WO2019209476A1

WO2019209476A1 - Method of depleting a volatile component in a mixture using a sorbent copolymer and apparatus for practicing the method

Info

Publication number: WO2019209476A1
Application number: PCT/US2019/025471
Authority: WO
Inventors: Dongchan Ahn; Aaron GREINER; James Thompson; Robert O. Huber; Kevin Wier
Original assignee: Dow Silicones Corporation
Priority date: 2018-04-26
Filing date: 2019-04-03
Publication date: 2019-10-31

Abstract

A method and apparatus for removing a volatile component from a mixture are disclosed. The method and apparatus employ a copolymer of a (meth)acrylate-functional polyorganosiloxane and an organic (meth)acrylic compound as the sorbent

Description

METHOD OF DEPLETING A VOLATILE COMPONENT IN A MIXTURE USING A SORBENT COPOLYMER AND APPARATUS FOR PRACTICING THE METHOD

Cross Reference to Related Applications

[0001] This application claims the benefit under 35 U.S.C. §1 19(e) of U.S. Provisional Patent Application Serial No. 62/662823 filed on 26 April 2018. U.S. Provisional Patent Application Serial No. 62/662823 is hereby incorporated by reference.

Technical Field

[0002] 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

polydiorganosiloxane and an organic (meth)acrylic compound. An apparatus for practicing the method is also disclosed.

Background

[0003] Reduction of volatile components, such as volatile organic compounds ( e.g ., aromatic hydrocarbons) or volatile polydiorganosiloxanes {e.g., cyclic polydialkylsiloxanes and/or linear polydialkylsiloxane oligomers) is often a cost-prohibitive step in chemical manufacturing, as well as in the treatment of effluent process gas or wastewater streams. Porous solid adsorbents such as activated carbon or molecular sieves have been used for such purposes. However because such 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.

[0004] 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. However, 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. To avoid such problems, methods employing membrane separators have been used. However, membrane separators suffer from the drawbacks that they may add equipment cost and be prone to fouling.

Problem to be Solved

[0005] There is an industry need for methods to remove volatile components from products, effluent process gas and/or wastewater streams, where the sorbents used in such methods and apparatus can be readily regenerated, are less prone to fouling, and/or have fewer mass transfer limitations than existing methods and apparatus. BRIEF SUMMARY OF THE INVENTION

[0006] 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

polydiorganosiloxane and an organic (meth)acrylic compound, thereby enriching the copolymer in the volatile component and depleting the mixture in the volatile component.

BRIEF DESCRIPTION OF THE DRAWINGS

[0007] Figure 1 is an example of an apparatus that can be used for practicing the method described herein.

DETAILED DESCRIPTION OF THE INVENTION

[0008] 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:

1 ) sorbing at least some of the volatile component by a copolymer of a (meth)acrylate- functional polydiorganosiloxane and an organic (meth)acrylic compound (copolymer), thereby forming the depleted mixture and enriching the copolymer with sorbed volatile component, thereby forming an enriched copolymer,

2) desorbing at least some of the volatile component from the enriched copolymer, thereby forming a desorbed volatile component and a regenerated copolymer, and

3) using the regenerated copolymer as all or a portion of the copolymer in repeating step 1 ). 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).

[0009] In step 1 ) of the method, 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. Alternatively, the temperature may be selected such that all of the volatile component is in the gas phase. Alternatively, 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. Without wishing to be bound by theory, it is thought that as long as the partial pressure of the volatile component in the mixture exceeds the partial pressure of the volatile component in the copolymer or on the copolymer surface, there will be a sufficient driving force for mass transfer of the volatile component into the bulk of the copolymer and/or onto the surface of the copolymer.

[0010] 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. Alternatively, 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.

[0011] Step 2) of the method may be performed to regenerate the copolymer. As the copolymer sorbs the volatile component, 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. During and/or after step 2), 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.

[0012] 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). For example, 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.

Alternatively, exposing the enriched copolymer to solvent with or without swelling the enriched copolymer may also be used to regenerate the enriched copolymer. Alternatively, liquid extraction, e.g., solvent or supercritical fluid extraction may be used to regenerate the enriched copolymer.

[0013] 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.

[0014] 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

component. Alternatively, the depleted mixture may be directed to a different operation, such as when the depleted mixture will be used as a reactant. Alternatively, 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. Alternatively, one or both of the depleted mixture and the volatile component may be directed to collection containers.

[0015] For example, when the method is being used to purify the mixture of the volatile component; 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 ).

[0016] Alternatively, 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. In one embodiment, 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. Using the method described herein on this mixture can produce a purified mixture comprising the polyorganosiloxane (free of 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.

[0017] Alternatively, when the mixture is waste water and the depleted mixture is purified water, the purified water may be directed by feeding ( e.g ., pumping) the purified water to a process to test, or to the environment. Alternatively, when the mixture is air, and the depleted mixture is purified air, the purified air may be directed blowing or pumping via ductwork into an air handling system or a ventilation system. It is understood that 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.

[0018] The volatile component may be recovered by any convenient means. For example, when the enriched copolymer is regenerated by sweeping with a dry gas stream, as described above, the gas stream containing the volatile component may be directed through a condenser to recover the volatile component. Alternatively, if a solvent is used to regenerate the enriched copolymer, the volatile component may be directed to an apparatus for stripping, extracting, or distilling to remove the solvent. Alternatively, 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.

