CN103521086A - Gas-assisting film-forming method - Google Patents
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Abstract
The invention discloses a gas-assisting film-forming method. The method particularly includes the following process steps: (1) preparing a film casting solution comprising the components by the mass percentage: 15-30% of a film-forming polymer, and 85-70% of a solvent, wherein the film-forming polymer contains a foaming agent with the mass being 0.1-20% of the film-forming polymer mass; adding the film-forming polymer and the foaming agent into the solvent, stirring for 2-20 hours at the temperature of 20-60 DEG C, dissolving fully, mixing evenly, and thus obtaining the film casting solution; (2) carrying out solidification forming: allowing the obtained film casting solution to stand for deaeration for 12-36 hours, and then scraping to prepare a flat-plate film; after placing in air for 10-30 seconds, putting the scraped film into a solidification liquid for solidification forming to obtain the product. The solidification liquid comprises 2-10% by mass of a catalyst which can catalyze the foaming agent to react and 98-90% by mass of distilled water.
Description
Technical field
The present invention relates to membrane technology field, be specially the auxiliary film build method of a kind of gas, the method, when inversion of phases film forming, produces by chemical blowing the performance that gas improves high-molecular porous film.
Background technology
Since nineteen sixty Loeb and sourirajan utilize phase inversion to prepare the reverse osmosis membrane of dissymmetrical structure, this film-forming method just becomes the masking means that the scope of application is the widest gradually.High-molecular porous film has good separating property and good mechanical stability and is widely used, but must add pore-foaming agent to improve the porosity of film during film forming, otherwise its water flux is less, has limited its application.Along with the numerous areas such as Chemical Manufacture improve constantly the requirement of film properties, researcher never stops improving the exploration of polymeric membrane water flux.At present, main method of modifying concentrates on the modification of macromolecule raw material and adding of additive, the general macromolecule pore former adding in casting solution has polyvinylpyrrolidone (PVP), polyethylene glycol (PEG), methylcellulose, Sodium Polyacrylate and polyacrylamide etc., non-solvent has ethylene glycol, propane diols, glycol monoethyl ether etc., surfactant has dodecyl sodium sulfate, neopelex etc., inorganic salts have lithium chloride, sodium nitrate, ammonium chloride etc., can significantly improve porosity and the water flux of hollow fiber polymer membrane, but adding of additive, part is trapped in film, while causing filtering, cause secondary pollution, and membrane structure and hole dimension are changed, thereby film strength is reduced, shorten service life.
Summary of the invention
For the deficiencies in the prior art, the technical problem that quasi-solution of the present invention is determined is: provide a kind of gas to assist film build method.The method produces the separated film forming of gas auxiliary phase with chemical blowing, forms the polymeric membrane with high porosity.It is simple that the method has method, and membrane pore size is controlled, do not need to add macromolecule or surfactant as pore-foaming agent, and gained film is additive-free residual, Stability Analysis of Structures, and quality is carried high.
The technical scheme that the present invention solve the technical problem is: provide a kind of gas to assist film build method.The method specifically comprises following processing step:
(1) preparation casting solution: the mass percent composition of casting solution is: film forming macromolecule 15-30% and solvent 85-70%, the blowing agent that wherein film forming macromolecule comprises film forming high molecule mass 0.1-20%; Film forming macromolecule and blowing agent are joined in solvent, at 20-60 ℃ of temperature, stir 2-20 hour, after fully dissolving mixes, obtain casting solution;
Described film forming macromolecule is Kynoar, polysulfones, polyether sulfone, polyvinyl chloride or polyacrylonitrile;
Described blowing agent is chemical hydride, comprises sodium borohydride, ammonia borine, lithium borohydride or tetrahydrochysene aluminium sodium; Carbonate or bicarbonate and ammonium salt;
Described solvent is dimethyl formamide, dimethylacetylamide, 1-METHYLPYRROLIDONE, dimethyl sulfoxide (DMSO), acetone or oxolane, or the mixed solution of its arbitrary proportion;
(2) solidification forming: gained casting solution standing and defoaming, after 12-36 hour, is scraped and made flat sheet membrane; Then in air, place 10-30 after second, the film of institute's striking is put into solidification liquid solidification forming and be get final product; The mass percent of described solidification liquid consist of 2-10% can catalytic reaction infusion the catalyst of reaction and the distilled water of 98-90%; Described catalyst is slaine, comprises cobalt chloride, nickel chloride or palladium; Inorganic acid, comprises hydrochloric acid, sulfuric acid and nitric acid; Organic acid and CNT.
