JP2008505197A - 親水性膜 - Google Patents
親水性膜 Download PDFInfo
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- JP2008505197A JP2008505197A JP2007518412A JP2007518412A JP2008505197A JP 2008505197 A JP2008505197 A JP 2008505197A JP 2007518412 A JP2007518412 A JP 2007518412A JP 2007518412 A JP2007518412 A JP 2007518412A JP 2008505197 A JP2008505197 A JP 2008505197A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0093—Chemical modification
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0093—Chemical modification
- B01D67/00931—Chemical modification by introduction of specific groups after membrane formation, e.g. by grafting
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
- B01J20/28021—Hollow particles, e.g. hollow spheres, microspheres or cenospheres
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28023—Fibres or filaments
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28033—Membrane, sheet, cloth, pad, lamellar or mat
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
- C08J5/2287—After-treatment
- C08J5/2293—After-treatment of fluorine-containing membranes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/056—Forming hydrophilic coatings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
- C08J7/123—Treatment by wave energy or particle radiation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/30—Cross-linking
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2339/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Derivatives of such polymers
- C08J2339/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
- C08J2339/06—Homopolymers or copolymers of N-vinyl-pyrrolidones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2427/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
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- Chemical & Material Sciences (AREA)
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- Organic Chemistry (AREA)
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- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Transplantation (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
- Graft Or Block Polymers (AREA)
Abstract
Description
−(−CH2−CH2−CFCl−CF2−)n−
を有する、エチレンとクロロトリフルオロエチレンとの1:1交互共重合体である。
第1の態様によれば、本発明は、重合体を被覆する方法であって、前記重合体を活性化剤で処理して、反応性重合体を製造する工程、および前記反応性重合体を反応性被覆剤と反応させて、被覆重合体を製造する工程を含む方法を提供する。
−(−CH2−CH2−CFCl−CF2−)n−
を有する。
i)前記halar精密濾過または限外濾過膜を塩基で処理して、HXを脱離させ、塩基処理済みの重合体を製造する工程;および
ii)前記塩基処理済みの重合体を架橋開始剤の存在下でPVPで処理して、PVPの架橋表面被膜を有するhalar精密濾過または限外濾過膜を製造する工程を含む方法を提供する。
本発明は、本明細書において、高分子限外濾過膜または精密濾過膜に関して開示される。しかし、記載しているような修飾が望ましい場合には、いずれの適当な高分子材料にも本方法を適用することができるということは、当業者には分かるであろう。好適な重合体から調製されるいずれの物も本発明に従って親水化することができる。
−(CH2−CH2−CCl2−CClF)n−
試験の結果および考察
1.エタノールにより湿潤させる(繊維をまだ水中に保存していない場合)(0.5時間)
2.水で洗浄する(0.5時間)
3.濃NaOH溶液に浸漬する(0.5時間)
4.高温下、異なる長さの時間、NaOH処理する
5.水で洗浄する(2〜3時間)
6.PVP/過硫酸塩溶液に浸漬する(1〜2時間)
7.100%湿潤雰囲気中、高温下で処理する(1〜2時間)
8.水で洗浄する(>2時間)
9.20%グリセロールに浸漬する
まず、孔径0.1μmの精密濾過膜において反応を行った。サンプルを温度90℃いて21時間(一晩)20%苛性溶液に曝した。全ての繊維を、過硫酸塩での処理の直後にエタノールで3時間洗浄したことを除き、それ以外は上記のとおり処理を行った。
MF繊維で、処理がうまくいくということを確認したところで、それを、一般にさらに小さな孔を有するUF繊維に適用した。MF繊維と同一パラメーターを用いて数多くの試みがなされ、MF繊維と同一条件下で膜の親水化を繰り返した。
