Method for producing a sulfonated block copolymer composition

• US 9,365,662 B2
• Filed: 10/14/2011
• Issued: 06/14/2016
• Est. Priority Date: 10/18/2010
• 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): Phasge, Arun S
• Application Number:
  US13/273,643
• Publication Number:
  US 20120267248A1
• Time in Patent Office: 1,705 Days
• Field of Search: 521/25, 521/28, 521/30
• US Class Current: 1/1
• CPC Class Codes: C08F 297/046 polymerising vinyl aromatic monomers and isoprene, optionally with other conjugated dienes
• CPC Class Codes: C08F 8/04 Reduction, e.g. hydrogenation
• CPC Class Codes: C08F 8/36 Sulfonation; Sulfation
• CPC Class Codes: Y02E 60/50 Fuel cells

Abstract

Sulfonated block copolymer composition formed by dissolving in an aprotic polar solvent at least one 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.

Claims

1. A solution having an inverted micelle sulfonated block copolymer composition comprising:

at least one 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,

said sulfonated block copolymer being dissolved in an aprotic polar solvent, and

wherein the sulfonated block copolymer is arranged in an inverted micelle structure having the sulfonic acid or sulfonate ester segments of the sulfonated block copolymer on the exterior of said micelle structure and the non-polar segments of the sulfonated block copolymer on the interior of said micelle structure, and

wherein the aprotic polar solvent is a compound containing at least one nitrogen atom.

2. The solution of claim 1, wherein the concentration of the sulfonated block copolymer in the solution is less than 15 wt %.

3. The solution of claim 1, wherein the ion exchange capacity is about 2 meq/g or less.

4. The solution of claim 1, wherein the ion exchange capacity is about 1.6 meq/g or less.

5. An aqueous dispersion formed from the solution of claim 1.

6. The solution of claim 1, wherein the sulfonated block copolymer has a general configuration A-B-A, A-B-A-B-A, (A-B-A)_nX, (A-B)_nX, A-D-B-D-A, A-B-D-B-A, (A-D-B)_nX, (A-B-D)_nX or mixtures thereof, where n is an integer from 2 to about 30, and X is a coupling agent residue and wherein each D block is a polymer block resistant to sulfonation and the plurality of A blocks, B blocks, or D blocks are the same or different.

7. The solution of claim 1, wherein each D block of the sulfonated block copolymer is selected from the group consisting of (i) a polymerized or copolymerized conjugated diene selected from isoprene, 1,3-butadiene having a vinyl content prior to hydrogenation of between 20 and 80 mol percent, (ii) a polymerized acrylate monomer, (iii) a silicon polymer, (iv) polymerized isobutylene and (v) mixtures thereof, wherein any segments containing polymerized 1,3-butadiene or isoprene are subsequently hydrogenated.

8. A sulfonated block copolymer composition formed by the process comprising:

dissolving in an aprotic polar solvent 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 sulfonated block copolymer in said solvent is arranged in an inverted micelle structure having the sulfonic acid or sulfonate ester segments of the sulfonated block copolymer on the exterior of said micelle structure and the non-polar segments of the sulfonated block copolymer on the interior of said micelle structure, and

wherein the aprotic polar solvent is a compound containing at least one nitrogen atom.

9. The composition of claim 8, wherein dissolving the sulfonated block copolymer in the aprotic polar solvent comprises heating the sulfonated block copolymer and the aprotic polar solvent at a temperature ranging from 40°

C. to the boiling point of the aprotic polar solvent.

10. The composition of claim 8, wherein the aprotic polar solvent is an amide.

11. The composition of claim 8, wherein the aprotic polar solvent is N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMA), N-methyl-2-pyrrolidone (NMP).

12. The composition of claim 8, wherein the ion exchange capacity is about 2 meq/g or less.

13. The composition of claim 8, wherein the ion exchange capacity is about 1.6 meq/g or less.

14. The composition of claim 8, wherein the sulfonated block copolymer is dissolved in the polar aprotic solvent at less than 15 wt %.

15. An aqueous dispersion formed with the sulfonated block copolymer composition of claim 8.

16. The composition of claim 8, wherein the sulfonated block copolymer has a general configuration A-B-A, A-B-A-B-A, (A-B-A)_nX, (A-B)_nX, A-D-B-D-A, A-B-D-B-A, (A-D-B)_nX, (A-B-D)_nX or mixtures thereof, where n is an integer from 2 to about 30, and X is a coupling agent residue and wherein each D block is a polymer block resistant to sulfonation and the plurality of A blocks, B blocks, or D blocks are the same or different.

17. A sulfonated block copolymer composition comprising:

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 and having an ion exchange capacity of 1.5 meq/g or less,

and wherein said block copolymer has an inverted cup moisture transmission rate greater than about 20 liters/m²/day; and

wherein the sulfonated block copolymer is dissolved in an aprotic polar solvent and the sulfonated block copolymer in said solvent is arranged in an inverted micelle structure having the sulfonic acid or sulfonate ester segments of the sulfonated block copolymer on the exterior of said micelle structure and the non-polar segments of the sulfonated block copolymer on the interior of the said micelle structure; and

wherein the aprotic polar solvent is a compound containing at least one nitrogen atom.

18. An aqueous dispersion formed with the sulfonated block copolymer composition of claim 17.