Another technical scheme that the present invention solve the technical problem is: provide a kind of gas to assist film build method.The method specifically comprises following processing step:
(1) preparation casting solution: the mass percent composition of casting solution is: film forming macromolecule 30-15% and solvent 70-85%, wherein film forming macromolecule comprise film forming high molecule mass 2-10% can catalytic reaction infusion the catalyst of reaction, film forming macromolecule and catalyst are joined in solvent, at 20-60 ℃ of temperature, stir 2-20 hour, after fully dissolving mixes, obtain casting solution;
Described film forming macromolecule is Kynoar, polysulfones, polyether sulfone, polyvinyl chloride or polyacrylonitrile;
Described catalyst is slaine, comprises cobalt chloride, nickel chloride or palladium; Inorganic acid, comprises hydrochloric acid, sulfuric acid and nitric acid; Organic acid and CNT;
Described solvent is dimethyl formamide, dimethylacetylamide, 1-METHYLPYRROLIDONE, dimethyl sulfoxide (DMSO), acetone or oxolane, or the mixed solution of its arbitrary proportion;
(2) solidification forming: described casting solution standing and defoaming, after 12-36 hour, is scraped and made flat sheet membrane; Then in air, place 10-30 after second, the film of institute's striking is put into solidification liquid solidification forming; Solidification liquid is the aqueous solution that contains blowing agent, and blowing agent quality is the 0.1-20% of film forming high molecule mass; Described blowing agent is chemical hydride, comprises sodium borohydride, ammonia borine, lithium borohydride or tetrahydrochysene aluminium sodium; Carbonate or bicarbonate and ammonium salt.
Compared with prior art, the beneficial effect of film build method of the present invention is: the character that produces gas according to chemical blowing, in casting solution, add blowing agent, by the method for gas auxiliary phase conversion film, prepare the polymeric membrane with high porosity, for preparing the polymeric membrane of high porosity, provide more simple and practical technology.Gas auxiliary law film forming is without adding pore-foaming agent, therefore also residual without pore-foaming agent, blowing agent used is of a great variety, select wide, be swift in response completely, and film forming rear foaming agent can all be removed from film, can control easily the content of blowing agent and porosity and membrane pore structure and the size that catalyst ability is carried out controlling diaphragm, improve the Performance and quality of film forming.
The specific embodiment
Below in conjunction with embodiment, further narrate the present invention.
The present invention has designed the auxiliary film build method (abbreviation method) of a kind of gas, and the method specifically comprises following processing step:
(1) preparation of casting solution: the mass percent of casting solution forms and is: film forming high molecule mass percentage 15-30%, wherein comprise film forming high molecule mass 0.1-20% can the reaction of catalytic reaction infusion blowing agent, solvent quality percentage 85-70%; Film forming macromolecule and blowing agent are joined in solvent, at 20-60 ℃ of temperature, stir 2-20 hour, after fully dissolving mixes, obtain casting solution;
Described film forming macromolecule is Kynoar, polysulfones, polyether sulfone, polyvinyl chloride, polyacrylonitrile etc.
Described blowing agent is chemical hydride (as sodium borohydride, ammonia borine, lithium borohydride, tetrahydrochysene aluminium sodium etc.), carbonate or bicarbonate, ammonium salt.
Described solvent is dimethyl formamide, dimethylacetylamide, 1-METHYLPYRROLIDONE, dimethyl sulfoxide (DMSO), acetone, oxolane etc. or its mixed solution etc.;
(2) solidification forming: gained casting solution standing and defoaming, after 12-36 hour, is scraped and made flat sheet membrane; In air, place 10-30 after second, the film of institute's striking is put into solidification liquid solidification forming and be get final product; The mass percent of described solidification liquid consist of 2-10% can catalytic reaction infusion the catalyst of reaction and the distilled water of 98-90%; Described catalyst is slaine, comprises cobalt chloride, nickel chloride or palladium; Inorganic acid, comprises hydrochloric acid, sulfuric acid and nitric acid; Organic acid and CNT.Described catalyst be can catalytic reaction infusion the catalyst of reaction.Be specially slaine (as cobalt chloride, nickel chloride, palladium etc.), inorganic acid (example hydrochloric acid, sulfuric acid, nitric acid etc.), organic acid and CNT.
