Sulfonated block copolymers, method for making same, and various uses for such block copolymers

• US 8,383,735 B2
• Filed: 04/20/2010
• Issued: 02/26/2013
• Est. Priority Date: 07/22/2005
• 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, Handlin, Dale Lee Jr., Trenor, Scott Russell, Mather, Brian Douglas
• Primary Examiner(s): Boyle, Robert C
• Application Number:
  US12/764,021
• Publication Number:
  US 20100204403A1
• Time in Patent Office: 1,043 Days
• Field of Search: 525/313, 525/314, 525/315, 525/316, 525/291, 525/333.5, 525/331.9, 525/332.8, 525/332.9, 525/333.1, 525/333.2, 526/287, 526/257, 526/335, 526/346, 526/347.1
• US Class Current: 525/332.9
• CPC Class Codes: A61F 2013/530489 being randomly mixed in with other material
• CPC Class Codes: B01D 69/10 Supported membranes; Membrane supports
• CPC Class Codes: B01D 69/1071 Woven, non-woven or net mesh
• CPC Class Codes: B01D 71/26 Polyalkenes
• CPC Class Codes: B01D 71/261 Polyethylene
• CPC Class Codes: B01D 71/28 Polymers of vinyl aromatic compounds
• CPC Class Codes: B01D 71/281 Polystyrene
• 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 71/401 Polymers based on the polymerisation of acrylic acid, e.g. polyacrylate
• 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 297/04 polymerising vinyl aromatic monomers and conjugated dienes
• CPC Class Codes: C08F 8/04 Reduction, e.g. hydrogenation
• CPC Class Codes: C08F 8/36 Sulfonation; Sulfation
• CPC Class Codes: H01M 2004/027 Negative electrodes
• CPC Class Codes: H01M 4/131 Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
• CPC Class Codes: H01M 4/661 Metal or alloys, e.g. alloy coatings H01M4/669 take precedence
• CPC Class Codes: H01M 50/446 Composite material consisting of a mixture of organic and inorganic materials
• CPC Class Codes: Y02E 60/10 Energy storage using batteries
• CPC Class Codes: Y10T 428/249921 Web or sheet containing structurally defined element or component
• CPC Class Codes: Y10T 428/31855 : Of addition polymer from unsaturated monomers
• CPC Class Codes: Y10T 428/31931 : Polyene monomer-containing
• CPC Class Codes: Y10T 428/31938 : Polymer of monoethylenically unsaturated hydrocarbon
• 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 442/387 : Vinyl polymer or copolymer sheet or film [e.g., polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, etc.]
• CPC Class Codes: Y10T 442/3886 : Olefin polymer or copolymer sheet or film [e.g., polypropylene, polyethylene, ethylene-butylene copolymer, etc.]
• CPC Class Codes: Y10T 442/3976 : Including strand which is stated to have specific attributes [e.g., heat or fire resistance, chemical or solvent resistance, high absorption for aqueous composition, water solubility, heat shrinkability, etc.]
• CPC Class Codes: Y10T 442/668 : Separate nonwoven fabric layers comprise chemically different strand or fiber material
• CPC Class Codes: Y10T 442/676 : Vinyl polymer or copolymer sheet or film [e.g., polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, etc.]
• CPC Class Codes: Y10T 442/678 : Olefin polymer or copolymer sheet or film [e.g., polypropylene, polyethylene, ethylene-butylene copolymer, etc.]

Abstract

A pre-cursor block copolymer for sulfonation which, prior to hydrogenation, 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, wherein A, B and D blocks do not contain any significant levels of olefinic unsaturation. Each A and D block is a polymer block resistant to sulfonation, and each B block is a polymer block susceptible to sulfonation. Each A block is a segment of one or more polymerized para-substituted styrene monomers, each B block contains 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 each D block contains polymers having a glass transition temperature less than 20° C. and a number average molecular weight of between 1,000 and 50,000.

Claims

1. A pre-cursor block copolymer for sulfonation which has the general configuration A-D-B-D-A, (A-D-B)nX, or mixtures thereof, where n is an integer from 2 to about 30, and X is a coupling agent residue and wherein:

a. each A block is a polymer block resistant to sulfonation, each D block is a polymer block resistant to sulfonation, and each B block is a polymer block susceptible to sulfonation, said A, D and B blocks containing no significant levels of olefinic unsaturation;

b. each A block independently having a number average molecular weight between 1,000 and 60,000, each D block independently having a number average molecular weight between 1,000 and 50,000, and each B block independently having a number average molecular weight between 10,000 and 300,000;

c. each A block is a segment of one or more polymerized para-substituted styrene monomers;

d. 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;

e. 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) silicone polymer, (iv) polymerized isobutylene and (v) mixtures thereof, wherein the selected polymers have a glass transition temperature of less than 20°

C. and a number average molecular weight of between 1000 and 50,000, wherein any segments containing polymerized 1,3-butadiene or isoprene are subsequently hydrogenated; and

f. the mol percent of vinyl aromatic monomers which are unsubstituted styrene monomers, ortho-substituted styrene monomers, meta-substituted styrene monomers, alpha-methylstyrene, 1,1-diphenylethylene and 1,2-diphenylethylene in each B block is between 10 mol percent and 100 mol percent.

2. The block copolymer according to claim 1, wherein the polymer in said A block further comprises up to 15 mol percent of polymerized monomers selected from (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.

3. The block copolymer according to claim 1, wherein said A block is a segment of one or more polymerized para-substituted styrene monomers selected from para-methylstyrene, para-ethylstyrene, para-n-propylstyrene, para-iso-propylstyrene, para-n-butylstyrene, para-sec-butylstyrene, para-iso-butylstyrene, para-t-butylstyrene, isomers of para-decylstyrene, and isomers of para-dodecylstyrene.

4. The block copolymer according to claim 1, wherein said A block is a polymerized segment of para-t-butylstyrene and said B block is a polymerized segment of unsubstituted styrene.

5. The block copolymer according to claim 1, wherein said A block is a polymerized segment of para-methylstyrene and said B block is a polymerized segment of unsubstituted styrene.

6. The block copolymer according to claim 1, wherein the interior block B is a hydrogenated copolymer of one or more unsubstituted styrene monomers, and monomers of conjugated dienes having a vinyl content of 20 to 80 mol percent prior to hydrogenation.

7. The block copolymer according to claim 1, wherein said D block prior to hydrogenation is polymer block of 1,3-butadiene, and wherein 20 to 80 mol percent of the condensed butadiene units in block D have 1,2-configuration prior to hydrogenation.