US 11,879,033 B2Granted

Polycyloolefinic polymers and anion exchange membranes derived therefrom

AssigneesPromerus, LLC, Georgia Tech Research Corporation

InventorsPaul A Kohl, Mrinmay Mandal, Matthew L Barchok, Doug Skilskyj, Larry F Rhodes

Life of this patent

Estimating the term…

Loading patent…

Abstract

Embodiments in accordance with the present invention encompass a variety of polymers derived from polycyclic olefin monomers, such as hydrocarbon functionalized norbornenes. The polymers so formed function as ionomers and are suitable as anion exchange membrane for fabricating a variety of electrochemical devices, among others. More specifically, the ionomeric polymers used herein are derived from a variety of quaternized amino functionalized norbornene monomers and are lightly crosslinked (less than ten mol %). The membranes made therefrom exhibit very high ionic conductivity of up to 198 mS/cm at 80° C. This invention also relates to using an anion conducting solid polymer electrolyte as the ion conducting medium between the two electrodes and the ion conducting medium within the electrodes acting as the ionic conduit between electroactive material and electrolyte. The electrochemical devices made in accordance of this invention are useful as fuel cells, gas separators, and the like.

Claims19

Dependent claims

A polymer comprising:

a) one or more first repeating unit of formula (IA) derived from a monomer of formula (I):
wherein:
represents a position at which the bonding takes place with another repeat unit;
Y and Y′ are the same or different and independently of each other selected from the group consisting of —CH2—, —CH2—CH2— and —O—;
m is an integer from 0 to 3;
at least one of R1, R2, R3 and R4 is a group of the formula R—X,
where R is selected from the group consisting of (C1-C10)alkylene, (C3-C8)cycloalkylene, (C1-C10)alkylene(C3-C8)cycloalkylene, (C1-C10)alkylene(C3-C8)cycloalkylene(C1-C10)alkylene, (C1-C10)alkylene(C6-C10)arylene and (C1-C10)alkylene(C6-C10)arylene(C1-C10)alkylene;
and
X is a group of the formula N(R5)(R6)(R7)⊕OH⊖, where
at least one of R5, R6 and R7 is selected from the group consisting of:
(C1-C10)alkyleneN(R5′)(R6′), (C3-C5)cycloalkyleneN(R5′)(R6′), (C1-C10)alkylene(C3-C8)cycloalkyleneN(R5′)(R6′), (C1-C10)alkylene(C3-C8)cycloalkylene(C1-C10)alkyleneN(R5′)(R6′), (C1-C10)alkylene(C6-C10)aryleneN(R5′)(R6′) and (C1-C10)alkylene(C6-C10)arylene(C1-C10)alkyleneN(R5′)(R6′);
wherein
R5 and R6′ are the same or different and independently of each other selected from the group consisting of linear or branched (C1-C10)alkyl, (C3-C8)cycloalkyl, (C1-C10)alkyl(C3-C8)cycloalkyl and (C1-C10)alkyl(C6-C10)aryl;
the remaining R5, R6 and R7 are the same or different and independently of each other selected from the group consisting of linear or branched (C1-C10)alkyl, (C3-C8)cycloalkyl, (C1-C10)alkyl(C3-C8)cycloalkyl and (C1-C10)alkyl(C6-C10)aryl;
and
the remaining R1, R2, R3 and R4 are independently of each other selected from the group consisting of hydrogen, linear or branched (C1-C10)alkyl, (C3-C8)cycloalkyl, (C1-C10)alkyl(C3-C8)cycloalkyl and (C1-C10)alkyl(C6-C10)aryl;
b) one or more second repeating unit of formula (IIA) derived from a monomer of formula (II):
wherein:
represents a position at which the bonding takes place with another repeat unit;
Z and Z′ are the same or different and independently of each other selected from the group consisting of —CH2—, —CH2—CH2— and —O—;
n is an integer from 0 to 3;
and
R8, R9, R10 and R11 are the same or different and independently of each other selected from the group consisting of hydrogen, linear or branched (C1-C10)alkyl, (C3-C8)cycloalkyl, (C1-C10)alkyl(C3-C8)cycloalkyl and (C1-C10)alkyl(C6-C10)aryl;
and
wherein the polymer is a random polymer and wherein the first repeat unit is crosslinked with another first repeat unit on the same or different polymer chains such that the polymer has at least two percent of the available sites reacted between the repeat units and exhibits ion conductivity of at least 150 mS/cm at 80° C.

22 more elements

A polymer comprising:

