Synthetic polymers and methods of making and using the same

Patent metadata

Field	Value
Publication number	US-10100150-B2
Application number	US-201615374955-A
Country	US
Kind code	B2
Filing date	Dec 9, 2016
Priority date	Sep 3, 2014
Publication date	Oct 16, 2018
Grant date	Oct 16, 2018

Abstract

Disclosed herein are monomer embodiments that can be used to make polymers, such as homopolymers, heteropolymers, and that can be used in particular embodiments to make sequence-defined polymers. Also disclosed herein are methods of making polymers using such monomer embodiments. Methods of using the polymers disclosed herein also are described.

First claim

We claim:

1. A polymer having a structure meeting a formula:

wherein
each T and T f is a terminal group independently selected from amine, hydroxyl, thiol, hydrogen; heteroaliphatic having 1, 2, 4, 5, or 7-10 carbon atoms; aliphatic; aryl; heteroaryl; aliphatic-aryl; aliphatic-heteroaryl; heteroaliphatic-aryl; or heteroaliphatic-heteroaryl;
each R 1 and R f independently are selected from hydrogen, heteroaliphatic, aliphatic, aryl, heteroaryl, aliphatic-aryl, aliphatic-heteroaryl, heteroaliphatic-aryl, or heteroaliphatic-heteroaryl;
each Y 1 and Y f independently are selected from a bond, C(R 4 ) 2 , oxygen, sulfur, or NR 4 , wherein each R 4 independently is selected from hydrogen, aliphatic, heteroaliphatic, aryl, or heteroaryl;
each W 1 independently is selected from —C(R 4 ) 2 , oxygen, sulfur, or NR 4 , wherein each R 4 independently is selected from hydrogen, aliphatic, heteroaliphatic, aryl, or heteroaryl;
each Z 1 independently is selected from heteroaryl, oxygen, sulfur, or NR 4 , wherein R 4 is selected from hydrogen, aliphatic, cyclic heteroaliphatic comprising one or more heteroatoms selected from oxygen, sulfur, selenium, phosphorous, or oxidized forms thereof, acyclic heteroaliphatic, heteroaryl, or aryl;
each L 1 independently is selected from aliphatic, heteroaliphatic, aryl, heteroaryl, carbosilane, silane, siloxane, polycarbosilane, polysilane, or polysiloxane;
m ranges from 2 to 1000;
p is 1; and
at least one of T or T f is different from a W 1 -L 1 -Z 1 linker section of the polymer.

2. The polymer of claim 1 , wherein at least one of R 1 and R f is hydrogen bound to Y 1 or Y f , respectively, with Y 1 or Y f being a bond that binds R 1 or R f to a triazine ring of the polymer.

3. The polymer of claim 1 , wherein at least one of R 1 and R f is hydrogen bound to Y 1 or Y f , respectively, with Y 1 or Y f being oxygen, sulfur, or —NH.

4. The polymer of claim 1 , wherein at least one of R 1 and R f is aliphatic bound to Y 1 or Y f , respectively, with Y 1 or Y f being oxygen, sulfur, or —NH.

5. The polymer of claim 1 , wherein each W 1 and each Z 1 independently is selected from —NH, S, or O.

6. The polymer of claim 1 , wherein each of L 1 independently is aliphatic.

7. The polymer of claim 1 , wherein T and T f independently are selected from —NH 2 ; —NHR b ; —NR b R c —SH; —SR b ; —OH; or —OR b ; wherein each R b and R c independently is selected from aliphatic or aryl.

8. The polymer of claim 1 , wherein each R 1 and R f independently is selected from phenyl, benzyl, halogen-substituted benzyl, dimethoxy-substituted benzyl, C 2-25 thiol, C 2-25 hydroxyl, or C 2-25 amine.

9. The polymer of claim 1 , having a structure selected from:

10. The polymer of claim 1 , wherein the polymer is assembled in the form of a membrane, an amorphous particle, a crystal, or a nanorod wherein a backbone of the polymer interacts to create a columnar structure and side chains of the polymer project outward from the column.

11. A plurality of polymers comprising two or more polymers of claim 1 , wherein each of the two or more polymers of claim 1 are the same or different and are assembled in the form of a nanorod wherein side chains of a polymer interacts with side chains of another polymer to form the nanorod.

