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WO2017205743A1 - Sorbants polymères et leurs procédés de fabrication - Google Patents

Sorbants polymères et leurs procédés de fabrication Download PDF

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Publication number
WO2017205743A1
WO2017205743A1 PCT/US2017/034683 US2017034683W WO2017205743A1 WO 2017205743 A1 WO2017205743 A1 WO 2017205743A1 US 2017034683 W US2017034683 W US 2017034683W WO 2017205743 A1 WO2017205743 A1 WO 2017205743A1
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Prior art keywords
polymer
styrenic
fluid
sorbent
resin
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PCT/US2017/034683
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English (en)
Inventor
Dmytro O. Tymoshenko
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SABIC Global Technologies BV
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SABIC Global Technologies BV
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/261—Synthetic macromolecular compounds obtained by reactions only involving carbon to carbon unsaturated bonds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61M—DEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
    • A61M1/00—Suction or pumping devices for medical purposes; Devices for carrying-off, for treatment of, or for carrying-over, body-liquids; Drainage systems
    • A61M1/14—Dialysis systems; Artificial kidneys; Blood oxygenators ; Reciprocating systems for treatment of body fluids, e.g. single needle systems for hemofiltration or pheresis
    • A61M1/16—Dialysis systems; Artificial kidneys; Blood oxygenators ; Reciprocating systems for treatment of body fluids, e.g. single needle systems for hemofiltration or pheresis with membranes
    • A61M1/1694—Dialysis systems; Artificial kidneys; Blood oxygenators ; Reciprocating systems for treatment of body fluids, e.g. single needle systems for hemofiltration or pheresis with membranes with recirculating dialysing liquid
    • A61M1/1696—Dialysis systems; Artificial kidneys; Blood oxygenators ; Reciprocating systems for treatment of body fluids, e.g. single needle systems for hemofiltration or pheresis with membranes with recirculating dialysing liquid with dialysate regeneration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/264—Synthetic macromolecular compounds derived from different types of monomers, e.g. linear or branched copolymers, block copolymers, graft copolymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid 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 surface properties or porosity
    • B01J20/28057—Surface area, e.g. B.E.T specific surface area
    • B01J20/28061—Surface area, e.g. B.E.T specific surface area being in the range 100-500 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid 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 surface properties or porosity
    • B01J20/28057—Surface area, e.g. B.E.T specific surface area
    • B01J20/28064—Surface area, e.g. B.E.T specific surface area being in the range 500-1000 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid 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 surface properties or porosity
    • B01J20/28057—Surface area, e.g. B.E.T specific surface area
    • B01J20/28066—Surface area, e.g. B.E.T specific surface area being more than 1000 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid 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 surface properties or porosity
    • B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid 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 surface properties or porosity
    • B01J20/28088—Pore-size distribution
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/281—Sorbents specially adapted for preparative, analytical or investigative chromatography
    • B01J20/282—Porous sorbents
    • B01J20/285—Porous sorbents based on polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078

Definitions

  • the present disclosure relates to polymer sorbent materials and methods of preparing polymer sorbent materials particularly those useful in the sorption of nitrogen- containing compounds.
  • Sorbent materials such as polymer sorbent materials
  • kidney dialysis sorbent materials have been used to extract or separate toxins from dialysate solutions in sorbent-based dialysis treatment.
  • sorbent-based dialysis There remains a need for efficient and effective sorbent systems, particularly sorbent polymer systems, which limit the amount of waste water used in dialysis as well as reduce the toxicity of the dialysate solution while improving also sorption capacity of existing sorbent dialysis systems.
  • the present disclosure relates to methods of material removal from a fluid.
  • the disclosure relates to sorbent polymer compositions configured for the extraction of nitrogen-containing compounds from aqueous and/or organic solvents.
  • Methods of material removal from a fluid may comprise: contacting the fluid with a polymer sorbent comprising a styrenic (co)polymer resin, the polymer sorbent exhibiting a mean pore size of 14 to 1000 Angstroms (A), a pore volume of 0.3 to 1.85 milliliters per gram (mL/g) and a surface area by nitrogen surface area (NSA) of 150-1100 square meters per gram (m 2 /g).
  • A mean pore size of 14 to 1000 Angstroms
  • mL/g a pore volume of 0.3 to 1.85 milliliters per gram
  • NSA nitrogen surface area
  • the disclosure relates to a method for material removal from a fluid, the method comprising contacting the fluid with a polymer sorbent comprising a styrenic (co)polymer resin having at least one glyoxal group with a loading of up to about 3 millimole per gram (mmol/g).
  • a polymer sorbent for use in material removal from a fluid the polymer sorbent comprising a styrenic (co)polymer resin having at least one glyoxal group with a loading of up to about 3 mmol/g.
  • the methods of the present disclosure relate to the removal of material from a fluid through the contact of a sorbent polymer with the fluid.
  • these polymer sorbents may provide a mechanism for the extraction of materials from a given liquid.
  • certain materials may be removed from a fluid when placed in contact with the sorbent.
  • the methods of the present disclosure may be used to remove nitrogen-containing materials from a given fluid.
  • the materials may comprise amines, amides, amidines, guanidines, thioureas, ammonia, urea, creatinine, or uremic toxins, or combinations thereof.
  • the methods disclosed herein and the polymer sorbents prepared therefrom may thus be useful for performing separation in a number of fluid systems.
