EP0008945A2
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EP
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Semipermeable composite membrane, process for producing said membrane, and method of desalination using said membrane
Assignee: Teijin Ltd
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Filing: 1979-09-05
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Granted: —
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Expires: 1999-09-05
Abstract
Abstract A semipermeable composite membrane comprising a thin semipermeable film of a polymeric material deposited on one side of a microporous substrate, said polymeric material being prepared by crosslinking a soluble polymer containing at least 30 mole % of a recurring unit of the formula wherein all symbols are as defined in claim 1 and having at least 0.2 milliequivalent, per gram of said polymer, of an amino group containing 1 to 2 active hydrogen atoms, with a polyfunctional compound containing at least two functional groups capable of reacting with the amino group having or 2 active hydrogen atoms; and a process for preparing the same The semipermeable composite membrane of this invention is especially useful for desalination of saline or brackish water by reverse osmosis. The membrane has good selective permeability characteristics and good chemical resistance and thermal stability.
Inventors
- 👤 Takeyuki Kawaguchi
- 👤 Yutaka Taketani
- 👤 Noriaki Sasaki
- 👤 Hiroyoshi Minematsu
- 👤 Yuzuru Hayashi
- 👤 Shigeyoshi Hara
Bibliographic Details
Application Number
—
Jurisdiction
EP
Data Source
google_patents
Last Synchronized
2026-10-24 00:29
CPC Classifications
B; B01; B01D; B01D71/00; B01D71/06; B01D71/58; B01D71/60; B01D71/601; B01D69/00; B01D69/12; B01D69/125; B01D71/44; C; C08; C08G; C08G85/00; C08G85/004
Claims Analysis
Total Claims: 39
Claim 1
Independent Claim
380 words
A semipermeable composite membrane comprising a thin semipermeable film of a polymeric material deposited on one side of a microporous substrate, said polymeric material being prepared by crosslinking a soluble polymer containing at least 30 mole% of a recurring unit of the formula wherein Q represents an organic radical containing 2 to 30 carbon atoms and having a valence of (3 + p) which optionally contains a heteroatom selected from oxygen, sulfur, nitrogen and halogen; Y is bonded to a carbon atom in group Q and represents a direct bond, an alkylene group containing 1 to 3 carbon atoms or an unsubstituted or substituted phenylene group; Z represents or -SO 2 -; R 1 represents a hydrogen atom, or a monovalent organic radical of 1 to 20 carbon atoms which may contain an amino group containing 1 or 2 active hydrogen atoms and a heteroatom selected from oxygen, nitrogen and halogen, and R 2 represents an amino group containing 1 oi 2 active hydrogen atoms or a monovalent organic radical containing 1 to 20 carbon atoms which contains at least one amine group containing 1 or 2 active hydrogen atoms and may contain a heteroatom selected from oxygen, nitrogen and halogen, or R 1 and R 2 , together with the nitrogen atom to which they are bonded, represent a 5. to 18-membered nitrogen-containing heterocyclic ring which contains at least one amino group having one active hydrogen atom; when group Y represents a direct bond and group Z represents R 1 may represent bonded to that carbon atom of the group Q which is bonded, either directly or through 1 or 2 carbon atoms, to the carbon atom to which the group Y is bonded; p is 0, 1 or 2; and when p is 1 or 2, L represents the group in which W represents a direct bond or an alkylene group of 1 to 3 carbon atoms and Z, R 1 and R 2 are as defined above, and having at least 0.2 milliequivalent, per gram of said polymer, of an amino group having 1 or 2 active hydrogen atoms, with a polyfunctional compound containing at least two functional groups capable of reacting with the amino group having 1 or 2 active hydrogen atoms of the soluble polymer.
