US4705636A
Expired / Lapsed
US
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Method of making a coating and a permselective membrane, ionic polymer therefor, and products thereof
Assignee: Dow Chemical Co
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Filing: 1985-07-19
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Granted: 1987-11-10
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Expires: 2005-07-19
Abstract
Abstract This invention relates to an ionic polymer, method for making a coating and a composite membrane therefrom and also relates to products derived from the disclosed methods and polymer. A new lipid-like permselective membrane is disclosed comprising an ultra-thin selective coating deposited on a non-selective but permeable substrate, which may be anionic or cationic, in hollow fiber, tubular or planar form. The method of preparation of the membrane comprises treating the permeable substrate with a solution of the ionic polymer. The polymer is the product of an aromatic monomer, acrylate and vinyl chloride quaternized with a tertiary amine in which at least one of the alkyl groups of the amine contain at least two carbon atoms. The polymer can also be the product of an aromatic monomer and acrylate and the polymer being partially sulfonated. The treatment produces an extremely thin coating that is held tenaciously by electrostatic forces and the hydrophobicity of the polymer determines its permeability. The membrane has improved flux and selectivity.
Inventors
- 👤 Hamish Small
- 👤 Inder Mani
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-31 04:56
CPC Classifications
B; B01; B01D; B01D67/00; B01D67/0081; B01D67/0088; B01D69/00; B01D69/12; B01D71/00; B01D71/06; B01D71/76; B01D71/82; C; C08; C08J; C08J5/00; C08J5/20; C08J5/22; C08J5/2287; C08J5/2293; C08J2327/00; C08J2327/02; C08J2327/04; C08J2333/00; C08J2333/04; C08J2333/06; C08J2333/10; C08J2333/12
Claims Analysis
Total Claims: 75
Claim 1
Independent Claim
87 words
A method for making a permselective membrane comprising polymerizing a mixture with aromatic monomer, acrylate and vinylbenzyl chloride, which polymer being quaternized with tertiary amine containing alkyl groups having C 1 to C 20 carbon atoms, in which at least one alkyl group has at least two carbon atoms, or aromatic monomer, acrylate and vinylbenzyl chloride, which polymer being partially sulfonated, and depositing the polymer on an oppositely charged, permeable substrate to form an ultra-thin coating thereon forming a permselective membrane having high flux and high selectivity.
Claim 2
Independent Claim
87 words
A method for making a permselective membrane comprising polymerizing a mixture with aromatic monomer, acrylate and vinylbenzyl chloride, which polymer being quaternized with tertiary amine containing alkyl groups having C 1 to C 20 carbon atoms, in which at least one alkyl group has at least two carbon atoms, or aromatic monomer, acrylate and vinylbenzyl chloride, which polymer being partially sulfonated, and depositing the polymer on an oppositely charged, permeable substrate to form an ultra-thin coating thereon forming a permselective membrane having high flux and high selectivity.
Claim 3
Independent Claim
76 words
A method for making a permselective membrane comprising polymerizing a mixture of aromatic monomer, acrylate and vinylbenzyl chloride, quaternizing the polymer with a tertiary amine containing alkyl groups having C 1 to C 20 carbon atoms, in which at least one alkyl group has at least two carbon atoms, and depositing the quaternized polymer on an oppositely charged, permeable substrate to form an ultra-thin coating thereon forming a permselective membrane having high flux and high selectivity.
Claim 4
Independent Claim
76 words
A method for making a permselective membrane comprising polymerizing a mixture of aromatic monomer, acrylate and vinylbenzyl chloride, quaternizing the polymer with a tertiary amine containing alkyl groups having C 1 to C 20 carbon atoms, in which at least one alkyl group has at least two carbon atoms, and depositing the quaternized polymer on an oppositely charged, permeable substrate to form an ultra-thin coating thereon forming a permselective membrane having high flux and high selectivity.
Claim 5
Dependent Claim
12 words
The method according to claim 2, further comprising the substrate being anionic.
Claim 6
Dependent Claim
20 words
The method according to claim 2, further comprising the substrate being a planar shape, tubular shape or a hollow fiber.
Claim 7
Dependent Claim
13 words
The method according to claim 2, further comprising the polymer containing cationic functionality.
Claim 8
Dependent Claim
25 words
The method according to claim 2, further comprising the membrane being essentially impermeable to the hydrophilic ions of Na, Li, Ca, H or the like.
Claim 9
Dependent Claim
16 words
The method according to claim 2, further comprising polymerizing in the presence of a cationic surfactant.
Claim 10
Dependent Claim
16 words
The method according to claim 7, further comprising the cationic surfactant being a quaternary ammonium salt.
Claim 11
Dependent Claim
15 words
The method according to claim 2, further comprising polymerizing in the presence of a catalyst.
