CN100337730C - Process for preparing structure symmetric polyether sulfone hydrophilic porous film - Google Patents
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- CN100337730C CN100337730C CNB2005100612418A CN200510061241A CN100337730C CN 100337730 C CN100337730 C CN 100337730C CN B2005100612418 A CNB2005100612418 A CN B2005100612418A CN 200510061241 A CN200510061241 A CN 200510061241A CN 100337730 C CN100337730 C CN 100337730C
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- 229920006393 polyether sulfone Polymers 0.000 title claims abstract description 77
- 239000004695 Polyether sulfone Substances 0.000 title claims abstract description 64
- 238000004519 manufacturing process Methods 0.000 title description 2
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 30
- 239000000203 mixture Substances 0.000 claims description 28
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 25
- 239000002904 solvent Substances 0.000 claims description 24
- 239000012982 microporous membrane Substances 0.000 claims description 23
- 239000007788 liquid Substances 0.000 claims description 21
- 238000002791 soaking Methods 0.000 claims description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 239000002562 thickening agent Substances 0.000 claims description 12
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 10
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 10
- 239000000654 additive Substances 0.000 claims description 10
- 230000000996 additive effect Effects 0.000 claims description 10
- 230000004888 barrier function Effects 0.000 claims description 10
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 8
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 7
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000000470 constituent Substances 0.000 claims description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 5
- 235000011187 glycerol Nutrition 0.000 claims description 4
- 238000006277 sulfonation reaction Methods 0.000 claims description 4
- DQYBDCGIPTYXML-UHFFFAOYSA-N ethoxyethane;hydrate Chemical compound O.CCOCC DQYBDCGIPTYXML-UHFFFAOYSA-N 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
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- 229910001220 stainless steel Inorganic materials 0.000 description 9
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
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- Separation Using Semi-Permeable Membranes (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The present invention relates to a preparation method for a polymer microporous film, which aims to provide a preparation method for a structurally-symmetrical hydrophilic microfiltration flat-plate film with polyethersulfone. The method provided by the present invention comprises the following procedures of preparation of a polyethersulfone microporous film casting solution, striking of primary solution film on a flat-plate carrier, partial gelation in a first coagulating bath, complete gelation in a second coagulating bath and water washing. The polyethersulfone microporous film prepared by the method provided by the present invention has a symmetrical structure, hydrophilicity and temperature tolerance. The pore diameter can be regulated between 0.5 mum and 10 mum. The film is especially suitable for being used as medical film materials.
Description
Technical field
The present invention relates to a kind of preparation method of polymer microporous film, the preparation method of the hydrophilic micro-filtering flat plate film of a kind of symmetrical structure polyether sulfone is provided particularly.
Background technology
Membrane separation technique is a kind of isolation technics of rising, and has high efficiency, low energy consumption, easily and advantage such as other technologies are integrated, is representing the developing direction of isolation technics.The core of membrane separation technique is the film with centrifugation.Ascending according to the aperture, diffusion barrier is divided into reverse osmosis membrane, NF membrane, milipore filter and micro-filtration membrane etc. successively, and wherein the microporous barrier (be micro-filtration membrane) of aperture more than 0.1 μ m is the film kind that application surface is the widest, use amount is maximum.Because the micro-pore-film filtration technology has advantages such as using method is simple, quick, energy-efficient, has great application value in fields such as oil, chemical industry, medicine/medical treatment, chemical industry, electronics, the energy and environmental protection.In decades, the micro-pore-film filtration technology progressively replaces or has promoted a lot of traditional separation, process for purifying, as: in beer clarification filters, replace original cardboard strainer, improved the limpid degree of beer; In air sterilization, replace original cotton, active carbon packed column, guaranteed bacteria-eliminating efficacy; In pharmacy, chemical industry, replace traditional distillation technique, realized concentrating under the low temperature and separating; Be used for fermentation and wastewater treatment with bioreactor in conjunction with the technology that the realization microorganism separates; Be used as lithium ion battery separator; Be used for infusion treatment herb liquid filtration etc.
From the kind of material, microporous barrier has inoranic membrane and organic polymer films two big classes, and the former characteristics are heatproof, good hydrophilic property, are difficult for polluting, but the preparation cost height; The latter's mainly is that material has nylon, cellulose, polysulfones, Kynoar, polyester etc., and characteristics are that preparation cost is low, and temperature tolerance is poor, the problem of hydrophily difference genetic system but exist.Simultaneously, the organic polymer microporous barrier mostly is the phase inversion preparation, the characteristics of existing phase inversion cause the hole when the polymer film of the macroporous structure of preparation aperture more than 1.0 μ m, symmetric being not easy of micropore size and film inner structure controlled in the film, most films are the different anisotropic membrane of film two sides hole size, and then have limited some important application of organic polymer microporous barrier.
