CN103349920B - 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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- 239000012528 membrane Substances 0.000 title claims abstract description 78
- 239000012510 hollow fiber Substances 0.000 title claims abstract description 63
- 238000000108 ultra-filtration Methods 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000004132 cross linking Methods 0.000 title claims abstract description 14
- 229920002554 vinyl polymer Polymers 0.000 title abstract 2
- 238000005345 coagulation Methods 0.000 claims abstract description 50
- 230000015271 coagulation Effects 0.000 claims abstract description 50
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- 239000000463 material Substances 0.000 claims abstract description 22
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- 238000010382 chemical cross-linking Methods 0.000 claims abstract description 17
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 58
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 58
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 38
- 239000007788 liquid Substances 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 22
- 239000003960 organic solvent Substances 0.000 claims description 16
- 239000002033 PVDF binder Substances 0.000 claims description 13
- 239000003431 cross linking reagent Substances 0.000 claims description 13
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 13
- 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
- 229920002492 poly(sulfone) Polymers 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 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
- 229920006393 polyether sulfone Polymers 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 7
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- 238000001035 drying Methods 0.000 abstract 1
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- 235000019422 polyvinyl alcohol Nutrition 0.000 description 50
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- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 7
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- JLFNLZLINWHATN-UHFFFAOYSA-N pentaethylene glycol Chemical compound OCCOCCOCCOCCOCCO JLFNLZLINWHATN-UHFFFAOYSA-N 0.000 description 5
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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
Ultra filtration membrane technology, in the Treated sewage reusing such as industrial wastewater, sanitary sewage, shows application prospect widely.But polymer ultrafiltration membrane material has stronger hydrophobicity mostly, can produce strong adsorption to the organic pollution in filter medium and cause fouling membrane, cause film properties deterioration, service life shortens.Research shows: hydrophilic ultrafiltration membrane in an aqueous medium, forms interface hydrated sheath on film surface between energy and hydrone, thus alleviates the absorption behavior of pollutant in film surface and filter medium, and is conducive to removing fouling membrane by physical cleaning method.Therefore, reducing fouling membrane by the hydrophily improving milipore filter, is the study hotspot in milipore filter field in recent years.
Hollow-fibre membrane not easily carries out film performing hydrophilic modification on surface because of the design feature of self.Patent CN1973971A(Peng Yue lotus) disclose with isocyanates as crosslinking agent, at the rear crosslinked fixing means of ultrafiltration membrane surface coating hydrophilic modification film.But isocyanates water breakthrough easily decomposes and toxicity is comparatively large, can only operate, easily cause destruction and the deterioration of milipore filter stuctures and properties, therefore limited in industrialization practical application at the medium of organic solvent.Blended hydrophilic material in casting solution is the effective ways improving milipore filter hydrophilicity.
Be rich in hydroxy functional group in PVA molecular structure, be the water-soluble high hydrophiling polymer of a kind of energy, with conventional membrane material as polyvinylidene fluoride, polysulfones etc. can blendedly be compatible in polar organic solvent, and prepare hollow-fibre membrane by dry-wet phase inversion.Hydroxyl in blend film on PVA strand, in an aqueous medium and can produce strong chemical hydrogen bond action and form hydrated sheath on film surface between hydrone, thus the absorption behavior between barrier film surface and pollutant.Such as ZL200710058333.x discloses and utilizes PVDF(Kynoar)/PVA(polyvinyl alcohol) blended in DMSO(dimethyl sulfoxide (DMSO)) middle preparation hollow fiber ultrafiltration membrane, but do not carry out the immobilization process of hydrophily composition.But due to PVA water soluble, carry out in the process of phase-splitting in the coagulation bath taking water as medium, and in long-term filtration operation, easily there is loss by dissolution and make 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 hydrophiling milipore filter prepared by existing PVA blending modification method, transform in film forming and film application process at gel phase, 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 comprises the following steps:
By core liquid and casting solution from the annular spinning head coextrusion of doughnut spinning equipment, after the dry journey of 1 ~ 10cm, obtain nascent state film silk;
The constitutive material of described core liquid and the mass percent of each raw material are: chemical cross-linking agent 0.1% ~ 3%, organic solvent 0 ~ 30%, aqueous hydrochloric acid solution 67% ~ the 99.9% and mass percent sum of three kinds of raw materials 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 constitutive material of described casting solution and the mass percent sum of each raw material are: macromolecular material 12% ~ 20%, hydrophilic polymer 1% ~ 8%, inorganic additive 0 ~ 5%, pore-foaming agent 3% ~ 8% and organic solvent 68% ~ 78% and the mass percent sum of five kinds of raw materials 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;
At 30 DEG C ~ 60 DEG C, the phase-splitting process in the first coagulation bath of nascent state film silk is obtained just become hollow fiber ultrafiltration membrane;
The constitutive material of described 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 kinds of raw materials is 100%;
Described organic solvent is one or more the mixed liquor in N, N dimethylacetylamide, DMF, METHYLPYRROLIDONE and dimethyl sulfoxide (DMSO);
At 20 DEG C ~ 30 DEG C, just will become hollow fiber ultrafiltration membrane point solidifying process further in the second coagulation bath;
Described second coagulation bath is water;
Obtain polyvinyl alcohol blending hollow fiber ultrafiltration membrane afterwards.
