CA1333238C - P-xylylenediamide/diimide composite reverse osmosis membranes - Google Patents
P-xylylenediamide/diimide composite reverse osmosis membranesInfo
- Publication number
- CA1333238C CA1333238C CA000577202A CA577202A CA1333238C CA 1333238 C CA1333238 C CA 1333238C CA 000577202 A CA000577202 A CA 000577202A CA 577202 A CA577202 A CA 577202A CA 1333238 C CA1333238 C CA 1333238C
- Authority
- CA
- Canada
- Prior art keywords
- membrane
- support
- hollow fiber
- membranes
- composite
- 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.)
- Expired - Fee Related
Links
Classifications
-
- 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
- B01D71/56—Polyamides, e.g. polyester-amides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
- B01D69/1251—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction by interfacial polymerisation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/28—Preparatory processes
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Artificial Filaments (AREA)
- Multicomponent Fibers (AREA)
Abstract
Composite RO membranes having good resistance to halogen attack and extraordinarily high fluxes are disclosed, the composite membranes comprising a micro-porous polymeric support with an interfacially poly-merized salt-rejecting layer thereon comprising an aromatic aliphatic diamide/diimide.
Description
p-XYLYLENEDIAMIDE/DIIMIDE COMPOSITE RO MEMBRANES
BACKGROUND OF THE INVENTION
Composite reverse osmosis (RO) membranes are known but there is still a need in the art for RO
membranes that are resistant to degradation by halogens such as chlorine, which is often present in the feed waters of an RO process stream. There is also an ongoing need in the art for membranes with high salt rejection and flux rates.
One method of making RO membranes is by interfacial polymerization of a salt-rejecting layer on a porous polymeric support so as to form a composite membrane. See, for example, U.S. Patent Nos. 4,039,440 and 4,277,344. Meta-xylylenediamine has been condensed with trimesoyl chloride in an interfacial polymeriza-tion reaction on a polysulfone support so as to form a meta-xylylenediamide composite RO membrane. See NTIS
Report No. PB83-243170 entitled "Novel Composite Membranes" by Eric K. L. Lee, et al. dated April 1983.
However, the membranes so prepared were not useful for practical desalination applications due to their poor chlorine resistance and low fluxes (on the order of 6 to 10 gfd for those with salt rejections of 95% or better).
SUMMARY OF THE INVENTION
The novel RO membranes of the present invention are composite membranes comprising a ~ra-aromatic aliphatic diamide or diimide salt-rejecting layer interfacially polymerized on a microporous polymeric support.
DETAILED DESCRIPTION OF THE INVENTION
According to the present invention, novel composite RO membranes are provided that possess good 133323~
- chlorine resistance, high salt rejection and extraor-dinarily high fluxes, the membranes comprising an interfacially-polymerized salt rejection layer on a microporous polymeric support. The salt-rejecting layer is the interfacial polymerization reaction product of an aromatic polyacylhalide cross-linking agent and an aromatic diamine or diimine of the general formula R2HNRl-Ph-RlNHR2 (I) where Ph is a para-substituted phenylene group, Rl is an alkylene group containing from 1 to 2 carbon atoms, and R2 is hydrogen or an alkyl group containing from 1 to 2 carbon atoms.
Examples of suitable aromatic polyacylhalides are isophthaloyl chloride (IPC), trimesoyl chloride (TMC) and terephthaloylchloride (TPC).
The microporous polymeric support may be in the form of flat sheets or hollow fibers and may be selected from polysulfones, polyethersulfones, poly-phenylsulfones, polyvinylidenehalides, including poly-vinyl chloride, polyimides and polyetherimides, poly-amides, polyesters, and polycarbonates. Such supports are available commercially in flat sheets typically 2 to 6 mils thick.
Preferred hollow fiber supports typically have an internal diameter of 260 microns and an external diameter of 620 microns. The salt-rejecting layer may be formed on either the inner or lumens side of such hollow fibers or on the outer or external side of the fiber.
