating to 110 ℃ at the speed of 5 ℃/min, keeping the temperature for 5h, forming, cooling to room temperature to obtain a semi-finished product A, dissolving chromium oxide and concentrated sulfuric acid in water to prepare a roughening solution, wherein the mass ratio of the chromium oxide to the concentrated sulfuric acid to the water is 1: 1: heating the coarsening liquid in a water bath at 40 ℃, immersing the semi-finished product A for 1min, taking out, washing a large amount of water to be neutral, drying the semi-finished product A at a low temperature of-60 ℃ by using a freeze drying method to obtain a semi-finished product B, cutting the semi-finished product B into a required shape, sequentially carrying out ultrasonic cleaning and drying by using absolute ethyl alcohol and water, irradiating each surface by using an ultraviolet lamp, wherein the irradiation time of each surface is 20min, finally immersing the semi-finished product B into a triethylchlorosilane normal hexane solution with the mass concentration of 3-8%, taking out and drying after immersing for 40min to obtain a semi-finished product C, and mixing the raw materials in a volume ratio of 1: 5: 40: 5, adding ammonia water, tetraethoxysilane, ethanol and water into a reactor, stirring at room temperature to obtain a milky white solution, immersing the semi-finished product C into the solution, taking out the semi-finished product C after 2 hours, drying in a 60 ℃ oven, taking out the semi-finished product C after drying, immersing in fresh ethanol for 20min, taking out, drying, immersing in fresh ethanol again, and repeating the steps for 4 times to finally obtain the finished product of the super-hydrophobic sponge material.
The preparation method of the polyether organic silicon comprises the following steps:
adding hydrogen-terminated hydrogen-containing polysiloxane and propenyl polyether into a reactor, stirring at room temperature for 5min under the protection of nitrogen, heating to 60 ℃, dropwise adding a platinum catalyst, stirring after dropwise adding, heating to 110 ℃, reacting for 4h, and removing low-boiling-point substances through reduced pressure distillation after the reaction is finished to obtain the polyether organic silicon.
Example 5:
a preparation method of a super-hydrophobic sponge material for oil-water separation comprises the following steps:
adding polyether organic silicon, polyoxypropylene glycol and toluene into a reactor, wherein the mass ratio of the polyether organic silicon to the polyoxypropylene glycol is 1:8, stirring and mixing uniformly, heating to 50 ℃, adding isophorone diisocyanate and dibutyltin laurate, continuously reacting for 5h, adding gamma-aminopropyl trimethoxy silane, stirring and mixing rapidly for 2min, injecting the mixture into a mold, placing the mold in an oven, heating to 70 ℃ at the speed of 2 ℃/min, keeping the temperature for 30min, heating to 110 ℃ at the speed of 6 ℃/min, keeping the temperature for 10h, forming, cooling to room temperature to obtain a semi-finished product A, dissolving chromium oxide and concentrated sulfuric acid in water to prepare a roughening solution, wherein the mass ratio of the chromium oxide to the concentrated sulfuric acid to the water is 1: 1: heating the coarsening liquid in a water bath at 40 ℃, immersing the semi-finished product A for 1min, taking out, washing a large amount of water to be neutral, drying the semi-finished product A at a low temperature of-60 ℃ by using a freeze drying method to obtain a semi-finished product B, cutting the semi-finished product B into a required shape, sequentially carrying out ultrasonic cleaning and drying by using absolute ethyl alcohol and water, irradiating each surface by using an ultraviolet lamp, wherein the irradiation time of each surface is 20min, finally immersing the semi-finished product B into a triethylchlorosilane normal hexane solution with the mass concentration of 3-8%, taking out and drying after immersing for 40min to obtain a semi-finished product C, and mixing the raw materials in a volume ratio of 1: 5: 40: 5, adding ammonia water, tetraethoxysilane, ethanol and water into a reactor, stirring at room temperature to obtain a milky white solution, immersing the semi-finished product C into the solution, taking out the semi-finished product C after 2 hours, drying in a 60 ℃ oven, taking out the semi-finished product C after drying, immersing in fresh ethanol for 20min, taking out, drying, immersing in fresh ethanol again, repeating the steps for 5 times, and finally obtaining the finished product of the super-hydrophobic sponge material.