Other technologies of the present invention are characterized as:
The preparation temperature of described casting solution is 60 DEG C ~ 90 DEG C.
The phase-splitting processing time in first coagulation bath is 10s ~ 60s.
In second coagulation bath, the time of point solidifying process is further 15min ~ 60min.
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 comprises the following steps:
By core liquid and casting solution after the annular spinning head coextrusion of doughnut spinning equipment, the dry journey through 1cm ~ 10cm obtains nascent state film silk;
At 30 DEG C ~ 60 DEG C, nascent state film silk enters phase-splitting process 10s ~ 60s in the first coagulation bath, obtains just becoming hollow fiber ultrafiltration membrane;
Be the second coagulation bath with the water under room temperature, just become hollow fiber ultrafiltration membrane point solidifying process 15 ~ 60min further in the second coagulation bath, after the abundant rinsing of water, be finally prepared into polyvinyl alcohol blending hollow fiber ultrafiltration membrane.
Dynamic crosslinking of the present invention prepares the method for PVA blending hollow fiber ultrafiltration membrane, mainly utilize nascent state hollow fiber film thread and the core liquid containing chemical cross-linking agent, carry out in the dynamic phase separation that solvent and non-solvent exchange in the coagulation bath jointly entering specified conditions, crosslinking agent is mixed in together between the PVA in casting solution and chemical crosslink reaction occurs, the network structure being formed in film silk and be mutually wound around between the main material macromolecular chain of film, thus water-soluble PVA is fixed in milipore filter, and unlikelyly to run off with the movement of aqueous media, and effectively can ensure the hydrophilic stability of milipore filter in application process.
Compared with prior art comparatively, the invention has the advantages that:
(1) in the first coagulation bath, dynamic phase separation and PVA immobilized reactant carry out simultaneously, do not need to carry out special transformation to doughnut spinning equipment, also do not need to carry out loaded down with trivial details film last handling process, easy to operation;
(2) organic chemistry crosslinking agent and hydrochloric acid are only present in core liquid, and consumption is less, and reaction is efficient, decreases carrying capacity of environment, and are easy to control.
(3) first coagulation baths provide gel phase to transform and environment needed for chemical crosslink reaction and temperature conditions, and equipment loss is less, mild condition, easy and safe to operate.
(4) in core liquid and the first coagulation bath, add solvent, the phase separation of regulation and control membrane structure is arranged, and does not have an impact to the condition of chemical crosslink reaction.And film silk be separated and between curing rate, mutual coordination is more of value to regulation and control chemical crosslink reaction degree, the hydrophiling realizing membrane structure controls, and can facilitate the hydrophiling hollow fiber ultrafiltration membrane controllably preparing stable performance.
(5) as shown in Figure 1, gained PVDF ultrafiltration membrane hydrophilic contact angle of the present invention drops between 65 ° ~ 35 ° in 30s, and hot strength is greater than 2.5Mpa in the PVA blending hollow fiber ultrafiltration membrane cross-linked network behavior of gained of the present invention; Pure water flux under 0.1MPa is not less than 200L/ (m
2h), BSA rejection is not less than 65%, BSA static adsorbance and is less than 45 μ g/cm
2, cleaning recovery rate is greater than 90%.
Accompanying drawing explanation
Fig. 1 is that the PVA-GA of PVA blending hollow fiber ultrafiltration membrane of the present invention is cross-linked grid schematic diagram;
Fig. 2 is the milipore filter scanning electron microscope (SEM) photograph of PVA blending hollow fiber ultrafiltration membrane prepared by embodiment 1.
Detailed description of the invention
A kind of dynamic crosslinking PVA provided by the invention prepares the method for blending hollow fiber ultrafiltration membrane, adopt hollow fiber spinning technology, by the homogeneous casting solution containing hydrophilic polymer PVA, in specific hollow fiber spinning core liquid and the first coagulation bath, the method for occurrence dynamics chemical crosslinking realizes.
