Quaternary ammonium-functionalized polymers and methods of making and using same

Patent metadata

Field	Value
Publication number	US-2024158564-A1
Application number	US-202218262677-A
Country	US
Kind code	A1
Filing date	Jan 24, 2022
Priority date	Jan 23, 2021
Publication date	May 16, 2024
Grant date	—

Abstract

Hydrocarbonbackbone polymers with pendant quaternary ammonium groups and methods of making and using same. A polymer can be made by a ring-opening polymerization of quaternary ammonium bearing monomer(s), and, optionally, non-quaternary ammonium bearing monomer(s). A film including a polymer can be used as an anion exchange membrane in a device, such as, for example, a battery, a fuel cell, or the like.

First claim

1 . A compound comprising the following structure:

wherein
A is a cyclooctenyl group or a norbornenyl group;
R 1 , R 2 , and R 3 are independently at each occurrence an aliphatic group, or
R 1 , R 2 , and N taken together form a heterocyclic group and R 3 is an aliphatic group, or
R 1 , R 2 , R 3 , and N taken together form an aliphatic group-bridged heterocyclic group, or
R 3 comprises a linking group and a

group, wherein a first terminus of the linking group is covalently bound to the quaternary ammonium nitrogen of the compound and a second terminus of the linking group is covalently bound the

group through the R 4 group, and R 1 and R 2 are independently at each occurrence an aliphatic group or R 1 , R 2 , and the N of the compound taken together form a heterocyclic group, and R 5 and R 6 are independently at each occurrence an aliphatic group or R 5 , R 6 , and the N of the

group taken together form a heterocyclic group, or
R 1 and/or R 2 each comprises a linking group and a

group, wherein a first terminus of the linking group is covalently bound to the quaternary ammonium nitrogen of the compound and a second terminus of the linking group is covalently bound the

group through the R 4 group, wherein the R 4 group is an aliphatic group, R 3 is an aliphatic group, and R 5 and R 6 are independently at each occurrence an aliphatic group or R 5 , R 6 , and the N of the

group taken together form a heterocyclic group, or
R 1 , R 2 , and N taken together form a heterocyclic linking group, wherein a first terminus of the heterocyclic linking group is covalently bound to the quaternary ammonium nitrogen of the compound and a second terminus of the heterocyclic linking group is covalently bound a

group through the R 4 group, wherein the R 4 group is an aliphatic group, R 3 is an aliphatic group, and R 5 and R 6 are independently at each occurrence an aliphatic group or R 5 , R 6 , and the N of the

group taken together form a heterocyclic group, or
R 1 , R 2 , and N taken together form an aliphatic group-bridged heterocyclic linking group, wherein a first terminus of the linking bridged heterocyclic group is covalently bound to the quaternary ammonium nitrogen of the compound and a second terminus of the aliphatic group-bridged heterocyclic linking group is covalently bound a

group, wherein the R 4 group is an aliphatic group, R 3 is an aliphatic group, and R 5 and R 6 are independently at each occurrence an aliphatic group or R 5 , R 6 , and the N of the

group taken together form a heterocyclic group; and
X is chosen independently at each occurrence from halide anions and complex anions.

2 . The compound of claim 1 , wherein the compound comprises the following structure:

3 . The compound of claim 1 , wherein R 1 and R 2 taken together with N form:
a piperidinyl group, pyrrolidinyl group, azepanyl group, morpholinyl group, piperazinyl group, or a 1,4-Diazabicyclo[2.2.2]octane (DABCO) group.

4 . The compound of claim 1 , wherein R 2 , and N taken together form a heterocyclic group, and wherein the compound comprises the following structure:

wherein y is 1, 2, 3, or 4.

5 . The compound of claim 1 , wherein R 1 and R 2 taken together with N form a piperidinium group or R 1 , R 2 , and R 3 taken together with N form an aliphatic-bridged piperidinium group, and wherein the compound comprises the following structure:

6 . The compound of claim 1 , wherein R 1 and R 2 taken together with N form a piperidinium group or R 1 , R 2 , and R 3 taken together with N form an aliphatic-bridged heterocyclic group and wherein the compound comprises the following structure:

wherein R is an aliphatic group or an aryl group.

7 . The compound of claim 1 , wherein the compound has the following structure:

wherein L is a linking group and R 4 , R 5 , and R 6 are independently at each occurrence an aliphatic group.

8 . A method of making a compound of claim 1 , the method comprising:
forming a first reaction mixture comprising:
1,5 cyclooctadiene, norbornadiene, or a combination thereof;
one or more secondary amine(s), one or more hydroxyalkyl secondary amine(s),
one or more multifunctional secondary amine(s) or any combination thereof;
one or more H-atom transfer (HAT) catalyst(s);
and one or more photocatalyst(s);
subjecting the first reaction mixture to electromagnetic radiation comprising wavelengths from about 350 nm to about 700 nm to form one or more tertiary amine-functionalized cyclooctene compound(s), one or more tertiary amine-functionalized norbornene compound(s), one or more functionalized tertiary amine-functionalized cyclooctene compound(s), one or more functionalized tertiary amine-functionalized norbornene compound(s), one or more hydroxyalkyl amine-functionalized cyclooctene compound(s), one or more hydroxyalkylamine-functionalized norbornene compound(s), or any combination thereof; forming a second reaction mixture comprising:
the tertiary amine-functionalized cyclooctene compound(s) and/or the tertiary amine-functionalized cyclooctene compound(s) and/or the functionalized tertiary amine-functionalized norbornene compound(s), or any combination thereof;
one or more alkylating agent(s), or a combination thereof; or
the hydroxyalkyl amine-functionalized cyclooctene compound(s), the hydroxyalkylamine-functionalized norbornene compound(s), functionalized tertiary amine-functionalized norbornene compound(s), or any combination thereof,
one or more reductant(s); and
one or more bromine source(s),

wherein one or more compound(s) of claim 1 is formed.

9 . The method of claim 8 , further comprising one or more or all of the following:
isolating the tertiary amine-functionalized cyclooctene compound(s), the tertiary amine-functionalized norbornene compound(s), the functionalized tertiary amine-functionalized cyclooctene compound(s), the functionalized tertia

Assignees

• Univ Cornell

Inventors

• Coates Geoffrey W
• You Wei
• Peltier Cheyenne

Classifications

• C08G61/08 Primary

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

• B01J41/05

  in the strongly basic form · CPC title

• B01J41/14

  obtained by reactions only involving unsaturated carbon-to-carbon bonds · CPC title

• B01J47/12

  characterised by the use of ion-exchange material in the form of ribbons, filaments, fibres or sheets, e.g. membranes (electrodialysis or electro-osmosis B01D61/42) · CPC title

• C07D295/037

  with quaternary ring nitrogen atoms · CPC title