  • fluid systems may include, but are not limited to, water, waste water, organic solvents, blood, blood serums, and dialysis fluid.
  • the disclosed polymer sorbents may be used to separate, or extract, materials from their aqueous and organic environments for purification or treatment purposes.
  • hemodialysis, or dialysis for the treatment of dialysis fluids such as dialysate.
  • dialysis fluids such as dialysate.
  • the medical process of dialysis features the removal of toxins and other solutes from blood. These toxins and solutes include nitrogen containing compounds, such as urea.
  • the toxins and solutes are generally removed from blood via a semi-permeable filtering membrane which is housed in a dialyzer.
  • the blood for treatment and an aqueous solution (referred to as a dialysate) are pumped in alternating directions about the semi-permeable membrane within the dialyzer.
  • Toxins accumulated within the flowing blood are extracted according to a combination of diffusion, convection, and osmosis process as the blood flows within the semi-permeable membrane and the dialysate flows outside of the membrane.
  • Conventional dialyzers may be characterized as single pass or sorbent-based.
  • a single pass dialyzer requires a continuous supply of clean water to facilitate toxin removal, amounting to significant amounts of water.
  • Sorbent-based dialyzers require that the dialysate is detoxified, or regenerated, by introducing the dialysate to chemical compounds to extract toxins, or undesired solutes.
  • discretely configured chemical layers are employed to remove toxins and compounds from the dialysate.
  • the discrete chemical layers of the dialysate detoxification process may be accompanied with unfavorable safety concerns including the toxicity of certain ion exchanger technologies.
  • Modem sorbent materials have been developed to avoid the disadvantages of ionic waste in the enzymatic layered process, but may require substantial synthetic steps to achieve the desired polymer.
  • the methods of the present disclosure provide polymer sorbents for selective removal of materials, or the undesired toxins, from a dialysate. Further, the polymer sorbents have improved sorption capacity and are prepared via fewer, and less intensive, synthetic steps.
  • the polymer sorbents disclosed herein may bind any present nitrogen-containing materials, including amines, amides, amidines, guanidines, thioureas, and ureas.
  • the polymer sorbent may be in contact with the fluid to be treated in a number of ways.
  • the polymer sorbent may be dispersed in the fluid comprising the material to be extracted.
  • the fluid may be agitated by some means, such as stirring, for the period of time necessary for removal of the material from the fluid.
  • the fluid may also be directed through a vessel, such as column, containing the polymer sorbent. As the fluid passes through the column, the fluid interacts with the polymer sorbent to facilitate binding of the material and, ultimately, its extraction.
  • the polymer sorbent may assume any number of forms to be in contact with a particular fluid.
  • the polymer sorbent may comprise a membrane through which the fluid, such as a dialysate, may pass.
  • the polymer sorbent may comprise a collection of fibers, a collection of hollow fibers, flat membranes or films, beads, powders, or a combination thereof through which a fluid, such as the dialysate, may flow.
  • the polymer sorbent may comprise a solution or gel in organic, aqueous or mixed aqueous- organic solvent. The polymer sorbent may remove contaminants from a fluid, such as dialysate, by inclusion of contaminants in gel or a contaminant-polymer co-precipitation from a solution.
  • the polymer sorbent for use in material removal may have certain surface characteristics that facilitate overall contact with the fluid.
  • the polymer sorbent may be configured as porous resin beads.
  • the porosity and surface are of the polymer solvent may be characteristics of any solid (or insoluble) form of the polymer solvent. Still, porosity and surface area may be characteristics most applicable to powders and beads.
  • the polymer sorbent may exhibit a mean pore size of from about 14 Angstroms (A) to 1000 A.
  • the polymer sorbent may exhibit a pore volume of from about 0.3 milliliters per gram (mL/g) to about 1.85 mL/g.
  • the polymer sorbent may also have a particular surface area for the extraction of nitrogen containing materials from a fluid, quantitatively characterized by nitrogen surface area (NSA).
  • the polymer sorbent may have a nitrogen surface area of from about 150 square meters per gram (m 2 /g) to about 1100 m 2 /g.
  • the polymer sorbent comprises a functionalized styrenic (co)polymer.
  • the styrenic (co)polymer may include at least one glyoxal group with a loading of up to about 3 millimole per gram (mmol/g).
  • the polymer sorbent may comprise a polymeric phenylglyoxal resin.
  • the phenylglyoxal resin may include repeating glyoxal or gly oxalic acid units.
  • the glyoxal or gly oxalic acid units may be disposed at the meta positions of the styrenic polymer chain or at the para positions of the styrenic polymer chain, or at a combination thereof.
  • the polymer sorbent may have a surface modified to include one or more functional groups. These functional groups may bind nitrogen containing materials through inter- or intramolecular hydrogen, covalent bonds or their combination.
  • the polymer sorbent comprising a styrenic (co)polymer resin may be modified to include certain functional groups.
  • the functional groups may include, but are not limited to carboxylates, aldehydes, keto-aldehydes, keto- carboxylates, hydroxyls, and hydroxy -ketones.
  • the disclosure in one aspect, relates to material removal from fluids achieved by contacting a fluid with polymer sorbents useful in selectively binding nitrogen containing materials, from organic and aqueous solution.
  • the polymer sorbent described herein may be derived from a polyvinyl polymer. More specifically, the present disclosure relates to methods of preparing a polymer sorbent from a styrenic (co)polymer resin.
