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US4260652A Expired / Lapsed US ⏱️ 0.0 years remaining

Preparation of permselective composite membrane

Assignee: Teijin Ltd
•
Filing: 1978-06-05
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Granted: 1981-04-07
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Expires: 1998-06-05
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Abstract

Abstract A process and composition for producing a permselective composite membrane. The process comprises dissolving a specified imidazolone ring-containing aromatic polymer in an aqueous liquid medium containing a water-miscible amine having a pKa of more than 5.0 in a concentration of at least 5% by weight, coating the polymer solution on a microporous substrate, and drying the coating to form an ultrathin film on the substrate. The permselective composite membrane obtained is especially useful as a reverse osomsis membrane.

Inventors

  • 👤 Yutaka Taketani
  • 👤 Yuzuru Hayashi
  • 👤 Takeyuki Kawaguchi
  • 👤 Tomoyoshi Ono
  • 👤 Ko Mori

Bibliographic Details

Application Number —
Jurisdiction US
Data Source google_patents
Last Synchronized 2026-11-03 17:23
CPC Classifications
C; C08; C08G; C08G73/00; C08G73/06; C08G73/18; B; B01; B01D; B01D71/00; B01D71/06; B01D71/58; B01D71/62; Y; Y10; Y10S; Y10S524/00; Y10S524/909

