Bottlebrush polymers and uses thereof
Provided are new bottlebrush polymers and diblock bottlebrush copolymers, which can self-assemble into structures of desired morphology (e.g., hexagonal cylindrical, gyroid). The self-assembled structures of the bottlebrush polymers and copolymers provide useful materials such as photonics (e.g., photonic crystals), functional materials, chromatography media, stimuli-responsive materials, lubricants, nanolithography, films, and coatings. In certain embodiments, the backbone repeating units of the bottlebrush polymers and copolymers have two different polymeric sidechains covalently attached to the backbone repeating unit through a branched linker, wherein one of the polymeric sidechain is a polysiloxane. Also provided are methods of preparing the bottlebrush polymers and copolymers described herein.
1. A bottlebrush polymer comprising a backbone of repeating units covalently linked to polymeric sidechains, wherein each repeating unit is linked to at least two different polymeric sidechains; and the polymer is capable of self-assembling into structures having a gyroid morphology.
2. The bottlebrush polymer of claim 1 , wherein at least one polymeric sidechain of each repeating unit is a polysiloxane.
3. The bottlebrush polymer of claim 2 , wherein the polysiloxane is of the formula:
wherein:
R 1 is optionally substituted alkyl, optionally substituted alkenyl, optionally substituted aryl, or optionally substituted alkoxy;
R 2 is optionally substituted alkyl, optionally substituted alkenyl, optionally substituted aryl, or optionally substituted alkoxy; and
q is an integer between 1 and 1000, inclusive.
4. The bottlebrush polymer of claim 2 , wherein the polysiloxane is polydimethylsiloxane (PDMS).
5. The bottlebrush polymer of claim 1 , wherein the bottlebrush polymer is of Formula (I):
or a salt thereof, wherein:
G A is optionally substituted alkylene, optionally substituted heteroalkylene, optionally substituted carbocyclylene, optionally substituted heterocyclylene, optionally substituted arylene, optionally substituted heteroarylene, or a combination thereof;
each of L 1 , L 3 , L A , and L B is independently a divalent linker selected from the group consisting of a bond, optionally substituted alkylene, optionally substituted heteroalkylene, optionally substituted alkenylene, optionally substituted alkynylene, optionally substituted carbocyclylene, optionally substituted heterocyclylene, optionally substituted arylene, optionally substituted heteroarylene, and combinations thereof;
L 2 is a trivalent linker comprising optionally substituted alkylene, optionally substituted heteroalkylene, optionally substituted alkenylene, optionally substituted alkynylene, optionally substituted carbocyclylene, optionally substituted heterocyclylene, optionally substituted arylene, optionally substituted heteroarylene, or a combination thereof;
each of T 1 and T 2 is independently a terminal group selected from the group consisting of hydrogen, halogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted acyl, optionally substituted hydroxyl, optionally substituted amino, and optionally substituted thio;
n is an integer between 1 and 4000, inclusive;
A is a polysiloxane having a number average molecular weight of about 1,000 Da to about 20,000 Da; and
B is a different polymer having a number average molecular weight of about 1,000 Da to about 20,000 Da.
6. The bottlebrush polymer of claim 5 , wherein the bottlebrush polymer is of Formula (I-a):
or a salt thereof.
7. The bottlebrush polymer of claim 5 , wherein A is polydimethylsiloxane (PDMS).
8. The bottlebrush polymer of claim 5 , wherein B is a polyether, a polyester, a polyacrylamide, a polyacrylate, or a vinyl polymer.
9. The bottlebrush polymer of claim 5 , wherein B is polystyrene.
10. The bottlebrush polymer of claim 5 , wherein A is polydimethylsiloxane (PDMS); and B is polystyrene.
11. The bottlebrush polymer of claim 5 , wherein B is a polyacrylate.
12. The bottlebrush polymer of claim 5 , wherein A is polydimethylsiloxane (PDMS); and B is poly(tert-butyl acrylate) (PtBA).
