AMINE NEUTRALIZED SULFONATED BLOCK COPOLYMERS AND METHOD FOR MAKING SAME

• US 20110086982A1
• 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 8,263,713 B2
• Time in Patent Office: Days
• US Class Current: 525/189
• CPC Class Codes: B01D 71/26 Polyalkenes
• CPC Class Codes: B01D 71/28 Polymers of vinyl aromatic compounds
• CPC Class Codes: B01D 71/40 Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
• 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: C08F 297/046 polymerising vinyl aromatic monomers and isoprene, optionally with other conjugated dienes
• CPC Class Codes: C08F 8/36 Sulfonation; Sulfation
• CPC Class Codes: H01M 8/1032 having sulfur, e.g. sulfonated-polyethersulfones [S-PES]
• 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

An Amine neutralized sulfonated block copolymer and a method for neutralizing a sulfonated block copolymer, the process including providing a solution comprising an organic solvent and the non-neutralized block copolymer in micellar form, and adding at least one amine to the solution.

Claims

1. A process for neutralizing 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 percent sulfonic acid or sulfonate ester functional groups based on the number of monomer units of the B block and which are not neutralized, which process comprises

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

adding at least one amine to the solution.

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

3. The process of claim 1 wherein the amine is added in an amount of from about 0.8 to about 10 equivalents of amine base per 1 equivalent of sulfonic acid or sulfonate ester 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 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.

6. The process of claim 1 wherein the amine is selected from the group consisting of multifunctional amines, monofunctional amines, and mixtures thereof, the amine groups in each case being primary, secondary or tertiary amine groups having one, two or three aliphatic and/or aromatic substituents, and wherein substituents of the primary, secondary and tertiary amine groups may be linear, branched, or cyclic aliphatic or aromatic moieties or mixtures of such substituents.

7. The process of claim 1 wherein the amine is a multi-functional amine having from two to four nitrogen functionalities

8. The process of claim 1 wherein each A block comprises one or more segments selected from polymerized (i) para-substituted styrene monomers, (ii) ethylene, (iii) alpha olefins of 3 to 18 carbon atoms;

(iv) 1,3-cyclodiene monomers, (v) monomers of conjugated dienes having a vinyl content less than 35 mol percent prior to hydrogenation, (vi) acrylic esters, (vii) methacrylic esters, and (viii) mixtures thereof.

9. The process of claim 1 wherein each B block comprises segments of one or more vinyl aromatic monomers selected from polymerized (i) unsubstituted styrene monomers, (ii) ortho-substituted styrene monomers, (iii) meta-substituted styrene monomers, (iv) alpha-methylstyrene, (v) 1,1-diphenylethylene, (vi) 1,2-diphenylethylene and (vii) mixtures thereof.

10. The process of claim 1, wherein the sulfonated block copolymer has the 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.

11. The process of claim 10 wherein each D block 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

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 percent sulfonic acid or sulfonate ester functional groups based on the number of monomer units of the B block;

b. the sulfonated B blocks are neutralized with a multi-functional amine having from two to four nitrogen functionalities, wherein from 95% to 100% of the sulfonic acid or sulfonate ester functional groups in the B block are neutralized.

13. The neutralized block copolymer of claim 12 wherein the multi-functional amine has 2 or 3 nitrogen functionalities.

14. The neutralized block copolymer of claim 12 wherein the multi-functional amine comprises at least two nitrogen functionalities which are linked to one another via a C₂-C₄ linear, branched, or cyclic aliphatic bridging moiety.

15. The neutralized block copolymer of claim 12, wherein the multifunctional amine has the general formulae:

R¹—

NH-A-NR²—

R³

wherein

A is a straight chain or branched alkylene moiety having from two to six carbon atoms;

R¹ is hydrogen or C₁-C₆-alkyl

R² is hydrogen or C₁-C₆-alkyl

R³ is C₁-C₆-alkyl;

or R² and R³ together with the nitrogen to which they are bonded form a 5 to 7 membered ring made up of 4 to 6 carbon atoms and optionally one or two additional nitrogen ring members wherein the additional nitrogen ring members are independently of one another substituted by hydrogen, C₁-C₆-alkyl or amino-substituted C₂-C₆-alkyl.

16. The neutralized block copolymer of claim 12, wherein the multi functional amine is selected from the group consisting of N,N-dimethylethylenediamine, N,N′

-dimethylethylennediamine, and 1,4-bis(3-aminopropyl)piperzaine, or mixture thereof.

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

a. the neutralized 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 block copolymer has a dry tensile modulus which is equal to or less than the dry tensile modulus of the corresponding, non-neutralized sulfonated block copolymer, the modulus measured according to ASTM D412.

18. The neutralized block copolymer of claim 12 having a water uptake value of less than 80% the water uptake value of a corresponding, non-neutralized sulfonated block copolymer.

19. The neutralized block copolymer of claim 12 having a water uptake value of less than 100% of its dry weight.

20. The neutralized block copolymer of claim 12 a water vapor transport rate of at least 15,000 g/m²/day/mil.

21. The neutralized block copolymer of claim 12, having a water transport rate of at least about 50% of the water transport rate of a corresponding non-neutralized block copolymer.

22. The neutralized block copolymer of claim 18, having a water transport rate of at least about 50% of the water transport rate of a corresponding non-neutralized block copolymer.

23. The neutralized block copolymer of claim 22, the neutralized block copolymer has a dry tensile modulus which is less than the dry tensile modulus of the corresponding, non-neutralized sulfonated block copolymer, the modulus measured according to ASTM D412

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

25. The hydrated, neutralized block copolymer of claim 24 which meets both of the following provisions:

a. the hydrated, neutralized 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 block copolymer a water uptake value of less than 80% the water uptake value of a corresponding, non-neutralized sulfonated block copolymer.

26. The neutralized block copolymer of claim 12, wherein each B block comprises segments of one or more vinyl aromatic monomers selected from polymerized (i) unsubstituted styrene monomers, (ii) ortho-substituted styrene monomers, (iii) meta-substituted styrene monomers, (iv) alpha-methylstyrene, (v) 1,1-diphenylethylene, (vi) 1,2-diphenylethylene and (vii) mixtures thereof.

27. The neutralized block copolymer of claim 12 having 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.

28. The neutralized block copolymer of claim 27 comprising one or more blocks D each block D being independently 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.

29. A membrane comprising the neutralized block copolymer defined in claim 12.