CN100522327C - Polyolefine hollow fiber micro-filtration film with permanent hydrophilicity, and its preparation method - Google Patents
Polyolefine hollow fiber micro-filtration film with permanent hydrophilicity, and its preparation method Download PDFInfo
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- CN100522327C CN100522327C CN 200510045233 CN200510045233A CN100522327C CN 100522327 C CN100522327 C CN 100522327C CN 200510045233 CN200510045233 CN 200510045233 CN 200510045233 A CN200510045233 A CN 200510045233A CN 100522327 C CN100522327 C CN 100522327C
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Abstract
A micro-filter membrane made of hollow polyolefin fibers and with permanent hydrophilicity is prepared from the ordinary basic membrane of hollow polyolefin fibers through immersing in alcohol or surfactant, filtering aldehyde solution and filming liquid containing PVA and/or polyethandiol or polyvinyl pyrrolidone, cross-linking reaction, immersing in deionized water and drying.
Description
Technical field:
The present invention relates to a kind of high molecule microfilter membrane and preparation method thereof, particularly relate to a kind of TPO hollow fiber microfiltration membrane and preparation method thereof with permanent hydrophilic.
Background technology:
Polyolefin is the separation membrane material of a class function admirable, have good physical property and chemical property, adopt the micro-filtration membrane of their preparations not only to have good separating property, and has a favorable mechanical performance, acid and alkali-resistance and the anti-microbial attack of other chemicals burn into are several membrane materials commonly used.Though its product has been applied to many fields, because polyolefin surfaces can be lower, have strong hydrophobicity, contact angle is 62 °～108 °, has seriously influenced applying of its film product.Therefore must carry out hydrophilic treated to it, make the hydrophilic fluid that comprises water can see through film, thereby its application is further widened.
At present, various countries research and production personnel have proposed many hydrophilic modification methods, and studying more is to carry out hydrophilic modifying on the surface of finished product polyolefin micro-filtration membrane, mainly are divided into two kinds of temporary hydrophilic and permanent hydrophilics.Temporary hydrophilic modifying mainly comprises infusion method and pressurization, mainly finishes by physical action.Operation is simple for temporary hydrophilic modification method, but water flux can descend along with the prolongation of time.This is that the hydrophilic agent quilt is the cause of flush away gradually when seeing through film owing to water.
The permanent hydrophilic modification is to carry out modification with chemical method, and the operation more complicated can be at the hydrophilicity that improves the film surface in varying degrees, and flux is all little, all can occur the phenomenon that micropore gets clogged to a certain extent.Method of modifying commonly used has surface irradiation processing, surface oxidation treatment, surface plasma to handle and chemical method grafting polar monomer.But, can be subjected to the restriction of some factors of film itself unavoidably, and the structure and the performance of film had certain infringement because chemical modification method is to carry out modification on the basis of existing microporous barrier.
In the diffusion barrier suitability for industrialized production, each corporate boss will adopt and make the TPO hollow fiber microfiltration membrane have the temporary transient hydrophilic measure of physics, promptly adopt infusion method, just the TPO hollow fiber microfiltration membrane is immersed in ethanol, glycerine, surfactant or its mixed liquor, make the micropore of its wetting micro-filtration membrane, carry out hygrometric state then or half hygrometric state is deposited.But what adopt when soaking owing to temporary hydrophilic method all is hydrophilic material, promptly easily is dissolved in the material of water, understands gradually by flush away in the use of micro-filtration membrane, thereby its hydrophily is weakened gradually, until its intrinsic hydrophobicity of final recovery.In addition, the film of hydrophilic treated is in case drying will lose its whole water permeability like this, and its water flux levels off to zero substantially under micro-filtration or ultrafiltration pressure.
How when obtaining permanent hydrophilic character, can guarantee that again membrane structure is not impaired, keep bigger water flux.This is the scientific research of various countries' film, the producers difficult problem thinking always and studying in recent years.In the chemical hydrophilic method that the front is introduced, chemical graft process-be about to some hydroaropic substances be grafted on the basement membrane of TPO hollow fiber microfiltration membrane is the approach of a good above-mentioned target of realization.But connect the general using plasma of skill and technique and connect skill and technique, light irradiation and radiation exposure method; these class methods not only need expensive Special Equipment; but also be difficult to accomplish scale production, equally to the production of hydrophilic polyolefin class micro-filtration membrane with apply and do not have what effect.Patent CN87100639 has introduced the cross-linked hydrophilic polymer that adopts DAAM to form, with physical method be fixed on porous polyolefin membrane to the small part hole wall, make its hydrophily and favorable mechanical performance, and the component stripping of denier is in use only arranged with durability.China does not see similar hydrophilic film production so far, does not see the article report of publishing yet.
