CN1640532A - Method for modifying polyolefin hollow fiber microporous membrane - Google Patents
Method for modifying polyolefin hollow fiber microporous membrane Download PDFInfo
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- CN1640532A CN1640532A CN 200410000640 CN200410000640A CN1640532A CN 1640532 A CN1640532 A CN 1640532A CN 200410000640 CN200410000640 CN 200410000640 CN 200410000640 A CN200410000640 A CN 200410000640A CN 1640532 A CN1640532 A CN 1640532A
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- microporous membrane
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Abstract
The present invention belongs to the field of polyolefine hollow fibre microporous membrane, in particular it relates to a method for making polyolefine hollow fibre microporous membrane implement modification treatment. Said method includes the following steps: placing polyolefine hollow fibre microporous membrane in a low-temperature plasma reactor, irradiating by plasma to produce lots of free radicals on the surface of membrane, then introducing active monomer and making graft polymerization reaction under a certain condition so as to obtain the membrane with required performance. after said membrane is undergone the process of modification treatment, its hydrophilic property is obviously raised, and its water permeable rate is 5-25 L/sq.m hr.
Description
Technical field
The invention belongs to polyolefin hollow fiber microporous membrane field, particularly the polyolefin hollow fiber microporous membrane is carried out the method that modification is handled.
Background technology
Polyolefin hollow fiber microporous membrane stable chemical performance, mechanical performance is strong, permeability is excellent, and raw material is cheap and easy to get in addition, manufacture craft is simple, is a kind of comparatively desirable miillpore filter.But polyolefin generally is the extremely strong material of hydrophobicity, and the typical hydrophobicity of polyolefin hollow-fibre membrane has limited its range of application.For making it in industrial circle, be able to extensive use, must improve the microporous barrier surface property or give its new separation function by surface modification.The most frequently used method of modifying is with ethanol the polyolefin hollow-fibre membrane to be handled, and makes it obtain hydrophily, and this all has argumentation in many documents.This method is simple to operate, realize easily, and modified effect is obvious.But the microporous barrier after the ethanol modification can not dry state be preserved, and transportation, storage and use are all very inconvenient.JP54-153872A discloses the method that adopts with anionic surfactant treatment polyolefin hollow-fibre membranes such as sulfate, phosphate or sulfonate and has made the tunica fibrosa hydrophiling, JP61-125408A and JP61-271003A all disclose with hydrophilic ethylene-vinyl alcohol copolymer coated at the polyolefin hollow-fibre membrane the surface and make the method for its hydrophiling.The hydrophilic effect that obtains with these methods also can keep under dry state, has overcome the shortcoming of can not dry state preserving with the ethanol modification.But because surfactant and hydrophilic polymer and water have intermiscibility, can be along with the prolongation of service time be dissolved in the water gradually, hydrophilicity is decayed gradually.Patent CN87100639 discloses the cross-linked hydrophilic polymer will be mainly be made up of DAAM and has been fixed on method on the porous polyolefin membrane with physical method, and the hydrophilic porous polyolefin film that makes has durable hydrophily and excellent mechanical intensity.But, therefore be difficult to obtain the surface of character homogeneous owing to be difficult to this cross-linked polymer is coated on the film equably.JP04-265134A discloses the method that will make used polyolefine material of film and hydrophilic material blend makes film obtain hydrophily, but the method for this blend not only requires very high, restive, but also can influence the physical and chemical performance of material itself, therefore cause very big difficulty to filming technology.
Summary of the invention
The objective of the invention is to overcome the polyolefin hollow fiber microporous membrane that obtains by existing method of modifying can not dry state preserve, transportation, storage inconvenience, microporous barrier can lose hydrophilicity gradually along with the prolongation of its service time, the film surface nature heterogeneity and the process conditions that make require high defective, provide a kind of the polyolefin hollow fiber microporous membrane is carried out the method that modification is handled, make the polyolefin hollow fiber microporous membrane physical and chemical performance of preparing stable.
