CN105107389A - Preparation method for gel composite separating membrane - Google Patents
Preparation method for gel composite separating membrane Download PDFInfo
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- CN105107389A CN105107389A CN201510505066.0A CN201510505066A CN105107389A CN 105107389 A CN105107389 A CN 105107389A CN 201510505066 A CN201510505066 A CN 201510505066A CN 105107389 A CN105107389 A CN 105107389A
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- membrane
- gel composite
- composite separating
- polymer
- separating film
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Abstract
The invention discloses a preparation method for a gel composite separating membrane. The preparation method comprises the following steps: 1) mixing a membrane-preparing polymer, a gel polymer, a pore-foaming agent and a solvent, mechanically stirring the mixture to fully dissolve the mixture, and defoaming and filtering the mixture to obtain a casting membrane solution, wherein the casting membrane solution comprises the components in percentage by weight: 10-30% of the membrane-preparing polymer, 1-5% of the gel polymer, 0-10% of the pore-foaming agent and 55-89% of the solvent; 2) coating or extruding the casting membrane solution by using a film forming machine, and immersing the casting membrane solution in a pure water bath to be cured and formed to obtain an initial polymer membrane; and 3) fully cleaning the initial polymer membrane in deionized water and then airing the membrane in air to obtain the gel composite separating membrane. The preparation method disclosed by the invention is simple in process and low in cost, and the obtained gel composite separating membrane has a wide application prospect in membrane separation fields such as sewage treatment, water purification, oil-water separation, protein separation, microbial filtration, dye separation and the like.
Description
Technical field
The invention belongs to functional material and technical field of membrane separation, be specifically related to a kind of preparation method of gel composite separating film.
Background technology
Membrane filtration technique is an energy-efficient filtering technique, for keeping the mechanical strength of diffusion barrier in filter process, generally adopts as membrane materials such as Kynoar, polyvinyl chloride, polysulfones, polyether sulfones.
These membrane body materials are generally faced with the problem of surface nature aspect.On the one hand, membrane body material surface energy is lower, and hydrophobicity is strong, and pollutant is very easily adsorbed in the surface and fenestra of film by hydrophobic interaction, causes fouling membrane, filtration flux is decayed serious.On the other hand; because membrane material polymer segment intermolecular forces is excessively strong, cause dry state to be preserved and make flux minimum, therefore general finished film needs hygrometric state to preserve; avoid air-dry by the protection liquid containing sodium hydrogensulfite and sodium metabisulfite, prevent microbial growth.This brings a lot of inconvenience to the storage of filter membrane and transport, so the film that research preparation can be preserved under dry state is significant.
Blending and modifying is a kind of conventional hydrophilic modification method, and common blending and modifying reagent comprises polyethylene glycol, amphoteric ion polymer, amphipathic nature block polymer, hydrophilic inorganic particles etc.As adopted the polyethylene of polyethylene glycol graft modification as blend modified poly ethylene hollow-fibre membrane in patent CN102002768A; Betaine type amphoteric ionomer blending and modifying pvdf membrane is adopted in patent CN104437122A; Prepare a kind of amphipathic three block copolymer in patent CN102432782A, it can be used as the blended reagent of poly (ether sulfone) film; Adopt the amphipathic graft copolymer of polyvinyl chloride as the hydrophilic modification reagent of Pvc Ultrafiltration Membrane in patent CN101293183; The titanium dioxide nano-particle blending and modifying polyvinylidene fluoride film adopting dopamine to modify in patent CN102614783A.In above-mentioned patent, all adopt the method modified hydrophobic film of in-situ blending, make it that there is hydrophily.Hydrophilic substance be added in the pollution decreased to a certain extent in the film course of work, but their lock water poor-performing, can not assist to keep the flux of dry film, therefore the blend finding a kind of water retention property good has great importance.
Macromolecule hydrogel is hydroaropic substance, and Absorbable rod keep large quantity of moisture.Commercially, cross-linked hydrogel is often used in the industries such as cosmetics, coating, food, in order to water conservation.The hydrogel product of business comprises starch based, cross-linking type polymethacrylates sodium etc.In laboratory research, prepare multiple cross-linked hydrogel, cross-linking type NIPA gellike [P (NIPAm-co-TMSPMA)/Silicahybridmicrogels:Structures, swellingpropertiesandapplicationsinfabricatingmacroporou ssilica, MaterialsChemistryandPhysics, 2013, 138:650-657], cross-linking type NVP gel [Poly (N-vinylpyrrolidinone) Microgels:Preparation, Biocompatibility, andPotentialApplicationasDrugCarriersBiomacromolecules20 14, 15:2285-2293], patent CN102977266A discloses the temperature and pH dual responsiveness gel that are obtained by 4-vinylpridine and NIPA copolymerization, also has cross-linking type carbopol gel in addition, crosslinked polyacrylamide gel etc.But these all come with some shortcomings and shortcoming, need further improvement.
