US4140815A
Expired / Lapsed
US
⏱️ 0.0 years remaining
Method of making single film, high performance bipolar membrane
Assignee: Marmon Industrial Water LLC
•
Filing: 1977-04-26
•
Granted: 1979-02-20
•
Expires: 1997-04-26
Abstract
Abstract Novel single film bipolar membranes, of substantially improved efficiency and durability, i.e. having an ion selectivity above 80% in an electrolyte medium of about one mole, are prepared from pre-swollen films containing a relatively high amount, i.e. at least 15% of an insoluble cross-linked aromatic polymer. Under controlled conditions, highly dissociable cationic-exchange groups are chemically bonded to the aromatic nuclei to a desired depth of the film from one side only; subsequently, highly dissociable anion-exchange groups are chemically bonded to the unreacted aromatic nuclei on the other side of the film. The functionalized, densely structured single film ion exchange membrane undergoes negligible degradation, is blister free, and is uniquely suited for electrodialysis particularly water-splitting operations due to its low electrical resistance and low salt leakage. The membrane operates with improved current efficiencies at both high electrolyte concentrations and high current densities, for time periods not previously achievable.
Inventors
- 👤 Gerald J. Dege
- 👤 Kang-Jen Liu
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-26 20:16
CPC Classifications
C; C08; C08J; C08J5/00; C08J5/20; C08J5/22; C08J5/2206; C08J5/2218; C08J5/2231; C08J5/2243; C08J5/2287; C08J2353/00; C08J2353/02
Claims Analysis
Total Claims: 28
Claim 1
Independent Claim
327 words
A process for the manufacture of a durable, high performance, single film bipolar membrane comprising impregnating a polymeric matrix film derived from monomers selected from the group consisting of ##STR6## wherein R 1 to R 7 are substituents selected from the group consisting of hydrogen, chlorine, fluorine, alkyl radicals of 1 to 5 carbon atoms and phenyl radicals and copolymers thereof, and chlorinated and fluorinated polymers and copolymers thereof; uniformly with an aromatic nuclei containing monomer selected from those having the formula ##STR7## wherein R 8 , R 9 and R 10 are substituents from the group consisting of hydrogen, alkyl radicals of 1 to 4 carbon atoms, phenyl substituted alkyl radicals of 2-4 carbon atoms, phenyl, phenoxy-, thiophenoxy, and naphthyl radicals and the hydroxyl, alkoxyl, and halo substituted phenyl, phenoxy, thiophenoxy, and naphthyl radicals and wherein at least one substituent is an aromatic radical, and polymerizing and cross-linking said impregnated film to an extent equivalent to that obtained by cross-linking a 2 to 20 percent mixture of a 55 percent divinyl benzene in styrene, to obtain at least 15 percent by weight based on the total weight of the film, of the cross-linked aromatic nuclei containing polymer within the film; removing essentially all excess aromatic polymerizate from the surface of said film; preswelling without substantially dissolving said cross-linked film in a solvent substantially inert to but miscible with a solvent system supplying cationic functional groups for a period of time sufficient to render the aromatic nuclei readily accessible thereto thereafter chemically bonding highly dissociable cation exchange groups to the aromatic nuclei from one side of said film to a depth of not more than about 98% of the films thickness and thereafter chemically bonding highly dissociable anionic exchange groups to the remaining aromatic nuclei on the opposite side of said film, and wherein the concentration of both the anionic and cationic functional groups is at least substantially equal and greater than 1.4 meg/g. of dry resin.
Claim 2
Dependent Claim
327 words
A process for the manufacture of a durable, high performance, single film bipolar membrane comprising impregnating a polymeric matrix film derived from monomers selected from the group consisting of ##STR6## wherein R 1 to R 7 are substituents selected from the group consisting of hydrogen, chlorine, fluorine, alkyl radicals of 1 to 5 carbon atoms and phenyl radicals and copolymers thereof, and chlorinated and fluorinated polymers and copolymers thereof; uniformly with an aromatic nuclei containing monomer selected from those having the formula ##STR7## wherein R 8 , R 9 and R 10 are substituents from the group consisting of hydrogen, alkyl radicals of 1 to 4 carbon atoms, phenyl substituted alkyl radicals of 2-4 carbon atoms, phenyl, phenoxy-, thiophenoxy, and naphthyl radicals and the hydroxyl, alkoxyl, and halo substituted phenyl, phenoxy, thiophenoxy, and naphthyl radicals and wherein at least one substituent is an aromatic radical, and polymerizing and cross-linking said impregnated film to an extent equivalent to that obtained by cross-linking a 2 to 20 percent mixture of a 55 percent divinyl benzene in styrene, to obtain at least 15 percent by weight based on the total weight of the film, of the cross-linked aromatic nuclei containing polymer within the film; removing essentially all excess aromatic polymerizate from the surface of said film; preswelling without substantially dissolving said cross-linked film in a solvent substantially inert to but miscible with a solvent system supplying cationic functional groups for a period of time sufficient to render the aromatic nuclei readily accessible thereto thereafter chemically bonding highly dissociable cation exchange groups to the aromatic nuclei from one side of said film to a depth of not more than about 98% of the films thickness and thereafter chemically bonding highly dissociable anionic exchange groups to the remaining aromatic nuclei on the opposite side of said film, and wherein the concentration of both the anionic and cationic functional groups is at least substantially equal and greater than 1.4 meg/g. of dry resin.
