Metal-neutralized sulfonated block copolymers

Abstract

The present disclosure relates to a process for neutralizing a sulfonated block copolymer with a metal compound, to metal-neutralized block copolymers, and to various articles comprising the metal-neutralized block copolymers, e.g., in form of a water vapor permeable membrane which comprises the metal-neutralized block copolymers. The present disclosure further relates to a means and a method for storing and stabilizing a polar component such as a metal compound in a non-polar liquid phase by immuring the polar component in micelles of the sulfonated block copolymer in the non-polar liquid phase.

1 .- 11 . (canceled) 
     
     
         12 . 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 functional groups and each B block is a polymer block containing from about 10 to about 100 mol-% sulfonic acid or sulfonate functional groups based on the number of monomer units of the B block; and   b. from 80% to 100% of the sulfonic acid or sulfonate functional groups of the sulfonated B blocks are neutralized with a metal compound, wherein the metal compound comprises magnesium, calcium, strontium, barium, aluminum, tin, lead, titanium, zirconium, vanadium, chromium, molybdenum, manganese, iron, cobalt, nickel, copper, silver, zinc, cadmium, or mercury.   
     
     
         13 . (canceled) 
     
     
         14 . The neutralized block copolymer of  claim 12  wherein the metal compound comprises magnesium, calcium, aluminum, lead, titanium, copper, or zinc. 
     
     
         15 . The neutralized block copolymer of  claim 12  wherein the metal is in an oxidation state of +2, +3 or +4. 
     
     
         16 . The neutralized block copolymer of  claim 12  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 wet tensile modulus which is equal to or greater than the wet tensile modulus of the corresponding, non-neutralized sulfonated block copolymer. 
 
     
     
         17 . The neutralized block copolymer of  claim 16  having a water uptake value of less than 80% the water uptake value of the corresponding, non-neutralized block copolymer. 
     
     
         18 . The neutralized block copolymer of  claim 12  having a water uptake value of less than 50%-wt. of its dry weigh. 
     
     
         19 . The neutralized block copolymer of  claim 16  having a water uptake value of at least 0.1%-wt. of its dry weight. 
     
     
         20 . The neutralized block copolymer of  claim 12  which is in hydrated form. 
     
     
         21 . The hydrated, neutralized block copolymer of  claim 20  which comprises at least 0.1% by weight, based on the dry weight of the neutralized block copolymer, of water in incorporated form. 
     
     
         22 . The hydrated, neutralized block copolymer of  claim 20  which has a water vapor transport rate of at least about 15,000 g/m 2 /day/mil. 
     
     
         23 . The hydrated, neutralized block copolymer of  claim 20  which meets one or both of the following provisions:
 a. the hydrated, neutralized block copolymer 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, neutralized block copolymer has a wet tensile modulus which is equal to or greater than the wet tensile modulus of the hydrated form of the corresponding, non-neutralized sulfonated block copolymer. 
 
     
     
         24 . The hydrated, neutralized block copolymer of  claim 20  having a water transport rate of at least about 75% of the water transport rate of a hydrated form of a corresponding non-neutralized block copolymer. 
     
     
         25 . An apparatus comprising a membrane which apparatus is selected from the group consisting of:
 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, and batteries,   wherein the membrane comprises the neutralized block copolymer defined in  claim 12 .   
     
     
         26 .- 28 . (canceled) 
     
     
         29 . The neutralized block copolymer of  claim 12  wherein each B block contains about 65 to 100 mol-% sulfonic acid or sulfonate functional groups. 
     
     
         30 . The neutralized block copolymer of  claim 12  wherein each B block contains about 10 to 70 mol-% sulfonic acid or sulfonate functional groups and from 90 to 100% of the functional groups are neutralized. 
     
     
         31 . A neutralized sulfonated block copolymer having a general configuration A-B-D-B-A, A-D-B-D-A, (A-D-B) n (A), (A-B-D) n (A), (A-B-D) n X, (A-D-B) n X, or mixtures thereof, which is solid in water, wherein
 a. each A block contains essentially no sulfonic acid or sulfonate functional groups and each B block is a polymer block containing from about 10 to about 100 mol-% sulfonic acid or sulfonate functional groups based on the number of monomer units of the B block, n is an integer from 2 to about 30, X is a coupling agent residue, and each D block is an impact modifier block having a glass transition temperature less than 20° C.; and   b. from 80% to 100% of the sulfonic acid or sulfonate functional groups of the sulfonated B blocks are neutralized with a metal compound, wherein the metal is selected from the metals of periods 3 through 6 and groups 2 through 14 of the Periodic Table of the Elements.   
     
     
         32 . The neutralized block copolymer of  claim 31  wherein each B block contains about 65 to 100 mol-% sulfonic acid or sulfonate functional groups. 
     
     
         33 . The neutralized block copolymer of  claim 31  wherein each B block contains about 10 to 70 mol-% sulfonic acid or sulfonate functional groups and from 90 to 100% of the functional groups are neutralized. 
     
     
         34 . The neutralized block copolymer of  claim 31  wherein the metal is selected from magnesium, aluminum, calcium, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, strontium, zirconium, molybdenum, ruthenium, rhodium, palladium, silver, cadmium, tin, barium, hafnium, platinum, gold, mercury and lead. 
     
     
         35 . An apparatus comprising a membrane which apparatus is selected from the group consisting of:
 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, and batteries,   wherein the membrane comprises the neutralized block copolymer defined in  claim 31 .