Sulfonated block copolymer laminates with polar or active metal substrates
Disclosed herein is a process for laminating a polar substrate with a film cast from a sulfonated block copolymer having 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. The film is exposed to water and dried onto a polar or active metal substrate. The laminates do not delaminate in the presence of water, or in a humidity of up to 85%, and at a temperature of at least 60° C. The laminates are used for a variety of applications including energy exchange applications.
1. A permanent laminate formed by a process comprising:
providing a film consisting essentially of a sulfonated block copolymer having 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,
wherein the sulfonated block copolymer has 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;
wherein n is an integer from 2 to about 30, and X is a coupling agent residue,
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) a polymerized isobutylene and (v) mixtures thereof, wherein any segments containing polymerized 1,3-butadiene or isoprene are subsequently hydrogenated;
and wherein the plurality of A blocks, B blocks, or D blocks are the same or different,
exposing the film to water to obtain a partially or fully hydrated film,
applying said partially or fully hydrated film directly to a polar surface or metal activated surface of a substrate, and
laminating said partially or fully hydrated film onto the polar surface or activated metal surface of the substrate by drying to form the permanent laminate,
wherein the polar surface or the metal activated surface has active metal and/or polar groups or moieties on the surface for forming any of a hydrogen bond, covalent bond, or ionic bond with the sulfonic acid or sulfonate ester functional groups of the film, and
wherein the film does not delaminate from the substrate after being exposed to humidity of up to 85%, at a temperature of at least 60° C., for a duration of at least 72 hours, forming the permanent laminate.
2. The permanent laminate of claim 1 , wherein the partially or fully hydrated film is applied directly to a metal activated surface of a substrate.
3. The permanent laminate of claim 1 , wherein the film of the sulfonated block copolymer has a water uptake value of from 10% to 150% by weight, relative to the weight of the film; and wherein the film is used as a moisture vapor transport membrane.
4. The permanent laminate of claim 1 , wherein said film does not delaminate from the substrate when soaked in water for 30 hours.
5. The permanent laminate of claim 1 , wherein the substrate surface comprises an active metal.
6. The permanent laminate of claim 1 , wherein the substrate surface comprises an active metal selected from the group consisting of Li, K, Ba, Ca, NA, MG, Al, Zn, Cr, Fe, Cd, Co, Ni, Sn, and Pb or an alloy thereof.
7. The permanent laminate of claim 1 , wherein the block copolymer has a configuration A-D-B-D-A, wherein the A block is poly(para-tert-butylstyrene), the D block is hydrogenated polyisoprene, and prior to sulfonation, the B block is polystyrene.
8. The permanent laminate of claim 1 , wherein the D block has a glass transition temperature of less than 20° C.
9. The permanent laminate of claim 1 , wherein the substrate surface comprises a metal of rows 2-4 of groups 2 through 13 of the periodic table of the elements, or an alloy of 2 or more of the metals.
10. The permanent laminate of claim 9 , wherein the substrate surface comprises aluminum.
11. The permanent laminate of claim 1 , wherein the 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, and
wherein the D block of the sulfonated block copolymer is selected from the group consisting of (i) a polymerized or copolymerized conjugated diene selected from isoprene, and 1,3-butadiene, having a vinyl content prior to hydrogenation of between 20 and 80 mole percent, and a number average molecular weight of between 1,000 and 50,000, (ii) a polymerized acrylate monomer, (iii) a silicon polymer, (iv) a polymerized isobutylene and (v) mixtures thereof,
wherein any segments containing polymerized 1,3-butadiene or isoprene are subsequently hydrogenated.
12. The permanent laminate of claim 11 , wherein the A block has a molecular weight of between 3,000 and 30,000.
13. The permanent laminate of claim 11 , wherein the B block has a molecular weight of between 30,000 and 100,000.
14. The permanent laminate of claim 11 , wherein the B block has a molecular weight of between 1,000 and 50,000.
15. A permanent laminate formed by a process comprising:
providing a film consisting essentially of a sulfonated pentablock copolymer of formula Poly(para-tert-butylstyrene-isoprene-styrene-isoprene-para-tert-butylstyrene),
wherein the poly(para-tert-butylstyrene) block contains essentially no sulfonic acid or sulfonate ester functional groups, and the polystyrene block contains from 10 to 100 mol percent sulfonic acid or sulfonate ester functional groups based on the number of monomer units;
exposing the film to water to obtain a partially or fully hydrated film,
applying said partially or fully hydrated film directly to a polar surface or metal activated surface of a substrate,
and laminating said partially or fully hydrated film onto the polar surface or activated metal surface of the substrate by drying to form the permanent laminate,
wherein the polar surface or the metal activated surface has active metal and/or polar groups or moieties on the surface for forming any of a hydrogen bond, covalent bond, or ionic bond with the sulfonic acid or sulfonate ester functional groups of the film, and
wherein the film does not delaminate from the substrate after being exposed to humidity of up to 85%, at a temperature of at least 60° C., for a duration of at least 72 hours, forming the permanent laminate.
16. The permanent laminate of claim 15 , wherein the partially or fully hydrated film is laminated on to an activated metal surface of a substrate, wherein the metal activated surface has an active metal selected from the Activity Series of elements or alloys thereof.