Claim 12
Dependent Claim
13 words
The method according to claim 9, further comprising the catalyst being hydrogen peroxide.
Claim 13
Dependent Claim
16 words
The method according to claim 9, further comprising the catalyst being iron halide and hydrogen peroxide.
Claim 14
Dependent Claim
15 words
The method according to claim 11, further comprising the iron halide being a ferric halide.
Claim 15
Dependent Claim
13 words
The method according to claim 2, further comprising adding a chain transfer agent.
Claim 16
Dependent Claim
19 words
The method according to claim 13, further comprising adding mercaptoethanol as the chain transfer agent to the polymerization mixture.
Claim 17
Dependent Claim
18 words
The method according to claim 2, further comprising the acrylate being butyl, methyl, ethyl or ethyl hexyl acrylate.
Claim 18
Dependent Claim
59 words
The method according to claim 2, further comprising the tertiary amine being (CH 3 ) 2 R 1 N; CH 3 R 1 R 2 N; R 1 R 2 R 3 N; where R 1 , R 2 , R 3 =C 1 to C 20 , except where R 1 =R 2 =R 3 =C 1 .
Claim 19
Dependent Claim
14 words
The method according to claim 2, further comprising the tertiary amine being dimethydodecyl amine.
Claim 20
Dependent Claim
13 words
The method according to claim 2, further comprising the aromatic monomer being styrene.
Claim 21
Dependent Claim
16 words
The method according to claim 18, further comprising the styrene being vinyl toluene, t-butylstyrene, or methylmethacrylate.
Claim 22
Dependent Claim
20 words
The method according to claim 2, further comprising the polymer being deposited on at least one surface of the substrate.
Claim 23
Dependent Claim
45 words
The method according to claim 2, further comprising the concentration of aromatic monomer being between about greater than 0 and 99%, the concentration of acrylate being between about greater than 0 and 99%, and the concentration of quaternary amine being between about 1 and 50%.
Claim 24
Dependent Claim
45 words
The method according to claim 2, further comprising the concentration of aromatic monomer being between about greater than 0 and 95%, the concentration of acrylate being between about greater than 0 and 95%, and the concentration of quaternary amine being between about 5 and 40%.
Claim 25
Dependent Claim
15 words
The method according to claim 2, further comprising the substrate being carboxylated or sulfonated polyethylene.
Claim 26
Dependent Claim
15 words
The method according to claim 2, further comprising polymerizing in the presence of deionized water.
Claim 27
Independent Claim
85 words
A method for making a permselective lipid-like membrane for separating ammonia from salt, alcohol from brine or iodine from salt comprising polymerizing a mixture of styrene, butyl acrylate and vinylbenzyl chloride with a quaternary ammonium salt and ferric halide/hydrogen peroxide catalyst in deionized water to form a water insoluble polymer, quaternizing the polymer with dimethyldodecylamine and electrostatically depositing the quaternized polymer on the surface of an anionic, permeable substrate forming an ultra-thin coating thereon forming a permselective lipid-like membrane having high flux and high selectivity.
Claim 28
Independent Claim
85 words
A method for making a permselective lipid-like membrane for separating ammonia from salt, alcohol from brine or iodine from salt comprising polymerizing a mixture of styrene, butyl acrylate and vinylbenzyl chloride with a quaternary ammonium salt and ferric halide/hydrogen peroxide catalyst in deionized water to form a water insoluble polymer, quaternizing the polymer with dimethyldodecylamine and electrostatically depositing the quaternized polymer on the surface of an anionic, permeable substrate forming an ultra-thin coating thereon forming a permselective lipid-like membrane having high flux and high selectivity.
Claim 29
Dependent Claim
66 words
A permselective membrane for fluid purification, comprising a charged, ultra-thin coating of a polymer of aromatic monomer, acrylate and vinylbenzyl chloride quaternized with a tertiary amine containing alkyl groups having C 1 to C 20 carbon atoms, in which at least one alkyl group has at least two carbon atoms on an oppositely charged, permeable substrate forming a permselective membrane having high flux and high selectivity.
Claim 30
Dependent Claim
66 words
A permselective membrane for fluid purification, comprising a charged, ultra-thin coating of a polymer of aromatic monomer, acrylate and vinylbenzyl chloride quaternized with a tertiary amine containing alkyl groups having C 1 to C 20 carbon atoms, in which at least one alkyl group has at least two carbon atoms on an oppositely charged, permeable substrate forming a permselective membrane having high flux and high selectivity.
Claim 31
Dependent Claim
11 words
The membrane according to claim 26, further comprising a rejuvenated membrane.
Claim 32
Dependent Claim
22 words
The permselective membrane of claim 26, wherein the thickness of the ultra-thin coating is between about 20 A and about 300 A.