Flat sheet support membranes may be prepared by machine casting in accordance with known prior art methods. Hollow fiber support membranes may also be prepared according to known methods of hollow fiber `35 spin casting.
The composite membrane of the present invention is typically prepared by first immersing the support membrane in an aqueous solution of the diamine or diimine for a short period of time, preferably 1 to 3 minutes, removing it from the aqueous and draining it of excess solution, then immersing it in a dilute solu-tion of a cross-linking agent in an organic solvent at ambient temperatures for less than one minute to form the interfacial polymer on the support. The composite membrane so formed is air-dried, then heat-cured at temperatures in the range of 40C to 120C for about 10 minutes to complete the reaction. The aqueous solution should contain from about 0.25 wt% to about 5 wt% of the amine or imine, 0.5 wt% to 2 wt~ being preferred.
The organic phase should contain from about 0.01 wt% to about 1.0 wt% of the cross-linking agent, preferably 0.05 wt% to about 0.5 wt%, together with additives of triethylamine (functioning as an acid scavenger), and a surfactant.
Two of the most preferred reactants in forming the salt-rejecting layer of the composite membrane of the present invention are TMC and ~ara-xylylenediamine (pXDA), which produce a salt rejection layer having the chemical structure shown below:
~ C~ NWCH 2 ~CH 2 N H -o ~ NHCH2-~=~CH2NHC~IC~ NHCH24,3CH2NH-The general class of composite RO membranesprepared according to the present invention and having the structure (I) exhibit salt rejections in excess of 95%, good chlorine resistance and extraordinary fluxes as high as 20 to 40 gfd, making them especially suitable for.desalination of sea water by RO.
_4_ I 3 3323 Examples 1-5 A series of composite membranes of the present invention were prepared as follows. An asym-metric microporous polysulfone support flat sheet membrane approximately 4 mils thick and having micro-porosity on one side was immersed in a 2 wt% aqueous solution of pXDA containing 0.5 wt% triethylamine (as an acid scavenger) and 0.01 wt% of a surfactant sold under the trademark "Iconol NP-9" (BASF Wyandotte Corporation of Parsippany, New Jersey), drained of excess solution, then immersed in a 0.5 wt% solution of TMC in hexane for 30 seconds at room temperature, causing formation of a para-xylylenediamide film on the microporous surface of the polysulfone support. The resulting composite membrane was air-dried at room tem-perature overnight, then heat-cured for 10 minutes at 100C. The so-formed membrane was then tested in an 800 psi RO test, the feed water containing 0.5 wt% NaCl at pH 6.0 and 25C. The results, with flux being expressed in gallons per square foot of membrane surface area per day (gfd), are shown in Table I.
Table I
Membrane/ Flux Rejection Example No. (gfd) (%) 1 19.5 96.4 2 23.4 95.8 3 20.9 96.9 4 23.5 96.6 23.1 96.5 Examples 6-13 Composite membranes prepared in essentially the same fashion as those in Examples 1-5 with the exceptions noted were prepared in batches of three membranes at a time, and RO-tested, the average results of each group of three being as noted in Table II.
Table II
Membrane/ pXDA TMC Heat Cure Flux Rejection Example No. (wt%) (wt%) (C) (gfd) (%) 6 2 0.1 100 20.5 99.0 7 2 0.5 100 22.1 96.4 8 2 0.1 60 26.6 98.8 9 2~ 0.5 60 21.6 98.1 2 0.05 none 20.6 97.5 11 0.5 0.1 60 25.5 97.2 12 2 0.1 60 36.6 97.1 13 1 0.1 60 42.8 96.4 Example 14 Chlorine resistance of an exemplary membrane prepared in essentially the same fashion as in Examples 1-5 was tested by subjecting the membrane to the same type of RO test conditions as set forth in Examples 6-13 for 40 days except that the pH was 4.5 and the feed water contained either 0, 0.5 or 10 ppm free chlorine in the form of NaOCl. In order to accelerate the effects of chlorine on the performance of the membrane, the test was run in an "on/off" scheme of six hours of chlorine-containing feed/18 hours of chlorine-free feed with a rinse of the membrane after each chlorination cycle. The results, taken in each instance after exposure to chlorine, are shown in Table III.
