CN102649029A - Method for modifying irradiation of polyethylene hollow fiber microporous membrane - Google Patents
Method for modifying irradiation of polyethylene hollow fiber microporous membrane Download PDFInfo
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- CN102649029A CN102649029A CN2011100458162A CN201110045816A CN102649029A CN 102649029 A CN102649029 A CN 102649029A CN 2011100458162 A CN2011100458162 A CN 2011100458162A CN 201110045816 A CN201110045816 A CN 201110045816A CN 102649029 A CN102649029 A CN 102649029A
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Abstract
The invention provides a method for modifying irradiation of a polyethylene hollow fiber microporous membrane. The method is characterized in that after the polyethylene hollow fiber microporous membrane is fully soaked in active monomer solution, membrane fibers which are processed by the active monomer solution are irradiated, a free radical is generated on the surface of the membrane, and a cross-linking and grafting reaction is generated, so that the polyethylene microporous membrane with high hydrophilcity is obtained. The surface water contact angle of the polyethylene hollow fiber microporous membrane after being irradiated is reduced, the hydrophilcity is obviously improved, and the prepared hollow fiber microporous membrane has stable performance.
Description
Technical field
The present invention relates to a kind of miillpore filter high-hydrophilic method of modifying that is used for the fluid separation applications field, more specifically be meant a kind of polyethylene hollow fiber microporous barrier radiation modification method.
Background technology
Polyethylene (PE) doughnut miillpore filter has high porosity; Mechanical strength is big; Have good chemically-resistant solvent corrosion, the erosion performance of anti-bacterium the and better biocompatibility; Raw material is cheap and easy to get in addition, manufacture craft is simple, is a kind of comparatively desirable miillpore filter, in stable, the difficult degraded of the medium-term and long-term serviceability of sewage disposal.But because PE is a non-polar material; The surface can be low, presents inertia and hydrophobicity, uses it as sewage treating material; There are shortcomings such as poor, the easy static electrification of water imbibition, resistance tocrocking difference; For making it in industrial circle, be able to extensive use, therefore must carry out hydrophilic modifying to it, improve its surface property to give its new separation function.Many polyethylene hollow fiber film method of modifying are arranged on the document, and the most frequently used method of modifying is that dish is handled the polyethylene hollow fiber film with ethanol, makes it obtain hydrophily; Or adopt anionic surfactant treatment polyolefin hollow-fibre membranes such as phosphate or sulfonate to make the fiber hydrophiling; The method that maybe will make used polythene material of film and hydrophilic material blend makes film obtain hydrophily, but these methods all have certain weak point.
Graft copolymerization is a kind ofly can give the polymer surfaces superior function and do not influence the method for its bulk properties; What application was more at present is initiation graftings such as gamma-rays, plasma, ozone activation; Mostly its modified membrane is polypropylene (PP), polysulfones (PS), Kynoar (PVDF) etc.The polyethylene main chain is the methylene of line style long-chain, symmetrical configuration, and the surface can be low; The surface is difficult for handling, and researcher's using plasma processing both at home and abroad or ozone activation carry out modification to fiber, and these method equipment requirements are high; Be difficult to realize producing continuously, the industrialization difficulty is bigger.
The radiation modification technology is to utilize the high energy electron ray of doses to act on the polyethylene hollow fiber microporous barrier surface; A part of main chain or side chain in the polyethylene molecule are cut off by ray; Produce free radical on the microporous barrier surface; These free radicals be bonded to each other or and the hydrophilic active monomer between react, activated monomer is grafted to the film surface, improves the hydrophilic microporous membrane performance; Form the permanent hydrophilic performance of microporous barrier, with satisfy water treatment especially in water purification, Zhong Shui, the sewage disposal membrane separation technique (like film-bioreactor) to the requirement of membrane material.This high performance new membrane parting material is in environmental protection, the utilization of water resource, and industries such as medicine and chemical separating have good prospects for application.
Summary of the invention
The objective of the invention is to propose a kind of polyethylene hollow fiber film radiation modification method,,, improve the hydrophily and the resistance tocrocking of microporous barrier at polyethylene hollow fiber film surface grafting hydrophilic modification material through radiation modification.
Method provided by the invention is characterized in that: adopt the mode of mutual radiation that the polyethylene hollow fiber microporous barrier is carried out the grafting of radiation guiding hydrophilic monomer, realization is hydrophilically modified to polyethene microporous membrane.The hydrophilic monomer material of choosing be mainly acrylic acid, acrylic amine, acrylic acid ester with and one or more mixture of derivative, these materials on the polyethene microporous membrane surface, improve hydrophilic microporous membrane property through the radiation initiation grafting; Described irradiation grafting condition is: under nitrogen protection, hydrophilic monomer material concentration 5～50wt% adopts cobalt source or electron accelerator irradiation, and irradiation dose is 10～100kGY.This method of modifying have that technology is simple, easy to operate, process velocity is fast, treatment effect good and lasting, cost is low, be difficult for causing environmental pollution, characteristics such as energy-conservation.
