CN107349792B - regenerated film device and manufacturing method thereof - Google Patents
regenerated film device and manufacturing method thereof Download PDFInfo
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- CN107349792B CN107349792B CN201610305873.2A CN201610305873A CN107349792B CN 107349792 B CN107349792 B CN 107349792B CN 201610305873 A CN201610305873 A CN 201610305873A CN 107349792 B CN107349792 B CN 107349792B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D65/00—Accessories or auxiliary operations, in general, for separation processes or apparatus using semi-permeable membranes
- B01D65/02—Membrane cleaning or sterilisation ; Membrane regeneration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2321/00—Details relating to membrane cleaning, regeneration, sterilization or to the prevention of fouling
- B01D2321/04—Backflushing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2321/00—Details relating to membrane cleaning, regeneration, sterilization or to the prevention of fouling
- B01D2321/16—Use of chemical agents
- B01D2321/162—Use of acids
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2321/00—Details relating to membrane cleaning, regeneration, sterilization or to the prevention of fouling
- B01D2321/16—Use of chemical agents
- B01D2321/164—Use of bases
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Abstract
The invention relates to a regenerated membrane device, which comprises an original membrane device and a cross-linking layer attached to the surface of the original membrane device, wherein the cross-linking layer is obtained by cross-linking and modifying the surface of the original membrane device through siloxane prepolymer liquid, the siloxane prepolymer liquid is composed of prepolymer and inert organic solvent, and the prepolymer is a copolymer obtained by polymerizing multi-alkoxy silane and functional monomers. The invention also relates to a preparation method of the regenerated membrane device.
Description
Technical Field
The invention relates to the field of application of membrane devices, in particular to a membrane device regenerated through surface crosslinking and a preparation method thereof.
Background
Since the beginning of the 20 th century, membrane separation technology has developed rapidly. The membrane separation technology has the functions of separation, concentration, purification and refining, and has the advantages of high efficiency, high precision, simple process, easy control and the like, so the membrane separation technology is widely applied to the fields of food, medicine, biology, environmental protection, chemical industry, water treatment and the like. The core component in membrane separation technology is a membrane device. Today, the types of membrane separation devices and corresponding membrane devices on the market are numerous.
However, various membrane devices such as organic membranes, inorganic membranes, reverse osmosis membranes, nanofiltration membranes, ultrafiltration membranes, microfiltration membranes, etc. have a problem of increased energy consumption and cost in the membrane separation operation process due to the interface contamination of the membranes. In use today, it is often necessary to periodically clean the membrane device to maintain the proper separation performance and flux of the membrane. However, as the separation time is prolonged, the membrane device gradually degrades or fails in performance due to accumulation of contaminants and growth and propagation of microorganisms such as bacteria. Thus, the membrane device needs to be replaced. At present, the replaced membrane devices are treated as industrial waste or household waste, which increases the investment of operation cost to a great extent and further brings environmental pollution.
Disclosure of Invention
In view of the above, the present invention provides a regenerated film device and a method for manufacturing the same, which can solve at least one of the existing technical problems.
The invention provides a regenerated membrane device, which comprises an original membrane device and a crosslinking layer attached to the surface of the original membrane device, wherein the crosslinking layer is obtained by crosslinking and modifying the surface of the original membrane device through siloxane prepolymer liquid, the siloxane prepolymer liquid consists of a prepolymer and an inert organic solvent, the prepolymer is a copolymer obtained by polymerizing multi-alkoxy silane and a functional monomer, the multi-alkoxy silane is at least one of vinyl trimethoxy silane, vinyl triethoxy silane, methyl vinyl diethoxy silane and methacryloxypropyl trimethyl silane, and the functional monomer is hydroxyethyl methacrylate, hydroxypropyl methacrylate, dimethylaminoethyl methacrylate, acrylic acid, N- (3-dimethylaminopropyl) methacrylamide, polyethylene glycol methacrylate, or polyethylene glycol methacrylate, At least one of methyl methacrylate, acrylamide and N-vinyl pyrrolidone.