[0019] Volatile Component: 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.

[0020] Organosilicon Component: The organosilicon component may be any organosilicon species that is desirably removed from the mixture. In the method described herein, 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.

[0021] 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. An 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.

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. Alternatively, 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),

(ix) pentamethylpentaphenylcyclopentasiloxane (D5^Ph), (x) dodecamethylcyclohexasiloxane

(Dg), (xi) hexamethylcyclohexasiloxane (DgH), (cϋ) hexamethylhexavinylcyclohexasiloxane

(Dg^i), (xiii) hexamethylhexaphenylcyclohexasiloxane

dimethyl/methylvinyl cyclic siloxanes with 3 to 6 silicon atoms, (xv) dimethyl/methyl hydrogen cyclic siloxanes with 3 to 6 silicon atoms, or (xvi) combinations of two or more of (i), (ii), (iii), (iv), (v), (vi), (vii), (viii), (ix), (x), (xi), (xii), (xiii), (xiv), and (xv). Alternatively, the organosilicon component may be selected from D3, D4, D5, Dg, and combinations of two or more of D3, D4, D5, and Dg. Alternatively, the organosilicon component may be D4.

[0022] Alternatively, the organosilicon component may be an organosilane or

polyorganosiloxane with a DP of 1 to 14. The organosilane may have formula: R¹ _vSiR²(4__v), where each R¹ is independently a monovalent hydrocarbon group or a monovalent halogenated hydrocarbon group, each R² 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.

[0023] Suitable monovalent hydrocarbon groups for R¹ are as described and exemplified above for R^{1 1}. Suitable halogen atoms for R² include F, Cl, Br, or I; alternatively F, Cl, or Br; alternatively Cl or Br; alternatively Cl; alternatively Br. Suitable hydrocarbonoxy groups for R² have formula OR², where R² 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.

[0024] Alternatively, 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

(R⁴3SiOi/2)_w(R⁴2Si02/2)x(R⁴SiC>3/2)y(Si04/2)_z, where R⁴ is a hydrogen atom, OH, or R^{1 1} as described and exemplified above, subscript w is > 0, subscript x ³ 0, subscript y is ³ 0, subscript z is ³ 0, with the proviso that a quantity (w + x + y + z) is < 14. Alternatively, y may be 0. Alternatively, z may be 0. Alternatively, w may be 2 and x may be 0 to 12, alternatively 0 to 2. Exemplary volatile polyorganosiloxanes may include those of formulae:

(R⁴3SiO-|/2)2(R⁴2^Si02/2)2, (R⁴3^Si01/2)2(^R42^Si02/2)l , (^R43^S'°1 /2)2, and/or

(R⁴3Si0-_|/2)4(Si04/2)i . Alternatively, each R⁴ may be independently a hydrogen atom, a methyl group, a vinyl group, or a phenyl group. Alternatively, each R⁴ may be methyl. Such volatile polyorganosiloxanes include hexamethyldisiloxane, octamethyltrisiloxane,

hexamethylcyclotrisiloxane, and other low molecular weight polyorganosiloxanes, such as 0.5 to 1 .5 cSt DOWSIL® 200 Fluids and DOWSIL® OS FLUIDS, which are commercially available from Dow Silicones Corporation of Midland, Michigan, U.S.A. Alternatively, the organosilicon compound to be removed from the mixture may be a neopentamer, of formula Si(OSiR⁴3)4, where R⁴ is as described above. Exemplary neopentamers include Si[OSi(CH3)3]4,

Si[OSi(CH₃)₂H]₄, and Si[OSi(CH₃)₂Vi]₄.

[0025] VOC: Alternatively, the volatile component may be a volatile organic compound (VOC). 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), (iii), (iv), (v), (vi), (vii) or (viii). Examples of aromatic compounds include aromatic hydrocarbons such as toluene, benzene, ethylbenzene, 1 - methylethyl benzene, propylbenzene, and/or xylenes. Examples of alkanes include methane, ethane, propane, butane pentane, hexanes, heptanes, octane, and/or isomers thereof, cyclohexane, and/or combinations thereof. Examples of alkenes include ethylene, propene, butene, pentene and/or isomers thereof and/or combinations thereof.

[0026] Alternatively, 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, acetonitrile; tetrahydrofuran; white spirits; mineral spirits;

naphtha; n-methyl pyrrolidone; halogenated volatile organic compounds, such as halogenated hydrocarbons, e.g., chlorofluorocarbons such as Freon, or a combination of two or more thereof.

[0027] Alternatively, 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 oligomeric liquid epoxy resin. The VOC may also be a petroleum-derived fuel or fuel mixture, such as diesel fuel, jet fuel or gasoline.

Alternatively, the VOC may be an organic noxious or odor causing compound such as organosulfur compound.

[0028] Mixture: 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. In certain embodiments, 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. For example, in one embodiment, 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. Alternatively, 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. Without wishing to be bound by theory, it is thought that 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.

[0029] 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:

(R⁴3SiO-|/2)p(R⁴2SiD2/2)q(^R4SiC>3/2)_r(SiC>4/2)_s, where R⁴ 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. 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. Representative, non-limiting examples of 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

[0030] Representative, non-limiting examples of such divalent organofunctional hydrocarbon groups include divalent bisphenol A derivatives, acrylate-functional alkylene groups and methacrylate-functional alkylene groups. Alternatively, each group D may be ethylene, propylene, butylene or hexylene. Alternatively, 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. Such 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. When the method described herein is used to remove a volatile polyorganosiloxane from a non-volatile polyorganosiloxane, then the volatile

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 R⁴ groups.