After the present invention utilizes plasma technique to the preliminary treatment of polyolefin hollow fiber microporous membrane, use the glycerol polymerization method again to realize modification to the polyolefin hollow fiber microporous membrane.At first the polyolefin hollow fiber microporous membrane is put into the reaction of low temperature plasma device,, produce a large amount of free radicals, feed activated monomer then, carry out graft polymerization reaction under certain condition, obtain the film of desired properties on the surface of film through plasma irradiating.
Of the present inventionly the polyolefin hollow fiber microporous membrane is carried out the method that modification handles may further comprise the steps:
(1) the polyolefin hollow-fibre membrane is put into the reaction of low temperature plasma device and handled 0.5～30 minute, 10～150 watts of discharge powers, plasma gas atmosphere can adopt non-polymerization gas; As air, nitrogen, oxygen, ammonia or argon gas etc.; Vacuum during plasma treatment is in 0.01～1 holder.
(2) feed activated monomer solution and carry out graft polymerization reaction, add solution the ratio of volume and the quality of processed doughnut be 50～100ml/g; Polymerization time is 0.5～24 hour; 40～100 ℃ of polymerization temperatures.
Described activated monomer comprises acrylic acid, methacrylic acid, acrylamide, Methacrylamide, N hydroxymethyl acrylamide, Hydroxyethyl Acrylate, methacrylic acid hydroxyl ethyl ester, acrylonitrile, methacrylonitrile, N-vinyl pyrrolidone, sodium vinyl sulfonate, SSS or their any mixture.
The concentration of described activated monomer solution is 2.5wt%～20wt%, and solvent is a water.
Raw material selected among the present invention is the commercially available prod.
The hydrophily of the polyolefin hollow-fibre membrane after the inventive method is handled obviously improves, and the permeability rate of film is 5～25L/m
2Hour.And the polyolefin hollow fiber microporous membrane physical and chemical performance of preparing is stable.
To help to understand the present invention by following examples, but not limit content of the present invention.
The specific embodiment
Embodiment 1
In reactor, place dry polyolefin hollow fiber microporous membrane 0.4g, be evacuated to 50Pa, charge into argon gas, repeat for several times, guarantee that in the reactor be argon gas atmosphere, be evacuated to 15Pa again.Reactor being placed between two electrodes of radio-frequency signal generator, is under the 80W condition at discharge power, and the polyolefin hollow fiber microporous membrane was carried out preliminary treatment 0.5 minute.Under the condition of secluding air, adding the mass percent concentration that vacuumizes expeling oxygen in advance is the acrylic acid aqueous solution 40ml of 2.5wt%, carries out graft polymerization reaction under 60 ℃ then.After reacting 4 hours, film is taken out, in water, soaked 24 hours, in extractor, use acetone extracting 12 hours then, with the homopolymers of removing unreacted monomer and may existing.With the polyolefin hollow fiber microporous membrane vacuum drying of gained, weighing, percent grafting G=2.6%.
The permeability rate of the polyolefin hollow-fibre membrane of handling through present embodiment is 18.57L/m
2Hour.
Embodiment 2
In reactor, place dry polyolefin hollow fiber microporous membrane 0.4g, be evacuated to 50Pa, charge into nitrogen, repeat for several times, guarantee that in the reactor be nitrogen atmosphere, be evacuated to 15Pa again.Reactor being placed between two electrodes of radio-frequency signal generator, is under the 40W condition at discharge power, and the polyolefin hollow fiber microporous membrane was carried out preliminary treatment 5 minutes.Under the condition of secluding air, adding the mass percent concentration that vacuumizes expeling oxygen in advance is the acrylamide aqueous solution 40ml of 5wt%, carries out graft polymerization reaction under 60 ℃ then.After reacting 4 hours, film is taken out, in water, soaked 24 hours, in extractor, use acetone extracting 12 hours then, with the homopolymers of removing unreacted monomer and may existing.With the polyolefin hollow fiber microporous membrane vacuum drying of gained, weighing, percent grafting G=11.7%.
The permeability rate of the polyolefin hollow-fibre membrane of handling through present embodiment is 10.34L/m
2Hour.
