CN101205305A - Negative electric charge polyvinylidene fluoride modified film and preparation thereof - Google Patents
Negative electric charge polyvinylidene fluoride modified film and preparation thereof Download PDFInfo
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Abstract
The invention discloses a negatively-charged modified membrane of the poly vinylidene fluoride (PVDF) and a preparation method thereof. The invention relates to a method for introducing the hydrophilic and negatively-charged group monomers so as to prepare the hydrophilic negatively-charged PVDF separation membrane by utilizing the modification technology of utilizing the low-temperature plasma to initiate the grafting on the surface of the materials. By dissolving the polyvinyl pyrrolidone and the PVDF resin in the N-methyipyrrolidone, the invention prepares the basement membrane and then the basement membrane is put in a low-temperature plasma device with the air serving as the working gas and the discharge treatment is carried out; the membrane after being treated is taken out and then put in the liquid phase solution containing the acrylamide, the sodium allylsulfonate and the 2-acrylamido-2-methylpropanesulfonic acid monomer to carry out a grafting reaction so as to prepare the hydropholic negatively-charged PVDF membrane. The modified PVDF membrane prepared by the invention has greatly enhanced hydropholicity, carries the negative charges on the surface and has very good separation performance and contamination resistance over the proteins.
Description
Technical field: the invention belongs to the polymeric membrane field, particularly the negative electric charge polyvinylidene fluoride separatory membrane.
Background technology: polyvinylidene difluoride (PVDF) (PVDF) has good chemical stability, thermotolerance, mechanical stability, and can under lower temperature, be dissolved in some strong polar organic solvent, be easy to inversion of phases legal system film, be a kind of new polymers mould material of excellent property, in membrane separation technique, caused the very big interest of people in recent years.But the surface energy of PVDF is extremely low, and hydrophobicity is stronger, when using in membrane bioreactor (MBR) reactor especially, is easier to be subjected to biological pollution, and The decline of membrane flux is very fast, and film is short work-ing life, has increased process cost, has restricted its application in the membrane sepn field.The high performance membrane parting material of exploitation stable against biological contamination type fundamentally controlling diaphragm pollutes, and effectively reduces the MBR working cost, further widens the range of application of MBR.
From the angle analysis of mould material, the resistance to soiling of the effect of surface tension film of film, the higher contaminated degree of mould material of wetting ability is lighter.Therefore, both at home and abroad the researchist has carried out a large amount of work aspect mould material hydrophilically modified.On the other hand, reducing bacterium and metabolite thereof and the absorption of extracellular polymeric (EPS) on the film surface also is the effective means of controlling diaphragm biological pollution.Protein and polysaccharose substance are lower because of its iso-electric point, have negative charge in neutrality or basic solution.Because contain membranin and phospholipid substance in the somatic cells, the somatic cells surface has electronegativity too.Therefore, can alleviate metabolite and the thalline adventitious deposit on film by the surface electrical behavior of improving mould material.Surface with the electronegativity group is introduced polymeric film by suitable manner makes film be modified as the electrical film of bear, since the repulsive interaction between same sex electric charge, the adhering on film that can stop organism and metabolite thereof.Simultaneously, the hydrophilicity that has the film surface of negative charge improves greatly, more helps improving the stable against biological contamination of film.Film after the modification of this kind mode also is easier to remove surface contaminant when cleaning.