Preferably, the mass of the cross-linked layer accounts for 3% -25% of the mass of the regenerated membrane device, and the thickness of the cross-linked layer is 1-100 nm.
Preferably, the raw membrane device is at least one of a tubular membrane, a curtain membrane, a column membrane and a flat membrane.
Preferably, the inert organic solvent is at least one of ethanol, triethyl phosphate, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone and trimethyl phosphate, and the ratio of the prepolymer to the inert organic solvent is (2 g-50 g):100 mL.
the invention also provides a preparation method of the regenerated membrane device, which comprises the following steps:
(1) Providing siloxane prepolymer liquid, and diluting the siloxane prepolymer liquid by a diluent;
(2) placing the original film device in diluted siloxane pre-polymerization liquid for dipping treatment; and
(3) And carrying out pre-crosslinking reaction on the original membrane device subjected to the dipping treatment to obtain the regenerated membrane device.
Preferably, the preparation method of the siloxane prepolymer fluid in the step (1) is as follows: adding a polyalkoxysilane, a functional monomer and an initiator into an inert organic solvent to obtain a mixture; and then heating the mixture and carrying out polymerization reaction under an inert atmosphere to obtain the siloxane prepolymer liquid.
Preferably, the initiator is at least one of dibenzoyl peroxide, dialkyl peroxide, azodiisobutyronitrile, azodiisoheptadecylamine, azodiisobutyronitrile and azoisobutyronitrile formamide, and the ratio of the polyalkoxysilane, the functional monomer, the initiator and the inert organic solvent is as follows: (1 g-25 g): (0.05 g-0.5 g):100mL, the reaction temperature of the polymerization reaction is 50-100 ℃, and the reaction time is 2-48 hours.
preferably, the diluent in the step (1) is a mixture of water and ethanol, and the volume ratio of the siloxane prepolymer liquid to the diluent is 1: 4-4: 1.
Preferably, the raw film device in the step (2) further includes a step of performing a cleaning process on the raw film device before the dipping process.
Preferably, the catalyst for the pre-crosslinking reaction in the step (3) is at least one of hydrochloric acid, sulfuric acid, acetic acid, citric acid, phosphoric acid, sodium hydroxide, potassium hydroxide, sodium citrate, sodium bicarbonate, ammonium chloride and ammonium sulfate, the reaction temperature of the pre-crosslinking reaction is 40-100 ℃, and the reaction time is 4-48 hours.
Compared with the prior art, the invention has the following advantages: firstly, the surface of the original membrane device is subjected to crosslinking modification through the siloxane prepolymer solution to form a crosslinking layer on the surface of the original membrane device, the crosslinking layer is tightly entangled with the surface of the original membrane device to be combined into an integral structure, the surface performance of the regenerated membrane device is stable, and the original morphological structure of the membrane surface is not damaged in the surface crosslinking modification process, and the physical and mechanical properties of the original membrane device are not damaged. The obtained regenerated membrane device can restore the original performance and be put into use again, thereby greatly reducing the operation cost and having the characteristic of environmental protection. Secondly, the cross-linking layer is formed by cross-linking modification of the surface of the original membrane device through a prepolymer obtained by polymerizing a functional monomer and a plurality of alkoxy silanes, so that the functional prepolymer can be formed through free combination of the functional monomer, and the surface of the regenerated membrane device has new functions of hydrophilicity, pollution resistance, bacteria resistance and the like.
The preparation method of the regenerated membrane device has the advantages of mild conditions and simple process, can realize batch regeneration or online regeneration of waste and old membrane devices, can also realize multiple regeneration of waste and old membrane devices, and is suitable for large-scale industrial production.
Drawings
Fig. 1 is a flowchart of a method for manufacturing a regenerated film device according to the present invention.
Detailed Description
The regenerated film device and the method for manufacturing the same according to the present invention will be further described below.