Polyether sulfone (PES) claim Poly-s 179 or polyether sulphone again, have the rigidity of phenyl ring, the flexibility of ether and the big conjugated system of sulfuryl and the formation of total unit in the strand simultaneously, have characteristics such as intensity height, heatproof (can use more than 180 ℃), anti-combustion, radiation hardness, antiacid, anti-oxidant, anti-solvent, bio-compatible, be a kind of polymeric material of excellent combination property, also more and more be subject to people's attention as separation membrane material in recent years.Preparation polyethersulfone separating membrane preparation method mainly is a phase inversion.Existing report has: Chinese patent 000125306 discloses a kind of preparation method of sulfonated polyether sulfone filtering film, and the molecular cut off that obtains film is 300～1000; Chinese patent 01139267.3 discloses the manufacture method of blend polyethersulfone doughnut dialysis membrane; Chinese patent 03130557.1 discloses the preparation method of polyether sulfone Hollow Fiber Ultrafiltration or dialysis membrane; United States Patent (USP) 5,869,174,4,629,563 and 4,774,039 has announced the method for the highly asymmetric poly (ether sulfone) film of preparation.Comprehensively it seems, have three outstanding features in these existing reports, the one, the method that adopts all is that the phase inversion that liquid film solidifies is finished in a step gelation, promptly just obtains solid-state poly (ether sulfone) film from nascent liquid film, the gelation of warp a coagulation bath; The 2nd, these films have unsymmetric structure, and a side surface of film is a layer dense layer surface, is macroporous structure on the opposite side surface, is used for super rate film and dialysis membrane more; The 3rd, hole path is mainly shape finger-hole structure in the film.Recently, United States Patent (USP) 6,056,903 have announced the preparation method of symmetrical configuration microporous membrane of polyethersulfone, but what adopt is that fatty alcohol and aqueous mixtures solution with 2～20 carbon is unique coagulating bath, the phase inversion of the once gelation curing that core still is, and obtain poly (ether sulfone) film and be still hydrophobicity.Separate with medical filtration etc. in order to satisfy water treatment, pharmacy, medical precision infusion set, the needs of membrane separation technique in the field of purification, the inventor obtains a kind of two-step gelation inversion of phases method for preparing symmetrical configuration, hydrophilic polyethersulfone microporous barrier on the basis of system test and result of study.
Summary of the invention
The objective of the invention is to overcome deficiency of the prior art, a kind of preparation method of symmetrical configuration hydrophilic polyethersulfone microporous barrier be provided, may further comprise the steps:
(1), after 20～100 ℃ stirring was dissolved in 10～30 hours down, in solution, slowly drips additive, again in the lasting down stirring of uniform temp 10～30 hours with polyether sulfone, hydrophilizing agent, thickener and solvent; Cool to room temperature, deaeration is 1～30 hour in a vacuum, obtains being used to prepare the casting solution of microporous membrane of polyethersulfone; Each component composition and each component mass percent in casting solution is:
Polyether sulfone: molecular weight is 2 * 10
4～5 * 10
5, 8～18%;
Hydrophilizing agent: sulfonation degree is 5～10% sulfonated polyether sulfone, 0.5～5%;
Thickener: molecular weight is 2 * 10
3～2 * 10
6Polyvinylpyrrolidone or polyethylene glycol wherein at least a, 1～7%;
Solvent: N, N '-dimethylacetylamide, N, N '-dimethyl formamide or N-methyl pyrrolidone wherein any one, 65～90%;
Additive: water, glycerine, ethylene glycol or diethylene glycol ether wherein any one, 1～10%;
More than each constituent content sum equal 100%;
(2) 10～70 ℃ casting solution is spread to the thick nascent liquid film of 100～600 μ m on dull and stereotyped carrier, and be that 10～40 ℃, relative humidity are to stop 5～60 seconds in 40～90% the air in temperature;
(3) the nascent liquid film on the dull and stereotyped carrier is immersed in 10～60 ℃ first coagulating bath and carry out partial gelization in 5～60 seconds; Described first coagulating bath is the mixed liquid that two kinds of components are formed, and the composition of each component and mass concentration are:
First component: N, N '-dimethylacetylamide, N, N '-dimethyl formamide or N-methyl pyrrolidone wherein any one with casting solution in identical solvent, 50～90%;
Second component: water or ethylene glycol wherein any one, 10～50%;
(4) liquid film of partial gelization is immersed 10～50 ℃ second coagulating bath abundant gelation in 50～180 seconds and obtain solid film; The composition of described second each component of coagulating bath and mass concentration are:
First component: N, N '-dimethylacetylamide, N, N '-dimethyl formamide or N-methyl pyrrolidone wherein any one with casting solution in identical solvent, 0～30%;
Second component: surfactant dodecyl sodium sulfate, 0～0.05%;
The 3rd component: water, 70～100%;
(5) the solid-state poly (ether sulfone) film after the abundant gelation is dry after 24～72 hours through 10～60 ℃ soaking and water washing.
As a kind of improvement of the present invention, the solid-state poly (ether sulfone) film after the described gelation also comprises the step that the 0.2～0.6wt% aqueous sodium hypochlorite solution that uses 10～60 ℃ soaked 24～72 hours before soaking and water washing.