Claim 3
Dependent Claim
11 words
The process of claim 1 wherein the matrix film is polyethylene.
Claim 4
Dependent Claim
11 words
The process of claim 1 wherein the matrix film is polypropylene.
Claim 5
Dependent Claim
13 words
The process of claim 1 wherein the matrix film is a polyethylene-polypropylene copolymer.
Claim 6
Dependent Claim
11 words
The process of claim 1 wherein the matrix film is polytrifluorochloroethylene.
Claim 7
Dependent Claim
30 words
The process of claim 1 wherein the initial matrix film to be impregnated with the aromatic nuclei containing monomer, has a thickness of from about 0.5 to about 20 mils.
Claim 8
Dependent Claim
29 words
The process of claim 1 wherein the concentration of the aromatic nuclei containing polymer comprises from about 15% to about 70% based on the total weight of the membrane.
Claim 9
Dependent Claim
31 words
The process of claim 1 wherein the mole ratio of the aromatic nuclei containing monomer to the di- or poly-functional cross-linking compound in the initial monomer mixture is less than 125/1.
Claim 10
Dependent Claim
45 words
The process of claim 1 wherein the initial polymeric film is cross-linked by electron beam radiation to a degree equivalent to that obtained from a styrenation mixture comprised of styrene and divinylbenzene in a mole ratio from 14 to 1 to 125 to 1, respectively.
Claim 11
Dependent Claim
57 words
The process of claim 1 wherein before polymerization excess liquid polymerizate is wiped from the films surface and after polymerization the last traces of solidified polymerizate are removed from the films surface with a solvent selected from the group consisting of carbon tetrachloride, chloroform, methylene chloride, 1,2-dichloroethane, 1,2-trichloroethane, 1,1,2,2-tetrachloroethane, dimethyl formamide, dimethyl acetamide, decalin, tetralin, and cyclohexane.
Claim 12
Dependent Claim
60 words
The process of claim 1 wherein the highly dissociable cationic groups are sulfonic acid groups and prior to sulfonation the polymeric film containing the insoluble, cross-linked aromatic polymer is preswollen in a solvent inert to but miscible with the sulfonating reagent or its mixture for a time period sufficient to render the aromatic nuclei readily accessible to the sulfonating reagent.
Claim 13
Dependent Claim
32 words
The process of claim 11 wherein the pre-swelling solvent is selected from the group consisting of carbon tetrachloride, chloroform, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, 1,1,2,2-tetrachloroethane, dimethyl formamide, dimethyl acetamide, decalin, tetralin, and cyclohexane.
Claim 14
Dependent Claim
38 words
The process of claim 1 wherein the highly dissociable cation exchange group is the sulfonic acid group, obtained with sulfonating agents selected from the group comprised of sulfonic acid, SO 3 , oleum, chlorosulfonic acid, or mixtures thereof.
Claim 15
Dependent Claim
40 words
The process of claim 1 wherein the sulfonic acid cation exchange group is obtained by chlorosulfonating with a solution of chlorosulfonic acid in carbon tetrachloride with at least 53% chlorosulfonic acid by volume and thereafter hydrolyzing the sulfonated reaction produced.
Claim 16
Dependent Claim
26 words
The process of claim 1 wherein the cationic functional groups are derived by chlorosulfonation and the chlorosulfonating agent comprises a mixture of chlorosulfonic acid and dichloroethane.
Claim 17
Dependent Claim
26 words
The process of claim 1 wherein the cationic functional groups are derived by chlorosulfonation and the chlorosulfonating agent comprises a mixture of chlorosulfonic acid and trichloroethane.
Claim 18
Dependent Claim
67 words
The process of claim 1 characterized in that the anionic functional groups are quaternary trimethyl amine anionic exchange groups obtained by chloromethylation of the film with reagents selected from the group consisting of (a) SO 2 Cl 2 with methylal and a Friedel-Crafts catalyst, (b) formaldehyde and hydrochloric acid and (c) chloromethyl methylether and tin tetrachloride; followed by quaternization with an organic solution of a trialkyl amine.