The invention provides a preparation method of a regenerated membrane device, which comprises the following steps:
s1, providing a siloxane prepolymer solution, and diluting the siloxane prepolymer solution by a diluent;
S2, placing the original film device in diluted siloxane pre-polymerization liquid for dipping treatment; and
and S3, carrying out pre-crosslinking reaction on the original membrane device after the dipping treatment to obtain the regenerated membrane device.
In step S1, the diluent is used to dilute the siloxane prepolymer solution. The diluent is a water and ethanol blend. The mixing ratio of the water and the ethanol is not limited. The volume ratio of the siloxane prepolymer liquid to the diluent is 1: 4-4: 1.
The preparation method of the siloxane prepolymer solution comprises the following steps:
S11, adding the polyalkoxysilane, the functional monomer and the initiator into an inert organic solvent to obtain a mixture;
S12, heating the mixture and carrying out polymerization reaction under inert atmosphere to obtain the siloxane prepolymer liquid.
In step S11, the functional monomer can be selected according to the functional requirements of surface modification, specifically, a monomer containing an unsaturated carbon-carbon double bond (C ═ C). The polyalkoxysilane is a polyalkoxysilane containing unsaturated carbon-carbon double bonds (C ═ C). And carrying out polymerization reaction on the multi-alkoxy silane and the functional monomer under the action of the initiator to obtain a prepolymer. Specifically, the polyalkoxysilane is at least one of vinyltrimethoxysilane, vinyltriethoxysilane, methylvinyldiethoxysilane and methacryloxypropyltrimethylsilane. The functional monomer is at least one of hydroxyethyl methacrylate, hydroxypropyl methacrylate, dimethylaminoethyl methacrylate, acrylic acid, N- (3-dimethylaminopropyl) methacrylamide, polyethylene glycol methacrylate, methyl methacrylate, acrylamide and N-vinyl pyrrolidone.
the initiator functions to initiate polymerization. The initiator is an organic peroxide initiator and/or an azo initiator. The organic peroxide initiator is at least one of dibenzoyl peroxide and dialkyl peroxide, and the azo initiator is at least one of azodiisobutyronitrile, azodiisoheptadecylne, dimethyl azodiisobutyrate and azoisobutyrylcyanamide. The amount of the initiator is small and can be determined according to specific reactants and the amount of the initiator.
The mass ratio of the multi-alkoxy silane to the functional monomer is 2: 1-1: 3, preferably 2: 1-1: 2.
the inert organic solvent is used for storing the obtained prepolymer in a liquid state, isolating induction of moisture and the like, preventing the prepolymer from being hydrolyzed and crosslinked in the storage process, and enabling the prepolymer to be in a relatively stable state so as to be stored for a long time. The inert organic solvent is at least one of ethanol, triethyl phosphate, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone and trimethyl phosphate. The amount of the inert organic solvent is determined according to specific needs, and generally, the amount of the inert organic solvent is small so as to facilitate the storage and transportation needs. That is, the ratio of the polyalkoxysilane to the inert organic solvent is: (1 g-25 g) (80 mL-150 mL).
Preferably, the ratio of the polyalkoxysilane, the functional monomer, the initiator and the inert organic solvent is as follows: (1 g-25 g), (0.05 g-0.5 g) and 100 mL.
In step S12, the polymerization reaction is performed at a reaction temperature of 50 to 100 degrees celsius for 2 to 48 hours. Preferably, the reaction temperature is 65-85 ℃, and the reaction time is 8-24 hours.
After the reaction, the ratio of the obtained prepolymer to the inert organic solvent is (2g to 50g) 100mL, preferably (5g to 30g) 100 mL.
In step S2, the dipping treatment is performed to attach the prepolymer to the surface of the original film device in advance. The time for the immersion treatment is 0.5 to 48 hours, preferably 1 to 12 hours.
The raw membrane device is made of at least one of a tubular membrane, a curtain membrane, a column membrane and a flat membrane.
