Ionomers and methods of making same and uses thereof

Patent metadata

Field	Value
Publication number	US-9493397-B2
Application number	US-201013322306-A
Country	US
Kind code	B2
Filing date	May 31, 2010
Priority date	May 29, 2009
Publication date	Nov 15, 2016
Grant date	Nov 15, 2016

Abstract

Ionomers comprising ionic groups such as, for example, tetraalkylammonium groups and methods of making such ionomers. For example, the ionomers can be produced by ring opening metathesis polymerization of alkene-containing monomers with tetraalkylammonium groups and, optionally, alkene-containing monomers without tetraalkylammonium groups. The ionomers can be used in applications such as, for example, fuel cell applications.

First claim

What is claimed is:

1. An ionomer comprising ionic strained olefin monomer (ISOM) units and optionally random or sequentially placed strained olefin monomer (SOM) units, having the following structure:
ISOM x SOM 1-x
wherein the ISOM and SOM units are connected by carbon-carbon single bonds and/or carbon-carbon double bonds,
wherein the ISOM unit has a non-aromatic hydrocarbon backbone and comprises one or more tetraalkylammonium groups connected to the backbone by an aliphatic polyatomic linkage or aliaromatic polyatomic linkage, and any carbon atoms in the beta position relative to an ammonium nitrogen do not bear hydrogen substituents,
wherein the SOM unit is a non-aromatic hydrocarbon unit,
wherein x is from 0.05 to 1.0, and
wherein the SOM units or ISOM units are formed from SOMs or ISOMs, respectively, that have a strained ring or carbocyclic structure and an alkene moiety in a ring-opening metathesis polymerization.

2. The ionomer of claim 1 , wherein the number average molecular weight of the ionomer, Mn, is from 5,000 to 1,000,000 g/mol and/or the weight average molecular weight of the ionomer, Mw, is from 5,000 to 2,000,000 g/mol.

3. The ionomer of claim 1 , wherein the end groups of the ionomer are independently selected from ═CH 2 , ═CHR (where R is CH 2 W where W is H, alkyl, halide, hydroxide or acetate), ═CHPh, —CH 3 , —CH 2 R (where R is CH 2 W where W is H, alkyl, halide, hydroxide or acetate) and —CH 2 Ph.

4. The ionomer of claim 1 , wherein the ISOM and SOM units are connected by a carbon-carbon double bond and the ionomer has the following structure:

wherein R 1 , R 2 and R 3 are each, independently, a C 1 to C 20 group, wherein if the C 1 to C 20 group has a carbon in the beta position relative to the ammonium nitrogen atom then the beta carbon of the C 1 to C 20 group does not have a hydrogen substituent,
wherein A − is selected from halide, hydroxide, hexafluorophosphate, borate, carbonate, bicarbonate and carboxylate, and
wherein x is from 0.05 to 1.0.

5. The ionomer of claim 1 , wherein the ISOM and SOM units are connected by a carbon-carbon single bond and the ionomer has the following structure:

wherein R 1 , R 2 and R 3 are each, independently, a C 1 to C 20 group, wherein if the C 1 to C 20 group has a carbon in the beta position relative to the ammonium nitrogen atom then the beta carbon of the C 1 to C 20 group does not have a hydrogen substituent,
wherein A − is selected from halide, hydroxide, hexafluorophosphate, borate, carbonate, bicarbonate and carboxylate, and
wherein x is from 0.05 to 1.

6. The ionomer of claim 1 , wherein at least one first ISOM or SOM unit is connected by a polyatomic linking group (PAL) or aliaromatic polyatomic linkage comprising a C 1 to C 20 group, wherein if the C 1 to C 20 group has a carbon in the beta position relative to the ammonium nitrogen atom then the beta carbon of the C 1 to C 20 group does not have a hydrogen substituent, to a second ISOM or SOM unit, and
wherein the second ISOM or SOM unit is in the same ionomer chain as the first ISOM or SOM unit or the second ISOM or SOM unit is a different ionomer chain than the first ISOM or SOM unit.

