CN1544135A - Dinitrogen phenodiazine polyethersulfone ketone hollow fiber ultra filtration membrane and fabrication method thereof - Google Patents
Dinitrogen phenodiazine polyethersulfone ketone hollow fiber ultra filtration membrane and fabrication method thereof Download PDFInfo
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- CN1544135A CN1544135A CNA2003101155444A CN200310115544A CN1544135A CN 1544135 A CN1544135 A CN 1544135A CN A2003101155444 A CNA2003101155444 A CN A2003101155444A CN 200310115544 A CN200310115544 A CN 200310115544A CN 1544135 A CN1544135 A CN 1544135A
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- 239000012528 membrane Substances 0.000 title claims abstract description 31
- 238000000108 ultra-filtration Methods 0.000 title claims abstract description 29
- 239000012510 hollow fiber Substances 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 title claims abstract description 14
- 239000004695 Polyether sulfone Substances 0.000 title claims description 17
- 229920006393 polyether sulfone Polymers 0.000 title claims description 17
- 150000002576 ketones Chemical class 0.000 title claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title 1
- 229910001873 dinitrogen Inorganic materials 0.000 title 1
- 238000004519 manufacturing process Methods 0.000 title 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000002904 solvent Substances 0.000 claims abstract description 24
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000000654 additive Substances 0.000 claims abstract description 14
- 230000000996 additive effect Effects 0.000 claims abstract description 13
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 10
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 10
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims description 36
- 238000002360 preparation method Methods 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- WCZVZNOTHYJIEI-UHFFFAOYSA-N cinnoline Chemical compound N1=NC=CC2=CC=CC=C21 WCZVZNOTHYJIEI-UHFFFAOYSA-N 0.000 claims description 16
- 229920000642 polymer Polymers 0.000 claims description 16
- 238000009987 spinning Methods 0.000 claims description 11
- 238000005345 coagulation Methods 0.000 claims description 10
- 230000015271 coagulation Effects 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 239000000835 fiber Substances 0.000 claims description 9
- 238000007872 degassing Methods 0.000 claims description 6
- 239000012768 molten material Substances 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 6
- 235000012489 doughnuts Nutrition 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- 230000008020 evaporation Effects 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 claims description 3
- 230000000630 rising effect Effects 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 239000000945 filler Substances 0.000 claims description 2
- 239000004094 surface-active agent Substances 0.000 claims description 2
- 230000004907 flux Effects 0.000 abstract description 10
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 abstract 2
- -1 sulphone ketone Chemical class 0.000 abstract 1
- 239000000463 material Substances 0.000 description 6
- 239000000956 alloy Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 108010074605 gamma-Globulins Proteins 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229920002582 Polyethylene Glycol 600 Polymers 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000001891 gel spinning Methods 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- XSCHRSMBECNVNS-UHFFFAOYSA-N quinoxaline Chemical compound N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000004017 vitrification Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
- Artificial Filaments (AREA)
Abstract
The invention is a phenodiazine sulphone ketone hollow fiber ultrafiltration membrane and its preparing method, its character: adopting phenodiazine PPESK as film raw material P, N,N-dimethylacetamide (DMAc), N-methyl pyrrolidone (NMP), or their mixture as solvent S, and polyethylene glycol (PEG) or oxalic acid as additive A, where P/(P+S)=15%-25% (weight ratio, the same below), A/P=0-4/5, and S1/(S1+S2)=0-1. At the same time, it gives the preparing method. It has high flux property besides the performance of resisting high temperature, oxidization and solvent.
Description
Technical field:
Benzodiazine polyethersulfone ketone hollow fiber ultrafiltration membrane and method for making thereof belong to the membrane separation technique field, relate in particular to the hollow fiber ultrafiltration membrane separation technology field.
Background technology:
Milipore filter is one of a kind of most widely used diffusion barrier.Be widely used in the regeneration of water treatment, wastewater treatment and water resource; Or be used for industry such as petrochemical industry, biochemical industry, fine chemistry industry, medication chemistry, textile printing and dyeing, food light industry and carry out the separation of raw material and product, purify and concentrate.In order to satisfy the market demand of each industrial circle, press for the milipore filter of the various different characteristics of exploitation, particularly high temperature resistant, resistance to oxidation, solvent-proof big flux milipore filter to milipore filter.
