CN1608718A - Hollow fiber film and its prepn process - Google Patents
Hollow fiber film and its prepn process Download PDFInfo
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- CN1608718A CN1608718A CN 200310106673 CN200310106673A CN1608718A CN 1608718 A CN1608718 A CN 1608718A CN 200310106673 CN200310106673 CN 200310106673 CN 200310106673 A CN200310106673 A CN 200310106673A CN 1608718 A CN1608718 A CN 1608718A
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Abstract
The present invention relates to one kind of hollow polyvinylidene fluoride fiber film, which has outer diameter of 0.3-3 mm, wall thickness of 0.05-1 mm, porosity of 50-90 %, separating pore size of 0.01-1 micron and pure water flux of 600-10000 L/sq m. hr at 0.1 MPa and 25 deg.c. The polyvinylidene fluoride is polyvinylidene fluoride homopolymer, polyvinylidene fluoride copolymer or their mixture, and the polyvinylidene fluoride copolymer has vinylidene fluoride chain unit content over 70 %. The present invention also relates to the preparation process of the hollow fiber film.
Description
Technical field
The present invention relates to a kind of hydrophobicity fluorine resin hollow-fibre membrane product, and the method for making this hollow-fibre membrane product.
Background technology
The hydrophobic hollow fiber film is mainly used in filtration or the dialysis in the various fields, is generally used for aspects such as film distillation, gas separation, air cleaning.
The radially section structure of doughnut perforated membrane is generally unsymmetric structure, promptly is made up of selective separating and porous support layer.Making in the method for hollow-fibre membrane with fluororesin, because fluororesin surface can be very low, hydrophobicity is stronger, forms fluid-tight compactness cortex during the spinning hollow-fibre membrane easily, thereby has lost the filtering function that the doughnut perforated membrane should have.
Can utilize the method for in the fluororesin spinning solution, adding various pore former and auxiliary agent to solve the problems referred to above.Usually with fluoropolymer resin, solvent, pore former mixed dissolution evenly after, adopt to do-the wet spinning technology spinning prepares hollow-fibre membrane.
Among the Japanese Patent Publication 62-017614, mixing Kynoar, macromolecule pore former polyethylene glycol, surfactant soil temperature-80 have been put down in writing, the method for phase transfer film forming then.The product rupture strength deficiency that this method obtained, the penetration speed of pure water is slower, can't satisfy the demand;
Put down in writing the method for Kynoar, solvent, macromolecule pore former, non-solvent, surfactant etc. being mixed the back film forming among the CN1128176A.Wherein macromolecule pore former, non-solvent, the surfactant that adds with proper proportion, even cosolvent, they interact, and coordinate mutually, obtain the hollow membrane of high permeation flux.But owing to added macromolecule pore former and surfactant, hollow-fibre membrane is difficult to macromolecule pore former and surfactant are removed from hollow-fibre membrane fully, thereby the hydrophobicity of hollow-fibre membrane is greatly reduced after being shaped.
Apply for, still undocumented Chinese patent now, application number is the method for preparing hollow-fibre membrane of also having put down in writing in 02158710.8,02158709.4,03129988.1,03130556.3.
The content of above-mentioned document is herein incorporated by reference.
The inventor has done further improvement on the basis of existing technology, improve the prescription of spinning solution, in spinning solution, no longer add macromolecule pore former and surfactant, thereby avoided from hollow-fibre membrane, to remove the problem that the hydrophobicity of the hollow-fibre membrane that causes greatly reduces fully because of macromolecule pore former and surfactant.
Summary of the invention
The present invention relates to a kind of Kynoar hollow-fibre membrane, its external diameter is 0.3～3mm, wall thickness 0.05～1mm, and porosity 50～90%, film separates 0.01～1 micron in aperture, and the pure water water flux is 600～10000L/m
2H@0.1MPa, 25 ℃, Kynoar is any two or more mixture of polymers in polyvinylidene fluoride homopolymer, polyvinylidene fluoride alkene copolymer or the above-mentioned substance, vinylidene link units content is more than 70% in the vinylidene fluoride copolymers.
