US20130095999A1 - Methods of making the supported polyamines and structures including supported polyamines - Google Patents

Methods of making the supported polyamines and structures including supported polyamines Download PDF

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US20130095999A1
US20130095999A1 US13/650,377 US201213650377A US2013095999A1 US 20130095999 A1 US20130095999 A1 US 20130095999A1 US 201213650377 A US201213650377 A US 201213650377A US 2013095999 A1 US2013095999 A1 US 2013095999A1
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Watcharop Chaikittisilp
Christopher W. Jones
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Georgia Tech Research Corp
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    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B01J20/22Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26Synthetic macromolecular compounds
    • B01J20/262Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon to carbon unsaturated bonds, e.g. obtained by polycondensation
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    • B01J20/10Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/103Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
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    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28033Membrane, sheet, cloth, pad, lamellar or mat
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    • B01J20/30Processes for preparing, regenerating, or reactivating
    • B01J20/32Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3202Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
    • B01J20/3204Inorganic carriers, supports or substrates
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30Processes for preparing, regenerating, or reactivating
    • B01J20/32Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3242Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
    • B01J20/3268Macromolecular compounds
    • B01J20/3278Polymers being grafted on the carrier
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G83/00Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • C08G83/001Macromolecular compounds containing organic and inorganic sequences, e.g. organic polymers grafted onto silica
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2220/80Aspects related to sorbents specially adapted for preparative, analytical or investigative chromatography
    • B01J2220/84Capillaries
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02CCAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C10/00CO2 capture or storage
    • Y02C10/08Capture by adsorption

Abstract

Methods of making supported polyamines, supported polyamines, and the like, are disclosed.

Description

    CLAIM OF PRIORITY TO RELATED APPLICATION
  • This application claims priority to co-pending U.S. provisional application entitled “Method of making supported polyamines and application thereof in extraction of carbon dioxide from carbon dioxide-containing gaseous streams” having Ser. No.: 61/546,760, filed on Oct. 13, 2011, which is entirely incorporated herein by reference.
  • BACKGROUND
  • Supported amines are of particular importance because these materials can be applied in a wide variety of potential applications such as base-catalyzed reactions, adsorption of heavy metal ions, immobilization of bio-molecules, and carbon dioxide (CO2) capture. Incorporation of amine moieties into/onto the support frameworks has been achieved mostly via four liquid phase synthetic routes: i) physical impregnation of monomeric or polymeric amines into/onto the porous supports, ii) covalent grafting of amines, most often aminosilanes, onto the support surfaces, iii) direct co-condensation amine-containing molecules and conventional precursors during materials syntheses, and iv) in situ polymerization of amine-containing monomers in the pores of supports, with the latter three methods resulting in amines or aminopolymers covalently bound to supports. Specifically, attaching amines via processes that require liquid reagents or solvents can be limiting in some cases. Thus, these approaches are not appropriate or do not provide satisfactory results in all situations and circumstances and there is a need to provide alternative processes in an attempt to overcome the aforementioned inadequacies and deficiencies.
  • SUMMARY
  • Briefly described, embodiments of this disclosure, among others, include methods of making a structure including polyamines, structure including polyamines, and the like.
  • In an embodiment, a method of making a structure including polyamines, among others, includes contacting a monomer having a nitrogen-containing heterocycle with a material, wherein the monomer is in the vapor phase; and forming a hyperbranched polymer on a surface of the material.
  • Other structures, methods, structures, features, and advantages will be, or become, apparent to one with skill in the art upon examination of the following drawings and detailed description. It is intended that all such additional structures, systems, methods, features, and advantages be included within this description, be within the scope of the present disclosure, and be protected by the accompanying claims.
  • BRIEF DESCRIPTION OF THE DRAWINGS
  • Many aspects of this disclosure can be better understood with reference to the following drawings. The components in the drawings are not necessarily to scale, emphasis instead being placed upon clearly illustrating the principles of this disclosure. Moreover, in the drawings, like reference numerals designate corresponding parts throughout the several views.
  • FIGS. 1 and 2 are schematics of illustrative embodiments of the present disclosure.
  • FIG. 3 is a schematic diagram depicting a cross-section of a high surface area structure having a pore that has hyperbranched polymer fabricated therein.
  • FIG. 4 illustrates a simplified reaction scheme for forming an embodiment of the material, wherein the monomer is in the vapor phase.
  • FIG. 5 illustrates a simplified reaction scheme for forming another embodiment of the material, wherein the monomer is in the vapor phase.
  • FIG. 6 illustrates XRD patterns of SBA-15 mesoporous silica (Example 2; bottom), Al-containing SBA-15 mesoporous aluminosilica (Example 5; middle), and Al-grafted SBA-15 mesoporous aluminosilica (Example 6; top).
  • FIG. 7 illustrates nitrogen adsorption-desorption isotherms of SBA-15 mesoporous silica (Example 2; bottom), Al-containing SBA-15 mesoporous aluminosilica (Example 5; middle), and Al-grafted SBA-15 mesoporous aluminosilica (Example 6; top). Filled and empty symbols represent adsorption and desorption branches, respectively.
  • FIG. 8 illustrates nitrogen adsorption-desorption isotherms of SBA-15-supported polyamines synthesized at 70° C. for 24 h (Example 3). Filled and empty symbols represent adsorption and desorption branches, respectively.
  • FIG. 9 illustrates SEM images of (a) VHAS1 and (b) VHAS4 (Example 3), where the scale bars are 1 nm.
  • FIG. 10 illustrates 27Al MAS NMR spectra of Al-containing SBA-15 mesoporous aluminosilica (Example 5; bottom) and Al-grafted SBA-15 mesoporous aluminosilica (Example 6; top).
  • DETAILED DESCRIPTION
  • Before the present disclosure is described in greater detail, it is to be understood that this disclosure is not limited to particular embodiments described, and as such may, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting, since the scope of the present disclosure will be limited only by the appended claims.
  • Where a range of values is provided, it is understood that each intervening value, to the tenth of the unit of the lower limit unless the context clearly dictates otherwise, between the upper and lower limit of that range and any other stated or intervening value in that stated range, is encompassed within the disclosure. The upper and lower limits of these smaller ranges may independently be included in the smaller ranges and are also encompassed within the disclosure, subject to any specifically excluded limit in the stated range. Where the stated range includes one or both of the limits, ranges excluding either or both of those included limits are also included in the disclosure.
  • Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. Although any methods and materials similar or equivalent to those described herein can also be used in the practice or testing of the present disclosure, the preferred methods and materials are now described.
  • All publications and patents cited in this specification are herein incorporated by reference as if each individual publication or patent were specifically and individually indicated to be incorporated by reference and are incorporated herein by reference to disclose and describe the methods and/or materials in connection with which the publications are cited. The citation of any publication is for its disclosure prior to the filing date and should not be construed as an admission that the present disclosure is not entitled to antedate such publication by virtue of prior disclosure. Further, the dates of publication provided could be different from the actual publication dates that may need to be independently confirmed.
  • As will be apparent to those of skill in the art upon reading this disclosure, each of the individual embodiments described and illustrated herein has discrete components and features which may be readily separated from or combined with the features of any of the other several embodiments without departing from the scope or spirit of the present disclosure. Any recited method can be carried out in the order of events recited or in any other order that is logically possible.
  • Embodiments of the present disclosure will employ, unless otherwise indicated, techniques of chemistry, organic chemistry, inorganic chemistry, and the like, which are within the skill of the art. Such techniques are explained fully in the literature.
  • The following examples are put forth so as to provide those of ordinary skill in the art with a complete disclosure and description of how to perform the methods and use the compositions and compounds disclosed and claimed herein. Efforts have been made to ensure accuracy with respect to numbers (e.g., amounts, temperature, etc.), but some errors and deviations should be accounted for. Unless indicated otherwise, parts are parts by weight, temperature is in ° C., and pressure is at or near atmospheric. Standard temperature and pressure are defined as 20° C. and 1 atmosphere.
  • Before the embodiments of the present disclosure are described in detail, it is to be understood that, unless otherwise indicated, the present disclosure is not limited to particular materials, reagents, reaction materials, manufacturing processes, or the like, as such can vary. It is also to be understood that the terminology used herein is for purposes of describing particular embodiments only, and is not intended to be limiting. It is also possible in the present disclosure that steps can be executed in different sequence where this is logically possible.
  • It must be noted that, as used in the specification and the appended claims, the singular forms “a,” “an,” and “the” include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to “a compound” includes a plurality of compounds. In this specification and in the claims that follow, reference will be made to a number of terms that shall be defined to have the following meanings unless a contrary intention is apparent.
  • Definitions:
  • The term “alkyl” refers to straight or branched chain hydrocarbon groups having 1 to 20 carbon atoms such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, pentyl, hexyl, heptyl, octyl, and the like. The alkyl group can be substituted (e.g., a halogen).
  • The term “alkenyl” refers to straight or branched chain hydrocarbon groups having 2 to 20 carbon atoms and at least one double carbon to carbon bond (either cis or trans), such as ethenyl. The alkenyl group can be substituted (e.g., a halogen).
  • The term “alkynyl” refers to straight or branched chain hydrocarbon groups having 2 to 20 carbon atoms and at least one triple carbon to carbon bond, such as ethynyl. The alkynyl group can be substituted (e.g., a halogen).
  • The term “aryl” refers to aromatic homocyclic (i.e., hydrocarbon) mono-, bi- or tricyclic ring-containing groups preferably having 6 to 12 members, such as phenyl, naphthyl and biphenyl. The aryl group can be substituted (e.g., a halogen).
  • A “hyperbranched polymer” may be defined as a polymer in which the structural repeating unit can have a connectivity of more than two and that can include either a single or double branching at each N atom except for the termination of the chain. Hyperbranched polymers are polydisperse.
  • Discussion
  • Methods of making supported polyamines, supported polyamines, and the like, are disclosed. In general, the supported polyamine can be a material that includes hyperbranched polymers (e.g., an ethylene-amine hyperbranched polymer, propylene-amine hyperbranched polymer, and the like). An embodiment of the method of forming the hyperbranched polymers on a surface of a material includes forming the hyperbranched polymers from a monomer having a nitrogen-containing heterocycle, where the monomers are in the vapor-phase. In short, monomers in the vapor-phase are contacted with a surface of a material and hyperbranched polymers are formed. In an embodiment, the hyperbranched polymers can be covalently bonded (e.g., directly to the surface or via a linker group, See Figures) to the surface of the material, which may include the surface of pores for a porous material, although the hyperbranched polymers can be otherwise bonded or attached to the surface (e.g., Van der Waals, ionic bonds or hydrogen bonds).
