CN102019150A - Polyether sulfone-polyurethane blend hollow fiber membrane and preparation method thereof - Google Patents
Polyether sulfone-polyurethane blend hollow fiber membrane and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a polyether sulfone-polyurethane blend hollow fiber membrane and a preparation method thereof. In the hollow fiber membrane, polyether sulfone is taken as a main membranous material; polyurethane is added for blending; and a high molecular pore forming agent, a surfactant, a solvent and the like are added to prepare casting solution; and the polyether sulfone-polyurethane blend hollow fiber membrane is prepared by a dry-wet method, namely, a nonsolvent induced phase separation method spinning process. The prepared polyether sulfone-polyurethane blend hollow fiber membrane has seven inner bores with the inner diameter of 0.8 to 1.0mm and the outer diameter of 3.8 to 4.5mm, has high hydrophilcity, the flux of pure water of 300 to 2,900 L/M<2>.H(0.1MPa and 25 DEG C), high intensity and the tensile breaking force of 30 to 62N, has the advantages of high flexibility, the breaking elongation of 60 to 110 percent, high chemical resistance, high pollution resistance, and the like, and is easy to clean.
Description
Technical field
The present invention relates to the preparation method that a kind of polyether sulfone-polyurethane comixing hollow-fibre membrane and non-solvent thereof cause phase separation method.
Background technology
Membrane separation technique is rapid in development in recent years, is widely used in the wastewater treatment of industry such as chemical industry, food, medicine, electronics, electric power, municipal tap water and sewage disposal, aspects such as family expenses and commercial drinking water filtration treatment.Compare with traditional separation method, membrane separating method has advantages such as low, the no phase transformation of efficiency, technology are simple, environmentally safe.Be used to make the material of diffusion barrier,, develop into polyethylene, polypropylene, polyvinyl chloride, polyacrylonitrile, polysulfones, Kynoar, polyether sulfone etc. from cellulose acetate; From develop into two or more material blend with homogenous material.
Polyether sulfone has excellent physical and mechanical properties, and it has intensity height, good rigidly; Good heat resistance, can be under 180 ~ 200 ℃ of temperature characteristic such as long-term use; Simultaneously, the polyether sulfone chemical proofing is good, and is stable to general acid, alkali, aliphatic hydrocarbon, grease, alcohols etc., at high temperature can be by acid and alkali corrosion yet, and can anti-gasoline, cleaning agents such as machine oil, lubricated wet goods oils and fluorine Lyons; The polyether sulfone ageing-resistant performance is good, long service life.The polyether sulfone high comprehensive performance is a kind of membrane material of excellent performance, and polyether sulfone has than better hydrophily of Kynoar and higher intensity, and with the doughnut film-strength height of polyether sulfone preparation, the film silk is easy fracture not; Good rigidly, the compressive resistance height; Chemical-resistance is good, cleans easily; Polyether sulfone is widely used in the manufacturing of various diffusion barriers.Polyether sulfone is widely adopted at the diffusion barrier manufacture view as a kind of polymers of excellent properties.Chinese patent publication number CN 1817425A introduces a kind of phenolic polyether sulphone hollow-fibre membrane, this hollow-fibre membrane adopts the preparation of dry-wet spinning technology, and the thickness of this hollow-fibre membrane is that 30 ~ 100 μ m, internal diameter 80 ~ 400 μ m, average pore size are 0.01 ~ 0.2 μ m, pure water flux 100 ~ 500 L/m
2H(0.1MPa), proof pressure 0.1 ~ 0.8MPa.The interior external diameter of hollow-fibre membrane is done more for a short time, and the tension failure brute force is more little, the easy more fracture of hollow-fibre membrane in use; The wall thickness of hollow-fibre membrane is too small, and except the tension failure brute force was low, the resistance to pressure of hollow-fibre membrane was also relatively poor.Chinese patent publication number CN 1375351A has introduced a kind of manufacture method of blend polyethersulfone doughnut dialysis membrane, adopting polyether sulfone is main material of preparing, with other high polymer blend, adopt non-solvent to cause the phase separation method spinning technique, carry out the biaxial tension in 2 ~ 4 roads to solidifying the nascent hollow-fibre membrane in back, thickness 30 ~ 250 μ m that make, the blend polyethersulfone doughnut dialysis membrane of external diameter 220 ~ 1400 μ m.Though hollow-fibre membrane increases through intensity after the biaxial tension, the amplitude that improves is limited.
