EP4150143A1 - Sulfonated polystyrene nonwoven - Google Patents
Sulfonated polystyrene nonwovenInfo
- Publication number
- EP4150143A1 EP4150143A1 EP21726819.2A EP21726819A EP4150143A1 EP 4150143 A1 EP4150143 A1 EP 4150143A1 EP 21726819 A EP21726819 A EP 21726819A EP 4150143 A1 EP4150143 A1 EP 4150143A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- meq
- fibers
- polystyrene
- nonwoven
- capacity
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920001467 poly(styrenesulfonates) Polymers 0.000 title claims abstract description 11
- 239000000835 fiber Substances 0.000 claims abstract description 32
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 29
- 239000004793 Polystyrene Substances 0.000 claims description 24
- 229920002223 polystyrene Polymers 0.000 claims description 23
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 239000003431 cross linking reagent Substances 0.000 claims description 7
- 150000002739 metals Chemical class 0.000 claims description 3
- 150000001299 aldehydes Chemical class 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims 2
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 19
- 239000012528 membrane Substances 0.000 description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 8
- 238000006277 sulfonation reaction Methods 0.000 description 8
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 5
- 239000003456 ion exchange resin Substances 0.000 description 5
- 229920003303 ion-exchange polymer Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000002121 nanofiber Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- QAEDZJGFFMLHHQ-UHFFFAOYSA-N trifluoroacetic anhydride Chemical compound FC(F)(F)C(=O)OC(=O)C(F)(F)F QAEDZJGFFMLHHQ-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000013270 controlled release Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000002198 insoluble material Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D39/00—Filtering material for liquid or gaseous fluids
- B01D39/14—Other self-supporting filtering material ; Other filtering material
- B01D39/16—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres
- B01D39/1607—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres the material being fibrous
- B01D39/1623—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres the material being fibrous of synthetic origin
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4282—Addition polymers
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/58—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
- B01D2239/02—Types of fibres, filaments or particles, self-supporting or supported materials
- B01D2239/025—Types of fibres, filaments or particles, self-supporting or supported materials comprising nanofibres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
- B01D2239/06—Filter cloth, e.g. knitted, woven non-woven; self-supported material
- B01D2239/0604—Arrangement of the fibres in the filtering material
- B01D2239/0631—Electro-spun
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
- B01D2239/12—Special parameters characterising the filtering material
- B01D2239/1233—Fibre diameter
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
Definitions
- This invention relates generally to sulfonated polystyrene nonwovens and a method for their preparation.
- the present invention is directed to a sulfonated polystyrene nonwoven having an average diameter from 450 nm to 2000 nm and a capacity from 0.05 meq/g to 2.0 meq/g.
- the polystyrene used to make the fibers is a high heat crystalline polystyrene, preferably one that is acceptable in pharmaceutical processing.
- the average diameter of the fibers is at least 480 nm, preferably at least 500 nm, preferably at least 520 nm; preferably no greater than 1750 nm, preferably no greater than 1500 nm, preferably no greater than 1200 nm, preferably no greater than 1000 nm, preferably no greater than 800 nm, preferably no greater than 750 nm, preferably no greater than 700 nm.
- the fibers are produced by Hybrid Membrane Technology (HMT). This technology is described, e.g., in US7618579.
- HMT Hybrid Membrane Technology
- fibers are made from a solution of polystyrene in an aprotic solvent.
- Preferred solvents are those capable of dissolving polystyrene at room temperature, and include, e.g., N,N-dimethylformamide (DMF), dimethylacetamide, methyl ethyl ketone, dichloromethane and toluene.
- the solution is processed via electroblowing under conditions which may be adjusted by known techniques to vary fiber properties, producing a nonwoven fiber mat.
- the concentration of polystyrene in the solvent is from 15 to 30 wt%, preferably 18 to 27 wt%.
- the solution is processed on a single hole or multi-hole electro-blowing unit.
- the fiber is spun onto a rotating drum.
- the fibers are treated with a crosslinking agent capable of crosslinking polystyrene prior to sulfonation.
- crosslinking agents are aldehydes and dialdehydes, preferably formaldehyde/sulfuric acid or glutaraldehyde/sulfuric acid, preferably formaldehyde/sulfuric acid.
- at least 90 wt% of the polystyrene molecules contain crosslinks, preferably at least 94 wt%, preferably at least 96 wt%, preferably at least 98 wt%.
- the wt% of polystyrene molecules that are crosslinked may be determined by immersing the fibers in dichloroethane and weighing the insoluble material, which is the polystyrene molecules containing crosslinks.
