FUNCTIONALIZED IONIC POLYMERS AND USES THEREOF
The disclosure relates to compositions comprising a first structure of the formula: or a salt thereof, wherein R 1 , R 2 , R 3 , Ar 1 , and n are defined herein. Materials, devices, and methods of using such compositions are also described.
1 . A composition comprising a first structure of the formula:
or a salt thereof, wherein:
each of R 1 and R 2 is, independently, an electron-withdrawing moiety, H, optionally substituted aliphatic, optionally substituted alkyl, optionally substituted heteroaliphatic, optionally substituted heteroalkyl, optionally substituted aromatic, optionally substituted aryl, or optionally substituted arylalkylene;
at least one of R 1 and R 2 comprises the electron-withdrawing moiety and at least one of R 1 and R 2 comprises an ionizable moiety or an ionic moiety; or
R 1 and R 2 , together with the carbon atom to which they are attached, form a cyclic group optionally substituted with an ionizable moiety or an ionic moiety;
R 3 is an optionally substituted aryl group;
Ar 1 is an optionally substituted aromatic group or optionally substituted arylene;
and n is an integer of 1 or more.
2 . The composition of claim 1 , wherein Ar 1 is:
wherein:
each of R 4 and R 5 is, independently, H, optionally substituted aliphatic, optionally substituted alkyl, optionally substituted heteroaliphatic, optionally substituted heteroalkyl, optionally substituted aromatic, optionally substituted aryl, or optionally substituted arylalkylene, or R 4 and R 5 , together with the carbon atom to which they are attached, form an optionally substituted cyclic group;
each of ring a, ring b, and/or ring c can be optionally substituted; and
one or more of rings a-c optionally comprises an ionizable moiety or an ionic moiety.
3 . The composition of claim 1 , wherein the first structure has the formula:
4 . The composition according to claim 1 , wherein the first structure has the formula:
5 . The composition according to claim 1 , wherein R 3 is:
wherein G 1 is C 1-10 alkyl, or OR X , wherein R X is H or C 1-10 alkyl; and
g is a integer from 0 to 3.
6 . The composition according to claim 1 , wherein the electron-withdrawing moiety is an optionally substituted haloalkyl, cyano (CN), phosphate, sulfate, sulfonic acid, sulfonyl, difluoroboranyl, borono, thiocyanato, or piperidinium.
7 . The composition according to claim 1 , wherein the ionizable moiety or the ionic moiety includes -L A -X A or -L A -(L A ′-X A ) 2 or -L A -(X A -L A ′-X A ′) 2 or -L A -X A -L A ′-X A ′-L A ″-X A ″, wherein each L A , L A ′, and L A ″ is a linking moiety; each X A , X A ′, and X A ″ includes, independently, is an acidic moiety, a basic moiety, a multi-ionic moiety, a cationic moiety, or an anionic moiety; and
L 2 is an integer of 1 or more.
8 . The composition of claim 7 , wherein L A , L A ′, and L A ″ includes, independently, an optionally substituted alkylene, optionally substituted alkyleneoxy, optionally substituted heteroalkylene, optionally substituted arylene, and/or optionally substituted aryleneoxy.
9 . The composition of claim 7 , wherein X A , X A ′, and X A ″ includes, independently, sulfo, sulfonate anion, sulfonium cation, carboxy, carboxylate anion, phosphono, phosphonate anion, phosphonium cation, phosphazenium cation, amino, ammonium cation, heterocyclic cation, piperidinium cation or azepanium cation.
10 . The composition according to claim 7 , wherein L A , L A ′, and L A ″ includes, independently, an optionally substituted alkylene.
11 . The composition according to claim 7 , wherein X A , X A ′, and X A ″ includes, independently, amino or ammonium cation.
12 . The composition according to claim 7 , wherein R 1 is optionally substituted haloalkyl; and R 2 is optionally substituted aliphatic.
13 . The composition according to claim 7 , wherein R 2 is -L A -X A , wherein each L A is optionally substituted aliphatic; each X A includes, independently, a cationic moiety; and L 2 is an integer of 1 or more.
14 . The composition of claim 13 , wherein each L A is optionally substituted alkylene.
15 . The composition of claim 13 , wherein L A is optionally substituted C 1-10 alkyl.
16 . The composition according to claim 13 , wherein X A is an ammonium cation.
17 . The composition according to claim 1 , wherein the first structure has the formula:
18 . The composition according to claim 1 , wherein the first structure has the formula:
19 . The composition according to claim 1 , wherein the first structure has the formula:
20 . The composition of claim 1 , wherein the first structure has a polydispersity index of less than 2.7 as determined by gel permeation chromatography (GPC).
21 . An electrochemical cell comprising:
an anode;
a cathode; and
a polymer electrolyte membrane disposed between the anode and the cathode, wherein the polymer electrolyte membrane comprises a composition according to any of claim 1 .
22 . A method of making a polymer, the method comprising:
contacting monomeric units with a Friedel-Crafts acylation agent comprising a reactive group in the presence of a strong acid to give an initial polymer; and
contacting the initial polymer with a terminating agent to give a polymer comprising the first structure according to claim 1 .
23 . The method of claim 22 , further comprising contacting the reactive group with an ionizable reagent to give an ionic polymer comprising a plurality of ionic moieties.
24 . The method of claim 22 , further comprising exchanging a counterion present in the composition with another counterion.
25 . The method of claim 23 , the ionic moiety is a cationic moiety.
26 . The method according to claim 22 , further comprising the step of contacting the polymer with methanol.
27 . The method according to claim 26 , wherein the contacting with methanol does not cause an exotherm.