Poor at existing polymer ultrafiltration membrane heat-resisting quantity, can not satisfy the high-temperature sterilization requirement; Flux is low to cause weakness such as equipment investment cost height, and that the present invention researches and develops is high temperature resistant, resistance to oxidation, big flux organic polymer milipore filter that solvent resistance is good.The application number of applying in April, 2003 is in patent benzodiazine polyethersulfone ketone high polymer alloy milipore filter of 03124222.7 and preparation method thereof, the hollow fiber ultrafiltration membrane that has prepared three kinds of novel high polymer membrane materials, they are benzodiazine polyether-ketone PPEK milipore filter, benzodiazine polyether sulfone PPES milipore filter and benzodiazine polyethersulfone ketone PPESK milipore filter.The present invention on this basis, the performance of phenopiazine polyethersulfone ketone PPESK milipore filter has been done further improvement, has obtained new big flux hollow fiber ultrafiltration membrane.
Summary of the invention:
The purpose of this invention is to provide a kind of benzodiazine polyethersulfone ketone hollow fiber ultrafiltration membrane and method for making thereof.
The present invention selects for use novel high polymer benzodiazine polyethersulfone ketone PPESK as membrane material, and the vitrification point of this material is 284 ℃, and is higher 94 ℃ than general commercial polysulfones PSF, and its weight average molecular weight is 218,900 (MW).
Benzodiazine polyethersulfone ketone hollow fiber ultrafiltration membrane of the present invention is characterized in that, contains in the preparation liquid:
High polymer P: benzodiazine polyethersulfone ketone PPESK, commercially available,
Solvent S:S
1, N, N-dimethylacetylamide DMAc, or
S
2,, N-methyl pyrrolidone NMP, or
S
1+ S
2, the two blend,
Additive A: polyethylene glycol PEG, or
Oxalic acid,
Wherein: P/ (P+S)=15%～25% (wt), simultaneously
A/P=0～4/5 (wt), simultaneously
S
1/(S
1+S
2)＝0～1???????????????(wt)。
The method for making of benzodiazine polyethersulfone ketone hollow fiber ultrafiltration membrane of the present invention contains preparation liquid preparation, and dissolving is filtered, and the degassing in each step of moulding, is characterized in that it contains following each step successively:
(1) preparation of preparation liquid
High polymer P, solvent S, additive A by after the described proportioning weighing, are successively placed molten material still successively,
(2) dissolving
The film liquid of being prepared was stirred 15～24 hours under 80 ℃～100 ℃ temperature, high polymer P and additive A fully are dissolved among the solvent S, filler F is dispersed in the film liquid, becomes uniform preparation liquid,
(3) filter
Under hot state, filter the uniform preparation liquid of dissolving removing insoluble impurity,
(4) degassing
Under 25 ℃～35 ℃ conditions, carry out vacuum outgas,
(5) moulding
Under following process conditions, following steps moulding successively:
Spinning still pressure: 0.1MPa～0.4MPa,
The temperature of spinning solution: 30 ℃～60 ℃,
Hauling speed: 10m/min～30m/min,
Core liquid: hardness is lower than the demineralized water of 3 μ mol/L, or
The aqueous solution that contains the above-mentioned solvent of 0%～10% (wt), 15 ℃～60 ℃ of temperature, flow
0.3L/h～3.0L/h, L be for rising, h is hour,
The air gap: 0mm～1500mm, evaporation atmosphere air themperature: room temperature,
First coagulation bath: hardness is lower than the demineralized water of 3 μ mol/L, or
The aqueous solution that contains the above-mentioned solvent of 0%～10% (wt), or
The aqueous solution that contains 0%～1% surfactant, temperature are 30 ℃～60 ℃,
Second coagulation bath: ultrafiltration water, temperature are 30 ℃～60 ℃,
Forming step is followed successively by:
(5.1) open molten material still baiting valve, make preparation liquid from the ejection of spinneret annular space,
(5.2) inner gel of opening the doughnut spinning-drawing machine is bathed, i.e. core liquid, and control valve is transferred to suitable aperture, and core liquid is flowed out from hydrojet plate centre bore, form the nascent state hollow-fibre membrane,
(5.3) the nascent state tunica fibrosa is introduced the first gel groove and the second gel groove through the air gap order, guides winding-roller again into,
(5.4) select suitable hauling speed, spinning still pressure and core flow quantity for use, make hollow-fibre membrane with suitable wall thickness.
Concrete embodiment:
PPESK of the present invention can represent with following general formula:
Solvent of the present invention comprises N, N-dimethylacetylamide DMAe, N-methyl pyrrolidone NMP, perhaps the two blend.
Additive of the present invention comprises polyethylene glycol (can be PEG400, poly-ethanol 600), oxalic acid, and the application number that is different from April, 2003 application is patent benzodiazine polyethersulfone ketone high polymer alloy milipore filter of 03124222.7 and preparation method thereof.
