Rapid self-assembly of block copolymers to photonic crystals

Patent metadata

Field	Value
Publication number	US-9382387-B2
Application number	US-201313800646-A
Country	US
Kind code	B2
Filing date	Mar 13, 2013
Priority date	Mar 13, 2012
Publication date	Jul 5, 2016
Grant date	Jul 5, 2016

Abstract

The invention provides a class of copolymers having useful properties, including brush block copolymers, wedge-type block copolymers and hybrid wedge and polymer block copolymers. In an embodiment, for example, block copolymers of the invention incorporate chemically different blocks comprising polymer size chain groups and/or wedge groups that significantly inhibit chain entanglement, thereby enhancing molecular self-assembly processes for generating a range of supramolecular structures, such as periodic nanostructures and microstructures. The present invention also provides useful methods of making and using copolymers, including block copolymers.

First claim

We claim:

1. A structure comprising a supramolecular assembly of a plurality of block copolymers; wherein each of said block copolymers independently comprises:
a first polymer block comprising first repeating units; wherein each of said first repeating units of said first polymer block comprises a first polymer backbone group covalently linked to a first polymer side chain group or a first wedge group characterized by at least three branch points each terminating in an independent branch moiety comprising at least 10 atoms; said first wedge group having a molecular weight greater than or equal to 50 Da; and
a second polymer block comprising second repeating units; wherein each of said second repeating units of said second polymer block comprises a second polymer backbone group covalently linked to a second wedge group or a second polymer side chain group that is different than said first wedge group or said first polymer side chain group; said second wedge group characterized by at least three branch points each terminating in an independent branch moiety comprising at least 10 atoms; and said second wedge group having a molecular weight greater than or equal to 50 Da;
wherein said first and second repeating units are directly or indirectly covalently linked along a backbone of said block copolymer;
wherein a domain length (DL) of the structure increases substantially linearly with molecular weight (MW) of said copolymer pursuant to the expression (E4) wherein 0.85<x<1:
DL∝MW x   (E4);

wherein said structure is characterized by at least one domain having a DL greater than 160 nm;
wherein said structure absorbs, scatters or reflects electromagnetic radiation having
wavelengths greater than or equal to 600 nm;
wherein each of said block copolymers has a molecular weight selected from the range of 2,000,000 Da to 30,000,000 Da; and
wherein each of said copolymers has the formula (FX1a):

wherein:
Z 1 is said first polymer backbone group and Z 2 is said second polymer backbone group;
Q 1 is a first backbone terminating group and Q 2 is a second backbone terminating group;
L 1 is a first linking group, and L 2 is a second linking group;
A is independently a polymer side chain group or a wedge group, wherein A is said first wedge group or said first polymer side chain group;
wherein B is said second polymer side chain group or said second wedge group; and
each of n and m is independently an integer selected from the range of 10 to 2000.

2. The structure of claim 1 , wherein
said second polymer block is directly covalently linked to said first polymer block along said backbone of said block copolymer.

3. The structure of claim 2 wherein a size (S) of the structure corresponds to said domain length of said supramolecular assembly of said plurality of said block copolymers; or wherein said size (S) of the structure corresponds to a route mean square radius (RMSR) of said supramolecular assembly of said plurality of said block copolymers.

4. The structure of claim 2 , wherein molecular self-assembly of said plurality of said block copolymers generate a periodic structure characterized by said domain length (DL) that increases substantially linearly with said molecular weight (MW) pursuant to the expression (E2) wherein 0.85<x<1:
DL∝MW x   (E2); or

wherein molecular self-assembly of said plurality of said block copolymers results in generation of said supramolecular assembly in the solution phase characterized by a route mean square radius (RMSR) that increases substantially linearly with said molecular weight (MW) pursuant to the expression (E3) wherein 0.85<x<1:
RMSR∝MW x   (E3).

5. The structure of claim 4 , wherein said periodic structure is a thin film lamellar structure having said domain length.

6. The structure of claim 2 , wherein said first polymer side chain group or said first wedge group and said second polymer side chain group or said second wedge group provide steric interactions within said block copolymer resulting in said backbone of said block copolymer being an extended backbone.