  • the polyvinyl polymer comprises a styrenic divinyl benzene (DVB) (co)polymer having a structure represented by one of the formulas:
  • R is each independently selected from, for example, hydrogen, C1-C3 alkyl, aryl (phenyl, substituted phenyl, naphthyl), substituted alkyl (hydroxyalkyl), formyl, carbonyl, carboxyl, carboxylate, substituted carboxylate (i.e. hydroxyalkyl carboxylate), amide, substituted amide (N-alkyl, N-hydroxy alkyl), hydroxyl and its derivatives (i.e., acetoxy).
  • the divinyl benzene (co)polymer has a divinyl benzene content between 50 wt. % and 100 wt. %.
  • the disclosure relates to methods of material removal comprising contacting a fluid with a polymer sorbent useful in extracting nitrogen containing compounds from aqueous and organic solutions.
  • the polymer sorbent for contact with a given fluid comprises a loading of up to about 3 mmol/g of glyoxal groups.
  • the disclosed polymer sorbents comprise the reaction products of the synthetic methods described herein.
  • the disclosed polymer sorbents comprise a compound produced by a synthetic method described herein.
  • the disclosure comprises a polymeric composition comprising the reaction product of the disclosed methods.
  • the polymer sorbents according to the disclosure can generally be prepared by a succession of reaction steps.
  • the polymer sorbents can be prepared according to the following synthesis methods.
  • the methods comprise at least one reaction or reacting step.
  • reacting or the reaction step comprises any reaction condition effective to produce a desired reaction product or result, for example, reacting a reactant under reaction conditions effective to provide a reaction product comprising at least one desired compound.
  • the method can comprise any number of reaction conditions, for example, a first, second, third, fourth, and fifth reaction condition, or any combination thereof.
  • each reacting step or reaction can comprise any number of reaction conditions, for example, a first, second, third, fourth, and fifth reaction condition, or any combination thereof.
  • the method can provide any number of reaction products, for example, a first, second, third, fourth, and fifth reaction product, or any combination thereof.
  • each reacting step or reaction can provide any number of reaction products, for example, a first, second, third, fourth, and fifth reaction product, or any combination thereof.
  • conditions effective comprise adjusting the temperature to between about 0 degrees Celsius (°C) to at least about 50 °C.
  • the temperature is adjusted to a temperature of from 50 °C to about 250 °C, including exemplary temperatures of about 0, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110, 1 15, 120, 125, 130, 135, 140, 145, 155, 160, 165, 170, 175, 180, 185, 190, 195, 200, 205, 210, 215, 220, 225, 230, 235, 240, and 245 °C.
  • conditions effective comprise maintaining the reaction for at least about 1 hour. In still further aspects, the reaction is maintained for about 1 to about 20 hours, including exemplary times of 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 1, 12, 13, 14, 15, 16, 17, 18, and 19 hours. [0025] In further aspects, conditions effective comprise adjusting the pH to a range of from 1 to about 14, including exemplary values of 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 1, 12, and 13.
  • the reaction conditions comprise one or more of an epoxidation, bromination, or oxidation, or a combination thereof to achieve the polymer sorbent disclosed herein.
  • the preparation of the polymer sorbent may comprise one or more of a first reaction conditions, a second reaction conditions, or a third reaction conditions wherein any of the reaction conditions may include one or more of epoxidation, bromination, or oxidation.
  • the reaction conditions may comprise epoxidation.
  • An exemplary epoxidation condition includes oxirane formation.
  • the reaction conditions may comprise reacting a reactant, such as the polyvinyl polymer, with an oxidizer, or an oxidizing agent, in the organic or aqueous-organic media compatible with the polymer.
  • exemplary oxidizers comprise but are not limited to hydrogen peroxide, tert-butyl peroxide, perbenzoic acid, substituted perbenzoic acid, peracetic acid, oxone, iodosylbenzene, or diacyl iodosobenzene, and any combinations thereof.
  • reaction conditions may comprise reacting a styrenic (co)polymer resin with hydrogen peroxide in acetic anhydride under first reaction conditions to provide a first reaction product comprising at least one epoxy group.
  • reaction conditions may comprise an epoxy -ring opening.
  • Epoxy (or oxirane) ring opening may be performed in organic solvent compatible with polymer and that can be mixed, or partially mixed, with water in the presence of a basic, acidic, or salt catalyst.
  • Suitable organic solvents may include, but are not limited to methanol, ethanol, C3-C 10 alcohols, acetonitrile, acetone, methylethyl ketone, acetic acid, C3-C5 carboxylic acids, dichloroethane, toluene, ⁇ , ⁇ -dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide or their mixtures.
  • Exemplary ring opening acidic catalysts may comprise, but are not limited to, protic acid, i.e., hydrochloric acid, sulfuric acid, perchloric acid, benzoic acid, substituted benzoic acid, benzene sulfonic acid, substituted benzene sulfonic acid, or Lewis acid, i.e. ferrous chloride, aluminum chloride, zinc chloride, or any combination thereof.
  • Oxirane ring opening basic catalyst may comprise, but are not limited to, sodium hydroxide, potassium hydroxide, sodium bicarbonate, potassium carbonate, organic linear or cyclic tertiary amines, i.e.
  • oxirane ring opening salt catalyst may comprise, but are not limited to, inorganic, i.e., sodium nitrite, and linear and cyclic tetraalkyl ammonium salts.