Summary of the invention:
The purpose of this invention is to provide and a kind ofly have permanent hydrophilic and after baking oven or air dry, still have good hydrophilicity, still have the TPO hollow fiber microfiltration membrane of bigger pure water infiltration coefficient after rehydration is handled; Simultaneously, another object of the present invention provides the preparation method of this TPO hollow fiber microfiltration membrane.
According to our research, in common physical absorption, merely adopt physisorphtion coating polyethylene resulting hydrophily effect of alcohol and bad on polyolefin film, especially adopt infusion method to handle to this hollow fiber microfiltration membrane.Because polyvinyl alcohol has the hydrophily of height, and the hydrophobicity of TPO basement membrane is often bigger, cause the interfacial tension of polyvinyl alcohol molecule and TPO membrane surface bigger, be difficult to make highly hydrophilic polyvinyl alcohol to form the layer of even coat in the light class membrane surface of hydrophobic polyene, and the fastness of the coat combination that forms is also relatively poor, be separated from each other easily, directly influenced hydrophilic durability of film and operation stability, stain resistance.
The present invention is achieved in that a kind of TPO hollow fiber microfiltration membrane with permanent hydrophilic, comprises TPO hollow fiber microfiltration membrane basement membrane and is fixed on the inwall, outer wall of basement membrane and the cross-linked hydrophilic polymer to the small part hole wall.In the preparation of polyolefin hollow fiber microfiltration membrane basement membrane, adopt fusion drawn method or thermally induced phase separation or traditional doing-wet method usually.Wherein, the fusion drawn method adopts single olefin polymer preparation; Thermally induced phase separation then adopts olefin polymer and some high boiling micromolecular compounds such as the preparation of plant wet goods; And dried-wet method is mainly used in the preparation of polyvinylidene fluoride film, and the raw material of its preparation also have pore-foaming agent polyethylene glycol, polyvinylpyrrolidone, solvent dimethyl formamide or dimethylacetylamide except polymer.The prescription of product and production technology, three kinds of methods have nothing in common with each other.A kind of polyolefin hollow fiber microfiltration membrane preparation method with permanent hydrophilic, it is characterized in that: after the immersion treatment such as the suitable TPO basement membrane process alcohols of employing method for preparing or surfactant, under 0.01～0.3MPa pressure-driven, make the aldehydes solution that contains 0.1%～10% (v/v) with dead-end filtration or the operation of cross-flow filtration form, the aldehydes flow of solution is through the surfaces externally and internally of basement membrane and pass fenestra, circular flow 10s～10min has so just adsorbed one deck aldehydes solution more equably on the polyolefin base membrane surface.Polyolefin-based membrane module is after aldehyde material is handled, under 0.01～0.5MPa pressure-driven, make the preparation liquid that contains 0.1%～10% (w/v) polyvinyl alcohol move 10s～10min in the mode of dead-end filtration or cross-flow filtration, preparation liquid the flow through surfaces externally and internally and the fenestra of basement membrane, adhere to the liquid film that one deck contains polyvinyl alcohol equably relatively on the surfaces externally and internally of basement membrane and the fenestra surface, finished the coating stage that TPO micro-filtration membrane hydrophily is handled; Under 15～65 ℃, make polyvinyl alcohol and aldehydes generation cross-linking reaction then, and react the surface that is fixed on the olefin polymer basement membrane through chemical bonding.Cross-linking reaction time is 1～9 hour.At last, the membrane module of finishing cross-linking reaction was soaked in 15～50 ℃ reverse osmosis water 12～60 hours, with the clean additive of rinsing and reach swelling equilibrium, make the TPO hollow fiber microfiltration membrane have permanent hydrophilic.Also the hydrophilic membrane for preparing can be carried out post processing 12～60 hours in 30-65 ℃ of reverse osmosis waters, with the pure water flux of further raising olefin polymer hollow fiber microfiltration membrane.The alcohols material that is adopted comprises ethanol, butanols, butanediol or its mixture, and concentration is 70%～100%; The aldehydes that is adopted is formaldehyde or glutaraldehyde, and concentration is 0.1%～10% (v/v); The ratio of the each several part of the preparation liquid that is adopted is: polyvinyl alcohol 0.1%～10% (w/v), additive 3%～30% (w/v), catalyst 0.01%～1% (v/v), buffer 0.01%～2% (v/v), curing agent 0.01%～1% (v/v), remaining is a deionized water.Described polyvinyl alcohol has 1788 or its mixture of 1799 and non-complete alcoholysis of complete alcoholysis.Described catalyst is the concentrated sulfuric acid or SPA, and buffer is an acetate, and curing agent is a methyl alcohol.Described additive is different molecular weight polyethylene glycol or polyvinylpyrrolidone or its mixture, and its content is 3%～30% (w/v); Described cross-linking reaction temperature is 15～65 ℃, and the reaction time is 1～9 hour; Soaking coolant-temperature gage is 15～50 ℃, and the processing time is 12～60 hours; The post processing water temperature is 30～65 ℃, and the post processing time is 12～60 hours.
