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

A sulfonated block copolymer which is solid in water after immersion in water for 24 hours and having the 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 coupling agent residue wherein:

• a. each A block and each D block is a polymer block resistant to sulfonation and each B block is a polymer block susceptible to sulfonation, said A, B and D 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 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 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;
• e. each D block comprises polymers having a glass transition temperature less than 20° C. and a number average molecular weight of between 1,000 and 50,000, said D block being 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;
• f. said B blocks are sulfonated to the extent of 10 to 100 mol percent, based on the units of vinyl aromatic monomer in said B blocks;
• g. 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 being between 10 mol percent and 100 mol percent;
• and
• h. wherein said sulfonated block copolymer is non-dispersible and solid in water, and has a tensile strength greater than 100 psi in the presence of water according to ASTM D412 after immersion in water for 24 hours.

A sulfonated block copolymer which is solid in water comprising at least two polymer end blocks A, at least one polymer interior block B, and at least one polymer block D, wherein:

• a. each A block and each D block is a polymer block resistant to sulfonation and each B block is a polymer block susceptible to sulfonation, said A and B blocks containing no significant levels of olefinic unsaturation;
• b. each A block is a segment of one or more polymerized para-substituted styrene monomers, and each A block independently having a number average molecular weight between 1,000 and 60,000 and each B block independently having a number average molecular weight between 10,000 and 300,000;
• c. said B blocks are sulfonated to the extent of 10 to 100 mol percent;
• and
• d. wherein said block copolymer is neither water soluble nor water dispersible, and is solid and has a tensile strength greater than 100 psi in the presence of water according to ASTM D412 after immersion in water for 24 hours;
• and
• e. each D block having a glass transition temperature of less than 20° C., said D block comprising a hydrogenated polymer or copolymer of a conjugated diene selected from isoprene, 1,3-butadiene having a vinyl content prior to hydrogenation of between 20 and 80 mol percent, and mixtures thereof, and having a number average molecular weight of between 1,000 and 50,000.

A sulfonated block copolymer which is solid in water at least two polymer end blocks A, at least one polymer interior block B, and at least one polymer block D wherein:

• a. each A block is a segment of one or more polymerized para-substituted styrene monomers, and each A block and each D block is a polymer block resistant to sulfonation and each B block is a polymer block susceptible to sulfonation, said A 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 and each B block independently having a number average molecular weight between 10,000 and 300,000;
• c. said B blocks are sulfonated to the extent of 10 to 100 mol percent;
• and
• d. wherein said block copolymer is neither water soluble nor water dispersible, and is a solid, and has a tensile strength greater than 100 psi in the presence of water according to ASTM D412 after immersion in water for 24 hours;
• and
• e. said D blocks having a glass transition temperature of less than 20° C., said D block comprising a polymer block of polymerized isobutylene, a polymerized ether, a polymer of an acrylic ester or a silicon polymer having a number average molecular weight of between 1000 and 50,000.