Adopt the doughnut film strength of melt spinning-stretching hole forming method spinning technique preparation higher, China Patent No. ZL 200410067007.1 discloses and a kind ofly has been equipped with the method for Kynoar hollow-fibre membrane with melt spinning-drawing process legal system, by melt extruding, technology such as hollow molding, coiling prepares doughnut, prepares the Kynoar hollow-fibre membrane by technologies such as heat treatment, cold stretch, hot-stretch, thermal finalizations then.The fracture strength of this hollow-fibre membrane is that 100 ~ 150MPa, elongation at break are 150 ~ 400%, porosity 25 ~ 65%, the average pore size of micropore is at 0.01 ~ 0.1 μ m.Though the doughnut film-strength of melt spinning-stretching hole forming method technology preparation is high, form because tear by pulling force in the hole on the wall, so the size in the size in the out-of-shape in hole, hole and skewness, hole is difficult to control, porosity is low.
Thermally induced phase separation is the manufacture method of a kind of hollow-fibre membrane of getting up of developed recently, doughnut film-strength height with the thermally induced phase separation preparation, use same material, the hot strength of the hollow-fibre membrane of thermally induced phase separation preparation causes the hot strength height of the hollow-fibre membrane of phase separation method preparation than non-solvent.With the pore size of the hollow-fibre membrane of thermally induced phase separation preparation and be evenly distributed, porosity is also high.But the thermally induced phase separation arts demand extracts processing to the doughnut of cooling forming, and technology causes the phase separation method complex process than non-solvent, and the cost of thermally induced phase separation technology is high more a lot of than the cost that non-solvent causes phase separation method technology.
Non-solvent causes phase separation method technical maturity, simple, but it a very big shortcoming is arranged is exactly that the doughnut film strength for preparing is relatively poor.Pore membrane was a good method that improves the doughnut film-strength in the preparation doughnut was many, Chinese patent publication number CN 101721928 has introduced a kind of high strength, hydrophilic polysulfones hollow fiber ultrafiltration membrane, utilize spinning equipment to prepare hollow-fibre membrane, particularly adopt multi-holed jet to prepare the porous hollow fiber membrane that three holes to the porous road of seven apertures in the human head supports mutually, improve film strength.
Polyurethane elastomer had not only had the characteristic of plastics but also had had the characteristic of rubber concurrently, the polyurethane elastomer softness, have other plastic material incomparable good toughness, shock-resistant, good springiness; Have simultaneously other elastomeric material incomparable high strength, tensile strength can reach more than the 25MPa; Have characteristics such as wear-resisting, cold-resistant, oil resistant, water-fast, ageing-resistant, weatherability, ozone resistance is good, chemical proofing is good.The price of thermoplastic polyurethane is more cheap than polyether sulfone.The intensity of polyether sulfone is big, and matter is hard but lack flexibility, adds an amount of polyurethane and carry out blend in polyether sulfone, can improve the flexibility of polyether sulfone, has also reduced the cost of material.
Cause phase separation method manufacturing polyether sulfone-polyurethane comixing hollow-fibre membrane with non-solvent and also do not have relevant report, therefore, the present invention also provides and has caused phase separation method with non-solvent and prepare polyether sulfone-polyurethane comixing doughnut film method, adopts the doughnut film strength of the method preparation high and have a good flexibility.
Summary of the invention
One object of the present invention is to provide a kind of polyether sulfone-polyurethane comixing hollow-fibre membrane, and it includes polyurethane and polyether sulfone.This hollow-fibre membrane has the seven apertures in the human head structure, forms a hollow-fibre membrane by seven endoporus, has very high resistance to compression and tensile strength, and has good flexibility.