The present invention mainly may further comprise the steps the method that the polyethylene hollow fiber microporous barrier carries out the radiation modification processing:
(1) preliminary treatment of polyethylene hollow fiber micro-filtration membrane: after the cleaning of polyethylene hollow fiber micropore process absolute ethyl alcohol, dry;
(2) the polyethylene hollow fiber microporous barrier of step (1) being handled is put into hydrophilic monomer solution and is soaked, and lets microporous barrier surface adsorption hydrophilic monomer; The hydrophilic monomer concentration of material is 5～50wt%, and preferred concentration is 10～20wt%;
(3) under nitrogen atmosphere, the polyethylene hollow fiber microporous barrier that step (2) is handled places initiation grafting and cross-linking reaction under the high-energy ray, lets the hydrophilic monomer material be grafted to the microporous barrier surface.Adopting radiation source is a kind of in electron accelerator or the cobalt source, and dose of radiation is 10～100kGY, and preferred dose of radiation is 30-60kGY;
(4) microporous barrier of step (3) being handled is removed unnecessary unreacted monomer with purified rinse water, dries, and obtains the film of desired properties.
The inventive method is to utilize radiation at the surperficial initiation grafting of microporous barrier, be the effective ways of preparation hydrophilic porous film, and miillpore filter keeps permanent hydrophily.This method is that the high-energy ray that utilizes radiation to produce is handled polyethylene hollow fiber microporous barrier surface; Make the film surface produce living radical; Utilize the characteristic that the free radical group can addition functional group; Specific hydrophilic radical is introduced the microporous barrier surface carry out grafting, obtain the lasting and controlled microporous barrier of hydrophily.The polyethylene hollow fiber film contact angle before the grafting is not greater than 100 °, and contact angle drops to 50 ° behind radiation grafting.
Help to understand the present invention through following inventive embodiments, but do not limit content of the present invention.
The specific embodiment
The present invention mainly may further comprise the steps the method that the polyethylene hollow fiber microporous barrier carries out the radiation modification processing:
(1) preliminary treatment of polyethylene hollow fiber micro-filtration membrane: after the cleaning of polyethylene hollow fiber micropore process absolute ethyl alcohol, dry;
(2) the polyethylene hollow fiber microporous barrier of step (1) being handled is put into hydrophilic monomer solution and is soaked, and lets microporous barrier surface adsorption hydrophilic monomer; The hydrophilic monomer concentration of material is 5～50wt%, and preferred concentration is 10～20wt%;
(3) under nitrogen atmosphere, the polyethylene hollow fiber microporous barrier that step (2) is handled places initiation grafting and cross-linking reaction under the high-energy ray, lets the hydrophilic monomer material be grafted to the microporous barrier surface.Adopting radiation source is a kind of in electron accelerator or the cobalt source, and dose of radiation is 10～100kGY, and preferred dose of radiation is 30～60kGY;
(4) microporous barrier of step (3) being handled is removed unnecessary unreacted monomer with purified rinse water, dries, and obtains the film of desired properties.
Embodiment 1: passed through pretreated polyethylene hollow fiber microporous barrier with a branch of, be immersed in the acrylic monomers solution of 20wt% after 2 hours, taken out and seal with sealed polyethylene plastic; Nitrogen filled protection carries out irradiation then under electron accelerator, irradiation dose is 50kGY; After irradiation finishes; Take out the polyethylene hollow fiber microporous barrier, neutral with washed with de-ionized water to film, prepared hydrophilic porous film contact angle is 52 °.
Embodiment 2: passed through pretreated polyethylene hollow fiber microporous barrier with a branch of, be immersed in the methyl acrylamide monomer solution of 15wt% after 2 hours, taken out and seal with sealed polyethylene plastic; Nitrogen filled protection carries out irradiation then under electron accelerator, irradiation dose is 40kGY; After irradiation finishes; Take out the polyethylene hollow fiber microporous barrier, neutral with washed with de-ionized water to film, prepared hydrophilic porous film contact angle is 61 °.
Embodiment 3: passed through pretreated polyethylene hollow fiber microporous barrier with a branch of, be immersed in the hydroxyethyl methacrylate methyl ethyl ester monomer solution of 10wt% after 2 hours, taken out and seal with sealed polyethylene plastic; Nitrogen filled protection carries out irradiation then under electron accelerator, irradiation dose is 45kGY; After irradiation finishes; Take out polyethylene hollow fiber microporous barrier silk, neutral with washed with de-ionized water to film, prepared hydrophilic porous film contact angle is 47 °.
Embodiment 4: passed through pretreated polyethylene hollow fiber microporous barrier with a branch of, be immersed in the SSS monomer solution of 15wt% after 2 hours, taken out and seal with sealed polyethylene plastic; Nitrogen filled protection carries out irradiation in the cobalt source then, and irradiation dose is 60kGY; After irradiation finishes; Take out polyethylene hollow fiber microporous barrier silk, neutral with washed with de-ionized water to film, prepared hydrophilic porous film contact angle is 48 °.