Claim 2
Dependent Claim
380 words
A semipermeable composite membrane comprising a thin semipermeable film of a polymeric material deposited on one side of a microporous substrate, said polymeric material being prepared by crosslinking a soluble polymer containing at least 30 mole% of a recurring unit of the formula wherein Q represents an organic radical containing 2 to 30 carbon atoms and having a valence of (3 + p) which optionally contains a heteroatom selected from oxygen, sulfur, nitrogen and halogen; Y is bonded to a carbon atom in group Q and represents a direct bond, an alkylene group containing 1 to 3 carbon atoms or an unsubstituted or substituted phenylene group; Z represents or -SO 2 -; R 1 represents a hydrogen atom, or a monovalent organic radical of 1 to 20 carbon atoms which may contain an amino group containing 1 or 2 active hydrogen atoms and a heteroatom selected from oxygen, nitrogen and halogen, and R 2 represents an amino group containing 1 oi 2 active hydrogen atoms or a monovalent organic radical containing 1 to 20 carbon atoms which contains at least one amine group containing 1 or 2 active hydrogen atoms and may contain a heteroatom selected from oxygen, nitrogen and halogen, or R 1 and R 2 , together with the nitrogen atom to which they are bonded, represent a 5. to 18-membered nitrogen-containing heterocyclic ring which contains at least one amino group having one active hydrogen atom; when group Y represents a direct bond and group Z represents R 1 may represent bonded to that carbon atom of the group Q which is bonded, either directly or through 1 or 2 carbon atoms, to the carbon atom to which the group Y is bonded; p is 0, 1 or 2; and when p is 1 or 2, L represents the group in which W represents a direct bond or an alkylene group of 1 to 3 carbon atoms and Z, R 1 and R 2 are as defined above, and having at least 0.2 milliequivalent, per gram of said polymer, of an amino group having 1 or 2 active hydrogen atoms, with a polyfunctional compound containing at least two functional groups capable of reacting with the amino group having 1 or 2 active hydrogen atoms of the soluble polymer.
Claim 3
Dependent Claim
22 words
A membrane according to claim 1 wherein said soluble polymer contains at least 50 mole% of the recurring unit of formula (I).
Claim 4
Dependent Claim
210 words
A membrane according to claim 1 or 2 wherein said recurring unit is represented by the formula (I-a) wherein R 3 represents a hydrogen atom or an alkyl group containing 1 to 5 carbon atoms; R 4 and R 5 , independently from each other, represent a hydrogen atom, an alkyl group containing 1 to 5 carbon atoms, or the group -R 7 -COOR 8 , -O-R 81 , or -O-R 82 -X', in which R 6 represents a hydrogen atom or an alkyl group containing 1 to 5 carbon atoms, R 7 represents a direct bond or an alkylene f roup containing 1 to 3 carbon atoms, R 8 represents a hydrogen atom, an alkali metal, a quaternary ammonium salt radical or an alkyl group containing 1 to 5 carbon atoms, R 81 represents an alkyl group containing 1 to 5 carbon atoms, R 82 represents an alkylene group containing 1 to 4 carbon atoms, and X' represents chlorine or bromine; W, Y, Z, R 1 and R 2 are as defined hereinabove; and a and b, independently from each oth;r, are 0 or 1; or by the formula (I-b) wherein F represents a hydrogen atom or the group and R 1 and R 2 are as defined hereinabove.
Claim 5
Dependent Claim
138 words
A membrane according to claim 1 or 2 wherein said recurring unit is represented by the formula (I-c) wherein R 9 represents a direct bond or the group U represents -0-, -CH 2 - or G 1 and G 2 , independently from each other, represent a halogen atom, an alkyl group containing 1 to 3 carbon atoms, a haloalkyl group containing 1 to-3 carbon atoms or the group c, d and e, independently from each other, are 0 or 1; G 3 and G 4 , independently from each other, represent a halogen atom,an alkyl group containing 1 to 3 carbon atoms, or a haloalkyl group containing 1 to 3 cerbon atoms; f and g, independently from each other, are integers of 0 to 2; and W, Z, R 1 and R 2 are as defined hereinabove.
Claim 6
Dependent Claim
40 words
A membrane according to any one of claims 1 to 4 wherein Y represents a direct bond, a methylene group or a phenylene group of the formula in which R 10 represents a hydrogen atom, -COOH, -SO 3 H, or
Claim 7
Dependent Claim
16 words
A membrance according to claim 4 wherein W represents a direct bond or a methylene group.
Claim 8
Dependent Claim
14 words
A membrane according to any one of claims 1 to 6 wherein Z is
Claim 9
Dependent Claim
52 words
A membrane according to any one of claims 1 to 7 wherein the group represents a monovalent substituted amino group resulting from the removal of one active hydrogen atom from one of the amino groups of a polyamino compound containing at least two amino groups with 1 or 2 active hydrogen atoms.
