CN1704152A - Preparation of hydrophilic polyvinylidene fluoride microporous membrane - Google Patents
Preparation of hydrophilic polyvinylidene fluoride microporous membrane Download PDFInfo
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Abstract
The invention relates to a method for preparing hydrophilic PVDF microporous barrier. The principal raw material is polyvinylidene fluoride with the range of molecular weight: 5000 to 50000. It prepares hydrophilic PVDF microporous barrier by the method of separating solution and compounding dip-coating modification. It especially suits the occasion of effluent treatment, medicine separation and biochemy. The technology can prepare microporous barriers with plate type and hollow fiber type.
Description
Technical field
Prepare resistant to pollution hydrophilicity kynoar microporous barrier, can be used for occasions such as bio-separation, wastewater treatment.The form of film comprises the structure of mesopore fiber formula and dull and stereotyped membrane type.
Background technology
Kynoar (PVDF) has fabulous against weather and chemical stability as a kind of novel fluoro-carbon thermoplastic, with wavelength is the ultra violet lamp 1 year of 20-400nm, its performance is constant substantially, its film places the be full of cracks that also do not become fragile in outdoor ten or twenty year, strong oxidizer such as acid and alkali, alkali and halogen corrosion at room temperature has only minority chemicals such as oleum, highly basic and dimethylacetylamide or to be partly dissolved its swelling.The poor thermal conductivity of PVDF, melt viscosity is higher.Made PVDF microporous barrier soaked 72h in kind of the solvent surplus 250 ℃, 20 after, the film various aspects of performance is constant substantially, because Kynoar has above-mentioned advantage, and can become performance film preferably by hydrostomia, so U.S. Millipore company releases filtration, the detection film of Kynoar in late 1970s.At present polyvinylidene fluoride microporous film be applied to successfully that air bacteriological filtration, industrial gasses filter, organic solvent is refining, water purification and processes such as separation and metal extraction.
PVDF is a kind of soluble polymer, and available immersion precipitation prepares its microporous barrier.The basic principle of immersion precipitation is to add non-solvent to polymer solution to make to produce and be separated, polymer gelization and coming out with the solid form precipitating.Its process generally is that the polymer solution film of liquid state is immersed in the non-solvent (coagulating bath).The interior solvent of polymer solution film this moment spreads in coagulating bath, and the non-solvent in the coagulating bath spreads in the polymer solution film, forms dynamic (dynamical) double diffusion process.Along with constantly carrying out of this process, system development of heat liquid, liquid phase-splitting are through the polymer film of inversion of phases (curing) formation different structure form and performance.Speed according to system generation phase-splitting can be divided into instantaneous liquid-liquid phase-splitting and time-delay liquid-liquid phase-splitting.General instantaneous liquid-liquid phase-splitting will obtain microporous barrier, and time-delay liquid-liquid phase-splitting can get dense film.In principle, immersion precipitation prepares polymer film will satisfy 3 conditions: the one, and polymer has optimum solvent, so that obtain the polymer solution of high concentration; The 2nd, optimum solvent can be miscible with some non-solvent of polymer; The 3rd, chemical reaction does not take place between polymer-solvent-non-solvent.Kynoar adopts immersion precipitation to prepare microporous barrier more at present, and the polymer solution concentration scope is between 8%-40%.The too low film-strength of solution concentration is poor, and the too high then polymer dissolution of concentration is not in good state.The solvent that adopts has dimethyl formamide (DMF), dimethylacetylamide (DMAc), dimethyl sulfoxide (DMSO) (DMSO), N-methyl arsenic pyrrolidone (NMP) isopolarity solvent; The mixture of small-molecule substances such as water, acetone, glycerine, ethylene glycol, ethanol, methyl alcohol or itself and aforementioned optimum solvent can be used as the non-solvent coagulating bath; Some little molecule (as LiCl etc.) or polyethylene arsenic pyrrolidone (PVP), polyethylene glycol big molecules such as (PEG) are often used as the system film additive and add in the preparation liquid; Can control the structure of PVDF microporous barrier by the selection of preparation liquid being formed film forming conditions such as (containing additive), coagulation bath composition and temperature, evaporation time, ambient humidity.Wherein the composition of coagulation bath also has a significant impact film properties.Big more such as NaCl concentration in the coagulation bath, film is fine and close more, and porosity is also low more, and ethanol is different fully with NaCl to the influence of film morphosis in addition, does not contain ethanol in the coagulation bath, has only water, easily forms finger.Along with the increase of ethanol content in the coagulation bath, corresponding prolongation hardening time of polymer helps the formation of spongelike structure when carrying out the mass transfer exchange.General the form of film carries out the transition to finger gradually from spongelike structure when the solubility parameter of precipitating reagent changes from small to large, and at the transition point place of two kinds of structures half and half, porosity and average pore size all are in minimum of a value [1-3].