Claim 33
Independent Claim
56 words
A method for making an ultra-thin lipid coating comprising polymerizing a mixture of aromatic monomer, acrylate and vinylbenzyl chloride, quaternizing the polymer with a tertiary amine containing alkyl groups having C 1 to C 20 carbon atoms, in which at least one alkyl group has at least two carbon atoms, and forming an ultra-thin lipid coating.
Claim 34
Independent Claim
56 words
A method for making an ultra-thin lipid coating comprising polymerizing a mixture of aromatic monomer, acrylate and vinylbenzyl chloride, quaternizing the polymer with a tertiary amine containing alkyl groups having C 1 to C 20 carbon atoms, in which at least one alkyl group has at least two carbon atoms, and forming an ultra-thin lipid coating.
Claim 35
Dependent Claim
22 words
The lipid coating of claim 29, wherein the thickness of the ultra-thin coating is between about 20 A and about 300 A.
Claim 36
Dependent Claim
44 words
An ultra-thin lipid coating comprising a quaternized polymer of aromatic monomer, acrylate and vinylbenzyl chloride quaternized with a tertiary amine containing alkyl groups having C 1 to C 20 carbon atoms, in which at least one alkyl group has at least two carbon atoms.
Claim 37
Dependent Claim
44 words
An ultra-thin lipid coating comprising a quaternized polymer of aromatic monomer, acrylate and vinylbenzyl chloride quaternized with a tertiary amine containing alkyl groups having C 1 to C 20 carbon atoms, in which at least one alkyl group has at least two carbon atoms.
Claim 38
Dependent Claim
22 words
The lipid coating of claim 31, wherein the thickness of the ultra-thin coating is between about 20 A and about 300 A.
Claim 39
Dependent Claim
39 words
A polymer comprising an aromatic monomer, acrylate and vinylbenzyl chloride quaternized with a tertiary amine containing alkyl groups having C 1 to C 20 carbon atoms, in which at least one alkyl group has at least two carbon atoms.
Claim 40
Dependent Claim
39 words
A polymer comprising an aromatic monomer, acrylate and vinylbenzyl chloride quaternized with a tertiary amine containing alkyl groups having C 1 to C 20 carbon atoms, in which at least one alkyl group has at least two carbon atoms.
Claim 41
Independent Claim
50 words
A method for making a permselective membrane comprising polymerizing a mixture of aromatic monomer, acrylate and aromatic vinyl chloride and partially sulfonating the polymer and depositing the polymer on an oppositely charged, permeable substrate to form an ultra-thin coating thereon forming a permselective membrane having high flux and high selectivity.
Claim 42
Independent Claim
50 words
A method for making a permselective membrane comprising polymerizing a mixture of aromatic monomer, acrylate and aromatic vinyl chloride and partially sulfonating the polymer and depositing the polymer on an oppositely charged, permeable substrate to form an ultra-thin coating thereon forming a permselective membrane having high flux and high selectivity.
Claim 43
Dependent Claim
12 words
The method according to claim 34, further comprising the substrate being cationic.
Claim 44
Dependent Claim
12 words
The method according to claim 34, further comprising sulfonating with chlorosulfonic acid.
Claim 45
Dependent Claim
20 words
The method according to claim 34, further comprising the substrate being a planar shape, tubular shape or a hollow fiber.
Claim 46
Dependent Claim
13 words
The method according to claim 34, further comprising the polymer containing anionic functionality.
Claim 47
Dependent Claim
25 words
The method according to claim 34, further comprising the membrane being essentially impermeable in the hydrophilic ions of Na, Li, Ca, H or the like.
Claim 48
Dependent Claim
16 words
The method according to claim 34, further comprising polymerizing in the presence of an anionic surfactant.
Claim 49
Dependent Claim
15 words
The method according to claim 34, further comprising polymerizing in the presence of a catalyst.
Claim 50
Dependent Claim
13 words
The method according to claim 41, further comprising the catalyst being sodium persulfate.
Claim 51
Dependent Claim
13 words
The method according to claim 34, further comprising adding a chain transfer agent.
Claim 52
Dependent Claim
19 words
The method according to claim 43, further comprising adding mercaptoethanol as the chain transfer agent to the polymerization mixture.
Claim 53
Dependent Claim
18 words
The method according to claim 34, further comprising the acrylate being butyl, methyl, ethyl or ethyl hexyl acrylate.
Claim 54
Dependent Claim
12 words
The method according to claim 34, further comprising aromatic monomer being styrene.
Claim 55
Dependent Claim
16 words
The method according to claim 46, further comprising the styrene being vinyl toluene, t-butylstyrene, or methylmethacrylate.
Claim 56
Dependent Claim
20 words
The method according to claim 34, further comprising the polymer being deposited on at least one surface of the substrate.