The original membrane device further comprises a step of cleaning the original membrane device before the dipping treatment. The cleaning treatment specifically comprises the following steps: and sequentially carrying out cleaning processes such as alkali cleaning, acid cleaning, oxidation reduction, backwashing and the like on the original membrane device to remove pollutants to obtain a clean original membrane device.
In step S3, the dipped raw film device may be moved into a solution containing a catalyst for pre-crosslinking reaction. The solvent in the catalyst-containing solution is water. The catalyst is at least one of hydrochloric acid, sulfuric acid, acetic acid, citric acid, phosphoric acid, sodium hydroxide, potassium hydroxide, sodium citrate, sodium bicarbonate, ammonium chloride and ammonium sulfate. The concentration of the catalyst is 0 to 1mol/L, preferably 0.01 to 0.5 mol/L. When the concentration of the catalyst is 0, it means that the pre-crosslinking reaction can be directly carried out in water without adding a catalyst. When no catalyst is added, the reaction environment suggests the use of deionized water. The reaction temperature of the pre-crosslinking reaction is 40-100 ℃, and the reaction time is 4-48 hours. Preferably, the reaction temperature of the pre-crosslinking reaction is 50-80 ℃, and the reaction time is 8-24 hours.
the invention also provides a regenerated film device prepared by the method. The regeneration film device comprises an original film device and a cross-linking layer attached to the surface of the original film device, wherein the cross-linking layer is obtained by cross-linking and modifying the surface of the original film device through siloxane pre-polymerization liquid.
The siloxane prepolymer liquid consists of a prepolymer and an inert organic solvent, wherein the prepolymer is a copolymer obtained by polymerizing multi-alkoxy silane and a functional monomer.
The mass of the cross-linking layer accounts for 3-25% of the mass of the regenerated membrane device, and the thickness of the cross-linking layer is 1-100 nm. Preferably, the mass of the cross-linked layer accounts for 3% -15% of the mass of the regenerated membrane device, and the thickness of the cross-linked layer is 10-50 nm.
Compared with the prior art, the invention has the following advantages: firstly, the surface of the original membrane device is subjected to crosslinking modification through the siloxane prepolymer solution to form a crosslinking layer on the surface of the original membrane device, the crosslinking layer is tightly entangled with the surface of the original membrane device to be combined into an integral structure, the surface performance of the regenerated membrane device is stable, and the original morphological structure of the membrane surface is not damaged in the surface crosslinking modification process, and the physical and mechanical properties of the original membrane device are not damaged. The obtained regenerated membrane device can restore the original performance and be put into use again, thereby greatly reducing the operation cost and having the characteristic of environmental protection. Secondly, the cross-linking layer is formed by cross-linking modification of the surface of the original membrane device through a prepolymer obtained by polymerizing a functional monomer and a plurality of alkoxy silanes, so that the functional prepolymer can be formed through free combination of the functional monomer, and the surface of the regenerated membrane device has new functions of hydrophilicity, pollution resistance, bacteria resistance and the like.
The preparation method of the regenerated membrane device has the advantages of mild conditions and simple process, can realize batch regeneration or online regeneration of waste and old membrane devices, can also realize multiple regeneration of waste and old membrane devices, and is suitable for large-scale industrial production.
Hereinafter, the regenerated membrane device and the method for manufacturing the same according to the present invention will be further described with reference to specific examples.
Example 1
(1) 3g of hydroxyethyl methacrylate, 2g of vinyltrimethoxysilane and 0.06g of benzoyl peroxide are sequentially added into 100mL of absolute ethanol, industrial nitrogen is introduced, and mechanical stirring is carried out at normal temperature of 200r/min for 20 min. Then the temperature is gradually increased to 65 ℃ by turning on the heating, and the reaction is mechanically stirred for 36 hours at 200r/min under the industrial nitrogen atmosphere. And (3) closing the heating, and fully cooling to obtain hydrophilic hydroxyethyl methacrylate/vinyl trimethoxy silane copolymer pre-polymerization liquid. Then, 40mL of deionized water was added to 100mL of the obtained prepolymer solution to obtain a diluted prepolymer solution.