In recent years, the researchist has carried out extensive work at the surface hydrophilicity study on the modification of PVDF both at home and abroad, and common method is mainly the strong acid and strong base chemical modification, physically modified, plasma modification, irradiation and photochemical modification.PVDF chemical stability height with strong acid and strong base it is carried out difficulty of chemical modification, and the physical strength of modification caudacoria and elasticity can be under some influence; The method of physically modified mode multimeter finishing coat, coating easily break away from from the film surface; Irradiation and photochemical modification adopt radioelement emission high energy hertzian wave or ultraviolet ray, and the atarting material surface produces free radical and other group graft polymerization, but the bad control of phenomenon of monomer generation homopolymerization in the grafting process.In numerous surface modifying methods, the low-temperature plasma surface grafting polymerization is to develop method faster.Low-temperature plasma is meant gas temperature at 300～500K, and pressure is at the thin low pressure plasma of 13.3～1333Pa, and this plasma body adopts discharge mode to produce mostly.Use in the plasma modification process, material is exposed in the plasma body, forms the active centre free radical on its surface, can carry out graft polymerization with the unsaturated link(age) monomer of introducing that contains.This method is simple to operate need not add initiator, and environment is not polluted, and need not the loaded down with trivial details postprocessing working procedures of other polymerization processs; Can handle the surface of different shape, and processed surface is only 5 * 10
-9～10 * 10
-9Physics or chemical transformation take place in the scope thin layer, do not influence the material body performance, and the improvement of surface property do not decay in time.
Contamination resistance for reinforcing membrane, at the hydrophilicity that improves the pvdf membrane surface simultaneously, have the researchist that electronegative sulfonic acid group is introduced the mould material surface, mould material produces the Coulomb repulsion effect and has alleviated contaminated degree bacterium and the microbial metabolites that has negative electricity after the modification.The film hydrophilicity that has sulfonic acid group further strengthens, and membrane flux improves greatly, and film also easier cleaning after use for some time.Most of researchists adopt sulphonating agents such as sulfuric acid, chlorsulfonic acid, sulphur trioxide to make the film surface introduce anionic group by sulfonation reaction.But it is, much more difficult with respect on aromatic ring, carrying out in the sulfonation reaction on the aliphatic carbon chain because sulfonation reaction is an electrophilic substitution reaction.The pvdf membrane that does not contain aromatic ring is carried out sulfonation modifying, and most of researchists adopt strong acid and strong base to handle and make PVDF take off HF, re-use sulfonated reagent film is carried out sulfonation.This kind method is owing to used strong oxidizer that the physical strength of film is had certain damage.Perhaps adopt group such as the vinylbenzene that earlier film surface grafting is had aromatic ring, again aromatic ring is carried out sulfonation, modifying process is complicated.The inventor seeks a kind of easy, film method of modifying efficiently, is the direct grafted aliphatic sulfonic acid monomer of pvdf membrane, strengthens the antifouling property of pvdf membrane material in the MBR bio-reactor.
Summary of the invention:
The invention provides and a kind of protein soln is had separation performance preferably and has the pvdf membrane of contamination resistance bear electricity; The present invention also provides a kind of production method of above-mentioned pvdf membrane.
The pvdf membrane of bear electricity is at pvdf membrane surface grafting aliphatic sulfonic group and amide group hydrophilic radical.Its preparation method is as follows:
Adopt the mode of air low temperature plasma body atarting material surface graft modification, at pvdf membrane surface grafting aliphatic sulfonic group and amide group hydrophilic radical.
The present invention is earlier with polyvinylpyrrolidone (PVP), and the PVDF resin dissolves prepares dull and stereotyped basement membrane in N-Methyl pyrrolidone; Again dull and stereotyped basement membrane is positioned in the low-temperature plasma device, working gas is an air, discharge process, film after the processing takes out to put into and contains acrylamide (AM), sodium allylsulfonate (SAS), 2-acrylamido-monomeric graft copolymer solution of 2-methyl propane sulfonic acid (AMPS) and carry out graft reaction, prepares hydrophilic bear electricity pvdf membrane.
Main technical schemes of the present invention is as follows:
1. dull and stereotyped basement membrane is positioned in the low-temperature plasma treatment unit, air is a working gas, and handle it on discharge generation plasma irradiation film surface.Film after handling is put into graft copolymer solution, and graft reaction 2-6h makes wetting ability bear electricity pvdf membrane.