The preparation method of the polyether organic silicon comprises the following steps:
adding hydrogen-terminated hydrogen-containing polysiloxane and propenyl polyether into a reactor, stirring at room temperature for 5min under the protection of nitrogen, heating to 80 ℃, dropwise adding a platinum catalyst, stirring after dropwise adding, heating to 105 ℃ for reaction for 5h, and removing low-boiling-point substances through reduced pressure distillation after the reaction is finished to obtain the polyether organic silicon.
Example 6:
a preparation method of a super-hydrophobic sponge material for oil-water separation comprises the following steps:
adding polyether organic silicon, polyoxypropylene glycol and toluene into a reactor, wherein the mass ratio of the polyether organic silicon to the polyoxypropylene glycol is 1:5, stirring and mixing uniformly, heating to 40 ℃, adding isophorone diisocyanate and dibutyltin laurate, continuously reacting for 10 hours, adding gamma-aminopropyl trimethoxysilane into the reactor, stirring and mixing rapidly for 5 minutes, injecting the mixture into a mold, placing the mold into an oven, heating to 80 ℃ at the speed of 2 ℃/min, keeping the temperature for 20 minutes, heating to 110 ℃ at the speed of 6 ℃/min, keeping the temperature for 5 hours, molding, cooling to room temperature to obtain a semi-finished product A, dissolving chromium oxide and concentrated sulfuric acid in water to prepare a roughening solution, wherein the mass ratio of the chromium oxide to the concentrated sulfuric acid to the water is 1: 1: heating the coarsening liquid in a water bath at 40 ℃, immersing the semi-finished product A for 2min, taking out, washing a large amount of water to be neutral, drying the semi-finished product A at a low temperature of-60 ℃ by using a freeze drying method to obtain a semi-finished product B, cutting the semi-finished product B into a required shape, sequentially carrying out ultrasonic cleaning and drying by using absolute ethyl alcohol and water, irradiating each surface by using an ultraviolet lamp, wherein the irradiation time of each surface is 20min, immersing the semi-finished product B into a triethylchlorosilane normal hexane solution with the mass concentration of 3-8%, taking out and drying after immersing for 35min to obtain a semi-finished product C, and mixing the raw materials in a volume ratio of 1: 5: 40: 5, adding ammonia water, tetraethoxysilane, ethanol and water into a reactor, stirring at room temperature to obtain a milky white solution, immersing the semi-finished product C into the solution, taking out the semi-finished product C after 4 hours, drying in a 60 ℃ oven, taking out the semi-finished product C after drying, soaking in fresh ethanol for 25min, taking out, drying, soaking in fresh ethanol again, and repeating the steps for 3 times to finally obtain the finished product of the super-hydrophobic sponge material.
The preparation method of the polyether organic silicon comprises the following steps:
adding hydrogen-terminated hydrogen-containing polysiloxane and propenyl polyether into a reactor, stirring at room temperature for 5min under the protection of nitrogen, heating to 60 ℃, dropwise adding a platinum catalyst, stirring after dropwise adding, heating to 100 ℃ for reaction for 4h, and removing low-boiling-point substances through reduced pressure distillation after the reaction is finished to obtain the polyether organic silicon.
