Cleavable block copolymers, functionalized nanoporous thin films and related methods of preparation
Cleavable, disulfide-coupled block copolymers as can be used in the preparation of nanoporous thin films, micellar configurations and related structures.
1. A block copolymer compound of a formula
wherein R 3 and R 4 are independently selected from H, alkyl, substituted alkyl, aryl, substituted aryl, carboxy, substituted carboxy, alkoxycarbonyl, substituted alkoxycarbonyl, aminocarbonyl and substituted aminocarbonyl moieties; m and n are independently selected from integers greater than 1, for each respective m and n block; n′ is an integer selected from 1 to about 3; A 3 is an alkylcarboxy moiety and A 4 are independently selected from non-halide moieties of atom transfer radical polymerization initiation reagents, and reversible addition fragmentation chain transfer initiation agents; and X 3 and X 4 are independently selected from other blocks of repeating monomeric units, halide moieties of said initiation reagents and polymer terminal moieties.
2. The compound of claim 1 wherein R 4 is a phenyl moiety, and said n block comprises repeating styrene monomeric units.
3. The compound of claim 2 wherein n′ is 2, and said m block comprises repeating propylene oxide monomeric units.
4. The compound of claim 3 wherein A 4 is an ethoxycarbonyl moiety, and said n block comprises an atom transfer radical polymerization product.
5. The compound of claim 4 wherein X 4 is selected from a bromide moiety and another block of repeating monomeric units.
6. The compound of claim 1 wherein A 4 is selected from alkoxycarbonylalkyl and alkoxycarboxy moieties.
7. The compound of claim 6 wherein A 4 is an ethoxycarbonyl moiety, R 4 is phenyl and said n block comprises a reversible addition fragmentation chain transfer polymerization product.
8. The compound of claim 1 wherein n′ is 2, and said m block comprises repeating propylene oxide monomeric units.
9. The compound of claim 1 in a thin film, and one said block comprises a volume fraction less than about 50 percent of said copolymer.
10. The compound of claim 9 wherein disulfide reduction and removal of said block provides said thin film comprising a plurality of nanopores therethrough and defining inner pore walls comprising a plurality of thiol moieties.
11. The compound of claim 10 wherein said thiol moieties are coupled to a thiol-reactive component.
12. The compound of claim 11 wherein said thiol moieties are coupled to a metal.