Graft copolymer solution is that massfraction is that acrylamide, the massfraction of 10-20 (wt) % is the sodium allylsulfonate of 10-20 (wt) % and the deoxidation solution of massfraction 10-20 (wt) %2-acrylamido-2-methyl propane sulfonic acid.
The preparation method is as follows in detail:
[one] preparation of polyvinylidene fluoride flat basement membrane.
1) massfraction is 0.5-2 (wt%) polyvinylpyrrolidone (PVP), the PVDF resin dissolves of 15-20 (wt) % is in N-Methyl pyrrolidone, and after the said mixture stirring and dissolving became film-casting liquid, film-casting liquid was positioned in the 55-60 ℃ of water-bath, leave standstill 22-26h, remove wherein micro-bubble;
2) film-casting liquid is poured on the sheet glass, evenly it is scraped with the glass stick that is tied with copper wire and make liquid film;
3) will scrape the film that makes in air, placing 1-2min on the sheet glass, then sheet glass be put into deionized water together with film, freezing film;
4) dull and stereotyped basement membrane is put into dehydrated alcohol and soaked 12 hours, remove residual solvent and impurity in the striping, carry out surface preparation.
[two] preparation process of the charged polyvinylidene fluoride separation membrane of low-temperature plasma initiation is as follows:
1) the polyvinylidene fluoride flat basement membrane is taken out from ethanol, be fixed in the round plastic frame and in air, dry, avoid Texturized in the film drying process;
2) will be fixed in the frame of plastic the dull and stereotyped basement membrane of air dried and be positioned in the plasma processing apparatus, be evacuated to 0.031-0.034MPa after, beginning discharge generation plasma body, the time of Cement Composite Treated by Plasma film is 1-3min;
3) behind the Cement Composite Treated by Plasma film, open purging valve in the treatment unit, treat that pressure recovery is closed purging valve to normal pressure in the device, the opening device door takes out film;
4) film after will taking out is put into graft copolymer solution immediately, in 50-60 ℃ of water-bath, and stirring reaction 2-6h in nitrogen atmosphere.Adopt in the grafting liquid and feed nitrogen bubble to remove the oxygen in the solution.
5) behind the graft reaction, take out film abundant rinsing in 60 ℃ of deionized waters and remove residual monomer.
The present invention adopts the mode of low-temperature plasma atarting material surface grafting polymerization, has efficient, easy, stable performance, advantage such as pollution-free; And the graft polymerization on using plasma atarting material surface, the homopolymer and the cross-linking agent of generation are few, can improve grafting efficiency greatly, material direct grafting functional monomer after plasma body cause to be handled; Invent used graft copolymer solution and contain three kinds of tool unsaturated double-bond monomers, acrylamide graft can improve the material hydrophilicity behind the film surface, sodium allylsulfonate and 2-acrylamido-2-methyl propane sulfonic acid have strong negative electricity group sulfonic group, by chemical titration film surface charge property and carrying capacity, show that bill of material wears negative charge and become charged membrane; Owing to have hydrophilic radical and negative electricity group, the permeation flux of the modified membrane that the present invention is prepared increases along with the increase of pH value, shows the pH value sensitive type; Can prepare the percentage of grafting difference, the modified membrane that charge density is different by controlling several monomeric concentration.
The modification pvdf membrane wetting ability of the present invention's preparation improves greatly, and the surface has negative charge, has good separation performance and contamination resistance for protein.Pvdf membrane wetting ability after this modification improves greatly than unmodified pvdf membrane, has anionic group simultaneously and the bear electricity, has preferably separation performance and has contamination resistance for protein soln; This method of modifying is easy, efficient, and is pollution-free, can directly will be with hydrophilic amide group, the monomer-grafted pvdf membrane surface of arriving of sulfonic group by the initiation of low-temperature plasma; This modification pvdf membrane can be used for the membrane module of MBR bio-reactor, improves the stable against biological contamination of membrane separation assemblies, prolongs the film life cycle.