Example 7:
a preparation method of a super-hydrophobic sponge material for oil-water separation comprises the following steps:
adding polyether organic silicon, polyoxypropylene glycol and toluene into a reactor, wherein the mass ratio of the polyether organic silicon to the polyoxypropylene glycol is 1:5, stirring and mixing uniformly, heating to 40 ℃, adding isophorone diisocyanate and dibutyltin laurate, continuously reacting for 5h, adding gamma-aminopropyl trimethoxy silane, stirring and mixing rapidly for 1min, injecting the mixture into a mold, placing the mold in an oven, heating to 60 ℃ at the speed of 1 ℃/min, keeping the temperature for 20min, heating to 110 ℃ at the speed of 5 ℃/min, keeping the temperature for 5h, forming, cooling to room temperature to obtain a semi-finished product A, dissolving chromium oxide and concentrated sulfuric acid in water to prepare a roughening solution, wherein the mass ratio of the chromium oxide to the concentrated sulfuric acid to the water is 1: 1: 15, heating the coarsening liquid in a water bath at 35 ℃, immersing the semi-finished product A for 1min, taking out, washing a large amount of water to be neutral, drying the semi-finished product A at a low temperature of-60 ℃ by using a freeze drying method to obtain a semi-finished product B, cutting the semi-finished product B into a required shape, sequentially carrying out ultrasonic cleaning and drying by using absolute ethyl alcohol and water, irradiating each surface by using an ultraviolet lamp, wherein the irradiation time of each surface is 20min, immersing the semi-finished product B into a triethylchlorosilane normal hexane solution with the mass concentration of 3-8%, taking out and drying after immersing for 30min to obtain a semi-finished product C, and mixing the coarse liquid A with the water in a volume ratio of 1: 5: 40: 5, adding ammonia water, ethyl orthosilicate, ethanol and water into a reactor, stirring at room temperature to obtain a milky white solution, immersing the semi-finished product C into the solution, taking out the semi-finished product C after 2 hours, drying in a 60 ℃ oven, taking out the semi-finished product C after drying, immersing in fresh ethanol for 20min, taking out, drying, immersing in fresh ethanol again, and repeating the steps for 3 times to finally obtain the finished product of the super-hydrophobic sponge material.
The preparation method of the polyether organic silicon comprises the following steps:
adding hydrogen-terminated hydrogen-containing polysiloxane and propenyl polyether into a reactor, stirring at room temperature for 5min under the protection of nitrogen, heating to 60 ℃, dropwise adding a platinum catalyst, stirring after dropwise adding, heating to 100 ℃ for reaction for 3h, and removing low-boiling-point substances through reduced pressure distillation after the reaction is finished to obtain the polyether organic silicon.
Example 8:
a preparation method of a super-hydrophobic sponge material for oil-water separation comprises the following steps:
adding polyether organic silicon, polyoxypropylene glycol and toluene into a reactor, wherein the mass ratio of the polyether organic silicon to the polyoxypropylene glycol is 1:10, stirring and mixing uniformly, heating to 60 ℃, adding isophorone diisocyanate and dibutyltin laurate, continuously reacting for 10 hours, adding gamma-aminopropyl trimethoxysilane into the reactor, stirring and mixing rapidly for 5 minutes, injecting the mixture into a mold, placing the mold into an oven, heating to 80 ℃ at the speed of 3 ℃/min, keeping the temperature for 40 minutes, heating to 120 ℃ at the speed of 8 ℃/min, keeping the temperature for 10 hours, molding, cooling to room temperature to obtain a semi-finished product A, dissolving chromium oxide and concentrated sulfuric acid in water to prepare a roughening solution, wherein the mass ratio of the chromium oxide to the concentrated sulfuric acid to the water is 1: 1: 20, heating the coarsening liquid in a water bath at 40 ℃, immersing the semi-finished product A for 3min, taking out, washing a large amount of water to be neutral, drying the semi-finished product A at a low temperature of-60 ℃ by using a freeze drying method to obtain a semi-finished product B, cutting the semi-finished product B into a required shape, sequentially carrying out ultrasonic cleaning and drying by using absolute ethyl alcohol and water, irradiating each surface by using an ultraviolet lamp, wherein the irradiation time of each surface is 40min, finally immersing the semi-finished product B into a triethylchlorosilane normal hexane solution with the mass concentration of 3-8%, taking out and drying after immersing for 40min to obtain a semi-finished product C, and mixing the volume ratio of 1: 5: 40: 5, adding ammonia water, tetraethoxysilane, ethanol and water into a reactor, stirring at room temperature to obtain a milky white solution, immersing the semi-finished product C into the solution, taking out the semi-finished product C after 5 hours, drying in an oven at 80 ℃, taking out the semi-finished product C after drying, immersing in fresh ethanol for 40min, taking out, drying, immersing in fresh ethanol again, and repeating the steps for 5 times to finally obtain the finished product of the super-hydrophobic sponge material.