  • reaction conditions may comprise reacting a styrenic (co)polymer resin having epoxy groups with sulfuric acid in glacial acetic acid in an amount of 5-10 % by volume of water.
  • the reaction conditions may comprise halogenation, or the addition of one or more halogen groups. More specifically, the reaction conditions may comprise the addition of one or more halogen groups to one or more vinylic groups of the styrenic (co)polymer resin.
  • the addition of one or more halogen groups may be achieved by reacting a reagent or a reaction product in the presence of a halogen source.
  • exemplary halogen sources may include, but are not limited to, hydrogen bromide, di-molecular bromine Br 2 and iodine h, N-bromosuccinimide (NBS), and potassium bromide/potassium persulfate salts.
  • the halogen sources may be used in 0.1-1.5 millimole (mmol) amounts per vinylic group.
  • the reaction conditions may comprise bromination at the vinylic groups of the styrenic (co)polymer resin.
  • reaction conditions may comprise reacting the polyvinyl polymer (a styrenic (co)polymer resin) with a halogen source under first reaction conditions effective to provide a first reaction product comprising at least one halogen.
  • the reaction conditions can comprise oxidative reaction conditions, or an oxidation reaction.
  • the reaction conditions comprise reacting a reactant, or a reaction product, in the presence of an oxidizing agent.
  • exemplary oxidizing agents may include hydrogen peroxide and tert-butylperoxide among others including dimethyl sulfoxide.
  • the reaction conditions comprise reacting a reaction product comprising at least one styrenic (co)polymer resin in the presence of an oxidizing agent to provide a ketoaldehyde functionalized styrenic (co)polymer (or a phenylglyoxal polymer).
  • reaction conditions comprise reacting a reaction product in the presence of an oxidizing agent, for example, reacting a reaction product in the presence of sodium bicarbonate and iodine in dimethylsulfoxide.
  • reaction conditions may comprise reacting a halogenated (brominated) reaction product in the presence of sodium bicarbonate and dimethylsulfoxide.
  • reaction conditions may comprise reacting a brominated styrenic (co)polymer resin in dimethyl sulfoxide with sodium bicarbonate under reaction conditions effective to provide a reaction product comprising at least one glyoxal group with a loading of up to about 3 mmol/g.
  • the polyvinyl polymer may be reacted under first, second, and third reaction conditions to provide a reaction product comprising at least one glyoxal group with a loading of up to about 3 mmol/g.
  • the polyvinyl polymer may react under first reaction conditions effective to provide a first reaction product comprising at least one epoxy group.
  • the polyvinyl polymer such as the styrenic (co)polymer resin may undergo epoxidation to provide a first reaction product comprising at least one epoxy group.
  • the first reaction product may be reacted under second reaction conditions effective to provide a second reaction product.
  • the second reaction conditions may comprise an epoxy ring opening reaction.
  • the second reaction conditions may be effective to provide, for example, a second reaction product comprising a diol, or a hydroxy bromo-substituted second reaction product, or a di-bromo substituted second reaction product.
  • the second reaction product may react under second reaction conditions to provide a third reaction product comprising at least one glyoxal group with a loading of up to about 3 mmol/g.
  • the second reaction product may undergo oxidation as the second reaction conditions to form a phenylglyoxal (or alpha-ketoaldehyde) styrenic polymer.
  • the polyvinyl polymer may be reacted under first and second reactions conditions to provide a second reaction product comprising at least one glyoxal group with a loading of up to about 3 mmol/g.
  • a polyvinyl polymer may react under first reaction conditions effective to provide a di-halogen derivative.
  • the first reaction conditions may comprise bromination of the styrenic (co)polymer resin to provide a di-bromoethyl functionalized styrenic (co)polymer resin.
  • the resultant di-bromo resin polymer undergoes second reaction conditions to provide the second reaction product comprising at least one glyoxal group with a loading of up to 3 mmol/g.
  • the second reaction conditions may include oxidation to convert the di-bromoethyl substituted styrenic
  • the polyvinyl polymer may be reacted under first reaction conditions to provide a reaction product comprising at least one glyoxal group with a loading of up to 3 mmol/g.
  • the first reaction conditions may comprise equimolar, or sub-equimolar, amount of a halogen source and a solvent.
  • Sub-equimolar may refer to less than equimolar. It also may comprise the use of equimolar or excess of a co-oxidizer and a base.
  • the halogen source may be selected from, but is not limited to bromine, iodine, N-bromosuccinimide, lithium bromide, and potassium iodide.
  • the solvent may comprise dimethylsulfoxide and its mixtures with water or mixable organic solvents, i.e. alcohols, ketones, dimethylformamide (DMF), and dimethylacetamide (DMA).
  • a suitable base may comprise but is not limited to sodium hydroxide, potassium hydroxide, sodium bicarbonate, potassium carbonate, cesium carbonate, linear or cyclic, i.e. N-alkylpiperidine, tertiary amines.
  • the co-oxidizer may comprise, but is not limited to, hydrogen peroxide, tert- butyl peroxide, perbenzoic acid, substituted perbenzoic acid, peracetic acid, oxone, iodosylbenzene, diacyl iodosobenzene, and any combinations thereof.
  • the method can further comprise purification of the reaction product.
  • the reaction product is subjected to at least one purification step.
  • the reaction product is purified under conditions effective to provide purified reaction product comprising at least 90 wt. % polymer sorbent.
