CN102266725A - Polytetrafluoroethylene hollow fiber membrane and preparation method thereof - Google Patents
Polytetrafluoroethylene hollow fiber membrane and preparation method thereof Download PDFInfo
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- CN102266725A CN102266725A CN2011101533226A CN201110153322A CN102266725A CN 102266725 A CN102266725 A CN 102266725A CN 2011101533226 A CN2011101533226 A CN 2011101533226A CN 201110153322 A CN201110153322 A CN 201110153322A CN 102266725 A CN102266725 A CN 102266725A
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Abstract
The invention discloses a polytetrafluoroethylene hollow fiber membrane which comprises polytetrafluoroethylene hollow fibers with a pore size range of 0.5-2 microns and at least one micropore polytetrafluoroethylene membrane layer which is disposed on the external circum-walls of the polytetrafluoroethylene hollow fibers and has a pore size range of 0.02-0.5 microns and a thickness of 5-100 microns. The invention also provides the preparation method of the polytetrafluoroethylene hollow fiber membrane. The polytetrafluoroethylene hollow fiber membrane of the invention has the advantages of small filtration pore size, high filtration accuracy, high porosity, high filtration flux, and high strength.
Description
Technical field
The present invention relates to a kind of method for preparing the polytetrafluoroethylene (PTFE) hollow-fibre membrane, the preparation method of the polytetrafluoroethylene (PTFE) hollow-fibre membrane that especially a kind of aperture is controlled.
Background technology
The main membrane material of production ultra filtration product comprises cellulose acetate, polysulfones, polyether sulfone, polyethylene, polypropylene, polyacrylonitrile, polyvinyl chloride and Kynoar etc. at present.Use amount is bigger comprises polysulfones, polyether sulfone, polyvinyl chloride, polypropylene and Kynoar.The porosity of the hollow-fibre membrane of current these materials lower (below 50%), the less (1kg/cm of filtration flux
2Under the operating pressure, it is following that filtration flux is generally less than 500L/m2h), energy consumption is higher.Simultaneously, the hollow-fibre membrane of these materials adopts the phase inversion preparation mostly, and film silk intensity height in use, the fracture of wire phenomenon occurs easily.Polytetrafluoroethylmaterial material has acid and alkali-resistance, high-low temperature resistant, corrosion-resistant, anti-oxidant, advantage such as skin-friction coefficient is low, have the title of " plastics king ".Adopt polytetrafluoroethylene (PTFE) hollow-fibre membrane paste-extruded and the expanded method preparation that stretches to have characteristics such as porosity is big, flux is high, good toughness, intensity height, can be applied in various filtration occasions, and life of product is longer, contamination resistance is higher, and product physicochemical property and operation energy consumption etc. all have obvious advantages.But only the aperture of the polytetrafluoroethylene (PTFE) hollow-fibre membrane by stretching expansion method preparation is bigger, generally more than 0.5 μ m, and the lower (0.5kg/cm of bubble point
2), can not adapt to the requirement that high accuracy is separated and filtered.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of polytetrafluoroethylene (PTFE) hollow-fibre membrane, and it has, and pore size filter is little, filtering accuracy is high, high porosity, high filtration flux, high-intensity advantage.
For solving the problems of the technologies described above, the present invention adopts following technical scheme, a kind of polytetrafluoroethylene (PTFE) hollow-fibre membrane is characterized in that: comprise that pore diameter range is the polytetrafluoroethylene (PTFE) doughnut of 0.5-2 μ m and is located at the pore diameter range of one deck at least 0.02-0.5 μ m on the polytetrafluoroethylene (PTFE) doughnut external annulus, the microporous poly tetrafluoroethylene layer of thickness 5-100 μ m.
Preferably, described microporous poly tetrafluoroethylene layer is to be that the microporous poly tetrafluoroethylene looping band looping of 3～20mm forms at polytetrafluoroethylene (PTFE) doughnut external annulus by the width that the expanded microporous polytetra fluoroethylene-EPTEE flat sheet membrane cuts into.
Preferably, the described looping number of plies is 1～5 layer.
Preferably, the heat treatment under 270-300 ℃ of temperature of described microporous poly tetrafluoroethylene layer is coated on polytetrafluoroethylene (PTFE) doughnut external annulus.
