POLY(CYCLOHEXYLETHYLENE)-POLYACRYLATE BLOCK COPOLYMERS, METHODS OF MANUFACTURE THEREOF AND ARTICLES COMPRISING THE SAME

• US 20140360975A1
• Filed: 06/07/2013
• Published: 12/11/2014
• Est. Priority Date: 06/07/2013
• Status: Active Grant

• Current Assignee: Dow Global Technologies LLC (Dow, Inc.), Regents of The University of Minnesota (University of Minnesota)
• Original Assignee: Dow Global Technologies LLC (Dow, Inc.), Regents of The University of Minnesota (University of Minnesota)
• Inventors: Bates, Frank Steven, Hillmyer, Marc Andrew, Kennemur, Justin Glenn, Hustad, Phillip Dene
• Granted Patent: US 10,202,479 B2
• Time in Patent Office: Days
• US Class Current: 216/49
• CPC Class Codes: C08F 2438/01 Atom Transfer Radical Polymerization [ATRP] or reverse ATRP
• CPC Class Codes: C08F 293/005 using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
• CPC Class Codes: G03F 7/0002 Lithographic processes using patterning methods other than those involving the exposure to radiation, e.g. by stamping

Abstract

Disclosed herein is a block copolymer comprising a first block derived from a cyclo-alkyl vinyl monomer, a hydrogenated vinyl aromatic polymer or a hydrogenated vinyl pyridine polymers; and a second block derived from an acrylate monomer. Disclosed herein too is a method comprising reacting a first block derived from a cyclo-alkyl vinyl monomer, a hydrogenated vinyl aromatic polymer or a hydrogenated vinyl pyridine polymers with an initiator to form a macroinitiator; and polymerizing a second block onto the first block to form a block copolymer; where the second block is derived by polymerizing an acrylate monomer; and where the block copolymer has a chi parameter of greater than or equal to about 0.05, when measured at a temperature of 200° C. to 210° C.; where the chi parameter is a measure of interactions between the first block and the second block of the copolymer.

Claims

1. A block copolymer comprising:

a first block derived from a cyclo-alkyl vinyl monomer, a hydrogenated vinyl aromatic polymer or a hydrogenated vinyl pyridine polymer; and

a second block derived from an acrylate monomer.

2. The block copolymer of claim 1, where a chi parameter that measures interactions between the first block and the second block is greater than or equal to about 0.1 when measured at a temperature of 200°

C. to 210°

C.

3. The block copolymer of claim 1, where the chi parameter is greater than or equal to 0.05 when measured at a temperature of 200°

C. to 210°

C.

4. The block copolymer of claim 1, where the cyclo-alkyl vinyl monomer is vinylcyclohexane.

5. The block copolymer of claim 4, where the vinyl aromatic polymer is derived from a vinyl aromatic monomer;

where the vinyl aromatic monomer is methylstyrene, p-methylstyrene, m-methylstyrene, α

-methylstyrene, o-ethylstyrene, m-ethylstyrene, pethylstyrene, α

-methyl-p-methylstyrene, 2,4-dimethylstyrene, monochlorostyrene, p-tertbutylstyrene, 4-tert-butylstyrene, vinyl-naphthalene, acenaphthylene, or a combination comprising at least one of the foregoing vinyl aromatic monomers.

6. The block copolymer of claim 1, where the first block is poly(cyclohexylethylene), poly(2-vinyl piperadine), poly(4-vinylpiperadine) or a combination thereof.

7. The block copolymer of claim 1, where the acrylate monomer has a structure represented by formula (2):

8. The block copolymer of claim 1, where the acrylate monomer has a structure represented by the formula (3):

9. The block copolymer of claim 1, where the acrylate monomer has a structure that comprises at least one fluorine atom substituent, where the structure represented by the formula (4):

10. The block copolymer of claim 1, where the second block is poly(methyl methacrylate).

11. The block copolymer of claim 1, where the block copolymer comprises cylindrical and/or lamellar domains and has an interdomain spacing of less than or equal to about 30 nanometers.

12. A method comprising:

reacting a first block derived from a cyclo-alkyl vinyl monomer, a hydrogenated vinyl aromatic polymer or a hydrogenated vinyl pyridine polymers with an initiator to form a macroinitiator;

polymerizing a second block onto the first block to form a block copolymer;

where the second block is derived by polymerizing an acrylate monomer; and

where the block copolymer has a chi parameter of greater than or equal to about 0.05, when measured at a temperature of 200°

C. to 210°

C.;

where the chi parameter is a measure of interactions between the first block and the second block of the copolymer.

13. The method of claim 12, where the first block is anionically polymerized and the second block is radically polymerized.

14. A method comprising:

disposing on a substrate a composition comprising;

a block copolymer comprising a first block derived from a cyclo-alkyl vinyl monomer, a hydrogenated vinyl aromatic polymer or a hydrogenated vinyl pyridine polymer and a second block derived from an acrylate monomer, where a chi parameter that measures interactions between the first block and the second block is greater than or equal to about 0.5 when measured at a temperature of 200°

C. to 210°

C.

15. The method of claim 14, further comprising etching at least one block of the block copolymer.

16. The method of claim 14, where the block copolymer comprises lamellae and/or cylinders that are perpendicular to or parallel to a surface of the substrate.