Moisture swing co2 sorbents with enhanced capacity and kinetics

Patent metadata

Field	Value
Publication number	US-2022323934-A1
Application number	US-202217688508-A
Country	US
Kind code	A1
Filing date	Mar 7, 2022
Priority date	Apr 2, 2021
Publication date	Oct 13, 2022
Grant date	—

Abstract

A composition of matter having a porous cross-linked polymer network, quaternary ammonium ions in the cross-linked polymer network, and at least one counter ion in the cross-linked polymer network that is at least one of hydroxide or a counter ion capable of forming hydroxide upon reaction with water. A method to produce a porous material includes polymerizing a compound containing quaternary ammonium and a cross-linker using controlled polymerization and ion exchange in the presence of at least one of hydroxide or a counter ion capable of forming hydroxide upon reaction with water. A method to capture CO2, includes employing a sorbent comprising a quaternary ammonium ions in a porous cross-linked polymer network in an environment to adsorb CO2.

First claim

What is claimed is:

1 . A composition of matter, comprising:
a porous cross-linked polymer network; quaternary ammonium ions in the cross-linked polymer network; and at least one counter ion in the cross-linked polymer network that is at least one of hydroxide or a counter ion capable of forming hydroxide upon reaction with water.

2 . The composition of matter of claim 1 , wherein the at least one counter ion in the cross-linked polymer network capable of forming hydroxide is one of bicarbonate, carbonate, phosphate, hydrogen phosphate, or dihydrogen phosphate.

3 . The composition of matter of claim 1 , wherein the porous cross-linked polymer network includes residual chemical moieties from controlled radical polymerization.

4 . The composition of matter of claim 3 , wherein the residual chemical moieties from controlled radical polymerization are formed from at least one of nitroxides, chain transfer agents, thiols, TEMPO-OH, nitroxide species derived from the decomposition of an alkoxyamine, 4-hydroxy-TEMPO, TEMPO derivatives, TIPNO, TIPNO derivatives, chlorobenzyl-TIPNO, SG1, SG1, thiocarbonylthio compounds, xanthates, trithiocarbonates, dithioesters, dithiocarbamates, dithiobenzoates, metal catalysts used in ATRP, copper, and iron.

5 . The composition of matter of claim 1 , wherein the porous cross-linked polymer network includes residue of at least one additional monomer.

6 . The composition of matter of claim 5 , wherein the residue of at least one additional monomer is formed from at least one of styrene, styrenic compounds, n-vinyl pyrrolidone, vinyl acetate, vinyl chloride, methacrylates, acrylates, methyl methacrylate, acrylonitrile, methyl acrylate, ethylene, propylene, dimethylsiloxane, fluorinated vinyl, acrylic, or methacrylic compounds, hexa-iso-fluoroisopropyl methacrylate, hexa-iso-fluoroisopropyl acrylate, 2,2,2-trifluoroethyl methacrylate, 2,2,2-trifluoroethyl acrylate, and 1H,1H,2H,2H-Heptadecafluorodecyl methacrylate.

7 . The composition of matter as claimed in claim 5 , wherein the residue of the at least one additional monomer comprises a hydrophobic monomer that contains at least one of fluorinated or aliphatic groups.

8 . The composition of matter as claimed in claim 1 , wherein the quaternary ammonium ions comprise moieties that result from polymerization of diallyldimethylammonium, trimethylammonium ion, 2-(Methacryloyloxy)ethyl]trimethylammonium, 2-(Acryloyloxy)ethyl]trimethylammonium, 3-(Methacryloylamino)propyl]trimethylammonium, (3-Acrylamidopropyl)trimethylammonium, or trimethyl-ammonium functional monomers.

9 . The composition of matter as claimed in claim 1 , wherein the composition of matter includes a cross-linker.

10 . The composition of matter as claimed in claim 9 , wherein the cross-linker is one selected from the group consisting of: divinylbenzene, 1,6-hexanediol diacrylate, groups including methyl, ethyl propyl, isopropyl, tri, tetra, penta or hexa-acrylates and methacrylates, trimethylolpropane triacrylate, trimethylolpropane ethoxylate triacrylate, di(trimethylolpropane) tetraacrylate, dipentaerythritol penta-/hexa-acrylate, trimethacryl adamantane, dipentaerithritol, trimethylolpropane trimethacrylate, phenylene dimethacrylate, phenylene diacrylate, and perfluorohexanediol diacrylate.