The present invention also provides the preparation method of above-mentioned polytetrafluoroethylene (PTFE) hollow-fibre membrane, it is characterized in that comprising the steps:
(1) cut the expanded microporous polytetra fluoroethylene-EPTEE flat sheet membrane of pore diameter range 0.02-0.5 μ m, thickness 5-100 μ m, obtaining width is the microporous poly tetrafluoroethylene looping band of 3-20mm;
(2) be perfluoroethylene-propylene (FEP) aqueous dispersions of 10-50% with microporous poly tetrafluoroethylene looping band dipping solid content;
(3) the microporous poly tetrafluoroethylene looping band looping after will flooding is a 0.5-2 μ m polytetrafluoroethylene (PTFE) doughnut external annulus at pore diameter range, the looping number of plies is 1～5 layer, heat treatment 5-10s under 270-300 ℃ of temperature obtains the controlled polytetrafluoroethylene (PTFE) hollow-fibre membrane in aperture then.
Certainly, under some specific versions, the expanded microporous polytetra fluoroethylene-EPTEE flat sheet membrane also can consider not cut into microporous poly tetrafluoroethylene looping band, but direct looping is at polytetrafluoroethylene (PTFE) doughnut external annulus, be the preparation method of above-mentioned polytetrafluoroethylene (PTFE) hollow-fibre membrane, it is characterized in that comprising the steps:
1) be perfluoroethylene-propylene (FEP) aqueous dispersions of 10-50% with expanded microporous polytetra fluoroethylene-EPTEE flat sheet membrane dipping solid content;
(2) to be coated on pore diameter range be 0.5-2 μ m polytetrafluoroethylene (PTFE) doughnut external annulus to the expanded microporous polytetra fluoroethylene-EPTEE flat sheet membrane after will flooding, the looping number of plies is 1～5 layer, heat treatment 5-10s under 270-300 ℃ of temperature obtains the controlled polytetrafluoroethylene (PTFE) hollow-fibre membrane in aperture then.
Above-mentioned pore diameter range is that 0.5-2 μ m polytetrafluoroethylene (PTFE) doughnut can adopt Chinese patent (application number 201010185858.1) and Chinese patent (application number: 201010508798.2) described method preparation; The expanded microporous polytetra fluoroethylene-EPTEE flat sheet membrane of pore diameter range 0.02-0.5 μ m, thickness 5-100 μ m adopts simple tension microporous poly tetrafluoroethylene or biaxial tension microporous teflon membran, can adopt satisfactory commercially available prod, step on a day fluorine Materials Co., Ltd product as Ningbo.Cutting of expanded microporous polytetra fluoroethylene-EPTEE flat sheet membrane can adopt the commercially available machinery of cutting to cut, and the looping of expanded microporous polytetra fluoroethylene-EPTEE flat sheet membrane can adopt satisfactory commercially available looping equipment to carry out looping.The perfluoroethylene-propylene that is adopted (FEP) aqueous dispersions can adopt the Related product of du pont company, Daikin company and hugeization of Zhejiang group.
The invention has the beneficial effects as follows:
(1) dwindles the pore size filter of polytetrafluoroethylene (PTFE) hollow-fibre membrane, improved the filtering accuracy of polytetrafluoroethylene (PTFE) hollow-fibre membrane;
(2) the microporous poly tetrafluoroethylene layer of preparing has high porosity (greater than 60%), high filtration flux (1kg/cm
2Filtration flux is greater than 2000L/m2h under the operating pressure), the advantage of high strength (150N/ root).
(3) preparation method is simple, and cost is low.
Description of drawings
The present invention is described further below in conjunction with accompanying drawing:
Fig. 1 is the structural representation of polytetrafluoroethylene (PTFE) hollow-fibre membrane of the present invention.
The specific embodiment
As Fig. 1, a kind of polytetrafluoroethylene (PTFE) hollow-fibre membrane of the present invention, comprise that pore diameter range is the polytetrafluoroethylene (PTFE) doughnut 1 of 0.5-2 μ m and is located at one deck pore diameter range 0.02-0.5 μ m on the polytetrafluoroethylene (PTFE) doughnut external annulus, the microporous poly tetrafluoroethylene layer 2 of thickness 5-100 μ m, described microporous poly tetrafluoroethylene layer by width be the microporous poly tetrafluoroethylene looping band looping of 3～20mm at polytetrafluoroethylene (PTFE) doughnut external annulus, described microporous poly tetrafluoroethylene layer heat treatment bag under 270-300 ℃ of temperature is connected on polytetrafluoroethylene (PTFE) doughnut external annulus.Above-mentioned microporous poly tetrafluoroethylene layer also can be selected 2～5 layers or more multi-layered.
