WO2019209476A1 - Procédé d'épuisement d'un composant volatil d'un mélange à l'aide d'un copolymère sorbant et appareil pour mettre en œuvre ce procédé - Google Patents

Procédé d'épuisement d'un composant volatil d'un mélange à l'aide d'un copolymère sorbant et appareil pour mettre en œuvre ce procédé Download PDF

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Publication number
WO2019209476A1
WO2019209476A1 PCT/US2019/025471 US2019025471W WO2019209476A1 WO 2019209476 A1 WO2019209476 A1 WO 2019209476A1 US 2019025471 W US2019025471 W US 2019025471W WO 2019209476 A1 WO2019209476 A1 WO 2019209476A1
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Prior art keywords
copolymer
mixture
meth
volatile component
acrylate
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PCT/US2019/025471
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English (en)
Inventor
Dongchan Ahn
Aaron GREINER
James Thompson
Robert O. Huber
Kevin Wier
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Dow Silicones Corporation
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Publication of WO2019209476A1 publication Critical patent/WO2019209476A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
    • B01D53/0407—Constructional details of adsorbing systems
    • B01D53/0423—Beds in columns
    • 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
    • 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
    • B01J20/262—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon to carbon unsaturated bonds, e.g. obtained by polycondensation
    • 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
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/34—Regenerating or reactivating
    • B01J20/3425—Regenerating or reactivating of sorbents or filter aids comprising organic materials
    • 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
    • B01J20/34—Regenerating or reactivating
    • B01J20/345—Regenerating or reactivating using a particular desorbing compound or mixture
    • B01J20/3458—Regenerating or reactivating using a particular desorbing compound or mixture in the gas phase
    • 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
    • B01J20/34—Regenerating or reactivating
    • B01J20/345—Regenerating or reactivating using a particular desorbing compound or mixture
    • B01J20/3475—Regenerating or reactivating using a particular desorbing compound or mixture in the liquid phase
    • 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
    • B01J20/34—Regenerating or reactivating
    • B01J20/3483—Regenerating or reactivating by thermal treatment not covered by groups B01J20/3441 - B01J20/3475, e.g. by heating or cooling
    • 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
    • B01J20/34—Regenerating or reactivating
    • B01J20/3491—Regenerating or reactivating by pressure treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/20—Organic adsorbents
    • B01D2253/202—Polymeric adsorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/55—Compounds of silicon, phosphorus, germanium or arsenic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B01D2257/708—Volatile organic compounds V.O.C.'s
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/40—Further details for adsorption processes and devices
    • B01D2259/40083—Regeneration of adsorbents in processes other than pressure or temperature swing adsorption
    • B01D2259/40088—Regeneration of adsorbents in processes other than pressure or temperature swing adsorption by heating
    • B01D2259/4009—Regeneration of adsorbents in processes other than pressure or temperature swing adsorption by heating using hot gas
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/40—Further details for adsorption processes and devices
    • B01D2259/402—Further details for adsorption processes and devices using two beds

Definitions

  • a method for depleting a volatile component in a mixture comprises sorbing at least some of the volatile component by a copolymer of a (meth)acrylate-functional
  • volatile components such as volatile organic compounds (e.g ., aromatic hydrocarbons) or volatile polydiorganosiloxanes ⁇ e.g., cyclic polydialkylsiloxanes and/or linear polydialkylsiloxane oligomers
  • volatile organic compounds e.g ., aromatic hydrocarbons
  • volatile polydiorganosiloxanes e.g., cyclic polydialkylsiloxanes and/or linear polydialkylsiloxane oligomers
  • Porous solid adsorbents such as activated carbon or molecular sieves have been used for such purposes.
  • solid adsorbents rely upon adsorption into pores, they may suffer from the drawbacks of being subject to mass transfer limitations, requiring significant energy input for regeneration by desorption, and/or being prone to fouling and capillary condensation.
  • Silicone liquids have also been used for organosilicon species removal because they may be more readily regenerated, feature faster dynamics, and/or are less prone to fouling than porous solid adsorbents.
  • existing methods using silicone liquids in which the feed mixture to be treated is directly contacted with the silicone liquid may require additional liquid separation steps if any of the silicone liquid is entrained or carried over into the feed mixture or vice versa.
  • methods employing membrane separators have been used.
  • membrane separators suffer from the drawbacks that they may add equipment cost and be prone to fouling.
  • a method for depleting a volatile component in a mixture comprises sorbing at least some of the volatile component by a copolymer of a (meth)acrylate-functional
  • Figure 1 is an example of an apparatus that can be used for practicing the method described herein.
  • a method for depleting a volatile component in a mixture comprising the volatile component and at least one other component (which is distinct from the volatile component) forms a depleted mixture, which contains less of the volatile component than the mixture before practicing the method.
  • the method comprises:
  • the method may optionally further comprise: directing ( e.g ., to a desired location) one or both of the depleted mixture after step 1 ) and/or the desorbed volatile component after step 2).
  • step 1 method conditions (such as pressure and temperature) may be such that at least some of the volatile component is in the gas phase.
  • the conditions may be such that the mixture is heated.
  • the temperature for heating may be above the boiling point of the volatile component.
  • the temperature may be selected such that all of the volatile component is in the gas phase.
  • the method may further comprise vaporizing the mixture before step 1 ).
  • the mixture may be vaporized by any convenient means such as heating e.g., above the boiling temperature of the mixture.
  • the mixture may be contacted with the copolymer for an amount of time sufficient to allow the copolymer to sorb at least some of the volatile component from the mixture.
  • the mixture may be contacted directly with the copolymer in step 1 ), i.e., without the use of a membrane.
  • the mixture may be a liquid.
  • the mixture may be in the gas phase during step 1 ).
  • the volatile compound may be adsorbed on the surface of the copolymer, absorbed into the bulk of the copolymer, or both.
  • Step 2) of the method may be performed to regenerate the copolymer.
  • sorption rate may decrease and/or the copolymer may swell. It is desirable to desorb at least some of the volatile component from the copolymer so that the copolymer can be regenerated and reused.
  • the volatile component may optionally be recovered.
  • Regenerating the copolymer may be performed by stopping step 1 ) of the method and regenerating the copolymer, then repeating step 1 ) after step 2). Alternatively, the mixture may be re-routed to continue step 1 ) while performing step 2) on the enriched copolymer. An example of this method is shown below in Figure 1.
  • Regenerating the enriched copolymer may be performed by any convenient means, such as heating, optionally with sweeping by a dry air gas stream or inert gas stream in contact with the enriched copolymer. It is also possible to desorb at lower temperature (e.g ., room temperature of 25°C or less) by exposing the enriched copolymer to a reduced pressure ⁇ e.g., less than atmospheric pressure), and/or contacting the enriched copolymer with a sweep stream (which has been depleted of the volatile component).
  • a reduced pressure e.g., less than atmospheric pressure
  • step 2) of the method may be performed by heating the enriched copolymer at 50°C to 150°C, alternatively 80°C, while reducing pressure below 760 mmFIg, e.g., to 1 to 10 mmFIg for 5 minutes to 10 hours.
  • exposing the enriched copolymer to solvent with or without swelling the enriched copolymer may also be used to regenerate the enriched copolymer.
  • liquid extraction e.g., solvent or supercritical fluid extraction may be used to regenerate the enriched copolymer.
  • the method further comprises step 3), in which the regenerated copolymer may be reused to repeat step 1 ).
  • the copolymer used in repeating step 1 ) may be all regenerated copolymer; alternatively, a portion of the copolymer used to repeat step 1 ) may be regenerated copolymer, with the balance being fresh copolymer.
  • the method may further comprise one or more additional steps selected from the group consisting of: 4) directing the depleted mixture during and/or after step 1 ), and 5) directing the desorbed volatile component during and/or after step 2).
  • the method may further comprise directing to a desired location one or both of i) the depleted mixture during and/or after step 1 ) and ii) the desorbed volatile component during and/or after step 2).
  • Directing may be performed by any convenient means such as feeding the depleted mixture through a channel such as a pipe, duct, or other conduit to the desired location, such as a recovery operation.
  • the recovery operation may include cooling apparatus, such as a heat exchanger or condenser.
  • the recovery operation may include a collection apparatus such as a tank, reservoir, or other container, for storing the depleted mixture and/or a tank for storing the organosilicon
  • the depleted mixture may be directed to a different operation, such as when the depleted mixture will be used as a reactant.
  • the volatile component may be directed to a different operation, such as when the volatile component will be used as a reactant or a solvent.
  • one or both of the depleted mixture and the volatile component may be directed to collection containers.
  • the depleted mixture is a purified mixture that may be recovered and/or directed by any convenient means, such as feeding the depleted mixture through a channel such as a pipe, duct, or other conduit to a heat exchanger or condenser and cooling therein, when the mixture was heated and/or in the gas phase in step 1 ).