That the PVDF polymer has is heat-resisting, resistance to chemical attack and be difficult for advantage such as degraded, but when its microporous barrier was used to handle water-based fluid, its strong-hydrophobicity can produce two problems: the one, pass through fenestra for making water, and high driving pressure be arranged.As the aperture is the pvdf membrane of 0.2 μ m, at 1.0kg/cm
2Still can not allow water pass through fenestra under the differential pressure action.Another is that film is subjected to the absorption of proteins pollution and causes membrane flux descending very fast easily.Thereby, making it be more suitable for the use in fields such as biochemistry, medicine, beverage, water purification in order to reduce pollution, life-saving and raising flux, the hydrophiling of pvdf membrane becomes one of main contents of its modification.Directly introduce OH, COOH, SO by technology such as plasma treatment, chemical treatments on the microporous barrier surface
3Strong polar group such as H is to strengthen the hydrophilic important means of pvdf membrane.If further connect on the skill some on PVDF microporous barrier surface to responsive side chain of environmental change (temperature, pH value etc.) or bioactive functions material etc., then can prepare the intelligent polymer functional film that wide potential using value is arranged in fields such as detection, separation and purifying, medicine control release and sensors.Concrete method commonly used is described as follows:
1, chemical modification: though PVDF has good stable, still chemical reaction can take place under certain condition, therefore can directly realize its microporous barrier surface modification by chemical reaction.Nineteen eighty-three, people such as Hideo Kase find that alkaline solution can make PVDF slough HF and form undersaturated two strands and three chains, takes the lead in having disclosed the possibility [1,2] of the PVDF material surface being carried out chemical modification under the condition that phase transfer catalyst exists.And then discover, after highly basic potassium hydroxide, strong oxidizer liquor potassic permanganate processing pvdf membrane surface make it slough HF, necleophilic reaction in the acidic reduction environment again, can generate in a large number through base on the film surface, and then can introduce some bigger hydrophilic radicals or side chain (as polyvinylpyrrolidone, polyethylene glycol, glycerine etc.), make the microporous barrier surface form the hydrophily top layer of stable bond, obtain the good pvdf membrane of hydrophily.
2, plasma technique: plasma technique is handled microporous barrier, and to have technology simple, pollution-free, and especially processing region is confined to the surface and does not influence advantages such as the structure of material body and performance.H.Iwata etc. [3,4] have carried out representative work.They will gather isopropyl propylene phthalein amine (PolyNIPAAm) respectively with plasma technique and polyacrylic acid (PAA) connects skill to porous pvdf membrane surface, have obtained environment temperature and pH value sensitive polymers functional membrane.
3, light, radiation and hot initiation grafting polymerization: hydrophilic monomer is grafted to hydrophobicity pvdf membrane surface, can improves character such as its surface hydrophilicity, biocompatibility, dyeability, adsorptivity, cementability and wear-resisting wiping.With irradiation gas phase grafting method study on the modification is carried out on PVDF milipore filter surface and find [5], through Co
60Gamma-ray irradiation, the free radical that the pvdf membrane surface is produced can cause the side chain that styrene polymerization forms certain-length, and further sulfonation obtains the PVDF microporous barrier of sulfonic acid surfactant base modification.The hydrophily of modification caudacoria increases, and is reduced to 58 with the contact angle value of water by 68, is that the jail of holding back of 0.5g bovine serum albumin(BSA) brings up to 99.2 from 97.8 to concentration, and contamination resistance also has change, dustiness decline nearly 10 percentage point.United States Patent (USP) 4,774,132 is pointed out the pvdf membrane alkali treatment, subsequently acrylic acid is grafted to its surface and prepares hydrophilic pvdf membrane, can add the intensity [6] that crosslinking agent strengthens hydrophilic grafting in the polymerization.
