CN1899677B - Method for producing hollow fiber film - Google Patents
Method for producing hollow fiber film Download PDFInfo
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- CN1899677B CN1899677B CN2005100145779A CN200510014577A CN1899677B CN 1899677 B CN1899677 B CN 1899677B CN 2005100145779 A CN2005100145779 A CN 2005100145779A CN 200510014577 A CN200510014577 A CN 200510014577A CN 1899677 B CN1899677 B CN 1899677B
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Abstract
The melt spinning process of producing hollow fiber membrane includes the first mixing glass fiber with inorganic particle, polymer pore creating agent, surfactant and non-solvent to constitute spinning composition, heating the composition to temperature higher than the smelting point of the polymer, the subsequent extruding the melt through spinning head and cooling to form hollow fiber, and final eliminating the inorganic particle, polymer pore creating agent, surfactant and non-solvent to produce the high strength hollow fiber membrane. The spinning composition consists of polymer 20-90 wt%, glass fiber 0.5-20 wt%, inorganic pore creating agent 5-50 wt%, polymer pore creating agent 2-30 wt%, surfactant 2-60 wt%, and organic non-solvent 10-60 wt%.
Description
Technical field
The present invention relates to a kind of method of melt spinning system hollow-fibre membrane, this method obtains a kind of high strength, the uniform hollow-fibre membrane of pore-forming by non-melt fibers such as interpolation glass fibres in the film forming polymer melt.
Background technology
Hollow-fibre membrane is mainly used in filtration or the dialysis in the various fields.Hollow-fibre membrane melt spinning method of the present invention is with non-melt fiber and inorganic particulate, macromolecule pore-foaming agent, surfactant and non-solvent composition spinning components such as glass fibres, mix and be heated to more than the polymer melting temperature, then melt is extruded in spinneret, be cooled to doughnut, make hollow-fibre membrane by inorganic particulate, macromolecule pore-foaming agent, surfactant and the non-solvent removed wherein.
Form fluid-tight compactness structure easily during spinning straight polymer doughnut, be difficult to obtain the porous doughnut, thereby do not have the filtering function of perforated membrane.Can utilize the method for in the spinning constituent, adding various pore former and auxiliary agent to solve the problems referred to above:
1. among the Japanese Patent Publication 62-017614, put down in writing film forming polymer, macromolecule pore-foaming agent polyethylene glycol, surfactant soil temperature-80 have been mixed the method for melt spinning system perforated membrane.Inhomogeneous because of disperseing easily in this method, cause the perforated membrane pore-size distribution that forms inhomogeneous, the permeable amount of film is little, can't satisfy the demand;
2. among the TOHKEMY 2002-253939, put down in writing and only used film forming polymer, not doping, the method for the pore that stretches again behind the polymer preformation fiber is not easy to obtain the hollow-fibre membrane of high porosity, high water flux, even aperture distribution;
3.CN1265048A in put down in writing Kynoar, organic liquid and inorganic granular mixing, the method for melt spinning then obtains the hollow-fibre membrane that internal diameter is big, be suitable for high viscosity liquid.
The content of these documents is herein incorporated by reference.
A little less than the hollow-fibre membrane that adopts above prior art to spin out becomes film-strength, can not satisfy high-intensity requirement.
Summary of the invention
Purpose of the present invention is for providing a kind of method of melt spinning system hollow-fibre membrane, non-melt fibers such as glass fibre and polymer, inorganic pore-foaming agent, macromolecule pore-foaming agent, surfactant and non-solvent etc. are mixed, melt spinning system hollow-fibre membrane, utilize the reinforcement humidification of non-melt fibers such as glass fibre, can obtain high-intensity hollow fiber separating film.
The invention provides a kind of method of melt spinning system hollow-fibre membrane, it is characterized in that: the melt spinning composition comprises: polymer: 20～90wt%, polymer are Kynoar or polyethersulfone resin; Glass fibre: 0.5～20wt%; Inorganic pore-foaming agent: 5～50wt%, inorganic pore-foaming agent are the mixture of following one or more materials: calcium carbonate, alundum (Al; Macromolecule pore-foaming agent: 2～30wt%, macromolecule pore-foaming agent are the mixtures of following one or more solvents: polyethylene glycol, polyvinylpyrrolidone, polyvinyl alcohol; Surfactant: 2～60wt%, surfactant are following one or more mixture: cationic surface active agent, anionic surfactant, amphoteric surfactant, nonionic surface active agent; Organic non-solvent: 10～60wt%, organic non-solvent are diethyl phthalate, dibutyl phthalate, glycol dimethyl ether or diethylene glycol ether; Wherein wt percentage is benchmark with the gross weight of melt spinning composition, in the spinning component percetage by weight of various materials and be 100wt%.