Claims Analysis

Total Claims: 31
Claim 1
Independent Claim 318 words
A process for producing a permselective composite membrane, which comprises (1) dissolving an imidazolone ring-containing aromatic polymer in an aqueous liquid medium containing a water-miscible amine having a pka of more than 5.0 in a concentration of at least 5% by weight to form a solution containing the polymer in a concentration of 0.01 to 20.0% by weight, said polymer comprising at least 30 mole %, based on the entire recurring units, of at least one recurring unit of the following formula ##STR114## wherein A 1 represents an aromatic group having a valence of (3+l), the dashed line represents the presence or absence of a bond, and the two nitrogen atoms and W 1 are all bonded to the nuclear carbon atoms of the aromatic group A 1 ; A 2 represents an aromatic group having a valence of (2+m); Y is --O-- or ##STR115## in which R 1 is a hydrogen atom or a monovalent hydrocarbon residue; and the two nitrogen atoms bonded to A 1 are bonded to the ring carbon atoms at the orthoposition of the aromatic group A 1 ; l and m are identical or different and each represent an integer of 0 to 3; when Y is ##STR116## and one of W 1 groups is bonded to the ring carbon atom at the ortho-position of the aromatic group A 1 together with Y, the W 1 , Y and A 1 can form a 5-membered ring same as ##STR117## in which all symbols are the same as defined above; and when W 1 does not form the 5-membered ring, W 1 and W 2 are identical or different and represent at least one group selected from substituted nitrogen-containing groups derived from a primary amino group; (2) coating the resulting polymer solution on a microporous substrate, and (3) drying the coating to form an ultrathin film of the polymer on the microporous substrate.
Claim 2
Dependent Claim 318 words
A process for producing a permselective composite membrane, which comprises (1) dissolving an imidazolone ring-containing aromatic polymer in an aqueous liquid medium containing a water-miscible amine having a pka of more than 5.0 in a concentration of at least 5% by weight to form a solution containing the polymer in a concentration of 0.01 to 20.0% by weight, said polymer comprising at least 30 mole %, based on the entire recurring units, of at least one recurring unit of the following formula ##STR114## wherein A 1 represents an aromatic group having a valence of (3+l), the dashed line represents the presence or absence of a bond, and the two nitrogen atoms and W 1 are all bonded to the nuclear carbon atoms of the aromatic group A 1 ; A 2 represents an aromatic group having a valence of (2+m); Y is --O-- or ##STR115## in which R 1 is a hydrogen atom or a monovalent hydrocarbon residue; and the two nitrogen atoms bonded to A 1 are bonded to the ring carbon atoms at the orthoposition of the aromatic group A 1 ; l and m are identical or different and each represent an integer of 0 to 3; when Y is ##STR116## and one of W 1 groups is bonded to the ring carbon atom at the ortho-position of the aromatic group A 1 together with Y, the W 1 , Y and A 1 can form a 5-membered ring same as ##STR117## in which all symbols are the same as defined above; and when W 1 does not form the 5-membered ring, W 1 and W 2 are identical or different and represent at least one group selected from substituted nitrogen-containing groups derived from a primary amino group; (2) coating the resulting polymer solution on a microporous substrate, and (3) drying the coating to form an ultrathin film of the polymer on the microporous substrate.
Claim 3
Dependent Claim 30 words
The process of claim 1 wherein the imidazolone ring-containing aromatic polymer comprises at least 80 mole %, based on the entire recurring units, of the recurring unit of formula (I).
Claim 4
Dependent Claim 124 words
The process of claim 1 the imidazolone ring-containing aromatic polymer comprises (1) 30 to 100 mole %, based on the entire recurring units, of the recurring unit of formula (I); and (2) 0 to 70 mole %, based on the entire recurring units, of an unsubstituted or substituted amino-containing recurring unit of the following formula ##STR118## wherein A 1 , A 2 , Y, W 2 , l and m and the dashed line are the same as defined in formula (I); and W 3 represents at least one group selected from the group consisting of a mono-substituted nitrogen-containing groups derived from the primary amino group, the total amount of the recurring units of formulae (I) and (II) being at least 80 mole %.
Claim 5
Dependent Claim 135 words
The process of claim 3 wherein the recurring unit of formula (II) is a recurring unit of the following formula ##STR119## wherein A 11 represents a member selected from the group consisting of ##STR120## A 21 represents a member selected from the group consisting of ##STR121## in which R 2 is a lower alkylene group, and the benzene ring A and/or B is optionally substituted by at least one member selected from the class consisting of lower alkyl groups, a carboxyl group and a sulfo group; and R 3 and R 4 reach represents a group selected from the group consisting of --COOR 5 , --SO 2 R 5 , --COR 5 and --CONH--R 5 in which R 5 represents an organic group having up to 15 carbon atoms; and Y' represents --O-- or --NH--.
Claim 6
Dependent Claim 54 words
The process of claim 1 wherein at least a part of the recurring units of formula (I) is recurring unit of the following formula ##STR122## wherein A 1 , A 2 , W 1 , W 2 , l and m are as defined with regard to formula (I), with the proviso that l-1≦0.
Claim 7
Dependent Claim 106 words
The process of claim 1 wherein in formula (I), A 1 represents an aromatic group having a valence of (3+l) and containing 6 to 20 carbon atoms and optionally including an inert substituent selected from the group consisting of lower alkyl groups and lower alkoxy groups in addition to the group W 1 ; and A 2 represents an aromatic group having a valence of (2+m) and containing 6 to 20 carbon atoms and optionally including an inert substituent selected from the group consisting of lower alkyl groups, lower alkoxy groups, a carboxyl group and a sulfo group in addition to the group W 2 .
Claim 8
Dependent Claim 37 words
The process of claim 1 wherein W 1 and W 2 in formula (I) each represents a member selected from the class consisting of a carbamide group, a sulfonamide group, a urea group and a urethane group.
Claim 9
Dependent Claim 87 words
The process of claim 1 wherein the recurring unit of formula (I) is a recurring unit of the following formula ##STR123## wherein A 11 represents a member selected from the group consisting of ##STR124## and A 21 represents a member selected from the group consisting of ##STR125## in which R 2 represents a lower alkyl group, and the benzene ring A and/or B is optionally substituted by at least one member selected from the group consisting of lower alkyl groups, a carboxyl group and a sulfo group.
Claim 10
Dependent Claim 32 words
The process of claim 1 wherein the aromatic polymer has an inherent viscosity, measured at 30° C. for an N-methylpyrrolidone solution in a concentration of 0.5 g/100 ml, of at least 0.1.
Claim 11
Dependent Claim 16 words
The process of claim 1 wherein the water-miscible amine has a pka of 5.1 to 12.
Claim 12
Dependent Claim 167 words