As a kind of improvement of the present invention, described aqueous sodium hypochlorite solution concentration is 0.3～0.5wt%, and soaking temperature is 40～50 ℃, and soak time is 40～50 hours; The temperature of soaking and water washing is 20～50 ℃, and the time is 40～50 hours; Baking temperature is controlled at below 80 ℃.
As a kind of improvement of the present invention, the consisting of of described first coagulating bath: first component is N, N '-dimethylacetylamide or N, and N '-dimethyl formamide is any one solvent wherein, with the second component water or the ethylene glycol mixed liquor of any one composition wherein; Wherein the mass content of first component solvent is 65%～85%; The temperature of first coagulating bath is 20～40 ℃; The time of part gelation is 10～40 seconds in first coagulating bath.
As a kind of improvement of the present invention, described second coagulating bath consist of N, the mixed liquor that N '-dimethylacetylamide, dodecyl sodium sulfate and water are formed, N wherein, the mass content of N '-dimethylacetylamide is 10～20%; The mass content of dodecyl sodium sulfate is 0.02～0.03%; The temperature of second coagulating bath is 20～40 ℃; Fully the time of gelation is 80～120 seconds in second coagulating bath.
As a kind of improvement of the present invention, each the component composition and the mass concentration of described preparation casting solution are:
Polyether sulfone concentration: 12～16%;
Sulfonated polyether sulfone concentration: 1～3%;
Thickener: molecular weight 5 * 10
4～2 * 10
5Polyvinylpyrrolidone, concentration 3～6%;
Solvent: N, N '-dimethylacetylamide, concentration 75～85%;
Additive: water or diethylene glycol ether, concentration 2-6%;
More than each constituent content sum equal 100%.
As a kind of improvement of the present invention, described casting solution temperature is 20～40 ℃; Described dull and stereotyped carrier is a corrosion resistant plate; When stopping in air, air themperature is 20～30 ℃, and relative humidity is 55～85%, and the time of staying is 10～35 seconds.
As a kind of improvement of the present invention, after the described casting solution preparation, also comprise the step that casting solution is filtered.
The invention has the beneficial effects as follows:
A gelation different from the past prepares the method for poly (ether sulfone) film, the present invention is to provide a kind of two-step gelation inversion of phases method, obtain microporous membrane of polyethersulfone and have symmetrical structure, having solved existing phase inversion, to prepare microporous barrier be the problem that unsymmetric structure, cortex influence flux.
Again, a kind of two-step gelation inversion of phases method that provides among the present invention, obtaining microporous membrane of polyethersulfone inner is spongy intercommunicating pore structure, have voidage high in, still have higher intensity, the microporous membrane of polyethersulfone inside that is different from existing phase inversion preparation is the finger-like pore structure, and intensity is low.
Again, in method provided by the invention, composition by adjusting casting solution, first coagulating bath and second coagulating bath and temperature and the aerial time of staying of nascent liquid film can be prepared the microporous membrane of polyethersulfone at 0.5～10 μ m of pore size.
Again, in the method provided by the invention, adopting sulfonated polyether sulfone is hydrophilizing agent and polyether sulfone blend in casting solution, can be by realizing the hydrophiling of microporous membrane of polyethersulfone in the preparation process simultaneously, and hydrophilic modification efficient height, cost are low; Simultaneously, because sulfonated polyether sulfone is non-water-soluble polymer, it is nonvolatil making the hydrophily that obtains microporous membrane of polyethersulfone.
Again, in the method provided by the invention, solid-state poly (ether sulfone) film is after aqueous sodium hypochlorite solution is handled, and the flux of film can further improve, and pore structure does not have significant change.
Synthetically, the microporous membrane of polyethersulfone by the invention provides the method preparation has symmetrical configuration, hydrophily and temperature tolerance, and the aperture can be adjusted between 0.5～10 μ m, especially is fit to be used as medical film material.
The specific embodiment
The preparation method of a kind of symmetrical configuration hydrophilic polyethersulfone microporous barrier provided by the invention is made up of five steps, and the specific embodiment of each step is followed successively by:
1) casting solution preparation:, stir dissolving in 20～50 hours down at 20～100 ℃ with polyether sulfone, sulfonated polyether sulfone, thickener, additive and solvent; Cool to room temperature, deaeration is 1～30 hour in a vacuum, obtains being used to prepare the casting solution of microporous membrane of polyethersulfone.
The specification of each composition and mass concentration are in the casting solution: polyether sulfone (PES): molecular weight is 2 * 10
4～5 * 10
5, 8～18%; Sulfonation degree is the sulfonated polyether sulfone (SPES) of 5-10%: 0.5～5%; Thickener: molecular weight is 2 * 10
3～2 * 10
6Polyvinylpyrrolidone (PVP) or polyethylene glycol (PEG) or both mixtures, 1～7%; Additive: water, glycerine, ethylene glycol or diethylene glycol ether, 1～10%; Solvent: N, N '-dimethylacetylamide (DMAC), N, N '-dimethyl formamide (DMF) or N-methyl pyrrolidone (NMP), 65～90%.