7. The ionomer of claim 6 , wherein the ISOM and SOM units are connected by a carbon-carbon double bond and the ionomer has the following structure:

wherein R 1 , R 2 and R 3 are, independently, a C 1 to C 20 group, wherein if the C 1 to C 20 group has a carbon in the beta position relative to the ammonium nitrogen atom then the beta carbon of the C 1 to C 20 group does not have a hydrogen substituent,
wherein R 4 is a C 1 to C 20 group,
wherein a first y unit is crosslinked to second y unit in a same or different ionomer chain than the first y unit,
wherein A − is selected from halide, hydroxide, hexafluorophosphate, borate, carbonate, bicarbonate, and carboxylate, and
wherein x is from 0.05 to 1 and x+y+z=1.

8. The ionomer of claim 6 , wherein the ISOM and SOM units are connected by a carbon-carbon single bond and the ionomer has the following structure:

wherein R 1 , R 2 and R 3 are, independently, a C 1 to C 20 group, wherein if the C 1 to C 20 group has a carbon in the beta position relative to the ammonium nitrogen atom then the beta carbon of the C 1 to C 20 group does not have a hydrogen substituent,
wherein R 4 is a C 1 to C 20 group,
wherein a first y unit is crosslinked to second y unit in a same or different ionomer chain than the first y unit,
wherein A − is selected from halide, hydroxide, hexafluorophosphate, borate, carbonate, bicarbonate, and carboxylate, and
wherein x is from 0.05 to 1, and x+y+z=1.

9. The ionomer of claim 6 , wherein the ISOM and SOM units are connected by a carbon-carbon double bond and the ionomer has the following structure:

wherein R 1 and R 2 are, independently, a C 1 to C 20 group, wherein if the C 1 to C 20 group has a carbon in the beta position relative to the ammonium nitrogen atom then the beta carbon of the C 1 to C 20 group does not have a hydrogen substituent,
wherein A − is selected from halide, hydroxide, hexafluorophosphate, borate, carbonate, bicarbonate and carboxylate, and
wherein x is from 0.05 to 1, and
wherein each PAL, independently, comprises a C 1 to C 20 group, wherein if the C 1 to C 20 group has a carbon in the beta position relative to the ammonium nitrogen atom then the beta carbon of the C 1 to C 20 group does not have a hydrogen substituent, and
wherein y is from 0 to 20.

10. The ionomer of claim 9 , wherein the ionomer has the following structure:

11. The ionomer of claim 1 , wherein the ISOM and SOM units are connected by a carbon-carbon single bond and the ionomer has the following structure:

wherein R 1 and R 2 are, independently, a C 1 to C 20 group, wherein if the C 1 to C 20 group has a carbon in the beta position relative to the ammonium nitrogen atom then the beta carbon of the C 1 to C 20 group does not have a hydrogen substituent,
wherein A − is selected from halide, hydroxide, hexafluorophosphate, borate, carbonate, bicarbonate and carboxylate,
wherein x is from 0.05 to 1, and
wherein each PAL or aliaromatic polyatomic linkage, independently, comprises a C 1 to C 20 group, wherein if the C 1 to C 20 group has a carbon in the beta position relative to the ammonium nitrogen atom then the beta carbon of the C 1 to C 20 group does not have a hydrogen substituent, and
wherein y is from 0 to 20.

12. The ionomer of claim 11 , wherein the ionomer has the following structure:

13. The ionomer of claim 1 , wherein the ionomer is synth

Assignees

• Coates Geoffrey W
• Kostalik Iv Henry A
• Clark Timothy J
• Robertson Nicholas J
• Univ Cornell

Inventors

• Coates Geoffrey W
• Kostalik Iv Henry A
• Clark Timothy J
• Robertson Nicholas J

Classifications

• C07C2102/42

  Chemistry & Metallurgy · mapped topic

• H01M8/103

  having nitrogen, e.g. sulfonated polybenzimidazoles [S-PBI], polybenzimidazoles with phosphoric acid, sulfonated polyamides [S-PA] or sulfonated polyphosphazenes [S-PPh] · CPC title

• Y02E60/523

  Cross-Sectional Technologies · mapped topic

• C07C211/63 Primary

  having quaternised nitrogen atoms bound to acyclic carbon atoms · CPC title

• H01M8/1023

  having only carbon, e.g. polyarylenes, polystyrenes or polybutadiene-styrenes · CPC title