  • Embodiments of the method can be advantageous in forming or reconstituting materials with hyperbranched polymers without the expense, complexity, and equipment needed when using a liquid-phase approach. In particular, embodiments of the method can be advantageous when the devices or equipment using the materials are disposed in the field where forming and/or reconstituting the hyperbranched polymers using a liquid-phase approach is not practical or in some instances impossible.
  • In particular, functionalization to solid supports with amines via gas phase or vapor phase processes may provide processing advantages. For example, after use of supported amines in applications such as those described herein, the amine may become deactivated. To allow for reuse of the solid supports, it is sometimes desired to regenerate the desired behavior of the amines or remove the amines from the support, to facilitate attachment of fresh amines This can be done in many ways, for example when the support is composed of an inorganic oxide, the organic amines can be removed via heat treatment (combustion), allowing for later re-addition of fresh amines. Addition of amines to the support via liquid phase processes can be slow and cumbersome, and use of approaches or processes to attach amines via vapor phase processes would provide advantages.
  • In an embodiment, the material can be used to adsorb CO2. In this regard, embodiments of the present disclosure can be used to remove CO2 from a gas produced by the use (e.g., burning) of fossil fuels or from CO2 in the ambient air. In general, the material includes one or more of the following: (i) a high loading of amines to facilitate a large CO2 capacity, (ii) adsorption sites (e.g., alkylamine groups) that are covalently linked to the material such as a high surface area solid support to provide stability, (iii) the ability to adsorb and desorb CO2 repeatedly by a temperature swing or other dynamic process, and (iv) a low synthesis and reconstitution cost that can be conducted in the field using the vapor-phase method described herein.
  • In particular, high surface area materials (e.g., silica structures or particles, or other porous materials) and the hyperbranching of the polymer enable the material to have a high CO2 sorption capacity. In addition, since the hyperbranched polymers are often covalently bonded to the material, the material is stable in uses having temperature swings. In an embodiment, the formation of the hyperbranched polymers can be controlled by the nature of the support, the concentration of the monomers in the vapor phase, the temperature, and the time of exposure. It should be noted that the pores are not overfilled by the hyperbranched polymers, and there exists suitable space for the transport of gases through the pores via diffusion, although other gas transport processes can occur (e.g., advection, convection, and the like). It is also contemplated that a system can be used where the transport of gases is through a pressure drop through the pores. In other embodiments where the pore size is sufficiently large and/or the material is a monolith, the gas can contact the hyperbranched polymers by controlling the flow of the gas relative to the orientation of the material to enhance the performance of the material.
  • In an embodiment, the hyperbranched polymer is synthesized on the surface of the material (e.g., directly with the metal, directly via the hydroxy group and/or carboxyl group, or indirectly via the linker) from monomers in the vapor phase. In an embodiment, the hyperbranched polymer can be covalently bonded to the support via one or more of the oxygen atoms (e.g., part of the material or a layer added to the material) on the surface of the material.
  • In general, the material having the hyperbranched polymer bonded or attached (e.g., covalently bonded) thereto can be formed by exposing (e.g., so as to contact the surface of) a material to a monomer having a nitrogen-containing heterocycle, where the monomer is in the vapor-phase in contrast to processes where the monomer is in the liquid-phase. In an embodiment, the size (e.g., length, molecular weight), amount (e.g., number of distinct hyperbranched polymers bonded to the surface), and/or type of hyperbranched polymer, can be controlled by the concentration of the monomer, temperature, and/or length of time of the exposure. In an embodiment, the temperature may be controlled by heating the monomer vapor phase and/or the material. In an embodiment, the material may be in a pressurized system or the monomer vapor-phase may be flowed across the material in a system near ambient pressure. In an embodiment, the concentration of the monomer can be controlled by flow meters and the like as well as mixing with appropriate flow gases (e.g., an inert gas such as Ar, He, N2 and the like). In an embodiment when the concentration is constant, the higher the temperature the shorter the time-frame to form the desired hyperbranched polymer. In an embodiment, the time-frame can be about 0.1 h to 200 h, about 24 to 168 h, about 2 to 24 h, or about 2 to 12 h. In an embodiment, the temperature is at a level so that the monomer is in the vapor-phase under conditions (e.g., pressure, flow of gas, and the like) present around the material. In an embodiment, the temperature can be about 0° to 200° C., about 20° to 120° C., or about 24° to 80° C. Once the material is formed having the hyperbranched polymer, the surface of the material can be rinsed with a solvent (e.g., toluene) and/or a gas (e.g., an inert gas) to remove unreacted monomer. Additional details regarding preparation of the material are described herein.
  • It should be noted that a linking group can be reacted with the surface of the material (e.g., hydroxyl groups) prior to introduction of the monomer. Typical linking groups will be organosilanes with a reactive atom on a carbon chain such as, but not limited to, N, S, P, or O. The linking group can be added using vapor-phase chemistry and/or liquid-phase chemistry. The linking group can be subsequently reacted with the monomer to form the hyperbranched polymer.
  • In an embodiment, the material can include particles, powders, porous films, or porous or non-porous macroscopic objects, such as monoliths. In an embodiment, the material can include, but is not limited to, silica, alumina, aluminosilicates, zirconia, germania, magnesia, titania, hafnia, iron oxide, and mixed oxides composed of those elements. In cases where the oxide contains a formal charge, the charge can be balanced by appropriate counter-ions, such as cations of NR4, Na, K, Ca, Mg, Li, H, Rb, Sr, Ba, Cs or anions including phosphate, phosphite, sulfate, sulfate, nitrate, nitrite, chloride, bromide and the like,
  • In an embodiment, the material can include porous structures (e.g., macroporous, mesoporous, microporous, nanoporous, or mixtures thereof). In an embodiment, the material can include organically modified moieties (e.g., hydroxyl groups, carboxylate groups, amines, phosphoric acid, sulfonic acid, thiols, phosphines, and the like) on the surface (e.g., outside and/or inside surfaces of pores) of the material. In an embodiment, the material can include surface hydroxyl groups, carboxylate groups, amines, phosphoric acid groups, sulfonic acid groups, thiols, phosphines, and the like, that the monomers can directly covalently bond and/or indirectly covalently bond (e.g., covalently bond to a linker covalently bonded to the material). In an embodiment, the material can include an organic polymer having one or more of the following groups: hydroxyl groups, carboxylate groups, amines, phosphoric acid groups, sulfonic acid groups, thiols, phosphines, and the like. In another embodiment, the material can be a carbon support, where the carbon support can include one or more of the following groups: hydroxyl groups, carboxylate groups, amines, phosphoric acid groups, sulfonic acid groups, thiols, phosphines, and the like.
  • In an embodiment, the material can have the form or a shape such as, but not limited to, a particle, a sphere, a polygon, a tube, a rod, a plate, an amorphous shape, a sheet, a monolith, a fiber, and a combination thereof In an embodiment, the material is porous, in particular, the material is a porous particle (e.g., porous silica particles). In an embodiment, the material can be relatively small and can have a first dimension (that is the largest dimension, e.g., diameter (e.g., particles)), where the first dimension is about 500 nm to 500 μm, about 500 nm to 5 μm, and about 1 μm to 5 μm. In an embodiment, the pore diameter can be about 1 nm to 50 nm, about 1 nm to 20 nm, about 1 to 10 nm, about 1 nm to 8 nm, or about 4 nm to 8 nm.
  • In some embodiments, the material is a composite of a plurality of smaller materials, so that the dimensions can be larger and include a wide range of pore sizes that can encompass those described for smaller and larger materials. For example, if a bed or film of particles is employed, the bed or film can be composed of primary particles of the size described above, that bond together to form larger particles in the size range of 1 μm to 1 cm, about 10 μm to 1 mm, or about 50 μm to 500 μm.
  • In an embodiment, the material (e.g., monolith) can have one or more dimensions on the scale of millimeters to centimeters to meters. The dimensions can be selected based on the use of the material and the flow of the gas.
  • In other embodiments, the material can have a dimension (perpendicular to the gas flow), where the dimension is on the scale of millimeters (e.g., about 2 mm) to centimeters (e.g., about 100 to 500 cm), where the pore size can be hundreds of microns to centimeters. In an embodiment, the dimensions of the material can be about fives to ten times or more than that of the dimension perpendicular to the gas flow.
  • In an embodiment, the materials can be used in fixed bed and/or fluidized bed processes. For example, the materials can be used in a fixed bed and/or fluidized bed adsorption system and process to remove CO2 from a gas stream.
  • As mentioned above the monomer includes a nitrogen-containing heterocycle, where the monomer can be an aziridine monomer, an azetidine monomer, a pyrrolidine monomer, or a diazetidine, monomer. In an embodiment, the monomer can be substituted (e.g., halogens, alkyl groups, etc.). In an embodiment, one or more types of monomers can be contacted with the surface of the material to produce one or multiple types of hyperbranched polymers.
  • In an embodiment, the monomer used to form the hyperbranched polymer can be an aziridine monomer (e.g., cyclo-(CH2)2—N(H or R3)) and/or a substituted aziridine monomer (e.g., cyclo-(CR1R2)2—N(H or R3)), where each of R1, R2, and R3 can be independently selected from: H, an alkyl, a substituted alkyl, an aryl, a substituted aryl, an alkenyl, a substituted alkenyl, an alkynyl, a substituted alkynyl, where the substitution can be from groups or moieties including: F, Cl, Br, I, N, P, S, O, and the like, and combinations thereof. The monomer can form highly branched polymer chains by either a single or double branching at each N atom, and in some instances no branching. The monomer can react directly with the hydroxyl groups and/or carboxyl groups on the surface of the high surface area structure, creating a covalent bond (via oxygen) with the polymer chain and/or can be indirectly bonded to the hydroxyl groups and/or carboxyl groups via a linker (and in some cases a carboxyl group can be a linker), as described in more detail herein.
  • In an embodiment, the monomer used to form the hyperbranched polymer can be an azetidine monomer (e.g., cyclo-(CH2)3—N(H or R3)) and/or a substituted azetidine monomer (e.g., cyclo-(CR1R2)3—N(H or R3)), where each of R1, R2, and R3 can be independently selected from: H, an alkyl, a substituted alkyl, an aryl, a substituted aryl, an alkenyl, a substituted alkenyl, an alkynyl, a substituted alkynyl, where the substitution can be from groups or moieties including: F, Cl, Br, I, N, P, S, O, and the like, and combinations thereof The monomer can form highly branched polymer chains by either a single or double branching at each N atom, and in some instances no branching. The monomer can react directly with the hydroxyl groups and/or carboxyl groups on the surface of the high surface area structure, creating a covalent bond (via oxygen) with the polymer chain and/or can be indirectly bonded to the hydroxyl groups and/or carboxyl groups via a linker, as described in more detail herein. For monomers having more carbons, the subscript 3 in either cyclo-(CH2)3—N(H or R3) or cyclo-(CR1R2)3—N(H or R3) can be increased accordingly.
