CN102061049B - 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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- CN102061049B CN102061049B CN 201010566793 CN201010566793A CN102061049B CN 102061049 B CN102061049 B CN 102061049B CN 201010566793 CN201010566793 CN 201010566793 CN 201010566793 A CN201010566793 A CN 201010566793A CN 102061049 B CN102061049 B CN 102061049B
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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 with thermoregulator polyvinylidene fluoride gel film and preparation method thereof, belong to polymer science and technical field.
Background technology
Polyvinylidene difluoride (PVDF) (PVDF) is ageing-resistant and anti-ultraviolet property excellent, and chemical stability is good, the corrosion of the 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, the industrial circles such as weaving.The 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 to be to its further modification.
The responsive to temperature type polymer gel belongs to stimulating responsive polymer, and it is one of study hotspot in the filed of functional.When small variation occured outside temperature, physics or chemical property can occur in the responsive to temperature type polymer gel, thereby give this base polymer temperature sensitive characteristic.The responsive to temperature type geopolymer gel material is introduced in the pvdf membrane, utilized the configuration of temperature-sensitive polymers gel, reach microstructure mutually and change with the outside temperature condition and occur reversible changely, give the pvdf membrane temperature response characteristics.This mould material shows huge potential in many Application Areass such as the aspects such as control release of selective permeation, protein identification, medicine 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 the original size of fenestra and distribution change, and membrane flux such as reduces at the defective.In order to overcome these defectives, some researchists adopt at first at PVDF bulk graft responsive to temperature type polymkeric substance, and inversion of phases masking is then come structure and the performance of controlling diaphragm by polymer architecture and filming condition.For example, at first with PVDF powder process ozonize, then itself and polymer monomer are dissolved in the corresponding solvent, carry out polymerization by thermal initiation, obtain temperature sensitivity pvdf membrane material.
Because the PVDF chemical resistance is strong, directly grafting, grafting PVDF need to pass through special treating processes (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, separation performance and the anti-fouling performance of film are not well improved.As everyone knows, separatory membrane fenestra area only has membrane pore structure to obtain large improvement widely greater than the surface-area of film, and desirable separation membrane just can obtain.Therefore, adopting the Temperature Responsive Polymer As geopolymer gel material to the fenestra modification, prepare desirable 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 not, 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.The Temperature Responsive Polymer As polymer gel is contained on this film fenestra surface, and the Temperature Responsive Polymer As polymer gel by environmental change responsive response occurs, and realizes the adjusting to the fenestra size.The present invention is made by Temperature Responsive Polymer As 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, the method is by polyvinylidene difluoride (PVDF) (PVDF) and Temperature Responsive Polymer As polymer gel physical blending gained, comprises the steps:
A) preparation of Temperature Responsive Polymer As 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 NIPA (PNIPAM) or (dimethylamino) ethyl-methyl acrylate (DMAEMA); Described temperature sensitive polymer refers to gather (NIPA (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, and dissolving is degassed, obtains film-casting liquid; Described organic solvent can be a kind of in DMF, 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 the mixture (ethanol and water volume ratio are less than 95) of water and ethanol.
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 Responsive Polymer As 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 advantages of the present invention is that the temperature sensitive polymer gel is fixed in the 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 easily the fenestra size, thereby regulating its filtering feature, is a kind of novel separation membrane.
Preparation method's technique 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 the 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 fluoride gel film and preparation method thereof.This film is to select polyvinylidene difluoride (PVDF) (PVDF) as the film forming main raw, with Temperature Responsive Polymer As polymer gel and its physical blending, adopts the method for solution phase conversion film to make.Its principle of design is that polyvinylidene difluoride (PVDF) (PVDF) and incompatible Temperature Responsive Polymer As polymer gel are formed dense dispersion liquid, and the mutual entanglement in the liquid-solid phase conversion film process between the polymer is fixed to the Temperature Responsive Polymer As gel in the polyvinylidene difluoride (PVDF); Simultaneously, incompatiblely between polyvinylidene difluoride (PVDF) and the Temperature Responsive Polymer As polymer gel cause them to be separated in film process, formation temperature sensitive high molecular weight polymer gel is positioned at the polyvinylidene fluoride gel film on fenestra surface.Preparation method of the present invention specifically selects respectively NIPA and (dimethylamino) ethyl-methyl acrylate (DMAEMA) equitemperature sensitive high molecular weight polymer gel and polyvinylidene difluoride (PVDF) physical blending inversion of phases film forming, and preparing fenestra can be with thermoregulator polyvinylidene difluoride (PVDF) (PVDF) gel-film.Have the temperature sensitive characteristic owing to being 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 the 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 Responsive Polymer As polymer gel of surface adsorption.
Although 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.
The below introduces specific embodiments of the invention:
Embodiment 1.