The present invention adopts dry-wet spinning, and dipping gel phase conversionization legal system is equipped with hollow fiber ultrafiltration membrane.Its preparation method comprises
The following step:
1. the composition of raw material in the preparation liquid
High polymer (P) shared mass percent concentration in the mixture of high polymer (P) and solvent (S) is 15%～25% (wt), i.e. P/ (P+S)=15%～25% (wt); Additive (A) is 0～(4/5) with the mass ratio of high polymer (P), A/P=0～(4/5); Solvent (S
1) shared ratio is 0～1 in solvent (S), i.e. S
1/ (S
1+ S
2)=0～1.
2. the preparation of preparation liquid
With high polymer (P), solvent (S), additive (A) by proportioning weighing in " 1 " after, be placed on earlier in the molten material still.
3. dissolving
The film liquid of preparation in " 2 " was stirred 15～24 hours under 80 ℃～100 ℃ temperature, high polymer and additive fully are dissolved in the solvent, become uniform preparation liquid.
4. filter
Under hot state, filter the uniform preparation liquid of dissolving to remove insoluble impurity.
5. the degassing
Under 25 ℃～35 ℃ conditions, carry out vacuum outgas.
6. hollow fiber ultrafiltration membrane forming method and process conditions
Forming method:
Open molten material still baiting valve, preparation liquid is sprayed from the spinneret annular space; Open the inner gel of doughnut spinning-drawing machine and bathe (core liquid), and control valve is transferred to suitable aperture, core liquid is flowed out from hydrojet plate centre bore, form the nascent state hollow-fibre membrane; The nascent state tunica fibrosa is introduced the first gel groove and the second gel groove in proper order through the air gap of certain altitude, guide winding-roller again into.Regulate suitable coiling (drawing-off) speed, spinning still pressure and core flow quantity, make hollow-fibre membrane with suitable wall thickness.
Process conditions:
Spinning still pressure: 0.1MPa～0.4MPa,
The temperature of spinning solution: 30 ℃～60 ℃,
Hauling speed: 10m/min～30m/min,
Core liquid: hardness is lower than the demineralized water of 3 μ mol/L, or
The aqueous solution that contains the above-mentioned solvent of 0%～10% (wt), 15 ℃～60 ℃ of temperature, flow
0.3L/h～3.0L/h, L be for rising, h is hour,
The air gap: 0mm～1500mm, evaporation atmosphere air themperature: room temperature,
First coagulation bath: hardness is lower than the demineralized water of 3 μ mol/L, or
The aqueous solution that contains the above-mentioned solvent of 0%～10% (wt), or
The aqueous solution that contains 0%～1% dodecyl sodium sulfate, temperature are 30 ℃～60 ℃,
Second coagulation bath: ultrafiltration water, temperature are 30 ℃～60 ℃,
The present invention is φ 0.5mm～φ 2mm by the external diameter of the hollow fiber ultrafiltration membrane of above-mentioned preparation method " 1～6 " preparation, and wall thickness is 0.1mm～0.4mm.
The present invention measures the pure water flux and the rejection of the hollow-fibre membrane made.Condition determination is the deionized water under 25 ℃, and operating pressure is 0.1MPa, and the molecular weight of gamma Globulin is 150000.
With the application number of in April, 2003 application is that patent benzodiazine polyethersulfone ketone high polymer alloy milipore filter of 03124222.7 and preparation method thereof is different, the PPESK hollow fiber ultrafiltration membrane that with oxalic acid is additive preparation has the excellent comprehensive performance, well high temperature resistant, resistance to oxidation, solvent resistance are not only arranged, and have big flux.The milipore filter of this big flux has spongelike structure, and the inner surface apertures of doughnut belongs to ultrafiltration, and the appearance face belongs to micro-filtration.
Introduce embodiments of the invention below:
Embodiment one: get membrane material PPESK (P) 125g, solvent DMAc (S
1) 175g and NMP (S
2) 200g forms mixed solvent, additives polyethylene glycol (PEG400) 100g, preparation 600g film liquid.Under 100 ℃ of temperature, stirred 15 hours, make uniform preparation liquid.After filtration, after the degassing, by preparation method of the present invention 6 preparation hollow-fibre membranes.The spinning still is pressed 0.4Mpa, 60 ℃ of spinning solution temperature (still temperature), hauling speed 30m/min, the core liquid temp is 60 ℃, and discharge is 3L/h, the air gap 1500mm, first coagulation bath is that hardness is the demineralized water of 3 μ mol/L, and temperature is 60 ℃, and second coagulation bath is 60 ℃ a ultrafiltration water.
