Modified sulfonated block copolymers and the preparation thereof

• US 9,861,941 B2
• Filed: 07/12/2011
• Issued: 01/09/2018
• Est. Priority Date: 07/12/2011
• 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 L.
• Primary Examiner(s): Nelson, Michael B
• Application Number:
  US13/181,306
• Publication Number:
  US 20130015071A1
• Time in Patent Office: 2,373 Days
• Field of Search: 428500, 429 33, 429 30, 260 79, 260 2
• CPC Class Codes: B01D 61/445 with bipolar membranes; Water splitting
• CPC Class Codes: B01D 61/48 having one or more compartments filled with ion-exchange material , e.g. electrodeionisation
• CPC Class Codes: B01D 71/28 Polymers of vinyl aromatic compounds
• CPC Class Codes: B01D 71/281 Polystyrene
• CPC Class Codes: B01D 71/68 Polysulfones; Polyethersulfones
• CPC Class Codes: B01D 71/80 Block polymers
• CPC Class Codes: C02F 1/441 by reverse osmosis
• CPC Class Codes: C02F 1/445 by forward osmosis
• CPC Class Codes: C02F 1/4693 electrodialysis
• CPC Class Codes: C02F 1/4695 electrodeionisation
• CPC Class Codes: C08F 297/02 using a catalyst of the anionic type
• CPC Class Codes: C08F 8/36 Sulfonation; Sulfation
• CPC Class Codes: H01M 8/1023 having only carbon, e.g. polyarylenes, polystyrenes or polybutadiene-styrenes
• CPC Class Codes: H01M 8/103 having nitrogen, e.g. sulfonated polybenzimidazoles [S-PBI], polybenzimidazoles with phosphoric acid, sulfonated polyamides [S-PA] or sulfonated polyphosphazenes [S-PPh]
• CPC Class Codes: Y02E 60/50 Fuel cells
• CPC Class Codes: Y10T 442/20 Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
• CPC Class Codes: Y10T 442/2762 Coated or impregnated natural fiber fabric [e.g., cotton, wool, silk, linen, etc.]

Abstract

Described herein are modified sulfonated block copolymers which comprise at least two polymer end blocks A and at least one polymer interior block B, wherein each A block contains essentially no sulfonic acid or sulfonate functional groups and each B block comprises sulfonation susceptible monomer units and, based on the number of the sulfonation susceptible monomer units, from about 10 to about 100 mol % of a functional group of formula (I)
—SO₂—NR¹R²  (I)
or of a salt thereof, methods of making them as well as methods of using them, e.g., as membrane materials for electrically or osmotically driven applications.

Claims

1. A membrane or film comprising a modified sulfonated block copolymer, the modified sulfonated block copolymer comprising at least two polymer end blocks A, at least one polymer interior block B, and one or more blocks D wherein

each A block contains no sulfonic acid or sulfonate functional groups and comprise 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 sulfonation susceptible monomer units comprising 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 and, based on the number of the sulfonation susceptible monomer units, from about 10 to about 100 mol % of a modified functional group of formula (I)

—

SO₂—

NR¹R² 

 

(I)

or of a salt thereof, wherein

R¹ is a moiety -(A¹-NR^a)_xR^b or a moiety -(A¹-NR^a)_y-A²-Z; and

R² is hydrogen, alkyl, or is one of the R¹ moieties;

or

R¹ and R² together with the nitrogen to which they are bonded form an optionally substituted 5- to 7-membered ring comprising 1-3 nitrogen atoms, 2-6 carbon, and optionally 1 or 2 non-adjacent oxygen and/or sulfur ring atoms;

x is 0, 1, 2 or 3;

y is 1 or 2;

A¹ and A², each independently, is straight chain alkylene optionally substituted by one or more methyl and/or ethyl groups;

R^a and R^b, each independently, is hydrogen or alkyl;

Z is —

CO₂H, —

SO₃H or —

P(O)(OH)₃; and

each D block being independently selected from the group consisting of (i) a polymerized or copolymerized conjugated diene selected from isoprene, and 1,3-butadiene, the polymerized conjugated diene 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, and wherein the modified sulfonated block copolymer has a general configuration 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; and

wherein the said membranes exhibit a conductivity of at least 0.5 mS/cm and wherein the dry tensile modulus of the modified sulfonated block copolymer is 10% to 99% of the dry tensile modulus of a corresponding unmodified sulfonated block copolymer that has sulfonic acid or sulfonate ester groups instead of the modified functional group.

2. The membrane or film of claim 1, wherein the B block comprises a functional group of the formula (I.1)

3. The membrane or film of claim 1, wherein the block B comprises the functional group of formula (I), wherein R¹ and R² together form a substituted or unsubstituted imidazole, or alternatively, R¹ forms a N,N-dimethylethylenediamine and R² is hydrogen or alkyl.

4. The membrane or film of claim 1, wherein the block B comprises from about 25 to about 80 mol % of the functional group of formula (I).