Wherein optimum condition is: PES concentration: 12～16%; SPES concentration: 1～3%; Thickener: molecular weight is 5 * 10
4～2 * 10
5PVP, concentration 3-6%; Solvent: DMAC, concentration 75～85%; Additive: water or diethylene glycol ether, concentration 2-6%.
The temperature and the mixing time of preparation casting solution operation reach fully with casting solution and evenly to be as the criterion.The vacuum outgas time, air is as the criterion in the casting solution fully to remove.
2) the nascent liquid film of striking and in air prevapourising: 10～70 ℃ casting solutions are spread to the nascent liquid film that thickness is 100～600 μ m on dull and stereotyped carriers such as glass, stainless steel or polyester, and are that 10～40 ℃, relative humidity are to stop 5～60 seconds in 40～90% the air in temperature.
Wherein optimum condition is: casting solution: 20～40 ℃; Carrier: stainless steel; Air themperature: 20～30 ℃; Relative air humidity: 55～85%; The time of staying: 5～35 seconds.
Wherein, the thickness of nascent liquid film depends on the thickness of last solid-state microporous membrane of polyethersulfone, and the degree of depth control of the scraper edge of a knife is arranged, and nascent liquid film optimum thickness is 200～400 μ m.To the inhomogeneity influence of poly (ether sulfone) film with eliminate pin hole, preparation liquid need be carried out suitable filtration for preventing in the casting solution very much not dissolved particles.
3) gelation for the first time: carry out partial gelization in 5～60 seconds with immersing in 10～60 ℃ first coagulating bath through the nascent liquid film that in air, stops on the carrier.Consisting of of coagulating bath: the mixed liquor that solvent DMAC, DMF or NMP and the second component water or ethylene glycol are formed, wherein the mass content of solvent is 50～90%.
Optimum condition: solvent DMAC or DMF, 65%～85%; Second component: ethylene glycol or water: 15～35%; Temperature: 20～40 ℃; Time: 10～40 seconds.
4. gelation for the second time: the second coagulating bath abundant gelation in 50～180 seconds with immerse 10～50 ℃ on the carrier through the nascent liquid film of first coagulating bath, partial gelization obtains solid-state poly (ether sulfone) film.The second coagulating bath composition: solvent DMAC, DMF or NMP, and water and surfactant dodecyl sodium sulfate (TOSN
a) mixture formed.Each constituent concentration wherein: solvent: 0～30%; Water: 70～100%; Dodecyl sodium sulfate: 0～0.05%.
Optimum condition: solvent: DMAC, 10～20%; Water: 80～90%; Dodecyl sodium sulfate: 20～40 ℃ of 0.02～0.03% temperature; The immersion time: 80～120 seconds.
5) solid film post processing: will be through gelation for the second time, the poly (ether sulfone) film that solidifies and peel off from carrier fully, dry through soaking in 24～72 hours, 10～60 ℃ the water soaking and washing 24～72 backs in 0.2～0.6wt% clorox (NaClO) aqueous solution of 10～60 ℃ successively.Optimum condition is: 40～50 ℃, concentration are to soak in 0.3～0.5wt% aqueous sodium hypochlorite solution 40～50 hours; Soaked 40～50 hours in 40～50 ℃ of water; Drying condition without limits, but temperature is below 80 ℃.
In described preparation method,, can prepare the different microporous membrane of polyethersulfone of pore size by adjusting composition and the temperature and the aerial time of staying of nascent liquid film of casting solution, first coagulating bath and second coagulating bath.The important method of controlling diaphragm pore size is: during the big microporous membrane of polyethersulfone in preparation aperture, and thickener and content of additive in the casting solution; Temperature raising, knifing air themperature, the humidity of the casting solution that requires are also higher, or nascent liquid film time of staying in air is long; The middle solvent height of first, second coagulating bath, temperature height.
When using thickener PVP, need to soak in the aqueous sodium hypochlorite solution post processing.Along with the raising of PVP content in the casting solution, suitably improve the concentration of aqueous sodium hypochlorite solution and temperature height, to prolong the processing time long; Water logging bubble cleaning temperature then is also higher, institute's time is also longer.When not adopting PVP to prepare, in the solid-state poly (ether sulfone) film post processing, handle not necessarily with aqueous sodium hypochlorite solution as the casting solution thickener.
Being the embodiment of hydrophily symmetrical structure microporous membrane of polyethersulfone preparation below, is every implementation condition of embodiment in the tabulation, and the implementation step of all embodiment is all identical with aforementioned implementation step.