[0031] 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. In certain applications, 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 R⁶ ₃SiO(R⁶ ₂SiO)_k(R⁶HSiO)_mSiR⁶3, formula (II) is R⁶ ₂HSiO(R⁶ ₂SiO)_n(R⁶HSiO)₀SiR⁶ ₂H, or a combination thereof.

[0032] In formulae (I) and (II) above, 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, and subscript o has an average value ranging from 0 to 2000. Each R⁶ 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} . Alternatively, 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,

carboxylates, and carboxylate esters. Alternatively, 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. Alternatively, 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. Alternatively, 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,

NO2, ONO2, azido, CF3, OCF3, R', O (oxo), S (thiono), C(O), S(O), methylenedioxy, ethylenedioxy, N(R')₂, SR', SOR', S0₂R', S0₂N(R')₂, S0₃R', C(0)R', C(0)C(0)R\

C(0)CH₂C(0)R', C(S)R', C(0)0R', 0C(0)R', C(0)N(R')₂, 0C(0)N(R')₂, C(S)N(R')₂, (CH₂)O- ₂N(R^,)C(0)R^, _I (CH₂)O-2^N(^R')^N(^R,)2- N(R^,)N(R')C(0)R', N(R^,)N(R')C(0)0R',

N(R')N(R')C0N(R^,)2, N(R')S0₂R', N(R')S0₂N(R^,)2, N(R')C(0)0R', N(R')C(0)R', N(R')C(S)R', N(R')C(0)N(R')2, N(R')C(S)N(R')2, N(COR')COR', N(OR')R', C(=NH)N(R')₂, C(0)N(0R')R', or C(=NOR')R' wherein 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, cycloalkyl, aryl, aralkyl, heterocyclic, heteroaryl, or heteroarylalkyl, or R’ can be independently mono- or multi-substituted; or wherein two R’ groups bonded to a nitrogen atom or to adjacent nitrogen atoms can together with the nitrogen atom or atoms form a heterocyclic, which can be mono- or independently multi-substituted. Examples of 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.

Examples of 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 allyloxy(polyoxyethylene), allyloxypoly(oxypropylene), and allyloxy- poly(oxypropylene)-co-poly(oxyethylene) groups; alkyloxypoly(oxyalkylene) groups such as propyloxy(polyoxyethylene), propyloxypoly(oxypropylene), and propyloxy-poly(oxypropylene)- co-poly(oxyethylene) groups; halogen substituted alkyloxypoly(oxyalkylene) groups such as perfluoropropyloxy(polyoxyethylene), perfluoropropyloxypoly(oxypropylene), and perfluoropropyloxy-poly(oxypropylene)-co-poly(oxyethylene) groups; alkoxy groups such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, and ethylhexyloxy groups; aminoalkyl groups such as 3-aminopropyl, 6-aminohexyl, 1 1 -aminoundecyl, 3-(N-allylamino)propyl, N-(2- aminoethyl)-3-aminopropyl, N-(2-aminoethyl)-3-aminoisobutyl, p-aminophenyl, 2-ethylpyridine, and 3-propylpyrrole groups; epoxyalkyl groups such as 3-glycidoxypropyl, 2-(3,4,- epoxycyclohexyl)ethyl, and 5,6-epoxyhexyl groups; ester functional groups such as acetoxyethyl and benzoyloxypropyl groups; hydroxy functional groups such as hydroxyethyl and 2- hydroxyethyl groups; masked isocyanate functional groups such as propyl-t-butylcarbamate, and propylethylcarbamate groups; aldehyde functional groups such as undecanal and butyraldehyde groups; anhydride functional groups such as 3-propyl succinic anhydride and 3- propyl maleic anhydride groups; and metal salts of carboxylic acids such as the zinc, sodium, or potassium salts of 3-carboxypropyl and 2-carboxyethyl.

[0033] Polyorganosiloxanes in the mixture to be purified are exemplified by: a) trimethylsiloxy- terminated polydimethylsiloxane, b) trimethylsiloxy-terminated

poly(dimethylsiloxane/methylphenylsiloxane), c) dimethylhydrogensiloxy-terminated

polydimethylsiloxane, d) dimethylhydrogensiloxy-terminated

poly(dimethylsiloxane/methylhydrogensiloxane), e) dimethylhydrogensiloxy-terminated polymethylhydrogensiloxane, f) trimethylsiloxy-terminated

poly(dimethylsiloxane/methylhydrogensiloxane), g) trimethylsiloxy-terminated

polymethylhydrogensiloxane, h) hydroxy-terminated polydimethylsiloxane, i) hydroxy-terminated poly(dimethylsiloxane/methylvinylsiloxane), j) hydroxy-terminated

poly(dimethylsiloxane/methylphenylsiloxane), k) a combination of two or more of a), b), c), d), e), f), g), h), i) and j).

