METAL-NEUTRALIZED SULFONATED BLOCK COPOLYMERS, PROCESS FOR MAKING THEM AND THEIR USE

• US 20110086977A1
• Filed: 10/13/2009
• Published: 04/14/2011
• 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
• Granted Patent: US 8,445,631 B2
• Time in Patent Office: Days
• US Class Current: 524/609
• 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 at least one end block A and at least one interior block B wherein each A block contains essentially no sulfonic acid or sulfonate ester functional groups and each B block is a polymer block containing from about 10 to about 100 mol % sulfonic acid or sulfonate ester functional groups based on the number of sulfonation susceptible monomer units of the B block, which process comprises

providing a solution comprising the non-neutralized sulfonated block copolymer and an organic solvent, 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 the solution comprises the dissolved, non-neutralized sulfonated block copolymer in micellar form.

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

4. The process of claim 2 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 ester functional group of the non-neutralized sulfonated block copolymer.

5. The process of claim 2 wherein the organic solvent is a non-halogenated aliphatic solvent.

6. The process of claim 2 wherein the organic solvent comprises at least a first and a second aliphatic solvent, and wherein the B block is substantially soluble in the first solvent and the A block is substantially soluble in the second solvent.

7. The process of claim 2 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.

8. The process of claim 2 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.

9. The process of claim 2 wherein the metal of the metal compound has an atom number of at least 12.

10. The process of claim 2 wherein the metal compound comprises magnesium, calcium, aluminum, lead, titanium, copper, or zinc.

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

12. A neutralized sulfonated block copolymer which is solid in water comprising at least two polymer end blocks A and at least one polymer interior block B, wherein

a. each A block contains essentially no sulfonic acid or sulfonate ester functional groups and each B block is a polymer block containing from about 10 to about 100 mol % sulfonic acid or sulfonate ester functional groups based on the number of sulfonation susceptible monomer units of the B block;

and

b. from 80% to 100% of the sulfonic acid or sulfonate ester functional groups of the sulfonated B blocks are neutralized with a metal compound, wherein the metal has an atom number of at least 11.

13. The neutralized sulfonated block copolymer of claim 12 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.

14. The neutralized sulfonated block copolymer of claim 12 wherein the metal compound comprises magnesium, calcium, aluminum, lead, titanium, copper, or zinc.

15. The neutralized sulfonated block copolymer of claim 12 wherein the metal is in an oxidation state of +2, +3 or +4.

16. The neutralized sulfonated block copolymer of claim 12 which meets one or both of the following provisions:

a. the neutralized sulfonated block copolymer has a water uptake value which is equal to or less than the water uptake value of a corresponding, non-neutralized sulfonated block copolymer; and

/or

b. the neutralized sulfonated block copolymer has a wet tensile modulus which is equal to or greater than the wet tensile modulus of the corresponding, non-neutralized sulfonated block copolymer.

17. The neutralized sulfonated block copolymer of claim 16 having a water uptake value of less than 80% the water uptake value of the corresponding, non-neutralized sulfonated block copolymer.

18. The neutralized sulfonated block copolymer of claim 12 having a water uptake value of less than 50%-wt. of its dry weigh.

19. The neutralized sulfonated block copolymer of claim 16 having a water uptake value of at least 0.1%-wt. of its dry weight.

20. The neutralized sulfonated block copolymer of claim 12 which is in hydrated form.

21. The hydrated, neutralized sulfonated block copolymer of claim 20 which comprises at least 0.1% by weight, based on the dry weight of the neutralized block copolymer, of water in incorporated form.

22. The hydrated, neutralized sulfonated block copolymer of claim 20 which has a water vapor transport rate of at least about 15,000 g/m²/day/mil.

23. The hydrated, neutralized sulfonated block copolymer of claim 20 which meets one or both of the following provisions:

a. the hydrated, neutralized sulfonated block copolymer has a water transport rate of at least about 50% of the water transport rate of a hydrated form of a corresponding, non-neutralized sulfonated block copolymer;

b. the hydrated, neutralized sulfonated block copolymer has a wet tensile modulus which is equal to or greater than the wet tensile modulus of the hydrated form of the corresponding, non-neutralized sulfonated block copolymer.

24. The hydrated, neutralized sulfonated block copolymer of claim 20 having a water transport rate of at least about 75% of the water transport rate of a hydrated form of a corresponding non-neutralized sulfonated block copolymer.

25. An apparatus comprising a membrane which apparatus is selected from the group consisting of:

devices for controlling humidity, devices for forward electrodialysis, devices for reverse electrodialysis, devices for pressure retarded osmosis, devices for forward osmosis, devices for reverse osmosis, devices for selectively adding water, devices for selectively removing water, and batteries,

wherein the membrane comprises the neutralized sulfonated block copolymer defined in claim 12.

26. A means for storing a polar component comprising a non-polar, liquid phase and a sulfonated block copolymer having at least one end block A and at least one interior block B wherein each A block contains essentially no sulfonic acid or sulfonate ester functional groups and each B block is a polymer block containing from about 10 to about 100 mol % sulfonic acid or sulfonate ester functional groups based on the number of sulfonation susceptible monomer units of the B block,

wherein the non-polar, liquid phase comprises the sulfonated block copolymer in micellar form adapted to immure the polar component.

27. 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 a sulfonated block copolymer having at least one end block A and at least one interior block B wherein each A block contains essentially no sulfonic acid or sulfonate ester functional groups and each B block is a polymer block containing from about 10 to about 100 mol % sulfonic acid or sulfonate ester functional groups based on the number of sulfonation susceptible monomer units of the B block

wherein the solution comprises the sulfonated block copolymer in micellar form, and

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

28. The process of claim 27 wherein the polar component is a metal compound.