Summary of the invention
The object of the invention is to solve problems of the prior art, and a kind of preparation method of gel composite separating film is provided, the hydratability of mechanical performance good for membrane body with gelatin polymer excellence is combined, make prepared gel composite separating film while the traditional phase inversion membrane mechanical strength of maintenance, possess again excellent hydrophily, moisture retention and antifouling property, Dry storage and transport can be carried out easily.Concrete technical scheme of the present invention is:
A kind of gel composite separating film preparation method, comprises the steps:
1) masking polymer, gelatin polymer, pore-foaming agent are mixed with solvent, fully dissolve through mechanical agitation, obtain casting solution after deaeration, filtration, each component weight percent content is as follows: masking polymer is 10 ~ 30%; Gelatin polymer is 1 ~ 5%; Pore-foaming agent is 0 ~ 10%; Solvent is 55 ~ 89%;
2) casting solution be coated with through film-forming machine or extrude, immersing curing molding in pure water bath, obtain nascent polymer film;
3) nascent polymer film is fully cleaned in deionized water, then dry in atmosphere, obtain gel composite separating film.
Described masking polymer is any one in Kynoar, polyvinyl chloride, polysulfones, polyether sulfone.
Described gelatin polymer is the one in crosslinked polyacrylamide, cross linked sodium polyacrylate, cross-linking type SANWET.
Described pore-foaming agent is polyethylene glycol or polyvinylpyrrolidone.
Described solvent is the one in DMA, DMF, 1-METHYLPYRROLIDONE.
The shape of described gel composite separating film is Flat Membrane or hollow-fibre membrane.
Described gel composite separating film is microfiltration membranes, milipore filter or NF membrane.
The present invention is to have the cross-linking type gelatin polymer of high water absorbing capacity as masking additive, polymer separation film is prepared by phase inversion, this diffusion barrier by Kynoar, polyvinyl chloride, polysulfones or polyether sulfone as main body material of preparing, form stephanoporate framework, swelling gelatin polymer is dispersed in stephanoporate framework, forms hydrone through passage.The present invention prepares gel composite separating film, by cross-linking type hydrogel and conventional membrane body material blended, due to the hydratability of gelatin polymer excellence, can water effective be remained in fenestra, thus prepared gel composite separating film can keep the mechanical strength of traditional phase inversion membrane material, there is again excellent hydrophily, moisture retention and antifouling property, Dry storage and transport can be carried out easily.This film-forming method technique is simple, and cost is low, and the gel composite separating film obtained has broad application prospects in UF membrane fields such as sewage disposal, purification of water quality, water-oil separating, Separation of Proteins, microbe filter, dye separation.
Detailed description of the invention
Introduce specific embodiments of the invention below, but the present invention is not by the restriction of embodiment.
The characterizing method of gel composite separation membrane structure and performance in the present invention:
Antifouling property is tested: cut diaphragm, and in flux tester, with pure water precompressed 30 minutes (min) under 0.2 MPa (MPa), then run under 0.1MPa, the pure water flux measured time 1 hour (h) is designated as J
w1(rise/square metre hour, L/m
2h); Afterwards, substitute deionized water with the BSA solution that concentration is 1.0 grams per liters (g/L), after running 2h under 0.1MPa, during 2h, flux is designated as J
p(L/m
2h); Diaphragm after oscillation cleaning 20min, is again measured pure water flux, is designated as J in pure water under 0.1MPa
w2.Gross contamination Rt, reversible membrane fouling Rr, irreversible membrane fouling Rir, can use three formulae discovery below respectively, each numerical value is larger, illustrates that pollution is more serious.
Rt＝1-J
p/J
w1
Rr＝(J
w2-J
p)/J
w1
Rir＝(J
w1-J
w2)/J
w1
Water-retaining property is tested: film is soaked in pure water after 30min, takes out and takes diaphragm 1g; Then film is placed in 25 DEG C without after cross-ventilated environment 24h, again measuring weight is Wg.Water-retaining property embodies by the value of W, and the larger explanation Water-saving effect of W value is better.