The present invention provides a kind of melt spinning composition to comprise in addition: polymer: 30～70wt%, polymer are Kynoar or polyethersulfone resin; Glass fibre: 1.0～5wt%; Inorganic pore-foaming agent: 10～40wt%, inorganic pore-foaming agent are the mixture of following one or more materials: calcium carbonate, alundum (Al; Macromolecule pore-foaming agent: 5～20wt%, macromolecule pore-foaming agent are the mixtures of following one or more solvents: polyethylene glycol, polyvinylpyrrolidone, polyvinyl alcohol; Surfactant: 2～60wt%, surfactant are following one or more mixture: cationic surface active agent, anionic surfactant, amphoteric surfactant, nonionic surface active agent; Organic non-solvent: 10～60wt%, organic non-solvent are diethyl phthalate, dibutyl phthalate, glycol dimethyl ether or diethylene glycol ether; Wherein wt percentage is benchmark with the gross weight of melt spinning composition, in the spinning component percetage by weight of various materials and be 100wt%.
In addition, the granularity of inorganic pore-foaming agent is less than 10 microns.
The present invention is by the acting in conjunction of non-melt fibers such as glass fibre and additives such as inorganic pore-foaming agent, macromolecule pore-foaming agent, surfactant and non-solvent, and then make all even porosity of hollow-fibre membrane pore-forming big, thereby the high strength of obtaining, high-throughout hollow-fibre membrane.
The specific embodiment
Under melt temperature, inorganic matter is heterogeneous even dispersion in macromolecule melt; The macromolecule pore-foaming agent polymer melt mutually in homogeneous phase disperse, effect is to improve flow properties of polymer melts and pore-creating character, also can reduce processing temperature; Organic non-solvent effect is and the inorganic particulate acting in conjunction, make polymer melt at high temperature be differential phase state, Action of Surfactant is that the polymer texture is uniformly dispersed, at high temperature differential is mutually in stable condition to make polymer melt, utilizes the reinforcement humidification of non-melt fibers such as glass fibre.Acting in conjunction by non-melt fibers such as glass fibre and additives such as inorganic pore-foaming agent, macromolecule pore-foaming agent, surfactant and non-solvent, and then make all even porosity of hollow-fibre membrane pore-forming big, thereby the high strength of obtaining, high-throughout hollow-fibre membrane.
The present inventor with non-melt fibers such as polymer and glass fibre with constitute thing and mix by in inorganic pore-foaming agent, macromolecule pore-foaming agent, the organic non-solvent one or more are composite, carry out melt spinning, make a kind of high-throughout porous hollow fiber membrane.The percetage by weight of following various materials is a benchmark with the gross weight of melt spinning composition, in the spinning component percetage by weight of various materials and be 100wt%.
Polymer is a kind of in Kynoar, polyethylene, polypropylene, the polyether sulfone, or one or more the mixture in a kind of and following polymer wherein: polymethyl methacrylate, polyvinyl alcohol, polyvinyl acetate, polyacrylonitrile, Pioloform, polyvinyl acetal etc.; Kynoar comprises polyvinylidene fluoride homopolymer and polyvinylidene fluoride alkene copolymer, and the polyvinylidene fluoride alkene copolymer is no less than 60% copolymer for the vinylidene repetitive.Polymer content is 20～90wt%, is preferably 30～70wt%.
Non-melt fiber such as glass fibre is meant infusible short fiber under the spinning temperature of film forming polymer, can be organic matter, also can be high-melting-point polymer fiber or cladding polymer fiber not.As glass fibre, asbestos fibre, polyphenylene sulfide fibre, carbon fiber etc.Addition is 0.5～20wt%, is preferably 1～5wt%
Inorganic pore-foaming agent is the mixture of following one or more materials: lithium nitrate, sodium chloride, calcium chloride, calcium carbonate, silica, alundum (Al, calcium nitrate, kaolin etc.Inorganic pore-foaming agent total amount is 5～50wt%, is preferably 10～40wt%, and inorganic pore-foaming agent granularity is preferably the particle of size about tens nanometer less than 10 microns.For calcium carbonate particle, can adopt the precipitated calcium carbonate powder, also can adopt heavy calcium carbonate.