Claim 19
Dependent Claim
20 words
The process of claim 1 wherein chloromethylation is accomplished with chloromethylmethylether containing from about 1-5 weight percent SnCl 4 .
Claim 20
Dependent Claim
22 words
The process of claim 1 wherein the chloromethylated film is substantially converted to highly dissociated anion exchange groups by quaternization with trimethylamine.
Claim 21
Dependent Claim
187 words
A process for the manufacture of a durable, high performance, single film bipolar membrane comprising impregnating a polyethylene film uniformly with a mixture of styrene monomer and a di- or poly-functional cross-linking agent, subsequently polymerizing said impregnated mixture to obtain at least 15 percent by weight based on the total weight of the film, of the cross-linked polystyrene within the film; removng essentially all excess polymerizate from the surface of said film; preswelling without substantially dissolving said cross-linked film in a solvent substantially inert to but miscible with a cationic functional group sulfonation reagent, for a period of time sufficient to render the aromatic nuclei of the polystyrene readily accessible to the sulfonating reagent, thereafter chemically bonding highly dissociable sulfonic groups to the aromatic nuclei from one side of said film to a depth of from about 50% to about 98% of the films thickness and thereafter chemically bonding highly dissociable anionic exchange groups to the remaining aromatic nuclei on the opposite side of said film, and wherein the concentration of both functional groups is at least substantially equal and greater than 1.4 meg/g. of dry resin.
Claim 22
Dependent Claim
187 words
A process for the manufacture of a durable, high performance, single film bipolar membrane comprising impregnating a polyethylene film uniformly with a mixture of styrene monomer and a di- or poly-functional cross-linking agent, subsequently polymerizing said impregnated mixture to obtain at least 15 percent by weight based on the total weight of the film, of the cross-linked polystyrene within the film; removng essentially all excess polymerizate from the surface of said film; preswelling without substantially dissolving said cross-linked film in a solvent substantially inert to but miscible with a cationic functional group sulfonation reagent, for a period of time sufficient to render the aromatic nuclei of the polystyrene readily accessible to the sulfonating reagent, thereafter chemically bonding highly dissociable sulfonic groups to the aromatic nuclei from one side of said film to a depth of from about 50% to about 98% of the films thickness and thereafter chemically bonding highly dissociable anionic exchange groups to the remaining aromatic nuclei on the opposite side of said film, and wherein the concentration of both functional groups is at least substantially equal and greater than 1.4 meg/g. of dry resin.
Claim 23
Dependent Claim
187 words
A process for the manufacture of a durable, high performance, single film bipolar membrane comprising impregnating a polypropylene film uniformly with a mixture of styrene monomer and a di- or poly-functional cross-linking agent, subsequently polymerizing said impregnated mixture to obtain at least 15 percent by weight based on the total weight of the film, of the cross-linked polystyrene within the film; removing essentially all excess polymerizate from the surface of said film; preswelling without substantially dissolving said cross-linked film in a solvent substantially inert to but miscible with a cationic functional group sulfonation reagent, for a period of time sufficient to render the aromatic nuclei of the polystyrene readily accessible to the sulfonating reagent, thereafter chemically bonding highly dissociable sulfonic groups to the aromatic nuclei from one side of said film to a depth of from about 50% to about 98% of the films thickness and thereafter chemically bonding highly dissociable anionic exchange groups to the remaining aromatic nuclei on the opposite side of said film, and wherein the concentration of both functional groups is at least substantially equal and greater than 1.4 meg/g. of dry resin.
Claim 24
Dependent Claim
187 words
A process for the manufacture of a durable, high performance, single film bipolar membrane comprising impregnating a polypropylene film uniformly with a mixture of styrene monomer and a di- or poly-functional cross-linking agent, subsequently polymerizing said impregnated mixture to obtain at least 15 percent by weight based on the total weight of the film, of the cross-linked polystyrene within the film; removing essentially all excess polymerizate from the surface of said film; preswelling without substantially dissolving said cross-linked film in a solvent substantially inert to but miscible with a cationic functional group sulfonation reagent, for a period of time sufficient to render the aromatic nuclei of the polystyrene readily accessible to the sulfonating reagent, thereafter chemically bonding highly dissociable sulfonic groups to the aromatic nuclei from one side of said film to a depth of from about 50% to about 98% of the films thickness and thereafter chemically bonding highly dissociable anionic exchange groups to the remaining aromatic nuclei on the opposite side of said film, and wherein the concentration of both functional groups is at least substantially equal and greater than 1.4 meg/g. of dry resin.