12. The plurality of polymers according to claim 11 , wherein the plurality of polymers is monodisperse, sequence-defined, or a combination thereof.

13. A polymer having a structure meeting a formula:

wherein
each T and T f independently is selected from hydrogen, amine, hydroxyl, thiol, or heteroaliphatic having 1, 2, 4, 5, or 7-10 carbon atoms;
R 1 , each R n , and R f independently is selected from hydrogen, heteroaliphatic, aliphatic, aryl, heteroaryl, aliphatic-aryl, aliphatic-heteroaryl, heteroaliphatic-aryl, or heteroaliphatic-heteroaryl;
Y 1 , each Y p , and Y f independently is selected from a bond, —C(R 4 ) 2 —, oxygen, sulfur, or NR 4 , wherein each R 4 independently is selected from hydrogen, aliphatic, heteroaliphatic, aryl, or heteroaryl and wherein;
W 1 and each W a independently is selected from —C(R 4 ) 2 , oxygen, sulfur, or NR 4 , wherein each R 4 independently is selected from hydrogen, aliphatic, heteroaliphatic, aryl, or heteroaryl;
Z 1 and each Z b independently is selected from heteroaryl, oxygen, sulfur, or NR 4 , wherein R 4 is selected from hydrogen, aliphatic, cyclic heteroaliphatic comprising one or more heteroatoms selected from oxygen, sulfur, selenium, phosphorous, or oxidized forms thereof, acyclic heteroaliphatic, heteroaryl, or aryl;
L 1 and each L q independently is selected from aliphatic, heteroaliphatic, aryl, heteroaryl, carbosilane, silane, siloxane, polycarbosilane, polysilane, or polysiloxane;
m ranges from 2 to 1000;
p is 1 or 0;
provided that when p is 1, then at least one of T or T f is different from a W 1 -L 1 -Z 1 or W a -L q -Z b linker section of the polymer; and
provided that when p is 0 then at least one of R 1 , Y 1 , W 1 , Z 1 , or L 1 is different from at least one R n , Y p , W a , Z b , or L q , respectively; and (i) any one or more of R 1 or R n are not hydrogen if Y 1 or Y p is NR 4 where R 4 is hydrogen and any one or more of L 1 or L q is phenyl; (ii) any one or more of R 1 or R n are not hydrogen if Y 1 or Y p is NR 4 where R 4 is hydrogen; (iii) any one or more of W 1 or W a is O; or (iv) any one or more of L 1 or L q is —CH 2 —C(4-decyloxybenzyl) 2 -CH 2 —; and any one of Z 1 or Z b is —NH.

14. The polymer of claim 13 , wherein T and T f independently are selected from —NH 2 ; —NHR b ; —NR b R c —SH; —SR b ; —OH; or —OR b ; wherein each R b and R c independently is selected from aliphatic or aryl.

15. The polymer of claim 13 , wherein T and T f independently are selected from NH 2 , —NHMe, —N(CH 2 ) 2 NH 2 , —SH, —SMe, —OH, or —OMe.

16. The polymer of claim 13 , wherein each R 1 and R f independently is selected from phenyl, benzyl, halogen-substituted benzyl, dimethoxy-substituted benzyl, C 2-25 thiol, C 2-25 hydroxyl, or C 2-25 amine.

17. The polymer of claim 13 , wherein the polymer is assembled in the form of a membrane, an amorphous particle, a crystal, or a nanorod wherein a backbone of the polymer interacts to create a columnar structure and side chains of the polymer project outward from the column.

18. A plurality of polymers comprising two or more polymers of claim 13 , wherein each of the two or more polymers of claim 13 are the same or different and are assembled in the form of a nanorod wherein side chains of a polymer interacts with side chains of another polymer to form the nanorod.

19. The plurality of polymers according to claim 18 , wherein the plurality of polymers is monodisperse, sequence-defined, or a combination thereof.

Assignees

• Battelle Memorial Institute

Inventors

• Grate Jay W
• Mo Kai-For
• Daily Michael D

Classifications

• C08L79/02

  Polyamines · CPC title

• C08G73/065

  Preparatory processes · CPC title

• C08G73/0273

  Polyamines containing heterocyclic moieties in the main chain · CPC title

• C08L79/04

  Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors · CPC title

• C08G73/0644 Primary

  Poly(1,3,5)triazines · CPC title