Heterocycle grafted monomers and related polymers and hybrid inorganic-organic polymer membranes

• US 7,576,165 B2
• Filed: 01/26/2005
• Issued: 08/18/2009
• Est. Priority Date: 01/27/2004
• Status: Active Grant

• Current Assignee: Toyota Motor Corporation, Georgia Institute of Technology (University System of Georgia)
• Original Assignee: Toyota Motor Engineering & Manufacturing North America Incorporated (Toyota Motor Corporation), Georgia Institute of Technology (University System of Georgia)
• Inventors: Zhou, Zhen, Li, Siwen, Li, Wen, Liu, Meilin, Hase, Kohai
• Primary Examiner(s): Cheung; William K
• Application Number:
  US11/044,527
• Publication Number:
  US 20060111530A1
• Time in Patent Office: 1,665 Days
• Field of Search: 526/258, 526/266
• US Class Current: 526/258
• CPC Class Codes: C07D 233/64 with substituted hydrocarbon radicals attached to ring carbon atoms, e.g. histidine
• CPC Class Codes: C07D 239/38 One sulfur atom
• CPC Class Codes: C07D 249/04 1,2,3-Triazoles; Hydrogenated 1,2,3-triazoles
• CPC Class Codes: C07D 249/12 Oxygen or sulfur atoms
• CPC Class Codes: C07F 7/1804 Compounds having Si-O-C linkages Si-O-acyl linkages C07F7/1896
• CPC Class Codes: C08F 226/06 by a heterocyclic ring containing nitrogen
• CPC Class Codes: C08F 228/02 by a bond to sulfur
• CPC Class Codes: C08G 75/20 Polysulfones
• CPC Class Codes: C08G 77/26 nitrogen-containing groups
• CPC Class Codes: C08J 2379/06 Polyhydrazides; Polytriazoles; Polyamino-triazoles; Polyoxadiazoles
• CPC Class Codes: C08J 5/2231 based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds
• CPC Class Codes: C08L 81/06 Polysulfones; Polyethersulfones
• CPC Class Codes: H01M 2300/0082 Organic polymers
• CPC Class Codes: H01M 8/1027 having carbon, oxygen and other atoms, e.g. sulfonated polyethersulfones [S-PES]
• CPC Class Codes: H01M 8/103 having nitrogen, e.g. sulfonated polybenzimidazoles [S-PBI], polybenzimidazoles with phosphoric acid, sulfonated polyamides [S-PA] or sulfonated polyphosphazenes [S-PPh]
• CPC Class Codes: H01M 8/1032 having sulfur, e.g. sulfonated-polyethersulfones [S-PES]
• CPC Class Codes: H01M 8/1037 having silicon, e.g. sulfonated crosslinked polydimethylsiloxanes
• CPC Class Codes: H01M 8/1039 halogenated, e.g. sulfonated polyvinylidene fluorides
• CPC Class Codes: H01M 8/1067 characterised by their physical properties, e.g. porosity, ionic conductivity or thickness
• CPC Class Codes: Y02E 60/50 Fuel cells

Abstract

Polymers, polymer precursors, and other materials are described, having at least one heterocycle and being useful for fabrication of proton-exchange membranes (PEMs). In representative examples, the heterocycle is a fluorinated imidazole ring. The heterocycle can be chosen to have a low value of pKa, and may be a triazole ring, other nitrogen-containing heterocycle, or derivative thereof. Polymers and composites were prepared having excellent proton conductivity. Applications of these materials include fuel cells and other ion-conducting applications.

Claims

1. A proton-conducting polymer including:

a hybrid inorganic-organic matrix including silicon atoms;

an acid group attached to the hybrid inorganic-organic matrix; and

a nitrogen-containing heterocycle attached to the hybrid inorganic-organic matrix,

wherein the nitrogen-containing heterocycle is selected from a group consisting of 1,2,4-triazole, 1,2,3-triazole, 1H-benzotriazole, pyrimidine, pyrazine, purine, imidazole, pyrazole, and pyridine.

2. The proton-conducting polymer of claim 1, wherein the nitrogen-containing heterocycle has at least one halogenated substituent group attached thereto.

3. The proton-conducting polymer of claim 1, wherein the nitrogen-containing heterocycle has an electron-withdrawing group attached thereto.

4. The proton-conducting polymer of claim 3, wherein the electron-withdrawing group includes at least one fluorine atom.

5. The proton-conducting polymer of claim 1, wherein the nitrogen-containing heterocycle is a fluorinated imidazole ring having a pKa of less than approximately 2.6.