Nanohoop-functionalized polymer embodiments and methods of making and using the same

Patent metadata

Field	Value
Publication number	US-11739178-B2
Application number	US-202017033376-A
Country	US
Kind code	B2
Filing date	Sep 25, 2020
Priority date	Sep 27, 2019
Publication date	Aug 29, 2023
Grant date	Aug 29, 2023

Abstract

Disclosed herein are embodiments of a nanohoop-functionalized polymer and methods of making and using the same. In particular embodiments, polymer comprises one or more nanohoops that extend from the polymer backbone. Also disclosed herein are polymerizable nanohoop monomer embodiments that can be used to make the polymer embodiments disclosed herein.

First claim

We claim:

1. A polymer having a structure according to Formula I

wherein PB is a polymer backbone; TG is a terminating group; the optional linker is selected from aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, or an organic functional group; the nanohoop comprises six or more aromatic ring systems, wherein each aromatic ring is directly bound to at least two other rings of the nanohoop by two separate single covalent bonds positioned para, ortho, or meta relative to one another, and wherein the nanohoop is not linearly conjugated with the PB; m is an integer ranging from two or greater; and q is an integer selected from 1 or 2.

2. The polymer of claim 1 , wherein the TG is an aromatic ring.

3. The polymer of claim 2 , wherein the aromatic ring is a phenyl ring.

4. The polymer of claim 1 , wherein the optional linker is not present and the PB is covalently attached to the nanohoop through two points of attachment.

5. The polymer of claim 4 , wherein the PB is a five-membered ring and two adjacent carbon atoms of the five-membered ring are attached to two adjacent carbon atoms of the nanohoop.

6. The polymer of claim 1 , wherein the optional linker is not present and the PB is covalently attached to the nanohoop through one point of attachment.

7. The polymer of claim 1 , wherein q is 2 and each PB is different from the other.

8. The polymer of claim 1 , wherein the polymer has a structure according to Formula II

wherein each of rings A, B, C, D, and E independently are aromatic ring systems; each R′ independently is a substituent other than hydrogen; each s independently is an integer selected from 0 to 10; and p is an integer selected from 1 to 1000.

9. The polymer of claim 8 , wherein each of rings A, B, C, D, and E independently are aryl or heteroaryl.

10. The polymer of claim 8 , wherein each of rings A, B, C, D, and E independently are phenyl or pyridinyl.

11. The polymer of claim 8 , wherein each R′ independently is selected from aliphatic, heteroaliphatic, haloaliphatic, aromatic, or an organic functional group.

12. The polymer of claim 1 , wherein the polymer has a structure according to Formula III or IV

wherein each R′ independently is a substituent other than hydrogen; each s independently is an integer selected from 0 to 10; and p is an integer selected from 1 to 1000.

13. The polymer of claim 12 , wherein each R′ independently is selected from aliphatic, aryl, heteroaryl, halogen, an electron-accepting group, an electron-donating group, or any combination thereof.

14. The polymer of claim 1 , wherein the polymer is

15. A method, comprising exposing one or more polymerizable nanohoop monomers to conditions that promote ring opening metathesis polymerization, reversible addition-fragmentation chain transfer, anionic polymerization, or condensation polymerization between the one or more polymerizable nanohoop monomers to thereby provide the nanohoop-functionalized polymer according to claim 1 , wherein bonds are formed between polymerizable functional groups of the one or more polymerizable nanohoop monomers; wherein the one or more polymerizable nanohoop monomers independently have a structure according to Formula V

wherein
each PFG independently is selected from a norbornene, an acrylate, a methacrylate, a methyacrylamide, a stryene, a diene, vinyl acetate, n-vinylpyrrolidone, an aldehyde, an epoxide, an acrylonitrile, a cyanoacrylate, an alcohol, a carboxylic acid, an amine, or an ether;
the optional linker is selected from aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, or an organic functional group;
the nanohoop comprises six or more aromatic ring systems and wherein each aromatic ring is directly bound to at least two other rings of the nanohoop by two separate single covalent bonds positioned para, ortho, or meta relative to one another; and
q is 1 or 2.

16. The method of claim 15 , wherein the method comprising exposing the one or more polymerizable nanohoop monomers to a ruthenium-based catalyst to promote a ring opening metathesis polymerization between the polymerizable functional groups of the one or more polymerizable nanohoop monomers and wherein the polymerizable nanohoop monomer has a structure according to Formula VII or VIII

.

Assignees

• Univ Oregon

Inventors

• Jasti Ramesh
• Maust Ruth
• Li Penghao

Classifications

• C08G61/10 Primary

  only aromatic carbon atoms, e.g. polyphenylenes · CPC title

• C08J3/24

  Crosslinking, e.g. vulcanising, of macromolecules (mechanical aspects B29C35/00; crosslinking agents C08K) · CPC title

• C08J2365/02

  Polyphenylenes · CPC title

• C08G61/08 Primary

  of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring · CPC title

• C08G2261/11

  Homopolymers · CPC title