a) one or more repeating unit of formula (IA) derived from a monomer of formula (I):
wherein:
represents a position at which the bonding takes place with another repeat unit;
Y and Y′ are the same or different and independently of each other selected from the group consisting of —CH2—, —CH2—CH2— and —O—;
m is an integer from 0 to 3;
at least one of R1, R2, R3 and R4 is a group of the formula R—X, where R is selected from the group consisting of (C1-C10)alkylene, (C3-C8)cycloalkylene, (C1-C10)alkylene(C3-C8)cycloalkylene, (C1-C10)alkylene(C3-C8)cycloalkylene(C1-C10)alkylene, (C1-C10)alkylene(C6-C10)arylene and (C1-C10)alkylene(C6-C10)arylene(C1-C10)alkylene;
and
X is a group of the formula N(R5)(R6)(R7)⊕OH⊖, where
at least one of R5, R6 and R7 is selected from the group consisting of:
(C1-C10)alkyleneN(R5′)(R6′), (C3-C8)cycloalkyleneN(R5′)(R6′), (C1-C10)alkylene(C3-C8)cycloalkyleneN(R5′)(R6′), (C1-C10)alkylene(C3-C8)cycloalkylene(C1-C10)alkyleneN(R5′)(R6′), (C1-C10)alkylene(C6-C10)aryleneN(R5′)(R6′) and (C1-C10)alkylene(C6-C10)arylene(C1-C10)alkyleneN(R5′)(R6′);
R5′ and R6′ are the same or different and independently of each other selected from the group consisting of linear or branched (C1-C10)alkyl, (C3-C8)cycloalkyl, (C1-C10)alkyl(C3-C8)cycloalkyl and (C1-C10)alkyl(C6-C10)aryl;
the remaining R5, R6 and R7 are the same or different and independently of each other selected from the group consisting of linear or branched (C1-C10)alkyl, (C3-C8)cycloalkyl, (C1-C10)alkyl(C3-C8)cycloalkyl and (C1-C10)alkyl(C6-C10)aryl;
and
the remaining R1, R2, R3 and R4 are independently of each other selected from the group consisting of hydrogen, linear or branched (C1-C10)alkyl, (C3-C8)cycloalkyl, (C1-C10)alkyl(C3-C8)cycloalkyl and (C1-C10)alkyl(C6-C10)aryl;
and
wherein the polymer is a random polymer when it contains more than one distinct repeat unit of formula (IA) and the repeat unit is crosslinked with another repeat unit on the same or different polymer chains such that the polymer has at least two percent of the available sites reacted between the repeat units and exhibits ion conductivity of at least 150 mS/cm at 80° C.

13 more elements

An anion exchange membrane comprising a random polymer having:

a) one or more first repeating unit of formula (IA) derived from a monomer of formula (I):
wherein:
represents a position at which the bonding takes place with another repeat unit;
Y and Y′ are the same or different and independently of each other selected from the group consisting of —CH2—, —CH2—CH2— and —O—;
m is an integer from 0 to 3;
at least one of R1, R2, R3 and R4 is a group of the formula R—X,
where R is selected from the group consisting of (C1-C10)alkylene, (C3-C8)cycloalkylene, (C1-C10)alkylene(C3-C8)cycloalkylene, (C1-C10)alkylene(C3-C8)cycloalkylene(C1-C10)alkylene, (C1-C10)alkylene(C6-C10)arylene and (C1-C10)alkylene(C6-C10)arylene(C1-C10)alkylene;
and
X is a group of the formula N(R5)(R6)(R7)⊕OH⊖, where at least one of R5, R6 and R7 is selected from the group consisting of:
(C1-C10)alkyleneN(R5′)(R6′), (C3-C8)cycloalkyleneN(R5′)(R6′), (C1-C10)alkylene(C3-C8)cycloalkyleneN(R5′)(R6′), (C1-C10)alkylene(C3-C8)cycloalkylene(C1-C10)alkyleneN(R5′)(R6′), (C1-C10)alkylene(C6-C10)aryleneN(R5′)(R6′) and (C1-C10)alkylene(C6-C10)arylene(C1-C10)alkyleneN(R5′)(R6′);
R5′ and R6′ are the same or different and independently of each other selected from the group consisting of linear or branched (C1-C10)alkyl, (C3-C8)cycloalkyl, (C1-C10)alkyl(C3-C8)cycloalkyl and (C1-C10)alkyl(C6-C10)aryl;
the remaining R5, R6 and R7 are the same or different and independently of each other selected from the group consisting of linear or branched (C1-C10)alkyl, (C3-C8)cycloalkyl, (C1-C10)alkyl(C3-C8)cycloalkyl and (C1-C10)alkyl(C6-C10)aryl;
and
the remaining R1, R2, R3 and R4 are independently of each other selected from the group consisting of hydrogen, linear or branched (C1-C10)alkyl, (C3-C8)cycloalkyl, (C1-C10)alkyl(C3-C8)cycloalkyl and (C1-C10)alkyl(C6-C10)aryl;
b) one or more second repeating unit of formula (IIA) derived from a monomer of formula (II):
wherein:
represents a position at which the bonding takes place with another repeat unit;
Z and Z′ are the same or different and independently of each other selected from the group consisting of —CH2—, —CH2—CH2— and —O—;
n is an integer from 0 to 3;
and
R8, R9, R10 and R11 are the same or different and independently of each other selected from the group consisting of hydrogen, linear or branched (C1-C10)alkyl, (C3-C8)cycloalkyl, (C1-C10)alkyl(C3-C8)cycloalkyl and (C1-C10)alkyl(C6-C10)aryl;
and
wherein the first repeat unit is crosslinked with another first repeat unit on the same or different polymer chains such that the polymer is having a crosslinking of at least two percent between the repeat units and exhibits ion conductivity of at least 150 mS/cm at 80° C.

20 more elements

Dependencies are inferred from the claim text.

Facts

Application: 17/389,593Filed 30 Jul 2021 · us provisional application
Priority: 30 Jul 2020
Published: US 2022/0033571 A13 Feb 2022
Granted: 23 Jan 2024
Term ends: Not estimatedThe source records don’t support an estimate.

Classification23 codes

C08G 61/02
Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule: macromolecular compounds…
H01M 8/1023
Characterised by the chemical structure of the main chain of the ion-conducting polymer: having only carbon, e.g. polyarylenes, polystyrenes or…
B01J 41/13
Macromolecular compounds: obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
C08G 61/125
Derived from five-membered heterocyclic compounds: with a five-membered ring containing one oxygen atom in the ring