  • recovering the purified mixture may comprise feeding the purified mixture from the condenser (described above) to a different reactor where the purified mixture is used as a reactant or solvent.
  • the mixture includes an organosilicon component, such as a cyclic polyorganosiloxane, as the volatile component and a polyorganosiloxane (distinct from the cyclic polyorganosiloxane) as at least one other component in the mixture.
  • an organosilicon component such as a cyclic polyorganosiloxane
  • a polyorganosiloxane distinct from the cyclic polyorganosiloxane
  • This purified mixture may be directed to a collection container to be tested, packaged and/or sold, or the purified mixture may be directed to a different process and used as a reactant or other ingredient in making a polyorganosiloxane containing product.
  • the purified water may be directed by feeding ( e.g ., pumping) the purified water to a process to test, or to the environment.
  • the purified air may be directed blowing or pumping via ductwork into an air handling system or a ventilation system.
  • conduit through which the one or both of the depleted mixture during and/or after step 1 ) and the desorbed volatile component during and/or after step 2) is directed may also contain in-line monitoring testing equipment, such as gauges, meters and sensors, along with conveying equipment such as pumps, fans, blowers, extruders, compounders, and valves.
  • in-line monitoring testing equipment such as gauges, meters and sensors
  • conveying equipment such as pumps, fans, blowers, extruders, compounders, and valves.
  • the volatile component may be recovered by any convenient means.
  • the gas stream containing the volatile component may be directed through a condenser to recover the volatile component.
  • the volatile component may be directed to an apparatus for stripping, extracting, or distilling to remove the solvent.
  • directing the volatile component may comprise feeding the volatile component from the condenser (described above), or the solvent containing the volatile component, to a different reactor where the volatile component is used as a reactant or solvent.
  • the volatile component may be any species that is desirably removed from the mixture and that is distinct from one or more other components in the mixture.
  • the volatile component may be an organosilicon component or a volatile organic compound.
  • Organosilicon Component may be any organosilicon species that is desirably removed from the mixture.
  • the organosilicon component may have a vapor pressure of 0.1 mmHg at 70°C to 760 mmHg at 70°C, alternatively 1 mmHg at 70°C to 100 mmHg at 70°C, alternatively 4 mmHg at 70°C to 82 mmHg, and alternatively 17 mmHg at 70°C to 82 mmHg at 70°C.
  • the product formed by step 1 ) of the method is a depleted mixture, wherein said depleted mixture is free of the
  • organosilicon component or contains less of the organosilicon component than the mixture before step 1 ). “Free of” means that the depleted mixture contains none of the organosilicon component or an amount of the organosilicon component that is non-detectable by GC analysis.
  • the organosilicon component may be a cyclic polyorganosiloxane with a DP from 3 to 12, alternatively the organosilicon component may be a cyclic polydialkylsiloxane with an average DP of 4.
  • the cyclic polyorganosiloxane may be have formula (R 1 1 R 1 2 SiC>2/2)k’ where subscript k is 3 to 12, each R 1 1 is independently a monovalent hydrocarbon group or monovalent halogenated hydrocarbon group, and each R 1 2 is independently R 1 1 , OH, or H.
  • Suitable monovalent hydrocarbon groups for R 1 1 include alkyl, alkenyl, alkynyl, aryl, aralkyl, and carbocyclic groups.
  • Alkyl groups include branched or unbranched, saturated monovalent hydrocarbon groups, which are exemplified by, but not limited to, methyl, ethyl, propyl ( e.g ., iso propyl and/or n-propyl), butyl ⁇ e.g., isobutyl, n-butyl, tert-butyl, and/or sec-butyl), pentyl ⁇ e.g., isopentyl, neopentyl, and/or tert-pentyl); and hexyl, heptyl, octyl, nonyl, and decyl, as well as branched isomers thereof; and linear or branched saturated monovalent hydrocarbon groups of > 10 carbon atoms.
  • alkenyl group is a monovalent hydrocarbon group containing a double bond.
  • Suitable alkenyl groups are exemplified by, but not limited to, ethenyl, propenyl (e.g ., iso- propenyl and/or n-propenyl), butenyl (e.g., isobutenyl, n-butenyl, tert-butenyl, and/or sec- butenyl), pentenyl (e.g., isopentenyl, n-pentenyl, and/or tert-pentenyl); and hexenyl, heptenyl, octenyl, nonenyl, and decenyl, as well as such branched groups isomers thereof; and linear or branched hydrocarbon groups containing a double bond and having > 10 carbon atoms.
  • An alkynyl group is a monovalent hydrocarbon group containing a triple bond.
  • Suitable alkynyl groups are exemplified by, but not limited to, ethynyl, propynyl (e.g., iso-propynyl and/or n- propynyl), butynyl (e.g., isobutynyl, n-butynyl, tert-butynyl, and/or sec-butynyl), pentynyl (e.g., isopentynyl, n-pentynyl, and/or tert-pentynyl); and hexynyl, heptynyl, octynyl, nonynyl, and decynyl, as well as branched isomers thereof; and linear or branched hydrocarbon groups containing a triple bond and having > 10 carbon atoms.
  • Aryl groups include cyclic, fully unsaturated, hydrocarbon groups exemplified by, but not limited to, cyclopentadienyl, phenyl, anthracenyl, and naphthyl.
  • Monocyclic aryl groups may have 5 to 9 carbon atoms, alternatively 6 to 7 carbon atoms, and alternatively 5 to 6 carbon atoms.
  • Polycyclic aryl groups may have 10 to 17 carbon atoms, alternatively 10 to 14 carbon atoms, and alternatively 12 to 14 carbon atoms.
  • Aralkyl group means an alkyl group having a pendant and/or terminal aryl group or an aryl group having a pendant alkyl group.
  • Exemplary aralkyl groups include tolyl, xylyl, benzyl, phenylethyl, phenyl propyl, and phenyl butyl.
  • Carbocyclic groups are hydrocarbon rings.
  • Carbocyclic groups may be monocyclic or alternatively may have fused, bridged, or spiro polycyclic rings.
  • Monocyclic carbocyclic groups may have 3 to 9 carbon atoms, alternatively 4 to 7 carbon atoms, and alternatively 5 to 6 carbon atoms.
  • Polycyclic carbocyclic groups may have 7 to 17 carbon atoms, alternatively 7 to 14 carbon atoms, and alternatively 9 to 10 carbon atoms.
  • Carbocycles may be saturated or partially unsaturated.
  • the carbocyclic group may be a cycloalkyl group, which is saturated. Suitable monocyclic cycloalkyl groups are exemplified by cyclobutyl, cyclopentyl, and cyclohexyl.
  • Suitable monovalent halogenated hydrocarbon groups refer to a monovalent hydrocarbon group where one or more hydrogen atoms bonded to a carbon atom have been formally replaced with a halogen atom.
  • Halogenated hydrocarbon groups include haloalkyl groups, halogenated carbocyclic groups, and haloalkenyl groups.
  • Haloalkyl groups include fluorinated alkyl groups such as trifluoromethyl (CF3), fluoromethyl, trifluoroethyl, 2-fluoropropyl, 3,3,3-trifluoropropyl, 4,4,4-trifluorobutyl, 4,4,4,3,3-pentafluorobutyl, 5,5,5,4,4,3,3-heptafluoropentyl, 6,6,6,5,5,4,4,3,3-nonafluorohexyl, and 8, 8, 8, 7, 7- pentafluorooctyl; and chlorinated alkyl groups such as chloromethyl and 3-chloropropyl.
  • fluorinated alkyl groups such as trifluoromethyl (CF3), fluoromethyl, trifluoroethyl, 2-fluoropropyl, 3,3,3-trifluoropropyl, 4,4,4-trifluorobutyl, 4,4,4,3,3-pentafluorobutyl, 5,5,5,
  • Halogenated carbocyclic groups include fluorinated cycloalkyl groups such as 2,2- difluorocyclopropyl, 2,3-difluorocyclobutyl, 3,4-difluorocyclohexyl, and 3,4-difluoro-5- methylcycloheptyl; and chlorinated cycloalkyl groups such as 2,2-dichlorocyclopropyl, 2,3- dichlorocyclopentyl.
  • Haloalkenyl groups include chloroallyl.
  • the organosilicon component may be a cyclic polydiorganohydrogensiloxane.
  • the organosilicon component may comprise (i) hexamethylcyclotrisiloxane (D3), (ii) octamethylcyclotetrasiloxane (D4), (iii) tetramethylcyclotetrasiloxane (D4 H ), (iv) tetramethyltetravinyl cyclotetrasiloxane (D4 Vi ), (v) tetramethyltetraphenylcyclotetrasiloxane (D4 Ph ), (vi) decamethylcyclopentasiloxane (D5), (vii) pentamethylcyclopentasiloxane (D5 H ), (viii) pentamethylpentavinylcyclopentasiloxane (D5 Vi ),
  • the organosilicon component may be selected from D3, D4, D5, Dg, and combinations of two or more of D3, D4, D5, and Dg.