Every implementation condition of embodiment 1 is as shown in Table 1:
Table one
| Casting solution | Composition and mass content (%) | Stirring condition | Vacuum outgas | ||||||||||
| PES | SPES | PEG | DMAC | Water | 50℃，24h | 20℃，5h | |||||||
| 17.0 | 1.5 | 2.5 | 77.0 | 2.0 | |||||||||
| Knifing | The casting solution temperature | Carrier | Scrape the edge of a knife degree of depth | Air ambient | The time of staying | ||||||||
| 20℃ | Stainless steel | 300μm | 20 ℃, relative humidity 65% | 5 seconds | |||||||||
| Gelation for the first time | The first coagulating bath quality is formed | Temperature (℃) | Time (second) | ||||||||||
| DMAc55%, water 45% | 20 | 5 | |||||||||||
| Gelation for the second time | The second coagulating bath quality is formed | Temperature (℃) | Time (second) | ||||||||||
| Water 100% | 20 | 50 | |||||||||||
| Post processing | Aqueous sodium hypochlorite solution soaks | The water logging bubble | Dry | ||||||||||
| / | 20℃，72h | 24h dries in the air | |||||||||||
Primary raw material: PES:RADEL
A100, Solvay Advanced Polymers, L.L.C); SPES: sulfonation degree 6.5%, Changchun Jida Advanced Material Co., Ltd; PEG:20000, Shanghai chemical reagents corporation of Chinese Medicine group; DMAc: Shanghai Jingwei Chemical Co., Ltd..
Every implementation condition of embodiment 2 is as shown in Table 2:
Table two
| Casting solution | Composition and mass content (%) | Stirring condition | Vacuum outgas | ||||||||||
| PES | SPES | PVP | DMAC | Water | 60℃，36h | 25℃，5h | |||||||
| 15.5 | 3.0 | 3.5 | 75.0 | 3.0 | |||||||||
| Knifing | The casting solution temperature | Carrier | Scrape the edge of a knife degree of depth | Air ambient | The time of staying | ||||||||
| 25℃ | Glass | 250μm | 25 ℃, relative humidity 70% | 10 seconds | |||||||||
| Gelation for the first time | The first coagulating bath quality is formed | Temperature (℃) | Time (second) | ||||||||||
| DMAc65%, water 35% | 30 | 20 | |||||||||||
| Gelation for the second time | The second coagulating bath quality is formed | Temperature (℃) | Time (second) | ||||||||||
| TOSN a0.01%, water 99.99% | 30 | 90 | |||||||||||
| Post processing | The NaClO aqueous solution soaking | The water logging bubble | Dry | ||||||||||
| NaClO concentration: 0.2%, 20 ℃, 48h | 30℃，48h | 24h dries in the air | |||||||||||
Wherein: PVP, K60, Shanghai chemical reagents corporation of Chinese Medicine group; Other raw materials are with every implementation condition of embodiment 1 embodiment 3 as shown in Table 3:
Table three
| Casting solution | Composition and mass content (%)) | Stirring condition | Vacuum outgas | |||||||||
| PES | SPES | PVP-K90 | DMAC | Ethylene glycol | 55℃，36 h | 25℃，15h | ||||||
| 12.5 | 4.0 | 3.5 | 75.0 | 5.0 | ||||||||
| Knifing | The casting solution temperature | Carrier | Scrape the edge of a knife degree of depth | Air ambient | The time of staying | |||||||
| 30℃ | Stainless steel | 250μm | 25 ℃, relative humidity 75% | 20 seconds | ||||||||
| Gelation for the first time | The first coagulating bath quality is formed | Temperature (℃) | Time (second) | |||||||||
| DMAc78%, water 22% | 35 | 30 | ||||||||||
| Gelation for the second time | The second coagulating bath quality is formed | Temperature (℃) | Time (second) | |||||||||
| TOSN a0.02%, water 89.98%, DMAC10% | 40 | 90 | ||||||||||
| Post processing | The NaClO aqueous solution soaking | The water logging bubble | Dry | |||||||||
| NaClO concentration: 0.4%, 45 ℃, 48h | 45℃，48h | 24h dries in the air | ||||||||||
Wherein: PVP, K90, Shanghai chemical reagents corporation of Chinese Medicine group; Other raw materials are with embodiment 1.
Every implementation condition of embodiment 4 is as shown in Table 4:
Table four
| Casting solution | Composition and mass content (%) | Stirring condition | Vacuum outgas | |||||||||
| PES | SPES | PVP-K90 | DMAC | Water | 60℃，48 h | 25℃，20h | ||||||
| 12.5 | 2.0 | 4.5 | 77.0 | 3.0 | ||||||||
| Knifing | The casting solution temperature | Carrier | Scrape the edge of a knife degree of depth | Air ambient | The time of staying | |||||||
| 35℃ | Stainless steel | 300μm | 25 ℃, relative humidity 80% | 30 seconds | ||||||||
| Gelation for the first time | The first coagulating bath quality is formed | Temperature (℃) | Time (second) | |||||||||
| DMAc82%, water 22% | 40 | 30 | ||||||||||
| Gelation for the second time | The second coagulating bath quality is formed | Temperature (℃) | Time (second) | |||||||||
| TOSN a0.04%, water 69.96%, DMAc30% | 40 | 120 | ||||||||||
| Post processing | The NaClO aqueous solution soaking | The water logging bubble | Dry | |||||||||
| / | 45℃，72h | 24h dries in the air | ||||||||||
Raw material is with embodiment 3.