Polyether sulfone-polyurethane comixing hollow-fibre membrane preferably comprises the component of following percetage by weight:
Polyurethane: 60 ~ 90%
Polyether sulfone: 10 ~ 40%
Macromolecule pore former: 0 ~ 24%
Surfactant: 0 ~ 15%
Preferably, described preparation raw material comprises following components in weight percentage:
Polyether sulfone 10 ~ 20%
Polyurethane 2 ~ 10%
Macromolecule pore former 10 ~ 25%
Surfactant 0 ~ 5%
Water 0 ~ 2%
Solvent 50 ~ 85%.
Preferably, the molecular weight of described polyether sulfone is 30000 ~ 100000, polyurethane is thermoplastic polyurethane, and the adding proportion between two kinds of materials of polyether sulfone and polyurethane is 6 ~ 9:4 ~ 1.
Preferably, described macromolecule pore former is selected from polyethylene glycol, one or more in polyvinylpyrrolidone, polyvinyl alcohol, polyoxyethylene, the methylcellulose.
Preferably, described surfactant is selected from one or more in lauryl sodium sulfate, neopelex, sodium dodecyl aminopropionitrile, softex kw, Tween-20, the Tween-80.
Preferably, described water is deionized water.
Preferably, described solvent is selected from one or more in dimethyl formamide, dimethylacetylamide, dimethyl sulfoxide (DMSO), N-methyl pyrrolidone, tricresyl phosphate methyl, the tricresyl phosphate ethyl.
Another object of the present invention is to provide the preparation method of a kind of polyether sulfone-polyurethane comixing hollow-fibre membrane, adopt non-solvent to cause phase separation method technology, and adopt unique seven hole spinneret, prepare hollow-fibre membrane.Its preparation process is as follows:
Step (1): at first, polyether sulfone, polyurethane, macromolecule pore former, surfactant, water and solvent are put into reactor by a certain percentage, stirring full and uniform dissolving more than the 20h under 50 ~ 90 ℃ of temperature;
Step (2): then, stop to stir, filter, vacuumizing and defoaming and lowering the temperature, obtain 30 ~ 70 ℃ casting solution;
Step (3): then, described casting solution is transported to 30 ~ 60 ℃ seven circular pipe type spinning heads, feeds 20 ~ 60 ℃ interior solidification liquids in seven pipes, form endoporus, the extrusion molding doughnut;
Step (4): last, with the air distance of described doughnut, enter coagulation forming in 20 ~ 60 ℃ the outer solidification liquid through 50 ~ 300mm, collect hollow-fibre membrane then, obtain described polyether sulfone-polyurethane comixing hollow-fibre membrane.
Preferably, in step (1) before, with polyether sulfone and polyurethane under 60 ~ 80 ℃ of temperature more than the dry 4h.
Preferably, described interior solidification liquid is the mixed solution of water and solvent, and the concentration of solvent is 0 ~ 80%, and outer solidification liquid is the mixed solution of water and solvent, and the concentration of solvent is 0 ~ 80%.
Compared with prior art, polyether sulfone of the present invention-polyurethane comixing hollow-fibre membrane has the following advantages:
(1) has seven unique inner hole structures, greatly improved the doughnut film strength, significantly reduce hollow-fibre membrane fracture of wire phenomenon in use;
(2) adding is thermoplastic polyurethane elastomer blended in polyether sulfone, and the adding proportion by control polyether sulfone and polyurethane had both guaranteed that hollow-fibre membrane had certain intensity, simultaneously, had increased the flexibility of film silk, and had reduced material cost;
(3) before reaction, polyurethane and polyether sulfone are carried out drying, remove moisture wherein, so that the tunica fibrosa of making has preferable combination property.
Description of drawings
Accompanying drawing 1 is the structural representation of hollow-fibre membrane of the present invention;
Accompanying drawing 2 is structural representations of seven hole spinneret of the present invention.
The specific embodiment
With specific embodiment the present invention further is illustrated below; embodiment is a part of the present invention; do not comprise of the present invention whole; be not construed as limiting the invention; all within content of the present invention; any modification of being done, replacement, improvement etc. all should be included within protection scope of the present invention.