  • the organosilicon component may be D4.
  • the organosilicon component may be an organosilane or
  • the organosilane may have formula: R 1 v SiR 2 (4_ v ), where each R 1 is independently a monovalent hydrocarbon group or a monovalent halogenated hydrocarbon group, each R 2 is independently a hydrogen atom, a halogen atom, a
  • hydrocarbonoxy group such as alkoxy, an amino functional group, an acyloxy group such as acetoxy, an epoxy-functional group, a methacrylate functional group, an oximo functional group such as ketoxime, an acrylate functional group, a polyol functional group such as polyether, a thiol functional group; and subscript v is 0 to 4, alternatively 0 to 3.
  • Suitable monovalent hydrocarbon groups for R 1 are as described and exemplified above for R 1 1 .
  • Suitable halogen atoms for R 2 include F, Cl, Br, or I; alternatively F, Cl, or Br; alternatively Cl or Br; alternatively Cl; alternatively Br.
  • Suitable hydrocarbonoxy groups for R 2 have formula OR 2 , where R 2 is a monovalent hydrocarbon group as described above for R ⁇ 1 .
  • Subscript v is 1 to 4, alternatively 1 to 3, and alternatively 1 to 2.
  • Exemplary organosilanes include trimethylsilane, vinyltrimethylsilane, allyltrimethylsilane, dimethyldimethoxysilane, and/or methyltrimethoxysilane.
  • the organosilicon compound to be removed from the mixture using the method described above may be a volatile polyorganosiloxane.
  • the volatile polyorganosiloxane may be linear or branched. Examples include polydimethylsiloxane oligomers and polymers.
  • the volatile polyorganosiloxane may have unit formula
  • R 4 is a hydrogen atom, OH, or R 1 1 as described and exemplified above
  • subscript w is > 0, subscript x 3
  • subscript y is 3
  • subscript z is 3 0, with the proviso that a quantity (w + x + y + z) is ⁇ 14.
  • y may be 0.
  • z may be 0.
  • w may be 2 and x may be 0 to 12, alternatively 0 to 2.
  • Exemplary volatile polyorganosiloxanes may include those of formulae:
  • each R 4 may be independently a hydrogen atom, a methyl group, a vinyl group, or a phenyl group. Alternatively, each R 4 may be methyl.
  • Such volatile polyorganosiloxanes include hexamethyldisiloxane, octamethyltrisiloxane,
  • the organosilicon compound to be removed from the mixture may be a neopentamer, of formula Si(OSiR 4 3)4, where R 4 is as described above.
  • exemplary neopentamers include Si[OSi(CH3)3]4,
  • VOC volatile organic compound
  • the VOC may be (i) an aldehyde, such as formaldehyde, acetaldehyde, butyraldehyde or benzaldehyde, (ii) an aromatic compound, (iii) an alkane or cycloalkane, (iv) an alkene, (v) an alkyne, (vi) a ketone such as acetone, 4-heptanone, 3-methyl-4-heptanone, benzophenone, methylvinylketone (vii) an ester such as butyl acetate, butyl butyrate, butyl propionate, hexyl butyrate or (viii) an alcohol such as methanol, ethanol, 1 -propanol, 2-propanol, 1 -butanol, or t- butanol or a combination of two or more of (i), (ii), (
  • aromatic compounds include aromatic hydrocarbons such as toluene, benzene, ethylbenzene, 1 - methylethyl benzene, propylbenzene, and/or xylenes.
  • alkanes include methane, ethane, propane, butane pentane, hexanes, heptanes, octane, and/or isomers thereof, cyclohexane, and/or combinations thereof.
  • alkenes include ethylene, propene, butene, pentene and/or isomers thereof and/or combinations thereof.
  • VOC may be an organic solvent.
  • the organic solvent can be an alcohol such as methanol, ethanol, isopropanol, butanol, or n-propanol; a ketone such as acetone, methylethyl ketone, or methyl isobutyl ketone; an aromatic hydrocarbon such as benzene, toluene, or xylene; an ether such as diethyl ether or n-butyl ether, a glycol ether such as propylene glycol methyl ether, dipropylene glycol methyl ether, propylene glycol n-butyl ether, propylene glycol n-propyl ether, or ethylene glycol n-butyl ether, a halogenated hydrocarbon such as dichloromethane, 1 ,1 ,1 -trichloroethane or methylene chloride; chloroform; dimethyl sulfoxide; dimethyl formamide
  • halogenated volatile organic compounds such as halogenated hydrocarbons, e.g., chlorofluorocarbons such as Freon, or a combination of two or more thereof.
  • the VOC may be an organic monomer used in polymerization or crosslinking such as ethylene, propylene, butene, isobutene, 1 ,3-butadiene, isoprene, vinyl chloride, vinyl acetate, vinyl fluoride, styrene, acrylonitrile, ethylene oxide, propylene oxide, acrylate and methacrylate monomers such as acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, butyl acrylate, 2-ethylhexyl acrylate, cyanoacrylates, isobornyl acrylate, tetrafluoroethylene, glycidyl methacrylate, tetrahydrofurfuryl methacrylate, isocyanates, such as methylene diphenyl diisocyanates, toluene diisocyanate, phosgene, amine compounds such as ethylene diamine, epoxy compounds such as an oligo
  • the VOC may be an organic noxious or odor causing compound such as organosulfur compound.
  • the mixture used in step 1 ) of the method described above may be any mixture from which it is desirable to remove some or all of the volatile component as described above.
  • the mixture comprises the volatile component and at least one other component.
  • the volatile component may have a vapor pressure less than a vapor pressure of the at least one other component in the mixture.
  • the volatile component may be distinguished from the at least one other component in the mixture by virtue of relative vapor pressures or differences in solubility of the volatile component, and solubility of the at least one other component, in the copolymer.
  • a species such as a linear polydimethylsiloxane may be a volatile component when the at least one other component in the mixture has a lower vapor pressure than the linear polydimethylsiloxane.
  • the same linear polydimethylsiloxane may be the at least one other component in the mixture when the volatile component is, for example, an organosiloxane resin having a vapor pressure higher than the vapor pressure of the linear polydimethylsiloxane.
  • the difference in vapor pressure (where the volatile component has a higher vapor pressure than the at least one other component in the mixture) or differences in solubility of the volatile component, and solubility of the at least one other component in the mixture, in the copolymer allow the volatile component in vapor phase to be preferentially removed from the mixture and be sorbed by the copolymer.
  • the at least one other component may be a relatively non-volatile polyorganosiloxane (e.g ., less volatile than the polyorganosiloxane described above for the volatile component).
  • the non-volatile polyorganosiloxane may have unit formula:
  • R 4 is as described above, D is an oxygen atom or a divalent hydrocarbon group, subscript p > 0, subscript q is > 0, subscript r is 3 0, subscript s is 3 0, with the proviso that a quantity (p + q + r + s) > 14.
  • Each D is an oxygen atom or a divalent group linking the silicon atom of one unit with another silicon atom in another unit.
  • D when D is the divalent linking group, D may be independently selected from divalent hydrocarbon groups containing 2 to 30 carbon atoms, divalent acrylate functional hydrocarbon groups containing 2 to 30 carbon atoms, and/or divalent methacrylate functional hydrocarbon groups containing 2 to 30 carbon atoms.
  • suitable divalent hydrocarbon groups include alkylene groups such as -C2H4- including ethylene -CH2- CH2- and a group of formula -CH(CH3)-, propylene (including isopropylene and n-propylene), and butylene (including n-butylene, t-butylene and isobutylene); and pentylene, hexylene, heptylene, octylene, and branched and linear isomers thereof; arylene groups such as
  • phenylene and alkylaralkylene groups such as: or
  • divalent organofunctional hydrocarbon groups include divalent bisphenol A derivatives, acrylate-functional alkylene groups and methacrylate-functional alkylene groups.
  • each group D may be ethylene, propylene, butylene or hexylene.
  • each instance of group D may be ethylene or propylene.
  • Non-volatile polyorganosiloxanes are known in the art and are commercially available. Suitable non-volatile polyorganosiloxanes are exemplified by, but not limited to, non volatile polydimethylsiloxanes.
  • non-volatile polydimethylsiloxanes include DOWSIL® 200 Fluids, which are commercially available from Dow Silicones Corporation of Midland, Michigan, U.S.A. and may have viscosity ranging from 10 cSt to 100,000 cSt, alternatively 20 cSt to 50,000 cSt, alternatively 50 cSt to 100,000 cSt, alternatively 50 cSt to 50,000 cSt, and alternatively 12,500 to 60,000 cSt.
  • DOWSIL® 200 Fluids which are commercially available from Dow Silicones Corporation of Midland, Michigan, U.S.A. and may have viscosity ranging from 10 cSt to 100,000 cSt, alternatively 20 cSt to 50,000 cSt, alternatively 50 cSt to 100,000 cSt, alternatively 50 cSt to 50,000 cSt, and alternatively 12,500 to 60,000 cSt.