Every implementation condition of embodiment 5 is as shown in Table 5:
Table five
| Casting solution | Composition and mass content (%) | Stirring condition | Vacuum outgas | ||||||||
| PES | SPES | PVP-K90 | DMAC | Water | 60℃，48h | 25℃，20h | |||||
| 12.5 | 1.0 | 4.5 | 79.0 | 3 | |||||||
| Knifing | The casting solution temperature | Carrier | Scrape the edge of a knife degree of depth | Air ambient | The time of staying | ||||||
| 35℃ | Stainless steel | 300μm | 25 ℃, relative humidity 80% | 30 seconds | |||||||
| Gelation for the first time | The first coagulating bath quality is formed | Temperature (℃) | Time (second) | ||||||||
| DMAc90%, water 10% | 40 | 30 | |||||||||
| Gelation for the second time | The second coagulating bath quality is formed | Temperature (℃) | Time (second) | ||
| TOSN a0.04%, water 69.96%, DMAc30% | 40 | 120 | |||
| Post processing | The NaClO aqueous solution soaking | The water logging bubble | Dry | ||
| NaClO concentration: 0.5%, 45 ℃, 40h | 45℃，24h | Dry back 65 ℃ of dry 10h | |||
Raw material is with embodiment 4.
Every implementation condition of embodiment 6 is as shown in Table 6:
Table six
| Casting solution | Composition and mass content (%) | Stirring condition | Vacuum outgas | |||||||||
| PES | SPES | PVP-K90 | DMAC | Water | 60℃，48 h | 10℃，24h | ||||||
| 14.5 | 0.5 | 3.5 | 79.0 | 2.5 | ||||||||
| Knifing | The casting solution temperature | Carrier | Scrape the edge of a knife degree of depth | Air ambient | The time of staying | |||||||
| 10℃ | Stainless steel | 600μm | 10 ℃, relative humidity 50% | 60 seconds | ||||||||
| Gelation for the first time | The first coagulating bath quality is formed | Temperature (℃) | Time (second) | |||||||||
| DMAc50%, water 50% | 40 | 60 | ||||||||||
| Gelation for the second time | The second coagulating bath quality is formed | Temperature (℃) | Time (second) | |||||||||
| TOSN a0.06%, water 69.94%, DMAc30% | 40 | 120 | ||||||||||
| Post processing | The NaClO aqueous solution soaking | The water logging bubble | Dry | |||||||||
| / | 10℃，72h | 24h dries in the air | ||||||||||
Raw material is with embodiment 5.
Every implementation condition of embodiment 7 is as shown in Table 7:
Table seven
| Casting solution | Composition and mass content (%) | Stirring condition | Vacuum outgas | ||||||
| PES | SPES | PVP | DMAC | Water | 60℃，48h | 25℃，5h | |||
| 9.0 | 0.5 | 2.0 | 87.5 | 1.0 | |||||
| Knifing | The casting solution temperature | Carrier | Scrape the edge of a knife degree of depth | Air ambient | The time of staying | ||||
| 70℃ | Glass | 100μm | 20 ℃, relative humidity 70% | 55 seconds | |||||
| Gelation for the first time | The first coagulating bath quality is formed | Temperature (℃) | Time (second) | ||
| DMAc25%, water 75% | 25 | 20 | |||
| Gelation for the second time | The second coagulating bath quality is formed | Temperature (℃) | Time (second) | ||
| TOSN a0.05%, water 99.95% | 45 | 180 | |||
| Post processing | The NaClO aqueous solution soaking | The water logging bubble | Dry | ||
| NaClO concentration: 0.6%, 20 ℃, 24h | 60℃，48h | 24h dries in the air | |||
Raw material is with embodiment 2
Every implementation condition of embodiment 8 is as shown in Table 8:
Table eight
| Casting solution | Composition and content (g) | Stirring condition | Vacuum outgas | |||||||||
| PES | SPES | PVP-K90 | DMAC | Glycerine | 60℃，48h | 15℃，20h | ||||||
| 13.5 | 5.0 | 7.0 | 65.5 | 10.0 | ||||||||
| Knifing | The casting solution temperature | Carrier | Scrape the edge of a knife degree of depth | Air ambient | The time of staying | |||||||
| 15℃ | Stainless steel | 300μm | 15 ℃, relative humidity 60% | 10 seconds | ||||||||
| Gelation for the first time | The first coagulating bath quality is formed | Temperature (℃) | Time (second) | |||||||||
| DMAc55%, water 45% | 15 | 30 | ||||||||||
| Gelation for the second time | The second coagulating bath quality is formed | Temperature (℃) | Time (second) | |||||||||
| Water 70%, DMAc30% | 15 | 180 | ||||||||||
| Post processing | The NaClO aqueous solution soaking | The water logging bubble | Dry | |||||||||
| / | 15℃，72h | 24h dries in the air | ||||||||||
Raw material is with embodiment 4.