Embodiment 3
In reactor, place dry polyolefin hollow fiber microporous membrane 0.4g, be evacuated to 50Pa, charge into air, be evacuated to 15Pa again.Reactor being placed between two electrodes of radio-frequency signal generator, is under the 80W condition at discharge power, and the polyolefin hollow fiber microporous membrane was carried out preliminary treatment 2 minutes.Under the condition of secluding air, adding the mass percent concentration that vacuumizes expeling oxygen in advance is the methacrylic acid hydroxyl ethyl ester aqueous solution 40ml of 5wt%, carries out graft polymerization reaction under 60 ℃ then.After reacting 4 hours, film is taken out, in water, soaked 24 hours, in extractor, use acetone extracting 12 hours then, with the homopolymers of removing unreacted monomer and may existing.With the polyolefin hollow fiber microporous membrane vacuum drying of gained, weighing, percent grafting G=13.4%.
The permeability rate of the polyolefin hollow-fibre membrane of handling through present embodiment is 8.34L/m
2Hour.
Embodiment 4
In reactor, place dry polyolefin hollow fiber microporous membrane 0.4g, be evacuated to 50Pa, charge into argon gas, repeat for several times, guarantee that in the reactor be argon gas atmosphere, be evacuated to 15Pa again.Reactor being placed between two electrodes of radio-frequency signal generator, is under the 80W condition at discharge power, and the polyolefin hollow fiber microporous membrane was carried out preliminary treatment 1 minute.Under the condition of secluding air, adding the mass percent concentration that vacuumizes expeling oxygen in advance is acrylic acid and the acrylamide mixed aqueous solution 40ml of 5wt%, carries out graft polymerization reaction under 60 ℃ then.After reacting 2 hours, film is taken out, in water, soaked 24 hours, in extractor, use acetone extracting 12 hours then, with the homopolymers of removing unreacted monomer and may existing.With the polyolefin hollow fiber microporous membrane vacuum drying of gained, weighing, percent grafting G=6.63%.
The permeability rate of the polyolefin hollow-fibre membrane of handling through present embodiment is 13.78L/m
2Hour.
Claims (7)
1. one kind is carried out the method that modification is handled to the polyolefin hollow fiber microporous membrane, and it is characterized in that: described method may further comprise the steps:
(1) the polyolefin hollow-fibre membrane is put into the reaction of low temperature plasma device and handle, 10～150 watts of discharge powers, plasma gas atmosphere adopts non-polymerization gas;
(2) feed activated monomer solution and carry out graft polymerization reaction, 40～100 ℃ of polymerization temperatures, the volume that wherein adds solution is 50～100ml/g with the ratio of the quality of processed doughnut.
2. method according to claim 1, it is characterized in that: described activated monomer comprises acrylic acid, methacrylic acid, acrylamide, Methacrylamide, N hydroxymethyl acrylamide, Hydroxyethyl Acrylate, methacrylic acid hydroxyl ethyl ester, acrylonitrile, methacrylonitrile, N-vinyl pyrrolidone, sodium vinyl sulfonate, SSS or their any mixture.
3. method as claimed in claim 1 or 2, it is characterized in that: the concentration of described activated monomer solution is 5wt%～20wt%.
4. method according to claim 1, it is characterized in that: described non-polymerization gas is air, nitrogen, oxygen, ammonia or argon gas.
5. method according to claim 1, it is characterized in that: the described Low Temperature Plasma Treating time is 0.5～30 minute.
6. method according to claim 1, it is characterized in that: described polymerization time is 0.5～24 hour.
7. method according to claim 1 is characterized in that: the vacuum during described plasma treatment is 0.01～1 holder.