13. A self-assembled material comprising the bottlebrush polymer of claim 1 .
14. A method of preparing a self-assembled material, the method comprising annealing the bottlebrush polymer of claim 1 .
15. A method of preparing a bottlebrush polymer of claim 1 , the method comprising forming the bottlebrush polymer via polymerization reactions.
16. The bottlebrush polymer of claim 1 , wherein one polymeric sidechain of each repeating unit is a polysiloxane; and another polymeric sidechain of each repeating unit is polystyrene.
17. The bottlebrush polymer of claim 1 , wherein one polymeric sidechain of each repeating unit is polydimethylsiloxane (PDMS); and another polymeric sidechain of each repeating unit is polystyrene.
18. The bottlebrush polymer of claim 17 , wherein the PDMS sidechains have a molecular weight from about 4,500 Da to about 5,500 Da; and the polystyrene sidechains have a molecular weight from about 8,000 Da to about 9,500 Da.
19. The bottlebrush polymer of claim 1 , wherein one polymeric sidechain of each repeating unit is a polysiloxane; and another polymeric sidechain of each repeating unit is a polyacrylate.
20. The bottlebrush polymer of claim 1 , wherein one polymeric sidechain of each repeating unit is polydimethylsiloxane (PDMS); and another polymeric sidechain of each repeating unit is poly(tert-butylacrylate) (PtBA).
21. The bottlebrush polymer of claim 20 , wherein the PDMS sidechains have a molecular weight from about 4,500 Da to about 5,500 Da; and the PtBA sidechains have a molecular weight from about 3,000 Da to about 4,000 Da.
22. The bottlebrush polymer of claim 1 , wherein one polymeric sidechain of each repeating unit is polystyrene; and another polymeric sidechain of each repeating unit is a polyester.
23. The bottlebrush polymer of claim 1 , wherein one polymeric sidechain of each repeating unit is polystyrene; and another polymeric sidechain of each repeating unit is polylactic acid (PLA).
24. The bottlebrush polymer of claim 23 , wherein the polystyrene sidechains have a molecular weight from about 4,000 Da to about 5,000 Da; and wherein the PLA sidechains have a molecular weight from about 3,000 Da to about 4,000 Da.
25. The bottlebrush polymer of claim 1 , wherein the bottlebrush polymer is selected from the group consisting of PS 8.2k -branch-PDMS 5k , PS 9.2k -branch-PDMS 5k , PDMS 5 -branch-PtBA 3.6k , and PS 4.7k -branch-PLA 3.8k .
26. A bottlebrush polymer, wherein the bottlebrush polymer is of Formula (I):
or a salt thereof, wherein:
G A is optionally substituted alkylene, optionally substituted heteroalkylene, optionally substituted carbocyclylene, optionally substituted heterocyclylene, optionally substituted arylene, optionally substituted heteroarylene, or a combination thereof;
each of L 1 , L 3 , L A , and L B is independently a divalent linker selected from the group consisting of a bond, optionally substituted alkylene, optionally substituted heteroalkylene, optionally substituted alkenylene, optionally substituted alkynylene, optionally substituted carbocyclylene, optionally substituted heterocyclylene, optionally substituted arylene, optionally substituted heteroarylene, and combinations thereof;
L 2 is a trivalent linker comprising optionally substituted alkylene, optionally substituted heteroalkylene, optionally substituted alkenylene, optionally substituted alkynylene, optionally substituted carbocyclylene, optionally substituted heterocyclylene, optionally substituted arylene, optionally substituted heteroarylene, or a combination thereof;
each of T 1 and T 2 is independently a terminal group selected from the group consisting of hydrogen, halogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted acyl, optionally substituted hydroxyl, optionally substituted amino, and optionally substituted thio;
n is an integer between 1 and 4000, inclusive;
A is a polysiloxane having a number average molecular weight of about 1,000 Da to about 20,000 Da; and
B is a different polymer having a number average molecular weight of about 1,000 Da to about 20,000 Da.
