CN103349920A - Dynamic-crosslinking preparation method of polyvinyl alcohol-blended hollow-fiber ultrafiltration membrane - Google Patents
Dynamic-crosslinking preparation method of polyvinyl alcohol-blended hollow-fiber ultrafiltration membrane Download PDFInfo
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- ultrafiltration membrane
- fiber ultrafiltration
- hollow fiber
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- 239000012510 hollow fiber Substances 0.000 title claims abstract description 66
- 238000000108 ultra-filtration Methods 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000004132 cross linking Methods 0.000 title claims abstract description 17
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
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- 239000003960 organic solvent Substances 0.000 claims description 16
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- 239000002994 raw material Substances 0.000 claims description 13
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 8
- 239000000654 additive Substances 0.000 claims description 8
- 230000000996 additive effect Effects 0.000 claims description 8
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 claims description 8
- 229920001477 hydrophilic polymer Polymers 0.000 claims description 8
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 claims description 8
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 8
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 7
- 239000004088 foaming agent Substances 0.000 claims description 7
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 235000012489 doughnuts Nutrition 0.000 claims description 5
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- 235000019270 ammonium chloride Nutrition 0.000 claims description 4
- 229940015043 glyoxal Drugs 0.000 claims description 4
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical group [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 4
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 4
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 3
- OOLBRPUFHUSCOS-UHFFFAOYSA-N Pimelic dialdehyde Chemical compound O=CCCCCCC=O OOLBRPUFHUSCOS-UHFFFAOYSA-N 0.000 claims description 3
- 239000004695 Polyether sulfone Substances 0.000 claims description 2
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- Artificial Filaments (AREA)
Abstract
The invention provides a dynamic-crosslinking preparation method of a polyvinyl alcohol-blended hollow-fiber ultrafiltration membrane. In the preparation method, a core solution and a PVA-containing blending membrane-casting solution are extruded from an annular spinneret of hollow-fiber spinning equipment, and nascent-state membrane filaments are obtained through a 1-10 cm dry process; then an early-formed hollow-fiber ultrafiltration membrane is obtained through dynamic chemistry fixing of PVA onto the nascent-state membrane filaments in a first coagulation bath and then through phase-separating processing at the temperature of 30 DEG C-60 DEG C; and then a product is obtained through further phase-separating solidification processing of the early-formed hollow-fiber ultrafiltration membrane in a second coagulation bath at the temperature of 20 DEG C-30 DEG C. Through use of the preparation method, the nascent-state membrane filaments and the core solution can together enter a solvent-nonsolvent exchanging dynamic phase-separating process in a coagulation bath of a certain temperature to carry out a chemical crosslinking reaction, and net structures which are mutually winded with polymer chains of membrane main materials are formed in membrane filaments, so that the water-soluble PVA is fixed on the ultrafiltration membrane.
Description
Technical field
The present invention relates to a kind of hollow-fibre membrane, particularly the dynamic crosslinking preparation method of a kind of polyvinyl alcohol (PVA) blending hollow fiber ultrafiltration membrane.
Background technology
The milipore filter isolation technics aspect the water reuse, has shown widely application prospect in industrial wastewater, sanitary sewage etc.But the polymer ultrafiltration membrane material has stronger hydrophobicity mostly, can cause the organic contamination deposits yields strong adsorption in the filter medium film to pollute, and causes film properties deteriorated, and shorten service life.Studies show that: hydrophilic ultrafiltration membrane in aqueous media, can and hydrone between form the interface hydrated sheath on film surface, thereby alleviate the absorption behavior of pollutant in film surface and the filter medium, and be conducive to remove film by physical cleaning method and pollute.Therefore, reducing film by the hydrophily that improves milipore filter and pollute, is the study hotspot in milipore filter field in recent years.
Hollow-fibre membrane is difficult for carrying out the film performing hydrophilic modification on surface because of the design feature of self.Patent CN1973971A(Peng Yue lotus) announced with isocyanates as crosslinking agent, at the rear crosslinked fixing means of milipore filter surface coating hydrophilic modification film.But the isocyanates water breakthrough easily decomposes and toxicity is larger, can only operate at the medium of organic solvent, easily causes the destruction of milipore filter structure and performance and deteriorated, is therefore limited in the industrialization practical application.Blend hydrophilic material in casting solution is the effective ways that improve the milipore filter hydrophilicity.