[0034] Alternatively, 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. An MQ resin may consist essentially of R⁶3SiO-_|/2 units and S1O4/2 units; a TD resin may consist essentially of R⁶Si03/2 units and R⁶2Si02/2 units; an MT resin may consist essentially of R⁶3SiO-|/2 units and R⁶Si03/2 units; an MTQ resin may consist essentially of R⁶3SiO-_| /2 units, R⁶Si03/2 units, and S1O4/2 units; and an MTD resin may consist essentially of R⁶3SiO-|/2 units, R⁶Si03/2 units, and R⁶2Si02 2 units; a silsesquioxane resin may consist essentially of R⁶Si03/2 units; or a combination of two or more of MQ, MT, DT, MTQ, MDT, and silsesquioxane resins; where

is as described above.

[0035] 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.

[0036] Methods of preparing resins are well known in the art. For example, 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

hexamethyldisiloxane, or mixtures thereof, and recovering a copolymer having M and Q units. The resulting resins generally contain from 2 to 5 percent by weight of hydroxyl groups.

[0037] 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

product. Examples of 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.

[0038] Alternatively, 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. Examples of 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. [0039] Alternatively, the mixture may be a process liquid stream. Examples include wastewater or an emulsion such as a silicone emulsion containing residual volatile

polyorganosiloxanes.

[0040] Applications/Use of the Method: The method may be used in various applications, for example, to remove VOCs from process vapor streams. Alternatively, 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. In some embodiments, the method described herein may be use to selectively remove a organosilicon component, while leaving behind a desired organosilicon component in the depleted mixture. In this embodiment, the solubility of one organosilicon component in the copolymer may be higher than solubility of a second organosilicon component having a higher vapor pressure. For example, in the case of a silicone emulsion, which contains water vapor and cyclic polyorganosiloxanes, such as D4 and D5, it may be desirable to remove the cyclic polyorganosiloxanes and leave non-volatile polyorganosiloxanes in the emulsion.

[0041] In one embodiment, 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:

1 ) contacting a vapor phase mixture directly with a copolymer of a (meth)acrylate- functional polydiorganosiloxane and an organic (meth)acrylic compound (copolymer), thereby forming a depleted mixture containing less of the organosilicon component than the mixture before sorbing and enriching the copolymer with sorbed organosilicon component, thereby forming an enriched copolymer,

2) recovering the depleted mixture during and/or after step 1 ),

3) desorbing at least some of the sorbed organosilicon component from the enriched copolymer, thereby forming a desorbed organosilicon component and a regenerated copolymer containing less of the sorbed organosilicon component than the enriched copolymer before desorbing,

4) using the regenerated copolymer as all or a portion of the copolymer in repeating step

1 ), and

optionally 5) recovering the desorbed organosilicon component during and/or after step

2). In this embodiment, 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.

[0042] In an alternative embodiment, 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:

1 ) contacting a vapor phase mixture directly with a copolymer of an organic

(meth)acrylate and a (meth)acrylate-functional polydiorganosiloxane, thereby forming a depleted mixture containing less of the VOC than the mixture before sorbing and enriching the copolymer with sorbed VOC, thereby forming an enriched copolymer,

2) recovering the depleted mixture during and/or after step 1 ),

3) desorbing at least some of the sorbed VOC from the enriched copolymer, thereby forming a desorbed VOC and a regenerated copolymer containing less of the sorbed VOC than the enriched copolymer before desorbing,

1 ), and

optionally 5) recovering the desorbed VOC during and/or after step 2). In this embodiment, 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.

[0043] 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. For example, the copolymer useful in the method described above may be prepared by a method comprising:

i) combining 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

(meth)acrylic compound), D) a nonionic surfactant, E) water, and optionally F) a solvent; optionally, ii) 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

iv) optionally recovering the copolymer.

[0044] 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.

[0045] The organoborane - organonitrogen compound complex may have formula:

, where subscript xx is 1 or more, subscript yy is 1 or more, 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. Alternatively, each subscript xx is 1 and each subscript yy is 1. Alternatively each subscript xx is 1.3 and each subscript yy is 1.

[0046] 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-butylborane complex with 3-aminopropyltriethoxysilane; xi) tri-n-butylborane complex with 3- aminopropyltrimethoxysilane; xii) triethylborane complex with 3-aminopropyltriethoxysilane; xiii) triethylborane complex with 3-aminopropyltrimethoxysilane, and a combination of two or more of i), ii), iii), iv), v), vi), vii), viii), ix), x), xi), xii), and xiii).

[0047] The organoborate containing at least one B-C bond can be an amido-borate. The

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.

10, line 67; U.S. Patent 7,683,132 at col. 3, line 3 to col. 12, line 54.

[0048] Alternatively, 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

commercially available under the trade name Luperox®.) Optionally, the organic peroxides may be used with a catalyst or accelerant to reduce the temperature of initiation. Examples include 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 thereof.

[0049] Starting material B) is a (meth)acryloxy-functional polyorganosiloxane. The

(meth)acryloxy-functional polyorganosiloxane has at least one (meth)acryloxy-functional group per molecule and may be linear, branched, hyperbranched or resinous; alternatively

substantially linear, and alternatively linear. 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

oth. In formulae B1 ) and B2), each R^E is independently selected from the group consisting of H

(acrylate functionality) and methyl (methacrylate functionality). 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-,

-C2H4-, and -C3H0-. 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.

[0050] The linear (meth)acryloxy-functional polyorganosiloxane may be a

polydimethylsiloxane terminated at both ends with a (meth)acryloxy-functional,dimethylsiloxy group. Alternatively, 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. Examples include 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.