(2) The tubular membrane filter element replaced by the household water purifier is firstly pickled and then is backwashed to obtain a clean filter element.
(3) And (3) injecting the pre-polymerization solution after sufficient dilution into the cleaned tubular membrane filter element, sealing the inlet and the outlet, and standing for 2 hours.
(4) And pouring out the diluted prepolymer solution in the filter element, injecting pure water, and standing at the constant temperature of 60 ℃ for 8 hours to obtain the tubular membrane filter element for the regenerative household water purifier.
Through tests, the water flux and the interception performance of the tubular membrane filter element for the regenerative household water purifier are recovered as before.
Example 2
(1) 4g of N-vinylpyrrolidone, 3g of vinyltriethoxysilane and 0.1g of azobisisoheptanide are added to 100mL of triethyl phosphate in this order, high-purity nitrogen gas is introduced, and mechanical stirring is carried out at 250r/min at normal temperature for 30 min. Then the temperature is gradually increased to 80 ℃ by turning on the heating, and the reaction is mechanically stirred for 24 hours at 250r/min under the industrial nitrogen atmosphere. And closing the heating, and fully cooling to obtain hydrophilic N-vinyl pyrrolidone/vinyl triethoxysilane copolymer pre-polymerization liquid. 100mL of 60% aqueous ethanol solution was added to 100mL of the obtained prepolymer solution to obtain a diluted prepolymer solution.
(2) And sequentially performing alkali washing, acid washing and sodium hypochlorite oxidation on the polluted waste polyvinylidene fluoride curtain type membrane, and backwashing to obtain a clean curtain type membrane.
(3) Soaking the cleaned curtain film into sufficient diluted pre-polymerization solution, and standing for 3 hours;
(4) And taking out the curtain type membrane, soaking the curtain type membrane into sufficient hydrochloric acid aqueous solution with the pH value of 5, and standing the curtain type membrane for 20 hours at the temperature of 65 ℃ to obtain the regenerated polyvinylidene fluoride curtain type membrane.
Through tests, the water flux and the interception performance of the regenerated polyvinylidene fluoride curtain membrane are recovered as before.
Example 3
(1) 6g of hydroxypropyl methacrylate, 5g of N-polyethylene glycol methacrylate, 5g of methyl vinyl diethoxysilane/3 g of vinyl triethoxysilane and 0.2g of azo isobutyryl cyano formamide are added in this order to 100mL of dimethyl sulfoxide, nitrogen is introduced, and mechanical stirring is carried out at normal temperature of 200r/min for 60 min. Then the temperature is gradually raised to 100 ℃ by opening the heating, and the reaction is carried out for 10 hours by mechanical stirring at 200r/min in the normal nitrogen atmosphere. And closing the heating, and fully cooling to obtain a pre-polymerization solution of hydroxypropyl methacrylate/N-polyethylene glycol methacrylate/methyl vinyl diethoxysilane/vinyl triethoxysilane copolymer. 60mL of 35% aqueous ethanol was added to 100mL of the obtained prepolymer solution to obtain a diluted prepolymer solution.
(2) And sequentially performing alkali washing and acid washing on the polluted waste polysulfone flat membrane, and then performing backwashing to obtain a clean flat membrane.
(3) The washed flat membrane was immersed in a sufficient amount of the diluted prepolymerization solution and allowed to stand for 2.5 hours.
(4) Taking out the flat membrane, soaking the flat membrane into sufficient sodium hydroxide aqueous solution with the pH value of 9, and standing the flat membrane for 24 hours at 70 ℃ to obtain the regenerated polysulfone flat membrane.