The macromolecule pore-foaming agent is following one or more mixture: polyethylene glycol, polyoxyethylene, polyvinylpyrrolidone, polyvinyl alcohol, methylcellulose, hydroxypropyl cellulose etc., wherein the molecular weight of polyethylene glycol is preferably 200～20000 dalton, polyoxyethylated molecular weight is preferably 100,000 dalton or bigger, and the molecular weight of polyvinylpyrrolidone is preferably 10,000～1,200,000 dalton.They are water-soluble, alkali solubility or solubility in acid macromolecule.Organic polymer pore-foaming agent content is 2～30wt%, is preferably 5～20wt%.
Surfactant is following one or more mixture: cationic surface active agent, anionic surfactant, amphoteric surfactant, nonionic surface active agent.As lauryl sodium sulfate, neopelex, softex kw, secondary octanol APEO, dodecyl sulfamic acid sodium, fluorine-containing surfactant, soil temperature-20, soil temperature-80 etc.The surfactant total content is 2～60wt%, and is also different according to the different additions of its kind, is preferably 2～10wt% as common nonionic surface active agent addition, and the fluorine-containing surfactant addition is preferably 0.05～1.5wt%.
Organic non-solvent is diethyl phthalate, dibutyl phthalate, diethylene glycol dimethyl ether, glycol dimethyl ether, acetin etc.The total addition of organic non-solvent is 10～60wt%, and is also different according to the different additions of its concrete kind.If excessive adding, can cause the doughnut film-strength that forms a little less than.
Can also add other additive, as pigment, filler, antioxidant, age resister, light stability agent etc.
By existing mixing in the prior art, granulation, melt spinning method system film, also can directly mix, extruding spinning by twin-screw.Again with strippings such as pore-foaming agent alkali, acid, water, organic solvents, obtain polymeric hollow fiber multihole film after the spinning.Melt extrude spinning temperature and generally be higher than 10～50 ℃ of melting point polymers, but be lower than the polymer unwinds temperature.To with a kind of polymer, the spin-drawing pore occurs in amorphous area in the prior art, and porosity is low, needs higher draw ratio, pore-forming lack of homogeneity in the industrial production.For the present invention, adopt the composite pore-forming film forming, the pore-forming good uniformity.
Spun doughnut also can adopt known technology (for example CN1203119A) to stretch 50～300% again, further improves the porosity of hollow-fibre membrane and the water flux of hollow-fibre membrane.Can with strippings such as inorganic and organic pore-foaming agent alkali, acid, water or organic solvents, obtain the hollow-fibre membrane product again with after the doughnut stretch processing.Also can be earlier with spun doughnut with alkali, acid, water or organic solvent etc. with inorganic and organic pore-foaming agent stripping, carry out stretch processing again, obtain the hollow-fibre membrane product.
After the hollow-fibre membrane moulding, membrane module is made in casting, with strippings such as inorganic and organic pore-foaming agent alkali, acid, water or organic solvents, obtains the hollow-fibre membrane product again.Also can be earlier with spun doughnut with alkali, acid, water or organic solvent etc. with inorganic and organic pore-foaming agent stripping, be cast into hollow fiber film assembly again.The advantage of casting back elution earlier: production technology is simple, the washing as none, post processing, drying process.But casting back elution earlier is subjected to the restriction of membrane module sheathing material, can not maybe can not carry out elution to the pore additive with organic solvents such as alcohol, chloroforms in high temperature, high acid-base value usually.
Adopt porous membrane manufacturing method of the present invention, the 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.