The invention still further relates to the method for the above-mentioned hollow-fibre membrane of preparation, spinning solution contains following material, and wherein wt percentage is benchmark with the gross weight of spinning solution,
Polymer: 15～35wt%;
Solvent: 50～80wt%;
Inorganic pore former: 0～20wt%;
Organic low molecular pore former: 2～30wt%;
The pore former total amount is 5～30wt%;
Spinning solution makes hollow-fibre membrane through wet method or dried-wet spinning.
The specific embodiment
The formation mechanism of hollow-fibre membrane of the present invention is the phase transfer film forming, and soon film forming polymer, organic solvent, pore former mix by a certain percentage, dissolves evenly after spinning nozzle enters in the coagulating bath.Solvent in the polymer solution enters coagulating agent mutually with the organic low molecular pore former, and polymer is because phase transfer and precipitating becomes the polymer hollow-fibre membrane.In the process of hollow fiber film, obtain the hollow fiber separating film of certain pore size by control spinning solution prescription, spinning technology parameter and doughnut post-treatment condition in the mill.The present invention obtains the excellent more hollow fiber separating film of performance by improving the spinning solution prescription, can further control the structure and the performance of hollow-fibre membrane by control spinning technology parameter and the post processing of employing doughnut.
The percetage by weight of following various materials is a benchmark with the gross weight of polymer spinning solution, in the spinning solution percetage by weight of various materials and be 100wt%.
Polymer is a kind of in Kynoar or the vinylidene fluoride copolymers, or two or more mixture of polymers in the above-mentioned polymer, vinylidene fluoride copolymers is vinylidene/TFE copolymer, vinylidene/hexafluoropropylene copolymer or vinylidene/chlorotrifluoroethylene etc.Vinylidene link units content is more than 70% in the vinylidene fluoride copolymers, if when vinylidene link units content is very few in the copolymer, then the solubility of copolymer in solvent is little, thereby can't adopt the spinning of solution phase transfer method.Polymer is preferably vinylidene/TFE copolymer or vinylidene/hexafluoropropylene copolymer among the present invention, and the hydrophobicity of these two kinds of copolymers all is higher than polyvinylidene fluoride resin.Fluororesin content is 15～35wt% in spinning solution, is preferably 20～30wt%.
Solvent for use is preferably intensive polar solvent in the spinning solution, and spin solvent can be the mixture of following one or more intensive polar solvents: dimethyl formamide (DMF), dimethylacetylamide (DMAc), N-methyl pyrrolidone, triethyl phosphate, sulfolane, dimethyl sulfoxide (DMSO) etc.The consumption of solvent is 50～80wt%, is preferably 60～75wt%.
The spinning pore former is the mixture of one or both or three kinds in inorganic pore former, organic low molecular pore former and three kinds of pore formers of water.The pore former total amount is preferably 5～30wt%.
Inorganic pore former is a used inorganic additive in existing doughnut membrane preparation method, can be the mixture of following one or more materials: lithium nitrate, sodium chloride, calcium chloride, calcium carbonate, calcium nitrate, silica, alundum (Al, kaolin etc.Inorganic pore former total amount 0.5～20wt% is preferably 1～10wt%, and the granularity of inorganic pore former is preferably the particle of nano-grade size less than 10 microns.
Kind for the organic low molecular pore former has no particular limits, as long as there is the organic low molecular of perforating action can be as pore former, but its molecular weight is preferably in below 200 dalton, and the organic low molecular pore former can be following one or more mixture: ethylene glycol, dioxane, butanone, acetone, glycol monoethyl ether, diethylene glycol dimethyl ether, glycerine etc.Organic low molecular pore former content 2～30wt% is preferably 5～20wt%.