Claim 10
Dependent Claim
221 words
A membrane according to any one of the preceding claims wherein R 1 represents a hydrogen atom, or an alkyl, cycloalkyl, aryl, aralkyl or heterocyclic group containing 1 to 20 carbon atoms which may contain 1 to 8 heteroatoms or heteroatom-containing atomic groupings selected from halogen atoms, hydroxyl groups, cyano groups, carboxyl groups, alkoxycarbonyl groups with the alkyl moiety containing 1 to 5 carbon atoms, primary amino groups (-NH 2 ), ether linkages (-0-), imino linkages ( ) and tertiary amino linkages (-N-); R 2 represents a primary amino group, a secondary amino group mono- substituted by an alkyl group containing 1 to 5 carbon atoms, or an alkyl, cycloalkyl, aryl, aralkyl or heterocyclic group containing 1 to 20 carbon atoms which contains 1 to 10 primary amino groups or imino linkages and may contain 1 to 9 heteroatoms or heteroatom-containing atomic groupings selected from halogen atoms, hydroxyl groups, cyano groups, carboxyl groups, alkoxycarbonyl groups with the alkyl moiety containing 1 to 5 carbon atoms, ether linkages and tertiary amino linkages ( ); or R 1 and R 2 , together with the nitrogen atom to which they are bonded, represents a 5- to 18-membered heterocyclic ring which contains at least one amino group having one active hydrogen atom and may contain 1 to 4 nitrogen or oxygen atoms as heteroatoms.
Claim 11
Dependent Claim
134 words
A membrane according to claim 1 or 2 wherein said recurring unit is represented by the formula (I-d) wherein R 11 and R12, independently from each other, represent a hydrogen atom or a methyl group; R 13 represents a primary amino group, a secondary amino group, a secondary amino group mono-substituted by an alkyl group containing 1 to 5 carbon atoms, or an alkyl, cycloalkyl, aryl, aralkyl or heterocyclic group containing 1 to 20 carbon atoms which contains 1 to 10 primary amino groups or imino linkages and nay contain 1 to 9 heteroatoms or heteroatom-containing atomic groupings selected from halogen atoms, hydroxyl groups, cyano groups, carboxyl groups, alkoxycarbonyl groups with the alkyl moiety containing 1 to 5 carbon atoms, ether linkages and tertiary amino linkages ( ); and h is 0 or 1.
Claim 12
Dependent Claim
333 words
A membrane according to claim 3 wherein said recurring unit is represented by the formula (I-a-1) wherein R 301 represents a hydrogen atom or a methyl group; R 401 and R 501 , independently from each other, represent a hydrogen atom, a methyl group, -COOR 801 , -OR 801 , in which X is chlorine or bromine, or -CH 2 -COOR 801 ; Y, represents a direct bond, a methylene group or a phenylene group of the formula in which R 10 represents a hydrogen atom, -COOH, -SO 3 H, or Z represents or -SO 2 -; R 101 represents a hydrogen atom,an alkyl, cycloalkyl, aryl, aralkyl or heterocyclic group containing 1 to 12 carbon atoms which may contain 1 to 8 heteroatoms or heteroatom-containing atomic groupings selected from halogen atoms, hydroxyl groups, cyano groups, carboxyl groups, alkoxycarbonyl groups with the alkyl moiety containing 1 to 5 carbon atoms, primary amino groups (-NH 2 ), ether linkages (-O-), imino linkages (-NH-), and tertiary amino linkages ( ); R 201 represents a primary amino group, a secondary amino group monosubstituted by an alkyl group containing 1 to 5 carbon atoms, or an alkyl, cycloalkyl, aryl, aralkyl or heterocyclic group containing 1 to 12 carbon atoms which contains 1 to 6 primary amino groups or imino linkages and may contain 1 to 6 heteroatoms or heteroatom-containing atomic groupings selected from halogen atoms, hydroxyl groups, cyano groups, carboxyl groups, alkoxycarbonyl groups with the alkyl moiety containing 1 to 5 carbon atoms, ether linkages and tertiary amino linkages ( ); or R 101 and R 201 , together with the nitrogen atom to which they are bonded, represents a 5- to 6-membered nitrogen-containing heterocyclic ring which contains at least one amino group having one active hydrogen atom and may contain 1 to 2 nitrogen or oxygen atoms as heteroatoms; R 801 represents a hydrogen atom or an alkyl group containing 1 to 3 carbon atoms; and a and b, independently from each other, are 0 or 1.