Core liquid used in the present invention is obtained according to mixing under certain mass ratio chemical cross-linking agent, organic solvent and hydrochloric acid solution; Wherein chemical cross-linking agent 0.1% ~ 3%, organic solvent 0 ~ 30%, aqueous hydrochloric acid solution 67% ~ the 99.9% and mass percent sum of three 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.
Casting solution used in the present invention is mixed according to certain mass percent macromolecular material, hydrophilic polymer, inorganic additive, pore-foaming agent and organic solvent, and at 60 DEG C ~ 90 DEG C, stirring and dissolving obtained after 20 ~ 36 hours, 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%, the main material of polymeric membrane is polysulfones (PS), polyether sulfone (PES), polyvinylidene fluoride (PVDF) or polyacrylonitrile (PAN), wherein preferred PVDF, 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 require according to aperture the polyethylene glycol that the molecular weight selected does not wait, molecular weight ranges is generally between 400 ~ 20,000.
First coagulation bath used in the present invention be water or for percent by volume be 40% ~ 100% water and percent by volume be 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, one or more the combination in N dimethylacetylamide DMAC, DMF DMF, METHYLPYRROLIDONE NMP and dimethyl sulfoxide (DMSO) DMSO.
Method of the present invention make use of hydroxyl on PVA main chain can in acid condition with the principle of chemical cross-linking agent generation cross-linking reaction, by the dynamic process that the solventnonsolvent when gel phase transforms exchanges, make the hollow fiber ultrafiltration membrane containing PVA in the acid gel bath of uniform temperature, rapid generation chemical crosslinking effect, form the network structure be mutually wound around between PVA and the main material macromolecular chain of film, thus avoid PVA in film, move the dissolving and loss behavior that cause with water.Good and the lasting stability of preparation-obtained milipore filter hydrophilic effect.
To the ratio of hydrophilic additive in casting solution and chemical cross-linking agent consumption in the present invention, the temperature of the first coagulation bath and the time of staying, the control of core liquid acidity etc. is committed step, in the preparation process that hollow fiber ultrafiltration membrane is concrete, can add other reagent according to actual needs.
Embodiment 1:
(1) core liquid is placed in core flow container, casting solution is placed in material liquid tank, and by flowmeter measure control core flow quantity, utilizes hollow fiber spinning equipment that core liquid and casting solution are obtained nascent state film silk after annular spinning head coextrusion after the dry journey of 3cm,
Core liquid: be the glutaraldehyde of 0.1% by mass percent, the concentration of 99.9% be the combined of 0.1mol/L even core liquid;
Casting solution: by mass percent be the Kynoar PVDF of 17%, 1% PVAC polyvinylalcohol (molecular weight is 120,000), the lithium chloride of 5%, the PEG400 of 5% and 72% N, N dimethylacetylamide DMAC mixes, at 90 DEG C, obtain casting solution after stirring and dissolving 20h standing and defoaming;
(2) nascent state film silk enters phase-splitting process 10s in first coagulation bath of 30 DEG C, in the dynamic process that nascent state film silk is transformed at gel phase, is fixed in film silk by PVA by chemical crosslinking, thus obtains just becoming hollow fiber ultrafiltration membrane; First coagulation bath used is water;
(3) being the second coagulation bath with the running water under room temperature, just becoming hollow fiber ultrafiltration membrane through leading the traction of silk wheel, point solidifying 15min further in the second coagulation bath, receives fully rinsing after silk through wire drawing wheel, prepares PVA blending hollow fiber ultrafiltration membrane.
25 DEG C, under 0.1MPa, the PVA blending hollow fiber ultrafiltration membrane water flux 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 after 30s is 55 °; 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, core liquid and casting solution obtained nascent state film silk after annular spinning head coextrusion after the dry journey of 1cm,
Core liquid: be the glutaraldehyde of 1.2% by mass percent, the concentration of 98.8% is that the combined of 1mol/L evenly obtains core liquid;
Casting solution: mass percent is respectively the Kynoar PVDF of 15%, 4% PVAC polyvinylalcohol (molecular weight is 250,000), the PEG400 of 3%, the METHYLPYRROLIDONE NMP of 78% mix, at 80 DEG C, obtain casting solution after stirring and dissolving 24h standing and defoaming;
At (2) 60 DEG C, nascent state film silk enters phase-splitting process 30s in the first coagulation bath and obtains just becoming hollow fiber ultrafiltration membrane; First coagulation bath is water;
(3) be the second coagulation bath with the running water under room temperature, just become hollow fiber ultrafiltration membrane point solidifying 40min further in the second coagulation bath, fully rinsing obtains the PVA blending hollow fiber ultrafiltration membrane of this embodiment afterwards.