Being rich in hydroxy functional group in the PVA molecular structure, is the water-soluble high hydrophiling polymer of a kind of energy, is compatible in the polar organic solvent with membrane material commonly used such as the energy blend such as polyvinylidene fluoride, polysulfones, and can prepares hollow-fibre membrane by dry-wet phase inversion.Hydroxyl in the blend film on the PVA strand can produce strong chemical hydrogen bond action and forms hydrated sheath on film surface in aqueous media and between hydrone, thus the absorption behavior between barrier film surface and pollutant.For example ZL200710058333.x discloses and has utilized the PVDF(Kynoar)/the PVA(polyvinyl alcohol) blend is in the DMSO(dimethyl sulfoxide (DMSO)) in the preparation hollow fiber ultrafiltration membrane, but the immobilization of not carrying out the hydrophily composition is processed.But because the PVA water soluble carries out in the process of phase-splitting in the coagulation bath take water as medium, and filters for a long time in the operation, loss by dissolution easily occurs and makes membrane material lose hydrophily in PVA.
Summary of the invention
The object of the present invention is to provide a kind of dynamic crosslinking preparation method of PVA blending hollow fiber ultrafiltration membrane.To solve the hydrophiling milipore filter of existing PVA blending modification method preparation, in gel phase conversion film and film application process, the problem that hydrophilic material PVA easily runs off.
For this reason, the dynamic crosslinking preparation method of PVA blending hollow fiber ultrafiltration membrane provided by the invention may further comprise the steps:
Core liquid and casting solution from the annular spinning head coextrusion of doughnut spinning equipment, are obtained nascent state film silk after the dried journey through 1～10cm;
The constitutive material of described core liquid and the mass percent of each raw material are: the mass percent sum of chemical cross-linking agent 0.1%～3%, organic solvent 0～30%, aqueous hydrochloric acid solution 67%～99.9% and three kind of raw material is 100%, described chemical cross-linking agent be glutaraldehyde, glyoxal or heptan dialdehyde, the concentration of hydrochloric acid of described aqueous hydrochloric acid solution is 0.1～1.0mol/L;
The mass percent sum of the constitutive material of described casting solution and each raw material is: the mass percent sum of macromolecular material 12%～20%, hydrophilic polymer 1%～8%, inorganic additive 0～5%, pore-foaming agent 3%～8% and organic solvent 68%～78% and five kind of raw material is 100%, described macromolecular material is polysulfones, polyether sulfone, polyvinylidene fluoride or polyacrylonitrile, described hydrophilic polymer is polyvinyl alcohol, described inorganic additive is lithium perchlorate, lithium nitrate, lithium chloride or ammonium chloride, and described pore-foaming agent is polyethylene glycol;
Under 30 ℃～60 ℃, the phase-splitting processing in the first coagulation bath of nascent state film silk is obtained just becoming hollow fiber ultrafiltration membrane;
The constitutive material of described the first coagulation bath and the percent by volume of each raw material are: water: 40%～100%, organic solvent: 0～60% and the percent by volume sum of two kind of raw material be 100%;
Described organic solvent is N, the mixed liquor of one or more in N dimethylacetylamide, DMF, METHYLPYRROLIDONE and the dimethyl sulfoxide (DMSO);
Under 20 ℃～30 ℃, will just become hollow fiber ultrafiltration membrane further minute solidifying processing in the second coagulation bath;
Described the second coagulation bath is water;
Obtain afterwards the polyvinyl alcohol blending hollow fiber ultrafiltration membrane.
Other technologies of the present invention are characterized as:
The preparation temperature of described casting solution is 60 ℃～90 ℃.
The phase-splitting processing time in the first coagulation bath is 10s～60s.
Further the time of minute solidifying processing is 15min～60min in the second coagulation bath.
The molecular weight of described polyvinyl alcohol is greater than 120,000.
The molecular weight of described polyethylene glycol is 400～20,000.