4, blending and modifying.As PVDF microporous barrier with the PMMA blending and modifying.The result shows that PMMA content is at 1% o'clock, and the rejection of modification caudacoria is constant, and the water flux of film improves 2 times.The pvdf membrane that utilized sulfonated poly aryl ether ketone (SPES-C) blending and modifying in addition.The test of vinegar clarification filtration finds that PVDF/SPE5-C blended ultrafiltration membrane flux is 1.5 times after the modification, and the hydrophily of film and contamination resistance strengthen, and is easy to clean after the film pollution.PVDF prepares milipore filter with chloromethyl polysulphone (CMPS) blend.When the mass ratio of PVDF/CMPS was 3/1, the polymer phase capacitive was better, and the smoothly all even rejection height of film outward appearance has fabulous contamination resistance when being used for cathode cell lacquer hyperfiltration treatment.In addition, the result of study of polypropylene fine (PAN) and polyvinyl acetate (PVAc) blending and modifying pvdf membrane shows further that also selecting suitable hydrophilic polymer blending and modifying for use is the effective means that improves the PVDF hydrophilic microporous membrane.United States Patent (USP) 6,024,872nd adopts the hydrophilic micro-filtration of the compound preparation of alpha-aluminium oxide and the milipore filter [7,8] of PVDF and sintering, and the content of alpha-aluminium oxide is not higher than 50%, and this method also can be used for preparing micro-filtration to be supported and milipore filter.
But said method all has its shortcoming, and chemical method relates to a large amount of hazardous chemicalses, the treatment conditions harshness.Plasma treatment requires very high to equipment, investment is big, and method efficient such as photopolymerization are on the low side.Blending and modifying influences the mechanical property of film easily.The present invention adopts the dry process polyvinylidene fluoride microporous film, is immersed in subsequently in the modified solution, and a step is realized the process of pore-forming and coating, the polyvinylidene fluoride microporous film of preparation hydrophilic modifying.
List of references:
[1] Du Qiyun, membrane science and technology .2003,23 (4) .80-85
[1]Hideo?K.etc.，J.Polym.Sci.Polym.Chem.Ed，1983，21：3443-3451
[2]Hietala?S，Holmberg?S，Karjalainen?M，et?al，J.Mater.Chem.1997，7(5)，721-726
[3]Iwata?H，Matsuda?T.etc，J.Memb.Sci.，1988，38：185-199.
[4] Lu Xiaofeng, Wang Genghua, Liang Guoming, etc., membrane science and technology, 1998,18 (6): 54-57.
[5]Detlef?D，Eberhard?S.J.Memb.Sci.，1993，78，45-51
[6]Joffee，I.B.et?al.US?Patent?4,774,132
[7]Mahendran；et?al，US?Patent?6,024,872
[8] YUN prolongs shore Liu and English Ma Runyu, membrane science and technology, 2003,23 (2) .57-61
Summary of the invention
Adopt solvent evaporated method to prepare the PVDF microporous barrier, with polymer dissolution in the bi-component solvent, this mixture is that the relative not volatile non-solvent with of a volatile good solvent is formed, with the casting liquid striking of the high thickness of preparation on smooth plate glass or other surface.At room temperature or in the drying box of higher temperature, under certain air velocity, from thin polymer film, evaporate a part of solvent then.Along with the evaporation of polymer solution internal solvent, the conversion of uniform liquid special product looks, promptly the macromolecule preparation liquid begins the interior single-phase two kinds of decentralized photos very uniformly that are separated into gradually.Countless superfine drops then spread to another liquid phase, most of macromolecule gather constantly that small echo drips around, the then very few no youngster of macromolecule that mother liquor is forced to stay in mutually, along with the continuation evaporation of solvent, drop will contact with each other.Final macromolecule precipitates, and forms film.Casting liquid can contain three even more component, depends on the requirement to film properties.Boiling point has a certain distance between solvent evaporated method requirement good solvent and the poor solvent.The solvent of selecting can comprise ketone for single solvent or double solvents, acid amides, alkyl halide and other low boiling point solvents.Poor solvent can select for use high boiling solvent such as water, alcohols with and composition thereof etc.
The dip-coating modification also is a kind of surface modifying method commonly used, and material is dipped in the modified solution, contains compositions such as polymer-modified, surfactant in the solution.Then material is taken out drying under uniform temperature and humidity, the polymer of modification will form the coating of a homogeneous at material surface.For stable coatings, can add crosslinking agent, perhaps post processing improves the stability of coating.The dip-coating modification is usually used in the chromatographic technique.Improve the selection separation of chromatograph packing material.