It should be noted that, in other conditions, (comprise macromolecule, solvent, catalyst, the kind of blowing agent and ratio etc.) under constant prerequisite, blowing agent and catalyst can transpositions described in the inventive method, be that blowing agent joins in solidification liquid, catalyst joins in casting solution.Its concrete processing step is:
(1) preparation casting solution: film forming high molecule mass percentage is 30-15%, comprising the 2-10% of high molecule mass can the reaction of catalytic reaction infusion catalyst, solvent quality percentage is 70-85%, macromolecule and catalyst are joined in solvent, at 20-60 ℃ of temperature, stir 2-20 hour, after fully dissolving mixes, obtain casting solution;
Described film forming macromolecule is Kynoar, polysulfones, polyether sulfone, polyvinyl chloride or polyacrylonitrile;
Described catalyst is slaine, comprises cobalt chloride, nickel chloride or palladium; Inorganic acid, comprises hydrochloric acid, sulfuric acid and nitric acid; Organic acid and CNT.
Described solvent is dimethyl formamide, dimethylacetylamide, 1-METHYLPYRROLIDONE, dimethyl sulfoxide (DMSO), acetone or oxolane, or the mixed solution of its arbitrary proportion;
(2) solidification forming: described casting solution standing and defoaming, after 12-36 hour, is scraped and made flat sheet membrane; Then in air, place 10-30 after second, the film of institute's striking is put into solidification liquid solidification forming and be get final product; Solidification liquid is the aqueous solution that contains blowing agent, and blowing agent quality is the 0.1-20% of film forming high molecule mass; Described blowing agent is chemical hydride, comprises sodium borohydride, ammonia borine, lithium borohydride or tetrahydrochysene aluminium sodium; Carbonate or bicarbonate and ammonium salt.
In addition, between blowing agent and catalyst and both and each component of casting solution all under nonreactive condition, also both can be joined in casting solution simultaneously, all the other techniques are constant.This being designed with is beneficial to simplification technique, is convenient to industrial applications.In casting solution, add blowing agent, blowing agent not with casting solution in macromolecule, the component reaction such as organic solvent, can stable existence, this design, by after casting solution knifing, while proceeding in solidification liquid, can be emitted gas by immediate response.
The present invention does not address part and is applicable to prior art.
Provide specific embodiments of the invention below, these embodiment only, for specifically describing the present invention, do not form the restriction to the application's claim protection domain.
embodiment 1
Design casting solution: the volume of solvent dimethylacetylamide is 45ml(85wt%), polyphosphazene polymer vinylidene 7.366g(14.985wt%), blowing agent sodium borohydride 0.074g(0.015wt%), catalyst nickel chloride 0.154g, the addition of blowing agent sodium borohydride is 3 times of nickel chloride; In the ground conical flask of magnetic stir bar is housed, 60 ℃ are stirred 2h, and Kynoar is fully dissolved, and obtain casting solution, then standing and defoaming 12h under room temperature; With knifing rod, on glass plate, scrape and make flat sheet membrane, after 10 seconds, the film of institute's striking is proceeded in distilled water solidification liquid, put into afterwards distilled water and preserve.
After testing, the film that diameter is 5.2cm is that under 0.1MPa, to record water flux be 3.0L/m at pressure
2h; In 40 ℃ of air dry ovens, drying the membrane porosity that 3h obtains is 60%.
embodiment 2
In casting solution, the volume of solvent dimethylacetylamide is 38ml(70wt%), polyphosphazene polymer vinylidene 12.71g(25wt%), blowing agent sodium borohydride 2.54g(5wt%).In the ground conical flask of magnetic stir bar is housed, 60 ℃ are stirred 20h, and Kynoar is fully dissolved, and obtain casting solution, then standing and defoaming 36h under room temperature.With knifing rod, on glass plate, scrape and make flat sheet membrane, after 30 seconds, the film of institute's striking is proceeded in the solidification liquid of 2L, in solidification liquid, contain the 10wt% that catalyst cobalt chloride 222g(mass fraction is solidification liquid), put into afterwards distilled water and preserve.