25 DEG C, under 0.1MPa, measuring hollow fiber ultrafiltration membrane water flux prepared by this embodiment 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 after 30s is 42 °; BSA dustiness is 21%, and cleaning recovery rate is 98%.
Embodiment 3:
(1) utilize hollow fiber spinning equipment, by core liquid and casting solution after annular spinning head coextrusion, after the dry journey of 5cm nascent state film silk,
Core liquid: be the glyoxal of 3% by mass percent, the DMAC of 30%, the 1mol/L combined of 67% evenly obtain core liquid;
Casting solution: mass percent is respectively the Kynoar PVDF of 12%, the PVAC polyvinylalcohol (molecular weight is 30,000) of 8%, lithium perchlorate, the PEG400 of 8%, the N of 68% of 4%, N dimethylacetylamide DMAC mixes, stirring and dissolving 36h at 90 DEG C, obtains homogeneous casting solution after standing and defoaming;
At (2) 50 DEG C, nascent state film silk enters phase-splitting process 30s in the first coagulation bath, in the dynamic process that nascent state film silk is transformed at gel phase, is fixed in film silk by PVA by chemical crosslinking, obtains just becoming hollow fiber ultrafiltration membrane; First coagulation bath is that the water of 70% and the N of 30%, N dimethylacetylamide DMAC are obtained by mixing by volume ratio;
(3) be the second coagulation bath with the running water under room temperature, just become hollow fiber ultrafiltration membrane point solidifying 60min further in the second coagulation bath, after abundant rinsing, obtain the PVA blending hollow fiber ultrafiltration membrane of this embodiment.
25 DEG C, under 0.1MPa, the water flux 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 after 30s is 45 °; Its dustiness of further test is 48%, and recovery rate is 99%.
Embodiment 4:
(1) utilize hollow fiber spinning equipment, by core liquid and casting solution after annular spinning head coextrusion, after the dry journey of 1cm nascent state film silk,
Core liquid: the dialdehyde in heptan, the DMAC of 20%, the 0.5mol/L combined of 79% that containing mass percent are 1% are evenly obtained core liquid;
Casting solution: mass percent is respectively the Kynoar PVDF of 15%, the PVAC polyvinylalcohol (molecular weight is 120,000) of 3%, ammonium chloride, the PEG400 of 5%, the N of 74% of 3%, N dimethylacetylamide DMAC mixes, stirring and dissolving 24h at 80 DEG C, obtains casting solution after standing and defoaming;
At (2) 40 DEG C, nascent state film silk enters phase-splitting process 60s in the first coagulation bath, in the dynamic process that nascent state film silk is transformed at gel phase, is fixed in film silk by PVA by chemical crosslinking, thus obtains just becoming hollow fiber ultrafiltration membrane; First coagulation bath is water;
(3) be the second coagulation bath with the running water under room temperature, just become hollow fiber ultrafiltration membrane point solidifying 30min further in the second coagulation bath, after abundant rinsing, obtain the PVA blending hollow fiber ultrafiltration membrane of this embodiment.
25 DEG C, under 0.1MPa, the PVA blending hollow fiber ultrafiltration membrane water flux 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 after 30s is 41 °; Its dustiness of further test is 53%, and recovery rate is 98%.
Embodiment 5:
(1) utilize hollow fiber spinning equipment, by core liquid and casting solution after annular spinning head coextrusion, after the dry journey of 5cm nascent state film silk,
Core liquid: by containing mass percent be 2% glutaraldehyde, 30% DMSO, 68% 1mol/L combined evenly after core liquid;
Casting solution: mass percent is respectively the Kynoar PVDF of 20%, the PVAC polyvinylalcohol (molecular weight is 120,000) of 3%, lithium nitrate, the PEG400 of 4%, the dimethyl sulfoxide (DMSO) DMSO of 70% of 3% mix, stirring and dissolving 24h at 90 DEG C, obtains casting solution after standing and defoaming;
(2) phase-splitting process 10s in nascent state film silk 40 DEG C, the first coagulation bath, in the dynamic process that nascent state film silk is transformed at gel phase, is fixed on PVA in film silk by chemical crosslinking, thus obtains just becoming hollow fiber ultrafiltration membrane; First coagulation bath is percent by volume is the water of 40% and the dimethyl sulfoxide (DMSO) DMSO mixed solution of 60%;
(3) be the second coagulation bath with the running water under room temperature, just become hollow fiber ultrafiltration membrane point solidifying 30min further in the second coagulation bath, after abundant rinsing, obtain the PVA blending hollow fiber ultrafiltration membrane of this embodiment.