In the preparation of TPO hollow fiber microfiltration membrane with permanent hydrophilic, by major parameters such as each concentration of component and flowing time in the control concentration of crosslinking agent and flowing time, the preparation liquid, can control level of coverage and the thickness of hydrophilic layer on film surface and internal surface of hole well, and size that can adjustment aperture.If crosslinker concentration, preparation liquid excessive concentration, running time is long, then may gather owing to the polyvinyl alcohol on membranous wall or fenestra too much and fenestra is blocked, and make the fibre wall thickening, thereby pure water flux is not high; Crosslinker concentration, preparation liquid concentration are too low, and running time is too short, then cause the pure water flux after the dry film rehydration lower owing to hydrophily is relatively poor.Adopt the prepared hydrophilic polyolefin class hollow fiber microfiltration membrane of this law, in 50 ℃ baking oven through fully dry more than 24 hours or about 20 ℃ air dries more than 120 hours, still has good hydrophilicity, after directly rehydration was handled, its water flux reached dry 85%-100% of the preceding water flux of handling.The inventive method is applicable to that also preparation has the TPO hollow fiber ultrafiltration membrane of permanent hydrophilic.
The specific embodiment:
Embodiment 1:
The aperture that the fusion drawn method is produced is 0.2 μ m polypropylene hollow fiber micro-filtration membrane, makes small-sized membrane module.Earlier membrane module is used soaked in absolute ethyl alcohol 30 minutes, membrane module is installed on ultrafiltration or the micro-filtration then, under 0.1MPa pressure, with 30 ℃, 2% glutaraldehyde solution dead-end filtration or cross-flow filtration 10 minutes, then on the hydrophilic membrane preparation facilities under 0.2MPa pressure with 30 ℃, the preparation liquid dead-end filtration or the cross-flow filtration that contain 3% polyvinyl alcohol and 17% polyethylene glycol circulated 5 minutes, after filtration is finished membrane module is placed under 30 ℃ of isoperibols and carries out cross-linking reaction, take out after 5 hours, putting into 30 ℃ of deionized waters soaked 24 hours, can make the polyolefin hollow fiber microfiltration membrane with permanent hydrophilic, its pure water infiltration coefficient is 650～1000L/m
2HrMPa.Prepared membrane module is placed 50 ℃ dry 24 hours of baking oven, take out directly rehydration of back, recording its pure water infiltration coefficient is 600～900L/m
2HrMPa.
Embodiment 2:
Changed the preparation liquid filtration time into 10 minutes by 5 minutes, remaining is with embodiment 1.Then the pure water infiltration coefficient of resulting hydrophilic membrane is 400～750L/m
2HrMPa.After the direct rehydration of dried film, recording its pure water infiltration coefficient is 350～650/m
2HrMPa.
Embodiment 3:
Change glutaraldehyde solution temperature, preparation liquid temperature, cross-linking reaction temperature and immersion into 50 ℃ with coolant-temperature gage by 30 ℃, all the other are with embodiment 1.Then the pure water infiltration coefficient of resulting hydrophilic membrane is 700～1000L/m
2HrMPa.After the direct rehydration of dried film, recording its pure water infiltration coefficient is 625～900L/m
2HrMPa.
Comparative example 1:
The aperture that the fusion drawn method is produced is 0.2 μ m polypropylene hollow fiber micro-filtration membrane, makes small-sized membrane module.Use soaked in absolute ethyl alcohol after 30 to 60 minutes membrane module, the pure water infiltration coefficient of the hydrophily micro-filtration membrane that records is 1000～1750L/m
2HrMPa.This hydrophilic membrane placed 50 ℃ dry 24 hours of baking oven.Direct rehydration, then recording its pure water infiltration coefficient is zero.
Claims (8)
1, a kind of TPO hollow fiber microfiltration membrane with permanent hydrophilic is characterized in that it comprises polyethylene or polypropylene hollow fiber micro-filtration membrane basement membrane and is fixed on the inwall, outer wall of basement membrane and the cross-linked hydrophilic polymer that is formed by aldehyde compound and polyvinyl alcohol to the small part hole wall.
2, TPO hollow fiber microfiltration membrane according to claim 1 is characterized in that described micro-filtration membrane basement membrane prepares pore-forming with fusion drawn method or thermally induced phase separation.
