Methods of making crosslinked copolymer films from inimer-containing random copolymers

1. A method of making a crosslinked copolymer film, the method comprising:

forming a random copolymer by polymerizing a first monomer comprising an alkyl halide functional group that is capable of acting as an ATRP initiator and a second monomer comprising a crosslinkable functional group, wherein the random copolymer comprises pendant alkyl halide functional groups and pendant crosslinkable groups;

subsequently depositing the polymerized random copolymer as a film on a substrate surface; and

subsequently crosslinking the crosslinkable functional groups of the deposited random copolymer, such that crosslinks are formed between chains of the random copolymer in the film, wherein the crosslinked copolymer film has a halogen atom density of at least 1.5 atoms/nm 3 ;

wherein the film comprising the crosslinked random copolymer is not covalently bonded to the substrate surface.

2. The method of claim 1 , wherein depositing the polymerized random copolymer on the substrate surface comprises spreading the polymerized random copolymer on the substrate surface.

3. The method of claim 1 , wherein the crosslinkable functional group comprises a thermally self-crosslinking functional group.

4. The method of claim 1 , wherein the random copolymer comprises 10% to about 99% of the first monomer and 1% to 30% of the second monomer as measured by 1 H NMR spectroscopy.

5. A method of making a crosslinked copolymer film, the method comprising:

forming a random copolymer by polymerizing a first monomer comprising an alkyl halide functional group that is capable of acting as an ATRP initiator and a second monomer comprising a crosslinkable functional group, wherein the random copolymer comprises pendant alkyl halide functional groups and pendant crosslinkable groups;

subsequently depositing the polymerized random copolymer as a film on a substrate surface; and

subsequently crosslinking the crosslinkable functional groups of the deposited random copolymer, such that crosslinks are formed between chains of the random copolymer in the film, wherein the crosslinked copolymer film has a thickness in the range from 2 nm to 6 nm;

wherein the film comprising the crosslinked random copolymer is not covalently bonded to the substrate surface.

6. A method of making a crosslinked copolymer film, the method comprising:

forming a random copolymer by polymerizing a first monomer comprising an alkyl halide functional group that is capable of acting as an ATRP initiator and a second monomer comprising a thermally crosslinkable epoxy group, wherein the random copolymer comprises pendant alkyl halide functional groups and pendant crosslinkable groups;

subsequently depositing the polymerized random copolymer as a film on a substrate surface; and

subsequently crosslinking the crosslinkable functional groups of the deposited random copolymer, such that crosslinks are formed between chains of the random copolymer in the film;

wherein the film comprising the crosslinked random copolymer is not covalently bonded to the substrate surface.

7. The method of claim 6 , wherein the first monomer is selected from acrylate monomers having an alkyl halide functional group, methacrylate monomers having an alkyl halide functional group, styrene monomers having an alkyl halide functional group, or combinations thereof.

8. A method of making a crosslinked copolymer film, the method comprising:

forming a random copolymer by polymerizing a first monomer comprising an alkyl halide functional group that is capable of acting as an ATRP initiator and a second monomer comprising a crosslinkable functional group, wherein the random copolymer comprises pendant alkyl halide functional groups and pendant crosslinkable groups and further wherein the random copolymer comprises 80% to about 98% of the first monomer and 2% to 20% of the second monomer as measured by 1 H NMR spectroscopy;

subsequently depositing the polymerized random copolymer as a film on a substrate surface; and

subsequently crosslinking the crosslinkable functional groups of the deposited random copolymer, such that crosslinks are formed between chains of the random copolymer in the film;

wherein the film comprising the crosslinked random copolymer is not covalently bonded to the substrate surface.

9. A method of making a polymer brush, the method comprising:

making a crosslinked copolymer film by:

forming a random copolymer by polymerizing a first monomer comprising an alkyl halide functional group that is capable of acting as an ATRP initiator and a second monomer comprising a crosslinkable functional group, wherein the random copolymer comprises pendant alkyl halide functional groups and pendant crosslinkable groups;

subsequently depositing the polymerized random copolymer as a film on a substrate surface; and

subsequently crosslinking the crosslinkable functional groups of the deposited random copolymer, such that crosslinks are formed between chains of the random copolymer in the film;

wherein the film comprising the crosslinked random copolymer is not covalently bonded to the substrate surface; and

exposing the crosslinked copolymer film to a solution comprising polymerizable monomers and a transition metal complex under reaction conditions in which the halides of the copolymer film initiate the polymerization of the polymerizable monomers into brush polymer chains via atom transfer radical polymerization.

10. The method of claim 9 , wherein the polymer brush has a grafting density of at least 0.5 brush polymer chains/nm 3 .

11. The method of claim 9 , wherein the polymer brush has a grafting density of at least 0.8 brush polymer chains/nm 3 .

12. The method of claim 9 , wherein the polymerizable monomers comprise vinyl monomers, acrylate monomers, methacrylate monomers, or a combination thereof.