27. The bottlebrush polymer of claim 26 , wherein the bottlebrush polymer is of Formula (I-a):
or a salt thereof.
28. The bottlebrush polymer of claim 26 , wherein A is polydimethylsiloxane (PDMS).
29. The bottlebrush polymer of claim 26 , wherein B is a polyether, a polyester, a polyacrylamide, a polyacrylate, or a vinyl polymer.
30. The bottlebrush polymer of claim 26 , wherein B is polystyrene.
31. The bottlebrush polymer of claim 26 , wherein A is polydimethylsiloxane (PDMS); and B is polystyrene.
32. The polymer of claim 26 , wherein B is a polyacrylate.
33. The bottlebrush polymer of claim 26 , wherein A is polydimethylsiloxane (PDMS);
and B is poly(tert-butyl acrylate) (PtBA).
34. The polymer of claim 26 , wherein B is a polyester.
35. The bottlebrush polymer of claim 26 , wherein A is polydimethylsiloxane (PDMS); and B is poly(lactic acid) (PLA).
36. The bottlebrush polymer of claim 26 , wherein the bottlebrush polymer is of Formula (I-c):
or a salt thereof, wherein:
each of T 1 and T 2 is independently hydrogen or phenyl;
n is an integer between 10 and 100, inclusive;
p is an integer between 10 and 100, inclusive; and
q is an integer between 25 and 260, inclusive; wherein the ratio of q:p is about 2.6:1.
37. The bottlebrush polymer of claim 26 , wherein the bottlebrush polymer is of Formula (I-d):
or a salt thereof, wherein:
each of T 1 and T 2 is independently hydrogen or phenyl;
n is an integer between 10 and 100, inclusive;
r is an integer between 20 and 200, inclusive; and
q is an integer between 20 and 200, inclusive; wherein the ratio of q:r is about 1:1.2 to about 1:1.3.
38. The bottlebrush polymer of claim 26 , wherein the bottlebrush polymer of Formula (I) is of Formula (I-e):
or a salt thereof, wherein:
each of T 1 and T 2 is independently hydrogen or phenyl;
n is an integer between 10 and 100, inclusive;
s is an integer between 20 and 200, inclusive; and
q is an integer between 20 and 200, inclusive.
39. A bottlebrush copolymer comprising a backbone of repeating units covalently linked to polymeric sidechains; wherein the bottlebrush copolymer is a diblock bottlebrush copolymer, and at least one block of the bottlebrush copolymer comprises polysiloxane sidechains linked to each repeating unit.
40. The bottlebrush copolymer of claim 39 , wherein at least one block of the bottlebrush copolymer comprises at least two different polymeric sidechains linked to each repeating unit.
41. The bottlebrush copolymer of claim 40 , wherein each block of the bottlebrush copolymer comprises at least two different polymeric sidechains linked to each repeating unit.