  • polyorganosiloxane has a vapor pressure lower than vapor pressure of the non-volatile polyorganosiloxane at the same temperature.
  • the non-volatile polyorganosiloxane and the volatile polyorganosiloxane will differ from one another in at least one property such as molecular weight, degree of polymerization, and selections for R 4 groups.
  • the non-volatile polyorganosiloxane may be a noncyclic polyorganosiloxane polymer and/or copolymer.
  • the method may be used to purify polyorganosiloxane intermediates and products such as linear and/or branched polydiorganosiloxane polymers and/or copolymers.
  • low or non-detectable (by GC) content of cyclic polydialkylsiloxanes is desired by customers, particularly in the beauty and healthcare industries.
  • Examples of such polydiorganosiloxane polymers and copolymers may have formulae (/) or (II), where formula (/) is R 6 3 SiO(R 6 2 SiO) k (R 6 HSiO) m SiR 6 3, formula (II) is R 6 2 HSiO(R 6 2 SiO) n (R 6 HSiO) 0 SiR 6 2 H, or a combination thereof.
  • subscript k has an average value ranging from 1 to 2000
  • subscript m has an average value ranging from 0 to 2000
  • subscript n has an average value ranging from 1 to 2000
  • subscript o has an average value ranging from 0 to 2000.
  • Each R 6 is independently a monovalent organic group.
  • the monovalent organic group may be a monovalent hydrocarbon group or a monovalent halogenated hydrocarbon group as described and exemplified above for R 1 1 .
  • the monovalent organic group may be a hydrocarbon group substituted with an oxygen-atom, such as, alkoxy groups, aryloxy groups, aralkyloxy groups, oxo(carbonyl) groups, carboxyl groups including carboxylic acids,
  • the monovalent organic group may be a hydrocarbon group substituted with a sulfur atom, such as thiol-functional groups, alkyl and aryl sulfide groups, sulfoxide-functional groups, sulfone functional groups, sulfonyl functional groups, and sulfonamide functional groups.
  • the monovalent organic group may be a hydrocarbon group substituted with a nitrogen atom such as amines, hydroxylamines, nitriles, nitro groups, N-oxides, hydrazides, azides, and enamines.
  • the monovalent organic group may be a hydrocarbon group substituted with another heteroatom-containing groups.
  • Non-limiting examples of atoms and groups substituted on a monovalent hydrocarbon group to form the monovalent organic groups include F, Cl, Br, I, OR', 0C(0)N(R')2, CN, NO,
  • R’ can be hydrogen or a carbon-based moiety, and wherein the carbon- based moiety can itself be further substituted; for example, wherein R’ can be hydrogen, alkyl, acyl, cycloalkyl, aryl, aralkyl, heterocyclic, heteroaryl, or heteroarylalkyl, wherein any alkyl, acyl,
  • organic groups include linear and/or branched groups such as alkyl groups, fully or partially halogen-substituted haloalkyl groups, alkenyl groups, alkynyl groups, aromatic groups, acrylate functional groups, and methacrylate functional groups; and other organic functional groups such as ether groups, cyanate ester groups, ester groups, carboxylate salt groups, mercapto groups, sulfide groups, azide groups, phosphonate groups, phosphine groups, masked isocyano groups, and hydroxyl groups.
  • organic groups include linear and/or branched groups such as alkyl groups, fully or partially halogen-substituted haloalkyl groups, alkenyl groups, alkynyl groups, aromatic groups, acrylate functional groups, and methacrylate functional groups; and other organic functional groups such as ether groups, cyanate ester groups, ester groups, carboxylate salt groups, mercapto groups, sulfide groups, azide
  • organic groups include, but are not limited to, alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, s-butyl, and t-butyl groups, acrylate functional groups such as acryloyloxypropyl groups and methacryloyloxypropyl groups; alkenyl groups such as vinyl, allyl, and butenyl groups; alkynyl groups such as ethynyl and propynyl groups; aromatic groups such as phenyl, tolyl, and xylyl groups; cyanoalkyl groups such as cyanoethyl and cyanopropyl groups; halogenated hydrocarbon groups such as 3,3,3-trifluoropropyl, 3-chloropropyl, dichlorophenyl, and 6,6,6,5,5,4,4,3,3-nonafluorohexyl groups; alkenyloxypoly(oxyalkylene) groups such as methyl
  • Polyorganosiloxanes in the mixture to be purified are exemplified by: a) trimethylsiloxy- terminated polydimethylsiloxane, b) trimethylsiloxy-terminated
  • polymethylhydrogensiloxane h) hydroxy-terminated polydimethylsiloxane, i) hydroxy-terminated poly(dimethylsiloxane/methylvinylsiloxane), j) hydroxy-terminated
  • the non-volatile polyorganosiloxane in the mixture to be purified may comprise a polyorganosiloxane resin, such as an MQ resin, an MT resin, a DT resin, an MTQ resin, an MDT resin, and/or a silsesquioxane resin.
  • a polyorganosiloxane resin such as an MQ resin, an MT resin, a DT resin, an MTQ resin, an MDT resin, and/or a silsesquioxane resin.
  • An MQ resin may consist essentially of R 6 3SiO-
  • /2 units and R 6 Si03/2 units; an MTQ resin may consist essentially of R 6 3SiO-
  • the resin may contain an average of 3 to 30 mole percent of functional substituents, such as hydrogen atoms, or groups such as hydroxyl, hydrolyzable, or aliphatically unsaturated organic groups.
  • the aliphatically unsaturated organic groups may be alkenyl groups, alkynyl groups, or a combination thereof.
  • the mole percent of functional substituents in the resin is the ratio of the number of moles of functional substituent-containing siloxane units in the resin to the total number of moles of siloxane units in the resin, multiplied by 100.
  • resin may be prepared by the silica hydrosol capping process of Daudt, et al. and optionally by treated with an endblocking reagent.
  • the method of Daudt et al. is disclosed in U.S. Patent 2,676,182. Briefly stated, the method of Daudt, et al. involves reacting a silica hydrosol under acidic conditions with a hydrolyzable triorganosilane such as trimethylchlorosilane, a siloxane such as
  • the resulting resins generally contain from 2 to 5 percent by weight of hydroxyl groups.
  • the resin which may contain less than 2 % of silicon-bonded hydroxyl groups, may be prepared by reacting the product of Daudt, et al. with a functional substituent-containing endblocking agent and/or an endblocking agent free of functional substituents, in an amount sufficient to provide from 3 to 30 mole percent of functional substituents in the final
  • endblocking agents include, but are not limited to, silazanes, siloxanes, and silanes. Suitable endblocking agents are known in the art and exemplified in U.S. Patents 4,584,355; 4,591 ,622; and 4,585,836. A single endblocking agent or a mixture of such agents may be used to prepare the resin.
  • the mixture may be a process gas or vapor stream.
  • examples include mixed overhead vapor streams from reactors, such as those used to polymerize, copolymerize or functionalize polyorganosiloxanes, those used to polymerize, copolymerize or functionalize organic polymers such as polyacrylates and polymethacrylates, as well as air streams and exhaust streams containing residual volatile siloxanes such as landfill gas.
  • types of reactions include hydrolysis, condensation, hydrosilylation, epoxidation, alkoxylation, trans esterification, trans-alcoholysis, radical polymerization, anionic or cationic polymerization.
  • Other examples of process gas streams include combustion exhaust from power plants, engines, heaters and furnaces.
  • the mixture may be a process liquid stream. Examples include wastewater or an emulsion such as a silicone emulsion containing residual volatile
  • the method may be used in various applications, for example, to remove VOCs from process vapor streams.
  • the method described herein may be used to reduce the amount of cyclic polydiorganosiloxanes (as described above), e.g., cyclic polydialkylsiloxanes in mixtures such as non-volatile polyorganosiloxanes (as described above), noncyclic polydiorganosiloxanes, process gas effluent, and/or process wastewater.
  • the method described herein may be use to selectively remove a organosilicon component, while leaving behind a desired organosilicon component in the depleted mixture.
  • the solubility of one organosilicon component in the copolymer may be higher than solubility of a second organosilicon component having a higher vapor pressure.
  • a silicone emulsion which contains water vapor and cyclic polyorganosiloxanes, such as D4 and D5
  • the method described herein may be used to remove an organosilicon component from a mixture comprising the organosilicon component and at least one other component.
  • This method comprises:
  • the organosilicon component may be a volatile contaminant.
  • the volatile contaminant may comprise a cyclic polyorganosiloxane with a degree of polymerization from 3 to 12 as described above.
  • the at least one other component in the mixture may comprise a linear polyorganosiloxane.