The preparation method of the polyether organic silicon comprises the following steps:
adding hydrogen-terminated hydrogen-containing polysiloxane and propenyl polyether into a reactor, stirring at room temperature for 10min under the protection of nitrogen, heating to 80 ℃, dropwise adding a platinum catalyst, stirring after dropwise adding, heating to 120 ℃ for reaction for 5h, and removing low-boiling-point substances through reduced pressure distillation after the reaction is finished to obtain the polyether organic silicon.
And (3) performance testing:
the contact angle is an important index for measuring the hydrophobic property of the sponge material, the sponge materials prepared in examples 1-3 of the present invention were subjected to contact angle measurement (first contact angle measurement), and then the sponge materials were repeatedly absorbed with n-hexane 10 times and subjected to contact angle measurement again (second contact angle measurement), and the results of the two measurements are shown in table 1 below:
table 1:
the sponge materials prepared in examples 1 to 3 according to the invention were each weighed W1Soaking in diesel oil for 5min, taking out, sucking excessive solvent with filter paper, and weighing2The adsorption capacity P of the sponge material is calculated by the following formula:
P＝(W2-W1)/W1
squeezing to remove diesel oil adsorbed in sponge material, washing with ethanol, drying in oven, and repeating the adsorption test, wherein the adsorption capacity of the sponge material without adsorption is recorded as P0P is recorded after one test1In this analogy, it is denoted as PnThe test results are shown in table 2 below.
Table 2:
as can be seen from the above table 1, the contact angle between the surface of the sponge material and water is more than 150 degrees, the sponge material has super-hydrophobic property, and the contact angle is only reduced a little after the sponge material absorbs n-hexane repeatedly for 10 times.
As can be seen from the above Table 2, the sponge material of the present invention has excellent adsorption capacity for diesel oil with high viscosity, and the adsorption capacity is not substantially reduced after repeated adsorption for many times.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other identical elements in a process, method, article, or apparatus that comprises the element.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. A preparation method of a super-hydrophobic sponge material for oil-water separation is characterized by comprising the following steps:
(1) adding polyether organic silicon, polyoxypropylene glycol and toluene into a reactor, stirring and mixing uniformly, heating to 40-60 ℃, adding isophorone diisocyanate and dibutyltin laurate, continuing to react for 5-10h, adding gamma-aminopropyl trimethoxysilane into the reactor, stirring and mixing rapidly for 1-5min, injecting the mixture into a mold, placing the mold into an oven, heating to 60-80 ℃ for heat preservation for 20-40min for once, heating to 110-120 ℃ for heat preservation for 5-10h for molding, and cooling to room temperature to obtain a semi-finished product A;
(2) dissolving chromium oxide and concentrated sulfuric acid in water to prepare coarsening liquid, heating the coarsening liquid in a water bath, immersing the semi-finished product A in the solution for 1-3min, taking out the semi-finished product A, washing the semi-finished product A to be neutral by a large amount of water, and drying the semi-finished product A at a low temperature of-60 ℃ by using a freeze drying method to obtain a semi-finished product B;
(3) cutting the semi-finished product B into a required shape, sequentially carrying out ultrasonic cleaning and drying by using absolute ethyl alcohol and water, irradiating each surface of the semi-finished product B by using an ultraviolet lamp, finally soaking the semi-finished product B into a triethylchlorosilane normal hexane solution with a certain mass concentration for 30-40min, taking out and drying to obtain a semi-finished product C;
(4) adding ammonia water, ethyl orthosilicate, ethanol and water into a reactor, stirring at room temperature to obtain a milky white solution, immersing the semi-finished product C into the solution, taking out the semi-finished product C after 2-5h, drying in a drying oven at 60-80 ℃, taking out the semi-finished product C after drying, soaking in fresh ethanol for 20-40min, taking out, drying, soaking in fresh ethanol, repeating the steps for multiple times, and finally obtaining the finished product of the super-hydrophobic sponge material.
