CN102061049A - Temperature sensitive polyvinylidene fluoride gel film and preparation method thereof - Google Patents
Temperature sensitive polyvinylidene fluoride gel film and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a temperature sensitive polyvinylidene fluoride (PVDF) gel film and a preparation method thereof. The temperature sensitive PVDF gel film comprises the following components in percentage by weight: 0.5-2.5 percent of temperature sensitive high polymer gel and 97.5-99.5 percent of PVDF polymer. The preparation method comprises the steps of: a, preparing the temperature sensitive high polymer gel: dissolving a temperature sensitive polymer monomer and a crosslinking agent into absolute ethyl alcohol, carrying out radical polymerization under the protection of nitrogen to obtain the temperature sensitive high polymer gel; b, preparing a film casting solution, dispersing the temperature sensitive high polymer gel obtained from the step a in an organic solvent, gradually adding a certain quantity of PVDF powder, dissolving, degassing to obtain the film casting solution; and c, preparing the gel film: scraping the film casting solution obtained from the step b on a clean and flat glass plate to form a liquid film, curing in a curing bath to form the film. The PVDF gel film prepared by using the method has aperture size ranging from 100 to 300nm, the surface in a hole of the PVDF gel film consists of the temperature sensitive high polymer gel, the temperature sensitive high polymer gel can generate response according to the environment temperature change so as to cause that the film hole size is changed; and the invention can be used in intelligent selective separation of separated matters.
Description
Technical field
The present invention relates to a kind of thermosensitive in situ gel film and preparation method thereof, being specially a kind of thermally sensitive high molecular polymer gel and polyvinylidene difluoride (PVDF) (PVDF) blend obtains fenestra and can belong to polymer science and technical field with thermoregulator polyvinylidene difluoride (PVDF) gel-film and preparation method thereof.
Background technology
Ageing-resistant and the anti-ultraviolet property excellence of polyvinylidene difluoride (PVDF) (PVDF), and chemical stability is good, the corrosion of strong oxidizer such as acid and alkali, alkali and halogen also has good thermostability and physical strength simultaneously under the room temperature, is the good separation membrane material of a kind of over-all properties.At present, the PVDF separatory membrane the success and be widely used in chemical industry, biochemistry, electronics, food, industrial circles such as weaving.Problems such as however, hydrophobic pvdf membrane often runs into the film physical contamination in application process, and the not high and separation function of separation efficiency is single need be to its further modification.
The responsive to temperature type polymer gel belongs to stimulating responsive polymer, and it is one of research focus in the filed of functional.When small variation took place outside temperature, physics can take place the responsive to temperature type polymer gel or chemical property changes, thereby give this base polymer temperature sensitive characteristic.Responsive to temperature type polymer gel material is introduced in the pvdf membrane, utilized the configuration of temperature-sensitive polymers gel, reach microstructure mutually and take place reversible changely with the outside temperature condition changing, give the pvdf membrane temperature response characteristics.This mould material shows huge potential in many Application Areass such as aspects such as selective permeation, protein identification, controlled delivery of pharmaceutical agents releases owing to the premium properties with PVDF and temperature-sensitive polymers gel makes it.
Relevant temperature-sensitive polymers mainly concentrates on the pvdf membrane surface grafting in the research of pvdf membrane modification both at home and abroad.This method exists destroys the original constitutional features of film, and original size of fenestra and distribution change, and membrane flux such as reduces at defective.In order to overcome these defectives, some researchists adopt at first at PVDF bulk graft responsive to temperature type polymkeric substance, inversion of phases system film then, the structure and the performance of coming controlling diaphragm by polymer architecture and filming condition.For example, at first, then itself and polymer monomer are dissolved in the corresponding solvent, carry out polymerization, obtain temperature sensitivity pvdf membrane material by thermal initiation with PVDF powder process ozonize.
Because the PVDF chemical resistance is strong, directly grafting, grafting PVDF need pass through particular processing process (such as high-energy ray irradiation, ozone or highly basic etc.), and cost consumption is higher.And temperature sensitive polymer molecule bulk deposition was on the film surface after all there was modification in film forming after surface grafting and the body modification, and obviously not enough to the modification degree of fenestra, the separation performance and the anti-fouling performance of film are not well improved.As everyone knows, separatory membrane fenestra area has only membrane pore structure to obtain big improvement widely greater than the surface-area of film, and the ideal separation membrane just can obtain.Therefore, adopting temperature sensitive high molecular polymer gelatinous material to the fenestra modification, prepare the ideal mould material from the functional membrane orifice angle, improve the use properties of film, is present urgent problem.