A kind of dynamic crosslinking preparation method of preferred PVA blending hollow fiber ultrafiltration membrane may further comprise the steps:
Core liquid and casting solution after the annular spinning head coextrusion of doughnut spinning equipment, are got nascent state film silk through the dried journey of 1cm～10cm;
Under 30 ℃～60 ℃, nascent state film silk enters phase-splitting processing 10s～60s in the first coagulation bath, obtains just becoming hollow fiber ultrafiltration membrane;
Water under the room temperature is as the second coagulation bath, just become hollow fiber ultrafiltration membrane in the second coagulation bath further minute solidifying process 15～60min, after the abundant rinsing of water, finally be prepared into the polyvinyl alcohol blending hollow fiber ultrafiltration membrane.
Dynamic crosslinking of the present invention prepares the method for PVA blending hollow fiber ultrafiltration membrane, mainly be to utilize the nascent state hollow fiber film thread and the core liquid that contains chemical cross-linking agent, in the coagulation bath that jointly enters specified conditions, carry out in the dynamic phase separation of solvent and non-solvent exchange, crosslinking agent is mixed in together between PVA in the casting solution chemical crosslink reaction occurs, the network structure that in the film silk, mutually twines between formation and film master material macromolecular chain, thereby water-soluble PVA is fixed in the milipore filter, and unlikely movement with aqueous media runs off, and can effectively guarantee the hydrophilic stability of milipore filter in application process.
Compared with prior art, the invention has the advantages that:
(1) in the first coagulation bath, dynamically phase separation and PVA immobilized reactant carry out simultaneously, do not need the doughnut spinning equipment is carried out special transformation, also do not need to carry out loaded down with trivial details film last handling process, and be easy to operation;
(2) organic chemistry crosslinking agent and hydrochloric acid only are present in the core liquid, and consumption is less, and reaction is efficient, has reduced carrying capacity of environment, and are easy to control.
(3) first coagulation baths provide gel phase to transform and required environment and the temperature conditions of chemical crosslink reaction, and equipment loss is less, and mild condition is easy and safe to operate.
(4) add solvent in core liquid and the first coagulation bath, the phase separation setting of regulation and control membrane structure does not exert an influence to the condition of chemical crosslink reaction.And the film silk be separated and curing rate between mutually coordination more be of value to regulation and control chemical crosslink reaction degree, realize the hydrophiling control of membrane structure, can make things convenient for the hydrophiling hollow fiber ultrafiltration membrane of controllably preparing stable performance.
(5) the PVA blending hollow fiber ultrafiltration membrane cross-linked network behavior of gained of the present invention as shown in Figure 1, the hydrophilic contact angle of gained PVDF milipore filter of the present invention drops in 30s between 65 °～35 °, hot strength is greater than 2.5Mpa; 0.1MPa under pure water flux be not less than 200L/ (m
2H), the BSA rejection is not less than 65%, BSA static adsorbance less than 45 μ g/cm
2, clean recovery rate greater than 90%.
Description of drawings
Fig. 1 is the crosslinked grid schematic diagram of the PVA-GA of PVA blending hollow fiber ultrafiltration membrane of the present invention;
Fig. 2 is the milipore filter scanning electron microscope (SEM) photograph of the PVA blending hollow fiber ultrafiltration membrane of embodiment 1 preparation.
The specific embodiment
A kind of dynamic crosslinking PVA provided by the invention prepares the method for blending hollow fiber ultrafiltration membrane, adopt the hollow fiber spinning technology, the crosslinked method of dynamic chemical occurs and realizes in the homogeneous casting solution that will contain hydrophilic polymer PVA in specific hollow fiber spinning core liquid and the first coagulation bath.
Used core liquid is that chemical cross-linking agent, organic solvent and hydrochloric acid solution are got according to mixing under the certain mass ratio among the present invention; Wherein chemical cross-linking agent 0.1%～3%, organic solvent 0～30%, aqueous hydrochloric acid solution 67%～99.9% and three's mass percent sum is 100%, chemical cross-linking agent be glutaraldehyde, glyoxal or heptan dialdehyde, the concentration of hydrochloric acid of aqueous hydrochloric acid solution is 0.1～1mol/L.
