Polymers having stable cationic pendant groups for use as anion exchange membranes

A polymer comprising a reaction product of a polymerization mixture comprising

• (i) a cation-functionalized trifluoroketone monomer having the formula:
• (ii) an aromatic monomer having the formula:
• or a crown ether monomer having the formula:
• and
• (iii) optionally, a trifluoromethyl ketone monomer having the formula:
• wherein:
• R1 are each independently a quaternary ammonium or phosphonium group or a nitrogen-containing heterocyclic group or a salt thereof, the quaternary ammonium or phosphonium group having the formula (5A):
• and the nitrogen-containing heterocyclic group being an optionally substituted pyrrole, pyrroline, pyrazole, pyrazoline, imidazole, imidazoline, triazole, pyridine, triazine, pyrazine, pyridazine, pyrimidine, azepine, quinoline, piperidine, pyrrolidine, pyrazolidine, imidazolidine, azepane, isoxazole, isoxazoline, oxazole, oxazoline, oxadiazole, oxatriazole, dioxazole, oxazine, oxadiazine, isoxazolidine, morpholine, thiazole, isothiazole, oxathiazole, oxathiazine, or caprolactam, wherein each substituent is independently alkyl, alkenyl, alkynyl, aryl, or aralkyl;
• R2, R3, R4, R5, R6, R7, R8, R9, R10, R13, R14, R15, R16, and R17 are each independently hydrogen, halide, alkyl, alkenyl, alkynyl or aryl, and the alkyl, alkenyl, alkynyl or aryl are optionally substituted with halide, and wherein R3 and R6 are optionally linked to form a five membered ring optionally substituted with halide or alkyl;
• each R12 is independently alkyl, alkenyl, alkynyl, or a substituent of formula (4C):
• and the alkyl, alkenyl, or alkynyl are optionally substituted with fluoride;
• R180 and R240 are each independently alkylene;
• R190, R200, R210, R220, and R230 are each independently alkyl, alkenyl, or alkynyl;
• m is 0, 1, 2, 3, 4, 5 or 6;
• n is 0, 1, 2 or 3;
• each m′ and each n′ is independently 0, 1 or 2;
• q is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20;
• X− is an anion;
• and
• Z is P when the aromatic monomer of formula (3) is present in the polymerization mixture but the crown ether monomer of formula (3′) is not present in the polymerization mixture, and Z is N or P when the crown ether monomer of formula (3′) is present in the polymerization mixture.

A polymer comprising a second reaction product of a second polymerization mixture comprising:

• a quaternary ammonium or phosphonium compound or a nitrogen-containing heterocycle or a salt thereof;
• and
• an intermediate polymer;
• wherein:
• the intermediate polymer comprises a first reaction product of a first polymerization mixture comprising:
• (i) a halogenated trifluoromethyl ketone monomer having the formula:
• (ii) an aromatic monomer having the formula:
• or
• a crown ether monomer having the formula:
• and
• (iii) optionally, a trifluoromethyl ketone monomer having the formula:
• wherein:
• the quaternary ammonium or phosphonium compound has the formula (5):
• the nitrogen-containing heterocycle is an optionally substituted pyrrole, pyrroline, pyrazole, pyrazoline, imidazole, imidazoline, triazole, pyridine, triazine, pyrazine, pyridazine, pyrimidine, azepine, quinoline, piperidine, pyrrolidine, pyrazolidine, imidazolidine, azepane, isoxazole, isoxazoline, oxazole, oxazoline, oxadiazole, oxatriazole, dioxazole, oxazine, oxadiazine, isoxazolidine, morpholine, thiazole, isothiazole, oxathiazole, oxathiazine, or caprolactam, wherein each substituent is independently alkyl, alkenyl, alkynyl, aryl, or aralkyl;
• R2, R3, R4, R5, R6, R7, R8, R9, R10, R13, R14, R15, R16, and R17 are each independently hydrogen, halide, alkyl, alkenyl, alkynyl or aryl, and the alkyl, alkenyl, alkynyl or aryl are optionally substituted with halide, and wherein R3 and R6 are optionally linked to form a five membered ring optionally substituted with halide or alkyl;
• each R12 is independently alkyl, alkenyl, alkynyl, or a substituent of formula (4C):
• and the alkyl, alkenyl, or alkynyl are optionally substituted with fluoride;
• R18 and R24 are each independently alkylene;
• R19, R20, R21, R22, and R23 are each independently alkyl, alkenyl, or alkynyl;
• R111 is a halide;
• m is 0, 1, 2, 3, 4, 5 or 6;
• n is 0, 1, 2 or 3;
• each m′ and each n′ is independently 0, 1 or 2;
• q is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20;
• X− is an anion;
• and
• Z is P when the aromatic monomer of formula (3) is present in the first polymerization mixture but the crown ether monomer of formula (3′) is not present in the first polymerization mixture, and Z is N or P when the crown ether monomer of formula (3′) is present in the first polymerization mixture.