  • the copolymer may be a reaction product of a mono- (meth)acrylate terminated polyorganosiloxane and an organic (meth)acrylate compound. This embodiment of the method may be used to remove D4 from various mixtures, including but not limited to linear polyorganosiloxanes.
  • the method described herein may be used to remove a VOC from a mixture comprising the VOC component and at least one other component. This method comprises:
  • the VOC may be an aromatic hydrocarbon such as toluene.
  • the copolymer may be a reaction product of a mono-(meth)acrylate terminated polyorganosiloxane and an organic (meth)acrylate compound.
  • Copolymer A copolymer of a (meth)acrylate-functional polydiorganosiloxane and an organic (meth)acrylic compound (copolymer) is useful as the sorbent in the method described above.
  • the copolymer may be a linear, cyclic, branched, hyperbranched or crosslinked to form a network.
  • the copolymer may be prepared by a method comprising radical polymerization by methods known in the art, such as that disclosed in U.S. Patents 9,624,334 or 5,998,498; PCT Publication WO2010/091001 ; Canadian Patent CA2386659C; or by practicing such a method but varying appropriate starting materials.
  • the copolymer useful in the method described above may be prepared by a method comprising:
  • starting materials comprising: A) a radical initiator (e.g ., an organoboron compound capable of forming free radical generating species, an azo compound, a persulphate compound, or an organic peroxide, as described below), B) a (meth)acryloxy-functional polyorganosiloxane, C) a radical polymerizable organic compound ⁇ e.g., an organic radical initiator (e.g ., an organoboron compound capable of forming free radical generating species, an azo compound, a persulphate compound, or an organic peroxide, as described below), B) a (meth)acryloxy-functional polyorganosiloxane, C) a radical polymerizable organic compound ⁇ e.g., an organic radical initiator (e.g ., an organoboron compound capable of forming free radical generating species, an azo compound, a persulphate compound, or an organic peroxide, as described below), B) a (meth)acryloxy-functional poly
  • Starting material A) the organoboron compound capable of forming free radical generating species.
  • Starting material A) may be selected from the group consisting of: A1 ) an organoborane - organonitrogen compound complex, A2) an organoborate containing at least one B-C bond, and A3) both A1 ) the organoborane - organonitrogen compound complex and A2) the organoborate containing at least one B-C bond.
  • the organoboron compound may be air stable.
  • the organoborane - organonitrogen compound complex may be an organoborane - amine complex, such as those disclosed in U.S. Patent 6,706,831 and U.S. Patent 8,097,689 at col. 10, line 39 - col. 12, line 35.
  • the organoborane - organonitrogen compound complex may have formula:
  • each R*- is independently an alkyl group of 1 to 12 carbon atoms, a cycloalkyl group of 3 to 12 carbon atoms, an alkylaryl group, an organosilane group such as an alkylsilane group or an arylsilane group, an organosiloxane group such as alkyl siloxane or arylsiloxane; and each R A is a primary amine-functional compound, a secondary amine-functional compound, or an amide- functional compound.
  • Each R L is covalently bonded to the boron atom, and R A forms a complex with boron. (The arrow in the formula represents a coordination, not a covalent bond.)
  • Alkyl groups and cycloalkyl groups suitable for R L are defined hereinbelow.
  • Suitable alkyl groups include ethyl, propyl and butyl.
  • Suitable compounds for R A include hydrocarbylene diamines such as 1 ,3-propylene diamine and isophorone diamine; alkoxyalkyl amines such as 3-methoxypropyl amine; amino-functional alkoxysilanes such as 3-aminopropyltriethoxysilane.
  • each subscript xx is 1 and each subscript yy is 1.
  • each subscript xx is 1.3 and each subscript yy is 1.
  • the organoborane - organonitrogen compound complex may be selected from the group consisting of i) tri-n-butyl borane complex with isophorone diamine; ii) tri-n-butyl borane complex with 1 ,3-propylene diamine; iii) tri-n-butyl borane complex with 3-methoxypropyl amine; iv) triethylborane complex with isophorone diamine; v) triethylborane complex with 1 ,3- propylene diamine; vi) triethylborane complex with 3-methoxypropyl amine; vii) tri-isobutyl borane complex with isophorone diamine; viii) tri-isobutyl borane complex with 1 ,3-propylene diamine; ix) tri-isobutyl borane complex with 3-methoxypropylamine; x) tri-n-butylboran
  • the organoborate containing at least one B-C bond can be an amido-borate.
  • amido - borate may have formula , where R A and R L are as described above, R A is bonded to the boron atom via a covalent bond or an ionic bond, and M is a cation. M may be a metal ion or a quaternary ammonium ion.
  • Exemplary amido - borates are exemplified by those disclosed, for example, in U.S. Patent 7,524,907 at col. 6, line 50 to col.
  • the radical initiator may be an azo compound, a persulphate compound, or an organic peroxide.
  • the radical initiator may be a solid or liquid in its neat form and may be oil soluble, water soluble or have some level of solubility in either oil or water.
  • Azo compounds are exemplified by azobisisobutyronitrile, 4,4’-azobis(4-cyanovaleric acid), 1 ,T- azobis(cyclohexane carbonitrile), 2,2’-azobis(2-methylpropionamide)dihydrochloride, and 2,2’- azobis(2-methylpropionitrile), and 2,2’-azodi(2-methylbutyronitrile).
  • Persulphate compounds useful as initiators include sodium, potassium, or ammonium persulphate or combinations thereof.
  • Organic peroxides are exemplified by benzoyl peroxide; tert-butyl hydroperoxide; tert- butyl peracetate; cumene hydroperoxide; 2,5-di(tert-butylperoxy)-2,5-dimetyl-3-hexyne; dicumyl peroxide; and 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane.
  • Organic peroxides are examples of organic peroxides.
  • the organic peroxides may be used with a catalyst or accelerant to reduce the temperature of initiation.
  • redox catalysts such as sodium metabisulphite, sodium bisulfite, sodium formaldehyde sulfoxylate, isoascorbic acid; transition metal chelate complexes including cobalt (II) or (III), bismuth, or iron chelate complexes such as, for example, dioxime complexes of cobalt (II), cobalt (II) porphyrin complexes, or cobalt (II) chelates of vicinal iminohydroxyimino compounds, dihydroxyimino compounds, diazadihydroxy-iminodialkyldecadienes, or diazadihydroxyiminodialkylundecadienes; or amine compounds such as triethyl amine, N,N- trimethylaniline, N,N-p-dimethyl toluidine, or combinations
  • Starting material B) is a (meth)acryloxy-functional polyorganosiloxane.
  • (meth)acryloxy-functional polyorganosiloxane has at least one (meth)acryloxy-functional group per molecule and may be linear, branched, hyperbranched or resinous; alternatively
  • the (meth)acryloxy-functional group may be located at one or more terminal positions, one or more pendant positions, or in both terminal and pendant positions.
  • Exemplary (meth)acryloxy-functional polyorganosiloxanes may have
  • each R E is independently selected from the group consisting of H
  • Each R M is a monovalent hydrocarbon group or a monovalent halogenated hydrocarbon group, as described and exemplified above for R 1 1 .
  • Each R D is a divalent hydrocarbon group, as described and exemplified above for D. Alternatively, each R D is selected from the group consisting of -CH2-,
  • Subscript b is 0 to 10,000, alternatively 1 to 8,000, alternatively and alternatively 2 to 1 ,000, alternatively 3 to 500, alternatively 4 to 100, alternatively 5 to 65.
  • the linear (meth)acryloxy-functional polyorganosiloxane may be a
  • polydimethylsiloxane terminated at both ends with a (meth)acryloxy-functional,dimethylsiloxy group.
  • the linear (meth)acryloxy-functional polyorganosiloxane may be a polydimethylsiloxane terminated at one end with the (meth)acryloxy-functional,dimethylsiloxy group and at the other end with a trimethylsiloxy group.
  • methacryloxypropyl terminated polydimethylsiloxanes such as a mono methacryloxypropyl terminated
  • polydimethylsiloxane having an average degrees of polymerization from 5 to 65 or average Mn of 1 ,000 g/mol to 10,000 g/mol, alternatively 4,000 g/mol to 9,000 g/mol g/mol; and a,w- methacryloxypropyldimethylsiloxy- terminated polydimethylsiloxane having Mn of 1 ,000 g/mol to 10,000 g/mol, alternatively 4,000 g/mol to 9,000 g/mol.
  • Starting material C) is a radical polymerizable organic compound.
  • Starting material C) may be an organic (meth)acrylic compound that may be selected from the group of acrylates and methacrylates (collectively, (meth)acrylates), (meth)acrylamides, halogen substituted homologs thereof, and combinations thereof.
  • the radical polymerizable organic compound includes an acrylate.