  • FIGS. 1 and 2 are schematics of illustrative embodiments of the present disclosure. FIG. 1 is a schematic that illustrates the hyperbranched polymer formed of aziridine monomers and/or substituted aziridine monomers (note, the carbon atoms of the monomers could include R rather than hydrogen as implicitly depicted). It should also be noted that R can be a functional group such as, but not limited to, H, an alkyl, a substituted alkyl, an aryl, a substituted aryl, an alkenyl, a substituted alkenyl, an alkynyl, a substituted alkynyl, and combinations thereof, where the substitution can be from groups or moieties including: F, Cl, Br, I, N, P, S, O, and the like. The degree of branching of the hyperbranched polymer shown in FIG. 1 is not limiting, and more or less degrees of branching and/or larger or smaller polymers (molecular weight) can be formed. In an embodiment, each N can have 0, 1, or 2 branches, and the degree of branching depends in part upon the number of branches for each N. It should be noted that a number of branching of N can be 1 or 2 due to the hyperbranching of the polymer and/or the synthesis employed. The hyperbranched polymer is covalently bonded to the high surface area structure via X—(CR1R2)2 (R1 and R2 are not depicted in FIG. 1), where a carbon is bonded to the oxygen atom and X is bonded to the hyperbranched polymer. It should be noted that each of R1 and R2 can be H, an alkyl, a substituted alkyl, an aryl, a substituted aryl, an alkenyl, a substituted alkenyl, an alkynyl, a substituted alkynyl, and combinations thereof, where the substitution can be from groups or moieties including: F, Cl, Br, I, N, P, S, O, and the like, and where X is N—R, S, or P—R. It should be noted that for X—(CR1R2)q, q is from 1 to 20. In an embodiment, X is NH. It should also be noted that if the aziridine monomer is replaced with an azetidine monomer, the (CR1R2)2 chain (not the linker) between N atoms would be changed to (CR1R2)3. Similar changes are envisioned for monomers including different numbers of carbons (e.g., from 2 to 10 carbons). It should also be noted that the carbon chain of the linker can be a shorter or longer (e.g., 4 to 10) carbon chain.
  • FIG. 2 is a schematic that illustrates the hyperbranched polymer formed of aziridine monomers and/or substituted aziridine monomers (note, the carbon atoms of the monomers could include R rather than hydrogen as implicitly depicted). It should also be noted that R is a functional group such as, but not limited to, H, an alkyl, a substituted alkyl, an aryl, a substituted aryl, an alkenyl, a substituted alkenyl, an alkynyl, a substituted alkynyl, and combinations thereof, where the substitution can be from groups or moieties including: F, Cl, Br, I, N, P, S, O, and the like. The degree of branching of the hyperbranched polymer shown in FIG. 2 is not limiting, and more or less degrees of branching and/or larger or smaller polymers (molecular weight) can be formed. The hyperbranched polymer is covalently bonded to the high surface area structure via X—(CR1R2)zSiR4 (R1 and R2 are not depicted in FIG. 2), where Si is bonded to two oxygen atoms (as depicted), where z can be from 1 to 20, and where X is bonded to the hyperbranched polymer. R4 can be selected from, but is not limited to, an alkyl, a substituted alkyl, an alkenyl, a substituted alkenyl, a methyl, a substituted methyl, an alkoxyl, a substituted alkoxyl, a methoxy, an ethoxy, a n-propoxy, an iso-propoxy, a halogen (e.g., chorine, bromine, iodine, and fluorine), N(R)2, and the like. It should also be noted that if the aziridine monomer is replaced with an azetidine monomer, the (CR1R2)2 chain (not the linker) between N atoms would be changed to (CR1R2)3. Similar changes are envisioned for monomers including different numbers of carbons (e.g., from 2 to 10 carbons). It should also be noted that the carbon chain of the linker can be a shorter or longer (e.g., 4 to 10) carbon chain.
  • It should be noted that Si can be bonded to 1, 2, or 3 surface oxygen atoms, and although FIG. 2 depicts Si bonded to 2 oxygen atoms, each Si can be bonded to 1, 2, or 3 surface oxygen atoms. If Si is bonded to only one oxygen, then Si can be bonded to groups such as, but not limited to, an alkyl, a substituted alkyl, an aryl, a substituted aryl, an alkenyl, a substituted alkenyl, a methyl, a substituted methyl, an alkoxyl, a substituted alkoxyl, a methoxy, an ethoxy, a n-propoxy, an isopropoxy, a halogen (e.g., chorine, bromine, iodine, and fluorine), N(R)2, and the like.
  • In general, the silicon compound used to form X—(CR1R2)zSiR4 should have at least one group that will bond to the surface (e.g., halides, an amine (silazanes), an alkoxyl, a substituted alkoxyl, a methoxy, an ethoxy, a n-propoxy, and an isopropoxy) and one chain (CR1R2)z, but the other two groups on the silicon can be groups such as, but not limited to, surface reactive groups, additional (CR1R2)z groups, and/or inert groups (e.g., an alkyl, an alkenyl, an aryl, and the like). Once the silicon compound bonds to the surface, it has at least one bond to an oxygen on the surface of the structure and at least one bond to a carbon chain (CR1R2)z, while the other bonds, if any, are to one or more groups described above. In an embodiment, z can be 2 to 10.
  • It should be noted that each of R1 and R2 can independently be H, an alkyl, a substituted alkyl, an aryl, a substituted aryl, an alkenyl, a substituted alkenyl, an alkynyl, a substituted alkynyl, and combinations thereof, where the substitution can be from groups such as but not limited to, F, Cl, Br, I, N, P, S, O, and the like, and where X is N—R, S, or P—R. It should be noted that if X is N—R or P—R, that R could be a branch of the hyperbranched polymer. In an embodiment, z is equal to 3. In an embodiment, R4 is -OMe.
  • FIG. 3 is a schematic diagram depicting a cross-section of a material 12 that includes a pore 14 that has hyperbranched polymers fabricated therein. As mentioned above, the monomers in the vapor-phase are contacted with the surface of the material and form the hyperbranched polymers. The material 12 includes a pore 14 having hyperbranched polymers 16 disposed on the inside surface of the pore 14 and an open region 18. In addition, FIG. 3 shows that many branches of the hyperbranched polymer 16 that can function as interaction sites for targets such as CO2.
  • FIG. 4 illustrates a simplified reaction scheme for forming an embodiment of the material including the hyperbranched polymers. In this embodiment the material includes hydroxyl groups on the surface that are exposed to aziridine (e.g., other monomers can be used with aziridine or replace aziridine) under appropriate conditions, as described in more detail herein. The aziridine reacts with some of the surface hydroxyl groups to ultimately from the hyperbranched polymer. The degree of branching and the size (molecular weight) of the hyperbranched polymer can be controlled by parameters such as, but not limited to, monomer loading, reaction time, temperature, and the like. It should be noted that R can be H or a branch of the hyperbranched polymer. In an embodiment, each N can have 0, 1, or 2 branches, and the degree of branching depends in part upon the number of branches for each N. It should be noted that a number of branching of N can be 1 or 2 due to the hyperbranching of the polymer and/or the vapor phase synthesis employed.
  • FIG. 5 illustrates a simplified reaction scheme for forming an embodiment of the material including the hyperbranched polymer. In this embodiment the material includes hydroxyl groups on the surface that are exposed to a silicon compound having the formula Si(OMe)3(CR2)2(CH2X), where X is NR2, S—R, or P—R2, and where R is a functional group such as, but not limited to, H, an alkyl, a substituted alkyl, an aryl, a substituted aryl, an alkenyl, a substituted alkenyl, an alkynyl, a substituted alkynyl, and combinations thereof, where the substitution can be from groups or moieties including: F, Cl, Br, I, N, P, S, O, and the like. A modified material is formed when the silicon compound reacts with the hydroxyl groups to form a bond from Si to 1, 2, or 3 oxygen groups. It should be noted that X is N—R, S, or P—R. It should also be noted that the linkers can bond to each other, through Si—O—Si bonds. Next, the modified material is exposed to aziridine (e.g., other monomers can be used with aziridine or replace aziridine) under appropriate conditions, as described in more detail herein. The aziridine reacts with the X group to from the hyperbranched polymer. It should be noted that R can be H or a branch of the hyperbranched polymer. In an embodiment, each N can have 0, 1, or 2 branches, and the degree of branching depends in part upon the number of branches for each N.
  • EXAMPLE
  • Now having described the embodiments of the sorbents in general, Example A describes some embodiments of the sorbents and uses thereof. The following is a non-limiting illustrative example of an embodiment of the present disclosure that is not intended to limit the scope of any embodiment of the present disclosure, but rather is intended to provide some experimental conditions and results. Therefore, one skilled in the art would understand that many experimental conditions can be modified, but it is intended that these modifications be within the scope of the embodiments of the present disclosure.
  • Example A
  • A novel synthetic route to prepare supported polyamine materials through vapor-phase transport is developed. In this method, the small nitrogen-containing heterocyclic monomers are transported into and onto solid supports in the vapor phase and subsequently polymerization is initiated at the support surface. The obtained supported polyamine materials can contain organic contents comparable to materials prepared via the conventional liquid-phase reactions. The amount of polyamines formed on the supports can be affected by several synthesis parameters including temperature and reaction time. This novel method can applied for efficient introduction of polyamines into other structural forms of supports including fibers, capillary tubes, disk and tubular membranes, and a monolith structure.