3, a kind of preparation method with TPO hollow fiber microfiltration membrane of permanent hydrophilic is characterized in that it comprises that step (1) polyolefin hollow fiber microfiltration membrane basement membrane is through the alcohol compound immersion treatment; Step (2) is adsorbed in aldehyde compound on the surface and hole wall of polyolefin hollow fiber microfiltration membrane basement membrane; Step (3) hydrophilic polyethene alcohol and aldehyde compound generation cross-linking reaction; Step (4) water logging bubble and swelling equilibrium; Step (5) adopts deionized water to soak post processing.
4, method according to claim 3 is characterized in that: the concentration of adsorbable aldehyde compound on film surface and hole wall is 0.1%～10% (v/v).
5, method according to claim 3 is characterized in that: the concentration of hydrophilic polyethene alcohol is 0.1%～10% (w/v).
6, according to the method for claim 3, it is characterized in that: the cross-linking reaction temperature in the preparation process is at 15～65 ℃, and the reaction time is 1～9 hour.
7, method according to claim 3 is characterized in that: at 15～50 ℃, soak time is 12～60 hours to the immersion in the preparation process with coolant-temperature gage.
8, method according to claim 3 is characterized in that: the temperature that deionized water soaks post processing is 30～65 ℃, and the processing time is 12～60 hours.
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| CN 200510045233 CN100522327C (en) | 2005-11-20 | 2005-11-20 | Polyolefine hollow fiber micro-filtration film with permanent hydrophilicity, and its preparation method |
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| CN 200510045233 CN100522327C (en) | 2005-11-20 | 2005-11-20 | Polyolefine hollow fiber micro-filtration film with permanent hydrophilicity, and its preparation method |
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| CN100522327C true CN100522327C (en) | 2009-08-05 |
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Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101422669B (en) * | 2008-11-26 | 2012-02-08 | 南昌大学 | Preparation method of hydrophilicity macromolecule micropore filter material |
| CN102423642B (en) * | 2011-12-13 | 2013-12-11 | 北京碧水源科技股份有限公司 | Permanent hydrophilic modification method for surface of porous membrane and porous membrane obtained by same |
| CN103007789A (en) * | 2012-12-13 | 2013-04-03 | 江南大学 | Preparation method of cross-linking oil-water separation film |
| CN103055718A (en) * | 2013-02-05 | 2013-04-24 | 天津天一爱拓科技有限公司 | Hydrophilic hollow fiber dry microporous membrane and preparation method thereof |
| CN103253736A (en) * | 2013-04-20 | 2013-08-21 | 马彰原 | Fluid hollow microfiltration membrane element |
| CN104248913B (en) * | 2013-06-28 | 2016-12-28 | 中国石油化工股份有限公司 | A kind of method of polyolefin hollow fiber ultrafiltration membrane hydrophilic modification |
| CN106823856B (en) * | 2017-03-21 | 2020-10-30 | 亚美滤膜（南通）有限公司 | Hydrophilic porous polyolefin material and hydrophilic modification treatment method thereof |
| CN108031306A (en) * | 2017-12-23 | 2018-05-15 | 刘顶康 | A kind of polyvinyl chloride filter membrane with hydrophilic stability |
| CN110760994B (en) * | 2018-07-25 | 2022-02-01 | 中国科学院宁波材料技术与工程研究所 | Three-dimensional cross-linked super-wetting nanofiber membrane and preparation method thereof |
| CN109248569A (en) * | 2018-10-19 | 2019-01-22 | 上海恩捷新材料科技有限公司 | A kind of seperation film and preparation method thereof |
| CN112044281B (en) * | 2019-06-06 | 2022-05-17 | 上海恩捷新材料科技有限公司 | Hydrophilic polyethylene microporous membrane and preparation method thereof |
| CN112295418B (en) * | 2019-07-30 | 2022-06-28 | 上海恩捷新材料科技有限公司 | Polyethylene-based composite graphene oxide nanofiltration membrane and preparation method thereof |
| CN115364702B (en) * | 2022-08-31 | 2024-05-28 | 哈尔滨工业大学 | Method for modifying organic film by nano hydrogel particles |
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Assignee: Qingdao Hainuo Water-Supply Engineering Co., Ltd. Assignor: Ocean University of China Contract fulfillment period: 2009.8.5 to 2015.1.15 contract change Contract record no.: 2009370000230 Denomination of invention: Polyolefine hollow fiber micro-filtration film with permanent hydrophilicity, and its prepn. method Granted publication date: 20090805 License type: Exclusive license Record date: 2009.8.20 |
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Free format text: EXCLUSIVE LICENSE; TIME LIMIT OF IMPLEMENTING CONTACT: 2009.8.5 TO 2015.1.15; CHANGE OF CONTRACT Name of requester: QINGDAO HEINUO WATER UTILITY TECHNOLOGY CO., LTD. Effective date: 20090820 |
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