2. The method for preparing the superhydrophobic sponge material for oil-water separation according to claim 1, wherein the polyether silicone is prepared by the following steps:
adding hydrogen-terminated hydrogen-containing polysiloxane and propenyl polyether into a reactor, stirring at room temperature for 5-10min under the protection of nitrogen, heating to 60-80 ℃, dropwise adding a platinum catalyst, stirring after dropwise adding, heating to 100-120 ℃, reacting for 3-5h, and removing low-boiling-point substances through reduced pressure distillation after the reaction is finished to obtain the polyether organic silicon.
3. The method for preparing the superhydrophobic sponge material for oil-water separation according to claim 1, wherein the mass ratio of the polyether silicone to the polyoxypropylene diol is 1: 5-10.
4. The method for preparing the superhydrophobic sponge material for oil-water separation according to claim 1, wherein the first temperature rise rate is 1-3 ℃/min and the second temperature rise rate is 5-8 ℃/min.
5. The method for preparing the superhydrophobic sponge material for oil-water separation according to claim 1, wherein the mass ratio of the chromium oxide to the concentrated sulfuric acid to the water is 1: 1: 15-20.
6. The method for preparing the superhydrophobic sponge material for oil-water separation according to claim 1, wherein the temperature of the heating in water bath of the coarsening liquid is 35-40 ℃.
7. The method of claim 1, wherein the irradiation time of the ultraviolet lamp to each surface of the semi-finished product B is 20-40 min.
8. The method for preparing a superhydrophobic sponge material for oil-water separation according to claim 1, wherein the mass concentration of the triethylchlorosilane n-hexane solution is 3-8%.
9. The method for preparing the superhydrophobic sponge material for oil-water separation according to claim 1, wherein the volume ratio of ammonia water, tetraethoxysilane, ethanol and water is 1: 5: 40: 5.
10. the method for preparing the superhydrophobic sponge material for oil-water separation according to claim 1, wherein the number of soaking, drying and re-soaking with fresh ethanol is 3-5.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112108130A (en) * | 2020-09-10 | 2020-12-22 | 辽宁大学 | Intelligent super-hydrophobic material and preparation method and application thereof |
| CN112452309A (en) * | 2020-12-15 | 2021-03-09 | 福建龙净环保股份有限公司 | Oil-water separation material and preparation method thereof |
| CN114345309A (en) * | 2022-01-24 | 2022-04-15 | 西南石油大学 | Benzene and benzene series adsorbent and preparation method thereof |
| CN115228305A (en) * | 2022-06-20 | 2022-10-25 | 深圳高性能医疗器械国家研究院有限公司 | Janus film and preparation method thereof |
-
2019
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112108130A (en) * | 2020-09-10 | 2020-12-22 | 辽宁大学 | Intelligent super-hydrophobic material and preparation method and application thereof |
| CN112108130B (en) * | 2020-09-10 | 2021-11-30 | 辽宁大学 | Intelligent super-hydrophobic material and preparation method and application thereof |
| CN112452309A (en) * | 2020-12-15 | 2021-03-09 | 福建龙净环保股份有限公司 | Oil-water separation material and preparation method thereof |
| CN112452309B (en) * | 2020-12-15 | 2023-05-16 | 福建龙净环保股份有限公司 | Oil-water separation material and preparation method thereof |
| CN114345309A (en) * | 2022-01-24 | 2022-04-15 | 西南石油大学 | Benzene and benzene series adsorbent and preparation method thereof |
| CN115228305A (en) * | 2022-06-20 | 2022-10-25 | 深圳高性能医疗器械国家研究院有限公司 | Janus film and preparation method thereof |
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