(1) preparation of intelligent macromolecule polymer gel: get 5.0g monomer NIPA (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; Solution is spin-dried under 55 ℃ after will reacting, and 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), 65 ℃ of lower stirrings obtain fully transparent solution, 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 smooth 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, come off until film moulding from the sheet glass and to clean with pure water afterwards, be immersed in the distilled water, namely 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, 75 ℃ of lower stirrings obtain fully transparent solution, 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, 75 ℃ of lower stirrings obtain fully transparent solution, 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 Responsive Polymer As 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; Solution is spin-dried under 55 ℃ after will reacting, and 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), 65 ℃ of lower stirrings obtain fully transparent solution, 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), 70 ℃ of lower stirrings obtain fully transparent solution, 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, 75 ℃ of lower stirrings obtain fully transparent solution, 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 pvdf membrane that contains temperature sensitivity high molecular polymer gel does not more 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 obvious dependency to temperature, changes the change that causes the fenestra size owing to temperature sensitivity high molecular polymer gel structure.
Temperature sensitive polyvinylidene fluoride 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 within 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 deemed to be included in spirit of the present invention, scope and the content.
Claims (4)
1. temperature sensitive polyvinylidene fluoride gel film, it is characterized in that this membrane component and weight percent are as follows: the weight fraction of poly N-isopropyl acrylamide gel or poly-(dimethylamino) ethyl-methyl acrylate gel is 0.5%-2.5%, and the weight fraction of polyvinylidene difluoride (PVDF) (PVDF) polymkeric substance is 97.5%-99.5%; The fenestra internal surface is comprised of poly N-isopropyl acrylamide gel or poly-(dimethylamino) ethyl-methyl acrylate gel, and the film surface is comprised of the PVDF polymkeric substance, and the membrane pore size magnitude range is 100-300nm.
2. a kind of temperature sensitive polyvinylidene fluoride gel film according to claim 1 is characterized in that referring to that in use the fenestra size changes with variation of ambient temperature.
3. the preparation method of a kind of temperature sensitive polyvinylidene fluoride gel film according to claim 1 is characterized in that step is as follows:
A) preparation of polymer gel: polymer monomer NIPA or dimethyl amino ethyl methacrylate and linking agent are dissolved in dehydrated alcohol, carry out radical polymerization under the nitrogen protection condition, obtain poly N-isopropyl acrylamide gel or poly-(dimethylamino) ethyl-methyl acrylate gel;
B) preparation film-casting liquid: the weight fraction that step (a) is obtained is that the polymer gel of 0.5%-2.5% is dispersed in the organic solvent, and progressively adding weight fraction is the PVDF powder of 97.5%-99.5%, and dissolving is degassed, 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 the mixture of water and ethanol, ethanol and water volume ratio are less than 95.
4. the preparation method of a kind of temperature sensitive polyvinylidene fluoride gel film according to claim 3, wherein organic solvent is a kind of in DMF, N,N-dimethylacetamide or the N-Methyl pyrrolidone.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005213425A (en) * | 2004-01-30 | 2005-08-11 | Nitto Denko Corp | Porous film and method for producing the same |
| CN1743351A (en) * | 2005-09-30 | 2006-03-08 | 天津工业大学 | Method for preparing temperature-sensitive polyvinylidene fluoride intelligent membrane material and its product |
| CN101073752A (en) * | 2007-03-30 | 2007-11-21 | 浙江大学 | Method for producing vinylidene difluoride planar ultrafiltration membrane with gradient structure |
| WO2007135651A1 (en) * | 2006-05-24 | 2007-11-29 | Koninklijke Philips Electronics N.V. | A biosensor solid substrate with integrated temperature control and a method to make the same |
| CN101239283A (en) * | 2008-03-21 | 2008-08-13 | 北京碧水源科技股份有限公司 | Convenient for cleaning hollow fiber membrane, preparation of the same and products produced thereby |
| CN101279211A (en) * | 2008-01-11 | 2008-10-08 | 北京工业大学 | Preparation of polyvinylidene fluoride dewatering microporous film |
| EP2231734A2 (en) * | 2007-12-12 | 2010-09-29 | 3M Innovative Properties Company | Methods of making an article and articles |
-
2010
- 2010-11-30 CN CN 201010566793 patent/CN102061049B/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005213425A (en) * | 2004-01-30 | 2005-08-11 | Nitto Denko Corp | Porous film and method for producing the same |
| CN1743351A (en) * | 2005-09-30 | 2006-03-08 | 天津工业大学 | Method for preparing temperature-sensitive polyvinylidene fluoride intelligent membrane material and its product |
| WO2007135651A1 (en) * | 2006-05-24 | 2007-11-29 | Koninklijke Philips Electronics N.V. | A biosensor solid substrate with integrated temperature control and a method to make the same |
| CN101073752A (en) * | 2007-03-30 | 2007-11-21 | 浙江大学 | Method for producing vinylidene difluoride planar ultrafiltration membrane with gradient structure |
| EP2231734A2 (en) * | 2007-12-12 | 2010-09-29 | 3M Innovative Properties Company | Methods of making an article and articles |
| CN101279211A (en) * | 2008-01-11 | 2008-10-08 | 北京工业大学 | Preparation of polyvinylidene fluoride dewatering microporous film |
| CN101239283A (en) * | 2008-03-21 | 2008-08-13 | 北京碧水源科技股份有限公司 | Convenient for cleaning hollow fiber membrane, preparation of the same and products produced thereby |
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