Table III
Chlorine Flux Rejection Day No. (ppm) (gfd) (%) 0 0 14.5 97.2 3.6 98.2 3.8 98.8 17 10 2.8 98.6 19 0.5 4.2 98.0 24 10 4.5 98.1 28 0.5 3.4 97.0 3.5 97.0 3.3 97.0
BACKGROUND OF THE INVENTION
Composite reverse osmosis (RO) membranes are known but there is still a need in the art for RO
membranes that are resistant to degradation by halogens such as chlorine, which is often present in the feed waters of an RO process stream. There is also an ongoing need in the art for membranes with high salt rejection and flux rates.
One method of making RO membranes is by interfacial polymerization of a salt-rejecting layer on a porous polymeric support so as to form a composite membrane. See, for example, U.S. Patent Nos. 4,039,440 and 4,277,344. Meta-xylylenediamine has been condensed with trimesoyl chloride in an interfacial polymeriza-tion reaction on a polysulfone support so as to form a meta-xylylenediamide composite RO membrane. See NTIS
Report No. PB83-243170 entitled "Novel Composite Membranes" by Eric K. L. Lee, et al. dated April 1983.
However, the membranes so prepared were not useful for practical desalination applications due to their poor chlorine resistance and low fluxes (on the order of 6 to 10 gfd for those with salt rejections of 95% or better).
SUMMARY OF THE INVENTION
The novel RO membranes of the present invention are composite membranes comprising a ~ra-aromatic aliphatic diamide or diimide salt-rejecting layer interfacially polymerized on a microporous polymeric support.
DETAILED DESCRIPTION OF THE INVENTION
According to the present invention, novel composite RO membranes are provided that possess good 133323~
- chlorine resistance, high salt rejection and extraor-dinarily high fluxes, the membranes comprising an interfacially-polymerized salt rejection layer on a microporous polymeric support. The salt-rejecting layer is the interfacial polymerization reaction product of an aromatic polyacylhalide cross-linking agent and an aromatic diamine or diimine of the general formula R2HNRl-Ph-RlNHR2 (I) where Ph is a para-substituted phenylene group, Rl is an alkylene group containing from 1 to 2 carbon atoms, and R2 is hydrogen or an alkyl group containing from 1 to 2 carbon atoms.
Examples of suitable aromatic polyacylhalides are isophthaloyl chloride (IPC), trimesoyl chloride (TMC) and terephthaloylchloride (TPC).
The microporous polymeric support may be in the form of flat sheets or hollow fibers and may be selected from polysulfones, polyethersulfones, poly-phenylsulfones, polyvinylidenehalides, including poly-vinyl chloride, polyimides and polyetherimides, poly-amides, polyesters, and polycarbonates. Such supports are available commercially in flat sheets typically 2 to 6 mils thick.
Preferred hollow fiber supports typically have an internal diameter of 260 microns and an external diameter of 620 microns. The salt-rejecting layer may be formed on either the inner or lumens side of such hollow fibers or on the outer or external side of the fiber.
Flat sheet support membranes may be prepared by machine casting in accordance with known prior art methods. Hollow fiber support membranes may also be prepared according to known methods of hollow fiber `35 spin casting.