Used casting solution is that macromolecular material, hydrophilic polymer, inorganic additive, pore-foaming agent and organic solvent are mixed according to certain mass percent among the present invention, obtains after 20～36 hours 60 ℃～90 ℃ lower stirring and dissolving; Wherein macromolecular material 12%～20%, hydrophilic polymer 1%～8%, inorganic additive 0～5%, pore-foaming agent 3%～8%, organic solvent 68%～78%, and the mass percent sum of five kinds of raw materials is 100%, polymeric membrane master material is polysulfones (PS), polyether sulfone (PES), polyvinylidene fluoride (PVDF) or polyacrylonitrile (PAN), preferred PVDF wherein, hydrophilic polymer is PVAC polyvinylalcohol, its molecular weight is between 3-25 ten thousand, wherein preferred molecular weight is greater than 120,000, inorganic additive is lithium perchlorate, lithium nitrate, lithium chloride or ammonium chloride, pore-foaming agent is the polyethylene glycol that requires the molecular weight of selection not wait according to the aperture, and molecular weight ranges is generally between 400～20,000.
Among the present invention the first used coagulation bath be water or for percent by volume be that 40%～100% water and percent by volume are the mixed liquor of 0～60% organic solvent.
Organic solvent in core liquid of the present invention, casting solution and the first coagulation bath is N, the combination of one or more among N dimethylacetylamide DMAC, DMF DMF, METHYLPYRROLIDONE NMP and the dimethyl sulfoxide (DMSO) DMSO.
Method of the present invention has utilized the hydroxyl on the PVA main chain can be under acid condition and the principle of chemical cross-linking agent generation cross-linking reaction, dynamic process by the exchange of the solvent non-solvent when gel phase transforms, make the hollow fiber ultrafiltration membrane that contains PVA in the acid gel of uniform temperature is bathed, the chemical crosslinking effect occurs rapidly, form the network structure that mutually twines between PVA and the film master material macromolecular chain, thus dissolving and the loss behavior of avoiding PVA in film, to cause with the water migration.Good and the lasting stability of preparation-obtained milipore filter hydrophilic effect.
Among the present invention to the ratio of hydrophilic additive in the casting solution and chemical cross-linking agent consumption, the temperature of the first coagulation bath and the time of staying, core liquid acidity etc. be controlled to be committed step, in the concrete preparation process of hollow fiber ultrafiltration membrane, can add according to actual needs other reagent.
Embodiment 1:
(1) core liquid is placed the core flow container, casting solution places material liquid tank, and by flowmeter measure control core flow quantity, utilize hollow fiber spinning equipment with core liquid and casting solution after the annular spinning head coextrusion through after the dried journey of 3cm nascent state film silk,
Core liquid: with mass percent be 0.1% glutaraldehyde, 99.9% concentration be the combined of 0.1mol/L even core liquid;
Casting solution: be 17% Kynoar PVDF, 1% PVAC polyvinylalcohol (molecular weight is 120,000), 5% lithium chloride, 5% PEG400 and 72% N with mass percent, N dimethylacetylamide DMAC mixes, and obtains casting solution after 90 ℃ of lower stirring and dissolving 20h standing and defoaming;
(2) nascent state film silk enters in the first coagulation bath of 30 ℃ phase-splitting and processes 10s, makes nascent state film silk in the dynamic process that gel phase transforms, and PVA is fixed in the film silk by chemical crosslinking, thereby obtains just becoming hollow fiber ultrafiltration membrane; Used the first coagulation bath is water;
(3) running water under the room temperature is as the second coagulation bath, just becomes hollow fiber ultrafiltration membrane through leading the traction of silk wheel, further minute solidifying 15min in the second coagulation bath, and fully rinsing prepares the PVA blending hollow fiber ultrafiltration membrane after wire drawing wheel is received silk.
Under 25 ℃, 0.1MPa, the PVA blending hollow fiber ultrafiltration membrane water flux of measuring this embodiment gained is 156L/(m
2H), be 97% to the rejection of bovine serum albumin; Hot strength and percentage elongation are respectively 4.2MPa and 147%; Hydrophilic contact angle behind the 30s is 55 °; The BSA dustiness is 51%, and cleaning recovery rate is 97%.Fig. 2 is the milipore filter profile scanning Electronic Speculum figure of this embodiment 1.