Claim 57
Dependent Claim
46 words
The method according to claim 34, further comprising the concentration of aromatic monomer being between about greater than 0 and 99% and the concentration of acrylate being between about greater than 0 and 99% and the concentration of sulfonating agent being between about 1 and 25%.
Claim 58
Dependent Claim
45 words
The method according to claim 34, further comprising the concentration of aromatic monomer being between about greater than 0 and 95%, the concentration of acrylate being between about greater than 0 and 95%, and the concentration of sulfonating agent being between about 5 and 20%.
Claim 59
Dependent Claim
15 words
The method according to claim 34, further comprising polymerizing in the presence of deionized water.
Claim 60
Independent Claim
55 words
A method for making a permselective lipid-like membrane comprising polymerizing a mixture of styrene, butyl acrylate and aromatic vinyl chloride to form a water insoluble polymer, and electrostatically depositing the polymer on the surface of a cationic, permeable substrate forming an ultra-thin film thereon forming a permselective lipid-like membrane having high flux and high selectivity.
Claim 61
Independent Claim
55 words
A method for making a permselective lipid-like membrane comprising polymerizing a mixture of styrene, butyl acrylate and aromatic vinyl chloride to form a water insoluble polymer, and electrostatically depositing the polymer on the surface of a cationic, permeable substrate forming an ultra-thin film thereon forming a permselective lipid-like membrane having high flux and high selectivity.
Claim 62
Dependent Claim
41 words
A permselective membrane, comprising a charged, ultra-thin coating for a sulfonated polymer of aromatic monomer, acrylate, and aromatic vinyl chloride and partially sulfonating the polymer on an oppositely charged, permeable substrate forming a permselective membrane having high flux and high selectivity.
Claim 63
Dependent Claim
41 words
A permselective membrane, comprising a charged, ultra-thin coating for a sulfonated polymer of aromatic monomer, acrylate, and aromatic vinyl chloride and partially sulfonating the polymer on an oppositely charged, permeable substrate forming a permselective membrane having high flux and high selectivity.
Claim 64
Dependent Claim
11 words
The membrane according to claim 53, further comprising a rejuvenated membrane.
Claim 65
Dependent Claim
22 words
The permselective membrane of claim 53, wherein the thickness of the ultra-thin coating is between about 20 A and about 300 A.
Claim 66
Independent Claim
30 words
A method for making an ultra-thin lipid coating comprising polymerizing a mixture of aromatic monomer, acrylate and aromatic vinyl chloride and partially sulfonating the polymer forming an ultra-thin lipid coating.
Claim 67
Independent Claim
30 words
A method for making an ultra-thin lipid coating comprising polymerizing a mixture of aromatic monomer, acrylate and aromatic vinyl chloride and partially sulfonating the polymer forming an ultra-thin lipid coating.
Claim 68
Dependent Claim
22 words
The lipid coating of claim 56, wherein the thickness of the ultra-thin coating is between about 20 A and about 300 A.
Claim 69
Dependent Claim
19 words
An ultra-thin lipid coating comprising a sulfonated or partially sulfonated polymer of aromatic monomer, acrylate and aromatic vinyl chloride.
Claim 70
Dependent Claim
19 words
An ultra-thin lipid coating comprising a sulfonated or partially sulfonated polymer of aromatic monomer, acrylate and aromatic vinyl chloride.
Claim 71
Dependent Claim
22 words
The lipid coating of claim 58, wherein the thickness of the ultra-thin coating is between about 20 A and about 300 A.
Claim 72
Dependent Claim
14 words
A sulfonated or partially sulfonated polymer comprising aromatic monomer, acrylate and aromatic vinyl chloride.
Claim 73
Dependent Claim
14 words
A sulfonated or partially sulfonated polymer comprising aromatic monomer, acrylate and aromatic vinyl chloride.
Claim 74
Independent Claim
80 words
A method for separating ammonia from salt, alcohol from brine or iodine from salt comprising passing a fluid containing such materials through a perselective membrane having a charged, ultra-thin coating of a polymer of aromatic monomer, acrylate and aromatic vinyl chloride quaternized with a tertiary amine containing alkyl groups having C 1 to C 20 carbon atoms, in which at least one alkyl group has at least two carbon atoms on an oppositely charged, permeable substrate forming the perselective membrane.
Claim 75
Independent Claim
80 words
A method for separating ammonia from salt, alcohol from brine or iodine from salt comprising passing a fluid containing such materials through a perselective membrane having a charged, ultra-thin coating of a polymer of aromatic monomer, acrylate and aromatic vinyl chloride quaternized with a tertiary amine containing alkyl groups having C 1 to C 20 carbon atoms, in which at least one alkyl group has at least two carbon atoms on an oppositely charged, permeable substrate forming the perselective membrane.
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