Claim 25
Dependent Claim
188 words
A process for the manufacture of a durable, high performance, single film bipolar membrane comprising impregnating a polytrifluoro chloroethylene film uniformly with a mixture of styrene monomer and a di- or poly-functional cross-linking agent, subsequently polymerizing said impregnated mixture to obtain at least 15 percent by weight based on the total weight of the film, of the cross-linked polystyrene within the film; removing essentially all excess polymerizate from the surface of said film; preswelling without substantially dissolving said cross-linked film in a solvent substantially inert to but miscible with a cationic functional group sulfonation reagent, for a period of time sufficient to render the aromatic nuclei of the polystyrene readily accessible to the sulfonating reagent, thereafter chemically bonding highly dissociable sulfonic groups to the aromatic nuclei from one side of said film to a depth of from about 50% to about 98% of the films thickness and thereafter chemically bonding highly dissociable anionic exchange groups to the remaining aromatic nuclei on the opposite side of said film, and wherein the concentration of both functional groups is at least substantially equal and greater than 1.4 meg/g. of dry resin.
Claim 26
Dependent Claim
188 words
A process for the manufacture of a durable, high performance, single film bipolar membrane comprising impregnating a polytrifluoro chloroethylene film uniformly with a mixture of styrene monomer and a di- or poly-functional cross-linking agent, subsequently polymerizing said impregnated mixture to obtain at least 15 percent by weight based on the total weight of the film, of the cross-linked polystyrene within the film; removing essentially all excess polymerizate from the surface of said film; preswelling without substantially dissolving said cross-linked film in a solvent substantially inert to but miscible with a cationic functional group sulfonation reagent, for a period of time sufficient to render the aromatic nuclei of the polystyrene readily accessible to the sulfonating reagent, thereafter chemically bonding highly dissociable sulfonic groups to the aromatic nuclei from one side of said film to a depth of from about 50% to about 98% of the films thickness and thereafter chemically bonding highly dissociable anionic exchange groups to the remaining aromatic nuclei on the opposite side of said film, and wherein the concentration of both functional groups is at least substantially equal and greater than 1.4 meg/g. of dry resin.
Claim 27
Dependent Claim
187 words
A process for the manufacture of a durable, high performance, single film bipolar membrane comprising impregnating a polyethylene-polypropylene copolymer film uniformly with a mixture of styrene monomer and a di- or poly-functional cross-linking agent, subsequently polymerizing said impregnated mixture to obtain at least 15 percent by weight based on the total weight of the film, of the cross-linked polystyrene within the film; removing essentially all excess polymerizate from the surface of said film; preswelling without substantially dissolving said cross-linked film in a solvent substantially inert to but miscible with a cationic functional group sulfonation reagent, for a period of time sufficient to render the aromatic nuclei of the polystyrene readily accessible to the sulfonating reagent, thereafter chemically bonding highly dissociable sulfonic groups to the aromatic nuclei from one side of said film to a depth of from about 50% to about 98% of the films thickness and thereafter chemically-bonding highly dissociable anionic exchange groups to the remaining aromatic nuclei on the opposite side of said film, and wherein the concentration of both functional groups is at least substantially equal and greater than 1.4 meg/g. of dry resin.
Claim 28
Dependent Claim
187 words
A process for the manufacture of a durable, high performance, single film bipolar membrane comprising impregnating a polyethylene-polypropylene copolymer film uniformly with a mixture of styrene monomer and a di- or poly-functional cross-linking agent, subsequently polymerizing said impregnated mixture to obtain at least 15 percent by weight based on the total weight of the film, of the cross-linked polystyrene within the film; removing essentially all excess polymerizate from the surface of said film; preswelling without substantially dissolving said cross-linked film in a solvent substantially inert to but miscible with a cationic functional group sulfonation reagent, for a period of time sufficient to render the aromatic nuclei of the polystyrene readily accessible to the sulfonating reagent, thereafter chemically bonding highly dissociable sulfonic groups to the aromatic nuclei from one side of said film to a depth of from about 50% to about 98% of the films thickness and thereafter chemically-bonding highly dissociable anionic exchange groups to the remaining aromatic nuclei on the opposite side of said film, and wherein the concentration of both functional groups is at least substantially equal and greater than 1.4 meg/g. of dry resin.
References Cited (Backward Citations)
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1982-02-19 | 1982-08-21 | 1983-02-20 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1986-02-19 | 1986-08-21 | 1987-02-20 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1990-02-19 | 1990-08-21 | 1991-02-20 | $7700.00 | Window Closed / Lapsed |