Claim 13
Dependent Claim
169 words
12 A membrane according to claim 8 wherein said polyamino compound is a compound of the formula wherein A 1 and A 3 , independently from each other, represent a hydrogen atom or a lower alkyl group; A? represents an alkylene group having 1 to 10 carbon atoms which may contain an ether linkage; A4 and A 5 , independently from each other, represent a hydrogen atom or a lower alkyl group optionally substituted with a cyano, hydroxyl or lower alkoxycarbonyl group; A 6 represents a hydrogen atom or a group of the formula -CH 2 -CH 2 -NH-A 4 ; A 7 represents a lower alkylene group; A 8 represerts a hydrogen atom or a lower alkyl group optionally substituted with a cyano, hydroxyl or lower alkoxycarbonyl group; A 9 represents a lower alkylene group; at least one of A 10 , A 11 and A 12 represents a lower alkyl group, and the remainder represent a hydrogen atom; and i is an integer of 2 to 6.
Claim 14
Dependent Claim
22 words
A membrane according to any one of the preceding claims wherein said soluble polymer consists essentially of the recurring unit (I) alone.
Claim 15
Dependent Claim
38 words
A membrane according to claim 3 or 10 wherein said polymer is a copolymer composed of the recurring unit of formula (I-a), (I-b) or (I-d) and at least one other recurring unit derived from a radical polymerizable monomer.
Claim 16
Dependent Claim
21 words
A membrane according to claim 14 wherein said radical polymerizable monomer is a compound containing one or two ethylenically unsaturated bonds.
Claim 17
Dependent Claim
22 words
A membrane according to claim 1 wherein said compound containing one or two ethylenically unsaturated bonds contains 2 to 15 carbon atoms.
Claim 18
Dependent Claim
26 words
A membrane according to claim 15 or 16 wherein said compound containing one or two ethylenically unsaturated bonds has a molecular weight of 28 to 300.
Claim 19
Dependent Claim
38 words
A membrane according to claim 15, 16 or 17 wherein said compound containing one or two ethylenically unsaturated bonds has a solubility of at least 0.5 g at 25°C in 100 g of water or a lower alcohol.
Claim 20
Dependent Claim
254 words
A membrane according to claim 14 wherein said monomer is a compound represented by the formula (III-1) wherein R 14 represents a hydrogen atom or an alkoxycarbonyl group with the alkyl moiety containing 1 to 10 carbon atoms; R 15 represents a hydrogen or halogen atom or a methyl group, R 16 represents a hydrogen or halogen atom, an alkoxy group containing 1 to 10 carbon atoms optionally substituted by a hydroxyl group and/or a halogen atom, an alkoxycarbonyl group with the alkyl moiety containing 1 to 10 carbon atoms, an alkanoyl group containing 1 to 10 carbon atoms, an alkanoyloxy group containing 1 to 10 carbon atoms, an alkyl group containing 1 to 10 carbon atoms substituted by the group -SO 3 M or hydroxyl group, a phenyl group optionally substituted by the group -SO 3 M or a methyl group, a glycidyloxy group, or a group of the formula -(̵ B-0 )̵H in which D represents an ethylene or propylene group, and j is an integer of 1 to 8; R 14 and R 15 , together, may represent an ethylenedioxy group; and M represents an alkali metal; or by the formula (III-2) wherein R 17 and R 18 , independently from each other, represent a hydrogen atom or a methyl group; J represents an oxygen atom or a group of the formula R 19 and R 20 , independently from each other, represent a hydrogen atom or an alkyl group containing 1 to 10 carbon atoms; and X⊖ represents an anion.
Claim 21
Dependent Claim
279 words
A membrane according to claim 3 or 10 wherein said polymer is a copolymer composed of (A) at least 50 mole% of the recurring unit of formula (I-a), (I-b) or (I-d), and (B) up to 50 mole% of at least one recurring unit selected from those of the formulae wherein R 21 represents a hydrogen atom or an alkoxycarbonyl group with the alkyl moiety containing 1 to 10 carbon atoms; R 22 represents a hydrogen or halogen atom or a methyl group; R 23 represents a hydrogen or halogen atom, an alkoxy group containing 1 to 10 carbon atoms optionally mono- or di-substituted by a hydroxyl group and/or a halogen atom, an alkoxycarbonyl group with the alkyl moiety containing 1 to 10 carbon atoms, an alkanoyl group containing 1 to 10 carbon atoms, an alkanoyloxy group containing 1 to 10 carbon atoms, an alkyl group containing 1 to 10 carbon atoms which may be' mono-substituted by the group -SO 3 M or a hydro- oxy group, a phenyl group optionally mon-substituted by the group -SO 3 M or a methyl group, a glycidyloxy group, a group of the formula (̵B-O)̵N in which B represents an ethylene or propylene group and j is an integer of 1 to 8, the group the group in which R 1 and R 2 are defined hereinabove; R 21 and R 22 together may represent an ethylenedioxy group; R 22 and R 23 together may represent -O- -O-; and M represents an alkali metal; and wherein R 17 , R 18 and J are as defined with regard to formula (III-a), and R 24 represents a direct bond or - 5 0 2 -.