After testing, the film that diameter is 5.2cm is that under 0.1MPa, to record water flux be 6.2L/m at pressure
2h; In 40 ℃ of air dry ovens, drying the membrane porosity that 3h obtains is 72%.
embodiment 3
Solvent dimethyl formamide 45ml(80wt% in casting solution), macromolecule polysulfones 9.71g(18.2wt%), blowing agent sodium carbonate 0.96g(1.8wt%), in the ground conical flask of magnetic stir bar is housed, 20 ℃ are stirred 20h, polysulfones is fully dissolved, obtain casting solution, then standing and defoaming 24h under room temperature.With knifing rod, on glass plate, scrape and make flat sheet membrane, after 20 seconds, the film of institute's striking is proceeded in the solidification liquid of 2L, the 1wt% that the hydrochloric acid 55.4g(mass fraction that contains catalyst 37% in solidification liquid is solidification liquid), put into afterwards distilled water and preserve.
After testing, the film that diameter is 5.2cm is that under 0.1MPa, to record water flux be 7.2L/m at pressure
2h.In 40 ℃ of air dry ovens, drying the membrane porosity that 3h obtains is 73%.
embodiment 4
Solvent dimethyl sulfoxide (DMSO) 40ml(80wt% in casting solution), high molecular polyether sulfone 10.45g(19wt%), blowing agent sodium acid carbonate 0.55g(1wt%), in the ground conical flask of magnetic stir bar is housed, 50 ℃ are stirred 10h, polyether sulfone is fully dissolved, obtain casting solution, then standing and defoaming 20h under room temperature.With knifing rod, on glass plate, scrape and make flat sheet membrane, after 15 seconds, the film of institute's striking is proceeded in the solidification liquid of 2L, in solidification liquid, contain the 2.2wt% that catalyst Graphene 45g(mass fraction is solidification liquid), put into afterwards distilled water and preserve.
After testing, the film that diameter is 5.2cm is that under 0.1MPa, to record water flux be 8.7L/m at pressure
2h.In 40 ℃ of air dry ovens, drying the membrane porosity that 3h obtains is 79%.
embodiment 5
Solvent 1-METHYLPYRROLIDONE 40ml(75wt% in casting solution), polyphosphazene polymer vinyl chloride 13.68g(25wt%), catalyst nickel nitrate 0.27g, for high molecular 2wt%, in the ground conical flask of magnetic stir bar is housed, 40 ℃ are stirred 15h, polyvinyl chloride is fully dissolved, obtain casting solution, then standing and defoaming 20h under room temperature.With knifing rod, on glass plate, scrape and make flat sheet membrane, after 15 seconds, the film of institute's striking is proceeded in the solidification liquid of 2L, in solidification liquid, contain blowing agent carbonic hydroammonium 0.27g(and be high molecule mass mark 2%), put into afterwards distilled water and preserve.
After testing, the film that diameter is 5.2cm is that under 0.1MPa, to record water flux be 5.8L/m at pressure
2h.In 40 ℃ of air dry ovens, drying the membrane porosity that 3h obtains is 65%.
embodiment 6
In casting solution, solvent is 1-METHYLPYRROLIDONE 45ml(80wt%), high molecular polyether sulfone 11.54g(20wt%), rare nitric acid 0.82ml of catalyst 65%, its mass fraction is high molecular 10%, in the ground conical flask of magnetic stir bar is housed, 50 ℃ are stirred 10h, polyether sulfone is fully dissolved, obtain casting solution, then standing and defoaming 20h under room temperature.With knifing rod, on glass plate, scrape and make flat sheet membrane, after 10 seconds, the film of institute's striking is proceeded in the solidification liquid of 2L, in solidification liquid, contain blowing agent ammonia borine 2.3g(and be high molecule mass mark 20%), put into afterwards distilled water and preserve.