Illustrate the preparation method of polytetrafluoroethylene (PTFE) hollow-fibre membrane of the present invention below:
(1) cut the polytetrafluoroethylene (PTFE) flat sheet membrane of aperture 0.02 μ m, thickness 5 μ m, obtaining width is the microporous poly tetrafluoroethylene looping band of 3mm;
(2) with microporous poly tetrafluoroethylene looping band dipping solid content be 10% perfluoroethylene-propylene (FEP) aqueous dispersions;
(3) the microporous poly tetrafluoroethylene looping band looping after will flooding is 0.5 μ m in the aperture, internal diameter 1mm, and the polytetrafluoroethylene (PTFE) doughnut external annulus of external diameter 1.8mm, looping one deck, heat treatment 10s under 270 ℃ of temperature then, obtaining bubble point is 5kg/cm
2, 1kg/cm
2Flux is the polytetrafluoroethylene (PTFE) hollow-fibre membrane of 2000L/m2h under the operating pressure.
(1) cut the polytetrafluoroethylene (PTFE) flat sheet membrane of aperture 0.1 μ m, thickness 20 μ m, obtaining width is the microporous poly tetrafluoroethylene looping band of 10mm;
(2) with microporous poly tetrafluoroethylene looping band dipping solid content be 20% perfluoroethylene-propylene (FEP) aqueous dispersions;
(3) the microporous poly tetrafluoroethylene looping band looping after will flooding is 1.0 μ m in the aperture, internal diameter 2mm, and external diameter 2.8mm polytetrafluoroethylene (PTFE) doughnut external annulus, looping is two-layer, heat treatment 5s under 285 ℃ of temperature then, obtaining bubble point is 2kg/cm
2, 1kg/cm
2Flux is the polytetrafluoroethylene (PTFE) hollow-fibre membrane of 3500L/m2h under the operating pressure.
Embodiment 3
(1) cut the polytetrafluoroethylene (PTFE) flat sheet membrane of aperture 0.5 μ m, thickness 100 μ m, obtaining width is the microporous poly tetrafluoroethylene looping band of 20mm;
(2) with expanded microporous polytetra fluoroethylene-EPTEE flat sheet membrane looping band dipping solid content be 50% perfluoroethylene-propylene (FEP) aqueous dispersions;
(3) the microporous poly tetrafluoroethylene looping band looping after will flooding is 2 μ m at pore diameter range, internal diameter 3mm, and external diameter 4mm polytetrafluoroethylene (PTFE) doughnut external annulus, five layers of loopings, heat treatment 8s under 300 ℃ of temperature then, obtaining bubble point is 1.5kg/cm
2, 1kg/cm
2Flux is the polytetrafluoroethylene (PTFE) hollow-fibre membrane of 5000L/m2h under the operating pressure.
Provide the specific embodiment of patent of the present invention above, embodiment is only in order to illustrate this patent as implementing, and any variation without prejudice to this patent principle is all in this patent protection domain.
Claims (6)
1. a polytetrafluoroethylene (PTFE) hollow-fibre membrane is characterized in that: comprise that pore diameter range is the dull and stereotyped rete of the polytetrafluoroethylene (PTFE) doughnut of 0.5-2 μ m and the expanded microporous polytetra fluoroethylene-EPTEE that is located at the pore diameter range of one deck at least 0.02-0.5 μ m, thickness 5-100 μ m on the polytetrafluoroethylene (PTFE) doughnut external annulus.
2. polytetrafluoroethylene (PTFE) hollow-fibre membrane according to claim 1 is characterized in that: the dull and stereotyped rete of described expanded microporous polytetra fluoroethylene-EPTEE is to be that the expanded microporous polytetra fluoroethylene-EPTEE flat sheet membrane looping band looping of 3～20mm forms at polytetrafluoroethylene (PTFE) doughnut external annulus by the width that the expanded microporous polytetra fluoroethylene-EPTEE flat sheet membrane cuts into.
3. polytetrafluoroethylene (PTFE) hollow-fibre membrane according to claim 2 is characterized in that: the described looping number of plies is 1～5 layer.