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| CN 200410000640 CN1640532A (en) | 2004-01-13 | 2004-01-13 | Method for modifying polyolefin hollow fiber microporous membrane |
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| CN 200410000640 CN1640532A (en) | 2004-01-13 | 2004-01-13 | Method for modifying polyolefin hollow fiber microporous membrane |
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Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100430118C (en) * | 2006-12-27 | 2008-11-05 | 南京工业大学 | Method for persistent hydrophilic modification of polypropylene porous membrane surface |
| CN100443151C (en) * | 2006-12-27 | 2008-12-17 | 南京工业大学 | Method for hydrophilic modification of polypropylene porous membrane surface by using amphipathic molecule |
| CN101890314A (en) * | 2010-07-20 | 2010-11-24 | 东华大学 | Surface hydrophilic modification method for polytetrafluoroethylene bulked membrane |
| CN102258947A (en) * | 2011-05-23 | 2011-11-30 | 苏州市新能膜材料科技有限公司 | Lecithin self-assembly cross-linking bionic modified polymer membrane material and preparation method thereof |
| CN102773020A (en) * | 2012-07-18 | 2012-11-14 | 北京理工大学 | Method for wholly chemically grafting membrane component by utilizing remote plasma |
| CN102908916A (en) * | 2012-11-09 | 2013-02-06 | 杭州水处理技术研究开发中心有限公司 | Preparation method of hollow fiber dispersion and dialysis alkali recycling membrane |
| CN102921319A (en) * | 2012-11-09 | 2013-02-13 | 杭州水处理技术研究开发中心有限公司 | Preparation method of hollow fiber diffusion dialysis acid recovery membrane |
| CN102949938A (en) * | 2011-08-18 | 2013-03-06 | 中国科学院化学研究所 | Preparation method of multi-layer composite-structure filter membrane |
| CN103285743A (en) * | 2013-06-28 | 2013-09-11 | 厦门建霖工业有限公司 | Hydrophilization modification method for polyvinyl chloride alloy ultrafiltration membrane |
| CN103933616A (en) * | 2014-03-20 | 2014-07-23 | 北京迪玛克医药科技有限公司 | Method for preparing coating on surface of intervention catheter, intervention catheter and interventional device |
| CN104001224A (en) * | 2014-06-12 | 2014-08-27 | 南京大学 | Low-temperature plasma membrane-type artificial lung modification method |
| CN104744720A (en) * | 2013-12-31 | 2015-07-01 | 吉林师范大学 | Preparation method of polyvinylpyrrolidone grafting modified polyethylene terephthalate film |
| CN105150643A (en) * | 2015-10-22 | 2015-12-16 | 江苏阳光股份有限公司 | Wool/graft modified polytetrafluoroethylene film compound fabrics |
| CN107074654A (en) * | 2014-10-09 | 2017-08-18 | 建筑研究和技术有限公司 | Drawing polyolefin fibers |
| CN109126483A (en) * | 2018-09-30 | 2019-01-04 | 上海恩捷新材料科技有限公司 | A kind of method of polyethene microporous membrane surface hydrophilic modification and the modified polyethylene film formed by it |
| CN114345141A (en) * | 2022-01-06 | 2022-04-15 | 中国科学技术大学 | Super-wettability modified polyolefin porous membrane, preparation method and application |
| CN114345146A (en) * | 2022-01-06 | 2022-04-15 | 中国科学技术大学 | Modified polypropylene oil-water separation membrane and preparation method thereof |
| CN114892400A (en) * | 2021-11-01 | 2022-08-12 | 中国电力科学研究院有限公司 | Material surface treatment device and method |
-
2004
- 2004-01-13 CN CN 200410000640 patent/CN1640532A/en active Pending
Cited By (27)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100443151C (en) * | 2006-12-27 | 2008-12-17 | 南京工业大学 | Method for hydrophilic modification of polypropylene porous membrane surface by using amphipathic molecule |
| CN100430118C (en) * | 2006-12-27 | 2008-11-05 | 南京工业大学 | Method for persistent hydrophilic modification of polypropylene porous membrane surface |
| CN101890314A (en) * | 2010-07-20 | 2010-11-24 | 东华大学 | Surface hydrophilic modification method for polytetrafluoroethylene bulked membrane |