After testing, the film that diameter is 5.2cm is that under 0.1MPa, to record water flux be 7.9L/m at pressure
2h.In 40 ℃ of air dry ovens, drying the membrane porosity that 3h obtains is 75%.
embodiment 7
In casting solution, solvent is dimethyl formamide 50ml(85wt%), high molecular polyether sulfone 8.38g(15wt%), catalyst acetic acid palladium, its mass fraction is high molecular 5%, in the ground conical flask of magnetic stir bar is housed, 60 ℃ are stirred 10h, polyether sulfone is fully dissolved, obtain casting solution, then standing and defoaming 36h under room temperature.With knifing rod, on glass plate, scrape and make flat sheet membrane, after 30 seconds, the film of institute's striking is proceeded in the solidification liquid of 2L, in solidification liquid, contain blowing agent ammonia borine 0.008g(and be high molecule mass mark 0.1%), put into afterwards distilled water and preserve.
After testing, the film that diameter is 5.2cm is that under 0.1MPa, to record water flux be 1.0L/m at pressure
2h.In 40 ℃ of air dry ovens, drying the membrane porosity that 3h obtains is 40%.
embodiment 8
In casting solution, solvent is the mixed solution (80wt%) of acetone and dimethyl formamide, (wherein acetone is 10ml, dimethyl formamide is 36.1ml), macromolecule polypropylene nitrile 9.99g(19wt%), blowing agent ammonia borine 0.53g(1wt%), in the ground conical flask of magnetic stir bar is housed, 35 ℃ are stirred 15h, and polyacrylonitrile is fully dissolved, obtain casting solution, then standing and defoaming 30h under room temperature.With knifing rod, on glass plate, scrape and make flat sheet membrane, after 15 seconds, the film of institute's striking is proceeded in the solidification liquid of 2L, in solidification liquid, contain the 5wt% that catalyst nickel chloride 105g(mass fraction is solidification liquid), put into afterwards distilled water and preserve.
After testing, the film that diameter is 5.2cm is that under 0.1MPa, to record water flux be 7.5L/m at pressure
2h.In 40 ℃ of air dry ovens, drying the membrane porosity that 3h obtains is 70%.
embodiment 9
In casting solution, solvent is oxolane 50ml(85wt%), polyphosphazene polymer vinylidene 7.13g(13.64wt%), blowing agent lithium borohydride 0.71g(1.36wt%), in the ground conical flask of magnetic stir bar is housed, 30 ℃ are stirred 20h, Kynoar is fully dissolved, obtain casting solution, then standing and defoaming 30h under room temperature.With knifing rod, on glass plate, scrape and make flat sheet membrane, after 10 seconds, the film of institute's striking is proceeded in the solidification liquid of 2L, in solidification liquid, contain the 5wt% that catalyst nickel chloride 105g(mass fraction is solidification liquid), put into afterwards distilled water and preserve.
After testing, the film that diameter is 5.2cm is that under 0.1MPa, to record water flux be 7.0L/m at pressure
2h.In 40 ℃ of air dry ovens, drying the membrane porosity that 3h obtains is 68%.
embodiment 10
Solvent dimethyl formamide 40ml(75wt% in casting solution), macromolecule polysulfones 12.51g(24.75wt%), pore-foaming agent polyethylene glycol 0.126g (0.25wt%), in the ground conical flask of magnetic stir bar is housed, 35 ℃ are stirred 20h, polysulfones is fully dissolved, obtain casting solution, then standing and defoaming 24h under room temperature.With knifing rod, on glass plate, scrape and make flat sheet membrane, after 10 seconds, the film of institute's striking is proceeded in the solidification liquid distilled water of 2L, put into afterwards distilled water and preserve.
After testing, the film that diameter is 5.2cm is that under 0.1MPa, to record water flux be 3.2L/m at pressure
2h.In 40 ℃ of air dry ovens, drying the membrane porosity that 3h obtains is 56%.