The process of claim 1 wherein the water-miscible amine represents a member selected from the group consisting of aliphatic amines of the formula ##STR126## wherein R 6 , R 7 and R 8 are identical or different and each represent a hydrogen atom, a lower alkyl group, a lower hydroxyalkyl group, or the group of the formula ##STR127## in which R 9 and R 10 each represent a lower alkylene group, k is an integer of 1 to 6, and l is 0 or an integer of 1 to 3, and when k is at least 2, the recurring units ##STR128## are identical or different, with the proviso that at least one of R 6 , R 7 and R 8 represents the above groups other than hydrogen; and pyridine of the following formula ##STR129## wherein R 11 represents a member selected from the group consisting of lower alkyl groups, lower alkoxy groups and amino groups, and j is 0 or an integer of 1 to 4.
Claim 13
Dependent Claim 19 words
The process of claim 1 wherein the water-miscible amine has a boiling point of not more than 200° C.
Claim 14
Dependent Claim 19 words
The process of claim 12 wherein the water-miscible amine has a boiling point of not more than 140° C.
Claim 15
Dependent Claim 34 words
The process of claim 1 wherein the water-miscible amine is selected from the group consisting of monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoethanolamine, diethanolamine, ethylenediamine, diethylenetriamine, triethylenetetramine, propylenediamine, pyridine, 2-aminopyridine, 4-aminopyridine, 2,4-dimethylpyridine and 2,6-dimethylpyridine.
Claim 16
Dependent Claim 23 words
The process of claim 1 wherein the aqueous liquid medium contains the water-miscible amine in a concentration of 10 to 90% by weight.
Claim 17
Dependent Claim 17 words
The process of claim 1 wherein the aqueous liquid medium further comprises an aprotic polar organic solvent.
Claim 18
Dependent Claim 20 words
The process of claim 16 wherein the concentration of the aprotic polar organic solvent is at most 15% by weight.
Claim 19
Dependent Claim 20 words
The process of claim 16 wherein the concentration of the aprotic polar organic solvent is up to 10% by weight.
Claim 20
Dependent Claim 29 words
The process of claim 16 wherein the aprotic polar organic solvent is selected from the group consisting of N-methylpyrrolidone, N-methylcaprolactam, N,N-dimethylformamide, N,N-dimethyl acetamide, hexamethylphosphoramide, tetramethyleneurea, dimethyl sulfoxide and tetramethylenesulfone.
Claim 21
Dependent Claim 20 words
The process of claim 16 wherein the aprotic polar organic solvent has a boiling point of at least 140° C.
Claim 22
Dependent Claim 20 words
The process of claim 20 wherein the aprotic polar organic solvent has a boiling point of 145° to 240° C.
Claim 23
Dependent Claim 23 words
The process of claim 16, 20 or 21 wherein the aprotic polar organic solvent has a higher boiling point than the water-miscible amine.
Claim 24
Dependent Claim 22 words
The process of claim 1 wherein the polymer solution contains the aromatic polymer in a concentration of 0.05 to 15% by weight.
Claim 25
Dependent Claim 28 words
The process of claim 1 wherein the microporous substrate has a maximum pore size of not more than 5,000 A and a thickness of 25 to 1,000 microns.
Claim 26
Dependent Claim 13 words
The process of claim 1 wherein the microporous substrate is a polysulfone substrate.
Claim 27
Dependent Claim 17 words
The process of claim 1 wherein the drying is carried out at room temperature to 250° C.
Claim 28
Dependent Claim 17 words
The process of claim 1 wherein the ultrathin film has a thickness of 100 to 10,000 A.
Claim 29
Dependent Claim 281 words
A polymer solution comprising (a) an aqueous liquid medium containing a water-miscible amine having a pka of more than 5.0 in a concentration of at least 5% by weight, and (b) 0.01 to 20.0% by weight, based on the weight of solution, of an imidazolone ring-containing aromatic polymer, said polymer comprising at least 30 mole %, based on the entire recurring units, of at least one recurring unit of the following formula ##STR130## wherein A 1 is an aromatic group having a valence of (3+l), the dashed line represents the presence or absence of a bond, and the two nitrogen atoms and W 1 are all bonded to the nuclear carbon atoms of the aromatic group A 1 ; A 2 represents an aromatic group having a valence of (2+m); Y is --O-- or ##STR131## in which R 1 is a hydrogen atom or a monovalent hydrocarbon residue; and the two nitrogen atoms bonded to A 1 are bonded to the ring carbon atoms at the ortho-position of the aromatic group A 1 ; l and m are identical or different and each represent an integer of 0 to 3; when Y is ##STR132## and one of W 1 groups is bonded to the ring carbon atom at the ortho-position of the aromatic group A 1 together with Y, the W 1 , Y and A 1 can form a 5-membered ring same as ##STR133## in which all symbols are the same as defined above; and when W 1 does not form the 5-membered ring, W 1 and W 2 are identical or different and represent at least one group selected from mono-substituted nitrogen-containing groups derived from a primary amino group.
Claim 30
Dependent Claim 281 words
A polymer solution comprising (a) an aqueous liquid medium containing a water-miscible amine having a pka of more than 5.0 in a concentration of at least 5% by weight, and (b) 0.01 to 20.0% by weight, based on the weight of solution, of an imidazolone ring-containing aromatic polymer, said polymer comprising at least 30 mole %, based on the entire recurring units, of at least one recurring unit of the following formula ##STR130## wherein A 1 is an aromatic group having a valence of (3+l), the dashed line represents the presence or absence of a bond, and the two nitrogen atoms and W 1 are all bonded to the nuclear carbon atoms of the aromatic group A 1 ; A 2 represents an aromatic group having a valence of (2+m); Y is --O-- or ##STR131## in which R 1 is a hydrogen atom or a monovalent hydrocarbon residue; and the two nitrogen atoms bonded to A 1 are bonded to the ring carbon atoms at the ortho-position of the aromatic group A 1 ; l and m are identical or different and each represent an integer of 0 to 3; when Y is ##STR132## and one of W 1 groups is bonded to the ring carbon atom at the ortho-position of the aromatic group A 1 together with Y, the W 1 , Y and A 1 can form a 5-membered ring same as ##STR133## in which all symbols are the same as defined above; and when W 1 does not form the 5-membered ring, W 1 and W 2 are identical or different and represent at least one group selected from mono-substituted nitrogen-containing groups derived from a primary amino group.
Claim 31
Dependent Claim 29 words
The polymer solution of claim 28 wherein the aqueous liquid medium contains at most 15% by weight, based on the aqueous liquid medium, of an aprotic organic polar solvent.

References Cited (Backward Citations)

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USPTO Annuity & Maintenance Windows

Annuity Stage Window Opens Payment Deadline Surcharge Period Until Estimated Fee Status
3.5 Years (Year 4) 1984-04-06 1984-10-06 1985-04-07 $2000.00 Window Closed / Lapsed
7.5 Years (Year 8) 1988-04-06 1988-10-06 1989-04-07 $3760.00 Window Closed / Lapsed
11.5 Years (Year 12) 1992-04-06 1992-10-06 1993-04-07 $7700.00 Window Closed / Lapsed

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