The invention provides a kind of polyether sulfone-polyurethane comixing hollow-fibre membrane, it includes polyurethane and polyether sulfone.By polyurethane polyether sulfone is carried out modification, both make made hollow-fibre membrane both have certain intensity with the certain proportion blend, have certain pliability again.
In the present invention, described polyether sulfone-polyurethane comixing hollow-fibre membrane includes the component of following percetage by weight:
Polyurethane: 60 ~ 90%
Polyether sulfone: 10 ~ 40%
Macromolecule pore former: 0 ~ 24%
Surfactant: 0 ~ 15%
The preparation raw material of described polyether sulfone-polyurethane comixing hollow-fibre membrane comprises following components in weight percentage:
Polyether sulfone 10 ~ 20%
Polyurethane 2 ~ 10%
Macromolecule pore former 10 ~ 25%
Surfactant 0 ~ 5%
Water 0 ~ 2%
Solvent 50 ~ 85%.
Wherein, the adding proportion of polyether sulfone and polyurethane is 6 ~ 9:4 ~ 1.The proper ratio of control polyether sulfone and polyurethane can make made blend hollow fiber membrane have preferable intensity and flexibility.
In the present invention, the molecular weight of described polyether sulfone is 30000 ~ 100000; Polyurethane is TPUE.Described macromolecule pore former is selected from polyethylene glycol, one or more in polyvinylpyrrolidone, polyvinyl alcohol, polyoxyethylene, the methylcellulose.Described surfactant is selected from one or more in lauryl sodium sulfate, neopelex, sodium dodecyl aminopropionitrile, softex kw, Tween-20, the Tween-80.Described solvent is selected from one or more in dimethyl formamide, dimethylacetylamide, dimethyl sulfoxide (DMSO), N-methyl pyrrolidone, tricresyl phosphate methyl, the tricresyl phosphate ethyl.
With reference to shown in Figure 1, described hollow-fibre membrane is seven inner hole structures, and it not only has very high resistance to compression and tensile strength, and has good flexibility.The internal diameter B of described hollow-fibre membrane is that 0.8 ~ 1.0mm, outer diameter A are 3.8 ~ 4.5mm, and the tension failure brute force is 30 ~ 62N, and elongation at break 60 ~ 110%, pure water flux are 300 ~ 2900L/M
2H(0.1MPa, 25 ℃), the average pore size of film is 0.01 ~ 0.4 μ m, fracture pressure〉1.0MPa.
In the present invention, also provide the preparation method of a kind of polyether sulfone-polyurethane comixing hollow-fibre membrane, adopted non-solvent to cause the phase separation method preparation, preparation process is as follows:
Step (1): at first, polyether sulfone, polyurethane, macromolecule pore former, surfactant, water and solvent are put into reactor by a certain percentage, stirring full and uniform dissolving more than the 20h under 50 ~ 90 ℃ of temperature;
Step (2): then, stop to stir, filter, vacuumizing and defoaming and lowering the temperature, obtain 30 ~ 70 ℃ casting solution;
Step (3): then, described casting solution is transported to 30 ~ 60 ℃ seven circular pipe type spinning heads, feeds 20 ~ 60 ℃ interior solidification liquids in seven pipes, form endoporus, the extrusion molding doughnut;
Step (4): last, with the air distance of described doughnut, enter coagulation forming in 20 ~ 60 ℃ the outer solidification liquid through 50 ~ 300mm, collect hollow-fibre membrane then, obtain described polyether sulfone-polyurethane comixing hollow-fibre membrane.
In a preferred embodiment of the invention, in step (1) before, with polyether sulfone and polyurethane under 60 ~ 80 ℃ of temperature more than the dry 4h.By removing the moisture in polyether sulfone and the polyurethane, so that the tunica fibrosa of making has preferable combination property.
Solidification liquid is the mixed solution of water and solvent in described, and the concentration of solvent is 0 ~ 80%; Described outer solidification liquid is the mixed solution of water and solvent, and the concentration of solvent is 0 ~ 80%.The concentration of solidification liquid and outer solidification liquid can be identical with composition in described.