The test shows that the water flux and the retention performance of the regenerated polysulfone flat sheet membrane are recovered as before. Meanwhile, the test result shows that the protein pollution resistance of the regenerated polysulfone flat membrane is superior to that of a newly produced flat membrane.
Example 4
(1) 8g of N- (3-dimethylaminopropyl) methacrylamide, 4g of N-polyethylene glycol methacrylate, 4g of hydroxyethyl methacrylate, 8g of vinyltrimethoxysilane and 0.25g of benzoyl peroxide were added in this order to 100mL of absolute ethanol, nitrogen was introduced, and mechanical stirring was carried out at 200r/min at normal temperature for 60 min. Then the temperature is gradually raised to 65 ℃ by opening the heating, and the reaction is carried out for 36 hours by mechanical stirring at 200r/min under the normal nitrogen atmosphere. And (3) closing the heating, and fully cooling to obtain the pre-polymerization solution of the N- (3-dimethylaminopropyl) methacrylamide/N-polyethylene glycol methacrylate/hydroxyethyl methacrylate/vinyl trimethoxy silane copolymer. 30mL of 75% aqueous ethanol solution was added to 100mL of the obtained prepolymer solution to obtain a diluted prepolymer solution.
(2) And sequentially carrying out online alkali washing, acid washing and sodium hypochlorite solution washing on the column type membrane after performance attenuation in the separation operation process, and then carrying out backwashing to remove pollutants adhered to the surface of the column type membrane.
(3) Sufficient diluted prepolymerization solution was injected into the column membrane on-line and circulated for 1.5 hours.
(4) And discharging the diluted prepolymerization solution, replacing the prepolymerization solution with an acetic acid aqueous solution with the pH of 5, circulating the solution at the temperature of 60 ℃ for 20 hours, and replacing the solution with deionized water to wash the solution for 30 minutes to obtain the regenerative column type membrane.
The water flux and the retention performance of the regenerated column type membrane are recovered as before through an online test. Meanwhile, under the same separation operation condition, the performance decay period of the regenerated column type membrane is longer than that of a newly produced column type membrane. This shows that the hydrophilic property of the column type membrane is restored and the anti-pollution property is improved after the regeneration treatment.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (9)
1. A regenerated membrane device is characterized by comprising an original membrane device and a cross-linking layer attached to the surface of the original membrane device, wherein the original membrane device is a waste or old membrane device, the mass of the cross-linking layer accounts for 3% -25% of the mass of the regenerated membrane device, and the thickness of the cross-linking layer is 1-100 nm;
The cross-linking layer is obtained by cross-linking and modifying the surface of the original membrane device through siloxane pre-polymerization liquid, the siloxane pre-polymerization liquid is composed of a pre-polymer and an inert organic solvent, the pre-polymer is a copolymer obtained by polymerizing multi-alkoxy silane and a functional monomer, the multi-alkoxy silane is at least one of vinyl trimethoxy silane, vinyl triethoxy silane, methyl vinyl diethoxy silane and methacryloxypropyl trimethyl silane, and the functional monomer is at least one of hydroxyethyl methacrylate, hydroxypropyl methacrylate, dimethylaminoethyl methacrylate, acrylic acid, N- (3-dimethylaminopropyl) methacrylamide, polyethylene glycol methacrylate, methyl methacrylate, acrylamide and N-vinyl pyrrolidone.
2. the regenerative membrane device according to claim 1, wherein the raw membrane device is at least one of a tubular membrane, a curtain membrane, a column membrane, and a flat sheet membrane.
3. The regenerated membrane device according to claim 1, wherein the inert organic solvent is at least one of ethanol, triethyl phosphate, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, and trimethyl phosphate, and the ratio of the prepolymer to the inert organic solvent is (2 g-50 g):100 mL.
4. A method for producing a regenerated film device according to any one of claims 1 to 3, comprising the steps of:
(1) Providing siloxane prepolymer liquid, and diluting the siloxane prepolymer liquid by a diluent;
(2) placing the original film device in diluted siloxane pre-polymerization liquid for dipping treatment; and
(3) And carrying out pre-crosslinking reaction on the original membrane device subjected to the dipping treatment to obtain the regenerated membrane device.