- fibers are treated with crosslinking agent at a temperature from 20 to 110°C, preferably at least 45°C, preferably at least 55°C; preferably no more than 100°C, preferably no more than 95°C. Both time and temperature may be adjusted to produce the desired degree of crosslinking, however typical times preferably are in the range from 30 minutes to 6 hours, preferably 1 to 4 hours.
- treatment with a crosslinking agent is done without a catalyst under the conditions given above. If a catalyst is used (e.g., Ag2SC>4), times will be much shorter at a given temperature and can be adjusted to provide desired properties.
- the fibers resulting from treatment with a crosslinking agent are sulfonated by contacting them with a sulfonating agent, preferably at least 80 wt% (remainder at least 95 wt% water), preferably at least 90 wt%, preferably at least 94 wt%.
- Sulfonating agents are reagents capable of sulfonating aromatic rings.
- Preferred sulfonating agents include sulfuric acid, chlorosulfonic acid and oleum; preferably sulfuric acid.
- sulfonation is performed at a temperature from 30 to 160°C, preferably at least 50°C, preferably at least 70°C; preferably no more than 120°C, preferably no more than 110°C. Both time and temperature may be adjusted to produce the desired capacity, however typical times preferably are in the range from 30 minutes to 6 hours, preferably 1 to 4 hours.
- fibers are contacted with concentrated sulfuric acid for a time sufficient to produce sulfonated polystyrene fibers having a capacity from 0.4 meq/g to 2.0 meq/g or in any desired range therein contained.
- sulfonation is done without a catalyst under the conditions given above. If a catalyst is used (e.g., Ag2SC>4, acetic anhydride, trifluoroacetic anhydride), time will be much shorter at a given temperature and can be adjusted to provide desired properties
- capacity of the sulfonated nonwoven is at least 0.2 meq/g, preferably at least 0.4 meq/g, preferably at least 0.45 meq/g, preferably at least 0.50 meq/g, preferably at least 0.55 meq/g, preferably at least 0.60 meq/g, preferably at least 0.65 meq/g; preferably no greater than 1.8 meq/g, preferably no greater than 1.6 meq/g, preferably no greater than 1.5 meq/g, preferably no greater than 1.4 meq/g, preferably no greater than 1.3 meq/g, preferably no greater than 1.2 meq/g, preferably no greater than 1.1 meq/g.
- C e.g., 30 C
- PS solutions were prepared using PS 685 D grade polystyrene obtained from Aldrich.
- the solvent was dimethylformamide (DMF). Solutions with concentrations in the range of 21 to 25 wt% were scouted. Sample solutions were spun on a single hole electro-blowing unit. The fiber was spun onto a rotating drum and the sample non-woven was collected from the drum after the run. Typical samples were prepared from a 21 wt% solution with 0.1 wt% salt added based on solution.
- the typical basis weight varied from 60 to 100 gsm. Typical distance between the spin pack and the drum collector was 33 cm.
- the typical applied voltage was 100 kV.
- the typical spin cell temperature was 30 C.
- the typical sample mean flow pour was 1 micron.
- the nanofiber membrane (1700 nm average fiber diameter) is immersed into a bath containing a mixture of reagent grade concentrated sulfuric acid and formalin (37 wt% formaldehyde), typically 90: 10 sulfuric acid : formalin (V/V).
- the bath is typically heated to 70 C for 3h and gently shaken on an orbital shaker at 60 -120 rpm.
- the bath is cooled to ⁇ 50 C, the reaction fluid is decanted, and membrane is slowly hydrated with 50% sulfuric acid, and the membrane is gradually diluted down to pure DI water.
- the nanofiber membrane after treatment with sulfuric acid/formalin is immersed in concentrated sulfuric acid (typically 96%), and then heated to 90 C for 0 to 8 h while shaking on an orbital. Next, the bath is cooled to ⁇ 50C, the reaction fluid is decanted, and the membrane is slowly hydrated with 50% sulfuric acid, and then gradually diluted down to pure DI water.
- concentrated sulfuric acid typically 96%
- volumetric Flow rate 6.9 ml/min for membrane, 5 ml/min for ion exchange resin.
- Metal content of the nonwoven PS membrane is reduced to 9.76 ppb in 210 minutes, at which time the resin still had a metal content of 20.26ppb. .
- the media is further rinsed with DI water to at least pH>5.
- Total metal content in the initial resin bed effluent was 512.7 ppb and total metal in the membrane disk effluent was 823.4 ppb.