Embodiment 1:
(1) concentration requirement of according to the form below 1 reference numeral, mixes Kynoar, crosslinked polyacrylamide, polyethylene glycol with DMA, fully dissolves through mechanical agitation, obtains casting solution after deaeration, filtration; (2) casting solution is coated with through film-forming machine, immerses curing molding in pure water bath, obtain flat micro-filtration; (3) flat micro-filtration is fully cleaned in deionized water, then dry in atmosphere, obtain gel composite separating film.
Table 1.1: the preparation condition of Kynoar/crosslinked polyacrylamide gel composite separating film
Table 1.2: Kynoar/crosslinked polyacrylamide gel composite separating film performance data
| Numbering | J w1(L/m 2h) | J p(L/m 2h) | J w2(L/m 2h) | Rt(％) | Rr(％) | Rir(％) | W(g) |
| 1-1 | 280.5 | 56.1 | 242.6 | 80 | 66.5 | 13.5 | 0.78 |
| 1-2 | 300.4 | 45.06 | 264.4 | 85 | 73 | 12 | 0.83 |
| 1-3 | 317.6 | 54 | 284.6 | 83 | 72.6 | 10.4 | 0.85 |
Embodiment 2:
(1) concentration requirement of according to the form below 2 reference numeral, mixes polyvinyl chloride, cross linked sodium polyacrylate, polyvinylpyrrolidone with DMF, fully dissolves through mechanical agitation, obtains casting solution after deaeration, filtration; (2) casting solution is extruded through film-forming machine, immerse curing molding in pure water bath, obtain hollow fiber ultrafiltration film; (3) hollow fiber ultrafiltration film is fully cleaned in deionized water, then dry in atmosphere, obtain gel composite separating film.
Table 2.1: the preparation condition of polyvinyl chloride/cross linked sodium polyacrylate gel composite separating film
Table 2.2: polyvinyl chloride/cross linked sodium polyacrylate gel composite separating film performance data
| Numbering | J w1(L/m 2h) | J p(L/m 2h) | J w2(L/m 2h) | Rt(％) | Rr(％) | Rir(％) | W(g) |
| 2-1 | 60.7 | 13 | 45.9 | 78.6 | 54.2 | 24.4 | 0.85 |
| 2-2 | 65 | 15.2 | 48 | 76.6 | 50.5 | 26.1 | 0.87 |
| 2-3 | 56.8 | 11.2 | 42.4 | 80.3 | 54.9 | 25.4 | 0.91 |
Embodiment 3:
(1) concentration requirement of according to the form below 3 reference numeral, mixes polysulfones, cross-linking type SANWET, polyvinylpyrrolidone with 1-METHYLPYRROLIDONE, fully dissolves through mechanical agitation, obtains casting solution after deaeration, filtration; (2) casting solution is coated with through film-forming machine, immerses curing molding in pure water bath, obtain dull and stereotyped NF membrane; (3) dull and stereotyped NF membrane is fully cleaned in deionized water, then dry in atmosphere, obtain gel composite separating film.
Table 3.1: the preparation condition of polysulfones/cross-linking type SANWET gel composite separating film
Table 3.2: polysulfones/cross-linking type SANWET gel composite separating film performance data
| Numbering | J w1(L/m 2h) | J p(L/m 2h) | J w2(L/m 2h) | Rt(％) | Rr(％) | Rir(％) | W(g) |
| 3-1 | 12.5 | 4.9 | 10.4 | 60.8 | 44 | 16.8 | 0.88 |
| 3-2 | 10.2 | 4 | 8.7 | 60.8 | 46.1 | 14.7 | 0.90 |
| 3-3 | 8.3 | 2.8 | 6.6 | 66.3 | 45.8 | 20.5 | 0.95 |
Embodiment 4:
(1) concentration requirement of according to the form below 4 reference numeral, mixes polyether sulfone, cross-linking type SANWET, polyvinylpyrrolidone with 1-METHYLPYRROLIDONE, fully dissolves through mechanical agitation, obtains casting solution after deaeration, filtration; (2) casting solution is extruded through film-forming machine, immerse curing molding in pure water bath, obtain hollow NF membrane; (3) hollow NF membrane is fully cleaned in deionized water, then dry in atmosphere, obtain gel composite separating film.