  • Suitable examples of (meth)acrylates include, but are not limited to, 2-ethylhexylacrylate, 2-ethylhexylmethacrylate, methylacrylate,
  • neopentylglycoldimethacrylate glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, allyl acrylate, allyl methacrylate, stearyl acrylate, stearyl methacrylate, tetrahydrofurfuryl acrylate, 2- hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, tetrahydrofurfuryl methacrylate,
  • organic (meth)acrylate compound may include only acrylate or methacrylate functionality.
  • the radical polymerizable organic compound may include both acrylate functionality and methacrylate functionality. It is to be understood that compounds having more than one radical polymerizable group will promote crosslinking, but can be used in lesser molar amounts if crosslinking is not desired.
  • starting material C) may comprise an organic (meth)acrylic compound,
  • RH is selected from the group consisting of oxygen and NH.
  • R ⁇ is an oxygen atom
  • the (meth)acrylic compound is i) a (meth)acrylate.
  • R H is NH
  • the (meth)acrylic compound is ii) a (meth)acrylamide.
  • Each R F is a monovalent group selected from the group consisting of monovalent hydrocarbon groups, as described above, hydroxyl groups, and amino groups. Alternatively, R F may be an aryl group such as benzyl or phenyl.
  • R F may be an amino group such as dimethylamino.
  • Exemplary organic (meth)acrylic compounds include i) (meth)acrylates selected from the group consisting of methyl methacrylate, methyl acrylate, butyl acrylate, benzyl acrylate, benzyl methacrylate, stearyl methacrylate, 2-(dimethylamino) ethylacrylate, 2-(dimethylamino) ethylmethacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, tetrahydrofurfuryl acrylate, and tetrahydrofurfurylmethacrylate; and ii) (meth)acrylamides selected from the group consisting of N-isopropylacrylamide and N-isopropylmethacrylamide.
  • Nonionic surfactants suitable for use as starting material D) are known in the art and commercially available. Some suitable nonionic surfactants which can be used include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, alkylglucosides,
  • polyoxyethylene fatty acid esters such as cetyl alcohol, stearyl alcohol, cetostearyl alcohol, oleyl alcohol, and polyvinyl alcohol.
  • Nonionic surfactants which are commercially available include compositions such as (i) 2,6,8-trimethyl-4-nonyl polyoxyethylene ether sold under the names Tergitol TMN-6 and Tergitol TMN-10; (ii) the C1 1 -15 secondary alkyl polyoxyethylene ethers sold under the names Tergitol 15-S-7, Tergitol 15-S-9, Tergitol 15-S-15, Tergitol 15-S-30, and Tergitol 15-S-40, by the Dow Chemical Company, Midland, Michigan; octylphenyl
  • alkyl-oxo alcohol polyglycol ethers such as ⁇ GENAPOL UD 050, and Genapol UD1 10
  • alkyl polyethylene glycol ether based on C10-Guerbet alcohol and ethylene oxide such as LUTENSOL® XP 79.
  • Suitable nonionic surfactants also include poly(oxyethylene)-poly(oxypropylene)-poly(oxyethylene) tri-block copolymers. Poly(oxyethylene)-poly(oxypropylene)-poly(oxyethylene) tri-block copolymers are also commonly known as Poloxamers.
  • nonionic triblock copolymers composed of a central hydrophobic chain of polyoxypropylene (polypropylene oxide)) flanked by two hydrophilic chains of polyoxyethylene (polyethylene oxide)).
  • Poly(oxyethylene)- poly(oxypropylene)-poly(oxyethylene) tri-block copolymers are commercially available from BASF (Florham Park, NJ) and are sold under the tradename PLURONIC®, such as Pluronic L61 , L62, L64, L81 , P84.
  • the nonionic surfactant may also be a silicone polyether (SPE).
  • the silicone polyether as an emulsifier may have a rake type structure wherein the polyoxyethylene or polyoxyethylene-polyoxypropylene copolymeric units are grafted onto the siloxane backbone, or the SPE can have an ABA block copolymeric structure wherein A represents the polyether portion and B the siloxane portion of an ABA structure.
  • Suitable silicone polyethers include DOWSIL® 5329 from Dow Silicones Corporation of Midland, Ml USA.
  • nonylphenoxy polyethoxy ethanol 10EO
  • MAKON® 10 polyoxyethylene 23 lauryl ether
  • BRIJ® 35L polyoxyethylene 23 lauryl ether
  • RENEX® 30 a polyoxyethylene ether alcohol sold by ICI Surfactants
  • the aqueous phase may contain 0.0001 to 10 parts nonionic surfactant per 100 parts of aqueous phase by weight.
  • the water may be deionized water or distilled water.
  • Suitable F) solvents for use in the method for preparing the copolymer include organic solvents which may or may not be hydrocarbon solvents.
  • Suitable hydrocarbon solvents include alkane solvents such as cyclohexane, heptane, octane, decane, and/or dodecane; and aryl solvents such as toluene, xylene, and/or mesitylene.
  • Starting material G) is an organoboron liberating compound capable of decomplexing the organoboron compound for initiating co-polymerization.
  • Suitable organoboron liberating compounds include the amine reactive compounds disclosed, for example, in U.S. Patent 8,097,689 at col. 12, line 55 - col. 13, line 46.
  • the term“organoborane liberating compound” means a compound that will at least partially react with starting material A) and release another organoboron compound that contains at least one B-C bond that can be readily oxidized and generate free radical.
  • the organoborane liberating compound may be selected from: i) an acid, ii) an aldehyde, iii) an isocyanate, iv) an epoxide, v) an acid chloride, vi) an anhydride, vii) an acyloxysilane, viii) an acyloxysiloxane, ix) a halosilane, x) a halosiloxane, xi) a carboxylic acid functional silane, xii) a carboxylic acid functional siloxane, xiii) an anhydride functional silane, xiv) an anhydride functional siloxane, xv) an epoxy functional silane, xvi) an epoxy functional siloxane, xvii) a sulphonyl chloride, and a combination of two or more of i), ii), iv), v), vi), vii), viii), ix),
  • Step i) of the for making the copolymer may be performed by mixing and optionally heating the starting materials.
  • Mixing may be done by any conventional means such as mechanical agitation in a stirred tank reactor. Mixing may be performed at RT. Alternatively, the starting materials may be heated, and heating may be performed at reflux temperature of the starting materials selected, e.g., 50°C to 100°C, alternatively 80°C.
  • Recovering the copolymer may be performed by any convenient means such as filtering the copolymer after step iii) and/or washing the copolymer after step iii) with water or an alcohol ⁇ e.g., methanol)
  • Figure 1 is an example of an apparatus 100 that can be used in practicing the method of this invention.
  • a first contactor 101 contains a first packed bed of particles 102 of a copolymer of a (meth)acrylate-functional polydiorganosiloxane and an organic (meth)acrylic compound.
  • the first contactor 101 has a first inlet 103 and a first outlet 104.
  • Feed line 105 can be used to feed the mixture described above into the first contactor 101 through inlet valve 106 into the first inlet 103. As the mixture passes through the first contactor 101 , the volatile component is sorbed into the particles 102. The depleted mixture exits the first contactor 101 through the first outlet 104, through outlet valve 107 and out through outlet line 108. The depleted mixture is a purified product that may be stored in a collection container, not shown.
  • the apparatus 100 may further comprise a second contactor 201 containing a second packed bed of particles 202 of a second copolymer of a (meth)acrylate-functional
  • the particles 202 may be the same as, or different from, the particles 102 in the first contactor 101 .
  • the second contactor 201 has a second inlet 203 and a second outlet 204.
  • valves 106 and 107 may be shut and feed valve 206 and outlet valve 207 may be opened.
  • the depleted mixture is a purified product that may be stored in the same or different collection container, not shown.
  • the particles 102 in the contactor 101 may be regenerated.
  • purge valves 109, 1 10 can be opened and a sweep gas (such as air or an inert gas) passed through the first contactor 101 through lines 1 1 1 , 1 12.
  • the first contactor 101 may optionally be heated, and/or the sweep gas may optionally be heated.
  • the valves 206, 207 may be closed and the mixture re-routed through the first contactor 101 again.
  • the particles 202 may be regenerated similarly as in the first contactor 101 through valves and lines, not shown. The method may be repeated using the apparatus 100.
  • the particles 202 in the second contactor 201 may be regenerated by opening purge valves 209, 210 can be opened and a sweep gas (such as air or an inert gas) passed through the second contactor 201 through lines 21 1 , 212.
  • a sweep gas such as air or an inert gas
  • the second contactor 201 may optionally be heated, and/or the sweep gas may optionally be heated.
  • the copolymer may have various forms, in addition to or instead of particles 102, 202, for example, said copolymer may be in the form of thin films, coated support materials (e.g ., packing, trays, plates, mesh), nanorods, nanospheres, beads, granules, powders, pellets, particulates, and/or fibers (hollow and not hollow).
  • coated support materials e.g ., packing, trays, plates, mesh
  • nanorods, nanospheres, beads granules, powders, pellets, particulates, and/or fibers (hollow and not hollow).