  • the purified reaction product comprises from about 90 to about 100 wt. % polymer sorbent, including exemplary values of 91, 92, 93, 94, 95, 96, 97, 98, and 99 wt. %.
  • the purification can further comprise the step of filtering, separating, washing, extraction, drying, or a combination thereof.
  • purification can comprise filtering, extracting and washing the product with portions of methanol.
  • the method can further comprise separation of the reaction product.
  • the reaction product is subjected to at least one separation step.
  • the compounds of this disclosure can be prepared by the disclosed methods employing reactions as shown in the disclosed schemes, in addition to other standard manipulations that are known in the literature, exemplified in the experimental sections or clear to one skilled in the art.
  • the following examples are provided so that the disclosure might be more fully understood, are illustrative only, and should not be construed as limiting. For clarity, examples having a fewer substituent can be shown where multiple substituents are allowed under the definitions disclosed herein.
  • each disclosed method can further comprise additional steps, manipulations, and/or components. It is also contemplated that any one or more step, manipulation, and/or component can be optionally omitted from the disclosure. It is understood that a disclosed method can be used to provide the disclosed compounds. It is also understood that the products of the disclosed methods can be employed in the disclosed compositions, methods, and uses. 1. SYNTHESIS ROUTE 1
  • a styrenic (co)polymer is epoxidized at a temperature effective and for a time effective to produce epoxy group, which in turn can readily undergo epoxide ring opening or hydroxybromination.
  • the resultant compound may be oxidized at a temperature effective and for a time effective to give the corresponding glyoxal polymer.
  • a styrenic (co)polymer is brominated at a temperature and for a time effective to produce a di-bromo derivative.
  • the resultant compound may be oxidized at a temperature effective and for a time effective to provide the corresponding glyoxal polymer.
  • a styrenic (co)polymer is reacted at a temperature effective and for a time effective to produce a phenylgloxal polymer.
  • the divinylbenzene (co)polymer may be reacted with an equimolar or sub-equimolar amount of a halogen source and a solvent to produce phenylglyoxal polymer.
  • the reaction may further optionally include equimolar amount or excess of co-oxidizer and base to produce phenylglyoxal polymer.
  • Ranges can be expressed herein as from one value (first value) to another value (second value). When such a range is expressed, the range includes in some aspects one or both of the first value and the second value. Similarly, when values are expressed as approximations, by use of the antecedent 'about,' it will be understood that the particular value forms another aspect. It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint. It is also understood that there are a number of values disclosed herein, and that each value is also herein disclosed as "about” that particular value in addition to the value itself. For example, if the value "10" is disclosed, then “about 10" is also disclosed. It is also understood that each unit between two particular units are also disclosed. For example, if 10 and 15 are disclosed, then 1 1 , 12, 13, and 14 are also disclosed.
  • the terms “about” and “at or about” mean that the amount or value in question can be the designated value, approximately the designated value, or about the same as the designated value. It is generally understood, as used herein, that it is the nominal value indicated ⁇ 10% variation unless otherwise indicated or inferred. The term is intended to convey that similar values promote equivalent results or effects recited in the claims. That is, it is understood that amounts, sizes, formulations, parameters, and other quantities and characteristics are not and need not be exact, but can be approximate and/or larger or smaller, as desired, reflecting tolerances, conversion factors, rounding off, measurement error and the like, and other factors known to those of skill in the art.
  • an amount, size, formulation, parameter or other quantity or characteristic is “about” or “approximate” whether or not expressly stated to be such. It is understood that where "about” is used before a quantitative value, the parameter also includes the specific quantitative value itself, unless specifically stated otherwise.
  • the terms “optional” or “optionally” means that the subsequently described event or circumstance can or cannot occur, and that the description includes instances where said event or circumstance occurs and instances where it does not.
  • the phrase “optionally substituted alkyl” means that the alkyl group can or cannot be substituted and that the description includes both substituted and unsubstituted alkyl groups.
  • compositions of the disclosure Disclosed are the components to be used to prepare the compositions of the disclosure as well as the compositions themselves to be used within the methods disclosed herein. These and other materials are disclosed herein, and it is understood that when combinations, subsets, interactions, groups, etc. of these materials are disclosed that while specific reference of each various individual and collective combinations and permutation of these compounds cannot be explicitly disclosed, each is specifically contemplated and described herein. For example, if a particular compound is disclosed and discussed and a number of modifications that can be made to a number of molecules including the compounds are discussed, specifically contemplated is each and every combination and permutation of the compound and the modifications that are possible unless specifically indicated to the contrary.
  • references in the specification and concluding claims to parts by weight of a particular element or component in a composition or article denotes the weight relationship between the element or component and any other elements or components in the composition or article for which a part by weight is expressed.
  • X and Y are present at a weight ratio of 2:5, and are present in such ratio regardless of whether additional components are contained in the compound.
  • weight percent As used herein the terms "weight percent,” “wt%,” and “wt. %,” which can be used interchangeably, indicate the percent by weight of a given component based on the total weight of the composition, unless otherwise specified. That is, unless otherwise specified, all wt. % values are based on the total weight of the composition. It should be understood that the sum of wt. % values for all components in a disclosed composition or formulation are equal to 100.