5. The method for producing a regenerated membrane device according to claim 4, characterized in that the siloxane prepolymer liquid in step (1) is produced by the following method: adding a polyalkoxysilane, a functional monomer and an initiator into an inert organic solvent to obtain a mixture; and then heating the mixture and carrying out polymerization reaction under an inert atmosphere to obtain the siloxane prepolymer liquid.
6. The method for producing a regenerative membrane device according to claim 5, wherein the initiator is at least one of dibenzoyl peroxide, dialkyl peroxide, azobisisobutyronitrile, azobisisoheptylcyanide, dimethyl azobisisobutyrate, and azobisisobutyronitrile formamide, and the ratio of the polyalkoxysilane, the functional monomer, the initiator, and the inert organic solvent is: (1 g-25 g): (0.05 g-0.5 g):100mL, the reaction temperature of the polymerization reaction is 50-100 ℃, and the reaction time is 2-48 hours.
7. The method for preparing a regenerated membrane device according to claim 4, wherein the diluent in the step (1) is a mixture of water and ethanol, and the volume ratio of the siloxane prepolymer solution to the diluent is 1: 4-4: 1.
8. The method for producing a regenerated membrane device according to claim 4, wherein the raw membrane device in the step (2) further comprises a step of performing a cleaning process on the raw membrane device before the dipping process.
9. the method for preparing a regenerated membrane device according to claim 4, wherein the catalyst for the pre-crosslinking reaction in the step (3) is at least one of hydrochloric acid, sulfuric acid, acetic acid, citric acid, phosphoric acid, sodium hydroxide, potassium hydroxide, sodium citrate, sodium bicarbonate, ammonium chloride and ammonium sulfate, the reaction temperature of the pre-crosslinking reaction is 40 ℃ to 100 ℃, and the reaction time is 4 hours to 48 hours.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1059534A (en) * | 1989-04-12 | 1992-03-18 | 能源科学公司 | Siloxane polymer and multipolymer barrier coating and barrier coat preparation method |
| CN1304437A (en) * | 1998-06-04 | 2001-07-18 | 日本板硝子株式会社 | Process for producing article coated with water-repellent film, article coated with water-repellent film, and liquid composition for water-repellent film coating |
| CN1432590A (en) * | 2002-01-10 | 2003-07-30 | 中国石油化工股份有限公司 | Prepn of phenyl sesquisiloxane prepolymer |
| CN1646607A (en) * | 2002-04-11 | 2005-07-27 | 瓦克聚合系统两合公司 | Organofunctional silicone copolymers and the saponification products thereof |
| CN102863647A (en) * | 2012-09-19 | 2013-01-09 | 合肥工业大学 | Preparation method of organic-inorganic hybrid ionic membrane |
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2016
- 2016-05-10 CN CN201610305873.2A patent/CN107349792B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1059534A (en) * | 1989-04-12 | 1992-03-18 | 能源科学公司 | Siloxane polymer and multipolymer barrier coating and barrier coat preparation method |
| CN1304437A (en) * | 1998-06-04 | 2001-07-18 | 日本板硝子株式会社 | Process for producing article coated with water-repellent film, article coated with water-repellent film, and liquid composition for water-repellent film coating |
| CN1432590A (en) * | 2002-01-10 | 2003-07-30 | 中国石油化工股份有限公司 | Prepn of phenyl sesquisiloxane prepolymer |
| CN1646607A (en) * | 2002-04-11 | 2005-07-27 | 瓦克聚合系统两合公司 | Organofunctional silicone copolymers and the saponification products thereof |
| CN102863647A (en) * | 2012-09-19 | 2013-01-09 | 合肥工业大学 | Preparation method of organic-inorganic hybrid ionic membrane |
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