[0051] 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. In one embodiment, the radical polymerizable organic compound includes an acrylate. Suitable examples of (meth)acrylates include, but are not limited to, 2-ethylhexylacrylate, 2-ethylhexylmethacrylate, methylacrylate,

methylmethacrylate, butylacrylate, ethylacrylate, hexylacrylate, isobutylacrylate,

butylmethacrylate, ethylmethacrylate, isooctylacrylate, decylacrylate, dodecylacrylate, vinyl acrylate, acrylic acid, methacrylic acid, neopentylglycol diacrylate,

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,

caprolactone acrylate, perfluorobutyl acrylate, perfluorobutyl methacrylate, 1 H, 1 H, 2H, 2H- heptadecafluorodecyl acrylate, 1 H, 1 H, 2H, 2H-heptadecafluorodecyl methacrylate,

tetrahydroperfluoroacrylate, phenoxyethyl acrylate, phenoxyethyl methacrylate, bisphenol A acrylate, ethoxylated bisphenol A acrylate, ethoxylated bisphenol A methacrylate, N-vinyl pyrrolidone, N-vinyl caprolactam, N-isopropyl acrylamide, N,N-dimethyl acrylamide, t-octyl acrylamide, cyanotethylacrylates, diacetoneacrylamide, N-vinyl acetamide, N-vinyl formamide, bisphenol A dimethacrylate, hexafluoro bisphenol A diacrylate, hexafluoro bisphenol A dimethacrylate, diethyleneglycol diacrylate, diethyleneglycol dimethacrylate, dipropyleneglycol diacrylate, dipropyleneglycol dimethacrylate, polyethyleneglycol diacrylate, polyethyleneglycol dimethacrylate, polypropyleneglycol diacrylate, polypropyleneglycol dimethacrylate,

trimethylolpropanetriacrylate, trimethylolpropanetrimethacrylate, ethoxylated

trimethylolpropanetriacrylate, ethoxylated trimethylolpropanetrimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate. The organic (meth)acrylate compound may include only acrylate or methacrylate functionality. Alternatively, 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. [0052] Alternatively, starting material C) may comprise an organic (meth)acrylic compound,

which may have formula

are as described above. RH is selected from the group consisting of oxygen and NH. When R^ is an oxygen atom, the (meth)acrylic compound is i) a (meth)acrylate. When R^H is NH, then 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.

Alternatively, R^F may be an amino group such as dimethylamino.

[0053] 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.

[0054] 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, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, and fatty alcohols, 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

polyoxyethylene (40) ether sold under the name Triton X405 by the Dow Chemical Company, Midland, Michigan; (iii) nonylphenyl polyoxyethylene (10) ether sold under the name Makon 10 by the Stepan Company, Northfield, Illinois; (iv) ethoxylated alcohols sold under the name Trycol 5953 by Henkel Corp./Emery Group, Cincinnati, Ohio; (v) ethoxylated alcohols sold under the name Brij L23 and Brij L4 by Croda Inc. Edison, NJ, (vi) alkyl-oxo alcohol polyglycol ethers such as ©GENAPOL UD 050, and Genapol UD1 10, (vii) 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. They are 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. Other useful commercial nonionic surfactants are nonylphenoxy polyethoxy ethanol (10EO) sold under the trademark MAKON® 10 by Stepan Company, Northfield, Illinois; polyoxyethylene 23 lauryl ether (Laureth- 23) sold commercially under the trademark BRIJ® 35L by ICI Surfactants, Wilmington,

Delaware; and RENEX® 30, a polyoxyethylene ether alcohol sold by ICI Surfactants,

Wilmington, Delaware. The aqueous phase may contain 0.0001 to 10 parts nonionic surfactant per 100 parts of aqueous phase by weight.

[0055] In the method described above, E) the water may be deionized water or distilled water.

[0056] 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.

[0057] 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), iii), iv), v), vi), vii), viii), ix), x), xi), xii), xiii), xiv), xv), xvi), and xvii). Alternatively, the liberating compound may be selected from, acetic acid, methacrylic acid, isophorone diisocyanate, or a combination thereof.

[0058] 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)

[0059] Svstem/Apparatus: 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.

[0060] 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

polydiorganosiloxane and an organic (meth)acrylic compound. In the second packed bed, 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. When desired, such as when the particles 102 in the first packed bed swell as they sorb the volatile component causing an undesirable increase in pressure drop through the packed bed, and/or the rate at which the particles 102 can sorb the volatile component slows to an undesired rate as the particles sorb more of the volatile component, valves 106 and 107 may be shut and feed valve 206 and outlet valve 207 may be opened. This will re-route the mixture to flow through feed line 205 into the second contactor 201 through inlet valve 206 into the second inlet 203. As the mixture passes through the second contactor 201 , the volatile component is sorbed into the particles 202. The depleted mixture exits the second contactor 201 through the second outlet 204, through outlet valve 207 and out through outlet line 208. The depleted mixture is a purified product that may be stored in the same or different collection container, not shown.

[0061] After the mixture stops flowing through the first contactor 101 , the particles 102 in the contactor 101 may be regenerated. For example, 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. After the particles 102 in the first contactor 101 are regenerated, 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. The second contactor 201 may optionally be heated, and/or the sweep gas may optionally be heated.