  • alkyl group is a branched or unbranched saturated hydrocarbon group of 1 to 24 carbon atoms, such as methyl, ethyl, n propyl, isopropyl, n butyl, isobutyl, t butyl, pentyl, hexyl, heptyl, octyl, decyl, tetradecyl, hexadecyl, eicosyl, tetracosyl and the like.
  • a "lower alkyl” group is an alkyl group containing from one to six carbon atoms.
  • aryl group as used herein is any carbon-based aromatic group including, but not limited to, benzene, naphthalene, etc.
  • aromatic also includes “heteroaryl group,” which is defined as an aromatic group that has at least one heteroatom incorporated within the ring of the aromatic group. Examples of heteroatoms include, but are not limited to, nitrogen, oxygen, sulfur, and phosphorus.
  • the aryl group can be substituted or unsubstituted.
  • the aryl group can be substituted with one or more groups including, but not limited to, alkyl, alkynyl, alkenyl, aryl, halide, nitro, amino, ester, ketone, aldehyde, hydroxy, carboxylic acid, or alkoxy.
  • alkenyl as used herein is a monovalent group characterized by C n H 2n -i, formed from an alkene by removal of one hydrogen atom from any carbon atom.
  • polyvinyl refers to a structure comprising multiple vinyl moieties.
  • carbonate group as used herein is represented by the formula OC(0)OR, where R can be hydrogen, an alkyl, alkenyl, alkynyl, aryl, aralkyl, cycloalkyl, halogenated alkyl, or heterocycloalkyl group described above.
  • oxirane or "oxiranyl group,” as used herein refers to ethylene oxide and is a cyclic ether comprising two carbon atoms.
  • oxiranyl group as used herein is synonymous with epoxy group and is represented by the formula C2H 3 O.
  • glycoxal group as used herein is represented by the formula C2H2O2 and is a representative bisaldehyde moiety.
  • phenylglyoxal or "phenylglyoxal group” as used herein is represented by the formula CgH 6 02 and is a representative bisaldehyde moiety.
  • organic residue defines a carbon containing residue, i.e., a residue comprising at least one carbon atom, and includes but is not limited to the carbon-containing groups, residues, or radicals defined hereinabove.
  • Organic residues can contain various heteroatoms, or be bonded to another molecule through a heteroatom, including oxygen, nitrogen, sulfur, phosphorus, or the like. Examples of organic residues include but are not limited alkyl or substituted alkyls, alkoxy or substituted alkoxy, mono or di-substituted amino, amide groups, etc.
  • Organic residues can preferably comprise 1 to 18 carbon atoms, 1 to 15, carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, 1 to 6 carbon atoms, or 1 to 4 carbon atoms.
  • an organic residue can comprise 2 to 18 carbon atoms, 2 to 15, carbon atoms, 2 to 12 carbon atoms, 2 to 8 carbon atoms, 2 to 4 carbon atoms, or 2 to 4 carbon atoms.
  • a very close synonym of the term "residue” is the term "radical,” which as used in the specification and concluding claims, refers to a fragment, group, or substructure of a molecule described herein, regardless of how the molecule is prepared.
  • radical refers to a fragment, group, or substructure of a molecule described herein, regardless of how the molecule is prepared.
  • a 2,4- dihydroxyphenyl radical in a particular compound has the structure:
  • radical for example an alkyl
  • substituted alkyl can be further modified (i.e., substituted alkyl) by having bonded thereto one or more "substituent radicals.”
  • the number of atoms in a given radical is not critical to the present disclosure unless it is indicated to the contrary elsewhere herein.
  • Organic radicals as the term is defined and used herein, contain one or more carbon atoms.
  • An organic radical can have, for example, 1-26 carbon atoms, 1 -18 carbon atoms, 1-12 carbon atoms, 1 -8 carbon atoms, 1-6 carbon atoms, or 1 -4 carbon atoms.
  • an organic radical can have 2-26 carbon atoms, 2-18 carbon atoms, 2-12 carbon atoms, 2-8 carbon atoms, 2-6 carbon atoms, or 2-4 carbon atoms.
  • Organic radicals often have hydrogen bound to at least some of the carbon atoms of the organic radical.
  • an organic radical that comprises no inorganic atoms is a 5, 6, 7, 8-tetrahydro-2- naphthyl radical.
  • an organic radical can contain 1-10 inorganic heteroatoms bound thereto or therein, including halogens, oxygen, sulfur, nitrogen, phosphorus, and the like.
  • organic radicals include but are not limited to an alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, mono-substituted amino, di-substituted amino, acyloxy, cyano, carboxy, carboalkoxy, alkylcarboxamide, substituted alkylcarboxamide,
  • dialkylcarboxamide substituted dialkylcarboxamide, alkylsulfonyl, alkylsulfinyl, thioalkyl, thiohaloalkyl, alkoxy, substituted alkoxy, haloalkyl, haloalkoxy, aryl, substituted aryl, heteroaryl, heterocyclic, or substituted heterocyclic radicals, wherein the terms are defined elsewhere herein.
  • organic radicals that include heteroatoms include alkoxy radicals, trifiuoromethoxy radicals, acetoxy radicals, dimethylamino radicals and the like.
  • weight percent As used herein the terms "weight percent,” “wt%,” and “wt. %,” which can be used interchangeably, indicate the percent by weight of a given component based on the total weight of the composition, unless otherwise specified. That is, unless otherwise specified, all wt. % values are based on the total weight of the composition. It should be understood that the sum of wt. % values for all components in a disclosed composition or formulation are equal to 100.