Summary of the invention
The objective of the invention is in order to solve existing polyvinylidene difluoride (PVDF) (PVDF) film fenestra functional modification degree inadequately, have the bad problem of separation performance and anti-fouling performance.The invention provides a kind of temperature sensitive PVDF gel-film and preparation method thereof.Temperature sensitive high molecular polymer gel is contained on this film fenestra surface, and temperature sensitive high molecular polymer gel by environmental change responsive response takes place, and realizes the adjusting to the fenestra size.The present invention is made by temperature sensitive high-molecular gel 0.5-2.5 part and PVDF polymkeric substance 97.5-99.5 part by weight.
The technical scheme that the present invention solves described product preparation method technical problem is: the preparation method who designs a kind of thermosensitive in situ gel film, this method is by polyvinylidene difluoride (PVDF) (PVDF) and temperature sensitive high molecular polymer gel physical blending gained, comprises the steps:
A) preparation of temperature sensitive high molecular polymer gel: temperature sensitive polymer monomer and linking agent are dissolved in dehydrated alcohol, carry out radical polymerization under the nitrogen protection condition, obtain the temperature sensitive polymer gel; Described temperature sensitive polymer monomer refers to N-N-isopropylacrylamide (PNIPAM) or (dimethylamino) ethyl-methyl acrylate (DMAEMA); Described temperature sensitive polymer is meant poly-(N-N-isopropylacrylamide (NIPAM)) or poly-(dimethylamino) ethyl-methyl acrylate (PDMAEMA); Described temperature sensitive polymer is crosslinked structure;
B) preparation film-casting liquid: the temperature sensitive polymer gel that step (a) is obtained is dispersed in the organic solvent, progressively adds a certain amount of PVDF powder, dissolving, and the degassing obtains film-casting liquid; Described organic solvent can be N, a kind of in dinethylformamide, N,N-dimethylacetamide or the N-Methyl pyrrolidone;
C) gel-film preparation: the film-casting liquid that step (b) is obtained is scraped on the smooth sheet glass of cleaning and is made liquid film, film-forming in the precipitation bath; Described precipitation bath is water and alcoholic acid mixture (ethanol and water volume ratio are less than 95).
The technical scheme that the present invention solves described product technology problem is: design a kind of thermosensitive in situ gel film, it is characterized in that this gel-film is by polyvinylidene difluoride (PVDF) and temperature sensitive high molecular polymer gel physical blending gained.The physical blending method is by preparation method's defined of the present invention.
Temperature sensitive polyvinylidene difluoride (PVDF) of the present invention (PVDF) gel-film, the temperature sensitive polymer gel is positioned at the fenestra surface, can respond variation of ambient temperature, and the variation by self structure realizes the adjusting to the fenestra size.Outstanding advantage of the present invention be with the temperature sensitive polymer gel sets in fenestra, thereby make the response function of intelligent polymer gel, the filtering function of separation membrane ideally combines, by regulating the structure of temperature-sensitive polymers gel chain in the fenestra, regulate the fenestra size easily, thereby regulating its filtering feature, is a kind of novel separation membrane.
Preparation method's technology of temperature sensitive PVDF gel-film of the present invention is simple, just can carry out under atmospheric pressure state, and used reagent is conventional reagent, and equipment used is simple, is easy to characteristics such as industrializing implementation.
Embodiment
Further narrate the present invention below in conjunction with embodiment:
The present invention is a kind of temperature sensitive polyvinylidene difluoride (PVDF) gel-film and preparation method thereof.This film is to select for use polyvinylidene difluoride (PVDF) (PVDF) as the film forming main raw, with temperature sensitive high molecular polymer gel and its physical blending, adopts the film forming method of solution inversion of phases to make.Its principle of design is with polyvinylidene difluoride (PVDF) (PVDF) and the dense dispersion liquid of incompatible temperature sensitive high molecular polymer gel formation, and liquid-solid phase changes into that the mutual entanglement between the polymer is fixed to the temperature sensitive high-molecular gel in the polyvinylidene difluoride (PVDF) in the membrane process; Simultaneously, incompatiblely between polyvinylidene difluoride (PVDF) and the temperature sensitive high molecular polymer gel cause them to be separated in film process, formation temperature sensitive high molecular weight polymer gel is positioned at the polyvinylidene difluoride (PVDF) gel-film on fenestra surface.Preparation method of the present invention selects N-N-isopropylacrylamide and (dimethylamino) ethyl-methyl acrylate (DMAEMA) equitemperature sensitive high molecular weight polymer gel and polyvinylidene difluoride (PVDF) physical blending inversion of phases film forming respectively, and preparing fenestra can be with thermoregulator polyvinylidene difluoride (PVDF) (PVDF) gel-film.Have the temperature sensitive characteristic owing to be positioned at the polymer gel of fenestra, the aperture of prepared film can change and change along with outside temperature.Therefore, product of the present invention can the variation by outside temperature be regulated the aperture of fenestra, thereby regulates the flux of film, film performance such as hold back, be a kind of new polyvinylidene difluoride (PVDF) (PVDF) gel-film parting material.