11 . The composition of matter as claimed in claim 9 , wherein the cross-linker is hydrophobic and contains at least one of fluorinated or aliphatic groups.

12 . The composition of matter as claimed in claim 1 , wherein the cross-linked polymer network comprise an aerogel.

13 . The composition of matter as claimed in claim 12 , wherein the aerogel of the sorbent may comprise one of a powder, a structured monolith, a self-supporting structure or includes a separate structural material.

14 . The composition of matter as claimed in claim 1 , wherein the composition of matter has a surface area that is greater than 100 m 2 /g, greater than 200 m 2 /g, or greater than 500 m 2 /g.

15 . The composition of matter as claimed in claim 1 , wherein the composition of matter has an average pore diameter between 2 and 50 nm.

16 . The composition of matter as claimed in claim 1 , wherein the mass fraction of the quaternary ammonium groups in the composition of matter has a range between 5% and 90%, between 20% and 70%, between 50% and 70%, or between 50% and 90%.

17 . The composition of matter as claimed in claim 1 , wherein at least 80 percent of the quaternary ammonium ions are linked directly to at least one other quaternary ammonium ion.

18 . The composition of matter as claimed in claim 1 , wherein the quaternary ammonium ions in the in the cross-linked polymer network are derived from monomers that have molecular weight below 200 g/mol, when the monomers are in a chloride ion-exchanged form.

19 . A method to produce a porous material, comprising:
polymerizing a compound containing quaternary ammonium and a cross-linker using controlled polymerization; and performing ion exchange in the presence of at least one of hydroxide or a counter ion capable of forming hydroxide upon reaction with water.

20 . The method of claim 19 , wherein the counter ion in the cross-linked polymer network capable of reacting with water to produce hydroxide is one of bicarbonate, carbonate, phosphate, hydrogen phosphate, or dihydrogen phosphate.

21 . The method as claimed in claim 19 , wherein the cross-linker contains quaternary ammonium groups.

22 . The method as claimed in claim 19 , wherein the compound contains residue of at least one additional monomer.

23 . The method of claim 22 , wherein the residue of the at least one additional monomer comprises at least one of styrene, styrenic compounds, n-vinyl pyrrolidone, vinyl acetate, vinyl chloride, methacrylates, acrylates, methyl methacrylate, acrylonitrile, methyl acrylate, ethylene, propylene, dimethylsiloxane, fluorinated compounds, hexa-iso-fluoroisopropyl methacrylate, hexa-iso-fluoroisopropyl acrylate, 2,2,2-trifluoroethyl methacrylate, 2,2,2-trifluoroethyl acrylate, and 1H,1H,2H,2H-Heptadecafluorodecyl methacrylate.

24 . The method as claimed in claim 19 , wherein the controlled polymerization comprises one of stable free radical polymerization (SFRP), atom-transfer radical polymerization, nitroxide-mediated polymerization, reversible addition-fragmentation chain-transfer polymerization, and sequential polymerization.

25 . The method as claimed in claim 24 , wherein the SFRP process includes dissolving the quaternary ammonium-containing monomer, crosslinkers, and optional other monomers in a solvent to form a precursor solution, with initiators, a nitroxide mediator, and optional reducing agents.

26 . The method as claimed in claim 24 , wherein the controlled polymerization includes addition of one or more of acetol, dicumyl peroxide or tertbutyl peroxide

27 . The method as claimed in claim 19 , further comprising first reacting the quaternary-ammonium-containing monomers together to form quaternary-ammonium-containing oligomers, and the crosslinker and any additional monomers are then reacted to form a polymer gel containing the quaternary-ammonium-containing oligomer residues.

28 . The method as claimed in claim 27 , wherein the quaternary-ammonium-containing oligomer residues are between 2 and 10 quaternary-ammonium-containing monomer units long.

Assignees

• Palo Alto Res Ct Inc

Inventors

• Meckler Stephen
• Chintapalli Mahati

Classifications

• Y02C20/40

  of CO2 · CPC title

• B01D53/28

  Selection of materials for use as drying agents · CPC title

• B01D53/02

  by adsorption, e.g. preparative gas chromatography {(solid sorbent compositions B01J20/00, preparation of inorganic compounds or elements C01)} · CPC title

• B01J20/3085

  Chemical treatments not covered by groups B01J20/3007 - B01J20/3078 · CPC title

• B01J20/28047

  Gels · CPC title