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: 1500 gram calcium carbonate (particle diameter 2-5 micron) particles, 2000 gram polyvinylidene fluoride resins, 500 gram Macrogol 2000s, 0,100 gram soil temperatures-20,100 are restrained glass fibres, 1500 gram dibutyl phthalates at 220 ℃ of blend granulations, melt spinning.Remove calcium carbonate in the Kynoar doughnut with hydrochloric acid solution, remove dibutyl phthalate with isopropyl alcohol, the Kynoar doughnut perforated membrane internal diameter 0.4mm that obtains, external diameter 0.6mm, rupture strength 1.32MPa, pure water penetration speed 970L/m
220 ℃ of h@0.1MPa, film separates aperture 0.10 μ m, porosity 72%.
Comparative example 1: with 1500 gram calcium carbonate (particle diameter 2-5 micron) particles, 2000 gram polyvinylidene fluoride resins, 500 gram Macrogol 2000s, 0,100 gram soil temperatures-20,1500 gram dibutyl phthalates are at 220 ℃ of blend granulations, melt spinning.Remove calcium carbonate in the Kynoar doughnut with hydrochloric acid solution, remove dibutyl phthalate with isopropyl alcohol, the Kynoar doughnut perforated membrane internal diameter 0.4mm that obtains, external diameter 0.6mm, rupture strength 0.92MPa, pure water penetration speed 970L/m
220 ℃ of h@0.1MPa, film separates aperture 0.10 μ m, porosity 72%.
Embodiment 2: with 500 gram alundum (Als 20～80 nano particles, 2000 gram polyvinylidene fluoride resins, 100 gram soil temperatures-80,100 gram glass fibres, 1500 gram diethylene glycol dimethyl ethers at 215 ℃ through twin-screw blend, melt spinning.Remove alundum (Al in the Kynoar doughnut with the NaOH aqueous solution, isopropyl alcohol is removed diethylene glycol dimethyl ether, the external pressure Kynoar doughnut perforated membrane internal diameter 0.5mm that obtains, wall thickness 0.15mm, rupture strength 1.32MPa, pure water penetration speed 1270L/m
220 ℃ of h@0.1MPa, film separates aperture 0.20 μ m, porosity 76%.
Comparative example 2: with 500 gram alundum (Als 20～80 nano particles, 2000 gram polyvinylidene fluoride resins, 100 gram soil temperatures-80,1500 gram diethylene glycol dimethyl ethers at 215 ℃ through twin-screw blend, melt spinning.Remove alundum (Al in the Kynoar doughnut with the NaOH aqueous solution, isopropyl alcohol is removed diethylene glycol dimethyl ether, 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 1230L/m
220 ℃ of h@0.1MPa, film separates aperture 0.20 μ m, porosity 77%.
Embodiment 3: with 800 gram calcium carbonate nano particles, 1800 gram polyvinylidene fluoride resins, 780 gram polyvinylpyrrolidones, 20 gram fluorine surfactant FC-4,800 gram triethyl phosphates, 100 gram carbon fibers, at 220 ℃ of blend granulations, melt spinning.Remove calcium carbonate in the Kynoar doughnut, triethyl phosphate etc., the Kynoar doughnut perforated membrane internal diameter 0.6mm that obtains, external diameter 1.0mm, rupture strength 1.23MPa, pure water penetration speed 1290L/m with hydrochloric acid solution
220 ℃ of h@0.1MPa, film separates aperture 0.50 μ m.
Embodiment 4: with 800 gram Nano particles of silicon dioxide, 1800 gram polyvinylidene fluoride resins, 780 gram polyvinyl alcohol, 20 gram dioctyl phthalates (DOP), 80 gram asbestos fibres, 200 ℃ of blend granulations, melt spinning.Remove silica, polyvinyl alcohol in the Kynoar doughnut, the Kynoar doughnut perforated membrane internal diameter 0.8mm that obtains, external diameter 1.4mm, rupture strength 1.53MPa, pure water penetration speed 1130L/m with sodium hydroxide solution
220 ℃ of h@0.1MPa, film separates aperture 0.45 μ m.