In polyvinylidene difluoride (PVDF) of the present invention (PVDF) the gel-film preparation process, resulting film will clean repeatedly with deionized water, and purpose is to remove the temperature sensitive high molecular polymer gel of surface adsorption.
Though the method that the present invention narrates is preferentially selected polyvinylidene difluoride (PVDF) (PVDF) flat sheet membrane, but it is equally applicable to the film of other form, comprise tubular membrane, other form such as hollow-fibre membrane, and prepare corresponding temperature sensitive polyvinylidene difluoride (PVDF) (PVDF) gel-film with this.
Introduce specific embodiments of the invention below:
Embodiment 1.
(1) preparation of intelligent macromolecule polymer gel: get 5.0g monomer N-N-isopropylacrylamide (NIPAM), 0.05g initiator Diisopropyl azodicarboxylate (AIBN), linking agent N, N '-methylene-bisacrylamide (MBAA) 0.3g and 500ml dehydrated alcohol, logical N
2Behind the 30min, with system sealing, 70 ℃ of isothermal reaction 8h; To react back solution and be spin-dried under 55 ℃, vacuum-drying 24h obtains solid product PNIPAM gel;
(2) preparation film-casting liquid: the PNIPAM gel that PVDF powder and step (1) are made is dissolved in N with the different mixture ratio, in the dinethylformamide (DMF), stir under 65 ℃ and obtain transparent solution fully, standing and defoaming 2h under the vacuum condition, obtaining the PNIPAM gel content is 0%, 0.5%, 1.5% and 2.5%, mass concentration is the film-casting liquid of 16% (wt%);
(3) gel-film preparation: step (2) gained film-casting liquid is inclined on drying, the slick sheet glass, with the even striking film forming of glass stick, immerse the middle solidification forming of 25 ℃ of ethanol water mixed solutions (the ethanol/water volume ratio was less than 5: 95) and make the PVDF/PNIPAM gel-film, treat that film moulding from the sheet glass back that comes off cleans with pure water, be immersed in the distilled water, promptly make described fenestra and can regulate polyvinylidene difluoride (PVDF) (PVDF) gel-film.
Embodiment 2.
(1) with embodiment 1;
(2) preparation film-casting liquid: the PNIPAM gel that PVDF powder and step (1) are made is dissolved in the N-Methyl pyrrolidone with the different mixture ratio, stir under 75 ℃ and obtain transparent solution fully, standing and defoaming 3h under the vacuum condition, obtain the PNIPAM gel content and be respectively 0%, 0.5%, 1.5% and 2.5%, mass concentration is the film-casting liquid of 16% (wt%);
(3) with embodiment 1.
Embodiment 3.
(1) with embodiment 1;
(2) preparation film-casting liquid: the PNIPAM gel that PVDF powder and step (1) are made is dissolved in N with the different mixture ratio, in the N-N,N-DIMETHYLACETAMIDE, stir under 75 ℃ and obtain transparent solution fully, standing and defoaming 3h under the vacuum condition, obtain the PNIPAM gel content and be respectively 0%, 0.5%, 1.5% and 2.5%, mass concentration is the film-casting liquid of 16% (wt%);
(3) with embodiment 1.
Embodiment 4.
(1) preparation of temperature sensitive high molecular polymer gel: get 4.0g monomer (dimethylamino) ethyl-methyl acrylate (DMAEMA), 0.05g initiator A IBN, linking agent MBAA 0.3g and 100ml dehydrated alcohol, logical N
2Behind the 30min, with system sealing, 45 ℃ of isothermal reaction 5h; To react back solution and be spin-dried under 55 ℃, vacuum-drying 24h obtains solid product PDMAEMA gel;
(2) preparation film-casting liquid: the PDMAEMA gel that PVDF powder and step (1) are made is scattered in N with the different mixture ratio, in the dinethylformamide (DMF), stir under 65 ℃ and obtain transparent solution fully, standing and defoaming 1h under the vacuum condition, obtain the PDMAEMA gel content and be respectively 0%, 0.5%, 1.5% and 2.5%, mass concentration is the film-casting liquid of 16% (wt%);
(3) with embodiment 1.
Embodiment 5.