Specific embodiment
Embodiment one:
[one] preparation of polyvinylidene fluoride flat basement membrane.
1) with 0.5 (wt%) polyvinylpyrrolidone (PVP), the PVDF resin dissolves of 15 (wt) % in N-Methyl pyrrolidone, said mixture stir all be dissolved into film-casting liquid after, film-casting liquid is positioned in 55 ℃ of water-baths, leave standstill 24h, remove wherein micro-bubble;
2) film-casting liquid is poured on the sheet glass, evenly it is scraped with the glass stick that is tied with copper wire and make liquid film.With scraping the film that makes, then sheet glass is put into deionized water together with film, freezing film in air, placing 1min on the sheet glass;
3) dull and stereotyped basement membrane is put into dehydrated alcohol and soaked 12 hours, remove residual solvent and impurity in the striping, carry out surface preparation.
[two] preparation of the charged hydrophilic polyvinylidene fluoride separation membrane of low-temperature plasma initiation:
1) will be fixed in the round plastic frame with the polyvinylidene fluoride flat basement membrane that alcohol immersion is crossed and in air, dry;
2) the dull and stereotyped basement membrane of air dried is positioned in the plasma processing apparatus, sets treatment time 1min, be evacuated to 0.031MPa after, be working gas with air in the device, beginning discharge generation plasma body shines film; The plasma irradiating time is 1min.
3) behind the Cement Composite Treated by Plasma film, open purging valve in the treatment unit, treat that pressure recovery is closed purging valve to normal pressure in the device, the opening device door takes out film.Film after taking out is put into graft copolymer solution immediately, in 55 ℃ of water-baths, stirring reaction 4h in nitrogen atmosphere.Graft copolymer solution feeds the nitrogen bubble deoxygenation for containing 10 (wt) % acrylamide, 10 (wt) % sodium allylsulfonate, 10 (wt) %2-acrylamido-monomeric graft copolymer solution of 2-methyl propane sulfonic acid before grafting liquid is used;
4) behind the graft reaction, take out film abundant rinsing in 60 ℃ of deionized waters and remove residual monomer.Performance measurement: measure the film contact angle with JY-82 type contact angle instrument, estimate instrument under 0.2MPa with flat sheet membrane, condition of different pH is measured pure water flux down, measures 0.5g/L bovine serum albumen solution rejection R (%) and dustiness (%).Concrete data see Table 1.
Embodiment two:
Present embodiment and embodiment one difference are, add 0.5 (wt%) polyvinylpyrrolidone in the configuration film-casting liquid, and the PVDF resin dissolves of 20 (wt) % is in N-Methyl pyrrolidone.After preparing film-casting liquid, carry out the modification of low-temperature plasma initiation grafting.
Behind the Cement Composite Treated by Plasma film, open purging valve in the treatment unit, treat that pressure recovery is closed purging valve to normal pressure in the device, the opening device door takes out film.Film after taking out is put into graft copolymer solution immediately, in 50 ℃ of water-baths, stirring reaction 2h in nitrogen atmosphere.
Performance measurement: measure the film contact angle with JY-82 type contact angle instrument, estimate instrument under 0.2MPa with flat sheet membrane, condition of different pH is measured pure water flux down, measures 0.5g/L bovine serum albumen solution rejection R (%) and dustiness (%).
Embodiment three:
Present embodiment and embodiment one difference are, add 1.5 (wt%) polyvinylpyrrolidone in the configuration film-casting liquid, and the PVDF resin dissolves of 18 (wt) % is in N-Methyl pyrrolidone.Behind the Cement Composite Treated by Plasma film, open purging valve in the treatment unit, treat that pressure recovery is closed purging valve to normal pressure in the device, the opening device door takes out film.Film after taking out is put into graft copolymer solution immediately, in 55 ℃ of water-baths, stirring reaction 6h in nitrogen atmosphere.
