Photonic Structures from Self Assembly of Brush Block Copolymers and Polymer Blends

Patent metadata

Field	Value
Publication number	US-2016356923-A1
Application number	US-201615243788-A
Country	US
Kind code	A1
Filing date	Aug 22, 2016
Priority date	Jun 28, 2012
Publication date	Dec 8, 2016
Grant date	—

Abstract

The invention provides a class of block copolymers having a plurality of chemically different blocks, at least a portion of which incorporating polymer side chain groups having a helical secondary structure. The invention also provides structures generated by self-assembly of polymer blends including at least one block copolymer component, such as a brush block polymer or wedge-type block polymer. The invention provides, for example, periodic nanostructures and microstructures generated by self-assembly of block copolymers and polymer blends comprising a mixture of at least one block copolymer component, such as a brush block copolymer, and at least a second component.

First claim

1 - 78 . (canceled)

79 . A structure comprising a supramolecular assembly of a polymer blend of at least one block copolymer and at least a second component; wherein said polymer blend comprises:
a first block copolymer comprising:
a first polymer block comprising at least 10 first repeating units; wherein each of said first repeating units of said first polymer block comprises a first polymer backbone group directly or indirectly covalently linked to a first polymer side chain group or a first wedge group; and
a second polymer block comprising at least 10 second repeating units; wherein each of said second repeating units of said second polymer block comprises a second polymer backbone group directly or indirectly covalently linked to a second polymer side chain group or second wedge group that is different than said first polymer side chain group and said first wedge group; wherein said first and second repeating units are directly or indirectly covalently linked along a backbone of said block copolymer; and the second component having a composition that is different from said first block copolymer.

80 . The structure of claim 79 , wherein said second component comprises a homopolymer, a copolymer, an oligomer, a solvent, a metal, a small molecule or particle.

81 . The structure of claim 79 , wherein said structure is formed via molecular self-assembly of said first block polymers and said second component of said polymer blend to generate said supramolecular assembly.

82 . The structure of claim 79 , wherein said structure is formed via thermal annealing, solvent annealing, spin coating, shear alignment, painting, tape casting, co-extrusion, drop casting, spray coating or by the application of an external pressure to said polymer blend.

83 . (canceled)

84 . The structure of claim 79 comprising a periodic structure or a photonic band gap material.

85 . (canceled)

86 . The structure of claim 79 , wherein said structure absorbs, scatters or reflects electromagnetic radiation having wavelengths greater than or equal to 400 nm.

87 - 89 . (canceled)

90 . The structure of claim 79 , wherein said structure is characterized by a periodically varying refractive index.

91 . The structure of claim 79 , wherein
a size (S) of the structure increases substantially linearly with molecular weight (MW) of said first block copolymer pursuant to the expression (E4) wherein 0.85<x<1:
S∝MW x   (E4).

92 - 101 . (canceled)

102 . The structure of claim 79 , wherein said second component is a second block copolymer comprising at least one polymer block different from said first polymer block and said second polymer block of said first block copolymer.

103 . (canceled)

104 . The structure of claim 102 , wherein the ratio of the molecular weight of the first block copolymer to the molecular weight of the second block copolymer is selected over the range of 0.2 to 5.

105 - 106 . (canceled)

107 . The structure of claim 79 , wherein said first block copolymer is a brush block copolymer or a wedge-type block copolymer.

108 - 122 . (canceled)

123 . The structure of claim 79 , wherein said first block copolymer has the formula (FX5a) or (FX5b1):

wherein J is a repeating group of said first polymer side chain group, K is a repeating group of said second polymer side chain group, G 2 is said second wedge group;
each of R 10 and R 11 is independently a polymer side chain terminating group; and
each of p and q is independently an integer selected from the range of 30 to 2000.

124 . The structure of claim 123 , wherein each of J and K is independently an unsubstituted or substituted isocyanate group, methacrylate group, acrylate group, acrylamide group, methacrylamide group, quinoxaline group, guanidine group, silane group, acetylene group, amino acid group, chloral group, lactide group, styrene group, acrylate group, tert-butyl, siloxane group, dimethylsiloxane group, n-butyl acrylate group, ethylene glycol group, ethylene oxide group, ethylene group, propylene group, tetrafluoroethylene group, or vinyl chloride group.

125 . The structure of claim 123 , wherein each of R 10 and R 11 is independently hydrogen, C 1 -C 10 alkyl, C 3 -C 10 cycloalkyl, C 5 -C 10 aryl, C 5 -C 10 heteroaryl, C 1 -C 10 acyl, C 1 -C 10 hydroxyl, C 1 -C 10 alkoxy, C 2 -C 10 alkenyl, C 2 -C 10 alkynyl, C 5 -C 10 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 10 alkyl halide, phosphonate, phosphonic acid, silane, siloxane acrylate, or catechol; wherein each of R 30 -R 42 is independently hydrogen or C 1 -C 5 alkyl.

126 - 127 . (canceled)

128 . The structure of claim 123 , wherein said first block copolymer has the formula (FX6A) or (FX6B1):

wherein R 1 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, C 2 -C 30 polyethylene glycol, a metal, or a metal complex, wherein each of R 30 -R 42 is independently H, C 5 -C 10 aryl or C 1 -C 10 alkyl.

129 . The structure of claim 128 , wherein said first block copolymer has the formula (FX7):

wherein R 12 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, C 2 -C 30 polyethylene glycol, a metal, or a metal complex, wherein each of R 30 -R 42 is independently H, C 5 -C 10 aryl or C 1 -C 10 alkyl; and wherein R 1 and R 12 are different groups.

130 . The block copolymer of claim 129 , wherein R 1 is a C 1 -C 30 alkyl and R 12 is a C 5 -C 30 aryl.

131 . The block copolymer of claim 129 , having the formula (FX8a) or (FX8b):

wherein each of r, s, t and v are independently an integer selected from the range of 1 to 10.

132 . The structure of claim 79 wherein said second polymer block comprises said second wedge groups.

133 - 134 . (canceled)

135 . The structure of claim 132 , wherein each of said second wedge groups is characterized by at least two branch points each terminating in an independent terminating branch moiety comprising at least 4 atoms.

Assignees

• California Inst Of Techn

Inventors

• Miyake Garret M
• Weitekamp Raymond
• Grubbs Robert H
• Piunova Victoria

Classifications

• C08L87/005

  Block or graft polymers not provided for in groups C08L1/00 - C08L85/04 · CPC title

• G02F1/0054

  Structure, phase transitions, NMR, ESR, Moessbauer spectra · CPC title

• G02F2202/32

  Photonic crystals · CPC title

• G02B1/005 Primary

  made of photonic crystals or photonic band gap materials (photonic band-gap structures or photonic lattices in integrated optics G02B6/1225; photonic band-gap structures or photonic lattices in optical fibres G02B6/02295) · CPC title

• C08F222/04

  Anhydrides, e.g. cyclic anhydrides · CPC title