Every implementation condition of embodiment 9 is as shown in Table 9:
Table nine
| Casting solution | Composition and mass content (%) | Stirring condition | Vacuum outgas | ||||
| PES | SPES | PVP-K90 | DMF | Diethylene glycol ether | 55℃，36h | 25℃，15h | |
| 11.5 | 1.0 | 6.5 | 79.5 | 3.0 | |||
| Knifing | The casting solution temperature | Carrier | Scrape the edge of a knife degree of depth | Air ambient | The time of staying | |||
| 70℃ | Stainless steel | 250μm | 25 ℃, relative humidity 85% | 50 seconds | ||||
| Gelation for the first time | The first coagulating bath quality is formed | Temperature (℃) | Time (second) | |||||
| DMAc85%, water 15% | 55 | 40 | ||||||
| Gelation for the second time | The second coagulating bath quality is formed | Temperature (℃) | Time (second) | |||||
| TOSN a0.05%, water 14.95%, DMAc 85% | 40 | 150 | ||||||
| Post processing | The NaClO aqueous solution soaking | The water logging bubble | Dry | |||||
| NaClO concentration: 0.4%, 45 ℃, 48h | 45℃，48h | 24h dries in the air | ||||||
Other raw materials are with embodiment 3.
Microporous membrane of polyethersulfone structures of samples and performance situation see Table ten among each embodiment, wherein:
The water flux test is fixed: the sample that with diameter is 10cm is tested under 1m water column static pressure;
Membrane aperture and voidage are measured: mercury injection method (instrument: DEMO9500 type mercury injection apparatus, Micromecritics Instrument Corp, the U.S.)
Table ten
| Sample number | Average pore size (μ m) | Voidage (%) | Film thickness (μ m) | 1m water column static pressure water flux L/ (m 2·h) |
| Embodiment 1 | 1.05 | 63.5 | 56 | 986 |
| Embodiment 2 | 2.65 | 68.3 | 63 | 2300 |
| Embodiment 3 | 5.12 | 77.4 | 70 | 8588 |
| Embodiment 4 | 8.86 | 75.8 | 77 | 14057 |
| Embodiment 5 | 9.03 | 76.6 | 74 | 15783 |
| Embodiment 6 | 0.52 | 61.5 | 214 | 395 |
| Embodiment 7 | 4.85 | 67.3 | 34 | 4340 |
| Embodiment 8 | 2.07 | 59.3 | 61 | 1930 |
| Embodiment 9 | 10.23 | 76.6 | 75 | 17250 |
At last, it is also to be noted that what more than enumerate only is specific embodiments of the invention.Obviously, the invention is not restricted to above embodiment, many distortion can also be arranged.All distortion that those of ordinary skill in the art can directly derive or associate from content disclosed by the invention all should be thought protection scope of the present invention.
Claims (8)
1, a kind of preparation method of symmetrical configuration hydrophilic polyethersulfone microporous barrier may further comprise the steps:
(1), after 20～100 ℃ stirring was dissolved in 10～30 hours down, in solution, slowly drips additive, again in the lasting down stirring of uniform temp 10～30 hours with polyether sulfone, hydrophilizing agent, thickener and solvent; Cool to room temperature, deaeration is 1～30 hour in a vacuum, obtains being used to prepare the casting solution of microporous membrane of polyethersulfone; Each component composition and each component mass percent in casting solution is:
Polyether sulfone: molecular weight is 2 * 10
4～5 * 10
5, 8～18%;
Hydrophilizing agent: sulfonation degree is 5～10% sulfonated polyether sulfone, 0.5～5%;
Thickener: molecular weight is 2 * 10
3～2 * 10
6Polyvinylpyrrolidone or polyethylene glycol wherein at least a, 1～7%;
Solvent: N, N '-dimethylacetylamide, N, N '-dimethyl formamide or N-methyl pyrrolidone wherein any one, 65～90%;
Additive: water, glycerine, ethylene glycol or diethylene glycol ether wherein any one, 1～10%;
More than each constituent content sum equal 100%;
(2) 10～70 ℃ casting solution is spread to the thick nascent liquid film of 100～600 μ m on dull and stereotyped carrier, and be that 10～40 ℃, relative humidity are to stop 5～60 seconds in 40～90% the air in temperature;
(3) the nascent liquid film on the dull and stereotyped carrier is immersed in 10～60 ℃ first coagulating bath and carry out partial gelization in 5～60 seconds; Described first coagulating bath is the mixed liquid that two kinds of components are formed, and the composition of each component and mass concentration are:
First component: N, N '-dimethylacetylamide, N, N '-dimethyl formamide or N-methyl pyrrolidone wherein any one with casting solution in identical solvent, 50～90%;
Second component: water or ethylene glycol wherein any one, 10～50%;
(4) liquid film of partial gelization is immersed 10～50 ℃ second coagulating bath abundant gelation in 50～180 seconds and obtain solid film; The composition of described second each component of coagulating bath and mass concentration are:
First component: N, N '-dimethylacetylamide, N, N '-dimethyl formamide or N-methyl pyrrolidone wherein any one with casting solution in identical solvent, 0～30%;
Second component: surfactant dodecyl sodium sulfate, 0～0.05%;
The 3rd component: water, 70～100%;
(5) the solid-state poly (ether sulfone) film after the abundant gelation is dry after 24～72 hours through 10～60 ℃ soaking and water washing.
