TUNABLE, RAPID UPTAKE, AMINOPOLYMER AEROGEL SORBENT FOR DIRECT AIR CAPTURE OF CO2
A method of fabrication of a porous polymer aerogel amine material includes preparing a solution comprising at least a solvent, amine monomers having protecting groups, one or more crosslinkers, and one or more radical initiators, heating the solution to promote polymerization and to produce a polymerized material, performing solvent exchange with the polymerized material, causing a deprotection reaction in the polymerized material to remove the protecting groups to produce a deprotected material, soaking and rinsing the deprotected material to remove excess reagents and any byproducts of the deprotection reaction, and drying the deprotecting material to produce the amine sorbent. A system to separate CO 2 from other gases has a polymer porous aerogel sorbent having greater than 5 wt % of amine containing vinyl monomers integrated into a polymer backbone, and the amine containing vinyl monomers may have a molecular weight of less than 100 g/mol.
1 . A method of fabrication of a porous polymer aerogel amine material, comprising:
preparing a solution comprising at least a solvent, amine monomers having protecting groups, one or more crosslinkers, and one or more radical initiators;
heating the solution to promote polymerization and to produce a polymerized material;
performing solvent exchange with the polymerized material;
causing a deprotection reaction in the polymerized material to remove the protecting groups to produce a deprotected material;
soaking and rinsing the deprotected material to remove excess reagents and any byproducts of the deprotection reaction; and
drying the deprotecting material to produce the amine sorbent.
2 . The method as claimed in claim 1 , wherein preparing a solution comprises preparing a solution that includes one or more reducing agents.
3 . The method as claimed in claim 1 , wherein preparing the solution comprising at least amine monomers comprises preparing the solution comprise one or more selected from the group consisting of: amine monomers having protected amino groups, low molecular weight vinyl amine monomers, vinyl monomers containing polymerizable double bonds, amine monomers containing polymerizable double bonds, vinyl amine, allyl amine, 3-buten-1-amine, 4-pentene-1-amine, 3-vinylaniline, 4-vinylaniline, diamine vinyl monomers including 4-cyclohexene-1,2-diamine, amines containing acrylates and methacrylates, 2-aminoethyl methacrylate, and 3-aminopropyl methacrylate, N-methylvinyl amine, N-ethyl vinyl amine, N-methyl-allyl amine, N-isopropylvinyl amine, N-tert-butylvinyl amine, and any derivatives thereof that result from substituting a hydrogen atom from a primary amine containing vinyl monomers.
4 . The method as claimed in claim 1 , wherein preparing the solution comprising at least one or more crosslinkers comprises preparing the solution in which the crosslinkers comprise one or more selected from the group consisting of: crosslinkers consisting of two or more vinyl groups, vinyl crosslinkers that include double bond polymerizable groups, —CH═CH 2 , —C(R)═CH 2 , —C(R 1 )═C(R 2 )H, —C(R 1 )═C(R 2 )(R 3 ), —CH═C(R 1 )(R 2 ), where R, R 1 , R 2 , R 3 are alkyl 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-acrylatetrimethacryl adamantane, dipentaerithritol, trimethylolpropane trimethacrylate, divinylbenzene, phenylene dimethacrylate, phenylene diacrylate, and 1,6-hexanediol diacrylate.
5 . The method as claimed in claim 1 , wherein preparing the solution comprising at least a solvent comprises preparing the solution in which the solvent comprises one or more selected from the group consisting of: a polar aprotic organic solvent, dimethylformamide, methyl ethyl ketone, tetrahydrofuran, diglyme (diethylene glycol dimethyl ether), 1,2-dimethoxy-ethane, ethyl acetate, high boiling solvents, acetophenone, dimethylsulfoxide (DMSO), sulfolane and n-methylpyrrolidone.
6 . The method as claimed in claim 1 wherein preparing the solution comprises at least a solvent comprises preparing the solution comprising a solvent having a concentration from 20-99 wt % of the overall solution.
7 . The method as claimed in claim 1 , wherein preparing the solution comprising at least a radical initiator comprises preparing the solution with one or more selected from the group consisting of: thermal initiators, photoinitiators, peroxides, benzoyl peroxide, diacetylperoxide, di t-butylperoxide, lauroyl peroxide, dicumyl peroxide, azo compounds, Azobisisobutyronitrile (AIBN), phenylazotriphenylmethane, benzophenone, anthaquinone, camphorquinone, benzyl, and benzoin.
8 . The method as claimed in claim 1 , wherein preparing the solution comprises preparing the solution to include a nitroxide mediator.
9 . The method as claimed in claim 8 , wherein preparing the solution to include the nitroxide mediator comprises preparing the solution to include one or more selected from the group consisting of: nitroxide species derived from the decomposition of an alkoxyamine, 4-hydroxy-TEMPO, TEMPO, TEMPO derivatives, TIPNO, TIPNO derivatives, chlorobenzyl-TIPNO, SG1, SG1 derivatives, and a methacrylic acid radical.
10 . The method as claimed in claim 1 , wherein heating the solution comprises heating the solution to a temperature in the range of from 70° C. to 200° C., where the temperature depends upon an initiating temperature of the radical initiator.
11 . The method as claimed in claim 1 , wherein drying the material comprises one of: ambient drying of the material at room temperature and pressure; ambient drying of the material at room temperature and pressure and then in vacuum; freeze-drying the material followed by removal of ice by sublimation in a vacuum; and performing solvent exchange with liquid CO 2 and supercritically drying the material.
12 . A system to separate CO 2 from other gases, comprising a polymer porous aerogel sorbent having greater than 5 wt % of amine containing vinyl monomers integrated into a polymer backbone.
13 . The system as claimed in claim 12 , wherein the polymer aerogel sorbent is one of binder-free pellets, binder-containing pellets, particles, monoliths, fluidizable particles, and particles cast onto other materials.
14 . The system as claimed in claim 12 , wherein the polymer aerogel sorbent is used in a sorber comprising one of a fixed bed, fluidized bed, and a monolith-type sorber.
15 . A system to separate CO 2 from other gases, comprising a polymer porous aerogel sorbent having greater than 5 wt % of amine containing vinyl monomers covalently integrated into a polymer backbone, wherein the amine containing vinyl monomers have a molecular weight of less than 100 g/mol.
16 . The system as claimed in claim 15 , wherein the polymer aerogel sorbent is one of binder-free pellets, binder-containing pellets, particles, monoliths, fluidizable particles, and particles cast onto other materials.
17 . The system as claimed in claim 15 , wherein the polymer aerogel sorbent is used in a sorber comprising one of a fixed bed, fluidized bed, and a monolith-type sorber.