Synthetic polymers and methods of making and using the same

Patent metadata

Field	Value
Publication number	US-9562137-B2
Application number	US-201615154842-A
Country	US
Kind code	B2
Filing date	May 13, 2016
Priority date	Sep 3, 2014
Publication date	Feb 7, 2017
Grant date	Feb 7, 2017

Abstract

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 are described. Also described are methods of making polymers using such monomer embodiments. Methods of using the polymers also are described.

First claim

We claim:

1. A polymer having a formula:

wherein p is 1 or 0 and wherein when p is 1,
each T and T f is a terminal group independently selected from hydrogen, heteroaliphatic, aliphatic, aryl, heteroaryl, aliphatic-aryl, aliphatic-heteroaryl, heteroaliphatic-aryl, or heteroaliphatic-heteroaryl;
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 R 4 of NR 4 and at least one of R 1 or R n are different;
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; and

when p is 0,
each T and T f is a terminal group independently selected from hydrogen, heteroaliphatic, aliphatic, aryl, heteroaryl, aliphatic-aryl, aliphatic-heteroaryl, heteroaliphatic-aryl, or heteroaliphatic-heteroaryl;
at least one of R 1 , R n , and R f is hydrogen, and remaining R 1 , R n , and R f independently are selected from heteroaliphatic, aliphatic, aryl, heteroaryl, aliphatic-aryl, aliphatic-heteroaryl, heteroaliphatic-aryl, or heteroaliphatic-heteroaryl;
at least one of Y 1 , Y p , and Y f independently is selected from a bond, oxygen, sulfur, or NR 4 , wherein R 4 is hydrogen, and remaining Y 1 , Y p , and Y f 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;
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, 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; and
provided that when p is 0
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;
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; any one or more of W 1 or W a is O; 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; and
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.

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

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

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

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

6. The polymer of claim 1 , wherein each of L 1 and L q independently are selected from a porphyrin, a poly(ethylene)glycol, a polyester, a polyamide, or a polyalkene.

7. The polymer of claim 1 , wherein the polymer is a heteropolymer having a formula selected from

wherein:
each R 2 and R 3 independently is selected from heteroaliphatic, aliphatic, aryl, heteroaryl, aliphatic-aryl, aliphatic-heteroaryl, heteroaliphatic-aryl, or heteroaliphatic-heteroaryl;
each Y 2 and Y 3 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 and wherein R 4 of NR 4 and at least one of R 1 or R n are different;
each W 2 and W 3 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 2 and Z 3 independently is selected from heteroaryl, oxygen, sulfur, or NR 4 , wherein R 4 is selected from hydrogen, aliphatic, heteroaliphatic, heteroaryl, or aryl;
each L 2 and L 3 independently is selected from aliphatic, heteroaliphatic, aryl, or heteroaryl;
at least one of R 1 , Y 1 , W 1 , Z 1 , or L 1 is different from at least one of R 2 or R 3 , at least one of Y 2 or Y 3 , at least one of W 2 or W 3 , at least one of Z 2 or Z 3 , or at least one of L 2 or L 3 , respectively; and
n′ and p′ independently are 1 to 1000.

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

9. A polymer according to 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.

10. A plurality of polymers according to claim 1 , wherein the polymers 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.

11. The plurality of polymers according to claim 10 , wherein the plurality of polymers is monodisperse, sequence-defined, or a combination thereof.

12. A method of making a linear heteropolymer, comprising:
coupling, at a first temperature, a first position of a first starting material with a terminal group;
coupling, at a second temperature, a second position of the first starting material with a linker group or a side chain group;
coupling, at a third temperature, a third position of the first starting material with a linker group or a side chain group to form a first monomer unit of the polymer;
coupling, at the first temperature, the first monomer unit of the polymer with a first position of a second starting material;
coupling, at the second temperature, a second position of the second starting material with a linker group or a side chain group;
coupling, at the third temperature, a third position of the second s

Assignees

• Battelle Memorial Institute

Inventors

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

Classifications

• C08G73/0655

  from polycyanurates · CPC title

• C08G73/0273

  Polyamines containing heterocyclic moieties in the main chain · CPC title

• C08L79/02

  Polyamines · 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