  • EXAMPLES Materials Characterization
  • Powder X-ray diffraction (XRD) patterns were collected on a Philips X'pert diffractometer using Cu Kα radiation. Nitrogen adsorption-desorption was performed on a Micromeritics TriStar II 3020 at 77 K. Before the measurement, the samples were degassed at 110° C. under vacuum for at least 8 h. Organic loadings were determined by thermogravimetric analysis (TGA) using a Netzsch STA409 instrument. Samples were heated under a mixed gas stream of air (90 mL/min) and nitrogen (30 mL/min) with a heating rate of 10 K/min. Solution-state nuclear magnetic resonance (NMR) spectra were recorded on a Varian Mercury Vx400 spectrometer. 27Al solid-state magic-angle spinning (MAS) NMR experiments were carried out on a Bruker DSX 300 spectrometer at a frequency of 78.2 MHz. The sample was spun at 5 kHz with a single pulse of π/6 and a recycle delay of 0.5 s. Scanning electron microscope (SEM) images were taken from a LEO 1530 instrument. Molecular weights of polyamines were estimated by gel permeation chromatography with a system comprised of a Shimadzu LC-20AD pump, a Shimadzu RID-10A RI detector, a Shimadzu SPD-20A UV detector, a Shimadzu CTO-20A column oven, and Tosoh Bioscience TSKgel PWXL Guard, Viscotek Viscogel G6000 and G4000 columns mounted in series.
  • Example 1 Synthesis of Aziridine
  • To a 250-mL round-bottom flask containing 2-chloroethylamine hydrochloride (Aldrich, 30 g) was add a sodium hydroxide aqueous solution (25.8 g of sodium hydroxide (VWR) in 170 g of deionized water). The resultant solution was heated to 50° C. and stirred at this temperature for 2 h. Aziridine was then recovered by a partial static vacuum distillation at 75° C. The collected distillate was dried over sodium hydroxide pellets. The upper layer of liquid was decanted and the purified aziridine was obtained as a colorless oil in 70-80% yield. 1H NMR (400.0 MHz, (CD3)2SO, TMS): δ (ppm) 1.17, 1.53; 13C NMR (100.6 MHz, (CD3)2SO, TMS): δ (ppm) 17.4.
  • Example 2 Preparation of SBA-15 Mesoporous Silica
  • Pluronic P123 EO20-PO70-EO20 triblock copolymer (Aldrich, 15.30 g), concentrated hydrochloric acid (BDH, 72 g) and deionized water (328 g) were mixed in a 1-L Erlenmeyer flask. After being stirred for 5 h at 40° C., 25.4 g of tetraethyl orthosilicate (TEOS, Aldrich) was added to the stirred solution. The resultant mixture was stirred for 21 h at 40° C., producing a cloudy solution with a white precipitate. Subsequently, this mixture was heated statically at 100° C. for 24 h. SBA-15 material was isolated by filtration and washed with a copious amount of deionized water. The obtained white solid was dried at 75° C. overnight. The organic template was removed by calcination at 550° C. for 6 h with an intermediate step at 150° C. for 2 h (a heating rate of 1° C./min). The resulting SBA-15 mesoporous silica was characterized by XRD and nitrogen physisorption. As shown in FIG. 6, the calcined SBA-15 material exhibits XRD peaks with (100), (110), and (200) reflections, which is the characteristic of a 2D hexagonal mesostructure. The nitrogen adsorption-desorption isotherm of the calcined SBA-15 shown in FIG. 7 is the IUPAC Type IV isotherm with hysteresis, indicating the presence of mesopores. The apparent Brunauer-Emmett-Teller (BET) specific surface area, total pore volume, and non-local density functional theory (NL-DFT) pore diameter of the calcined SBA-15 were calculated to be 920 m2/g, 1.07 cm3/g, and 8.0 nm, respectively.
  • Example 3 Preparation of Polyamines on SBA-15 Mesoporous Silica Via Vapor-Phase Transport
  • For the laboratory scale experiment, polymerization of aziridine on the calcined SBA-15 via vapor-phase transport was carried out in a 15-mL glass pressure tube. Typically, the calcined SBA-15 was hand-ground by a mortar and pestle and then dried at 105° C. for at least 48 h. About 0.15 g of the well ground and dried SBA-15 was added into the pressure tube. A small glass test tube (12×75 mm, VWR) containing a different amount of aziridine was then placed inside the pressure tube. The pressure tube was closed tightly and heated to a desired temperature for a specified period of reaction time. The reaction was quenched by adding the pressure tube into an ice bath. The solid sample was washed with excess amounts of methanol and acetone and recovered by filtration. The resulting solid was dried under high vacuum at room temperature overnight.
  • Aziridine was polymerized on SBA-15 with the different aziridine-to-SBA-15 ratios. In contrast to the liquid-phase synthesis, during polymerization the aziridine monomers are transported into the solid supports in the vapor phase and subsequently polymerization is initiated at the support surface. As shown in Table 1, the amount of aziridine affected the final organic content of the obtained materials. As the amount of aziridine was increased, the organic content was increased while the BET surface area and total pore volume were reduced. Comparing with the calcined SBA-15, the reduction of BET surface area and total pore volume indicated that at least some portions, if not all, of the polyamines are occluded in the pore space of the SBA-15 support. The nitrogen adsorption-desorption isotherms of the SBA-15-supported polyamines shown in FIG. 8 also suggested that the pore diameters of the obtained materials was decreased as the amount of aziridine was increased because the hysteresis loops shifted to the lower relative pressures. SEM images of VHAS1 and VHAS4 depicted in FIG. 9 further supported that the exteriors of the materials are not covered with polyamines
  • TABLE 1 The SBA-15-supported polyamines synthesized at 70° C. for 24 h with a different amount of aziridine* Organic Amine Total pore Amount of content (wt loading BET surface volume Sample aziridine (g) %) (mmol N/g) area (m2/g) (cm3/g) VHAS1 0.15 30.61  7.12 180 0.34 VHAS2 0.30 34.84  8.10 170 0.31 VHAS3 0.45 42.49  9.88  40 0.09 VHAS4 0.60 45.47 10.58  20 0.06 *The organic content and amine loading were identified by TGA measurement, while the BET surface area and total pore volume were calculated from nitrogen physisorption measurement.
  • Effects of reaction temperature and time on the organic content were also investigated. As shown in Table 2, both parameters influenced the organic contents of the obtained materials. The higher temperature and the longer reaction time resulted in the higher organic loadings. Interestingly, the materials with significant content of organic moieties can also be prepared at room temperature.
  • TABLE 2 The SBA-15-supported polyamines synthesized with 0.15 g of SBA-15:0.6 g of aziridine at different reaction temperature and time* Reaction Reaction Organic content Amine loading Sample temperature (° C.) time (h) (wt %) (mmol N/g) VHAS5 25 168 31.05  7.22 VHAS6 50  24 35.13  8.17 VHAS7 50  48 43.31 10.07 VHAS8 60  24 39.34  9.15 VHAS9 80  24 44.62 10.38 *The organic content and amine loading were identified by TGA measurement.
  • Example 4 Preparation of Mesoporous Alumina
  • Mesoporous γ-alumina was synthesized by surfactant-mediated self-assembly of pseudobomite nanoparticles. First, 13.75 g of commercial pseudoboehmite received from Sasol North America (Catapal B, 74.3% Al2O3) was dispersed in a mixture of nitric acid (Fisher Scientific, ˜70%, 1.27 g) and deionized water (200 mL). The suspension was sonicated at room temperature for 90 min and then stirred at 60° C. for 17 h. After cooling down to room temperature, the obtained alumina sol was added slowly to a stirred ethanol (Sigma, 200 proof, 200 mL) solution of Pluronic P123 EO20-PO70-EO20 triblock copolymer (Aldrich, 15.30 g). The resulting solution was stirred at room temperature for 24 h. Subsequently, the solvent was evaporated in an open beaker at 60° C. for 60 h. The obtained P123-alumina composite was further dried at 75° C. for 24 h. This composite was calcined at 700° C. for 4 h with an intermediate step at 150° C. for 1 h (a heating rate of 1 K/min), resulting in the white peptized-sol-gel derived mesoporous γ-alumina. Its apparent BET specific surface area, total pore volume, and NL-DFT pore diameter were calculated to be 240 m2/g, 1.2 cm3/g, and 19.9 nm, respectively.
  • Example 5 Preparation of Al-Containing SBA-15 Mesoporous Aluminosilica
  • SBA-15 mesoporous aluminosilica was directly synthesized similar to the procedures described in Example 2 with the initial pH of 2. Typically, 8 g of P123 triblock copolymer (Aldrich) and 0.1 g of ammonium fluoride (NH4F, Sigma) were dissolved in 300 mL of 0.0316 M hydrochloric acid. The resulting mixture was vigorous stirred at room temperature for 5 h. Separately, 16.9 g of TEOS (Aldrich) was pre-hydrolyzed in 20 mL of 0.0316 M hydrochloric acid for 30 min. Then, 0.83 g of aluminum isopropoxide (Aldrich) was added to the pre-hydrolyzed TEOS solution. The obtained aluminosilicate solution was vigorous stirred at room temperature for 3 h. To the P123-NH4F solution was added dropwise the aluminosilicate solution while stirring. The mixture was stirred for 21 h at 40° C. and subsequently heated at 100° C. for 24 h without stirring. The white powder was isolated by filtration, washed with a copious amount of deionized water, and dried at 75° C. overnight. The organic P123 template was removed by calcination at 550° C. for 6 h with an intermediate step at 150° C. for 2 h (a heating rate of 1 K/min). As shown in FIG. 6, the calcined SBA-15 material exhibits a distorted 2D hexagonal mesostructure. The nitrogen adsorption-desorption isotherm of the calcined SBA-15 shown in FIG. 7 is the IUPAC Type IV isotherm with hysteresis, indicating the presence of mesopores. Its apparent BET specific surface area and total pore volume were calculated to be 890 m2/g and 1.0 CM3/g, respectively. The presence of aluminum species was confirmed by solid-state MAS NMR as shown in FIG. 10.
  • Example 6 Post-Modification of SBA-15 Mesoporous Silica by Grafting
  • The acidity of SBA-15 material was modified by post-synthetic grafting of aluminum species onto the SBA-15 surface. The pristine SBA-15 material was synthesized according to the procedures in Example 2. The aluminate solution was prepared by dissolving 0.26 g of aluminum isopropoxide (Aldrich) in 60 mL of 0.03 M hydrochloric acid. After being stirred at room temperature for 6 h, the aluminate solution was added 1.5 g of the calcined SBA-15. The suspension was stirred at room temperature for 18 h. The suspension was filtered and washed with deionized water. The recovered SBA-15 was dried at 75° C. overnight and then calcined at 550° C. for 6 h with an intermediate step at 150° C. for 2 h (a heating rate of 1 K/min) As shown in FIG. 6, the Al-grafted SBA-15 material exhibits XRD peaks with (100), (110), and (200) reflections, which is the characteristic of a 2D hexagonal mesostructure. Its nitrogen adsorption-desorption isotherm shown in FIG. 7 is the IUPAC Type IV isotherm with hysteresis, indicating the presence of mesopores. Its apparent BET specific surface area and total pore volume were calculated to be 710 m2/g and 0.87 cm3/g, respectively. The presence of aluminum species was confirmed by solid-state MAS NMR as shown in FIG. 10.