7. The structure of claim 2 wherein said first polymer block comprises said first polymer side chain group.

8. The structure of claim 7 wherein said first polymer side chain group has a molecular weight selected from the range of 5,000 to 30,000 Da.

9. The structure of claim 7 wherein said second polymer block comprises said second polymer side chain group.

10. The structure of claim 9 wherein said second polymer side chain group has a molecular weight selected from the range of 5,000 to 30,000 Da.

11. The structure of claim 7 wherein said second polymer block comprises said second wedge group.

12. The structure of claim 11 wherein the second wedge group has a molecular weight selected from the range of 50 Da to 1500 Da.

13. The structure of claim 11 , wherein said second wedge group independently comprises a C 2 -C 30 alkyl, C 3 -C 30 cycloalkyl, C 5 -C 30 aryl, C 5 -C 30 heteroaryl, C 2 -C 30 ester, C 2 -C 30 ether, C 2 -C 30 thioether, C 2 -C 30 amine, C 2 -C 30 imide, C 2 -C 30 halocarbon chain, C 2 -C 30 perfluorocarbon or C 2 -C 30 polyethylene glycol; or wherein said first wedge group comprises a group derived from a substituted or unsubstituted adamantane, silsesquioxane, norbornane, terpenoid, polyethylene glycol, or borneol.

14. The structure of claim 11 , wherein said second wedge group has the formula (W1), (W2), (W3), (W4), (W5), (W6), or (W7):

wherein each of W 1 -W 5 is independently a linking group; wherein Bn is a benzyl group; and
each of Y 1 -Y 5 is independently a hydrogen, C 1 -C 30 alkyl, C 3 -C 30 cycloalkyl, C 5 -C 30 aryl, C 5 -C 30 heteroaryl, C 1 -C 30 acyl, C 1 -C 30 hydroxyl, C 1 -C 30 alkoxy, C 2 -C 30 alkenyl, C 2 -C 30 alkynyl, C 5 -C 30 alkylaryl, —CO 2 R 30 , —CONR 31 R 32 , —COR 33 , —SOR 34 , —OSR 35 , —SO 2 R 36 , —OR 37 , —SR 38 , —NR 39 R 40 , —NR 41 COR 42 , C 1 -C 30 alkyl halide, phosphonate, phosphonic acid, silane, siloxane, silsesquioxane, C 2 -C 30 halocarbon chain, C 2 -C 30 perfluorocarbon, or C 2 -C 30 polyethylene glycol; wherein each of R 30 -R 42 is independently hydrogen, C 5 -C 10 aryl or C 1 -C 10 alkyl.

15. The structure of claim 2 , wherein said first polymer block comprises said first wedge group.

16. The structure of claim 15 , wherein said first wedge group has a molecular weight selected from the range of 50 Da to 1500 Da.

17. The structure of claim 15 , wherein said second polymer block comprises said second wedge group.

18. The structure of claim 17 , wherein said second wedge group has a molecular weight selected from the range of 50 Da to 1500 Da.

19. The structure-of claim 2 , wherein each of said block copolymers further comprises a third polymer block comprising at least 10 third repeating units; said third polymer block indirectly or directly covalently linked to said first polymer block and said second polymer block along the backbone of said block copolymer; wherein each of said third repeating units of said third polymer block comprises a third polymer backbone group covalently linked to a third polymer side chain group or a third wedge group characterized by at least three branch points each t

Assignees

• California Inst Of Techn
• Univ Massachusetts

Inventors

• Xia Yan
• Sveinbjornsson Benjamin R
• Grubbs Robert H
• Weitekamp Raymond
• Miyake Garret M
• Atwater Harry A
• Piunova Victoria
• Daeffler Christopher Scot
• Hong Sung Woo
• Gu Weiyin
• Russell Thomas P

Classifications

• C08G83/008 Primary

  Supramolecular polymers · CPC title

• C08G81/027 Primary

  containing polyester or polycarbonate sequences · CPC title