Poly(aryl piperidinium) polymers including those with stable cationic pendant groups for use as anion exchange membranes and ionomers

Patent metadata

Field	Value
Publication number	US-11512156-B2
Application number	US-201816651622-A
Country	US
Kind code	B2
Filing date	Sep 28, 2018
Priority date	Sep 28, 2017
Publication date	Nov 29, 2022
Grant date	Nov 29, 2022

Abstract

Poly(aryl piperidinium) polymers with pendant cationic groups are provided which have an alkaline-stable cation, piperidinium, introduced into a rigid aromatic polymer backbone free of ether bonds. Hydroxide exchange membranes or hydroxide exchange ionomers formed from these polymers exhibit superior chemical stability, hydroxide conductivity, decreased water uptake, good solubility in selected solvents, and improved mechanical properties in an ambient dry state as compared to conventional hydroxide exchange membranes or ionomers. Hydroxide exchange membrane fuel cells comprising the poly(aryl piperidinium) polymers with pendant cationic groups exhibit enhanced performance and durability at relatively high temperatures.

First claim

What is claimed is:

1. A polymer comprising a reaction product of a polymerization mixture comprising
(i) a piperidone monomer or salt or hydrate thereof having the formula:

or
an azoniaspiro salt monomer having the formula:

(ii) an aromatic monomer having the formula:

and
(iii) optionally, a trifluoromethyl ketone monomer having the formula:

wherein:
R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 13 , R 14 , R 15 , R 16 and R 17 are each independently hydrogen, halide, alkyl, alkenyl, alkynyl or aryl, and the alkyl, alkenyl, alkynyl or aryl are optionally substituted with halide, and wherein R 3 and R 6 are optionally linked to form a five membered ring optionally substituted with halide or alkyl;
each R 12 is independently alkyl, alkenyl, alkynyl, or

and the alkyl, alkenyl, or alkynyl are optionally substituted with fluoride;
m is 1, 2, 3, 4, 5, 6, 7 or 8;
n is 0, 1, 2 or 3;
X 31 is an anion; and
wherein in the case that the polymerization mixture comprises the azoniaspiro salt monomer of formula (2), either the polymerization mixture comprises the trifluoromethyl ketone monomer of formula (4), or the monomers used in a polymerization reaction to form the polymer are dissolved in an organic solvent and maintained at a temperature from −78° C. to 0° C. in the presence of a polymerization catalyst for 1 to 121 hours.

2. A polymer comprising a reaction product of an alkylating agent and the polymer of claim 1 comprising the reaction product of the polymerization mixture comprising the piperidone monomer.

3. A polymer comprising a reaction product of a base and the polymer of claim 2 .

4. A piperidinium polymer comprising a second reaction product of a second polymerization mixture comprising a neutral piperidine-functionalized polymer and either a quaternary ammonium or phosphonium compound or a nitrogen-containing heterocycle,
the quaternary ammonium or phosphonium compound having the formula:

the nitrogen-containing heterocycle comprising 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;
the piperidine-functionalized polymer comprising the polymer of claim 1 comprising the piperidone monomer or salt or hydrate thereof of formula (1), the aromatic monomer of formula (3) and optionally, the trifluoromethyl ketone monomer of formula (4),
wherein:
R 18 and R 24 are each independently alkylene;
R 19 , R 20 , R 21 , R 22 , and R 23 are each independently alkyl, alkenyl, aryl, or alkynyl;
q is 0, 1, 2, 3, 4, 5, or 6;
X 31 is an anion; and
Z is N or P.

5. An anion exchange polymer comprising a reaction product of a base and the piperidinium polymer of claim 4 .

6. The polymer of claim 5 , wherein the polymerization mixture further comprises the azoniaspiro salt monomer having the formula (2).