Below the present invention is described in detail by specific embodiment.
Embodiment 1: take by weighing polyether sulfone 15% by weight percentage, polyurethane 2%, polyethylene glycol 15%, polyvinylpyrrolidone 3%, water 1%, dimethylacetylamide 64% is put into reactor, under 80 ℃ of temperature, stir 20h, stop then stirring, filter, vacuumizing and defoaming is also lowered the temperature and is obtained 50 ℃ casting solution, the process measuring pump is transported to 50 ℃ seven circular pipe type spinning heads, 7 interior deionized waters that feed 30 ℃ of pipe, be extruded into doughnut with seven inner hole structures, pass through the air distance of 200mm then, enter 30 ℃, coagulation forming in the aqueous solution of 30% dimethylacetylamide content, then the film silk is collected, obtained polyether sulfone-polyurethane and mix hollow-fibre membrane.Internal diameter 0.92mm, external diameter 4.26mm, the pure water flux of the polyether sulfone-polyurethane comixing hollow-fibre membrane of preparation are 1800L/M
2H(0.1MPa, 25 ℃), average pore size is 0.13 μ m, tension failure powerful for 55.5N, elongation at break be 70%.
Comparing embodiment 1: press the raw material weight percentage among the embodiment 1, adopt the spinning technique of embodiment 1, seven circular pipe type spinning heads are changed into single bushing type spinning head, prepare single endoporus polyether sulfone-polyurethane hollow fiber film, the internal diameter of this hollow-fibre membrane is that 0.92mm, external diameter are that 1.50mm, pure water flux are 1750L/M
2H(0.1MPa, 25 ℃), average pore size is 0.12 μ m, tension failure powerful for 6.9N, elongation at break be 75%.
From comparing embodiment 1, find out, raw material and spinning technique are identical, adopt different spinning heads, the aperture of the seven apertures in the human head hollow-fibre membrane of preparing respectively and the flux of single hole film is very close, and the tension failure brute force differs 8 times, adopts the seven apertures in the human head structure to improve the tension failure brute force of polyether sulfone-polyurethane comixing hollow-fibre membrane greatly.
Embodiment 2: take by weighing polyether sulfone 13% by weight percentage, polyurethane 3%, polyethylene glycol 15%, water 1%, dimethylacetylamide 68% is put into reactor, under 80 ℃ of temperature, stir 20h, stop then stirring, filter, vacuumizing and defoaming is also lowered the temperature and is obtained 50 ℃ casting solution, the process measuring pump is transported to 50 ℃ seven circular pipe type spinning heads, 7 interior aqueous solution that feed 30 ℃ 20% dimethylacetylamide content of pipe, be extruded into doughnut with seven inner hole structures, pass through the air distance of 200mm then, enter 30 ℃, coagulation forming in the aqueous solution water of 30% dimethylacetylamide content, then the film silk is collected, obtained polyether sulfone-polyurethane comixing hollow-fibre membrane.Internal diameter 0.96mm, external diameter 4.30mm, the pure water flux of the polyether sulfone-polyurethane comixing hollow-fibre membrane of preparation are 2150L/M
2H(0.1MPa, 25 ℃), average pore size is 0.22 μ m, tension failure powerful for 58.2N, elongation at break be 80%.
Embodiment 3: take by weighing polyether sulfone 14%, polyurethane 4%, polyethylene glycol 15%, polyvinylpyrrolidone 3%, tween 3%, water 1%, dimethyl formamide 60% by weight percentage and put into reactor, under 80 ℃ of temperature, stir 20h, stop then stirring, filtration, vacuumizing and defoaming and lower the temperature and obtain 50 ℃ casting solution, adopt the spinning technique identical with embodiment 1, the internal diameter 0.90mm of the polyether sulfone of preparation-polyurethane comixing hollow-fibre membrane, external diameter 4.20mm, pure water flux are 1650L/M
2H(0.1MPa, 25 ℃), average pore size is 0.1 μ m, tension failure powerful for 65.3N, elongation at break be 95%.