The composite membrane of the present invention is typically prepared by first immersing the support membrane in an aqueous solution of the diamine or diimine for a short period of time, preferably 1 to 3 minutes, removing it from the aqueous and draining it of excess solution, then immersing it in a dilute solu-tion of a cross-linking agent in an organic solvent at ambient temperatures for less than one minute to form the interfacial polymer on the support. The composite membrane so formed is air-dried, then heat-cured at temperatures in the range of 40C to 120C for about 10 minutes to complete the reaction. The aqueous solution should contain from about 0.25 wt% to about 5 wt% of the amine or imine, 0.5 wt% to 2 wt~ being preferred.
The organic phase should contain from about 0.01 wt% to about 1.0 wt% of the cross-linking agent, preferably 0.05 wt% to about 0.5 wt%, together with additives of triethylamine (functioning as an acid scavenger), and a surfactant.
Two of the most preferred reactants in forming the salt-rejecting layer of the composite membrane of the present invention are TMC and ~ara-xylylenediamine (pXDA), which produce a salt rejection layer having the chemical structure shown below:
~ C~ NWCH 2 ~CH 2 N H -o ~ NHCH2-~=~CH2NHC~IC~ NHCH24,3CH2NH-The general class of composite RO membranesprepared according to the present invention and having the structure (I) exhibit salt rejections in excess of 95%, good chlorine resistance and extraordinary fluxes as high as 20 to 40 gfd, making them especially suitable for.desalination of sea water by RO.
_4_ I 3 3323 Examples 1-5 A series of composite membranes of the present invention were prepared as follows. An asym-metric microporous polysulfone support flat sheet membrane approximately 4 mils thick and having micro-porosity on one side was immersed in a 2 wt% aqueous solution of pXDA containing 0.5 wt% triethylamine (as an acid scavenger) and 0.01 wt% of a surfactant sold under the trademark "Iconol NP-9" (BASF Wyandotte Corporation of Parsippany, New Jersey), drained of excess solution, then immersed in a 0.5 wt% solution of TMC in hexane for 30 seconds at room temperature, causing formation of a para-xylylenediamide film on the microporous surface of the polysulfone support. The resulting composite membrane was air-dried at room tem-perature overnight, then heat-cured for 10 minutes at 100C. The so-formed membrane was then tested in an 800 psi RO test, the feed water containing 0.5 wt% NaCl at pH 6.0 and 25C. The results, with flux being expressed in gallons per square foot of membrane surface area per day (gfd), are shown in Table I.
Table I
Membrane/ Flux Rejection Example No. (gfd) (%) 1 19.5 96.4 2 23.4 95.8 3 20.9 96.9 4 23.5 96.6 23.1 96.5 Examples 6-13 Composite membranes prepared in essentially the same fashion as those in Examples 1-5 with the exceptions noted were prepared in batches of three membranes at a time, and RO-tested, the average results of each group of three being as noted in Table II.
Table II
Membrane/ pXDA TMC Heat Cure Flux Rejection Example No. (wt%) (wt%) (C) (gfd) (%) 6 2 0.1 100 20.5 99.0 7 2 0.5 100 22.1 96.4 8 2 0.1 60 26.6 98.8 9 2~ 0.5 60 21.6 98.1 2 0.05 none 20.6 97.5 11 0.5 0.1 60 25.5 97.2 12 2 0.1 60 36.6 97.1 13 1 0.1 60 42.8 96.4 Example 14 Chlorine resistance of an exemplary membrane prepared in essentially the same fashion as in Examples 1-5 was tested by subjecting the membrane to the same type of RO test conditions as set forth in Examples 6-13 for 40 days except that the pH was 4.5 and the feed water contained either 0, 0.5 or 10 ppm free chlorine in the form of NaOCl. In order to accelerate the effects of chlorine on the performance of the membrane, the test was run in an "on/off" scheme of six hours of chlorine-containing feed/18 hours of chlorine-free feed with a rinse of the membrane after each chlorination cycle. The results, taken in each instance after exposure to chlorine, are shown in Table III.