[0062] Figure 1 is included to demonstrate the invention to those of ordinary skill in the art. Flowever, those of skill in the art should, in light of the present disclosure, appreciate that many changes can be made in the specific embodiments which are disclosed and still obtain a like or similar result without departing from the spirit and scope of the invention set forth in the claims. For example, 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). 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. Alternatively, 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. Alternatively, additional contactors (not shown) may be configured in parallel or in series configuration with the contactors 101 , 201 . Optionally, when 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. EXAMPLES

[0063] These examples are intended to illustrate some embodiments of the invention and should not be interpreted as limiting the scope of the invention set forth in the claims.

[0064] In this Reference Example 1 , equilibrium toluene vapor sorption isotherm experiments were conducted with a VTI-SA+ vapor sorption analyzer from TA Instruments. Samples in the amount of 5 mg each of sorbent were placed onto a suspended microbalance. The samples were dried with nitrogen gas at 80°C for 3 h to remove sorbed water vapor and contaminants, and initial mass was recorded, before exposure to a mixture of nitrogen gas and toluene vapor at 20°C and toluene relative pressures of 0.20, 0.40, 0.60, and 0.80. At each relative pressure, the system was allowed sufficient time to reach an equilibrium state. Toluene from Fischer Scientific was used.

[0065] The resulting equilibrium sample mass was then recorded and compared to the initial mass to determine the quantity of toluene sorbed. After completion of the isotherm at 20°C, each sample was exposed to dry nitrogen at 80°C for 3 h to fully desorb toluene and regenerate the sorbent before exposure to toluene vapor at 40°C and identical relative pressures as at 20°C. All sorption isotherms were performed at a total pressure of 1 bar.

[0066] In this Reference Example 1A, equilibrium octamethylcyclotetrasiloxane (D4) vapor sorption isotherm experiments were conducted with a VTI-SA+ vapor sorption analyzer from TA Instruments. Samples in the amount of 10-20 mg each of sorbent were placed onto a suspended microbalance. The samples were dried with nitrogen gas at 120°C for 6 h to remove sorbed water vapor and contaminants, and initial mass was recorded, before exposure to a mixture of nitrogen gas and D4 vapor at 30°C and D4 relative pressures of 0.05, 0.10, 0.20,

0.40, and 0.60. At each relative pressure, the system was allowed sufficient time to reach an equilibrium state.

[0067] The resulting equilibrium sample mass was then recorded and compared to the initial mass to determine the quantity of D4 sorbed. After completion of the isotherm at 30°C, each sample was exposed to dry nitrogen at 120°C for 6 h to fully desorb toluene and regenerate the sorbent before exposure to toluene vapor at 40°C and identical relative pressures as at 30°C.

All sorption isotherms were performed at a total pressure of 1 bar.

[0068] 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.

¾? = w - ?_t) (1 ) [0069] Sorption coefficients were calculated by fitting the integrated form of Equation (1 ), with boundary conditions q_t = 0 at t= 0 and q_t = q^* as t to experimental data using a least squares objective function. The initial condition corresponded to the equilibrium condition at 20°C and a toluene relative pressure of 0.20 while the equilibrium condition as t

corresponded to q^* at 20°C and a toluene relative pressure of 0.40.

[0070] In this Reference Example 2, 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. To enhance the image contrast, 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. For Z-contrast image, scanning TEM (STEM) with JEOL STEM control system was used. For 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.

[0071] To get quantitative phase maps of the pHEMA and PDMS in the copolymerized particles, the 2-D spectrum imaging of EELS with scanning TEM (STEM) were processed via multiple least square (MLS) fitting techniques. The 2-D chemical maps of pHEMA and PDMS showed that the pHEMA formed dispersed domains in the PDMS matrix. The core-loss EELS spectra for Si, C and O and the spectrum images were detected using a Gatan GIF system together with a STEM of JEOL 21 OOF TEM. The pixel size was 4 nm.

[0072] For a multicomponent system, the observed spectral intensity at a given pixel (i,j) of an EELS spectrum-image dataset can be represented by:

where hot is the total number of collected electrons in the energy loss spectrum, l₀ represents the zero loss peak, y is the relative specimen thickness and S(E) is the normalized single scattering distribution. The relative specimen thickness (y) can be expressed in terms of the inelastic mean free path (A)·, y= t/l, where t is the specimen thickness. To get the compositional map from the multicomponent system, the raw spectrum h_j(E) generated at each pixel (i,j) of a dataset was processed following a series of steps to recover the single-scattering distribution Si_j(E)^{18 19}. MLS fitting was applied to experimental spectra, Si_j(E), via equation (1 ) using a linear combination of characteristic reference spectra, S_q(E), obtained from each pure component after single-scattering deconvolution:

where Q is the number of components (reference spectra) of the system and a_q(i,j ) is the fitting coefficient, which is the fraction of each spectral component S_q(E) that contributes to Si_j(E).

[0073] Using the fitting coefficients, the mass fraction F_q(i,j) at pixel (i,j) of each component q

where 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. To calculate mass fraction of each component in the system, it was assumed that the total inelastic scattering cross-sections for both PDMS and pHEMA were the same.

[0074] In this Reference Example 3, Differential Scanning Calorimetry was performed as follows. Each sample (8 to 1 1 mg) was placed in an aluminum (Al) pan with crimped lid, which was placed in the cell of a TA Instruments 2920 Differential Scanning Calorimeter under He purge, pre-heated at 160°C for 5 min, cooled to -150°C, and re-heated to 160°C at 10°C/min.