In 25 ℃ water, soak after 24 hours the performance of test membrane.At operating pressure is 0.1Mpa, and under the condition that temperature is 25 ℃, the pure water flux of film is 250L/m
2.h, the rejection to gamma Globulin is 99.7%.
Following examples see Table 1.
The preparation condition of table 1. example 2～8 and film properties tabulation
(1)
| Embodiment number | ????2 | ????????3 | ????4 | ????5 | ????6 | ????7 | ????8 | ||
| Film liquid is formed | Membrane material P (g) | ????PPESK[75] | ???PPESK[90] | ????PPESK[90] | ????PPESK[90] | ????PPESK[90] | ????PPESK[75] | ????PPESK[75] | |
| Solvent S (g) | ????DMAc[425] | ???DMAc[205]， ???NMP[205] | ????NMP[410] | ????NMP[410] | ????NMP[410] | ????NMP[425] | ????NMP[425] | ||
| Additive A (g) | ????0 | ???PEG600[72] | Oxalic acid [54] | Oxalic acid [54] | Oxalic acid [54] | Oxalic acid [60] | Oxalic acid [60] | ||
| Dissolution conditions | Temperature (℃) | ????80 | ???90 | ????100 | ????100 | ????100 | ????90 | ????90 | |
| Time (h) | ????15 | ???15 | ????20 | ????20 | ????20 | ????24 | ????24 | ||
| Hollow-fibre membrane preparation technology | Still is pressed (MPa) | ????0.1 | ???0.2 | ????0.3 | ????0.3 | ????0.3 | ????0.14 | ????0.14 | |
| The still temperature (℃) | ????25 | ???30 | ????30 | ????30 | ????30 | ????25 | ????25 | ||
| Draft speed (m/min) | ????10 | ???15 | ????15 | ????15 | ????15 | ????10 | ????10 | ||
| The air gap (mm) | ????200 | ???30 | ????500 | ????500 | ????500 | ????0 | ????0 | ||
| Evaporating temperature (℃) | Room temperature | Room temperature | Room temperature | Room temperature | Room temperature | Do not have | Do not have | ||
| Core liquid, demineralized water | Temperature (℃) | ????15 | ???40 | ????15 | ????40 | ????15 | ????60 | ????60 | |
| Hardness | ????3μmol/L | ???3μmol/L | ????3μmol/L | ????3μmol/L | ????2μmol/L | ????2μmol/L | Water+10%NMP | ||
| First coagulation bath, demineralized water | Temperature (℃) | ????30 | ???40 | ????15 | ????40 | ????15 | ????60 | ????60 | |
| Hardness | ????3μmol/L | ???3μmol/L | ????3μmol/L | ????3μmol/L | ????2μmol/L | ????2μmol/L | Water+10%NMP | ||
| Second coagulation bath | Temperature (℃) | ????30 | ???40 | ????40 | ????40 | ????40 | ????60 | ????60 | |
| Form | Ultrafiltration water | Ultrafiltration water | Ultrafiltration water | Ultrafiltration water | Ultrafiltration water | Ultrafiltration water | Ultrafiltration water | ||
| Film properties (2) | Pure water flux (L/m 2.h) | ????402 | ???520 | ????570 | ????800 | ????630 | ????1150 | ????1034 | |
| Gamma Globulin rejection (%) | ????97 | ???96 | ????95 | ????97 | ????94 | ????96 | ????94 | ||
Annotate: 1.[] interior quantity is for making the quality (g) of pleurodiaphragmatic in terspace material;
2. test condition: operating pressure 0.1Mpa, 25 ℃ of operating temperatures
Claims (2)
1. benzodiazine polyether sulfone ketone hollow fiber ultrafiltration membrane is characterized in that, contains in the preparation liquid:
High polymer P: benzodiazine polyethersulfone ketone PPESK, commercially available,
Solvent S:S
1, N, N-dimethylacetylamide DMAc, or
S
2,, N-methyl pyrrolidone NMP, or
S
1+ S
2, the two blend,
Additive A: polyethylene glycol PEG, or
Oxalic acid,
Wherein: P/ (P+S)=15%～25% (wt), simultaneously
A/P=0～4/5 (wt), simultaneously
S
1/(S
1+S
2)＝0～1????(wt)。
2. the method for making of benzodiazine polyethersulfone ketone hollow fiber ultrafiltration membrane contains the preparation liquid preparation, and dissolving is filtered, and the degassing in each step of moulding, is characterized in that it contains following each step successively:
(1) preparation of preparation liquid
High polymer P, solvent S, additive A by after the described proportioning weighing, are successively placed molten material still successively,
(2) dissolving
The film liquid of being prepared was stirred 15～24 hours under 80 ℃～100 ℃ temperature, high polymer P and additive A fully are dissolved among the solvent S, filler F is dispersed in the film liquid, becomes uniform preparation liquid,
(3) filter
Under hot state, filter the uniform preparation liquid of dissolving removing insoluble impurity,