Performance measurement: measure the film contact angle with JY-82 type contact angle instrument, estimate instrument under 0.2MPa with flat sheet membrane, condition of different pH is measured pure water flux down, measures 0.5g/L bovine serum albumen solution rejection R (%) and dustiness (%).
Embodiment four:
Present embodiment and embodiment one difference are, contain 0.5 (wt%) polyvinylpyrrolidone in the film-casting liquid, and the PVDF resin dissolves of 20 (wt) % is in N-Methyl pyrrolidone.Carry out in the low-temperature plasma initiation grafting process, the plasma irradiating time is 2min.The used monomer of grafting is 15 (wt) % acrylamide, 10 (wt) % sodium allylsulfonate, 10 (wt) %2-acrylamido-2-methyl propane sulfonic acid.
Performance measurement: measure the film contact angle with JY-82 type contact angle instrument, estimate instrument under 0.2MPa with flat sheet membrane, condition of different pH is measured pure water flux down, measures 0.5g/L bovine serum albumen solution rejection R (%) and dustiness (%).
Embodiment five:
5) present embodiment and embodiment one difference are, in the plasma processing apparatus, are evacuated to
0.034MPa after.Carry out in the low-temperature plasma initiation grafting process, the plasma irradiating time is 3min.
Present embodiment and embodiment one difference are, carry out containing 20 (wt) % acrylamide, 15 (wt) % sodium allylsulfonate, 15 (wt) %2-acrylamido-2-methyl propane sulfonic acid monomer in the solution in the liquid-phase grafting reaction.
Performance measurement: measure the film contact angle with JY-82 type contact angle instrument, estimate instrument under 0.2MPa with flat sheet membrane, condition of different pH is measured pure water flux down, measures 0.5g/L bovine serum albumen solution rejection R (%) and dustiness (%).
Embodiment six:
Present embodiment and embodiment one difference are, carry out containing 10 (wt) % acrylamide, 20 (wt) % sodium allylsulfonate, 20 (wt) %2-acrylamido-2-methyl propane sulfonic acid monomer in the solution in the liquid-phase grafting reaction.In the prepared film-casting liquid, comprise the PVDF resin of 15 (wt) %, 0.5 (wt%) polyvinylpyrrolidone, solvent is in the N-Methyl pyrrolidone, the time of carrying out the low-temperature plasma irradiation is 1min.
Performance measurement: measure the film contact angle with JY-82 type contact angle instrument, estimate instrument under 0.2MPa with flat sheet membrane, condition of different pH is measured pure water flux down, measures 0.5g/L bovine serum albumen solution rejection R (%) and dustiness (%).
Table 1 modified membrane performance index
| Numbering | Film-casting liquid is formed | Monomer solution is formed | Performance index | |||||||||
| PVP (wt)％ | PVDF (wt)％ | AM | SAS | AMPS | Irradiation time min | Contact angle θ | Flux (Lm -2h -1) | R(％) | Dustiness (%) | |||
| pH＝2 | pH＝4 | pH＝6 | ||||||||||
| 1 | 0.5 | 15 | 10 | 10 | 10 | 1 | 44.33 | 125.3 | 181.0 | 256.9 | 74.1 | 21.2 |
| 2 | 0.5 | 20 | 10 | 10 | 10 | 1 | 43.33 | 126.2 | 162.9 | 279.7 | 81.1 | 24.5 |
| 3 | 1.5 | 18 | 10 | 10 | 10 | 1 | 39.50 | 112.8 | 153.9 | 267.3 | 73.4 | 25.6 |
| 4 | 0.5 | 20 | 15 | 10 | 10 | 2 | 37.58 | 107.9 | 158.31 | 268.6 | 79.5 | 25.5 |
| 5 | 0.5 | 15 | 20 | 15 | 15 | 3 | 50.08 | 105.9 | 149.9 | 201.5 | 88.9 | 35.6 |
| 6 | 0.5 | 15 | 10 | 20 | 20 | 1 | 35.25 | 144.6 | 154.8 | 275.6 | 87.3 | 28.8 |
| 7 (unmodified) | 0 | 15 | 0 | 0 | 0 | 0 | 103.7 | 128.6 | 124.8 | 92.88 | 51.6 | 41.5 |
Annotate: R (%) is a 0.5g/L bovine serum albumen solution rejection, dustiness (%) is the reduction degree of pure water flux before and after the membrane sepn protein solution, water flux % before dustiness=(water flux behind water flux before the membrane sepn protein solution-membrane sepn protein solution)/membrane sepn protein solution.