Use organic low molecular pore former or inorganic pore former just can obtain the hydrophobic hollow fiber film separately.When inorganic pore former and organic low molecular pore former use together, because inorganic pore former does not dissolve, be the suspended dispersed state in spinning solution, when spinning solution entered coagulating bath generation phase transfer freezing film, inorganic pore former played nuclear effect mutually; And behind the freezing film, again with the stripping from film of inorganic pore former; Such two kinds of pore formers play a role jointly, help forming more perforation fenestra, help obtaining high-throughout hollow-fibre membrane.
The water that in spinning solution, also can add 0.1～10wt%.Add entry and can make spinning solution produce differential to act on mutually, can with the organic low molecular pore former or (with) inorganic pore former performance synergy, reach extraordinary effect, help obtaining high-throughout hollow-fibre membrane.
Under the prerequisite of the performance that does not influence the hollow-fibre membrane that spins out, spinning solution can also add other additive, as pigment, filler, antioxidant, age resister, light stability agent etc.
Spinning core liquid can be water or other organic liquid such as the dimethylacetylamide aqueous solution etc. also can be compressed air or nitrogen for spinning core liquid commonly used in the spinning doughnut film method.
Adopt conventional dissolving phase transfer method, polymer and inorganic pore former and/or organic molecule pore former and/or water etc. are mixed in intensive polar solvent, carry out wet method or dry-wet spinning, after the spinning again with pore former with strippings such as alkali, acid, water or organic solvents, by phase transfer, make high strength, high-throughout hydrophobic hollow fiber perforated membrane.
Technology and the technological parameter that uses in the spinning process had no particular limits, use the technology of existing spinning hollow-fibre membrane in the prior art to prepare hollow-fibre membrane.Use method well known in the prior art to prepare interior die mould hollow-fibre membrane and External Pressure Type hollow-fibre membrane respectively, the interior hollow-fibre membrane compacted zone of pressing is in the inboard, desire is filtered the inboard of stoste contact membranes, and external pressure hollow-fibre membrane compacted zone is in the outside, and desire is filtered the outside of stoste contact membranes.
Use porous membrane manufacturing method of the present invention, the Kynoar hollow-fibre membrane external diameter that obtains is 0.3～3mm, wall thickness 0.05～1mm, and porosity 50～90%, film separates 0.01～1 micron in aperture, and the pure water water flux is 600～10000L/m
2H@0.1MPa, 25 ℃.
Adopt method of the present invention, the hollow-fibre membrane hydrophobicity that obtains is strong, can perform well in aspects such as film distillation, gas separation, air cleaning.
Can carry out further post processing to the film that makes.Spun Kynoar doughnut also can adopt known technology to stretch 100～300% again, further improves the porosity of fluororesin hollow-fibre membrane and the permeation flux of hollow-fibre membrane.
Further describe the present invention with embodiment below.Just to the further explanation of invention, it does not limit protection scope of the present invention to embodiment.
Embodiment 1: under 500 gram calcium carbonate, 2 micro particles high-speed stirred, be dispersed in 5 kilograms of dimethylacetamide solvents, add 2 kilograms of dimethylacetylamides again, 2 kilograms of vinylidenes and hexafluoropropylene copolymer resin (vinylidene repetitive account for copolymer repetitive sum 80%), 500 gram ethylene glycol, 50 gram water, stirring and dissolving is even, spinning, coagulating agent is a water in the coagulating bath.Remove calcium carbonate in the Kynoar doughnut, the interior pressure Kynoar doughnut perforated membrane internal diameter 0.8mm that obtains, wall thickness 0.25mm, rupture strength 0.92MPa, pure water penetration speed 970L/m with hydrochloric acid solution
220 ℃ of h@0.1MPa, film separates aperture 0.10 μ m, porosity 72%, hollow-fibre membrane contact angle 90 degree.
