CN104043344A - Polyvinylidene fluoride hollow fiber microporous membrane and preparation method - Google Patents
Polyvinylidene fluoride hollow fiber microporous membrane and preparation method Download PDFInfo
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- CN104043344A CN104043344A CN201310084232.5A CN201310084232A CN104043344A CN 104043344 A CN104043344 A CN 104043344A CN 201310084232 A CN201310084232 A CN 201310084232A CN 104043344 A CN104043344 A CN 104043344A
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Abstract
The invention discloses a polyvinylidene fluoride hollow fiber microporous membrane. By the use of a water-soluble diluent, cooling and extraction processes are carried out simultaneously. Thus, membrane preparation process is simplified; membrane preparation time is shortened; and membrane preparation costs are minimized.
Description
Technical field
The invention belongs to polymer material science and technical field, relate to a kind of polyvinylidene fluoride hollow fiber microporous membrane and preparation method thereof.
Background technology
Hollow-fibre membrane is a kind of important diffusion barrier, and its inwall or outer wall have selection permeability, can make some composition in liquid or admixture of gas see through hollow-fibre membrane, holds back a part simultaneously and forms.Be compared to the other forms of films such as flat sheet membrane, rolled film, hollow-fibre membrane has advantages of unit volume loading density greatly and self-supporting, can be made into the device of small portable.
Kynoar (PVDF) possesses excellent mechanical strength and chemical stability, can resistance to municipal wastewater in hypochlorous corrosion, therefore PVDF microporous barrier is widely used in pure water manufacture and sewage disposal.
Preparation for PVDF microporous barrier mainly contains two kinds of methods: (1) phase separation (NIPS) method.This method be by the dissolved solution of PVDF in solvent, form homogeneous phase casting solution, after standing and defoaming, put into coagulation bath, coagulation bath and solvent generation mass transport process, cause casting solution film-forming.There is finger-like pore, the lower problem of intensity in the standby PVDF microporous barrier of this legal system, so it is subject to certain limitation at membrane bioreactor (MBR) etc. in to the application in the higher field of requirement of strength.(2) thermic (TIPS) method that is separated.This method is proposed at 20 century 70s by Castro the earliest, its masking principle is that macromolecule and diluent high temperature form homogeneous phase casting solution, be placed in the rear casting solution generation solid-liquid phase of cooling bath cooling or liquid-liquid phase separation, the rich solidifying film forming of polymer, the stingy pore-forming of polymer, obtains the homogeneous spongelike structure perforated membrane that intensity is higher after extraction polymer is stingy.And cooling bath does not generally exchange with diluent, making film is microfiltration membranes.
Preparation to PVDF microporous barrier in prior art, mainly contains following report:
The mixed solvent that Chinese patent ZL200810147491.7 adopts the high-temperature solvent diphenyl carbonate of Kynoar and the alcohols non-solvent of Kynoar to form is diluent, this diluent is water insoluble, in film forming procedure, system generation thermic is separated, make there is high strength, high porosity, high-throughout homogeneous spongelike structure polyvinylidene fluoride film.The method only can make polyvinylidene fluoride microporous filtering film, cannot make the milipore filter that separation accuracy is higher.
In Chinese patent 200910085585.0, disclose employing alcohol or ether extractant extracts water-fast composite thinning agent, after extraction, needed to adopt water to wash residual alcohol or ether extractant in film, this extraction process comparatively complexity and masking cost relatively high.
Chinese patent 200810172232.X discloses a kind of composite thermotropic phase separation film-making method.The compound system of binary, ternary and even quaternary that employing is comprised of water-soluble good solvent and water-soluble additives is diluent, film-forming process is that by thermic, to be separated be main, phase separation process is auxiliary a kind of recombination process, can make the polyvinylidene fluoride (PVDF) ultrafiltration membrane of homogeneous spongelike structure.But the good solvent that comprises polymer in the diluent that the method adopts, after thermic has been separated, in film body, solid phase is the interpenetrating network membrane (ipn) skeleton that polymer-rich phase forms, and the polymer that liquid phase is comprised of good solvent and additive and a small amount of polymer dissolving is stingy.In the middle of the stingy process of extraction polymer, can there is secondary phase separation, the secondary deposition of initiated polymerization thing.Therefore, need to select suitable diluent system, suitable cooling fluid composition and chilling temperature to control the solubility of the stingy middle polymer of polymer and select suitable extract composition, to eliminate the harmful effect of secondary deposition to membrane structure.This process has greatly increased difficulty, cost of material and the human cost in its suitability for industrialized production.