4. according to claim 1 or 2 or 3 described polytetrafluoroethylene (PTFE) hollow-fibre membranes, it is characterized in that: the dull and stereotyped rete of described expanded microporous polytetra fluoroethylene-EPTEE heat treatment bag under 270-300 ℃ of temperature is connected on polytetrafluoroethylene (PTFE) doughnut external annulus.
5. the preparation method of a polytetrafluoroethylene (PTFE) hollow-fibre membrane is characterized in that comprising the steps:
(1) cut the expanded microporous polytetra fluoroethylene-EPTEE flat sheet membrane of pore diameter range 0.02-0.5 μ m, thickness 5-100 μ m, obtaining width is the microporous poly tetrafluoroethylene looping band of 3-20mm;
(2) be perfluoroethylene-propylene (FEP) aqueous dispersions of 10-50% with microporous poly tetrafluoroethylene looping band dipping solid content;
(3) the microporous poly tetrafluoroethylene looping band looping after will flooding is a 0.5-2 μ m polytetrafluoroethylene (PTFE) doughnut external annulus at pore diameter range, the looping number of plies is 1～5 layer, heat treatment 5-10s under 270-300 ℃ of temperature obtains the controlled polytetrafluoroethylene (PTFE) hollow-fibre membrane in aperture then.
6. the preparation method of a polytetrafluoroethylene (PTFE) hollow-fibre membrane is characterized in that comprising the steps:
(1) be perfluoroethylene-propylene (FEP) aqueous dispersions of 10-50% with expanded microporous polytetra fluoroethylene-EPTEE flat sheet membrane dipping solid content;
(2) to be coated on pore diameter range be 0.5-2 μ m polytetrafluoroethylene (PTFE) doughnut external annulus to the expanded microporous polytetra fluoroethylene-EPTEE flat sheet membrane after will flooding, the looping number of plies is 1～5 layer, heat treatment 5-10s under 270-300 ℃ of temperature obtains the controlled polytetrafluoroethylene (PTFE) hollow-fibre membrane in aperture then.
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|---|---|---|---|---|
| CN102941025A (en) * | 2012-11-20 | 2013-02-27 | 浙江理工大学 | Preparation method of teflon hollow fiber membrane for membrane distillation |
| CN103007788A (en) * | 2012-12-17 | 2013-04-03 | 浙江理工大学 | Preparation method of wrapped polytetrafluoroethylene ultra-micro filter tube membrane |
| CN103386261A (en) * | 2013-07-03 | 2013-11-13 | 浙江理工大学 | Super hydrophobic polytetrafluoroethylene hollow fiber membrane preparation method |
| CN105664733A (en) * | 2016-01-21 | 2016-06-15 | 巨化集团技术中心 | Preparation method of perfluoro hollow fiber composite film |
| WO2017080456A1 (en) * | 2015-11-11 | 2017-05-18 | 重庆润泽医药有限公司 | Polytetrafluoroethylene ultrafine hollow fiber membrane |
| WO2017080457A1 (en) * | 2015-11-11 | 2017-05-18 | 重庆润泽医药有限公司 | Polytetrafluoroethylene hollow fiber membrane |
| CN106807248A (en) * | 2017-03-23 | 2017-06-09 | 长江大学 | A kind of antipollution hollow-fibre membrane and its manufacture method |
| CN107576546A (en) * | 2017-10-23 | 2018-01-12 | 攀钢集团攀枝花钢铁研究院有限公司 | A kind of decomposition method of continuous casting covering slag and the assay method of free carbon |
| CN107764622A (en) * | 2017-10-23 | 2018-03-06 | 攀钢集团攀枝花钢铁研究院有限公司 | A kind of filter method of the decomposed solution of continuous casting covering slag |
| CN109529639A (en) * | 2018-11-05 | 2019-03-29 | 宁波水艺膜科技发展有限公司 | The preparation method of high bond strength polytetrafluoroethylhollow hollow fiber membrane |
| CN109529640A (en) * | 2018-11-05 | 2019-03-29 | 宁波水艺膜科技发展有限公司 | The preparation method of low-temperature sintering polytetrafluoroethylhollow hollow fiber membrane |