Comparative example 1: with 7 kilograms of dimethylacetylamides, 2 kilograms of polyvinylidene fluoride resins, 1 kilogram of polyethylene glycol, 100 gram soil temperatures-20, stirring and dissolving is even, spinning, coagulating agent is a water in the coagulating bath.The interior pressure Kynoar doughnut perforated membrane internal diameter 0.8mm that obtains, wall thickness 0.25mm, rupture strength 0.42MPa, pure water penetration speed 470L/m
220 ℃ of h@0.1MPa, film separates aperture 0.10 μ m, porosity 85%, hollow-fibre membrane contact angle 67 degree.
Embodiment 2: 500 gram alundum (Als, 20～80 nanoparticles at high speed are stirred down, be dispersed in 7 kilograms of N-crassitude ketone solvents, add 2 kilograms of vinylidenes and tetrafluoroethylene copolymer resins (vinylidene chain link 80%), 50 gram water again, stirring and dissolving is even, spinning, coagulating agent is a water in the coagulating bath, and spinning core liquid is the 60wt% dimethylacetylamide aqueous solution.Remove alundum (Al in the Kynoar doughnut, the external pressure Kynoar doughnut perforated membrane internal diameter 0.5mm that obtains, wall thickness 0.15mm, rupture strength 0.62MPa, pure water penetration speed 1270L/m with the NaOH aqueous solution
220 ℃ of h@0.1MPa, film separates aperture 0.20 μ m, porosity 78%, hollow-fibre membrane contact angle 91 degree.
Comparative example 2: in 7 kilograms of N-crassitude ketone solvents, add 2 kilograms of vinylidenes and tetrafluoroethylene copolymer resins (vinylidene chain link 80%), 1000 gram polyvinylpyrrolidones, 100 gram soil temperatures-80 again, stirring and dissolving is even, spinning, coagulating agent is a water in the coagulating bath, the spinning core liquid 60wt% dimethylacetylamide aqueous solution.The external pressure Kynoar doughnut perforated membrane internal diameter 0.5mm that obtains, wall thickness 0.15mm, rupture strength 0.32MPa, pure water penetration speed 770L/m
220 ℃ of h@0.1MPa, film separates aperture 0.20 μ m, porosity 85%, hollow-fibre membrane contact angle 81 degree.
Embodiment 3: under 1.8 kilograms of vinylidenes and hexafluoropropylene copolymer resin (vinylidene chain link 80%) high-speed stirred, solve homogeneously in 6.8 kilograms of dimethylacetylamides, add 780 gram glycol monoethyl ethers, 20 gram water, stirring and dissolving is even, spinning, coagulating agent is a water in the coagulating bath.The interior pressure Kynoar doughnut perforated membrane internal diameter 0.8mm that obtains, wall thickness 0.30mm, rupture strength 0.93MPa, pure water penetration speed 1310L/m
220 ℃ of h@0.1MPa, film separates aperture 0.50 μ m, hollow-fibre membrane contact angle 91 degree.
Embodiment 4: under 500 gram calcium carbonate, 2 micro particles high-speed stirred, be dispersed in 5 kilograms of dimethylacetamide solvents, add 2.6 kilograms of dimethylacetylamides again, 2 kilograms of vinylidenes and hexafluoropropylene copolymer resin (vinylidene repetitive account for copolymer repetitive sum 80%), 500 gram diethylene glycol dimethyl ethers, stirring and dissolving is even, spinning, coagulating agent is a water in the coagulating bath, the spinning core feeds industrial nitrogen.Remove calcium carbonate in the Kynoar doughnut, the external pressure Kynoar doughnut perforated membrane internal diameter 0.3mm that obtains, wall thickness 0.1mm, rupture strength 0.72MPa, pure water penetration speed 470L/m with hydrochloric acid solution
220 ℃ of h@0.1MPa, film separates aperture 0.10 μ m, porosity 72%, hollow-fibre membrane contact angle 90 degree.