The present invention adopts one-step method to prepare hydrophilic PVDF microporous barrier in conjunction with these two kinds of methods.Both when solvent evaporated method prepares the PVDF microporous barrier, film was immersed in the modified solution, and utilized the polymer of modification to introduce wherein, then dryness finalization.Simultaneously also can add crosslinking agent, the polymer of modification is combined by chemical crosslinking.The conventional relatively solvent evaporated method of this method has added a step dip-coating process, realizes hydrophilic preparation film.It is similar although go up on the surface with respect to immersion precipitation, and basic difference is arranged.For immersion precipitation, the film that is formed at of membrane structure is immersed in the coagulation bath.Both immersed coagulation bath conditional decision the structure and the form of film, and its preparation hydrophilic membrane is very difficult, need to introduce hydrophilic polymer and is prepared into polymer solution and waters film.The present invention is by changing the microporous barrier that different dip-coating solution can prepare different performances.Two processes have the difference of essence on coagulation bath is formed in addition, and the former coagulation bath mainly is a poor solvent, and that the latter is contained is a large amount of polymer-modified, and crosslinking agent etc.The polymer of modification can be selected hydrophilic macromolecule for use, comprises polyvinyl alcohol, shitosan, polyethylene pyrrolidone, polyacrylic acid etc.Modified solution adopts the aqueous solution, can add crosslinking agent, catalyst in addition.It is that with the coagulation bath difference that immerses the precipitation method coagulation bath is mainly the poor solvent of polymer, micromolecular compound.
This method is with respect to ready-made PVDF microporous modification, and technical process is simplified greatly, because the pvdf membrane surface can be low, simple dip-coating is difficult to form homogeneous and stable way layer.This also is the reason that can not directly carry out coating modified report to pvdf membrane.A lot of reports is modification again after the employing PVDF chemical surface treatment.Be to be convenient to surface modification like this in order to reduce its surface or to change its surface texture.And this technology has solved this problem, has realized that one-step method prepares hydrophilic PVDF microporous barrier.
This law can prepare flat sheet membrane and mesopore tunica fibrosa in addition.General diameter＜the 0.5mm of hollow-fibre membrane is a class self-support type film.The film making solution of being made up of polymer, solvent, additive is after filtering with the pump spinning head of hitting the person, be extruded with the form that forms the tubulose liquid film around the wire core liquid by the spinning head central supply, the immersion coagulating bath is solidified into doughnut and is collected in godet roller again after processing such as washing after " the air gap " is pulled, is stretched to certain radial dimension.Compare effective loading density height that characteristics that it is outstanding and advantage are film in the membrane module with flat sheet membrane, tubular membrane.Its basic principle is all the same.
The specific embodiment
Example 1: the preparation of flat sheet membrane
With acetone, diglycol, water (volume ratio is 91: 7: 2) is the PVDF solvent, is made into 10% solution, and the aqueous solution that consists of polyvinyl alcohol of modification liquid (concentration 6%) wherein contains 1% (with respect to polyvinyl alcohol) glutaraldehyde, 1% sulfuric acid.Preparation is during flat sheet membrane, PVDF solution scraped the polymer preparation liquid with scraper under the 50-60 degree formed solution film on supporters such as nonwoven or glass plate, and 5 seconds kinds of stop immerse supporter and solution film in the modified solution more in the lump in air.Take out after half an hour, in water, clean, remove the polyvinyl alcohol on surface, in baking oven under 80 degree dry 2 hours then.Get final product.Measuring its water flux is under 0.2 atmospheric pressure, 5.6kg/min.m
2
Example 2: the preparation of flat sheet membrane
With acetone, ethanol, water (volume ratio is 88: 10: 2) is the PVDF solvent, is made into 18% solution, and the aqueous solution that consists of shitosan of modification liquid (concentration 3%) wherein contains 5% (with respect to shitosan) glutaraldehyde, 1% sulfuric acid.Preparation is during flat sheet membrane, PVDF solution scraped the polymer preparation liquid with scraper under the 50-60 degree formed solution film on supporters such as nonwoven or glass plate, and 5 seconds kinds of stop immerse supporter and solution film in the modified solution more in the lump in air.Take out after half an hour, in water, clean, remove the polyvinyl alcohol on surface, in baking oven under 80 degree dry 2 hours then.Get final product.Measuring its water flux is under 0.2 atmospheric pressure, 2.5kg/min.m