  • Example 7 Preparation of Carboxylate (COOH) Functionalized SBA-15 Mesoporous Aluminosilica
  • SBA-15 mesoporous silica was organically functionalized with carboxylate groups (—COOH). In a typical synthesis, 6 g of P123 triblock copolymer (Aldrich) was weighed into a 500-mL Erlenmeyer flask. Then, 36 g of concentrated hydrochloric acid (J. T. Baker) and 167 g of deionized water were added and stirred at 40° C. for 2 h. 12 g of TEOS (Aldrich) was then added and the mixture was stirred at 40° C. for another 45 min pre-hydrolysis time. Then, 2.4 g of carboxyethylsilanetriol sodium salt (Gelest) was added. The resulting mixture was stirred at 40° C. for 20 h and then aged statically at 100° C. for 24 h. The resulting solid was filtered, washed with excess deionized water and then dried overnight on the aspirator. The P123 template was removed by Soxhlet extraction with tetrahydrofuran (THF). Finally, the solid material was refluxed in 50% sulfuric acid to completely remove P123. The organic moieties were determined to be 11.52 wt %. The apparent BET specific surface area, total pore volume, and NL-DFT pore diameter of the extracted material were calculated to be 620 m2/g, 1.07 cm3/g, and 9.4 nm, respectively.
  • Example 8 Preparation of Polyamines on Various Supports Via Vapor-Phase Transport
  • The same procedure described in Example 3 was used to prepare polyamines on disordered amorphous silica (CS-6080, PQ Corporation) and various supports prepared in Examples 4-7. As shown in Table 3, increase in acidity of SBA-15 material by incorporation of aluminum, either via direct synthesis (Example 5) or by post-synthetic modification (Example 6), enhanced the polymerization of aziridine. The results in Table 3 also suggest that the polymerization of aziridine by vapor phase transport is universal on various supports. In general, any supports containing hydroxyl (—OH) and thiol (—SH) groups on the surface can be used to prepare polyamine via ring-opening polymerization.
  • TABLE 3 The polyamines prepared on various supports* Reaction Organic Amine temper- content loading Sample Support ature (° C.) (wt %) (mmol N/g) VHAS10 CS-6080 silica 70 20.2  4.7 VHAS11 Mesoporous alumina 50 5.8  1.3 (Example 4) VHAS12 Mesoporous alumina 70 9.8  2.3 (Example 4) VHAS13 Al-containing SBA-15 50 36.5  8.5 (Example 5) VHAS14 Al-containing SBA-15 60 45.6 10.6 (Example 5) VHAS15 Al-grafted SBA-15 50 36.7  8.5 (Example 6) VHAS16 Al-grafted SBA-15 60 41.8  9.7 (Example 6) VHAS17 Carboxylate SBA-15 50 31.7**  7.4 (Example 7) *The support to aziridine mass ratio and reaction time were fixed at 0.15 g: 0.6 g and 24 h, respectively. The organic content and amine loading were identified by TGA measurement. **The total organic content was 39.56 wt % with a polyamine content of 31.69 wt %.
  • Example 9 Estimation of Molecular Weights of the Polyamines
  • Molecular weights of the supported polyamines were estimated by GPC technique. The supported polyamines were cleaved from the solid support by alkali treatment. About 0.5 g of supported polyamines was dispersed in 100 mL of deionized water. Then, 35 g of potassium hydroxide (Fluka) was added to the dispersion. The resulting mixture was stirred at 50° C. for 24 h, after which after which the support was degraded into soluble species. At least 70 g of water was removed by rotary evaporation at about 60° C. The remaining solution was kept in a freezer overnight. The polyamines were phase-separated and recovered for GPC analysis. Commercial poly(ethylenimine)s with molecular weights of 800, 1300, 2000, and 25,000 Daltons (all from Aldrich) were used to generate a calibration curve. The estimated molecular weights are summarized in Table 4.
  • TABLE 4 The polyamines prepared on various supports* Molecular weight Sample (Dalton) VHAS4  950 VHAS6  530 VHAS8  620 VHAS9 1060
  • Example 10 Synthesis of Azetidine
  • Azetidine was prepared by distillation of azetidine hydrochloride over potassium hydroxide. To a 100-mL round-bottom flask was added potassium hydroxide (Fluka, 7.1 g) and deionized water (4 mL). The mixture was stirred until potassium hydroxide was completely dissolved. Then, 5 g of azetidine hydrochloride (Aldrich) was added to the stirred potassium hydroxide solution. Azetidine was isolated by distillation and stored in a freezer. 1H NMR (400.0 MHz, CDCl3, TMS): δ (ppm) 1.99, 2.25, 3.55; 13C NMR (100.6 MHz, CDCl3, TMS): δ (ppm) 22.1, 48.2.
  • Example 11 Preparation of Supported-Polyamines from Azetidine Via Vapor-Phase Transport
  • The same procedure described in Example 3 was used to prepare polyamines from azetidine synthesized in Example 10 on SBA-15 mesoporous silica prepared in Example 2. The material prepared at 80° C. for 24 h had the organic loading of 16.7 wt % (equivalent to 2.93 mmol N/g) with the BET surface area and total pore volume of 340 m2/g and 0.66 cm3/g, respectively. This result suggested that the present method is not limited to aziridine but is also applicable for larger nitrogen-containing heterocycles such as azetidine.
  • Example 12 Adsorption of CO2 by Supported Polyamine Materials
  • CO2 adsorption measurements were performed on VHAS 7 as an example under anhydrous conditions using a TA Q500 thermogravimetric analyzer. Certified mixtures of CO2 and argon with CO2 concentrations of 10% and 400 ppm (Matheson Tri-Gas) were used to simulate flue gas and ambient air, respectively. To remove moisture and CO2 pre-adsorbed on the adsorbents, the samples were loaded in a platinum pan and subjected to pretreatment under a flow of argon (Airgas South, UHP grade) at 110° C. for 3 h with a heating rate of 5 K/min. Then, the temperature was decreased to 25° C. with a rate of 5 K/min and held for 1 h to stabilize the sample weight and temperature before introducing the CO2-containing gas. Adsorption experiments were started by exposing the samples to a flow of dry CO2—Ar gas mixture. Adsorption capacities were 0.64 and 0.69 mmol CO2/g measured using 400 ppm CO2 for 12 h and 10% CO2 for 6 h, respectively.
  • SUMMARY
  • Preparation of supported polyamines via vapor-phase transport has been presented. In contrast to the conventional solution-phase method, in which the supports are dispersed in the organic solution, typically toluene, of aziridine, in the vapor-phase method the liquid aziridine and the solid support are placed separately in the same environment. The aziridine is transported into the support surface via vapor-phase. Ring-opening polymerization then occurs on the support surface, resulting in polyamine covalently tethered to the supports, although other types of bonds could be formed. The data shown here suggest that this method can be carried out in a wide range of preparation parameters. The advantage of the present method over the previous solution-based method is that this vapor-phase method can be applied to the structural forms of supports such as membranes and monoliths in the large scale operation in a straightforward manner. In an embodiment, a carrier gas can transport the monomer vapor. It is anticipated that vapor phase synthesis could allow structured adsorbents to be regenerated in the field via vapor phase treatments.
  • It should be noted that ratios, concentrations, amounts, dimensions, and other numerical data may be expressed herein in a range format. It is to be understood that such a range format is used for convenience and brevity, and thus, should be interpreted in a flexible manner to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited. To illustrate, a range of “about 0.1% to about 5%” should be interpreted to include not only the explicitly recited range of about 0.1% to about 5%, but also include individual ranges (e.g., 1%, 2%, 3%, and 4%) and the sub-ranges (e.g., 0.5%, 1.1%, 2.2%, 3.3%, and 4.4%) within the indicated range. In an embodiment, the term “about” can include traditional rounding according to the numerical value and measurement technique. In addition, the phrase “about ‘x’ to ‘y’” includes “about ‘x’ to about ‘y’”.
  • It should be emphasized that the above-described embodiments of this disclosure are merely possible examples of implementations, and are set forth for a clear understanding of the principles of this disclosure. Many variations and modifications may be made to the above-described embodiments of this disclosure without departing substantially from the spirit and principles of this disclosure. All such modifications and variations are intended to be included herein within the scope of this disclosure and protected by the following claims.

Claims (18)

Therefore, the following is claimed:
1. A method of making a structure including polyamines, comprising:
contacting a monomer having a nitrogen-containing heterocycle with a material, wherein the monomer is in the vapor phase; and
forming a hyperbranched polymer on a surface of the material.
2. The method of claim 1, wherein forming is conducted at a temperature of about 0° to 200° C. for a time period of about 2 h to 200 h.
3. The method of claim 1, wherein the monomer is selected from the group consisting of: an aziridine monomer, an azetidine monomer, a pyrrolidine monomer, or a diazetidine monomer, and a combination thereof.
4. The method of claim 1, wherein the material is selected from the group consisting of: silica, alumina, aluminosilicates, zirconia, germania, magnesia, titania, hafnia, iron oxide, mixed oxides composed of those elements, and an organically modified derivatives of each of these.
5. The method of claim 4, wherein the organically modified silicate includes carboxylate groups on the surface of the material.
6. The method of claim 1, wherein the hyperbranched polymer is covalently bonded to an oxygen of the hydroxyl group on the surface of the material.
7. The method of claim 1, wherein the hyperbranched polymer is an ethylene-amine hyperbranched polymer.
8. The method of claim 1, wherein the hyperbranched polymer includes units having the formula R,N-CR2-CR2, wherein R is selected from H and a functional group, wherein w is 0, 1, or 2.
9. The method of claim 1, wherein the hyperbranched polymer includes units having the formula HwN—CH2—CH2, wherein w is 0, 1, or 2.
10. The method of claim 1, wherein the hyperbranched polymer is covalently bonded via a silicon compound to one or more oxygen atoms on the surface of the pore, wherein the silicon compound has the formula Si(OCH3), wherein Si forms bonds to one, two, or three oxygen atoms on the surface of the pore.