Summary of the invention
The object of the present invention is to provide a kind of PVF hollow fiber microporous membrane, use water-soluble diluent, in film-forming process, in same water-bath, there is the preparation of cooling and extraction process simultaneously, have easy to operate, cost is low, be applicable to the advantages such as suitability for industrialized production.
For reaching goal of the invention the technical solution used in the present invention, be:
A polyvinylidene fluoride hollow fiber microporous membrane, is characterized in that being prepared as follows:
(1) masking formula is counted with mass percent ratio: Kynoar 20%～50%, diluent 80%～50%, masking formula is fully mixed at 120 ℃～180 ℃ temperature, and obtain homogeneous phase solution; Described diluent water soluble; The weight average molecular weight of described Kynoar is 200,000～1000,000;
(2) homogeneous phase solution step (1) being obtained is spun into the casting solution of hollow fiber by spinning head, casting solution is immersed to cooling bath, make diluent and cooling bath exchange that cooling and extraction process occur simultaneously, casting solution is separated and is solidified into polyvinylidene fluoride hollow fiber microporous membrane.
The diluent water soluble that the present invention uses, preferably a kind of, more than two or three combination in, oleic acid sad from triethyl citrate, phenmethylol, gaultherolin, triethyl phosphate, cyclohexanone, cyclohexanol, diethyl malonate, ethylene dimethyl, trimethyl phosphate, GBL, ethylene glycol, 1-, polyvinyl alcohol, dibenzoic diglycol laurate and APEO; More preferably a kind of, more than two or three combination in triethyl citrate, phenmethylol, gaultherolin, trimethyl phosphate, cyclohexanone, cyclohexanol, GBL and APEO.
The present invention has used water-soluble diluent, and make water as cooling bath medium, can in film-forming process, make diluent and cooling bath exchange in masking formula, and cooling and extraction process occurs simultaneously, simplify processing step, shortened the masking time.Cooling and extraction process temperature is preferably 20 ℃～70 ℃.In addition by regulating the temperature difference of diluent and cooling bath, can make the homogeneous spongelike structure PVDF supermicro filtration membrane in a series of different surfaces aperture.As preferred mode, when diluent and cooling bath temperature range are 50 ℃～160 ℃, the surface apertures of described polyvinylidene fluoride hollow fiber microporous membrane is 17nm～0.2 μ m.
The polyvinylidene fluoride hollow fiber microporous membrane that the present invention makes, its preferred technical indicator is: section average pore size is 0.4 μ m～2.1 μ m, porosity is 50%～80%, fracture strength is 4～13MPa, surface average pore size is 17nm～0.2 μ m, and under 0.1MPa, the pure water flux of 25 ℃ is 240LMH～1600LMH.
Accompanying drawing explanation
Fig. 1 is the film section structure of the polyvinylidene fluoride hollow fiber microporous membrane that makes of embodiment 1.
Fig. 2 is the film section structure for amplifying of the polyvinylidene fluoride hollow fiber microporous membrane that makes of embodiment 1.
Fig. 3 is the membrane superficial tissue of the polyvinylidene fluoride hollow fiber microporous membrane that makes of embodiment 1.
Fig. 4 is the film section structure for amplifying of the polyvinylidene fluoride hollow fiber microporous membrane that makes of embodiment 2.
Fig. 5 is the middle membrane superficial tissue of the polyvinylidene fluoride hollow fiber microporous membrane that makes of embodiment 2.
Fig. 6 is the film section structure for amplifying of the polyvinylidene fluoride hollow fiber microporous membrane that makes of embodiment 3.
Fig. 7 is the film section structure for amplifying of the polyvinylidene fluoride hollow fiber microporous membrane that makes of embodiment 4.
The specific embodiment
Below in conjunction with specific embodiment, the present invention is further described, but does not limit the invention to these specific embodiment.One skilled in the art would recognize that the present invention contained all alternatives, improvement project and the equivalents that within the scope of claims, may comprise.
Embodiment 1
By Kynoar, (weight average molecular weight is 1000,000) with triethyl citrate and phenmethylol, its proportioning is that Kynoar mass percent is 50%, triethyl citrate mass percent is 20%, the mass percent of phenmethylol is 30%, put into high-temperature stirring still and be heated to 180 ℃, be uniformly mixed and form polymer homogeneous phase solution, standing 24 hours.Then polymer homogeneous phase solution is spun into hollow fiber by spinning head, and the cooling bath that enters into 20 ℃ makes solution phase-splitting film-forming, cooling bath plays extraction simultaneously, completes extraction process in cooling procedure simultaneously, makes polyvinylidene fluoride hollow fiber microporous membrane.