Table III
Chlorine Flux Rejection Day No. (ppm) (gfd) (%) 0 0 14.5 97.2 3.6 98.2 3.8 98.8 17 10 2.8 98.6 19 0.5 4.2 98.0 24 10 4.5 98.1 28 0.5 3.4 97.0 3.5 97.0 3.3 97.0
Claims (7)
1. A composite membrane comprising:
(a) a microporous polymeric support; and (b) an aromatic aliphatic diamide/diimide membrane formed on said support by inter-facial polymerization of an aromatic polyacylhalide and an aromatic aliphatic amine/imine of the formula R2HNR1-Ph-R1NHR2 where Ph is a para-substituted phenylene group, R1 is an alkylene group containing from 1 to 2 carbon atoms, and R2 is hydrogen or an alkyl group containing from 1 to 2 carbon atoms.
(a) a microporous polymeric support; and (b) an aromatic aliphatic diamide/diimide membrane formed on said support by inter-facial polymerization of an aromatic polyacylhalide and an aromatic aliphatic amine/imine of the formula R2HNR1-Ph-R1NHR2 where Ph is a para-substituted phenylene group, R1 is an alkylene group containing from 1 to 2 carbon atoms, and R2 is hydrogen or an alkyl group containing from 1 to 2 carbon atoms.
2. The membrane of claim 1 wherein the microporous polymeric support is selected from poly-sulfones, polyethersulfones, polyphenylsulfones, poly-vinylidenehalides, polyimides and polyetherimides, polyamides, polyesters, and polycarbonates.
3. The membrane of claim 1 wherein the aromatic polyacylhalide is trimesoyl chloride, the aromatic aliphatic amine/imine is para-xylylenediamine, and R2 is hydrogen.
4. The membrane of claim 1 wherein the support is selected from flat sheets and hollow fibers.
5. The membrane of claim 3 wherein the support is a hollow fiber and the membrane is formed on the inside of said hollow fiber.
6. The membrane of claim 4 wherein the support is a hollow fiber and said membrane is formed on the outer surface of said hollow fiber.
7. A process for desalination of saline water by reverse osmosis comprising contacting the saline water under pressure with the membrane of claim 1, 2, 3 or 4.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/098,201 US4853122A (en) | 1987-09-15 | 1987-09-15 | P-xylylenediamide/diimide composite RO membranes |
| US098,201 | 1987-09-15 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1333238C true CA1333238C (en) | 1994-11-29 |
Family
ID=22267944
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000577202A Expired - Fee Related CA1333238C (en) | 1987-09-15 | 1988-09-13 | P-xylylenediamide/diimide composite reverse osmosis membranes |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US4853122A (en) |
| EP (1) | EP0308153B1 (en) |
| JP (1) | JPH01135504A (en) |
| AT (1) | ATE69969T1 (en) |
| AU (1) | AU601622B2 (en) |
| CA (1) | CA1333238C (en) |
| DE (1) | DE3866651D1 (en) |
| ES (1) | ES2027766T3 (en) |
| GR (1) | GR3003311T3 (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4978455A (en) * | 1987-09-15 | 1990-12-18 | Bend Research, Inc. | P-xylylenediamide/diimide composite RO membranes |
| US5693227A (en) * | 1994-11-17 | 1997-12-02 | Ionics, Incorporated | Catalyst mediated method of interfacial polymerization on a microporous support, and polymers, fibers, films and membranes made by such method |
| US6083297A (en) * | 1995-12-13 | 2000-07-04 | Whatman, Inc. | Gas dehydration membrane with low oxygen and nitrogen permeability |
| CN1110354C (en) * | 1999-12-28 | 2003-06-04 | 世韩工业株式会社 | Polyamide reverse osmosis composite film and its producing method |