Claims (37)
- 重合体を被覆する方法であって、前記重合体を活性化剤で処理して、反応性重合体を製造する工程、および前記反応性重合体を反応性被覆剤と反応させて、被覆重合体を製造する工程を含む、方法。
- 前記重合体が少なくとも1個のX(ハロゲン)基と少なくとも1個のHとを有する、請求項1に記載の方法。
- XがFまたはClおよび少なくとも1個のHである、請求項2に記載の方法。
- 前記重合体が、水素に対してα位の炭素と結合されている少なくとも1個のX(ハロゲン)を有する、請求項3に記載の方法。
- 少なくとも1個のX基を有する前記重合体が、完全もしくは部分的ハロゲン化単独重合体、共重合体または三元共重合体、あるいはそれらのブレンドである、請求項1〜4のいずれか一項に記載の方法。
- 完全もしくは部分的ハロゲン化単独重合体、共重合体または三元共重合体、あるいはそれらのブレンドが、混和性非ハロゲン化重合体、重合体ブレンドまたは重合体混合物をさらに含んでなる、請求項5に記載の方法。
- 重合体がpvdf(ポリフッ化ビニリデン)単独重合体、エチレン−クロロトリフルオロエチレン共重合体(halar)またはアクリル酸n−ブチルとのエチレン−クロロトリフルオロエチレン三元共重合体、フッ化/塩化ビニルの三元共重合体;フッ化/塩化ビニリデン、ヘキサフルオロプロピレン、クロロトリフルオロエチレン、テトラフルオロエチレンである、請求項1〜6のいずれか一項に記載の方法。
- 重合体が以下のモノマー:クロロトリフルオロエチレンフッ化ビニル、塩化ビニル;フッ化ビニリデン/塩化ビニリデン;ヘキサフルオロプロピレン、クロロトリフルオロエチレン、テトラフルオロエチレンの1以上を含む、それ、又は、それらから製造した、耐塩基侵蝕性を有する重合体である、請求項1〜7のいずれか一項に記載の方法。
- 前記重合体がポリ(エチレンクロロトリフルオロエチレン)、すなわちhalar、エチレンとクロロトリフルオロエチレンとの1:1交互共重合体であり、以下の構造:
−(−CH2−CH2−CFCl−CF2−)n−
を有する、請求項8に記載の方法。 - 前記活性化剤が前記重合体からHXを脱離させるように作用して、反応性重合体を製造する、請求項1〜9のいずれか一項に記載の方法。
- 前記活性化剤が塩基である、請求項1〜10のいずれか一項に記載の方法。
- 前記塩基がアルカリ土類水酸化物である、請求項11に記載の方法。
- 前記アルカリ土類水酸化物が水酸化ナトリウム、水酸化カリウム、水酸化リチウムまたは水酸化カルシウムである、請求項12に記載の方法。
- 前記塩基がアルカリ金属アルコキシドである、請求項11に記載の方法。
- 前記アルカリ金属アルコキシドがナトリウムメトキシド、ナトリウムエトキシド、ナトリウムプロポキシド、カリウムメトキシド、カリウムエトキシド、カリウムプロポキシドである、請求項14に記載の方法。
- 前記塩基が強アミン塩基である、請求項11に記載の方法。
- 前記強アミン塩基がテトラエチレンペンタミンである、請求項16に記載の方法。
- 前記反応性重合体が二重結合を有する、請求項1〜17のいずれか一項に記載の方法。
- 前記反応性被覆剤が親水性重合体である、請求項1〜18のいずれか一項に記載の方法。
- 前記反応性被覆剤が親水性重合体である、請求項1〜19のいずれか一項に記載の方法。
- 前記反応性被覆剤がPVPである、請求項1〜20のいずれか一項に記載の方法。
- 前記反応性被覆剤が開始剤の存在下で反応性重合体に対して反応する、請求項1〜21のいずれか一項に記載の方法。
- 前記開始剤が過硫酸塩(S2O8 2−)である、請求項22に記載の方法。
- 前記過硫酸塩が過硫酸カリウム、過硫酸アンモニウム、二過硫酸ナトリウムまたは一過硫酸ナトリウム形態である、請求項21に記載の方法。
- 重合体を親水化する方法であって、適用できる場合には、架橋性基を組み込むように重合体を修飾する工程、および架橋性基を有する前記重合体を架橋性親水化剤で処理し、架橋条件を適用する工程を含む、方法。
- 前記架橋性基が二重結合である、請求項25に記載の方法。
- 前記架橋性親水化剤がPVPである、請求項25または請求項26に記載の方法。
- 架橋条件に開始剤および/または架橋放射線の使用が含まれる、請求項25〜27のいずれか一項に記載の方法。
- halar精密濾過または限外濾過膜を親水化する方法であって、
i)前記halar精密濾過または限外濾過膜を塩基で処理して、HXを脱離させ、塩基処理済みの重合体を製造する工程;および
ii)前記塩基処理済みの重合体を架橋開始剤の存在下でPVPで処理して、PVPの架橋表面被膜を有するhalar精密濾過または限外濾過膜を製造する工程を含む、方法。 - PVPの架橋表面被膜を有するhalar精密濾過または限外濾過膜。
- 非対称膜形態の、請求項30に記載の膜。
- 平板形態の、請求項31に記載の膜。
- 中空繊維形態の、請求項31に記載の膜。
- 本発明に従って調製される、水および廃水の精密濾過および限外濾過に用いるための機能性膜。
- 本発明に従って調製される、親和性膜として用いるための機能性膜。
- 本発明に従って調製される、タンパク質吸着に用いるための機能性膜。
- 本発明に従って調製される、生体適合性のある機能性膜を必要とする方法に用いるための機能性膜。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU2004903680A AU2004903680A0 (en) | 2004-07-05 | Modification of halar membranes | |
AU2005901689A AU2005901689A0 (en) | 2005-04-06 | Hydrophilic membranes | |
PCT/AU2005/000975 WO2006002479A1 (en) | 2004-07-05 | 2005-07-04 | Hydrophilic membranes |
Publications (2)
Publication Number | Publication Date |
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JP2008505197A true JP2008505197A (ja) | 2008-02-21 |
JP2008505197A5 JP2008505197A5 (ja) | 2012-01-19 |
Family
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2007518412A Ceased JP2008505197A (ja) | 2004-07-05 | 2005-07-04 | 親水性膜 |
Country Status (7)
Country | Link |
---|---|
US (1) | US8524794B2 (ja) |
EP (1) | EP1773477B1 (ja) |
JP (1) | JP2008505197A (ja) |
AT (1) | ATE523240T1 (ja) |