5. The membrane or film of claim 1, wherein each A block comprises para-substituted styrene monomers and each B block comprises unsubstituted styrene monomers.

6. The membrane or film of claim 1, having a general configuration A-D-B-D-A, A-B-D-B-A, or mixtures thereof, 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 membrane or film of claim 1 which has an anion exchange selectivity of at least 80%.

8. The membrane or film of claim 1 which has a water absorption of at most 20% by weight, based on a dry weight of the membrane.

9. The membrane or film of claim 1 which is obtained by

a) providing a composition comprising the modified sulfonated block copolymer in a liquid phase comprising one or more aprotic organic solvents,

b) casting the composition, and

c) evaporating the liquid phase.

10. The membrane or film of claim 6 wherein the A block comprises segments of para-tertbutyl styrene, the B block comprises segments of unsubstituted styrene monomers, and the D block comprises segments of hydrogenated isoprene.

11. The membrane or film of claim 1 wherein the block B comprises the functional group of formula (I) or a salt thereof, wherein R¹ and R² are identical and are -(A¹-NR^a)_xR^b or -(A¹-NR^a)_y-A SO₃H moieties.

12. An apparatus selected from the group consisting of fuel cells, filtration devices, devices for controlling humidity, devices for forward electrodialysis, devices for reverse electrodialysis, devices for pressure retarded osmosis, devices for forward osmosis, devices for reverse osmosis, devices for selectively adding water, devices for selectively removing water, devices for capacitive deionization, devices for molecular filtration, devices for removing salt from water, devices for treating produced water from hydraulic fracturing applications, devices for ion transport applications, devices for softening water, and batteries, and comprising the membrane or film of claim 1.

13. An electro-deionization assembly comprising at least one anode, at least one cathode, and one or more membrane(s) wherein at least one membrane is the membrane of claim 1.

14. The electro-deionization assembly of claim 13 which comprises at least two membranes wherein at least one membrane is a cation-exchange membrane.

15. The electro-deionization assembly of claim 14 wherein the cation exchange membrane comprises a sulfonated block copolymer comprising at least two polymer end blocks A and at least one polymer interior block B, wherein each A block contains no sulfonic acid or sulfonated ester functional groups and each B block comprises sulfonation susceptible monomer units and, based on the number of the sulfonation susceptible monomer units, from about 10 to about 100 mol % of sulfonic acid or sulfonate ester functional groups.

16. The electro-deionization assembly of claim 15 which comprises at least two membranes wherein at least one membrane is an anion-exchange membrane.

17. The electro-deionization assembly of claim 13 which comprises at least two membranes wherein at least one membrane is a bipolar membrane.

18. A coated article comprising a substrate and the membrane or film of claim 1.

19. The coated article of claim 18, wherein the substrate is a natural material, a synthetic material, a woven or a non-woven material, or a mixture thereof.

20. A membrane or film comprising a modified sulfonated block copolymer, the modified sulfonated block copolymer comprising at least two polymer end blocks A, at least one polymer interior block B, and one or more blocks D wherein each A block contains essentially no sulfonic acid or sulfonate functional groups and comprise 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 sulfonation susceptible monomer units comprising 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 and, based on the number of the sulfonation susceptible monomer units, from about 10 to about 100 mol % of a modified functional group of formula (I)

—

SO₂—

NR¹R² 

 

(I)

or of a salt thereof, wherein

R¹ is a moiety -(A¹-NR^a)_xR^b or a moiety -(A¹-NR^a)_y-A²-Z; and

R² is hydrogen, alkyl, or is one of the R¹ moieties;

or

R¹ and R² together with the nitrogen to which they are bonded form an optionally substituted 5- to 7-membered ring comprising 1-3 nitrogen atoms, 2-6 carbon, and optionally 1 or 2 non-adjacent oxygen and/or sulfur ring atoms;

x is 0, 1, 2 or 3;

y is 1 or 2

A¹ and A², each independently, is straight chain alkylene optionally substituted by one or more methyl and/or ethyl groups;

R^a and R^b, each independently, is hydrogen or alkyl;

Z is —

CO₂H, —

SO₃H or —

P(O)(OH)₃;

each D block being independently selected from the group consisting of (i) a polymerized or copolymerized conjugated diene selected from isoprene, and 1,3-butadiene, the polymerized conjugated diene 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, and wherein the modified sulfonated block copolymer has a general configuration 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; and

wherein the modified sulfonated block copolymer has a water vapor transport rate ranging from about 1,000 to 20,000 g/m²/day, wherein the water vapor transport rate is measured at 50% relative humidity and 25°

C. with a test membrane having 1 m² of exposed area and 1 mil of thickness, and wherein the dry tensile modulus of the modified sulfonated block copolymer is 10% to 99% of the dry tensile modulus of a corresponding unmodified sulfonated block copolymer that has sulfonic acid or sulfonate ester groups instead of the modified functional group.

21. The membrane or film of claim 20 having a thickness of 20-45 μ

m and an area resistance of no more than 5 Ω

cm2.