Claim 22
Dependent Claim
35 words
A membrane according to any one of the preceding claims wherein said soluble polymer has a solubility of at least 0.1 g at 25°C in 100 g of water or a water-miscible polar organic solvent.
Claim 23
Dependent Claim
31 words
A membrane according to claim 21 wherein said soluble polymer has a solubility of at least 0.5 g at 25°C in 100 g of water or a water-miscible polar organic solvent.
Claim 24
Dependent Claim
24 words
A membrane according to claim 21 or 22 wherein said organic solvent is selected from lower alcohols, formic acid, dimethylformamide, dimethyl-sulfoxide, tetramethylenesulfone and N-methylpyrrolidone.
Claim 25
Dependent Claim
44 words
A membrane according to any one of the preceding claims wherein said soluble polymer has an inherent viscosity, determined at 30°C in the solvent of claim 21, 22 or 23 with 0.5% by weight of the polymer in solution, of at least 0.1 dl/g.
Claim 26
Dependent Claim
19 words
A membrane according to claim 24, wherein said soluble polymer has an inherent viscosity of 0.15 to 5.0 dl/g.
Claim 27
Dependent Claim
40 words
A membrane according to any one of the preceding claims wherein said polyfunctional compound is a polyfunctional compound containing at least two functional groups selected from acid halide, sulfonyl halide, isocyanate, N-haloformyl, haloformate and acid anhydride groups, or cyanuric chloride.
Claim 28
Dependent Claim
21 words
A membrane according to any one of the preceding claims wherein the polyfunctional compound is an aromatic., heterocyclic or alicyclic compound.
Claim 29
Dependent Claim
34 words
A membrane according to claim 26 or 27 wherein the polyfunctional compound is a di- or tri-funqtional aromatic compound containing two or three functional groups selected from acid halide, sulfonyl halide and.acid anhydride groups.
Claim 30
Dependent Claim
21 words
A membrane according to claim 26 or 27 wherein the polyfunctional compound is a difunctional aromatic compound containing two isocyanate groups.
Claim 31
Dependent Claim
30 words
A membrane according to claim 26 or 27 wherein the polyfunctional compound is a trifunctional aromatic compound, or a mixture of a difunctional aromatic compound and a trifunctional aromatic compound.
Claim 32
Dependent Claim
26 words
A membrane according to claim 30 wherein the di-or tri-functional aromatic compound is isophthaloyl chloride, terephthaloyl chloride, trimesoyl chloride, 3-chloro- sulfonylisophthaloyl chloride, or cyanuric acid chloride.
Claim 33
Dependent Claim
23 words
A membrane according to any one of the preceding claims wherein said thin semipermeable film has a thickness of at least 100 A.
Claim 34
Dependent Claim
24 words
A membrane according to any one of the preceding claims wherein said microporous substrate is composed of an asymmetrical membrane of an aromatic polysulfone.
Claim 35
Dependent Claim
69 words
A process for producing a semipermeable composite membrane as claimed in any one of the preceding claims, which process comprises (a) treating a microporous substrate with a solution containing the soluble polymer, (b) contacting the treated microporous substrate interfacially with a solution of the polyfunctional compound, and (c) optionally heating them to form a thin film of the crosslinked polymer having semipermeability on one side of the microporous substrate.
Claim 36
Dependent Claim
18 words
A process according to claim 34 wherein the resulting composite membrane is coated with a water-soluble organic polymer.
Claim 37
Dependent Claim
21 words
A process according to c aim 35 wherein the water-soluble organic polymer is polyvinyl alcohol, polyvinyl pyrrolidone or polyvinyl methyl ether.
Claim 38
Dependent Claim
21 words
A process according to c aim 35 wherein the water-soluble organic polymer is polyvinyl alcohol, polyvinyl pyrrolidone or polyvinyl methyl ether.
Claim 39
Independent Claim
40 words
A method for the desalination of saline or brackish water by reverse osmosis which comprises contacting the saline or brackish water under pressure with, as reverse osmosis membrane, a membrane as claimed in any one of claims 1 to 33.
References Cited (Backward Citations)
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