Claims (3)
1. the method for a melt spinning system hollow-fibre membrane, it is characterized in that: the melt spinning composition comprises:
Polymer: 20～90wt%, polymer are Kynoar or polyethersulfone resin;
Glass fibre: 0.5～20wt%;
Inorganic pore-foaming agent: 5～50wt%, inorganic pore-foaming agent are the mixture of following one or more materials: calcium carbonate, alundum (Al;
Macromolecule pore-foaming agent: 2～30wt%, macromolecule pore-foaming agent are the mixtures of following one or more solvents: polyethylene glycol, polyvinylpyrrolidone, polyvinyl alcohol;
Surfactant: 2～60wt%, surfactant are following one or more mixture: cationic surface active agent, anionic surfactant, amphoteric surfactant, nonionic surface active agent;
Organic non-solvent: 10～60wt%, organic non-solvent are diethyl phthalate, dibutyl phthalate, glycol dimethyl ether or diethylene glycol ether;
Wherein wt percentage is benchmark with the gross weight of melt spinning composition, in the spinning component percetage by weight of various materials and be 100wt%.
2. according to the method for claim 1, it is characterized in that: the melt spinning composition comprises
Polymer: 30～70wt%, polymer are Kynoar or polyethersulfone resin;
Glass fibre: 1.0～5wt%;
Inorganic pore-foaming agent: 10～40wt%, inorganic pore-foaming agent are the mixture of following one or more materials: calcium carbonate, alundum (Al;
Macromolecule pore-foaming agent: 5～20wt%, macromolecule pore-foaming agent are the mixtures of following one or more solvents: polyethylene glycol, polyvinylpyrrolidone, polyvinyl alcohol;
Surfactant: 2～60wt%, surfactant are following one or more mixture: cationic surface active agent, anionic surfactant, amphoteric surfactant, nonionic surface active agent;
Organic non-solvent: 10～60wt%, organic non-solvent are diethyl phthalate, dibutyl phthalate, glycol dimethyl ether or diethylene glycol ether;
Wherein wt percentage is benchmark with the gross weight of melt spinning composition, in the spinning component percetage by weight of various materials and be 100wt%.
3. according to the method for claim 1 or 2, it is characterized in that: the granularity of inorganic pore-foaming agent is less than 10 microns.
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| CN2005100145779A CN1899677B (en) | 2005-07-19 | 2005-07-19 | Method for producing hollow fiber film |
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| CN2005100145779A CN1899677B (en) | 2005-07-19 | 2005-07-19 | Method for producing hollow fiber film |
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| CN1899677B true CN1899677B (en) | 2010-04-28 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2598232A1 (en) * | 2010-07-30 | 2013-06-05 | Schaefer Kalk GmbH & Co. KG | Porous hollow fiber |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102350231B (en) * | 2011-06-27 | 2014-01-22 | 张会艳 | Method for manufacturing polyvinylidene fluoride separation membrane |
| CN102266728A (en) * | 2011-07-05 | 2011-12-07 | 惠州七芯膜净化环保有限公司 | Polyvinylidene fluoride hollow fiber membrane and preparation method thereof |
| CN102634857B (en) * | 2012-04-01 | 2015-01-21 | 东华大学 | Preparation method for melt spinning of polycarbonate butanediol hollow fibrous membranes |
| CN103007782B (en) * | 2012-12-12 | 2014-10-15 | 天津工业大学 | Method for preparing hollow glass fiber film with waste glass serving as raw material |
| CN103041712A (en) * | 2013-01-10 | 2013-04-17 | 浙江开创环保科技有限公司 | High-strength hollow fiber membrane |
| CN105688688A (en) * | 2016-02-26 | 2016-06-22 | 苏州市贝克生物科技有限公司 | Hollow fiber ultrafiltration membrane suitable for instant drinking machine and preparing method thereof |
| CN109605899A (en) * | 2018-12-12 | 2019-04-12 | 深圳麦德利宇航材料科技有限公司 | A kind of aero seat sticky cloth production technology |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1265048A (en) * | 1996-12-10 | 2000-08-30 | 旭化成工业株式会社 | Porous polyvinylidene fluoride resin film and process for producing same |
| KR20030068017A (en) * | 2002-02-09 | 2003-08-19 | 박헌휘 | High tension hollow fiber membrane, and method of manufacture the same |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1265048A (en) * | 1996-12-10 | 2000-08-30 | 旭化成工业株式会社 | Porous polyvinylidene fluoride resin film and process for producing same |
| KR20030068017A (en) * | 2002-02-09 | 2003-08-19 | 박헌휘 | High tension hollow fiber membrane, and method of manufacture the same |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2598232A1 (en) * | 2010-07-30 | 2013-06-05 | Schaefer Kalk GmbH & Co. KG | Porous hollow fiber |
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