11. The method of claim 1, wherein a molecule having the formula —(CR1R2)s—X—HP is covalently bonded to the oxygen of the hydroxyl group on the inside surface of the pore, wherein s is 1 to 10, wherein each of R1 and R2 are independently selected from the group consisting of: H, an alkyl, a substituted alkyl, an aryl, a substituted aryl, an alkenyl, a substituted alkenyl, an alkynyl, a substituted alkynyl, and a combination thereof, where a substitution is from a group selected from the group consisting of: F, Cl, Br, I, N, P, S, and O, wherein X is selected from the group consisting of: N—R, S, and P—R, where N or P bonds to the HP, wherein R is selected from the group consisting of: H, an alkyl, a substituted alkyl, an aryl, a substituted aryl, an alkenyl, a substituted alkenyl, an alkynyl, a substituted alkynyl, and a combination thereof, where the substitution is from a group selected from the group consisting of: F, Cl, Br, I, I, N, P, S, and O, wherein if X is N—R or P—R, then R is selected from the group consisting of: HP, H, an alkyl, a substituted alkyl, an aryl, a substituted aryl, an alkenyl, a substituted alkenyl, an alkynyl, a substituted alkynyl, and a combination thereof, where the substitution is from a group selected from the group consisting of: F, Cl, Br, I, N, P, S, and O, and wherein HP is the hyperbranched polymer.
12. The method of claim 1, wherein a molecule having the formula —SiR4q-(CR1R2)s-X—HP is covalently bonded to one, two, or three oxygen atoms on the surface of the pore, wherein s is 1 to 10, wherein each of R1 and R2 are selected from the group consisting of: H, an alkyl, a substituted alkyl, an aryl, a substituted aryl, an alkenyl, a substituted alkenyl, an alkynyl, a substituted alkynyl, and a combination thereof, where a substitution is from a group selected from the group consisting of: F, Cl, Br, I, N, P, S, and O, wherein X is selected from the group consisting of: N—R, S, and P—R, where P bonds to the HP, wherein R is selected from the group consisting of: H, an alkyl, a substituted alkyl, an aryl, a substituted aryl, an alkenyl, a substituted alkenyl, an alkynyl, a substituted alkynyl, and a combination thereof, where the substitution is from a group selected from the group consisting of: F, Cl, Br, I, N, P, S, and O, wherein R4 is selected from the group consisting of: an alkyl, a substituted alkyl, an alkenyl, a substituted alkenyl, a methyl, a substituted methyl, an alkoxyl, a substituted alkoxyl, a methoxy, a n-propoxy, an iso-propoxy, a halogen, and N(R)2, wherein q is 1 or 2, and wherein HP is the hyperbranched polymer.
13. The method of claim 1, further comprising:
removing unreacted monomer from the material.
14. The method of claim 13, wherein removing includes flowing a gas across the surface of the material to remove unreacted monomer.
15. The method of claim 1, wherein the structure is selected from the group consisting of: a porous structure, a fiber, a capillary tube, a disk membrane, a tubular membrane, a sheet, and a monolith.
16. The method of claim 1, wherein the material is an organic polymer.
17. The method of claim 1, wherein the material has a longest dimension of about 500 nm to 500 μm.
18. The method of claim 1, wherein the material has a dimension perpendicular to the gas flow of about 2 mm to 100 cm.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9452946B2 (en) 2013-10-18 2016-09-27 Corning Incorporated Locally-sintered porous soot parts and methods of forming
US10315185B2 (en) * 2016-07-14 2019-06-11 University Of Oregon Polyfunctional sorbent materials

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130095999A1 (en) * 2011-10-13 2013-04-18 Georgia Tech Research Corporation Methods of making the supported polyamines and structures including supported polyamines

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030194504A1 (en) * 1999-10-19 2003-10-16 Alexander Bilyk Preparation of functional polymeric surface
US20040229045A1 (en) * 2001-08-22 2004-11-18 Stahl International B.V. Process for the preparation of a coating, a coated substrate, an adhesive, film or sheet
US20050096438A1 (en) * 2003-11-03 2005-05-05 Symyx Therapeutics, Inc. Polyamine polymers
US20050142296A1 (en) * 2003-12-30 2005-06-30 3M Innovative Properties Company Substrates and compounds bonded thereto
US20070065490A1 (en) * 2003-12-30 2007-03-22 Schaberg Mark S Substrates and compounds bonded thereto
US20080187755A1 (en) * 2005-02-01 2008-08-07 Basf Aktiengesellschaft Polyamine-Coated Superabsorbent Polymers
US20080199613A1 (en) * 2007-02-21 2008-08-21 Micron Technology, Inc. Thermal chemical vapor deposition methods, and thermal chemical vapor deposition systems
US20080227169A1 (en) * 2006-12-21 2008-09-18 3M Innovative Properties Company Surface-bound fluorinated esters for amine capture
US7795175B2 (en) * 2006-08-10 2010-09-14 University Of Southern California Nano-structure supported solid regenerative polyamine and polyamine polyol absorbents for the separation of carbon dioxide from gas mixtures including the air

Family Cites Families (171)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3466138A (en) 1966-06-07 1969-09-09 United Aircraft Corp Process and system for removal of acidic gases from influent gas to fuel cell
US3491031A (en) 1966-11-18 1970-01-20 Calgon C0Rp Reactivation of monoethanolamine impregnated activated carbon
US3725387A (en) 1971-04-21 1973-04-03 Dow Chemical Co Aminoethylation of flour and starch with ethylenimine
US3798881A (en) 1971-07-22 1974-03-26 Bessam Mfg Inc Liquid sprayer
US3865924A (en) 1972-03-03 1975-02-11 Inst Gas Technology Process for regenerative sorption of CO{HD 2
US3880981A (en) 1972-10-10 1975-04-29 Renato M Garingarao Cyclic acid leaching of nickel bearing oxide and silicate ores with subsequent iron removal from leach liquor
DE2326070C3 (en) 1973-05-22 1979-10-25 Siemens Ag, 1000 Berlin Und 8000 Muenchen
JPS5915688B2 (en) 1976-08-10 1984-04-11 Chiyoda Chem Eng Construct Co
DE2743113C3 (en) 1977-09-24 1980-09-04 Chemische Werke Huels Ag, 4370 Marl
US4455153A (en) 1978-05-05 1984-06-19 Jakahi Douglas Y Apparatus for storing solar energy in synthetic fuels
US4152217A (en) 1978-06-30 1979-05-01 Exxon Research & Engineering Co. Amine regeneration process
US4197421A (en) 1978-08-17 1980-04-08 The United States Of America As Represented By The United States Department Of Energy Synthetic carbonaceous fuels and feedstocks
US4285918A (en) 1980-02-25 1981-08-25 The United States Of America As Represented By The Secretary Of The Navy Regenerative CO2 absorbent
JPS56162813U (en) 1980-05-07 1981-12-03
JPS6214464B2 (en) 1981-10-27 1987-04-02 Murata Machinery Ltd
JPS58122022A (en) 1982-01-14 1983-07-20 Shin Nisso Kako Co Ltd Body and implement for absorbing harmful gas
US4472178A (en) 1983-07-05 1984-09-18 Air Products And Chemicals, Inc. Adsorptive process for the removal of carbon dioxide from a gas
US4497641A (en) 1983-11-18 1985-02-05 Colorado School Of Mines Apparatus and method for dust control by condensation enlargement
US4808317A (en) 1985-03-19 1989-02-28 Advanced Separation Technologies Incorporated Process for continuous contacting of fluids and solids
US4528248A (en) 1984-07-30 1985-07-09 Lockheed Missiles & Space Company, Inc. Electrochemical cell and method
US4579723A (en) 1985-03-28 1986-04-01 The Boc Group, Inc. Methods for purifying inert gas streams
US5443804A (en) 1985-12-04 1995-08-22 Solar Reactor Technologies, Inc. System for the manufacture of methanol and simultaneous abatement of emission of greenhouse gases
US4711645A (en) 1986-02-10 1987-12-08 Air Products And Chemicals, Inc. Removal of water and carbon dioxide from atmospheric air
US4762528A (en) 1986-09-05 1988-08-09 Reichl Eric H Fluid fuel from coal and method of making same
US5061455A (en) 1987-04-30 1991-10-29 United Technologies Corporation Apparatus for removing carbon dioxide from air
US4822383A (en) 1987-04-30 1989-04-18 United Technologies Corporation Method and apparatus for removing carbon dioxide from air
US4810266A (en) 1988-02-25 1989-03-07 Allied-Signal Inc. Carbon dioxide removal using aminated carbon molecular sieves
JPH02209678A (en) 1989-02-08 1990-08-21 Diesel Kiki Co Ltd Solenoid valve
JPH03245811A (en) 1990-02-21 1991-11-01 Sumitomo Heavy Ind Ltd Method for removing, concentrating and fixing carbon dioxide in atmosphere
JPH0751537Y2 (en) 1990-06-06 1995-11-22 大建工業株式会社 Roofing materials
US5087597A (en) 1990-07-19 1992-02-11 Armada De La Republica De Venezuela Carbon dioxide adsorbent and method for producing the adsorbent
DE4210956A1 (en) 1991-08-02 1993-02-04 Bosch Gmbh Robert Means for controlling the output power of a drive unit of a vehicle
US5424051A (en) 1992-01-14 1995-06-13 Uop Process for the removal of carbon dioxide and mercaptans from a gas stream
US5871646A (en) 1992-06-02 1999-02-16 British Gas Plc Porous amorphous silica-alumina refractory oxides, their preparation and use as separation membranes
NL9201179A (en) 1992-07-02 1994-02-01 Tno A process for the regenerative removal of carbon dioxide from gas streams.
DE4239904C2 (en) 1992-11-27 2003-06-05 Mg Technologies Ag A process for the production of methanol
IL103918A (en) 1992-11-29 1996-10-16 Hamit Energy As Method for reducing atmospheric pollution caused by SO2
US5376614A (en) 1992-12-11 1994-12-27 United Technologies Corporation Regenerable supported amine-polyol sorbent
JPH0662677U (en) 1993-02-05 1994-09-02 株式会社富士通ゼネラル Wiper unit driving mechanism
JP3245263B2 (en) 1993-06-08 2002-01-07 株式会社リコー Image forming apparatus
JPH06346856A (en) 1993-06-08 1994-12-20 Nippon Soken Inc Diaphragm pump
JP3104113B2 (en) 1993-08-24 2000-10-30 日立造船株式会社 The method of regenerated adsorbent in the NOx adsorption and removal apparatus
EP0652047B1 (en) 1993-11-10 1999-10-27 Agency of Industrial Science and Technology of Ministry of International Trade and Industry Method for separation of nitrogen and carbon dioxide by use of ceramic materials as separating agent
US5595238A (en) 1994-09-16 1997-01-21 Engelhard/Icc Rotatably supported regenerative fluid treatment wheel assemblies
ES2138763T3 (en) 1994-12-23 2000-01-16 Allied Signal Inc A filtration device that uses absorption to remove pollutants in gas phase.
