IP Library Granted Patent US 9,365,662
Granted Patent B2
US 9,365,662 · App. 13/273,643 · Granted Jun 14, 2016

Method for producing a sulfonated block copolymer composition

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Quick Facts
Patent No.
US 9,365,662
App. No.
13/273,643
Granted
Jun 14, 2016
Kind
B2
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 (29)

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) n X, (A-B) n X, A-D-B-D-A, A-B-D-B-A, (A-D-B) n X, (A-B-D) n X 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) n X, (A-B) n X, A-D-B-D-A, A-B-D-B-A, (A-D-B) n X, (A-B-D) n X 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/m 2 /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 .

Assignments (10)
RELEASE OF SECURITY INTEREST IN PATENTS Recorded Jul 24, 2024
From: GOLDMAN SACHS BANK USA, AS COLLATERAL AGENT
To: KRATON CHEMICAL, LLC; KRATON CORPORATION
Reel/Frame 068671/0836 →
CORRECTIVE ASSIGNMENT TO CORRECT THE PATENT NO. 8837224 TO PATENT NO. 7737224 PREVIOUSLY RECORDED AT REEL: 037448 FRAME: 0453. ASSIGNOR(S) HEREBY CONFIRMS THE ASSIGNMENT. Recorded Jun 11, 2022
From: KRATON POLYMERS U.S. LLC; ARIZONA CHEMICAL COMPANY, LLC
To: BANK OF AMERICA, N.A.
Reel/Frame 060344/0919 →
SECURITY INTEREST Recorded Mar 18, 2022
From: KRATON CHEMICAL, LLC; KRATON POLYMERS LLC; KRATON POLYMERS U.S. LLC
To: GOLDMAN SACHS BANK USA, AS COLLATERAL AGENT
Reel/Frame 059525/0804 →
SECURITY INTEREST Recorded Mar 18, 2022
From: KRATON CHEMICAL, LLC; KRATON POLYMERS LLC; KRATON POLYMERS U.S. LLC
To: GOLDMAN SACHS BANK USA, AS COLLATERAL AGENT
Reel/Frame 059864/0455 →
RELEASE OF SECURITY INTEREST Recorded Mar 16, 2022
From: BANK OF AMERICA, N.A.
To: KRATON POLYMERS U.S. LLC; KRATON CHEMICAL, LLC F/K/A ARIZONA CHEMICAL COMPANY, LLC; KRATON POLYMERS LLC; KRATON CORPORATION; KRATON CHEMICAL B.V.
Reel/Frame 059910/0017 →
RELEASE OF SECURITY INTEREST Recorded Mar 15, 2022
From: CREDIT SUISSE AG, CAYMAN ISLANDS BRANCH, AS COLLATERAL AGENT
To: KRATON POLYMERS U.S. LLC
Reel/Frame 059366/0611 →
SECURITY INTEREST Recorded Apr 16, 2020
From: KRATON POLYMERS U.S. LLC; KRATON CHEMICAL, LLC F/K/A ARIZONA CHEMICAL COMPANY, LLC; KRATON POLYMERS LLC; KRATON CORPORATION
To: BANK OF AMERICA, N.A.
Reel/Frame 053020/0101 →
PATENT SECURITY AGREEMENT Recorded Jan 7, 2016
From: KRATON POLYMERS U.S. LLC
To: CREDIT SUISSE AG, CAYMAN ISLANDS BRANCH, AS COLLATERAL AGENT
Reel/Frame 037457/0843 →
CORRECTIVE ASSIGNMENT TO CORRECT THE PATENT NUMBER 8837224 TO PATENT NUMBER 7737224 PREVIOUSLY RECORDED AT REEL: 037448 FRAME: 0453. ASSIGNOR(S) HEREBY CONFIRMS THE SECURITY INTEREST. Recorded Jan 6, 2016
From: KRATON POLYMERS U.S. LLC; ARIZONA CHEMICAL COMPANY, LLC
To: BANK OF AMERICA, N.A.
Reel/Frame 037448/0453 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Oct 14, 2011
From: WILLIS, CARL LESLEY
To: KRATON POLYMERS U.S. LLC
Reel/Frame 027064/0750 →