After tested, the film section of the polyvinylidene fluoride hollow fiber microporous membrane making is the spongelike structure of homogeneous, and section average pore size is 0.4 μ m, porosity is 53%, fracture strength 12.7MPa, surperficial average pore size is 0.2 μ m, under 0.1MPa, the pure water flux of 25 ℃ is 1580L/m
2h.
Embodiment 2
By Kynoar, (weight average molecular weight is 600,000) and gaultherolin, its proportioning is that Kynoar mass percent is 40%, gaultherolin mass percent is 60%, put into high-temperature stirring still and be heated to 170 ℃, be uniformly mixed and form polymer homogeneous phase solution, standing 24 hours.Then polymer homogeneous phase solution is spun into hollow fiber by spinning head, and the cooling bath that enters into 20 ℃ makes solution phase-splitting film-forming, cooling bath plays extraction simultaneously, completes extraction process in cooling procedure simultaneously, makes polyvinylidene fluoride hollow fiber microporous membrane.
After tested, the film section of the polyvinylidene fluoride hollow fiber microporous membrane making is the spongelike structure of homogeneous, and section average pore size is 0.8 μ m, porosity is 61%, fracture strength 9.2MPa, surperficial average pore size is 17nm, under 0.1MPa, the pure water flux of 25 ℃ is 240L/m
2h.
Embodiment 3
By Kynoar, (weight average molecular weight is 500,000) with trimethyl phosphate and phenmethylol, its proportioning is that Kynoar mass percent is 30%, trimethyl phosphate mass percent is 35%, the mass percent of phenmethylol is 35%, put into high-temperature stirring still and be heated to 170 ℃, be uniformly mixed and form polymer homogeneous phase solution, standing 24 hours.Then polymer homogeneous phase solution is spun into hollow fiber by spinning head, and the cooling bath that enters into 50 ℃ makes solution phase-splitting film-forming, cooling bath plays extraction simultaneously, completes extraction process in cooling procedure simultaneously, makes polyvinylidene fluoride hollow fiber microporous membrane.
After tested, the film section of the polyvinylidene fluoride hollow fiber microporous membrane making is the spongelike structure of homogeneous, and section average pore size is 1.3 μ m, porosity is 68%, fracture strength 7.5MPa, surperficial average pore size is 26nm, under 0.1MPa, the pure water flux of 25 ℃ is 336L/m
2h.
Embodiment 4
By Kynoar, (weight average molecular weight is 200,000) with cyclohexanone and cyclohexanol, its proportioning is that Kynoar mass percent is 20%, cyclohexanone mass percent is 40%, the mass percent of cyclohexanol is 40%, put into high-temperature stirring still and be heated to 120 ℃, be uniformly mixed and form polymer homogeneous phase solution, standing 24 hours.Then polymer homogeneous phase solution is spun into hollow fiber by spinning head, and the cooling bath that enters into 70 ℃ makes solution phase-splitting film-forming, cooling bath plays extraction simultaneously, completes extraction process in cooling procedure simultaneously, makes polyvinylidene fluoride hollow fiber microporous membrane.
After tested, the film section of the polyvinylidene fluoride hollow fiber microporous membrane making is the spongelike structure of homogeneous, and section average pore size is 2.1 μ m, porosity is 78%, fracture strength 4.3MPa, surperficial average pore size is 34nm, under 0.1MPa, the pure water flux of 25 ℃ is 528L/m
2h.
Claims (6)
1. a polyvinylidene fluoride hollow fiber microporous membrane, is characterized in that being prepared as follows:
(1) masking formula is counted with mass percent ratio: Kynoar 20%～50%, diluent 80%～50%, masking formula is fully mixed at 120 ℃～180 ℃ temperature, and obtain homogeneous phase solution; Described diluent water soluble; The weight average molecular weight of described Kynoar is 200,000～1000,000;
(2) homogeneous phase solution step (1) being obtained is spun into the casting solution of hollow fiber by spinning head, casting solution is immersed to cooling bath, make diluent and cooling bath exchange that cooling and extraction process occur simultaneously, casting solution is separated and is solidified into polyvinylidene fluoride hollow fiber microporous membrane.
2. according to polyvinylidene fluoride hollow fiber microporous membrane claimed in claim 1, it is characterized in that described diluent is selected from that triethyl citrate, phenmethylol, gaultherolin, triethyl phosphate, cyclohexanone, cyclohexanol, diethyl malonate, ethylene dimethyl, trimethyl phosphate, GBL, ethylene glycol, 1-are sad, a kind of, more than two or three combination in oleic acid, polyvinyl alcohol, dibenzoic diglycol laurate and APEO.