[0075] In this Comparative Example C1 , a crosslinked PDMS silicone elastomer was prepared by mixing 10.00 g of Sylgard™ 184 Base and 1.00 g of Sylgard™ 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 small sample was cut from the cured disk of crosslinked silicone elastomer and tested for toluene vapor sorption using the method of Reference Example 1. The results are shown below. These samples each had a rubbery texture. This showed the typical toluene absorption capacities for a crosslinked silicone elastomer. Table C1 : Equilibrium uptake of toluene vapor at 20°C and 40°C in silicone rubber, Comparative Example C1.

[0076] In this Comparative Example C2, a moderate viscosity trimethylsilyl-terminated PDMS fluid (DOWSIL® 350 cSt 200 Fluid) was obtained from Dow Silicones Corporation. A sample of this fluid, which was an oily liquid, was placed into the sample pan and tested for equilibrium toluene absorption using the method of Reference Example 1. The results are shown below. This example showed typical toluene absorption capacities for a silicone liquid.

Table C2: Equilibrium uptake of toluene vapor at 20°C and 40°C in silicone oil, Comparative Example C2.

[0077] In this Comparative Example C3, pellets of poly(methylmethacrylate) (PMMA) of average number molecular weight 350,000 were obtained from Sigma-Aldrich. Several pellets were placed onto the sample pan and tested for equilibrium octamethylcyclotetrasiloxane (D4) vapor absorption using the method of Reference Example 1 A. The results are shown below. This example showed typical D4 vapor absorption capacities for a neat PMMA material.

[0078] In this Example 1 , 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

SpeedMixer for 30 seconds. Then the contents were diluted by adding 2 ml. increments of deionized water and mixing for 30 seconds after each increment for a total of 20 ml. additional water. The resulting emulsion was transferred to a clean glass vial containing a stir bar, and 0.074 g of glacial acetic acid (Aldrich) was added. The sample was allowed to react for 2 h, after which the particles were washed and recovered by vacuum filtration over a Buchner funnel then oven dried in a vacuum oven with pressure of < 25 mm Hg overnight at 25°C. The DSC method of Reference Example 3 showed that the resulting copolymer had two glass transition temperatures, one associated with the PDMS segments at -124°C and one associated with the pHEMA phase at 99°C.

[0079] 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. In addition to introducing polarity to the particles, 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.

Table 1

[0080] 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. In a dark field STEM image of the inside structure of the particle, lighter density region (PHEMA) revealed darker contrast, while heavier density region (PDMS) revealed darker contrast in the bright filed TEM image. The results indicated that the constituents of the particles did not undergo large scale phase separation into silicone-free bulk domains as by conventional free-radical based emulsion polymerization techniques, but rather formed a particle that comprised microphase- separated organic rich domains in a continuous silicone matrix. Also, agreement between the theoretical monomer loading and actual particle composition provided confirmation that the copolymerization efficiency was high.

[0081] Equilibrium toluene vapor sorption isotherm capacity (mg toluene/g sorbent) was measured as a function of toluene relative pressure and temperature for Example 1 , using the method of Reference Example 1 . The results are shown in Table 2, below.

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.

[0082] In this Example 2, a sorbent copolymer was prepared by copolymerizing 1.22 g of NIPAAM with 2.376 g of a mono-methacryloxypropyl-terminated PDMS macromonomer having Mn = 5,000 g/mol (Gelest MCR-M17) in an 18% solution of THF (Sigma-Aldrich) in a 40 mL scintillation vial. This was done by pre-blending the NIPAAM and MCR-M17 into THF, then adding 0.57 g TEB-PDA along with a clean magnetic stir bar. While mixing at room

temperature, a solution of 0.420 g of glacial acetic acid in 9.574 g of THF was added to decomplex the initiator and initiate co-polymerization. The samples were allowed to stir overnight to react completely. The samples were then washed with methanol and water before being allowed to dry in a vacuum oven at 40°C. These particles showed two distinct glass transition temperatures by DSC, one for the PDMS segments of -125°C by DSC, and one corresponding to the pNIPAAM segments at 122°C. The resulting sample was semi-rigid solid material that could be divided into smaller particles. [0083] Equilibrium toluene vapor sorption isotherm capacity (mg toluene/g sorbent) was measured as a function of toluene relative pressure and temperature for Example 2, using the method of Reference Example 1 . The results are shown in Table 3.

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.

[0084] In this Example 3, 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.

To this mixture was added a clean Teflon-coated magnetic stir bar and 0.103 g of glacial acetic acid. The resulting reaction mixture was allowed to stir for 2 h at room temperature and ambient pressure. The resulting product was washed and filtered using a Buchner funnel then dried overnight in a vacuum oven at 54°C and a pressure of < 25 mm Fig. The resulting copolymer was in the form of solid particles. These particles showed two distinct glass transition temperatures by DSC, one for the PDMS segments of -123°C, and one corresponding to the pTHFMA segments at 60 °C. This copolymer was a solid, non-tacky powder.

[0085] Equilibrium toluene vapor sorption isotherm capacity (mg toluene/g sorbent) was measured as a function of toluene relative pressure and temperature for Example 3, using the method of Reference Example 1 . The results are shown in Table 4.