| CN102258947A (en) * | 2011-05-23 | 2011-11-30 | 苏州市新能膜材料科技有限公司 | Lecithin self-assembly cross-linking bionic modified polymer membrane material and preparation method thereof |
| CN102949938A (en) * | 2011-08-18 | 2013-03-06 | 中国科学院化学研究所 | Preparation method of multi-layer composite-structure filter membrane |
| CN102949938B (en) * | 2011-08-18 | 2014-08-13 | 中国科学院化学研究所 | Preparation method of multi-layer composite-structure filter membrane |
| CN102773020A (en) * | 2012-07-18 | 2012-11-14 | 北京理工大学 | Method for wholly chemically grafting membrane component by utilizing remote plasma |
| CN102921319B (en) * | 2012-11-09 | 2015-02-25 | 杭州水处理技术研究开发中心有限公司 | Preparation method of hollow fiber diffusion dialysis acid recovery membrane |
| CN102921319A (en) * | 2012-11-09 | 2013-02-13 | 杭州水处理技术研究开发中心有限公司 | Preparation method of hollow fiber diffusion dialysis acid recovery membrane |
| CN102908916B (en) * | 2012-11-09 | 2015-04-01 | 杭州水处理技术研究开发中心有限公司 | Preparation method of hollow fiber dispersion and dialysis alkali recycling membrane |
| CN102908916A (en) * | 2012-11-09 | 2013-02-06 | 杭州水处理技术研究开发中心有限公司 | Preparation method of hollow fiber dispersion and dialysis alkali recycling membrane |
| CN103285743B (en) * | 2013-06-28 | 2015-03-25 | 厦门建霖工业有限公司 | Hydrophilization modification method for polyvinyl chloride alloy ultrafiltration membrane |
| CN103285743A (en) * | 2013-06-28 | 2013-09-11 | 厦门建霖工业有限公司 | Hydrophilization modification method for polyvinyl chloride alloy ultrafiltration membrane |
| CN104744720A (en) * | 2013-12-31 | 2015-07-01 | 吉林师范大学 | Preparation method of polyvinylpyrrolidone grafting modified polyethylene terephthalate film |
| CN104558658A (en) * | 2014-03-20 | 2015-04-29 | 北京迪玛克医药科技有限公司 | Method for preparing coating on surface of interventional catheter, interventional catheter and interventional device |
| CN103933616A (en) * | 2014-03-20 | 2014-07-23 | 北京迪玛克医药科技有限公司 | Method for preparing coating on surface of intervention catheter, intervention catheter and interventional device |
| CN104558658B (en) * | 2014-03-20 | 2017-11-28 | 北京迪玛克医药科技有限公司 | In the method for interposing catheter surface prepares coating, interposing catheter and intervention apparatus |
| CN104001224A (en) * | 2014-06-12 | 2014-08-27 | 南京大学 | Low-temperature plasma membrane-type artificial lung modification method |
| CN104001224B (en) * | 2014-06-12 | 2016-02-17 | 南京大学 | A kind of low-temperature plasma modified membrane artificial lungs method |
| CN107074654A (en) * | 2014-10-09 | 2017-08-18 | 建筑研究和技术有限公司 | Drawing polyolefin fibers |
| CN105150643A (en) * | 2015-10-22 | 2015-12-16 | 江苏阳光股份有限公司 | Wool/graft modified polytetrafluoroethylene film compound fabrics |
| CN105150643B (en) * | 2015-10-22 | 2017-06-13 | 江苏阳光股份有限公司 | A kind of wool/graft modification poly tetrafluoroethylene composite material |
| CN109126483A (en) * | 2018-09-30 | 2019-01-04 | 上海恩捷新材料科技有限公司 | A kind of method of polyethene microporous membrane surface hydrophilic modification and the modified polyethylene film formed by it |
| CN114892400A (en) * | 2021-11-01 | 2022-08-12 | 中国电力科学研究院有限公司 | Material surface treatment device and method |
| CN114892400B (en) * | 2021-11-01 | 2023-12-26 | 中国电力科学研究院有限公司 | Material surface treatment device and method |
| CN114345141A (en) * | 2022-01-06 | 2022-04-15 | 中国科学技术大学 | Super-wettability modified polyolefin porous membrane, preparation method and application |
| CN114345146A (en) * | 2022-01-06 | 2022-04-15 | 中国科学技术大学 | Modified polypropylene oil-water separation membrane and preparation method thereof |
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