(1) with embodiment 4;
(2) preparation film-casting liquid: the PDMAEMA gel that PVDF powder and step (1) are made is scattered in N with the different mixture ratio, in the N-N,N-DIMETHYLACETAMIDE (DMAc), stir under 70 ℃ and obtain transparent solution fully, standing and defoaming 1h under the vacuum condition, obtain the PDMAEMA gel content and be respectively 0%, 0.5%, 1.5% and 2.5%, mass concentration is the film-casting liquid of 16% (wt%);
(3) with embodiment 1.
Embodiment 6.
(1) with embodiment 4;
(2) preparation film-casting liquid: the PDMAEMA gel that PVDF powder and step (1) are made is scattered in the N-Methyl pyrrolidone with the different mixture ratio, stir under 75 ℃ and obtain transparent solution fully, standing and defoaming 1h under the vacuum condition, obtain the PDMAEMA gel content and be respectively 0%, 0.5%, 1.5% and 2.5%, mass concentration is the film-casting liquid of 16% (wt%);
(3) with embodiment 1.
After testing, the pvdf membrane that the contains temperature sensitivity high molecular polymer gel pvdf membrane that more do not contain temperature sensitivity high molecular polymer gel has more fenestra, fenestra particle diameter 100-300nm.The film that contains temperature sensitivity high molecular polymer gel has tangible dependency to temperature, changes the change that causes the fenestra size owing to temperature sensitivity high molecular polymer gel structure.
Temperature sensitive polyvinylidene difluoride (PVDF) gel-film that the present invention proposes and preparation method thereof, be described by embodiment, person skilled obviously can be changed content as herein described in not breaking away from content of the present invention, spirit and scope or suitably be changed with combination and realize the present invention.Special needs to be pointed out is, the replacement that all are similar and change apparent to those skilled in the artly, they are regarded as being included in spirit of the present invention, scope and the content.
Claims (9)
1. temperature sensitive polyvinylidene difluoride (PVDF) gel-film, its component and weight percent are as follows:
Temperature sensitive high molecular polymer gel 0.5%-2.5%
PVDF polymkeric substance 97.5%-99.5%
2. temperature sensitive polyvinylidene difluoride (PVDF) gel-film according to claim 1 is characterized in that referring to flat sheet membrane.
3. temperature sensitive polyvinylidene difluoride (PVDF) gel-film according to claim 1 is characterized in that referring to that the membrane pore size magnitude range is 100-300nm.
4. temperature sensitive polyvinylidene difluoride (PVDF) gel-film according to claim 1 is characterized in that referring to that the fenestra internal surface is made up of temperature sensitive high molecular polymer gel, and the film surface is PVDF polymkeric substance composition.
5. temperature sensitive high molecular polymer according to claim 4 is meant poly-(N-N-isopropylacrylamide (NIPAM)) or poly-(dimethylamino) ethyl-methyl acrylate (PDMAEMA).
6. temperature sensitive polyvinylidene difluoride (PVDF) gel-film according to claim 1 is characterized in that referring to that in use the fenestra size can change according to variation of ambient temperature.
7. preparation method's step of a temperature sensitive polyvinylidene difluoride (PVDF) gel-film is as follows:
A) preparation of temperature sensitive high molecular polymer gel: temperature sensitive polymer monomer and linking agent are dissolved in dehydrated alcohol, carry out radical polymerization under the nitrogen protection condition, obtain the temperature sensitive polymer gel;
B) preparation film-casting liquid: the temperature sensitive polymer gel that step (a) is obtained is dispersed in the organic solvent, progressively adds a certain amount of PVDF powder, dissolving, and the degassing obtains film-casting liquid;
C) gel-film preparation: the film-casting liquid that step (b) is obtained is scraped on the smooth sheet glass of cleaning and is made liquid film, film-forming in the precipitation bath, and described precipitation bath is water and alcoholic acid mixture (ethanol and water volume ratio are less than 95).
8. the preparation method of a kind of temperature sensitive polyvinylidene difluoride (PVDF) gel-film according to claim 7, wherein the temperature sensitive polymer monomer refers to N-N-isopropylacrylamide (NIPAM) or (dimethylamino) ethyl-methyl acrylate (DMAEMA).
9. the preparation method of a kind of temperature sensitive polyvinylidene difluoride (PVDF) gel-film according to claim 7, wherein organic solvent can be N, a kind of in dinethylformamide, N,N-dimethylacetamide or the N-Methyl pyrrolidone.
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| CN105854646B (en) * | 2016-06-12 | 2018-06-01 | 天津工业大学 | A kind of narrow pore-size distribution hydrophilic filter film of temperature and pH sensitivities and preparation method thereof |
| CN105854646A (en) * | 2016-06-12 | 2016-08-17 | 天津工业大学 | Narrow pore size distributed hydrophilic filtering membrane sensitive to temperature and pH and preparation method thereof |
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