2
Example 3: the preparation of hollow-fibre membrane
Acetone, glycerine, Macrogol 200 (volume ratio is 86: 10: 4) are the PVDF solvent, be made into 12% solution behind the high-temperature digestion, the aqueous solution that consists of shitosan of modification liquid (concentration 5%) wherein contains 5% (with respect to shitosan) glutaraldehyde, the sulfuric acid of 1-8%.The film making solution that polymer, solvent, additive are formed is after filtering with the pump spinning head of hitting the person, be extruded with the form that around wire core liquid, forms the tubulose liquid film by the spinning head central supply, after being pulled, being stretched to certain radial dimension, " the air gap " be solidified into doughnut in the aqueous solution of immersion shitosan again through washing, in baking oven under 80 degree dry 2 hours then, get final product.Measuring its water flux is under 0.2 atmospheric pressure, 4.5kg/min.m
2
Example 4: the preparation of hollow-fibre membrane
Acetone, butanols, triethylene-glycol (volume ratio is 88: 8: 4) are the PVDF solvent, are made into 13% solution, and the aqueous solution that consists of polyvinyl alcohol of modification liquid (concentration 8%) wherein contains 3% (with respect to polyvinyl alcohol) glutaraldehyde, 1% sulfuric acid.The film making solution that polymer, solvent, additive are formed is after filtering with the pump spinning head of hitting the person, be extruded with the form that around wire core liquid, forms the tubulose liquid film by the spinning head central supply, after being pulled, being stretched to certain radial dimension, " the air gap " be solidified into doughnut in the aqueous solution of immersion polyvinyl alcohol again through washing, in baking oven under 80 degree dry 2 hours then, get final product.Measuring its water flux is under 0.2 atmospheric pressure, 6.5kg/min.m
2
Claims (4)
1. two processes below these hydrophilic membrane preparation process characteristics are to comprise two: in the time of solvent evaporation phase separation method in conjunction with dip coating, enter into hydrophilic polymer solution when promptly adopting solvent evaporation back to form microporous barrier, carry out dip-coating, the crosslinked back of coating forms the polyvinylidene fluoride microporous film of hydrophilic modifying.
2. the form of microporous barrier can be flat sheet membrane or mesopore tunica fibrosa.The pore diameter range of microporous barrier is between the 0.01-2 micron.Adjustable continuously according to prescription.
3. the Kynoar mean molecule quantity is 5,000 to 1,000,000.It is primary solvent that polymer solution adopts acetone, concentration is between 8-20%, with water, alcohols is poor solvent, and concentration also can be added some other high boiling solvent such as diglycol, triethylene-glycol and low molecular poly etc. between 8-20%.
4. hydrophilic coating adopts hydrophilic polymer, and coating realizes stable coating structure after crosslinking Treatment, the material that adopts is, polyvinyl alcohol, shitosan, sodium alginate, polyethylene arsenic are pressed against alkane ketone, and their mixture etc., molecular weight ranges is 5000-20,000.Concentration is between 1-20%.
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| US11883784B2 (en) | 2017-09-11 | 2024-01-30 | Fresenius Medical Care Holdings, Inc. | Microporous membrane and methods to make same |
| CN109692577A (en) * | 2017-10-20 | 2019-04-30 | 宁波方太厨具有限公司 | The cross-linking modified preparation method of total coating of hollow fiber ultrafiltration membrane |
| CN110575761A (en) * | 2019-08-28 | 2019-12-17 | 韩旭霞 | Fiber-reinforced PVDF ultrafiltration membrane and application thereof in municipal sewage and industrial wastewater |
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| CN110575760A (en) * | 2019-08-28 | 2019-12-17 | 韩旭霞 | preparation method of fiber-reinforced PVDF ultrafiltration membrane |
| CN112619432A (en) * | 2019-09-24 | 2021-04-09 | 中国石油化工股份有限公司 | Ultrafiltration membrane and preparation method thereof |
| CN110756066A (en) * | 2019-11-25 | 2020-02-07 | 中南大学 | Sulfonated citric acid chitosan modified polysulfone hemodialysis membrane and preparation method thereof |
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| CN114276505B (en) * | 2021-12-31 | 2024-01-30 | 安徽师范大学 | Poly (arylene piperidine) copolymer containing polyethylene glycol flexible hydrophilic side chain, preparation method, anion exchange membrane and application |
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