Claims (9)
1, a kind of Kynoar hollow-fibre membrane, wherein external diameter is 0.3～3mm, wall thickness 0.05～1mm, porosity 50～90%, film separates 0.01～1 micron in aperture, and the pure water water flux is 600～10000L/m
2H@0.1MPa, 25 ℃, Kynoar is any two or more mixture of polymers in polyvinylidene fluoride homopolymer, polyvinylidene fluoride alkene copolymer or the above-mentioned substance, vinylidene link units content is more than 70% in the vinylidene fluoride copolymers.
2, Kynoar hollow-fibre membrane according to claim 1 is characterized in that: polymer is vinylidene/TFE copolymer or vinylidene/hexafluoropropylene copolymer.
3, prepare the method for claim 1 or 2 described hollow-fibre membranes, wherein spinning solution contains following material, and wherein wt percentage is benchmark with the gross weight of spinning solution,
Polymer: 15～35wt%;
Solvent: 50～80wt%;
Inorganic pore former: 0～20wt%;
Organic low molecular pore former: 2～30wt%;
The pore former total amount is 5～30wt%;
Spinning solution makes hollow-fibre membrane through wet method or dry-wet spinning.
4, method according to claim 3 is characterized in that, spinning solution contains following material, and wherein wt percentage is benchmark with the gross weight of spinning solution,
Polymer: 15～35wt%;
Solvent: 50～80wt%;
Inorganic pore former: 0.5～20wt%;
Organic low molecular pore former: 2～30wt%;
Spinning solution makes hollow-fibre membrane through wet method or dry-wet spinning.
According to the method for claim 3, it is characterized in that 5, spinning solution contains following material, wherein wt percentage is benchmark with the gross weight of spinning solution,
Polymer: 20～30wt%;
Solvent: 60～75wt%;
Inorganic pore former: 1～10wt%;
Organic low molecular pore former: 5～20wt%;
Spinning solution makes hollow-fibre membrane through wet method or dry-wet spinning.
6, according to claim 3,4 or 5 described methods, it is characterized in that: contain also water 0.1～10wt% in the spinning solution as pore former.
7, according to the described method of each claim of claim 3～6, it is characterized in that: the granularity of inorganic pore former is less than 10 microns.
8, method according to claim 7 is characterized in that: inorganic pore former is the particle of nano-grade size.
9, according to the described method of each claim of claim 3～8, it is characterized in that the organic low molecular pore former can be following one or more mixture: ethylene glycol, dioxane, butanone, acetone, glycol monoethyl ether, diethylene glycol dimethyl ether, glycerine.
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| CN 200310106673 CN1608718A (en) | 2003-10-17 | 2003-10-17 | Hollow fiber film and its prepn process |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100417434C (en) * | 2006-05-19 | 2008-09-10 | 广州美能材料科技有限公司 | Process for preparing composite hollow fiber membrane |
| CN102151489A (en) * | 2011-03-21 | 2011-08-17 | 凌雪萍 | Multi-core hollow fiber porous membrane and preparation method thereof |
| CN101422707B (en) * | 2008-11-26 | 2011-08-31 | 北京碧水源膜科技有限公司 | Recovery method of tape liner type polyvinylidene fluoride hollow fiber membrane |
| CN101422708B (en) * | 2008-11-26 | 2011-08-31 | 北京碧水源膜科技有限公司 | Recovery method of polyvinylidene fluoride hollow fiber membrane |
| CN102228806A (en) * | 2010-08-27 | 2011-11-02 | 北京伟思德克科技有限责任公司 | High-strength high-flux hollow fiber membrane and preparation method thereof |