- the membrane disk removes 96% of the initial metals at the first residence time of 3.5 seconds while ion exchange resin removes 94% of the initial metals at the first residence time of 15 min.
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Nonwoven Fabrics (AREA)
- Artificial Filaments (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US202063022718P | 2020-05-11 | 2020-05-11 | |
| PCT/US2021/030406 WO2021231114A1 (en) | 2020-05-11 | 2021-05-03 | Sulfonated polystyrene nonwoven |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP4150143A1 true EP4150143A1 (en) | 2023-03-22 |
Family
ID=76012067
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP21726819.2A Pending EP4150143A1 (en) | 2020-05-11 | 2021-05-03 | Sulfonated polystyrene nonwoven |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP4150143A1 (ja) |
| JP (1) | JP2023526197A (ja) |
| KR (1) | KR20230041959A (ja) |
| CN (1) | CN115702268A (ja) |
| WO (1) | WO2021231114A1 (ja) |
Family Cites Families (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5213722A (en) * | 1987-11-17 | 1993-05-25 | Matsushita Electric Industrial Co., Ltd. | Method of making a separator material for a storage battery |
| TW288051B (ja) * | 1994-11-22 | 1996-10-11 | Ebara Corp | |
| KR100549140B1 (ko) | 2002-03-26 | 2006-02-03 | 이 아이 듀폰 디 네모아 앤드 캄파니 | 일렉트로-브로운 방사법에 의한 초극세 나노섬유 웹제조방법 |
| WO2007135689A2 (en) * | 2006-05-24 | 2007-11-29 | Ben Gurion University Of The Negev R&D Authority | Membranes, coatings and films and methods for their preparation |
| JP5172859B2 (ja) * | 2007-01-19 | 2013-03-27 | ザ・ピュロライト・カンパニー | 逆浸透膜の汚染減少 |
| KR20080090079A (ko) * | 2007-04-04 | 2008-10-08 | 성균관대학교산학협력단 | 다공성 이온교환 촉매 멤브레인 및 그 제조방법 |
| JP5062630B2 (ja) * | 2008-05-14 | 2012-10-31 | 栗田工業株式会社 | 複合繊維体、その製造方法、フィルタ及び流体濾過方法 |
| KR100992557B1 (ko) * | 2008-08-30 | 2010-11-08 | 충남대학교산학협력단 | 고분기 폴리스틸렌과 반응형 아크릴산 수지를 이용한 이온선택성 나노섬유 구조체 제조방법 |
| JP5867828B2 (ja) * | 2011-04-28 | 2016-02-24 | 日本バイリーン株式会社 | 複合膜およびその製造方法 |
| US9096959B2 (en) * | 2012-02-22 | 2015-08-04 | Ut-Battelle, Llc | Method for production of carbon nanofiber mat or carbon paper |
| CN105103654B (zh) * | 2013-02-14 | 2017-06-23 | 纳米帕雷尔股份有限公司 | 纳米纤维混合毛毡 |
| KR101628899B1 (ko) * | 2013-05-22 | 2016-06-21 | 주식회사 아모그린텍 | 술폰화된 나노 섬유 웹을 이용한 액체처리 케미컬 필터 및 그의 제조방법 |
| JP6256443B2 (ja) * | 2015-09-30 | 2018-01-10 | 栗田工業株式会社 | 製品洗浄方法 |
| CN109647534A (zh) * | 2018-12-18 | 2019-04-19 | 辽宁石油化工大学 | 一种NiB/PANI纳米纤维催化剂的制备方法及其在硼氢化钠水解制氢中的应用 |
| CN109898322A (zh) * | 2019-03-15 | 2019-06-18 | 天津工业大学 | 一种磺化非织造布及制备方法 |
-
2021
- 2021-05-03 JP JP2022568370A patent/JP2023526197A/ja active Pending
- 2021-05-03 KR KR1020227042286A patent/KR20230041959A/ko active Search and Examination
- 2021-05-03 WO PCT/US2021/030406 patent/WO2021231114A1/en unknown
- 2021-05-03 EP EP21726819.2A patent/EP4150143A1/en active Pending
- 2021-05-03 CN CN202180038094.XA patent/CN115702268A/zh active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| KR20230041959A (ko) | 2023-03-27 |
| CN115702268A (zh) | 2023-02-14 |
| WO2021231114A1 (en) | 2021-11-18 |
| JP2023526197A (ja) | 2023-06-21 |
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