Claims (6)
1. a negative electric charge polyvinylidene fluoride modified film comprises polyvinylidene difluoride (PVDF), it is characterized in that described modification film of polyvinylidene fluoride surface grafting aliphatic sulfonic group and amide group hydrophilic radical, described modification film of polyvinylidene fluoride bear.
2. the preparation method of a kind of negative electric charge polyvinylidene fluoride modified film according to claim 1, its preparation method is as follows: (1) prepares dull and stereotyped basement membrane: polyvinylpyrrolidone, the PVDF resin dissolves is in N-Methyl pyrrolidone; (2) preparation of negative electric charge polyvinylidene fluoride separatory membrane: dull and stereotyped basement membrane is positioned in the low-temperature plasma device, and working gas is an air, discharge process, and the film after the processing is put into graft copolymer solution, prepares hydrophilic bear electricity pvdf membrane.
3. the preparation method of a kind of negative electric charge polyvinylidene fluoride modified film according to claim 2 is characterized in that the preparation method of described dull and stereotyped basement membrane is as follows:
1) massfraction is 0.5-2 (wt%) polyvinylpyrrolidone (PVP), the PVDF resin dissolves of 15-20 (wt) % in N-Methyl pyrrolidone, said mixture stir all dissolve film-casting liquid, film-casting liquid is positioned in 55～60 ℃ of water-baths, leave standstill 24h, remove bubble;
2) film-casting liquid is poured on the sheet glass, makes liquid film; Place 1～2min in the air, band film glass plate is put into deionized water, freezing film;
3) dull and stereotyped basement membrane being put into dehydrated alcohol soaked 12 hours.
4. the preparation method of a kind of negative electric charge polyvinylidene fluoride modified film according to claim 2 is characterized in that being prepared as follows of described negative electric charge polyvinylidene fluoride separatory membrane:
1) dull and stereotyped basement membrane is fixing dry;
2) dull and stereotyped basement membrane is positioned in the plasma processing apparatus, is evacuated to 0.031～0.034MPa, the dull and stereotyped basement membrane 1～3min of Cement Composite Treated by Plasma;
3) purging valve cuts out purging valve to normal pressure in the unlatching plasma processing apparatus, takes out dull and stereotyped basement membrane;
4) dull and stereotyped basement membrane is put into graft copolymer solution, in 50～60 ℃ of water-baths in nitrogen atmosphere stirring reaction 2-6h;
5) dull and stereotyped basement membrane rinsing in deionized water.
5. according to the preparation method of claim 2 or 4 described a kind of negative electric charge polyvinylidene fluoride modified films, it is characterized in that described graft copolymer solution is that massfraction is that acrylamide (AM), the massfraction of 10～20 (wt) % is that sodium allylsulfonate (SAS) and the massfraction of 10～20 (wt) % is the deoxidation solution of 10～20 (wt) %2-acrylamido-2-methyl propane sulfonic acid (AMPS).
6. the preparation method of a kind of negative electric charge polyvinylidene fluoride modified film according to claim 5, it is characterized in that described graft copolymer solution is that massfraction is the acrylamide (AM) of 15～20 (wt) %, massfraction is that sodium allylsulfonate (SAS), the massfraction of 15～20 (wt) % is the deoxidation solution of 15～20 (wt) %2-acrylamido-2-methyl propane sulfonic acid (AMPS).
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