Amine neutralized sulfonated block copolymers and method for making same
View Patent ↗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.
1. A process for preparing a membrane comprising a sulfonated block copolymer, said process comprising:
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, wherein the amine is a multi-functional amine having from two to four nitrogen functionalities, and comprises at least two nitrogen functionalities which are linked to one another via a linear, branched, or cyclic aliphatic bridging moiety, and subsequently forming said solution into a membrane comprising the sulfonated block copolymer,
wherein the sulfonated block copolymer prior to neutralization has 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,
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;
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.
2. The process of claim 1 wherein from 80% or more 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 a multi-functional amine having from two to three nitrogen functionalities.
7. 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) 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.
8. The process of claim 7 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.
9. A membrane comprising 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. 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;
c. 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,
d. 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,
wherein the multi-functional amine comprises at least two nitrogen functionalities which are linked to one another via a linear, branched, or cyclic aliphatic bridging moiety.
10. The membrane of claim 9 wherein the multi-functional amine has 2 or 3 nitrogen functionalities.
11. The membrane of claim 9 wherein the bridging moiety has 2 to 4 carbons.
12. The membrane of claim 9 , wherein the multifunctional amine has the general formulae:
R 1 —NH-A-NR 2 —R 3
wherein
A is a straight chain or branched alkylene moiety having from two to six carbon atoms;
R 1 is hydrogen or C 1 -C 6 -alkyl
R 2 is hydrogen or C 1 -C 6 -alkyl
R 3 is C 1 -C 6 -alkyl;
or R 2 and R 3 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, C 1 -C 6 -alkyl or amino-substituted C 2 -C 6 -alkyl.
13. The membrane of claim 9 , wherein the multi-functional amine is selected from the group consisting of N,N-dimethylethylenediamine, N,N′-dimethylethylenediamine and 1,4-bis(3-aminopropyl)piperzine, or mixture thereof.
14. The membrane of claim 9 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.
15. The membrane of claim 9 having a water uptake value of less than 80% the water uptake value of a corresponding, non-neutralized sulfonated block copolymer.
16. The membrane of claim 9 having a water uptake value of less than 100% of its dry weight.
17. The membrane of claim 9 a water vapor transport rate of at least 15,000 g/m 2 /day/mil.
18. The membrane of claim 9 , having a water transport rate of at least about 50% of the water transport rate of a corresponding non-neutralized block copolymer.
19. The membrane of claim 15 , having a water transport rate of at least about 50% of the water transport rate of a corresponding non-neutralized block copolymer.
20. The membrane of claim 19 , 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.
21. The membrane of claim 9 which is in hydrated form.
22. The hydrated membrane of claim 21 which meets both of the following provisions:
a. the hydrated membrane 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 membrane has a water uptake value of less than 80% the water uptake value of a corresponding, non-neutralized sulfonated block copolymer.
23. The membrane of claim 9 having 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.
24. The membrane of claim 23 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.
25. The process of claim 1 , wherein the multi-functional amine is selected from the group consisting of N,N-dimethylethylenediamine, N,N′-dimethylethylenediamine, and 1,4-bis(3-aminopropyl)piperzine, or a mixture thereof.
26. The process of claim 1 , wherein the multi-functional amine is selected from the group consisting of N,N-dimethylethylenediamine, N,N′-dimethylethylenediamine, or a mixture thereof.
27. The membrane of claim 9 , wherein the multi-functional amine is selected from the group consisting of N,N-dimethylethylenediamine, N,N′-dimethylethylenediamine, or a mixture thereof.