2, according to the preparation method of the described microporous membrane of polyethersulfone of claim 1, it is characterized in that, solid-state poly (ether sulfone) film after the described gelation also comprises the step that the 0.2～0.6wt% aqueous sodium hypochlorite solution that uses 10～60 ℃ soaked 24～72 hours before soaking and water washing.
According to the preparation method of the described microporous membrane of polyethersulfone of claim 2, it is characterized in that 3, described aqueous sodium hypochlorite solution concentration is 0.3～0.5wt%, soaking temperature is 40～50 ℃, and soak time is 40～50 hours; The temperature of soaking and water washing is 20～50 ℃, and the time is 40～50 hours; Baking temperature is controlled at below 80 ℃.
4, according to the preparation method of the described microporous membrane of polyethersulfone of claim 1, it is characterized in that, consisting of of described first coagulating bath: first component is N, N '-dimethylacetylamide or N, N '-dimethyl formamide is any one solvent wherein, with the second component water or the ethylene glycol mixed liquor of any one composition wherein; Wherein the mass content of first component solvent is 65%～85%; The temperature of first coagulating bath is 20～40 ℃; The time of part gelation is 10～40 seconds in first coagulating bath.
5, according to the preparation method of the described microporous membrane of polyethersulfone of claim 1, it is characterized in that, described second coagulating bath consist of N, the mixed liquor that N '-dimethylacetylamide, dodecyl sodium sulfate and water are formed, N wherein, the mass content of N '-dimethylacetylamide is 10～20%; The mass content of dodecyl sodium sulfate is 0.02～0.03%; The temperature of second coagulating bath is 20～40 ℃; Fully the time of gelation is 80～120 seconds in second coagulating bath.
According to the preparation method of the described microporous membrane of polyethersulfone of claim 1, it is characterized in that 6, each the component composition and the mass concentration of described preparation casting solution are:
Polyether sulfone concentration: 12～16%;
Sulfonated polyether sulfone concentration: 1～3%;
Thickener: molecular weight 5 * 10
4～2 * 10
5Polyvinylpyrrolidone, concentration 3～6%;
Solvent: N, N '-dimethylacetylamide, concentration 75～85%;
Additive: water or diethylene glycol ether, concentration 2-6%;
More than each constituent content sum equal 100%.
According to the preparation method of the described microporous membrane of polyethersulfone of claim 1, it is characterized in that 7, described casting solution temperature is 20～40 ℃; Described dull and stereotyped carrier is a corrosion resistant plate; When stopping in air, air themperature is 20～30 ℃, and relative humidity is 55～85%, and the time of staying is 10～35 seconds.
8, according to the preparation method of the described microporous membrane of polyethersulfone of claim 1, it is characterized in that, after the described casting solution preparation, also comprise the step that casting solution is filtered.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2644261A1 (en) * | 2012-03-30 | 2013-10-02 | Pall Corporation | Large pore polymeric membrane with defined pore density |
| EP2698194A1 (en) * | 2012-08-16 | 2014-02-19 | Pall Corporation | Membrane with multiple size fibers |
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| CN102512972B (en) * | 2011-12-09 | 2013-10-02 | 西安建筑科技大学 | Method for preparing double-surface composite flat membrane |
| CN102698618B (en) * | 2012-04-16 | 2015-11-18 | 中国科学院过程工程研究所 | A kind of polyethersulfone porous membrane for Membrane Materials process and preparation method thereof |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6056903A (en) * | 1999-02-08 | 2000-05-02 | Osmonics, Inc. | Preparation of polyethersulfone membranes |
| CN1288776A (en) * | 2000-09-21 | 2001-03-28 | 华东理工大学 | Preparation of sulfonated polyether sulfone filtering film |
| CN1621140A (en) * | 2004-10-12 | 2005-06-01 | 浙江大学 | Method for preparing polyvinylidene fluoride flat plate microporous compound film |
-
2005
- 2005-10-24 CN CNB2005100612418A patent/CN100337730C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6056903A (en) * | 1999-02-08 | 2000-05-02 | Osmonics, Inc. | Preparation of polyethersulfone membranes |
| CN1288776A (en) * | 2000-09-21 | 2001-03-28 | 华东理工大学 | Preparation of sulfonated polyether sulfone filtering film |
| CN1621140A (en) * | 2004-10-12 | 2005-06-01 | 浙江大学 | Method for preparing polyvinylidene fluoride flat plate microporous compound film |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2644261A1 (en) * | 2012-03-30 | 2013-10-02 | Pall Corporation | Large pore polymeric membrane with defined pore density |
| CN103357282A (en) * | 2012-03-30 | 2013-10-23 | 帕尔公司 | Large pore polymeric membrane |
| US9248414B2 (en) | 2012-03-30 | 2016-02-02 | Pall Corporation | Large pore polymeric membrane |
| CN103357282B (en) * | 2012-03-30 | 2016-06-22 | 帕尔公司 | Macroporous polymer film |
| EP2698194A1 (en) * | 2012-08-16 | 2014-02-19 | Pall Corporation | Membrane with multiple size fibers |
| JP2014054626A (en) * | 2012-08-16 | 2014-03-27 | Pall Corp | Film including fiber of a plurality of sizes |
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