Embodiment 4: take by weighing polyether sulfone 16%, polyurethane 4%, polyethylene glycol 10%, polyvinylpyrrolidone 2%, tween 2%, water 1%, dimethylacetylamide 65% by weight percentage and put into reactor, under 80 ℃ of temperature, stir 20h, stop then stirring, filtration, vacuumizing and defoaming and lower the temperature and obtain 50 ℃ casting solution, adopt the spinning technique identical with embodiment 1, the internal diameter 0.90mm of the polyether sulfone of preparation-polyurethane comixing hollow-fibre membrane, external diameter 4.24mm, pure water flux are 780L/M
2H(0.1MPa, 25 ℃), average pore size is 0.05 μ m, tension failure powerful for 60.1N, elongation at break be 90%.
Relatively implement 4: do not add polyurethane among the embodiment 4, the percentage by weight of polyether sulfone is 20%, the ratio of other material is identical with embodiment's 4, and spinning technique is identical with embodiment 4, and the internal diameter of the polyether sulfone hollow-fibre membrane that makes is that 0.91mm, external diameter are that 4.19mm, pure water flux are 710 L/M
2H(0.1MPa, 25 ℃), average pore size is 0.04 μ m, and the tension failure brute force is 75.4N, and elongation at break is 39%.
Can find out that from comparing embodiment 4 do not add polyurethane, the elongation at break of polyether sulfone hollow-fibre membrane obviously descends, the hardening of film silk, flexibility descends, and adds the flexibility that polyurethane can obviously improve polyether sulfone.
This hollow-fibre membrane adopts polyether sulfone as main membrane material, add polyurethane comixing, and add macromolecule pore former, surfactant and solvent etc. and make casting solution, adopt to do-wet method is that non-solvent causes the phase separation method spinning technique, use seven unique inner hole structure spinning heads, preparation polyether sulfone-polyurethane comixing hollow-fibre membrane.Polyether sulfone-polyurethane comixing the hollow-fibre membrane of preparation has seven endoporus, and internal diameter is that 0.8 ~ 1.0mm, external diameter are 3.8 ~ 4.5mm, has good hydrophilicity, pure water flux is 300 ~ 2900L/M
2H(0.1MPa, 25 ℃), have higher intensity, the tension failure brute force is 30 ~ 62N, has good flexibility simultaneously, elongation at break is 60 ~ 110%, chemical-resistance is good, has advantages such as resistance tocrocking is good, easy cleaning.Polyether sulfone-polyurethane comixing the hollow-fibre membrane of the present invention's preparation can be applied to the filtration and the purified treatment of drinking water filtration treatment, wine brewing, food and medicine, municipal tap water and sewage disposal, and trade effluent is handled, the aspects such as pre-treatment of desalinization.
Claims (11)
1. polyether sulfone-polyurethane comixing hollow-fibre membrane, it is characterized in that: membrane material includes polyether sulfone and polyurethane.
2. polyether sulfone according to claim 1-polyurethane comixing hollow-fibre membrane is characterized in that: the component that includes following percetage by weight:
Polyurethane: 60 ~ 90%
Polyether sulfone: 10 ~ 40%
Macromolecule pore former: 0 ~ 24%
Surfactant: 0 ~ 15%.
3. polyether sulfone according to claim 2-polyurethane comixing hollow-fibre membrane, it is characterized in that: the internal diameter of described hollow-fibre membrane is that 0.8 ~ 1.0mm, external diameter are 3.8 ~ 4.5mm, the average pore size of film is 0.01 ~ 0.4 μ m, and pure water flux is 300 ~ 2900L/M2H(0.1MPa, 25 ℃).
4. polyether sulfone according to claim 2-polyurethane comixing hollow-fibre membrane is characterized in that: the endoporus of described tunica fibrosa is 7.
5. polyether sulfone according to claim 1-polyurethane comixing hollow-fibre membrane is characterized in that: the preparation raw material comprises following components in weight percentage:
Polyether sulfone 10 ~ 20%
Polyurethane 2 ~ 10%
Macromolecule pore former 10 ~ 25%
Surfactant 0 ~ 5%
Water 0 ~ 2%
Solvent 50 ~ 85%.
