High performance cross-linked triblock cationic functionalized polymer for electrochemical applications, methods of making and methods of using

Patent metadata

Field	Value
Publication number	US-10836874-B2
Application number	US-201816150113-A
Country	US
Kind code	B2
Filing date	Oct 2, 2018
Priority date	Oct 2, 2017
Publication date	Nov 17, 2020
Grant date	Nov 17, 2020

Abstract

The present invention relates to a high performance cross-linked triblock cationic functionalized polymer for electrochemical applications, and methods of making and using the same. The invention also relates to a tunable hydrogenated polymer, that can be functionalized with a particular cation for a particular application, and the method of making the hydrogenated polymer and tuning the hydrogenated polymer for the application.

First claim

The invention claimed is:

1. A method of preparing a triblock cationic functionalized polymer, comprising:
dissolving a first polymer in a solvent, wherein the first polymer comprises a triblock polymer comprising a hydrophobic polymer and two hydrophilic polymers;
mixing the first polymer in the solvent to produce a hydrogenated triblock polymer;
evaporating the solvent;
subjecting the hydrogenated triblock polymer to a cation;
crosslinking at least one of the two hydrophilic polymers; and
crosslinking the hydrophobic polymer.

2. The method of claim 1 , wherein the solvent is a xylene.

3. The method of claim 1 , wherein the cation is a benzyl methylpiperidinum (MPRD), a trimethylbenzyl ammonium, a tris(2,4,6-trimethoxyphenyl) phosphonium (TTMPP), a dimethylpiperidinium, a dimethylpyrrolidinium, a quaternized chlorinated polymer, and combinations thereof.

4. The method of claim 1 , wherein the crosslinking of the hydrophobic polymer occurs before subjecting the hydrogenated triblock polymer to the cation.

5. The method of claim 1 , wherein at least one of the two hydrophilic polymer is a halogenated polyvinyl benzyl or a halogenated polymethyl styrene.

6. A triblock cationic functionalized polymer, comprising:
a hydrophobic polymer, wherein the hydrophobic polymer is crosslinked;
two hydrophilic polymers, wherein at least one of the two hydrophilic polymer is crosslinked; and
a cation.

7. The triblock cationic functionalized polymer of claim 6 , wherein the hydrophobic polymer is a polycyclooctene, a polycyclooctadiene, or a polycyclooctatriene.

8. The triblock cationic functionalized polymer of claim 6 , wherein the hydrophilic polymer is a polyvinyl benzyl chloride, or a polycholorostyrene.

9. The triblock cationic functionalized polymer of claim 6 , wherein the cation is a benzyl methylpiperidinum (MPRD), a trimethylbenzyl ammonium, a tris(2,4,6-trimethoxyphenyl) phosphonium (TTMPP), a dimethylpiperidinium, a dimethylpyrrolidinium, a quaternized chlorinated polymer, and combinations thereof.

10. The triblock cationic functionalized polymer of claim 6 , wherein the cation is the quaternized chlorinated polymer is at least one of a benzyl trimethyl ammonium (BTMA), a benzyl TTMPP, a MPRD, or a benzyl methyl pyrrolidinium (MPY).

11. The triblock cationic functionalized polymer of claim 6 , wherein a conductivity of the triblock cationic functionalized polymer is between about 0.001 S/cm to about 0.4 S/cm.

12. The triblock cationic functionalized polymer of claim 11 , wherein the conductivity of the triblock cationic functionalized polymer continually increases between about 15 degrees Celsius to about 100 degrees Celsius.

13. A method of cross-linking the mid-block of a triblock polymer, the method comprising the steps of:
a) selecting a triblock polymer, wherein a structure of the polymer consists of A-B-A, wherein unit A is hydrophilic and is selected from the group consisting of a halogenated polyvinyl benzyl and a halogenated polymethyl styrene, and wherein unit B is hydrophobic and selected from the group consisting of a polyisoprene, a polycycloctene, a polycycloocadiene, and a polycyclooctatriene;
b) dissolving the triblock polymer, a photoinitiator and a alkyldithiol in a solvent to form a solution;
c) adding the solution to a substrate;
d) evaporating the solvent to make a film on the substrate;
e) crosslinking at least one double bond of the unit B of the triblock polymer by applying UV radiation to produce a crosslinked triblock A-B-A polymer; and
f) crosslinking the unit A of the triblock polymer.

14. The method of claim 13 , further comprising converting the unit A to a cationic polymer by quaternizing the unit A with a base.

15. The method of claim 14 , wherein the base is selected from the group consisting of a trimethyl amine, a trihexylamine, a methylpyrolidine, a methylpiperidine, a hexyl pyrrolidine and a hexylpiperidine.

16. The method of claim 13 , wherein a halogen of the halogenated polyvinyl benzene or the halogenated polymethyl styrene is chloride.

17. The method of claim 13 , wherein the substrate is a glass, a polytetrafluoroethylene, a polyether ether ketone (PEEK), or a polyimide.

18. The method of claim 13 , wherein the photoinitiator is a 2-Hydroxy-4′-(2-hydroxyethoxy)-2-methylpropiophenone.

19. The method of claim 14 , wherein a cation of the cationic polymer is a trimethylbenzyl ammonium, a benzyl tris(2,4,6-trimethoxyphenyl) phosphonium, a benzylmethylpiperidinium, a benzylhexylpiperidinium, a benzylmethylpyrrolidinium, a benzylhexylpyrrolidium, an attached hexylmethylpyrrolidinium, an attached hexylhexylpyrrolidinium, and combinations thereof.

20. The method of claim 1 , wherein the cation is in a methanol solution at a concentration between 0.1 M and 0.9 M.

Assignees

• Herring Andrew M
• Kuo Mei Chen
• Coughlin E Bryan
• Buggy Nora
• Du Yifeng
• Colorado School Of Mines
• Univ Massachusetts

Inventors

• Herring Andrew M
• Kuo Mei-Chen
• Coughlin E Bryan
• Buggy Nora
• Du Yifeng

Classifications

• B01D71/80

  Block polymers · CPC title

• C08F2438/02

  Stable Free Radical Polymerisation [SFRP]; Nitroxide Mediated Polymerisation [NMP] for, e.g. using 2,2,6,6-tetramethylpiperidine-1-oxyl [TEMPO] · CPC title

• C08F8/04

  Reduction, e.g. hydrogenation · CPC title

• C08F8/40

  Introducing phosphorus atoms or phosphorus-containing groups · CPC title

• C08F8/34

  Introducing sulfur atoms or sulfur-containing groups · CPC title