25 DEG C, under 0.1MPa, the PVA blending hollow fiber ultrafiltration membrane water flux 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 after 30s is 64 °; Its dustiness of further 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 is only limitted to this; for general technical staff of the technical field of the invention; without departing from the inventive concept of the premise; some simple deduction or replace can also be made, all should be considered as belonging to the present invention by submitted to claims determination scope of patent protection.
Claims (4)
1. a dynamic crosslinking preparation method for polyvinyl alcohol blending hollow fiber ultrafiltration membrane, it is characterized in that, the method comprises the following steps:
(1) by core liquid and casting solution from the annular spinning head coextrusion of doughnut spinning equipment, after the dry journey of 1 ~ 10cm, obtain nascent state film silk;
The constitutive material of described core liquid and the mass percent of each raw material are: chemical cross-linking agent 0.1% ~ 3%, organic solvent 0 ~ 30%, aqueous hydrochloric acid solution 67% ~ the 99.9% and mass percent sum of three kinds of raw materials 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 constitutive material of described casting solution and the mass percent sum of each raw material are: the main material 12% ~ 20% of polymeric membrane, hydrophilic polymer 1% ~ 8%, inorganic additive 0 ~ 5%, pore-foaming agent 3% ~ 8% and organic solvent 68% ~ 78% and the mass percent sum of five kinds of raw materials is 100%, the main material of described polymeric membrane 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; The preparation temperature of described casting solution is 60 DEG C ~ 90 DEG C;
Described organic solvent is one or more the mixed liquor in N, N dimethylacetylamide, DMF, METHYLPYRROLIDONE and dimethyl sulfoxide (DMSO);
At (2) 30 DEG C ~ 60 DEG C, the phase-splitting process in the first coagulation bath of nascent state film silk is obtained just become hollow fiber ultrafiltration membrane; The time of phase-splitting process in the first coagulation bath is 10s ~ 60s;
The constitutive material of described 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 kinds of raw materials is 100%;
Described organic solvent is one or more the mixed liquor in N, N dimethylacetylamide, DMF, METHYLPYRROLIDONE and dimethyl sulfoxide (DMSO);
At (3) 20 DEG C ~ 30 DEG C, just will become hollow fiber ultrafiltration membrane point solidifying process further in the second coagulation bath; In second coagulation bath, the time of point solidifying process is further 15min ~ 60min;
Described second coagulation bath is water;
Polyvinyl alcohol blending hollow fiber ultrafiltration membrane is obtained behind above-mentioned steps (1), (2), (3).
2. the dynamic crosslinking preparation method of polyvinyl alcohol blending hollow fiber ultrafiltration membrane as claimed in claim 1, it is characterized in that, the molecular weight of described polyvinyl alcohol is greater than 120,000.
3. the dynamic crosslinking preparation method of polyvinyl alcohol blending hollow fiber ultrafiltration membrane as claimed in claim 1, it is characterized in that, the molecular weight of described polyethylene glycol is 400 ~ 20,000.
4. the dynamic crosslinking preparation method of polyvinyl alcohol blending hollow fiber ultrafiltration membrane as claimed in claim 1, it is characterized in that, method comprises the following steps:
By core liquid and casting solution after the annular spinning head coextrusion of doughnut spinning equipment, the dry journey through 1cm ~ 10cm obtains nascent state film silk;
At 30 DEG C ~ 60 DEG C, nascent state film silk enters phase-splitting process 10s ~ 60s in the first coagulation bath, obtains just becoming hollow fiber ultrafiltration membrane;
Be the second coagulation bath with the water under room temperature, just become hollow fiber ultrafiltration membrane point solidifying 15 ~ 60min further in the second coagulation bath, after the abundant rinsing of water, be finally prepared into polyvinyl alcohol blending hollow fiber ultrafiltration membrane.
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| 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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| 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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| WO2020261116A1 (en) * | 2019-06-27 | 2020-12-30 | 3M Innovative Properties Company | Reactive additives in membrane preparation |
| EP3756754A1 (en) * | 2019-06-27 | 2020-12-30 | 3M Innovative Properties Company | Reactive additives in membrane preparation |
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