US5593475A (en) 1995-04-13 1997-01-14 Liquid Air Engineering Corporation Mixed bed adsorber
FR2738501B1 (en) 1995-09-07 1997-10-17 Inst Francais Du Petrole Method and device for purifying veins CHARGED-gas pollutants
JPH09104419A (en) 1995-10-13 1997-04-22 Touyoubou Packaging Plan Service:Kk Evaluating method of self-sealing degassing valve
US5642630A (en) 1996-01-16 1997-07-01 Abdelmalek; Fawzy T. Process for solids waste landfill gas treatment and separation of methane and carbon dioxide
JPH09262432A (en) 1996-03-29 1997-10-07 Kansai Electric Power Co Inc:The Method for recovering basic amine compound in waste gas of decarboxylation column
US5700311A (en) 1996-04-30 1997-12-23 Spencer; Dwain F. Methods of selectively separating CO2 from a multicomponent gaseous stream
US6106595A (en) 1996-04-30 2000-08-22 Spencer; Dwain F. Methods of selectively separating CO2 from a multicomponent gaseous stream
US5906806A (en) 1996-10-16 1999-05-25 Clark; Steve L. Reduced emission combustion process with resource conservation and recovery options "ZEROS" zero-emission energy recycling oxidation system
US5876488A (en) 1996-10-22 1999-03-02 United Technologies Corporation Regenerable solid amine sorbent
US5885921A (en) 1996-10-25 1999-03-23 Ligochem, Inc. Hydrophobic silica adsorbents for lipids
US5928806A (en) 1997-05-07 1999-07-27 Olah; George A. Recycling of carbon dioxide into methyl alcohol and related oxygenates for hydrocarbons
JP3634115B2 (en) 1997-05-23 2005-03-30 大陽日酸株式会社 Gas purification method and apparatus
JPH11244652A (en) 1998-03-02 1999-09-14 Matsushita Electric Ind Co Ltd Gaseous carbon dioxide adsorbent, gaseous carbon dioxide adsorptive body, removal of gaseous carbon dioxide and device therefor
WO2000010691A1 (en) 1998-08-18 2000-03-02 United States Department Of Energy Method and apparatus for extracting and sequestering carbon dioxide
EP1005904A3 (en) 1998-10-30 2000-06-14 The Boc Group, Inc. Adsorbents and adsorptive separation process
US6174506B1 (en) 1999-06-10 2001-01-16 Praxair Technology, Inc. Carbon dioxide recovery from an oxygen containing mixture
JP2001068487A (en) 1999-08-31 2001-03-16 Toray Eng Co Ltd Method and device for chip bonding
US6873267B1 (en) 1999-09-29 2005-03-29 Weatherford/Lamb, Inc. Methods and apparatus for monitoring and controlling oil and gas production wells from a remote location
US6790430B1 (en) 1999-12-09 2004-09-14 The Regents Of The University Of California Hydrogen production from carbonaceous material
DE19963066A1 (en) 1999-12-24 2001-06-28 Dornier Gmbh Absorber of carbon dioxide for narcosis units incorporates macro-porous ion exchanger resin with primary benzyl amine groups
JP2001205045A (en) 2000-01-25 2001-07-31 Tokyo Electric Power Co Inc:The Method of removing carbon dioxide and carbon dioxide removing apparatus
DE20001385U1 (en) 2000-01-27 2000-08-10 Li Zhiqiang Floating bed scrubber
US7141859B2 (en) 2001-03-29 2006-11-28 Georgia Tech Research Corporation Porous gas sensors and method of preparation thereof
AT4281U1 (en) 2000-03-31 2001-05-25 Tesma Motoren Getriebetechnik filler pipe
JP2001300250A (en) 2000-04-27 2001-10-30 Ishikawajima Harima Heavy Ind Co Ltd Carbon dioxide concentration device
AT4444U1 (en) 2000-05-23 2001-07-25 Tesma Motoren Getriebetechnik filler cap
US6540936B1 (en) 2000-06-19 2003-04-01 Toagosei Co., Ltd. Aldehyde gas absorbent and process for absorbing aldehyde gas
US6387337B1 (en) 2000-07-14 2002-05-14 The United States Of America As Represented By The United States Department Of Energy Carbon dioxide capture process with regenerable sorbents
US6755892B2 (en) 2000-08-17 2004-06-29 Hamilton Sundstrand Carbon dioxide scrubber for fuel and gas emissions
US6364938B1 (en) 2000-08-17 2002-04-02 Hamilton Sundstrand Corporation Sorbent system and method for absorbing carbon dioxide (CO2) from the atmosphere of a closed habitable environment
AT4928U1 (en) 2001-03-29 2002-01-25 Plansee Tizit Ag A process for producing a hard-metal feedstock
AT4929U1 (en) 2001-03-29 2002-01-25 Plansee Tizit Ag A process for the production of hard metal granulate
US20020187372A1 (en) 2001-05-14 2002-12-12 Hall John C. Lithium ion battery passive charge equalization
US6612485B2 (en) 2001-07-06 2003-09-02 Paper Products Co., Inc. Food container with condiment container support and method for making food container with condiment container support
US6547854B1 (en) 2001-09-25 2003-04-15 The United States Of America As Represented By The United States Department Of Energy Amine enriched solid sorbents for carbon dioxide capture
JP2003326155A (en) 2002-05-09 2003-11-18 Kaken:Kk Method for reducing carbon dioxide in atmosphere and its device
US7870073B2 (en) 2002-05-10 2011-01-11 Nxp B.V. Method to pay with a smart card
WO2004005923A1 (en) 2002-07-10 2004-01-15 Exelixis, Inc. RABS AS MODIFIERS OF THE p53 PATHWAY AND METHODS OF USE
AU2003259717A1 (en) 2002-08-07 2004-02-25 Bristol-Myers Squibb Company Modulators of rabggt and methods of use thereof
US6960242B2 (en) 2002-10-02 2005-11-01 The Boc Group, Inc. CO2 recovery process for supercritical extraction
CA2510235A1 (en) 2002-12-18 2004-07-01 University Of Ottawa Amine modified adsorbent, its preparation and use for dry scrubbing of acid gases
US6797039B2 (en) 2002-12-27 2004-09-28 Dwain F. Spencer Methods and systems for selectively separating CO2 from a multicomponent gaseous stream
JP3843429B2 (en) 2003-01-23 2006-11-08 ソニーケミカル&インフォメーションデバイス株式会社 Electronics and antenna-mounted printed circuit board
AT6486U1 (en) 2003-02-10 2003-11-25 Plansee Tizit Ag A process for producing a hard-metal feedstock
US7666250B1 (en) 2003-11-12 2010-02-23 Ut-Battelle, Llc Production of magnesium metal
US6908497B1 (en) 2003-04-23 2005-06-21 The United States Of America As Represented By The Department Of Energy Solid sorbents for removal of carbon dioxide from gas streams at low temperatures
US20040213705A1 (en) 2003-04-23 2004-10-28 Blencoe James G. Carbonation of metal silicates for long-term CO2 sequestration
US7132090B2 (en) 2003-05-02 2006-11-07 General Motors Corporation Sequestration of carbon dioxide
PL1627041T3 (en) 2003-05-19 2010-06-30 Michael Trachtenberg Method and apparatuses for gas separation
US7056482B2 (en) 2003-06-12 2006-06-06 Cansolv Technologies Inc. Method for recovery of CO2 from gas streams
US20050027081A1 (en) 2003-07-29 2005-02-03 Ube Industries, Ltd., A Corporation Of Japan Polyoxalate resin and shaped articles and resin compositions comprising same
WO2005026694A2 (en) 2003-09-12 2005-03-24 Nanomix, Inc. Carbon dioxide nanoelectronic sensor
US6929680B2 (en) 2003-09-26 2005-08-16 Consortium Services Management Group, Inc. CO2 separator method and apparatus
RU2372318C2 (en) 2003-10-15 2009-11-10 Иском Холдингз Лимитед Method of catalytic conversion of lower alkane and use of catalyst in said conversion
US7594393B2 (en) 2004-09-07 2009-09-29 Robert Bosch Gmbh Apparatus for introducing a reducing agent into the exhaust of an internal combustion engine
US7722842B2 (en) 2003-12-31 2010-05-25 The Ohio State University Carbon dioxide sequestration using alkaline earth metal-bearing minerals
US7452406B2 (en) 2004-03-12 2008-11-18 Mmr Technologies Inc. Device and method for removing water and carbon dioxide from a gas mixture using pressure swing adsorption
DE102004018221A1 (en) 2004-04-15 2005-11-10 Robert Bosch Gmbh A method for introducing a reagent into an exhaust gas passage of an internal combustion engine and device for carrying out the method
WO2006009600A2 (en) 2004-05-04 2006-01-26 The Trustees Of Columbia University In The City Of New York Systems and methods for extraction of carbon dioxide from air
US7699909B2 (en) 2004-05-04 2010-04-20 The Trustees Of Columbia University In The City Of New York Systems and methods for extraction of carbon dioxide from air
US7947239B2 (en) 2004-05-04 2011-05-24 The Trustees Of Columbia University In The City Of New York Carbon dioxide capture and mitigation of carbon dioxide emissions
US7128777B2 (en) 2004-06-15 2006-10-31 Spencer Dwain F Methods and systems for selectively separating CO2 from a multicomponent gaseous stream to produce a high pressure CO2 product
US20060105419A1 (en) 2004-08-16 2006-05-18 Biosite, Inc. Use of a glutathione peroxidase 1 as a marker in cardiovascular conditions
WO2006023743A2 (en) 2004-08-20 2006-03-02 The Trustees Of Columbia University In The City Of New York Laminar scrubber apparatus for capturing carbon dioxide from air and methods of use
EP1793913A2 (en) 2004-08-20 2007-06-13 Global Research Technologies, LLC Removal of carbon dioxide from air
US20060051274A1 (en) 2004-08-23 2006-03-09 Wright Allen B Removal of carbon dioxide from air
JP2006061758A (en) 2004-08-24 2006-03-09 Daikin Ind Ltd Carbon dioxide remover
JP2006075717A (en) 2004-09-09 2006-03-23 Nippon Steel Corp Utilization method of carbon dioxide
DE102004062014A1 (en) 2004-12-23 2006-07-27 Robert Bosch Gmbh Method and device for an exhaust gas purification system
US7288136B1 (en) 2005-01-13 2007-10-30 United States Of America Department Of Energy High capacity immobilized amine sorbents
WO2006077623A1 (en) 2005-01-18 2006-07-27 Toho Chemical Industry Co., Ltd. Biodegradable polyester resin composition