  • compositions disclosed herein have certain functions.
  • compositions and methods include at least the following aspects.
  • a method of material removal from a fluid comprising contacting the fluid with a polymer sorbent comprising a styrenic (co)polymer resin, the polymer sorbent exhibiting a mean pore size of 14 to 1000 Angstrom, a pore volume of 0.3 to 1.85 mL/g and a surface area by nitrogen surface area (NSA) of 150 - 1100 m 2 /g.
  • a polymer sorbent comprising a styrenic (co)polymer resin, the polymer sorbent exhibiting a mean pore size of 14 to 1000 Angstrom, a pore volume of 0.3 to 1.85 mL/g and a surface area by nitrogen surface area (NSA) of 150 - 1100 m 2 /g.
  • NSA nitrogen surface area
  • Aspect 2 The method of aspect 1, wherein the material removed comprises amines, amides, amidines, guanidines, thioureas, ammonia, urea, creatine, or uremic toxins, or a combination thereof.
  • Aspect 3 The method of any one of aspects 1-2, wherein the fluid comprises water, organic solvent, blood, blood serum, or dialysis fluid, or a combination thereof.
  • Aspect 4 The method of any one of aspects 1-3, wherein the styrenic (co)polymer resin comprises a polymeric phenylglyoxal resin.
  • Aspect 5 The method of aspect 4, wherein the polymeric phenylglyoxal resin comprises glyoxal or gly oxalic acid units.
  • Aspect 6 The method of aspect 5, wherein the glyoxal or gly oxalic acid units are attached to meta- and/or para-positions of the polymer chain.
  • Aspect 7 The method of any one of aspects 1-6, wherein the styrenic (co)polymer resin comprises a functional group including aldehydes, keto-aldehydes, or keto-carboxylates, or a combination thereof.
  • a method of material removal from a fluid comprising contacting the fluid with a polymer sorbent comprising a styrenic (co)polymer resin having at least one glyoxal group with a loading of up to about 3 mmol/g.
  • Aspect 9 The method of aspect 8, wherein the polymer sorbent exhibits a mean pore size of 14 to 1000 Angstrom.
  • Aspect 10 The method of any one of aspects 8-9, wherein the polymer sorbent exhibits a pore volume of 0.3 to 1.85 mL/g.
  • Aspect 11 The method of any one of aspects 8-10, wherein the polymer sorbent exhibits a surface area by nitrogen surface area (NSA) of 150 - 1100 m 2 /g.
  • NSA nitrogen surface area
  • Aspect 12 The method of any one of aspects 7-11, wherein the material removed comprises amines, amides, amidines, guanidines, thioureas, ammonia, urea, creatine, or uremic toxins, or a combination thereof.
  • Aspect 13 The method of any one of aspects 7-12, wherein the fluid comprises water, organic solvent, blood, blood serum, or dialysis fluid, or a combination thereof.
  • Aspect 14 The method of any one of aspects 7-13, wherein the styrenic
  • (co)polymer resin comprises a polymeric phenylglyoxal resin.
  • Aspect 15 The method of aspect 14, wherein the polymeric phenylglyoxal resin comprises glyoxal or gly oxalic acid units.
  • Aspect 16 The method of aspect 15, wherein the glyoxal or glyoxalic acid units are attached to meta- and/or para-positions of the polymer chain.
  • Aspect 17 The method of any one of aspects 7-16, wherein the styrenic
  • (co)polymer resin comprises a functional group including aldehydes, keto-aldehydes, or keto- carboxylates, or a combination thereof.
  • a polymer sorbent for use in material removal from a fluid comprising a styrenic (co)polymer resin having at least one glyoxal group with a loading of up to about 3 mmol/g.
  • Aspect 19 The polymer sorbent of aspect 18, wherein the polymer sorbent exhibits a mean pore size of 14 to 1000 Angstrom, a pore volume of 0.3 to 1.85 mL/g and a surface area by nitrogen surface area (NSA) of 150 -1 100 m 2 /g.
  • NSA nitrogen surface area
  • Aspect 20 The polymer sorbent of any one of aspects 18-19, wherein the styrenic (co)polymer resin comprises a polymeric phenylglyoxal resin, and wherein the (co)polymer styrenic resin comprises a functional group including aldehydes, keto-aldehydes, or keto- carboxylates, or a combination thereof.
  • a 100 mL scintillation vial equipped with a magnetic stirring bar was charged with 20 ml of acetic anhydride and 6 g of styrenic resin having a surface area of 725 square meters per gram (m 2 /g) and an average pore diameter of 50 A.
  • the mixture was cooled to 0 degrees Celsius (°C) and hydrogen peroxide (2 mL, 40% aqueous solution) was added and the reaction mixture was stirred at 10-15 °C for 8 hours.
  • the resultant resin was filtered, washed with acetic acid in two 100 mL portions, washed with methanol (100 mL) and dried in a vacuum oven at 70 °C overnight.
  • the resin had an infrared (IR) frequency of 1250 inverse centimeters (cm -1 ) and 870 cm "1 as determined by an FTIR analysis.
  • Example 5 Ketoaldehyde Functionalized Styrenic (co)Polymer from 1- Hydroxy-2-bromoethyl Substituted (co)Polymer
  • a 100 ml vial equipped with a magnetic stirring bar was charged with 2 g of the resin of Example 3, suspended in 40 ml of dimethylsulfoxide.