  • the copolymer may be porous or non- porous.
  • the contactors 101 , 201 may be vertically oriented or horizontally oriented as shown.
  • the contactor 101 , 201 may be a packed bed, fluidized bed, a tower containing plates, trays or disks coated with the copolymer.
  • the contactor 101 , 201 may be a sorbent wheel, such as a desiccant wheel, or other rotating disc or wheel apparatus wherein the copolymer is coated on all or a portion of the surface of the wheel.
  • additional contactors may be configured in parallel or in series configuration with the contactors 101 , 201 .
  • the contactor is a sorbent wheel or disc, the wheel may rotate through a sector or zone in which regeneration occurs, allowing continuous sorption and regeneration in a single device.
  • Equation (1 ) A first order model akin to Equation (1 ) was assumed to analyze toluene vapor sorption kinetics, where q t and q * represent the time-dependent and equilibrium capacities, respectively, and k represents the first order mass transfer coefficient that includes both external and internal transport resistances.
  • Electron Energy Loss Spectroscopy (EELS) analysis was performed as follows. Pure crosslinked silicone elastomer and pure pHEMA particles were microtomed at -120 °C to make electron transparent thin sections, and the thin sections were collected and placed on hole carbon film coated Cu TEM grids. For cross-sectional TEM, the particles were epoxy embedded and cured at room temperature for 24 h. The epoxy embedded sample was cross-sectioned to 60 nm thick sections using a diamond knife, and collected on a carbon film coated Cu TEM grid using a floating method at RT in a microtome instrument and air dried. The specimens were loaded in JEOL 21 OOF TEM and the internal morphology were observed at 200 KeV under bright field TEM mode.
  • size 2 high contrast objective aperture 100 micron was used.
  • the digital images were taken using Gatan CCD camera attached under the TEM column and Digital Micrograph software.
  • STEM scanning TEM
  • JEOL STEM control system was used for Z-contrast image.
  • dark field STEM 0.5 nm beam probe and #3 condenser aperture were used and the digital images were taken using a Gatan bright field/dark field detector.
  • the observed spectral intensity at a given pixel (i,j) of an EELS spectrum-image dataset can be represented by:
  • m q ( i , j ) is the mass of component q at pixel (i,j) and o q is the total inelastic scattering cross section per unit mass of component q.
  • a crosslinked PDMS silicone elastomer was prepared by mixing 10.00 g of SylgardTM 184 Base and 1.00 g of SylgardTM 184 Curing Agent from Dow Silicones Corporation of Midland, Michigan, USA in a polypropylene mixing cup using a Flaktek rotary SpeedMixer. The resulting mixture was poured into an Al pan and de-aired by pulling vacuum for 1 min, then transferred to a forced convection oven and allowed to cure for 1 h at 150°C. The resulting cured disk of crosslinked silicone elastomer was removed and allowed to cool.
  • a copolymer was prepared as follows. In a polypropylene mixing cup, 0.446 g Tergitol 15-5-40 surfactant, 0.087 Tergitol 15-5-3 surfactant, 0.160 g of an ambient free radical initiator comprising an equimolar triethylborane-propanediamine complex (TEB- PDA, Callery Chemical), 4.032 g of (MA-PDMS), 1.032 g 2-hydroxyethyl methacrylate (HEMA, Aldrich), and 0.280 g of deionized water was combined and mixed in a FlackTek rotary
  • This copolymer was a solid, non-tacky powder that was significantly less soft than a silicone elastomer particle that did not include an organic component.
  • the hardness was quantified using a Shore A Scale Durometer tested at ambient temperature. Results shown in Table 1 below demonstrated the pronounced increase in hardness of the particles with incorporation of 20% HEMA into the crosslinked MA-PDMS particles as compared to PDMS particles prepared by an identical radical polymerization protocol but absent the HEMA.
  • the presence of the organic component imparted more favorable physical properties, such as increased hardness, that can be helpful in packed bed separations because they help reduce the tackiness of the particles and the tendency of the particles to agglomerate.
  • EELS analysis performed using the method of Reference Example 2 indicated that particles of Example 1 were nanophase segregated into pHEMA-rich domains that were interspersed within a PDMS matrix.
  • Quantified phase maps (not shown) obtained by applying multiple least square fit to the core energy loss signals from the pure components and the particle specimen indicated that there was 21% of HEMA in a PDMS matrix in the EELS observed region. This figure was in good agreement with the theoretical pHEMA content expected from the fact that HEMA comprised 20% of the monomers added.
  • lighter density region (PHEMA) revealed darker contrast
  • heavier density region (PDMS) revealed darker contrast in the bright filed TEM image.
  • Table 2 Equilibrium uptake of toluene vapor at 20°C and 40°C in particles of PDMS-co- p(HEMA) synthesized with 20% HEMA, Example 1.
  • Table 3 Equilibrium uptake of toluene vapor at 20°C and 40°C in particles of PDMS-co- pNIPAAM synthesized with 34% NIPAAM, Example 2.
  • a sorbent copolymer was prepared by copolymerizing 1 .002 g of THFMA with 4.018 g of MA-PDMS. This was done by weighing the THFMA and MA-PDMS into a polypropylene mixing cup along with 0.57 g TEB-PDA and mixing for 30 s in a FlackTek rotary SpeedMixer. To this mixture was added 0.175 g Tergitol- 15-2-40 and 0.175 g Tergitol 15-S-3 surfactants, and 0.300 g of initial deionized water, and the resulting mixture was mixed for 30 s more. This mixture was then further diluted by adding 15 mL of deionized water in 2 mL increments, with a final addition of 3 mL. Each increment was followed by a 30 s mixing step.
  • Table 4 Equilibrium uptake of toluene vapor at 20°C and 40°C in particles of PDMS-co- p(TFIFMA) synthesized with 20% THFMA, Example 3.
  • a sorbent copolymer was prepared as follows. In a polypropylene mixing cup, 0.419 g Tergitol 15-5-40 surfactant, 0.077 Tergitol 15-5-3 surfactant, 0.159 g of TEB-PDA, 0.250 g of BzMA, 4.753 g of MA-PDMS, and 0.272 g of deionized water was combined and mixed in a FlackTek rotary SpeedMixer for 30 s to form a concentrated emulsified reaction mixture. In a clean 4 oz. glass jar, 0.057 g of glacial acetic acid (Aldrich) was added to 20.913 g of deionized water and mixed until homogeneous.
  • Aldrich glacial acetic acid
  • Table 5 Equilibrium uptake of toluene vapor at 20°C and 40°C in particles of PDMS-co- p(HEMA) synthesized with 5% BzMA, Example 4.
  • a sorbent copolymer was prepared by copolymerizing 1.000 g of DMAEMA with 4.002 g of MA-PDMS. This was done by weighing the DMAEMA and MA-PDMS into a polypropylene mixing cup along with 0.129 g TEB-PDA and mixing for 30 s in a FlackTek rotary SpeedMixer. To this mixture was added 0.199 g Tergitol-15-2-40 and 0.075 g Tergitol 15-S-3 surfactants, and 0.305 g of initial deionized water and mixed for 30 s more. This mixture was then further diluted by adding 15 mL of deionized water in 2 ml. increments, with a final addition of 3 mL.
  • Table 6 Equilibrium uptake of toluene vapor at 20°C and 40°C in particles of PDMS-co- p(DMAEMA) synthesized with 20% DMAEMA, Example 5.
  • polydiorganosiloxane and an organic (meth)acrylic compound exhibited an order of magnitude more toluene sorption than polydimethylsiloxanes (without an organic (meth)acrylic compound reacted into a copolymer).
  • a sorbent copolymer was prepared by copolymerizing 0.255 g of methyl methacrylate (MMA, Sigma-Aldrich) with 4.758 g of MA-PDMS. This was done by weighing the MMA and MA-PDMS into a polypropylene mixing cup along with 0.160 g TEB-PDA and mixing for 15 s in a FlackTek rotary SpeedMixer. To this mixture was added 0.078 g Tergitol-15-S-3 and 0.461 g Tergitol 15-S-40 surfactants, and 0.288 g of initial deionized water and mixed for 30 s more.
  • MMA methyl methacrylate
  • MA-PDMS methyl methacrylate
  • the method described herein is particularly useful for separating a gas or vapor (e.g ., VOCs such as toluene) from a mixture by contacting the mixture comprising at least one vapor phase volatile component with a sorbent comprising a copolymer of an organic (meth)acrylate and a (meth)acrylate-functional polydiorganosiloxane.
  • a gas or vapor e.g ., VOCs such as toluene
  • a sorbent comprising a copolymer of an organic (meth)acrylate and a (meth)acrylate-functional polydiorganosiloxane.
  • the copolymer is prepared in the presence of a solvent which is then subsequently substantially removed.
  • the resulting copolymer exhibits an unusually high capacity to sorb toluene.
  • the method described herein employing a copolymer as the sorbent has significant potential consequences for energy and cost-efficiency gains in traditional gas separations.