| US7347855B2 (en) * | 2001-10-29 | 2008-03-25 | Ultrashape Ltd. | Non-invasive ultrasonic body contouring |
| BR0215785A (en) * | 2002-06-25 | 2006-06-06 | Ultrashape Inc | Useful devices and methodologies for body aesthetics |
| CN101146574A (en) * | 2005-02-06 | 2008-03-19 | 超形态公司 | Non-thermal acoustic tissue modification |
| GB201012083D0 (en) | 2010-07-19 | 2010-09-01 | Imp Innovations Ltd | Thin film composite membranes for separation |
| GB201117950D0 (en) | 2011-10-18 | 2011-11-30 | Imp Innovations Ltd | Membranes for separation |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3612282A (en) * | 1969-08-14 | 1971-10-12 | Sing Wang Cheng | Supporting structures and containing vessels for reverse osmosis and filtration |
| US3744642A (en) * | 1970-12-30 | 1973-07-10 | Westinghouse Electric Corp | Interface condensation desalination membranes |
| US3830733A (en) * | 1972-03-09 | 1974-08-20 | Union Carbide Corp | Diffusion membranes of controlled permeability,apparatus and process |
| US4039440A (en) * | 1972-09-19 | 1977-08-02 | The United States Of America As Represented By The Secretary Of The Interior | Reverse osmosis membrane |
| JPS5543367B2 (en) * | 1975-01-08 | 1980-11-06 | ||
| US4259183A (en) * | 1978-11-07 | 1981-03-31 | Midwest Research Institute | Reverse osmosis membrane |
| US4277344A (en) * | 1979-02-22 | 1981-07-07 | Filmtec Corporation | Interfacially synthesized reverse osmosis membrane |
| JPS5824303A (en) * | 1981-08-03 | 1983-02-14 | Teijin Ltd | Oxidation resistant composite semipermeable membrane |
| US4606943A (en) * | 1983-03-18 | 1986-08-19 | Culligan International Company | Method for preparation of semipermeable composite membrane |
| US4659475A (en) * | 1984-03-19 | 1987-04-21 | Midwest Research Institute | Composite reverse osmosis membrane comprising crosslinked poly(amine-epihalohydrin adduct) |
| JPS6295105A (en) * | 1985-10-16 | 1987-05-01 | イ−・アイ・デユポン・デ・ニモアス・アンド・カンパニ− | Method for coating composite reverse osmosis membrane |
| US4626468A (en) * | 1986-04-23 | 1986-12-02 | E. I. Du Pont De Nemours And Company | Microporous support layer with interfacially polymerized copolyamide thereon |
-
1987
- 1987-09-15 US US07/098,201 patent/US4853122A/en not_active Expired - Fee Related
-
1988
- 1988-09-12 EP EP88308389A patent/EP0308153B1/en not_active Expired - Lifetime
- 1988-09-12 DE DE8888308389T patent/DE3866651D1/en not_active Expired - Fee Related
- 1988-09-12 ES ES198888308389T patent/ES2027766T3/en not_active Expired - Lifetime
- 1988-09-12 AT AT88308389T patent/ATE69969T1/en not_active IP Right Cessation
- 1988-09-13 AU AU22173/88A patent/AU601622B2/en not_active Ceased
- 1988-09-13 CA CA000577202A patent/CA1333238C/en not_active Expired - Fee Related
- 1988-09-14 JP JP63228860A patent/JPH01135504A/en active Pending
-
1991
- 1991-12-11 GR GR91401935T patent/GR3003311T3/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01135504A (en) | 1989-05-29 |
| ATE69969T1 (en) | 1991-12-15 |
| US4853122A (en) | 1989-08-01 |
| AU2217388A (en) | 1989-03-16 |
| DE3866651D1 (en) | 1992-01-16 |
| GR3003311T3 (en) | 1993-02-17 |
| AU601622B2 (en) | 1990-09-13 |
| EP0308153A1 (en) | 1989-03-22 |
| ES2027766T3 (en) | 1992-06-16 |
| EP0308153B1 (en) | 1991-12-04 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKLA | Lapsed |