Claims (5)
1. polyethylene hollow fiber membrane micropore radiation modification method, it is characterized in that: described method may further comprise the steps:
(1) polyethylene hollow fiber microporous barrier preliminary treatment is cleaned the film silk with absolute ethyl alcohol;
(2) get pretreated polyethylene hollow fiber microporous barrier and put into activated monomer solution and fully soak, make to take out behind the micro-porous adsorption activated monomer and dry;
(3) the polyethylene hollow fiber microporous barrier after activated monomer is handled carries out crosslinking with radiation and grafting under nitrogen atmosphere;
(4) the polyethylene hollow fiber microporous barrier post processing behind the radiation modification cleans up with deionized water, dries.
2. method described in claim 1 is characterized in that: described activated monomer comprises one or more the mixture in acrylic acid and derivative, acrylic amine and derivative thereof, acrylate and derivative, the SSS etc.
According to claim 1 or claim 2 the concentration of activated monomer solution be 5～50wt%, preferred 10～20wt%.
4. radiation modification in the method described in claim 1 is that the polyethylene hollow fiber film is carried out irradiation, irradiation dose 10～100kGY, preferred dose 30～60kGY under the irradiation bomb effect.
5. method radiation modification irradiation bomb is electron accelerator or cobalt source described in claim 1.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2011100458162A CN102649029A (en) | 2011-02-25 | 2011-02-25 | Method for modifying irradiation of polyethylene hollow fiber microporous membrane |
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| CN2011100458162A CN102649029A (en) | 2011-02-25 | 2011-02-25 | Method for modifying irradiation of polyethylene hollow fiber microporous membrane |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108695571A (en) * | 2018-04-28 | 2018-10-23 | 杭州电子科技大学 | A kind of method that gamma-ray irradiation improves waste lithium cell FLOTATION SEPARATION effect |
| CN111658863A (en) * | 2020-07-02 | 2020-09-15 | 威海威高血液净化制品有限公司 | Method for reducing dissolving-out of PVP in hollow fiber dialyzer |
| CN112105436A (en) * | 2018-02-15 | 2020-12-18 | 唐纳森公司 | Substrate treatment |
| CN112403282A (en) * | 2019-08-23 | 2021-02-26 | 中国石油化工股份有限公司 | Amphiphilic polypropylene porous membrane and preparation method and application thereof |
| CN112409628A (en) * | 2019-08-23 | 2021-02-26 | 中国石油化工股份有限公司 | Super-wetting surface and preparation method and application thereof |
| CN112495191A (en) * | 2020-10-31 | 2021-03-16 | 上海师范大学 | Three-dimensional modified polymer filter membrane material and preparation method and application thereof |
| TWI789615B (en) * | 2019-08-23 | 2023-01-11 | 大陸商中國石油化工科技開發有限公司 | Superwetting surface and its preparation method and application |
| US11806650B2 (en) | 2016-08-16 | 2023-11-07 | Donaldson Company, Inc. | Hydrocarbon fluid-water separation |
| US12017161B2 (en) | 2019-02-14 | 2024-06-25 | Donaldson Company, Inc. | Filter media configurations |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11806650B2 (en) | 2016-08-16 | 2023-11-07 | Donaldson Company, Inc. | Hydrocarbon fluid-water separation |
| CN112105436A (en) * | 2018-02-15 | 2020-12-18 | 唐纳森公司 | Substrate treatment |
| CN108695571A (en) * | 2018-04-28 | 2018-10-23 | 杭州电子科技大学 | A kind of method that gamma-ray irradiation improves waste lithium cell FLOTATION SEPARATION effect |
| CN108695571B (en) * | 2018-04-28 | 2019-12-31 | 杭州电子科技大学 | Method for improving flotation separation effect of waste lithium battery through gamma ray irradiation |
| US12017161B2 (en) | 2019-02-14 | 2024-06-25 | Donaldson Company, Inc. | Filter media configurations |
| CN112403282A (en) * | 2019-08-23 | 2021-02-26 | 中国石油化工股份有限公司 | Amphiphilic polypropylene porous membrane and preparation method and application thereof |
| CN112409628A (en) * | 2019-08-23 | 2021-02-26 | 中国石油化工股份有限公司 | Super-wetting surface and preparation method and application thereof |
| CN112409628B (en) * | 2019-08-23 | 2022-03-29 | 中国石油化工股份有限公司 | Super-wetting surface and preparation method and application thereof |
| CN112403282B (en) * | 2019-08-23 | 2022-06-03 | 中国石油化工股份有限公司 | Amphiphilic polypropylene porous membrane and preparation method and application thereof |
| TWI789615B (en) * | 2019-08-23 | 2023-01-11 | 大陸商中國石油化工科技開發有限公司 | Superwetting surface and its preparation method and application |
| CN111658863A (en) * | 2020-07-02 | 2020-09-15 | 威海威高血液净化制品有限公司 | Method for reducing dissolving-out of PVP in hollow fiber dialyzer |
| CN112495191A (en) * | 2020-10-31 | 2021-03-16 | 上海师范大学 | Three-dimensional modified polymer filter membrane material and preparation method and application thereof |
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Application publication date: 20120829 |