  • Sodium bicarbonate (1.68 g, 20 mmol) was added in a single portion to each vial.
  • the vials were capped and the contents stirred at 100 °C for six hours.
  • the resultant resin was filtered, washed with methanol in five 20 ml portions, and dried in a vacuum oven at 70 °C.
  • the resin had an IR frequency of 1850- 1590 cm "1 as determined by an FTIR analysis and a urea sorption capacity of 12.4 g/kg.
  • a 40 ml scintillation vial equipped with a magnetic stirring bar was charged with 2g styrenic resins in 20 ml chloroform.
  • a sample of 5.6 ml of bromine was dissolved in 80 ml chloroform to provide a 1.4 molar (M) bromine solution.
  • the bromine solution was added in one 4 ml portion to each scintillation vial.
  • the scintillation vials were capped and the contents stirred at room temperature for three 8 hour intervals for a total of 24 hours.
  • the resultant resin was filtered, washed with methanol in two 100 ml portions, and dried in a vacuum oven at 70 °C overnight.
  • the resin had a Br 2 content of 23.14 wt. %.
  • Example 6 resin A 100 ml vial equipped with a magnetic stirring bar was charged with 2 g of the Example 6 resin, suspended in 40 ml of dimethylsulfoxide. Sodium bicarbonate (1.68 g, 20 mmol) was added in a single portion to each vial. The vials were capped and the contents stirred at 100 °C for six hours. The resultant resin was filtered, washed with methanol in five 20 ml portions, and dried in a vacuum oven at 70 °C. The resin had an IR frequency of 1850-1590 cm "1 as determined by an FTIR analysis and a urea sorption capacity of 15.4 g/kg.
  • Example 8 Ketoaldehyde Functionalized Styrenic (co)Polymer from Styrenic Resin
  • a 40 ml scintillation vial equipped with a magnetic stirring bar was charged with polymer resin XAD-4 (approximately 5 mmol) in 20 ml of dimethylsulfoxide. Iodine (1 mmol, 0.25 g) and sodium bicarbonate (1.26 g, 15 mmol) were added in a single portion to each vial. The vials were capped and the contents stirred for eight hours at 110 °C. The vials were cooled to room temperature and the resultant resins were filtered, washed with two 100 ml portions of methanol, and dried in a vacuum oven at 70 °C. The resin had an IR frequency of 1850-1590 cm "1 as determined by an FTIR analysis and a urea sorption capacity of 18.2 g/kg.
  • reaction conditions e.g., component concentrations, desired solvents, solvent mixtures, temperatures, pressures and other reaction ranges and conditions that can be used to optimize the product purity and yield obtained from the described process. Only reasonable and routine experimentation will be required to optimize such process conditions.

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Abstract

L'invention concerne des procédés d'élimination de matière en mettant un fluide en contact avec un sorbant polymère dérivé d'un (co)polymère de divinyl-benzène. En particulier, un procédé d'élimination de matière à partir d'un fluide consiste à mettre le fluide en contact avec un sorbant polymère comprenant une résine de (co)polymère styrénique, le sorbant polymère présentant une taille de pore moyenne de 14 à 1000 angström, un volume de pore de 0,3 à 1,85 mL/g et une aire par surface d'azote (NSA) de 150 à 1100 m2/g. Dans certains aspects, un procédé d'élimination de matière à partir d'un fluide consiste à mettre le fluide en contact avec un sorbant polymère comprenant une résine de (co)polymère styrénique ayant au moins un groupe glyoxal avec une charge allant jusqu'à environ 3 mmol/g. Un sorbant polymère destiné à être utilisé dans l'élimination de matière à partir d'un fluide comprend une résine de (co)polymère styrénique ayant au moins un groupe glyoxal avec une charge allant jusqu'à environ 3 mmol/g.
PCT/US2017/034683 2016-05-27 2017-05-26 Sorbants polymères et leurs procédés de fabrication Ceased WO2017205743A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021099577A1 (fr) * 2019-11-22 2021-05-27 Stichting Voor De Technische Wetenschappen Compositions macromoléculaires pour la liaison de petites molécules

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US4012317A (en) * 1972-02-04 1977-03-15 Rhone-Poulenc S.A. Process for extracting urea from a solution with alkenylaromatic polymers with α-ketoalhydic groups
US20040171754A1 (en) * 2003-02-28 2004-09-02 Poss Mitchell J. Macromolecular ketoaldehydes

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Publication number Priority date Publication date Assignee Title
US3933753A (en) * 1972-02-04 1976-01-20 Rhone-Poulenc S.A. Alkenylaromatic polymers with α-ketoalhydic groups
US4012317A (en) * 1972-02-04 1977-03-15 Rhone-Poulenc S.A. Process for extracting urea from a solution with alkenylaromatic polymers with α-ketoalhydic groups
US20040171754A1 (en) * 2003-02-28 2004-09-02 Poss Mitchell J. Macromolecular ketoaldehydes

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021099577A1 (fr) * 2019-11-22 2021-05-27 Stichting Voor De Technische Wetenschappen Compositions macromoléculaires pour la liaison de petites molécules
CN115279802A (zh) * 2019-11-22 2022-11-01 德国科技术基金会 用于结合小分子的大分子组合物
CN115279802B (zh) * 2019-11-22 2024-04-12 德国科技术基金会 用于结合小分子的大分子组合物

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