  • contacting devices that comprise such sorbents and products purified by such contacting processes, including silicone products and intermediates. Compared to conventional solid adsorbent media or porous organic, polymeric or organometallic structures, the copolymer may be less prone to fouling and mass transfer limitations.
  • disclosure of a range of, for example, 2.0 to 4.0 includes the subsets of, for example, 2.1 to 3.5, 2.3 to 3.4, 2.6 to 3.7, and 3.8 to 4.0, as well as any other subset subsumed in the range.
  • disclosure of Markush groups includes the entire group and also any individual members and subgroups subsumed therein.
  • disclosure of the Markush group a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group includes the member alkyl individually; the subgroup alkyl and aryl; and any other individual member and subgroup subsumed therein.
  • the term“depleted” and its derivatives each mean that the amount of volatile component in the mixture before step 1 ) is reduced to a lower amount after practicing step 1 ) of the method described herein.
  • the term“enriched” and its derivatives mean that the amount of volatile component in the crosslinked elastomer is greater during and after practicing step 1 ) than before practicing step 1 ) of the method described herein.
  • substituted refers to a monovalent hydrocarbon group in which one or more bonds to a hydrogen atom contained therein are replaced by one or more bonds to a non-hydrogen atom and/or one or more carbon atoms are replaced with a heteroatom (e.g ., halogen, N, O, or S).
  • a heteroatom e.g ., halogen, N, O, or S.
  • sorb and its derivatives, means absorbing and/or adsorbing; alternatively adsorbing, and alternatively absorbing.
  • sorb can include both absorbing and adsorbing.
  • volatile and its derivatives, means that one component may have a higher vapor pressure than another component.
  • the volatile component may be distinguished from the at least one other component in the mixture by virtue of relative vapor pressures.
  • the volatile component may have a vapor pressure higher than the vapor pressure of the at least other component in the mixture.
  • the volatile component may have a pure component vapor pressure of at least 0.1 mm Hg at 70°C.
  • the at least one other component in the mixture may be a non-volatile component that has a vapor pressure less than 0.1 mmHg at 70°C.
  • Volatility refers to the tendency of a substance to vaporize. Volatility is directly related to the vapor pressure of a substance.
  • the volatile component may have a vapor pressure lower than vapor pressure of at least one other component in the mixture, when solubility of the volatile component is higher in the nonporous crosslinked elastomer than solubility of the at least one other component in the nonporous crosslinked elastomer.
  • a method for depleting a volatile component in a mixture comprising the volatile component and at least one other component comprises:
  • the method of the first embodiment further comprises one or more additional steps selected from the group consisting of: 4) directing the depleted mixture during and/or after step 1 ), and 5) directing the desorbed volatile component during and/or after step 2).
  • (meth)acrylate-functional polyorganosiloxane is a (meth)acrylate-functional
  • polydiorganosiloxane selected from the group consisting of a-(meth)acrylate-functional dimethylsiloxy group, w-trimethylsiloxy group-terminated polydimethylsiloxane and a,w- (meth)acrylate-functional dimethylsiloxy group terminated polydimethylsiloxane.
  • the organic (meth)acrylic compound is selected from the group consisting of i) (meth)acrylate compounds such as benzyl methacrylate, 2-(dimethylamino) ethylmethacrylate, 2-hydroxyethyl methacrylate, methyl methacrylate, and tetrahydrofurfurylmethacrylate; and ii) (meth)acryl amide compounds such as N-isopropylacrylamide.
  • the volatile component is a volatile organic compound.
  • the volatile component is selected from the group consisting of a cyclic polyorganosiloxane with a degree of polymerization from 3 to 12, a silane, and a noncyclic polyorganosiloxane with a degree of polymerization up to 14.
  • the at least one other component of the mixture comprises a non-volatile organic liquid or a non volatile polyorganosiloxane liquid distinct from the volatile component.
  • the mixture is a process vapor/gas stream and the depleted mixture is a depleted process vapor/gas.
  • the copolymer is prepared by a method comprising:
  • starting materials comprising A) a radical initiator, B) a (meth)acryloxy- functional polyorganosiloxane, C) an organic radical polymerizable compound, D) a nonionic surfactant, E) water, and optionally F) a solvent;
  • additional E) water may be added with mixing to form an emulsion, and iii) adding G) a an organoboron liberating compound capable of decomplexing the organoboron compound for initiating co-polymerization, and
  • starting material A) is selected from the group consisting of a1 ) an organoboron compound capable of forming free radical generating species, a2) an azo compound, a3) a persulphate compound, a4) an organic peroxide, and a5) two or more of a1 ), a2), a3), and a4).
  • starting material B) is selected from the group consisting of:
  • each R E is independently selected from the group consisting of H and methyl; each R M is a monovalent hydrocarbon group or a monovalent halogenated hydrocarbon group; each R D is a divalent hydrocarbon group; and subscript b is 0 to 10,000.
  • starting material C) has formula C1 ):
  • each R E is independently selected from the group consisting of H and methyl; each R ⁇ is a monovalent hydrocarbon group or a monovalent halogenated hydrocarbon group; each R D is a divalent hydrocarbon group; subscript b is 1 to 100; R H is selected from the group consisting of oxygen and NH.
  • starting material C) is selected from the group consisting of i) (meth)acrylates and ii) (meth)acrylamides.
  • the (meth)acrylate is selected from the group consisting of methyl methacrylate, methyl acrylate, butyl acrylate, benzyl acrylate, benzyl methacrylate, stearyl methacrylate, 2- (dimethylamino) ethylacrylate, 2-(dimethylamino) ethylmethacrylate, 2-hydroxyethyl acrylate, 2- hydroxyethyl methacrylate, tetrahydrofurfuryl acrylate, and tetrahydrofurfurylmethacrylate; and the (meth)acrylamide is selected from the group consisting of N-isopropylacrylamide and N- isopropylmethacrylamide.
  • starting material F the solvent is used in step i).
  • the method further comprises, after step ii) and before step iii) additional step ii), which comprises adding additional E) water with mixing to form an emulsion.
  • step 2) is performed by a technique selected from a) heating, b) reducing the partial pressure of the volatile component, or c) both a) and b).
  • an apparatus 100 for depleting a volatile component in a mixture comprises:
  • a contactor 101 defining an internal volumetric space and having an inlet 103 and an outlet 104 in fluid communication with the inlet 103 via the internal volumetric space, wherein the internal volumetric space of the contactor contains a copolymer of a (meth)acrylate-functional polyorganosiloxane and an organic (meth)acrylic compound 102, wherein during operation of the apparatus a mixture comprising the volatile component and at least one other component enters the contactor 101 through the inlet 103, contacts the copolymer 102 such that at least some of the volatile component is sorbed by the copolymer 102, and a depleted mixture exits the contactor 101 through the outletl 04,
  • a collector in fluid communication with the outlet 104 of the contactor and configured for collecting the depleted mixture
  • a recovery apparatus in fluid communication with the copolymer 102 and configured for collecting desorbed volatile component from the copolymer 102.
  • the contactor 101 is a packed bed apparatus comprising a packed bed of a coated support material, nanorod, nanosphere, particulate, bead, granule, powder, pellet, or fiber form of the copolymer 102.
  • the apparatus 100 of the eighteenth or nineteenth embodiment further comprises: a splitter or second mixture feed 205 to a second inlet 203 of a second contactor 201 disposed with the apparatus 100 for parallel flow of the mixture, where the second contactor 201 defines a second internal volumetric space and has a second outlet 204 in fluid communication with the second inlet 203 via the second internal volumetric space, wherein the second internal volumetric space of the second contactor 201 contains a second copolymer 202 of a (meth)acrylate-functional polyorganosiloxane and an organic (meth)acrylic compound, which may be the same as or different from the copolymer 102 of the

Abstract

L'invention concerne un procédé et un appareil pour éliminer un composant volatil à partir d'un mélange. Le procédé et l'appareil utilisent un copolymère d'un polyorganosiloxane à fonction (méth)acrylate et d'un composé (méth)acrylique organique en tant que sorbant
PCT/US2019/025471 2018-04-26 2019-04-03 Procédé d'épuisement d'un composant volatil d'un mélange à l'aide d'un copolymère sorbant et appareil pour mettre en œuvre ce procédé WO2019209476A1 (fr)

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US5998498A (en) 1998-03-02 1999-12-07 Johnson & Johnson Vision Products, Inc. Soft contact lenses
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US2676182A (en) 1950-09-13 1954-04-20 Dow Corning Copolymeric siloxanes and methods of preparing them
US4584355A (en) 1984-10-29 1986-04-22 Dow Corning Corporation Silicone pressure-sensitive adhesive process and product with improved lap-shear stability-I
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US5998498A (en) 1998-03-02 1999-12-07 Johnson & Johnson Vision Products, Inc. Soft contact lenses
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