FR2881361B1 (en) 2005-01-28 2007-05-11 Inst Francais Du Petrole Method of decarbonizing combustion smoke with solvent extraction from the purified smoke
CN101128248A (en) 2005-02-02 2008-02-20 环球研究技术有限公司 Removal of carbon dioxide from air
US9108140B2 (en) 2005-03-16 2015-08-18 Gs Cleantech Corporation Method and systems for washing ethanol production byproducts to improve oil recovery
US20130213280A9 (en) 2005-04-18 2013-08-22 Klaus S. Lackner Methods and systems for reducing carbon dioxide emissions
US7594956B2 (en) 2005-04-19 2009-09-29 Adsorption Research, Inc. Temperature swing adsorption system
CN1709553A (en) 2005-06-02 2005-12-21 中国科学院过程工程研究所 Amino acid ion liquid for acidic gas absorption
US20070187247A1 (en) 2005-07-20 2007-08-16 Lackner Klaus S Electrochemical methods and processes for carbon dioxide recovery from alkaline solvents for carbon dioxide capture from air
CA2616701C (en) 2005-07-28 2018-10-02 Global Research Technologies, Llc Removal of carbon dioxide from air
US9266051B2 (en) 2005-07-28 2016-02-23 Carbon Sink, Inc. Removal of carbon dioxide from air
US7409745B2 (en) 2005-08-09 2008-08-12 The Scott Fetzer Company Cleaning pad for vacuum cleaner
AT8697U1 (en) 2005-10-14 2006-11-15 Plansee Se Tube target
WO2007114991A2 (en) 2006-03-08 2007-10-11 Global Research Technologies, Llc Air collector with functionalized ion exchange membrane for capturing ambient co2
EP2007674A4 (en) 2006-03-31 2014-03-19 Univ Columbia Methods and systems for gasifying a process stream
US7799310B2 (en) 2006-04-07 2010-09-21 The Trustees Of Columbia University In The City Of New York Systems and methods for generating sulfuric acid
DE102006042026B4 (en) 2006-09-07 2016-08-04 Infineon Technologies Ag Device for holding a substrate and method for treating a substrate
WO2008042919A2 (en) 2006-10-02 2008-04-10 Global Research Technologies, Llc Method and apparatus for extracting carbon dioxide from air
AT504398B1 (en) 2006-10-24 2008-07-15 Windhager Zentralheizung Techn Porenburner, and method for operating a porn burner
US7827778B2 (en) 2006-11-07 2010-11-09 General Electric Company Power plants that utilize gas turbines for power generation and processes for lowering CO2 emissions
JP2008122598A (en) 2006-11-10 2008-05-29 Olympus Corp Microscopic system and extension unit
US20100095842A1 (en) 2006-11-15 2010-04-22 Lackner Klaus S Removal of carbon dioxide from air
US7584171B2 (en) 2006-11-17 2009-09-01 Yahoo! Inc. Collaborative-filtering content model for recommending items
NO333144B1 (en) 2006-11-24 2013-03-18 Aker Clean Carbon As The process feed and regenerator for regenerating absorbent which has absorbed CO2
CN101687141B (en) 2007-04-12 2012-09-05 Cefco有限责任公司 Process and apparatus for carbon capture and elimination of multi-pollutants in flue gas from hydrocarbon fuel sources and recovery of multiple by-products
US20080264029A1 (en) 2007-04-30 2008-10-30 Stephen Vogt Sepaniak Biodegradable grass and debris catcher
AU2008254516B2 (en) 2007-05-18 2012-04-05 Exxonmobil Upstream Research Company Removal of a target gas from a mixture of gases by swing adsorption with use of a turboexpander
US20080289499A1 (en) 2007-05-21 2008-11-27 Peter Eisenberger System and method for removing carbon dioxide from an atmosphere and global thermostat using the same
ES2629091T3 (en) 2007-05-21 2017-08-07 Peter Eisenberger Removal of carbon dioxide in the atmosphere and global thermostat
US20080289495A1 (en) 2007-05-21 2008-11-27 Peter Eisenberger System and Method for Removing Carbon Dioxide From an Atmosphere and Global Thermostat Using the Same
US8163066B2 (en) 2007-05-21 2012-04-24 Peter Eisenberger Carbon dioxide capture/regeneration structures and techniques
US20080289500A1 (en) 2007-05-22 2008-11-27 Peter Eisenberger System and method for removing carbon dioxide from an atmosphere and global thermostat using the same
US20080289319A1 (en) 2007-05-22 2008-11-27 Peter Eisenberger System and method for removing carbon dioxide from an atmosphere and global thermostat using the same
US7909911B2 (en) 2007-10-18 2011-03-22 The Trustees Of Columbia University In The City Of New York Carbon dioxide permeable membrane
WO2009055654A1 (en) 2007-10-26 2009-04-30 Eltron Research & Development, Inc. A metal oxide system for adsorbent applications
US20090110907A1 (en) 2007-10-29 2009-04-30 Jiang Dayue D Membranes Based On Poly (Vinyl Alcohol-Co-Vinylamine)
CA2703617A1 (en) 2007-11-05 2009-05-14 Global Research Technologies, Llc Removal of carbon dioxide from air
EP2214814A4 (en) 2007-11-08 2011-04-27 Univ Akron Amine absorber for carbon dioxide capture and processes for making and using the same
ES2648799T3 (en) * 2007-11-19 2018-01-08 Basf Se Use of highly branched polymers in polymer dispersions for bright paints
CA2715874C (en) 2008-02-19 2019-06-25 Global Research Technologies, Llc Extraction and sequestration of carbon dioxide
CA2723289A1 (en) 2008-05-05 2009-12-17 Klaus S. Lackner Systems and methods for sequestering sulfur
WO2009149292A1 (en) 2008-06-04 2009-12-10 Global Research Technologies, Llc Laminar flow air collector with solid sorbent materials for capturing ambient co2
WO2010019600A2 (en) 2008-08-11 2010-02-18 Global Research Technologies, Llc Method and apparatus for extracting carbon dioxide from air
US20110206588A1 (en) 2008-08-11 2011-08-25 Lackner Klaus S Method and apparatus for removing ammonia from a gas stream
WO2010022399A1 (en) 2008-08-22 2010-02-25 Global Research Technologies, Llc Removal of carbon dioxide from air
US8118914B2 (en) 2008-09-05 2012-02-21 Alstom Technology Ltd. Solid materials and method for CO2 removal from gas stream
US8123842B2 (en) 2009-01-16 2012-02-28 Uop Llc Direct contact cooling in an acid gas removal process
US8052776B2 (en) 2009-05-29 2011-11-08 Corning Incorporated Poly(amino-alcohol)-silica hybrid compositions and membranes
EP2266680A1 (en) 2009-06-05 2010-12-29 ETH Zürich, ETH Transfer Amine containing fibrous structure for adsorption of CO2 from atmospheric air
US8491705B2 (en) 2009-08-19 2013-07-23 Sunho Choi Application of amine-tethered solid sorbents to CO2 fixation from air
WO2011035195A1 (en) 2009-09-18 2011-03-24 Nano Terra Inc. Functional nanofibers and methods of making and using the same
US8414689B2 (en) 2009-10-19 2013-04-09 Lanxess Sybron Chemicals Inc. Process and apparatus for carbon dioxide capture via ion exchange resins
US9028592B2 (en) 2010-04-30 2015-05-12 Peter Eisenberger System and method for carbon dioxide capture and sequestration from relatively high concentration CO2 mixtures
WO2011137398A1 (en) 2010-04-30 2011-11-03 Peter Eisenberger System and method for carbon dioxide capture and sequestration
US20130095999A1 (en) * 2011-10-13 2013-04-18 Georgia Tech Research Corporation Methods of making the supported polyamines and structures including supported polyamines
US20140026751A1 (en) 2012-07-25 2014-01-30 General Electric Company System and method for capturing carbon dioxide from flue gas
US9539540B2 (en) 2013-07-08 2017-01-10 Exxonmobil Research And Engineering Company Rotary moving bed for CO2 separation and use of same

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030194504A1 (en) * 1999-10-19 2003-10-16 Alexander Bilyk Preparation of functional polymeric surface
US20040229045A1 (en) * 2001-08-22 2004-11-18 Stahl International B.V. Process for the preparation of a coating, a coated substrate, an adhesive, film or sheet
US20050096438A1 (en) * 2003-11-03 2005-05-05 Symyx Therapeutics, Inc. Polyamine polymers
US20050142296A1 (en) * 2003-12-30 2005-06-30 3M Innovative Properties Company Substrates and compounds bonded thereto
US20070065490A1 (en) * 2003-12-30 2007-03-22 Schaberg Mark S Substrates and compounds bonded thereto
US20080187755A1 (en) * 2005-02-01 2008-08-07 Basf Aktiengesellschaft Polyamine-Coated Superabsorbent Polymers
US7795175B2 (en) * 2006-08-10 2010-09-14 University Of Southern California Nano-structure supported solid regenerative polyamine and polyamine polyol absorbents for the separation of carbon dioxide from gas mixtures including the air
US20080227169A1 (en) * 2006-12-21 2008-09-18 3M Innovative Properties Company Surface-bound fluorinated esters for amine capture
US20080199613A1 (en) * 2007-02-21 2008-08-21 Micron Technology, Inc. Thermal chemical vapor deposition methods, and thermal chemical vapor deposition systems

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Park, Jung Woo, et al., "Strontium B-diketonate complexes with polyamine donor ligands: the synthesis and structural characterization of [Sr(thd)2(L)]n (n=2; L=diethylenetriamine, n+1; L=triethylenetetramine, tetraethylenepentamine and tris(2-aminoethyl)amine) complex". Polyhedron 19 (2000) 2547-2555. *
Vaartstra, Brian A., et al., "Advances in Precursor Development for CVD of Barium-Containing Materials". Mat. Res. Soc. Symp. Proc. Vol.335, pp.203-208, 1994 Materials Research Society. *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9452946B2 (en) 2013-10-18 2016-09-27 Corning Incorporated Locally-sintered porous soot parts and methods of forming
US10315185B2 (en) * 2016-07-14 2019-06-11 University Of Oregon Polyfunctional sorbent materials

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