Amine neutralized sulfonated block copolymers and method for making same
원문보기
IPC분류정보
국가/구분
United States(US) Patent
등록
국제특허분류(IPC7판)
C08F-008/36
C08F-006/14
C08F-008/32
출원번호
US-0578401
(2009-10-13)
등록번호
US-8263713
(2012-09-11)
발명자
/ 주소
Willis, Carl Lesley
출원인 / 주소
Kraton Polymers U.S. LLC
대리인 / 주소
Novak Druce & Quigg, LLP
인용정보
피인용 횟수 :
1인용 특허 :
81
초록
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.
대표청구항▼
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, andadding at least one amine to the solution, wherein the amine is a multi-functional a
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, andadding 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)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. 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: R1—NH-A-NR2—R3 whereinA is a straight chain or branched alkylene moiety having from two to six carbon atoms;R1 is hydrogen or C1-C6-alkylR2 is hydrogen or C1-C6-alkylR3 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. 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/orb. 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/m2/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)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. 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.
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