Table 4.1: the preparation condition of polyether sulfone/cross-linking type SANWET gel composite separating film
Table 4.2: polyether sulfone/cross-linking type SANWET gel composite separating film performance data
| Numbering | J w1(L/m 2h) | J p(L/m 2h) | J w2(L/m 2h) | Rt(％) | Rr(％) | Rir(％) | W(g) |
| 4-1 | 9.5 | 4 | 6.6 | 57.9 | 27.4 | 30.5 | 0.88 |
| 4-2 | 8.2 | 2 | 4.7 | 75.6 | 32.9 | 42.7 | 0.93 |
| 4-3 | 6.3 | 1.4 | 2.6 | 77.8 | 19 | 58.8 | 0.96 |
Claims (7)
1. a gel composite separating film preparation method, is characterized in that, comprises the steps:
1) masking polymer, gelatin polymer, pore-foaming agent are mixed with solvent, fully dissolve through mechanical agitation, obtain casting solution after deaeration, filtration, each component weight percent content is as follows: masking polymer is 10 ~ 30%; Gelatin polymer is 1 ~ 5%; Pore-foaming agent is 0 ~ 10%; Solvent is 55 ~ 89%;
2) casting solution be coated with through film-forming machine or extrude, immersing curing molding in pure water bath, obtain nascent polymer film;
3) nascent polymer film is fully cleaned in deionized water, then dry in atmosphere, obtain gel composite separating film.
2. gel composite separating film preparation method according to claim 1, is characterized in that, described masking polymer is any one in Kynoar, polyvinyl chloride, polysulfones, polyether sulfone.
3. a kind of gel composite separating film according to claim 1 and preparation method thereof, is characterized in that, described gelatin polymer is the one in crosslinked polyacrylamide, cross linked sodium polyacrylate, cross-linking type SANWET.
4. gel composite separating film preparation method according to claim 1, is characterized in that, described pore-foaming agent is polyethylene glycol or polyvinylpyrrolidone.
5. gel composite separating film preparation method according to claim 1, is characterized in that, described solvent is the one in DMA, DMF, 1-METHYLPYRROLIDONE.
6. gel composite separating film preparation method according to claim 1, is characterized in that, the shape of described gel composite separating film is Flat Membrane or hollow-fibre membrane.
7. gel composite separating film preparation method according to claim 1, is characterized in that, described gel composite separating film is microfiltration membranes, milipore filter or NF membrane.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104607068A (en) * | 2015-01-20 | 2015-05-13 | 苏州信望膜技术有限公司 | Bio-adhesion-resistant porous separation membrane as well as preparation method and application thereof |
| CN106745507A (en) * | 2016-12-30 | 2017-05-31 | 常州碳星科技有限公司 | A kind of resistant to pollution oil-water separation mesh film and preparation method thereof |
| CN107149882A (en) * | 2016-03-02 | 2017-09-12 | 天津工业大学 | A kind of Kynoar pollution-resistant membrane and preparation method thereof |
| CN114917764A (en) * | 2022-04-29 | 2022-08-19 | 浙江理工大学 | Method for preparing high-selectivity high-flux PES ultrafiltration membrane by utilizing monomer self-crosslinking |
-
2015
- 2015-08-17 CN CN201510505066.0A patent/CN105107389B/en active Active
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104607068A (en) * | 2015-01-20 | 2015-05-13 | 苏州信望膜技术有限公司 | Bio-adhesion-resistant porous separation membrane as well as preparation method and application thereof |
| CN104607068B (en) * | 2015-01-20 | 2017-04-12 | 苏州信望膜技术有限公司 | Bio-adhesion-resistant porous separation membrane as well as preparation method and application thereof |
| CN107149882A (en) * | 2016-03-02 | 2017-09-12 | 天津工业大学 | A kind of Kynoar pollution-resistant membrane and preparation method thereof |
| CN107149882B (en) * | 2016-03-02 | 2019-11-08 | 天津工业大学 | A kind of Kynoar pollution-resistant membrane and preparation method thereof |
| CN106745507A (en) * | 2016-12-30 | 2017-05-31 | 常州碳星科技有限公司 | A kind of resistant to pollution oil-water separation mesh film and preparation method thereof |
| CN114917764A (en) * | 2022-04-29 | 2022-08-19 | 浙江理工大学 | Method for preparing high-selectivity high-flux PES ultrafiltration membrane by utilizing monomer self-crosslinking |
| CN114917764B (en) * | 2022-04-29 | 2023-10-24 | 浙江理工大学 | Method for preparing high-selectivity high-flux PES (polyether sulfone) ultrafiltration membrane by using monomer self-crosslinking |
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