42. The copolymer of claim 39 , wherein the polysiloxane sidechains are polydimethylsiloxane (PDMS).
43. The bottlebrush copolymer of claim 39 , wherein the bottlebrush copolymer is of Formula (II):
or a salt thereof, wherein:
each of G A and G B is independently optionally substituted alkylene, optionally substituted heteroalkylene, optionally substituted carbocyclylene, optionally substituted heterocyclylene, optionally substituted arylene, optionally substituted heteroarylene, or a combination thereof;
each of L 1 , L 3 , and L 5 is independently a divalent linker selected from the group consisting of a bond, optionally substituted alkylene, optionally substituted heteroalkylene, optionally substituted alkenylene, optionally substituted alkynylene, optionally substituted carbocyclylene, optionally substituted heterocyclylene, optionally substituted arylene, optionally substituted heteroarylene, and combinations thereof;
each of L 2 and L 4 is independently a trivalent linker comprising optionally substituted alkylene, optionally substituted heteroalkylene, optionally substituted alkenylene, optionally substituted alkynylene, optionally substituted carbocyclylene, optionally substituted heterocyclylene, optionally substituted arylene, optionally substituted heteroarylene, or combinations thereof;
each of L A , L B , L c , and L D is independently a linker selected from the group consisting of a bond, optionally substituted alkylene, optionally substituted heteroalkylene, optionally substituted alkenylene, optionally substituted alkynylene, optionally substituted carbocyclylene, optionally substituted heterocyclylene, optionally substituted arylene, optionally substituted heteroarylene, and combinations thereof;
each of T 1 and T 2 is independently a terminal group selected from the group consisting of hydrogen, halogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted acyl, optionally substituted hydroxyl, optionally substituted amino, and optionally substituted thio;
n is an integer between 1 and 4000, inclusive;
m is an integer between 1 and 4000, inclusive; and
each of A, B, C, and D is independently a polymer or hydrogen;
provided that one of A, B, C, and D is a polysiloxane;
provided that no two of A, B, C, or D are the same polymer type; and
provided that no more than one of A, B, C, or D is hydrogen.
44. The bottlebrush copolymer of claim 43 , wherein the bottlebrush copolymer is of Formula (II-a):
or a salt thereof.
45. The bottlebrush copolymer of claim 43 , wherein B is polydimethylsiloxane (PDMS).
46. The bottlebrush copolymer of claim 43 , wherein B is a polysiloxane; and each of A, C, and D is independently a polyether, a polyester, a polyacrylamide, a polyacrylate, or a vinyl polymer.
47. The bottlebrush copolymer of claim 43 , wherein B is a polysiloxane; and each of A, C, and D is independently a polyacrylate, polyester, or polystyrene.
48. The bottlebrush copolymer of claim 43 , wherein A is a poly(tert-butyl acrylate) (PtBA); B is polydimethylsiloxane (PDMS); C is poly(lactic acid) (PLA); and D is polystyrene.
49. The bottlebrush copolymer of claim 43 , wherein L A is a bond; A is hydrogen; B is a polysiloxane; C is a polyester; and D is polystyrene.
50. The bottlebrush copolymer of claim 43 , wherein L A is a bond; A is hydrogen; B is polydimethylsiloxane (PDMS); C is poly(lactic acid); and D is polystyrene.
51. A bottlebrush polymer, wherein the bottlebrush polymer is of Formula (I):
or a salt thereof, wherein:
G A is optionally substituted alkylene, optionally substituted heteroalkylene, optionally substituted carbocyclylene, optionally substituted heterocyclylene, optionally substituted arylene, optionally substituted heteroarylene, or a combination thereof;
each of L 1 , L 3 , L A , and L B is independently a divalent linker selected from the group consisting of a bond, optionally substituted alkylene, optionally substituted heteroalkylene, optionally substituted alkenylene, optionally substituted alkynylene, optionally substituted carbocyclylene, optionally substituted heterocyclylene, optionally substituted arylene, optionally substituted heteroarylene, and combinations thereof;
L 2 is a trivalent linker comprising optionally substituted alkylene, optionally substituted heteroalkylene, optionally substituted alkenylene, optionally substituted alkynylene, optionally substituted carbocyclylene, optionally substituted heterocyclylene, optionally substituted arylene, optionally substituted heteroarylene, or a combination thereof;
each of T 1 and T 2 is independently a terminal group selected from the group consisting of hydrogen, halogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted acyl, optionally substituted hydroxyl, optionally substituted amino, and optionally substituted thio;
n is an integer between 1 and 4000, inclusive;
A is a polymer having a number average molecular weight of about 1,000 Da to about 20,000 Da; and
B is a different polymer having a number average molecular weight of about 1,000 Da to about 20,000 Da;
wherein the bottlebrush polymer has a gyroid morphology.