7. The polymer of claim 6 , wherein the azoniaspiro salt monomer comprises 3-oxo-6-azoniaspiro[5.5]undecane halide.

8. The polymer of claim 1 , wherein:
R 1 is alkyl; and R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 13 , R 14 , R 15 , R 16 , and R 17 are each independently hydrogen, or alkyl optionally substituted with fluoride, and R 12 is alkyl optionally substituted with fluoride or

R 1 is methyl, ethyl, propyl, butyl, pentyl, or hexyl; and R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 13 , R 14 , R 15 , R 16 , and R 17 are each independently hydrogen, methyl, ethyl, propyl, butyl, pentyl, or hexyl, or methyl, ethyl, propyl, butyl, pentyl, or hexyl optionally substituted with fluoride, and R 12 is methyl, ethyl, propyl, butyl, pentyl, or hexyl optionally substituted with fluoride or

9. The polymer of claim 1 , wherein:
the piperidone monomer or salt or hydrate thereof comprises N-methyl-4-piperidone or 4-piperidone; or
the salt of the piperidone monomer comprises hydrochloride, hydrofluoride, hydrobromide, hydroiodide, trifluoroacetate, acetate, triflate, methanesulfonate, sulfate, nitrate, tetrafluoroborate, hexafluorophosphate, formate, benzenesulfonate, toluate, perchlorate, or benzoate, or any hydrate of the salt, or any combination thereof; or
the salt of the piperidone monomer comprises 4-piperidone hydrofluoride, 4-piperidone hydrochloride, 4-piperidone hydrobromide, 4-piperidone hydroiodide, 4-piperidone trifluoroacetate, 4-piperidone tetrafluoroborate, 4-piperidone hexafluorophosphate, 4-piperidone acetate, 4-piperidone triflate, 4-piperidone methanesulfonate, 4-piperidone formate, 4-piperidone benzenesulfonate, 4-piperidone toluate, 4-piperidone sulfate, 4-piperidone nitrate, 4-piperidone perchlorate, 4-piperidone benzoate, N-methyl-4-piperidone hydrofluoride, N-methyl-4-piperidone hydrochloride, N-methyl-4-piperidone hydrobromide, N-methyl-4-piperidone hydroiodide, N-methyl-4-piperidone trifluoroacetate, N-methyl-4-piperidone tetrafluoroborate, N-methyl-4-piperidone hexafluorophosphate, N-methyl-4-piperidone acetate, N-methyl-4-piperidone triflate, N-methyl-4-piperidone methanesulfonate, N-methyl-4-piperidone formate, N-methyl-4-piperidone benzenesulfonate, N-methyl-4-piperidone toluate, N-methyl-4-piperidone sulfate, N-methyl-4-piperidone nitrate, N-methyl-4-piperidone perchlorate, N-methyl-4-piperidone benzoate or any hydrate of the salt, or any combination thereof.

10. The polymer of claim 1 , wherein the aromatic monomer comprises biphenyl, para-terphenyl, meta-terphenyl, para-quaterphenyl, 9,9-dimethyl-9H-fluorene, or benzene.

11. The polymer of claim 3 , wherein the base comprises a hydroxide-, bicarbonate-, or carbonate-containing base.

12. The polymer of claim 11 , wherein the hydroxide-containing base comprises sodium hydroxide or potassium hydroxide; the bicarbonate-containing base comprises sodium bicarbonate or potassium bicarbonate; or the carbonate-containing base comprises sodium carbonate or potassium carbonate.

13. The polymer of claim 6 , wherein the piperidone monomer or salt or hydrate thereof comprises N-methyl-4-piperidone or 4-piperidone; the azoniaspiro salt monomer comprises 3-oxo-6- azoniaspiro [5.5] undecane halide; the trifluoromethyl ketone monomer comprises 2,2,2-trifluoroacetophenone or 1,1,1-trifluoroacetone; and the aromatic monomer comprises biphenyl, para-terphenyl, meta-terphenyl, para-quaterphenyl, 9,9-dimethyl-9H-fluorene, or benzene.

14. The polymer of clai

Assignees

• Univ Delaware

Inventors

• Yan Yushan
• Hu Keda
• Wang Junhua
• Wang Lan
• Xu Bingjun
• Zhao Yun

Classifications

• H01M8/1062

  characterised by the physical properties of the porous support, e.g. its porosity or thickness · CPC title

• Y02E60/50

  Fuel cells · CPC title

• C08G10/00

  Condensation polymers of aldehydes or ketones with aromatic hydrocarbons or halogenated aromatic hydrocarbons only · CPC title

• B01J41/14 Primary

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

• Y02P70/50

  Manufacturing or production processes characterised by the final manufactured product · CPC title