| CN102764595A (en) * | 2011-05-03 | 2012-11-07 | 吕晓龙 | Polyvinylidene fluoride separation membrane and its preparation method |
| CN103304088A (en) * | 2013-03-12 | 2013-09-18 | 何涛 | Recycling method of high brine waste water based on forward osmosis |
| CN103894078A (en) * | 2012-12-26 | 2014-07-02 | 山东招金膜天有限责任公司 | High-flux polyvinylidene fluoride hollow fiber film and preparation method thereof |
| CN104984663A (en) * | 2015-06-15 | 2015-10-21 | 黄义忠 | Film casting liquid for PVDF flat membrane and preparing method for PVDF flat membrane |
| CN105214527A (en) * | 2015-10-12 | 2016-01-06 | 中南大学 | A kind of preparation technology of ultra-hydrophobic polyvinylidene fluoride hexafluoropropene perforated membrane |
| CN107020019A (en) * | 2017-04-20 | 2017-08-08 | 厦门智蓝环保科技有限公司 | A kind of ultra-fine polyvinylidene fluoride hollow fiber dry state film of high flux and preparation method thereof |
| CN108786468A (en) * | 2018-06-26 | 2018-11-13 | 黑龙江大学 | A kind of method that the thermotropic phase inversion of low temperature prepares flushing-free PVDF tube-type micropore films |
| CN109906112A (en) * | 2016-10-26 | 2019-06-18 | 新加坡国立大学 | Hollow-fibre membrane |
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- 2003-10-17 CN CN 200310106673 patent/CN1608718A/en active Pending
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100417434C (en) * | 2006-05-19 | 2008-09-10 | 广州美能材料科技有限公司 | Process for preparing composite hollow fiber membrane |
| CN101422707B (en) * | 2008-11-26 | 2011-08-31 | 北京碧水源膜科技有限公司 | Recovery method of tape liner type polyvinylidene fluoride hollow fiber membrane |
| CN101422708B (en) * | 2008-11-26 | 2011-08-31 | 北京碧水源膜科技有限公司 | Recovery method of polyvinylidene fluoride hollow fiber membrane |
| CN102228806A (en) * | 2010-08-27 | 2011-11-02 | 北京伟思德克科技有限责任公司 | High-strength high-flux hollow fiber membrane and preparation method thereof |
| CN102151489A (en) * | 2011-03-21 | 2011-08-17 | 凌雪萍 | Multi-core hollow fiber porous membrane and preparation method thereof |
| CN102764595A (en) * | 2011-05-03 | 2012-11-07 | 吕晓龙 | Polyvinylidene fluoride separation membrane and its preparation method |
| CN103894078A (en) * | 2012-12-26 | 2014-07-02 | 山东招金膜天有限责任公司 | High-flux polyvinylidene fluoride hollow fiber film and preparation method thereof |
| CN103304088A (en) * | 2013-03-12 | 2013-09-18 | 何涛 | Recycling method of high brine waste water based on forward osmosis |
| CN104984663A (en) * | 2015-06-15 | 2015-10-21 | 黄义忠 | Film casting liquid for PVDF flat membrane and preparing method for PVDF flat membrane |
| CN105214527A (en) * | 2015-10-12 | 2016-01-06 | 中南大学 | A kind of preparation technology of ultra-hydrophobic polyvinylidene fluoride hexafluoropropene perforated membrane |
| CN109906112A (en) * | 2016-10-26 | 2019-06-18 | 新加坡国立大学 | Hollow-fibre membrane |
| CN107020019A (en) * | 2017-04-20 | 2017-08-08 | 厦门智蓝环保科技有限公司 | A kind of ultra-fine polyvinylidene fluoride hollow fiber dry state film of high flux and preparation method thereof |
| CN107020019B (en) * | 2017-04-20 | 2019-10-22 | 厦门唯科健康产业有限公司 | A kind of ultra-fine polyvinylidene fluoride hollow fiber dry state film of high throughput and preparation method thereof |
| CN108786468A (en) * | 2018-06-26 | 2018-11-13 | 黑龙江大学 | A kind of method that the thermotropic phase inversion of low temperature prepares flushing-free PVDF tube-type micropore films |
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