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| CN109550411A (en) * | 2018-12-13 | 2019-04-02 | 宁波水艺膜科技发展有限公司 | A kind of polytetrafluoroethylhollow hollow fiber composite membrane and low temperature looping preparation method |
| CN111111471A (en) * | 2020-01-14 | 2020-05-08 | 浙江开创环保科技股份有限公司 | PTFE hollow fiber composite membrane with high peel strength and preparation method thereof |
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| CN202129031U (en) * | 2011-06-09 | 2012-02-01 | 浙江东大环境工程有限公司 | Wrapped type polytetrafluoroethylene hollow fiber membrane |
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| CN101642681A (en) * | 2008-08-04 | 2010-02-10 | 中国科学院生态环境研究中心 | Surface coating modification and flattened membrane component for glass fiber woven pipe |
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Cited By (19)
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| CN102941025A (en) * | 2012-11-20 | 2013-02-27 | 浙江理工大学 | Preparation method of teflon hollow fiber membrane for membrane distillation |
| CN103007788A (en) * | 2012-12-17 | 2013-04-03 | 浙江理工大学 | Preparation method of wrapped polytetrafluoroethylene ultra-micro filter tube membrane |
| CN103007788B (en) * | 2012-12-17 | 2014-11-12 | 浙江理工大学 | Preparation method of wrapped polytetrafluoroethylene ultra-micro filter tube membrane |
| CN103386261A (en) * | 2013-07-03 | 2013-11-13 | 浙江理工大学 | Super hydrophobic polytetrafluoroethylene hollow fiber membrane preparation method |
| CN103386261B (en) * | 2013-07-03 | 2014-12-31 | 浙江理工大学 | Super hydrophobic polytetrafluoroethylene hollow fiber membrane preparation method |
| WO2017080456A1 (en) * | 2015-11-11 | 2017-05-18 | 重庆润泽医药有限公司 | Polytetrafluoroethylene ultrafine hollow fiber membrane |
| WO2017080457A1 (en) * | 2015-11-11 | 2017-05-18 | 重庆润泽医药有限公司 | Polytetrafluoroethylene hollow fiber membrane |
| CN105664733B (en) * | 2016-01-21 | 2019-08-02 | 巨化集团技术中心 | A kind of preparation method of perfluor hollow fiber composite membrane |
| CN105664733A (en) * | 2016-01-21 | 2016-06-15 | 巨化集团技术中心 | Preparation method of perfluoro hollow fiber composite film |
| CN106807248A (en) * | 2017-03-23 | 2017-06-09 | 长江大学 | A kind of antipollution hollow-fibre membrane and its manufacture method |
| CN107764622A (en) * | 2017-10-23 | 2018-03-06 | 攀钢集团攀枝花钢铁研究院有限公司 | A kind of filter method of the decomposed solution of continuous casting covering slag |
| CN107576546A (en) * | 2017-10-23 | 2018-01-12 | 攀钢集团攀枝花钢铁研究院有限公司 | A kind of decomposition method of continuous casting covering slag and the assay method of free carbon |
| CN109529639A (en) * | 2018-11-05 | 2019-03-29 | 宁波水艺膜科技发展有限公司 | The preparation method of high bond strength polytetrafluoroethylhollow hollow fiber membrane |
| CN109529640A (en) * | 2018-11-05 | 2019-03-29 | 宁波水艺膜科技发展有限公司 | The preparation method of low-temperature sintering polytetrafluoroethylhollow hollow fiber membrane |
| CN109529639B (en) * | 2018-11-05 | 2021-08-17 | 宁波水艺膜科技发展有限公司 | Preparation method of polytetrafluoroethylene hollow fiber membrane with high bonding strength |
| CN109550410A (en) * | 2018-12-13 | 2019-04-02 | 宁波水艺膜科技发展有限公司 | A kind of polytetrafluoroethylhollow hollow fiber membrane and manufacturing method |
| CN109550411A (en) * | 2018-12-13 | 2019-04-02 | 宁波水艺膜科技发展有限公司 | A kind of polytetrafluoroethylhollow hollow fiber composite membrane and low temperature looping preparation method |
| CN111111471A (en) * | 2020-01-14 | 2020-05-08 | 浙江开创环保科技股份有限公司 | PTFE hollow fiber composite membrane with high peel strength and preparation method thereof |
| CN111359442A (en) * | 2020-03-16 | 2020-07-03 | 中国科学院宁波材料技术与工程研究所 | PTFE composite membrane for MABR and preparation method thereof |
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Application publication date: 20111207 |