Embodiment 2:
(1) utilize hollow fiber spinning equipment, with core liquid and casting solution after the annular spinning head coextrusion through after the dried journey of 1cm nascent state film silk,
Core liquid: be that 1.2% glutaraldehyde, 98.8% concentration are that the combined of 1mol/L evenly obtains core liquid with mass percent;
Casting solution: mass percent is respectively 15% Kynoar PVDF, 4% PVAC polyvinylalcohol (molecular weight is 250,000), 3% PEG400,78% METHYLPYRROLIDONE NMP mixes, after 80 ℃ of lower stirring and dissolving 24h standing and defoaming, obtain casting solution;
Under (2) 60 ℃, nascent state film silk enters and becomes hollow fiber ultrafiltration membrane at the beginning of phase-splitting processing 30s obtains in the first coagulation bath; The first coagulation bath is water;
(3) running water under the room temperature is as the second coagulation bath, just becomes hollow fiber ultrafiltration membrane further minute solidifying 40min in the second coagulation bath, and fully rinsing obtains the PVA blending hollow fiber ultrafiltration membrane of this embodiment afterwards.
Under 25 ℃, 0.1MPa, the hollow fiber ultrafiltration membrane water flux of measuring this embodiment preparation is 372L/(m
2H), be 84% to the rejection of bovine serum albumin; Hot strength and percentage elongation are respectively: 2.6MPa and 107%; Hydrophilic contact angle behind the 30s is 42 °; The BSA dustiness is 21%, and cleaning recovery rate is 98%.
Embodiment 3:
(1) utilize hollow fiber spinning equipment, with core liquid and casting solution after annular spinning head coextrusion, through after the dried journey of 5cm nascent state film silk,
Core liquid: be that 3% glyoxal, 30% DMAC, 67% 1mol/L combined evenly obtain core liquid with mass percent;
Casting solution: mass percent is respectively 12% Kynoar PVDF, 8% PVAC polyvinylalcohol (molecular weight is 30,000), 4% lithium perchlorate, 8% PEG400,68% N, N dimethylacetylamide DMAC mixes, at 90 ℃ of lower stirring and dissolving 36h, obtain the homogeneous casting solution after the standing and defoaming;
Under (2) 50 ℃, nascent state film silk enters phase-splitting processing 30s in the first coagulation bath, makes nascent state film silk in the dynamic process that gel phase transforms, and PVA is fixed in the film silk by chemical crosslinking, obtains just becoming hollow fiber ultrafiltration membrane; The first coagulation bath is to be 70% water and 30% N with volume ratio, and N dimethylacetylamide DMAC mixes and gets;
(3) running water under the room temperature is as the second coagulation bath, just becomes hollow fiber ultrafiltration membrane further minute solidifying 60min in the second coagulation bath, fully obtains the PVA blending hollow fiber ultrafiltration membrane of this embodiment after the rinsing.
Under 25 ℃, 0.1MPa, the water flux of measuring the PVA blending hollow fiber ultrafiltration membrane of this embodiment is 568L/(m
2H), be 92% to the rejection of bovine serum albumin; Hot strength and percentage elongation are respectively 3.2MPa and 121%; Hydrophilic contact angle behind the 30s is 45 °; Further its dustiness of test is 48%, and recovery rate is 99%.
Embodiment 4:
(1) utilize hollow fiber spinning equipment, with core liquid and casting solution after annular spinning head coextrusion, through after the dried journey of 1cm nascent state film silk,
Core liquid: will contain mass percent and be 1% dialdehyde in heptan, 20% DMAC, 79% 0.5mol/L combined and evenly obtain core liquid;
Casting solution: mass percent is respectively 15% Kynoar PVDF, 3% PVAC polyvinylalcohol (molecular weight is 120,000), 3% ammonium chloride, 5% PEG400,74% N, N dimethylacetylamide DMAC mixes, at 80 ℃ of lower stirring and dissolving 24h, obtain casting solution after the standing and defoaming;
Under (2) 40 ℃, nascent state film silk enters phase-splitting processing 60s in the first coagulation bath, makes nascent state film silk in the dynamic process that gel phase transforms, and PVA is fixed in the film silk by chemical crosslinking, thereby obtains just becoming hollow fiber ultrafiltration membrane; The first coagulation bath is water;
(3) running water under the room temperature is as the second coagulation bath, just becomes hollow fiber ultrafiltration membrane further minute solidifying 30min in the second coagulation bath, fully obtains the PVA blending hollow fiber ultrafiltration membrane of this embodiment after the rinsing.