(4) degassing
Under 25 ℃～35 ℃ conditions, carry out vacuum outgas,
(5) moulding
Under following process conditions, following steps moulding successively:
Spinning still pressure: 0.1MPa～0.4MPa,
The temperature of spinning solution: 30 ℃～60 ℃,
Hauling speed: 10m/min～30m/min,
Core liquid: hardness is lower than the demineralized water of 3 μ mol/L, or
The aqueous solution that contains the above-mentioned solvent of 0%～10% (wt), 15 ℃～60 ℃ of temperature, flow
0.3L/h～3.0L/h, L be for rising, h is hour,
The air gap: 0mm～1500mm, evaporation atmosphere air themperature: room temperature,
First coagulation bath: hardness is lower than the demineralized water of 3 μ mol/L, or
The aqueous solution that contains the above-mentioned solvent of 0%～10% (wt), or
The aqueous solution that contains 0%～1% surfactant, temperature are 30 ℃～60 ℃,
Second coagulation bath: ultrafiltration water, temperature are 30 ℃～60 ℃,
Forming step is followed successively by:
(5.1) open molten material still baiting valve, make preparation liquid from the ejection of spinneret annular space,
(5.2) inner gel of opening the doughnut spinning-drawing machine is bathed, i.e. core liquid, and control valve is transferred to suitable aperture, and core liquid is flowed out from hydrojet plate centre bore, form the nascent state hollow-fibre membrane,
(5.3) the nascent state tunica fibrosa is introduced the first gel groove and the second gel groove through the air gap order, guides winding-roller again into,
(5.4) select suitable hauling speed, spinning still pressure and core flow quantity for use, make hollow-fibre membrane with suitable wall thickness.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2003101155444A CN100506365C (en) | 2003-11-28 | 2003-11-28 | Dinitrogen phenodiazine polyethersulfone ketone hollow fiber ultra filtration membrane and fabrication method thereof |
| PCT/CN2004/000295 WO2004096418A1 (en) | 2003-05-01 | 2004-03-31 | Hollow fiber ultrafilter membrane with poly(phthalazinone ether fulfone), poly(phthalazinone ether ketone) or poly(phthalazinone ether sulfone ketone) and preparation thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2003101155444A CN100506365C (en) | 2003-11-28 | 2003-11-28 | Dinitrogen phenodiazine polyethersulfone ketone hollow fiber ultra filtration membrane and fabrication method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1544135A true CN1544135A (en) | 2004-11-10 |
| CN100506365C CN100506365C (en) | 2009-07-01 |
Family
ID=34337348
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2003101155444A Expired - Fee Related CN100506365C (en) | 2003-05-01 | 2003-11-28 | Dinitrogen phenodiazine polyethersulfone ketone hollow fiber ultra filtration membrane and fabrication method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100506365C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100443543C (en) * | 2005-09-09 | 2008-12-17 | 大连理工大学 | Method for interface modification of continuous fibre reinforced polyarylether resin-base composite materials containing diazacyclo group |
| CN103191656A (en) * | 2013-03-29 | 2013-07-10 | 中国科学技术大学 | Preparation method of polymer micro-filtration membrane |
| CN112705054A (en) * | 2020-12-24 | 2021-04-27 | 健帆生物科技集团股份有限公司 | Hollow fiber membrane, preparation method thereof and dialyzer |
-
2003
- 2003-11-28 CN CNB2003101155444A patent/CN100506365C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100443543C (en) * | 2005-09-09 | 2008-12-17 | 大连理工大学 | Method for interface modification of continuous fibre reinforced polyarylether resin-base composite materials containing diazacyclo group |
| CN103191656A (en) * | 2013-03-29 | 2013-07-10 | 中国科学技术大学 | Preparation method of polymer micro-filtration membrane |
| CN103191656B (en) * | 2013-03-29 | 2015-01-28 | 中国科学技术大学 | Preparation method of polymer micro-filtration membrane |
| CN112705054A (en) * | 2020-12-24 | 2021-04-27 | 健帆生物科技集团股份有限公司 | Hollow fiber membrane, preparation method thereof and dialyzer |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100506365C (en) | 2009-07-01 |
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