3. according to polyvinylidene fluoride hollow fiber microporous membrane claimed in claim 2, it is characterized in that described diluent is selected from a kind of, more than two or three combination in triethyl citrate, phenmethylol, gaultherolin, trimethyl phosphate, cyclohexanone, cyclohexanol, GBL and APEO.
4. according to polyvinylidene fluoride hollow fiber microporous membrane claimed in claim 1, it is characterized in that described cooling and extraction process temperature is 20 ℃～70 ℃.
5. according to polyvinylidene fluoride hollow fiber microporous membrane claimed in claim 1, the temperature difference that it is characterized in that described diluent and cooling bath is 50 ℃～160 ℃, and the surface apertures of described polyvinylidene fluoride hollow fiber microporous membrane is 17nm～0.2 μ m.
6. according to polyvinylidene fluoride hollow fiber microporous membrane claimed in claim 1, the section average pore size that it is characterized in that described polyvinylidene fluoride hollow fiber microporous membrane is 0.4 μ m～2.1 μ m, porosity is 50%～80%, fracture strength is 4～13MPa, surface average pore size is 17nm～0.2 μ m, and under 0.1MPa, the pure water flux of 25 ℃ is 240LMH～1600LMH.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104492281A (en) * | 2014-12-04 | 2015-04-08 | 菏泽学院 | Method for preparing polyvinylidene fluoride membrane by using water-soluble diluent |
| CN105126648A (en) * | 2015-09-21 | 2015-12-09 | 江苏凯米膜科技股份有限公司 | Method for preparing meshed PVDF (polyvinylidene fluoride) film based on PVA (polyvinyl alcohol) gel |
| CN108325398A (en) * | 2018-02-07 | 2018-07-27 | 江苏理工学院 | A kind of preparation method of pollution-resistant membrane material |
| CN108430610A (en) * | 2015-12-28 | 2018-08-21 | 东丽株式会社 | Hollow fiber membrane module and its method of operation |
| CN109289545A (en) * | 2018-10-18 | 2019-02-01 | 浙江工业大学 | A kind of preparation method of polyvinylidene fluoride hollow fiber microporous membrane |
| CN113648844A (en) * | 2021-08-25 | 2021-11-16 | 贵州省材料产业技术研究院 | Polyvinylidene fluoride hollow fiber membrane with reticular pore structure and preparation method thereof |
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| CN101370572A (en) * | 2006-01-11 | 2009-02-18 | 东洋纺织株式会社 | Polyvinylidene fluoride hollow yarn type microporous film and process for production of the same |
| CN101569837A (en) * | 2009-05-26 | 2009-11-04 | 清华大学 | Polyvinylidene fluoride microporous film preparation method |
| CN102764595A (en) * | 2011-05-03 | 2012-11-07 | 吕晓龙 | Polyvinylidene fluoride separation membrane and its preparation method |
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| CN101370572A (en) * | 2006-01-11 | 2009-02-18 | 东洋纺织株式会社 | Polyvinylidene fluoride hollow yarn type microporous film and process for production of the same |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104492281A (en) * | 2014-12-04 | 2015-04-08 | 菏泽学院 | Method for preparing polyvinylidene fluoride membrane by using water-soluble diluent |
| CN105126648A (en) * | 2015-09-21 | 2015-12-09 | 江苏凯米膜科技股份有限公司 | Method for preparing meshed PVDF (polyvinylidene fluoride) film based on PVA (polyvinyl alcohol) gel |
| US10335741B2 (en) | 2015-09-21 | 2019-07-02 | Jiangsu Kaimi Membrane Technology Co., Ltd | Method for preparing the network-pore polyvinylidene fluoride membrane based on polyvinyl alcohol gel |
| CN108430610A (en) * | 2015-12-28 | 2018-08-21 | 东丽株式会社 | Hollow fiber membrane module and its method of operation |
| CN108430610B (en) * | 2015-12-28 | 2021-04-09 | 东丽株式会社 | Hollow fiber membrane module and method for operating same |
| US11141698B2 (en) | 2015-12-28 | 2021-10-12 | Toray Industries, Inc. | Hollow fiber membrane module and method for operating same |
| CN108325398A (en) * | 2018-02-07 | 2018-07-27 | 江苏理工学院 | A kind of preparation method of pollution-resistant membrane material |
| CN109289545A (en) * | 2018-10-18 | 2019-02-01 | 浙江工业大学 | A kind of preparation method of polyvinylidene fluoride hollow fiber microporous membrane |
| CN113648844A (en) * | 2021-08-25 | 2021-11-16 | 贵州省材料产业技术研究院 | Polyvinylidene fluoride hollow fiber membrane with reticular pore structure and preparation method thereof |
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