CA (1) | CA2571502A1 (ja) |
MY (1) | MY140168A (ja) |
WO (1) | WO2006002479A1 (ja) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2009543675A (ja) * | 2006-07-14 | 2009-12-10 | シーメンス・ウォーター・テクノロジーズ・コーポレーション | 向上した、膜のモノ過硫酸塩処理 |
Families Citing this family (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AU2003903507A0 (en) | 2003-07-08 | 2003-07-24 | U. S. Filter Wastewater Group, Inc. | Membrane post-treatment |
CA2571498A1 (en) | 2004-07-02 | 2006-01-12 | U.S. Filter Wastewater Group, Inc. | Gas transfer membrane |
EP1773477B1 (en) | 2004-07-05 | 2011-09-07 | Siemens Water Technologies Corp. | Hydrophilic membranes |
ATE511915T1 (de) | 2004-12-03 | 2011-06-15 | Siemens Industry Inc | Membrannachbehandlung |
AU2006261581B2 (en) * | 2005-06-20 | 2012-03-15 | Evoqua Water Technologies Llc | Cross linking treatment of polymer membranes |
KR20080033279A (ko) * | 2005-06-20 | 2008-04-16 | 지멘스 워터 테크놀로지스 코포레이션 | 중합체 막의 가교 결합 처리 |
NZ564968A (en) | 2005-07-14 | 2011-11-25 | Siemens Water Tech Corp | Monopersulfate treatment of membranes |
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US20070107884A1 (en) * | 2005-10-27 | 2007-05-17 | Sirkar Kamalesh K | Polymeric hollow fiber heat exchange systems |
MY145939A (en) * | 2006-07-14 | 2012-05-31 | Siemens Industry Inc | Improved monopersulfate treatment of membranes |
EP2137107A4 (en) * | 2007-03-12 | 2013-08-28 | Jong-Hoon Kim | PROCESS FOR THE PREPARATION OF NANODIAMANT AND NANOCARBON HAVING A SIMILAR ATOMIC REPORTING OF HYDROGEN AND HALOGEN IN THE CHEMICAL COMPOUND OF CARBON, HYDROGEN AND HALOGEN BY DEHYDROHALOGENATION AND THEIR PRODUCTION |
US20110147308A1 (en) * | 2009-12-21 | 2011-06-23 | Siemens Water Technologies Corp. | Charged Porous Polymeric Membranes and Their Preparation |
-
2005
- 2005-07-04 EP EP05757000A patent/EP1773477B1/en not_active Not-in-force
- 2005-07-04 US US11/571,101 patent/US8524794B2/en active Active
- 2005-07-04 WO PCT/AU2005/000975 patent/WO2006002479A1/en active Application Filing
- 2005-07-04 CA CA002571502A patent/CA2571502A1/en not_active Abandoned
- 2005-07-04 AT AT05757000T patent/ATE523240T1/de not_active IP Right Cessation
- 2005-07-04 JP JP2007518412A patent/JP2008505197A/ja not_active Ceased
- 2005-07-05 MY MYPI20053059A patent/MY140168A/en unknown
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JPS6475542A (en) * | 1987-09-17 | 1989-03-22 | Terumo Corp | Hydrophilic porous membrane of polyvinylidene fluoride and production thereof |
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Cited By (1)
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JP2009543675A (ja) * | 2006-07-14 | 2009-12-10 | シーメンス・ウォーター・テクノロジーズ・コーポレーション | 向上した、膜のモノ過硫酸塩処理 |
Also Published As
Publication number | Publication date |
---|---|
EP1773477A4 (en) | 2009-04-29 |
EP1773477A1 (en) | 2007-04-18 |
CA2571502A1 (en) | 2006-01-12 |
US8524794B2 (en) | 2013-09-03 |
EP1773477B1 (en) | 2011-09-07 |
MY140168A (en) | 2009-11-30 |
US20080058440A1 (en) | 2008-03-06 |
ATE523240T1 (de) | 2011-09-15 |
WO2006002479A1 (en) | 2006-01-12 |
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