Under 25 ℃, 0.1MPa, the PVA blending hollow fiber ultrafiltration membrane water flux of measuring this embodiment is 586L/(m
2H), be 90% to the rejection of bovine serum albumin; Hot strength and percentage elongation are respectively: 3.5MPa and 125%; Hydrophilic contact angle behind the 30s is 41 °; Further its dustiness of test is 53%, and recovery rate is 98%.
Embodiment 5:
(1) utilize hollow fiber spinning equipment, with core liquid and casting solution after annular spinning head coextrusion, through after the dried journey of 5cm nascent state film silk,
Core liquid: will contain mass percent and be 2% glutaraldehyde, 30% DMSO, 68% 1mol/L combined after evenly core liquid;
Casting solution: mass percent is respectively 20% Kynoar PVDF, 3% PVAC polyvinylalcohol (molecular weight is 120,000), 3% lithium nitrate, 4% PEG400,70% dimethyl sulfoxide (DMSO) DMSO mixes, at 90 ℃ of lower stirring and dissolving 24h, obtain casting solution after the standing and defoaming;
(2) 10s is processed in phase-splitting in 40 ℃ of nascent state film silks, the first coagulation bath, makes nascent state film silk in the dynamic process that gel phase transforms, and PVA is fixed in the film silk by chemical crosslinking, thereby obtains just becoming hollow fiber ultrafiltration membrane; The first coagulation bath is that percent by volume is 40% water and 60% dimethyl sulfoxide (DMSO) DMSO mixed solution;
(3) running water under the room temperature is as the second coagulation bath, just becomes hollow fiber ultrafiltration membrane further minute solidifying 30min in the second coagulation bath, fully obtains the PVA blending hollow fiber ultrafiltration membrane of this embodiment after the rinsing.
Under 25 ℃, 0.1MPa, the PVA blending hollow fiber ultrafiltration membrane water flux of measuring this embodiment is 276L/(m
2H), be 94% to the rejection of bovine serum albumin; Hot strength and percentage elongation are respectively: 3.8MPa and 138%; Hydrophilic contact angle behind the 30s is 64 °; Further its dustiness of test is 67%, and recovery rate is 91%.
Above content is in conjunction with concrete preferred embodiment further description made for the present invention; can not assert that the specific embodiment of the present invention only limits to this; for the general technical staff of the technical field of the invention; without departing from the inventive concept of the premise; can also make some simple deduction or replace, all should be considered as belonging to the present invention and determine scope of patent protection by claims of submitting to.
Claims (7)
1. the dynamic crosslinking preparation method of a polyvinyl alcohol blending hollow fiber ultrafiltration membrane is characterized in that, the method may further comprise the steps:
(1) with core liquid and casting solution from the annular spinning head coextrusion of doughnut spinning equipment, obtain nascent state film silk after the dried journey through 1～10cm;
The constitutive material of described core liquid and the mass percent of each raw material are: the mass percent sum of chemical cross-linking agent 0.1%～3%, organic solvent 0～30%, aqueous hydrochloric acid solution 67%～99.9% and three kind of raw material is 100%, described chemical cross-linking agent be glutaraldehyde, glyoxal or heptan dialdehyde, the concentration of hydrochloric acid of described aqueous hydrochloric acid solution is 0.1～1.0mol/L;
The mass percent sum of the constitutive material of described casting solution and each raw material is: the mass percent sum of polymeric membrane master material 12%～20%, hydrophilic polymer 1%～8%, inorganic additive 0～5%, pore-foaming agent 3%～8% and organic solvent 68%～78% and five kind of raw material is 100%, described polymeric membrane master material is polysulfones, polyether sulfone, polyvinylidene fluoride or polyacrylonitrile, described hydrophilic polymer is polyvinyl alcohol, described inorganic additive is lithium perchlorate, lithium nitrate, lithium chloride or ammonium chloride, and described pore-foaming agent is polyethylene glycol;
Described organic solvent is N, the mixed liquor of one or more in N dimethylacetylamide, DMF, METHYLPYRROLIDONE and the dimethyl sulfoxide (DMSO);
Under (2) 30 ℃～60 ℃, the phase-splitting processing in the first coagulation bath of nascent state film silk is obtained just becoming hollow fiber ultrafiltration membrane;
The constitutive material of described the first coagulation bath and the percent by volume of each raw material are: water: 40%～100%, organic solvent: 0～60% and the percent by volume sum of two kind of raw material be 100%;
Described organic solvent is N, the mixed liquor of one or more in N dimethylacetylamide, DMF, METHYLPYRROLIDONE and the dimethyl sulfoxide (DMSO);
Under (3) 20 ℃～30 ℃, will just become hollow fiber ultrafiltration membrane further minute solidifying processing in the second coagulation bath;
Described the second coagulation bath is water;
Behind above-mentioned steps (1), (2), (3), get the polyvinyl alcohol blending hollow fiber ultrafiltration membrane.
