Metal-neutralized sulfonated block copolymers, process for making them and their use

• US 8,445,631 B2
• Filed: 10/13/2009
• Issued: 05/21/2013
• Est. Priority Date: 10/13/2009
• Status: Active Grant

• Current Assignee: Kraton Polymers US LLC (DL Holdings Co., Ltd.)
• Original Assignee: Kraton Polymers US LLC (DL Holdings Co., Ltd.)
• Inventors: Willis, Carl Lesley
• Primary Examiner(s): Yoon, Tae H
• Application Number:
  US12/578,210
• Publication Number:
  US 20110086977A1
• Time in Patent Office: 1,316 Days
• Field of Search: 528/482, 528/488, 528/489, 528/490, 525/333.5, 525/357
• US Class Current: 528/489
• CPC Class Codes: B01D 61/002 Forward osmosis or direct osmosis
• CPC Class Codes: B01D 61/0022 Apparatus therefor
• CPC Class Codes: B01D 61/44 Ion-selective electrodialysis
• CPC Class Codes: B01D 71/80 Block polymers
• CPC Class Codes: B01D 71/82 characterised by the presence of specified groups, e.g. introduced by chemical after-treatment
• CPC Class Codes: B01J 47/12 characterised by the use of ion-exchange material in the form of ribbons, filaments, fibres or sheets, e.g. membranes electrodialysis or electro-osmosis B01D61/42
• CPC Class Codes: C08F 2810/50 wherein the polymer is a copolymer and the modification is taking place only on one or more of the monomers present in minority
• CPC Class Codes: C08F 297/00 Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
• CPC Class Codes: C08F 297/046 polymerising vinyl aromatic monomers and isoprene, optionally with other conjugated dienes
• CPC Class Codes: C08F 36/08 Isoprene
• CPC Class Codes: C08F 8/04 Reduction, e.g. hydrogenation
• CPC Class Codes: C08F 8/36 Sulfonation; Sulfation
• CPC Class Codes: C08F 8/44 Preparation of metal salts or ammonium salts
• CPC Class Codes: C08G 85/004 Modification of polymers by chemical after-treatment
• CPC Class Codes: H01M 8/102 characterised by the chemical structure of the main chain of the ion-conducting polymer
• CPC Class Codes: Y02E 60/50 Fuel cells
• CPC Class Codes: Y02P 70/50 Manufacturing or production processes characterised by the final manufactured product

Abstract

The present disclosure relates to a process for neutralizing a sulfonated block copolymer with a metal compound, to metal-neutralized block copolymers, and to various articles comprising the metal-neutralized block copolymers, e.g., in form of a water vapor permeable membrane which comprises the metal-neutralized block copolymers. The present disclosure further relates to a means and a method for storing and stabilizing a polar component such as a metal compound in a non-polar liquid phase by immuring the polar component in micelles of the sulfonated block copolymer in the non-polar liquid phase.

Claims

1. A process for neutralizing a non-neutralized sulfonated block copolymer having a general configuration A-B-D-B-A, A-D-B-D-A, (A-D-B)_n(A), (A-B-D)_n(A), (A-B-D)_nX, (A-D-B)_nX, or mixtures thereof, wherein n is an integer from 2 to about 30, X is coupling agent residue, each A block contains essentially no sulfonic acid or sulfonate functional groups, each B block is a polymer block containing from about 10 to about 100 mol-% sulfonic acid or sulfonate functional groups based on the number of monomer units of the B block, and each D block is an impact modifier block having a glass transition temperature less than 20°

C., which process comprises

providing a micellar solution comprising from about 1 to about 30%-wt, of the non-neutralized block copolymer and an organic solvent, wherein the organic solvent consists of one or more aprotic, apolar aliphatic solvents, and

adding at least one metal compound to the solution, wherein the metal has an atom number of at least 11.

2. The process of claim 1 wherein from about 80% to about 100% of the sulfonic acid or sulfonate functional groups are neutralized.

3. The process of claim 1 wherein the metal compound is added in an amount of from about 0.8 to about 10 metal equivalents per 1 equivalent of sulfonic acid or sulfonate functional group of the non-neutralized block copolymer.

4. The process of claim 1 wherein the organic solvent is a non-halogenated aliphatic solvent.

5. The process of claim 1 wherein the metal compound is selected from the group of organometal compounds, metal hydrides, metal oxides, metal hydroxides, metal alkoxides, metal carbonates, metal hydrogencarbonates, and metal carboxylates.

6. The process of claim 1 wherein the metal compound comprises sodium, potassium, cesium, magnesium, calcium, strontium, barium, aluminum, tin, lead, titanium, zirconium, vanadium, chromium, molybdenum, manganese, iron, cobalt, nickel, copper, silver, zinc, cadmium, or mercury.

7. The process of claim 1 wherein the metal of the metal compound has an atom number of at least 12.

8. The process of claim 1 wherein the metal compound comprises magnesium, calcium, aluminum, copper, or zinc.

9. The process of claim 1 wherein the metal is in an oxidation state of +2, +3 or +4.

10. A means for storing a polar component comprising a non-polar, liquid phase and from about 1 to about 30%-wt, of a sulfonated block copolymer having a general configuration A-B-D-B-A, A-D-B-D-A, (A-D-B)_n(A), (A-B-D)_n(A), (A-B-D)_nX, (A-D-B)_nX, or mixtures thereof, wherein n is an integer from 2 to about 30, X is coupling agent residue, each A block contains essentially no sulfonic acid or sulfonate functional groups, each B block is a polymer block containing from about 10 to about 100 mol-% sulfonic acid or sulfonate functional groups based on the number of monomer units of the B block, and each D block is an impact modifier block having a glass transition temperature less than 20°

C.,

wherein the non-polar, liquid phase consists of one or more aprotic, non-polar aliphatic solvents, and the sulfonated block copolymer is present in the non-polar, liquid phase in micellular form adapted to immure the polar component.

11. A process for stabilizing or storing a polar component in a non-polar liquid phase which comprises

a. providing solution comprising a non-polar, liquid phase and from about 1 to about 30%-wt, of a sulfonated block copolymer having a general configuration A-B-D-B-A, A-D-B-D-A, (A-D-B)_n(A), (A-B-D)_n(A), (A-B-D)_nX, (A-D-B)_nX, or mixtures thereof, wherein n is an integer from 2 to about 30, X is coupling agent residue, each A block contains essentially no sulfonic acid or sulfonate functional groups, each B block is a polymer block containing from about 10 to about 100 mol-% sulfonic acid or sulfonate functional groups based on the number of monomer units of the B block, and each D block is an impact modifier block having a glass transition temperature less than 20°

C.,

wherein the solution comprises the sulfonated block copolymer in micellular form,

wherein the non-polar, liquid phase consists of one or more aprotic, non-polar aliphatic solvents, and

b. adding at least one polar component to the solution (a) whereby the polar component is immured in the micelles.

12. The process of claim 11 wherein the polar component is a metal compound.