6. polyether sulfone according to claim 5-polyurethane comixing hollow-fibre membrane is characterized in that: the adding proportion of polyether sulfone and polyurethane is 6 ~ 9:4 ~ 1.
7. polyether sulfone according to claim 1-polyurethane comixing hollow-fibre membrane is characterized in that: the molecular weight of described polyether sulfone is 30000 ~ 100000; Polyurethane is TPUE.
8. polyether sulfone according to claim 5-polyurethane comixing hollow-fibre membrane is characterized in that described macromolecule pore former is selected from polyethylene glycol, one or more in polyvinylpyrrolidone, polyvinyl alcohol, polyoxyethylene, the methylcellulose; Described surfactant is selected from one or more in lauryl sodium sulfate, neopelex, sodium dodecyl aminopropionitrile, softex kw, Tween-20, the Tween-80; Described solvent is selected from one or more in dimethyl formamide, dimethylacetylamide, dimethyl sulfoxide (DMSO), N-methyl pyrrolidone, tricresyl phosphate methyl, the tricresyl phosphate ethyl.
9. the preparation method of polyether sulfone-polyurethane comixing hollow-fibre membrane adopts non-solvent to cause the phase separation method preparation, it is characterized in that preparation process is as follows:
Step (1): at first, polyether sulfone, polyurethane, macromolecule pore former, surfactant, water and solvent are put into reactor by a certain percentage, stirring full and uniform dissolving more than the 20h under 50 ~ 90 ℃ of temperature;
Step (2): then, stop to stir, filter, vacuumizing and defoaming and lowering the temperature, obtain 30 ~ 70 ℃ casting solution;
Step (3): then, described casting solution is transported to 30 ~ 60 ℃ seven circular pipe type spinning heads, feeds 20 ~ 60 ℃ interior solidification liquids in seven pipes, form endoporus, the extrusion molding doughnut;
Step (4): last, with the air distance of described doughnut, enter coagulation forming in 20 ~ 60 ℃ the outer solidification liquid through 50 ~ 300mm, collect hollow-fibre membrane then, obtain described polyether sulfone-polyurethane comixing hollow-fibre membrane.
10. polyether sulfone according to claim 9-polyurethane comixing doughnut membrane preparation method is characterized in that:
In step (1) before, with polyether sulfone and polyurethane under 60 ~ 80 ℃ of temperature more than the dry 4h.
11. polyether sulfone according to claim 9-polyurethane comixing doughnut membrane preparation method is characterized in that described interior solidification liquid is the mixed solution of water and solvent, the concentration of solvent is 0 ~ 80%; Described outer solidification liquid is the mixed solution of water and solvent, and the concentration of solvent is 0 ~ 80%.
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Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3162430A1 (en) * | 2015-10-27 | 2017-05-03 | Basf Se | Process for the preparation of a membrane which comprises a polyethersulfone polymer and a polyurethane polymer |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0674938B1 (en) * | 1994-03-31 | 1998-11-18 | PERMEA, Inc. | Process for producing composite membranes |
| CN101837248A (en) * | 2010-06-24 | 2010-09-22 | 厦门绿邦膜技术有限公司 | Production method of cellosilk enhanced compound hollow fiber membrane |
-
2010
- 2010-12-21 CN CN201010597561.6A patent/CN102019150B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0674938B1 (en) * | 1994-03-31 | 1998-11-18 | PERMEA, Inc. | Process for producing composite membranes |
| CN101837248A (en) * | 2010-06-24 | 2010-09-22 | 厦门绿邦膜技术有限公司 | Production method of cellosilk enhanced compound hollow fiber membrane |
Non-Patent Citations (1)
| Title |
|---|
| 《Journal of Membrane Science》 20081231 L.T. Duarte et al. Polyurethane/polyethersulphone composite hollow fibers produced by simultaneous spinning of two polymer solutions 12-22 1-11 第311卷, * |
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