2. the dynamic crosslinking preparation method of polyvinyl alcohol blending hollow fiber ultrafiltration membrane as claimed in claim 1 is characterized in that, the preparation temperature of described casting solution is 60 ℃～90 ℃.
3. the dynamic crosslinking preparation method of polyvinyl alcohol blending hollow fiber ultrafiltration membrane as claimed in claim 1 is characterized in that, the time that phase-splitting is processed in the first coagulation bath is 10s～60s.
4. the dynamic crosslinking preparation method of polyvinyl alcohol blending hollow fiber ultrafiltration membrane as claimed in claim 1 is characterized in that, further the time of minute solidifying processing is 15min～60min in the second coagulation bath.
5. the dynamic crosslinking preparation method of polyvinyl alcohol blending hollow fiber ultrafiltration membrane as claimed in claim 1 is characterized in that, the molecular weight of described polyvinyl alcohol is greater than 120,000.
6. the dynamic crosslinking preparation method of polyvinyl alcohol blending hollow fiber ultrafiltration membrane as claimed in claim 1 is characterized in that, the molecular weight of described polyethylene glycol is 400～20,000.
7. the dynamic crosslinking preparation method of polyvinyl alcohol blending hollow fiber ultrafiltration membrane as claimed in claim 1 is characterized in that, method may further comprise the steps:
Core liquid and casting solution after the annular spinning head coextrusion of doughnut spinning equipment, are got nascent state film silk through the dried journey of 1cm～10cm;
Under 30 ℃～60 ℃, nascent state film silk enters phase-splitting processing 10s～60s in the first coagulation bath, obtains just becoming hollow fiber ultrafiltration membrane;
Water under the room temperature is as the second coagulation bath, just becomes hollow fiber ultrafiltration membrane further minute solidifying 15～60min in the second coagulation bath, finally is prepared into the polyvinyl alcohol blending hollow fiber ultrafiltration membrane after the abundant rinsing of water.
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| CN108671775A (en) * | 2018-02-02 | 2018-10-19 | 南京久盈膜科技有限公司 | Application of the polymer in the tensile strength for improving PVDF hollow-fibre membranes |
| CN114080266A (en) * | 2019-06-27 | 2022-02-22 | 3M创新有限公司 | Reactive additives in film manufacture |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1552507A (en) * | 2003-05-27 | 2004-12-08 | 天津膜天膜工程技术有限公司 | Method and apparatus for primary shaping composite or modified hollow fibre membrane |
| CN102512987A (en) * | 2011-12-09 | 2012-06-27 | 苏州有色金属研究院有限公司 | Method for preparing high-flux polyvinylidene fluoride hollow fiber membrane |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1552507A (en) * | 2003-05-27 | 2004-12-08 | 天津膜天膜工程技术有限公司 | Method and apparatus for primary shaping composite or modified hollow fibre membrane |
| CN102512987A (en) * | 2011-12-09 | 2012-06-27 | 苏州有色金属研究院有限公司 | Method for preparing high-flux polyvinylidene fluoride hollow fiber membrane |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108671775A (en) * | 2018-02-02 | 2018-10-19 | 南京久盈膜科技有限公司 | Application of the polymer in the tensile strength for improving PVDF hollow-fibre membranes |
| CN114080266A (en) * | 2019-06-27 | 2022-02-22 | 3M创新有限公司 | Reactive additives in film manufacture |
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