Claims (4)
1. gas is assisted a film build method, and the method specifically comprises following processing step:
(1) preparation casting solution: the mass percent composition of casting solution is: film forming macromolecule 15-30% and solvent 85-70%, the blowing agent that wherein film forming macromolecule comprises film forming high molecule mass 0.1-20%; Film forming macromolecule and blowing agent are joined in solvent, at 20-60 ℃ of temperature, stir 2-20 hour, after fully dissolving mixes, obtain casting solution;
Described film forming macromolecule is Kynoar, polysulfones, polyether sulfone, polyvinyl chloride or polyacrylonitrile;
Described blowing agent is chemical hydride, comprises sodium borohydride, ammonia borine, lithium borohydride or tetrahydrochysene aluminium sodium; Carbonate or bicarbonate and ammonium salt;
Described solvent is dimethyl formamide, dimethylacetylamide, 1-METHYLPYRROLIDONE, dimethyl sulfoxide (DMSO), acetone or oxolane, or the mixed solution of its arbitrary proportion;
(2) solidification forming: gained casting solution standing and defoaming, after 12-36 hour, is scraped and made flat sheet membrane; Then in air, place 10-30 after second, the film of institute's striking is put into solidification liquid solidification forming and be get final product; The mass percent of described solidification liquid consist of 2-10% can catalytic reaction infusion the catalyst of reaction and the distilled water of 98-90%; Described catalyst is slaine, comprises cobalt chloride, nickel chloride or palladium; Inorganic acid, comprises hydrochloric acid, sulfuric acid and nitric acid; Organic acid and CNT.
2. gas is assisted a film build method, and the method specifically comprises following processing step:
(1) preparation casting solution: the mass percent composition of casting solution is: film forming macromolecule 30-15% and solvent 70-85%, wherein film forming macromolecule comprise film forming high molecule mass 2-10% can catalytic reaction infusion the catalyst of reaction, film forming macromolecule and catalyst are joined in solvent, at 20-60 ℃ of temperature, stir 2-20 hour, after fully dissolving mixes, obtain casting solution;
Described film forming macromolecule is Kynoar, polysulfones, polyether sulfone, polyvinyl chloride or polyacrylonitrile;
Described catalyst is slaine, comprises cobalt chloride, nickel chloride or palladium; Inorganic acid, comprises hydrochloric acid, sulfuric acid and nitric acid; Organic acid and CNT;
Described solvent is dimethyl formamide, dimethylacetylamide, 1-METHYLPYRROLIDONE, dimethyl sulfoxide (DMSO), acetone or oxolane, or the mixed solution of its arbitrary proportion;
(2) solidification forming: described casting solution standing and defoaming, after 12-36 hour, is scraped and made flat sheet membrane; In air, place 10-30 after second, the film of institute's striking is put into solidification liquid solidification forming and be get final product; Solidification liquid is the aqueous solution that contains blowing agent, and blowing agent quality is the 0.1-20% of film forming high molecule mass; Described blowing agent is chemical hydride, comprises sodium borohydride, ammonia borine, lithium borohydride or tetrahydrochysene aluminium sodium; Carbonate or bicarbonate and ammonium salt.
3. gas according to claim 1 is assisted film build method, it is characterized in that under described catalyst and the nonreactive condition of each component of casting solution, catalyst described in (2) solidification forming technique is directly added in the preparing process of (1) casting solution, and all the other techniques are constant.
4. gas according to claim 2 is assisted film build method, it is characterized in that under described blowing agent and the nonreactive condition of each component of casting solution, blowing agent described in (2) solidification forming technique is directly added in the preparing process of (1) casting solution, and all the other techniques are constant.
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| CN103706259A (en) * | 2014-01-09 | 2014-04-09 | 天津工业大学 | Porous membrane and pore-forming method thereof |
| CN107441949A (en) * | 2017-09-30 | 2017-12-08 | 盐城海普润膜科技有限公司 | A kind of method for improving hollow Flat Membrane backwash ability |
| CN107930408A (en) * | 2017-12-15 | 2018-04-20 | 天津膜天膜科技股份有限公司 | A kind of preparation method of woven tube enhancement type hollow fiber film |
| CN108126540A (en) * | 2017-12-15 | 2018-06-08 | 天津膜天膜科技股份有限公司 | A kind of big flux woven tube enhancement type hollow fiber film and preparation method thereof |
| CN110882634A (en) * | 2018-09-07 | 2020-03-17 | 浙江省化工研究院有限公司 | Formula of ethylene-chlorotrifluoroethylene copolymer microporous membrane and method for preparing microporous membrane by using formula |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103706259A (en) * | 2014-01-09 | 2014-04-09 | 天津工业大学 | Porous membrane and pore-forming method thereof |
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| CN110882634A (en) * | 2018-09-07 | 2020-03-17 | 浙江省化工研究院有限公司 | Formula of ethylene-chlorotrifluoroethylene copolymer microporous membrane and method for preparing microporous membrane by using formula |
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| CN103521086B (en) | 2015-02-11 |
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