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.

[0086] In this Example 4, 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. 5 ml. of the emulsified reaction mixture was transferred to a clean glass vial with a magnetic stir bar. A micropipette was then used to add the acidified water solution to the emulsified reaction mixture to commence copolymerization. The mixture was allowed to stir at 780 rpm for 2 hours. The resulting product was washed and recovered by vacuum filtration over a Buchner funnel then oven dried in a vacuum oven with pressure of < 25 mm Hg overnight at 25°C. The DSC method of Reference Example 3 showed that the resulting copolymer had two glass transition temperatures, one associated with the PDMS segments at -123 °C and one associated with the pBzMA phase near 50°C. This copolymer was a solid, non-tacky powder that was significantly less soft as compared to a silicone elastomer particle that did not include an organic

component.

[0087] Equilibrium toluene vapor sorption isotherm capacity (mg toluene/g sorbent) was measured as a function of toluene relative pressure and temperature for Example 4, using the method of Reference Example 1 . The results are shown in Table 5.

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.

[0088] In this Example 5, 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. Each increment was followed by a 30 s mixing step. To this mixture was added a clean Teflon-coated magnetic stir bar and 0.090 g of glacial acetic acid. The reaction was allowed to stir for 2 hours at ambient temperature and pressure. The product was washed and filtered using a Buchner funnel then dried overnight in a vacuum oven at 54°C and a pressure of < 25 mm Hg overnight. The resulting product was in the form of solid particles. These particles showed two distinct glass transition temperatures by DSC, one for the PDMS segments of -123°C, and one corresponding to the pDMAEMA segments at near 6°C. The resulting sample was a solid, non-tacky powder.

[0089] Equilibrium toluene vapor sorption isotherm capacity (mg toluene/g sorbent) was measured as a function of toluene relative pressure and temperature for Example 5, using the method of Reference Example 1 . The results are shown in Table 6.

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.

[0090] The overall toluene vapor sorption mass transfer coefficients (min^-1) at 20°C and toluene relative pressure 0.40 are summarized below for all examples. The initial mass of sorbed toluene corresponded to equilibrium conditions at 20°C, relative pressure 0.20.

Table 7 - Comparison

[0091] These results demonstrated favorable mass transfer characteristics of the copolymers as sorbents, which imparted process and cost advantages for methods of separating a gas as compared to pure polyorganosiloxanes. Under the conditions tested in the examples and comparative examples above, the copolymers of a (meth)acrylate-functional

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).

[0092] In this Example 6, 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. To a separate polypropylene mixing cup was added about a clean Teflon-coated magnetic stir bar, about 20 g of deionized water and 0.076 g of glacial acetic acid. The initiated monomer and surfactant emulsion was added dropwise into the acidified water solution which was stirred continuously at 200 rpm. The reaction was allowed to stir for 4 hours at ambient temperature and pressure. The product was washed and filtered using a Buchner funnel then dried overnight in a vacuum oven at 40°C and a pressure of < 25 mm Hg overnight. The resulting product was in the form of solid particles. The dried particles were tested for D4 vapor sorption as follows.

[0093] Equilibrium D4 vapor sorption isotherm capacity (mg D4/g sorbent) was measured as a function of D4 relative pressure and temperature for Example 6, using the method of Reference Example 1A. The results are shown in Table 7.

Table 7: Equilibrium uptake of D4 vapor at 30°C and 40°C in PDMS/PMMA, Example 6.

[0094] Industrial Applicability: 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. Optionally, 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. Due to the availability and sometimes necessity to separate volatile components from streams that are already warm without heat loss from contacting a cold sorbent, as well as the energy and cost savings of being able to use unheated air and/or inert gas streams to regenerate the sorbent, the method described herein employing a copolymer as the sorbent has significant potential consequences for energy and cost-efficiency gains in traditional gas separations. Also disclosed are 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.

[0095] Definitions and Usage of Terms: All amounts, ratios, and percentages are by weight unless otherwise indicated. The articles‘a’,‘an’, and‘the’ each refer to one or more, unless otherwise indicated by the context of the specification. The disclosure of ranges includes the range itself and also anything subsumed therein, as well as endpoints. For example, disclosure of a range of 2.0 to 4.0 includes not only the range of 2.0 to 4.0, but also 2.1 , 2.3, 3.4, 3.5, and 4.0 individually, as well as any other number subsumed in the range. Furthermore, 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. Similarly, the disclosure of Markush groups includes the entire group and also any individual members and subgroups subsumed therein. For example, 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.

[0096] 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. [0097] 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.

[0098] The term“substituted” as used herein 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).

[0099] The term“sorb” and its derivatives, means absorbing and/or adsorbing; alternatively adsorbing, and alternatively absorbing. Alternatively, sorb can include both absorbing and adsorbing.

[0100] The term“volatile” and its derivatives, means that one component may have a higher vapor pressure than another component. In certain embodiments, 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. At a given temperature, a substance with a higher vapor pressure vaporizes more readily than a substance with a lower vapor pressure.) In other embodiments, 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.

[0101] The following abbreviations used throughout this application have the meanings set forth in Table 8.

Table 8: Abbreviations

Embodiments of the Invention

[0102] In a first embodiment, a method for depleting a volatile component in a mixture comprising the volatile component and at least one other component comprises:

1 ) sorbing at least some of the volatile component by a copolymer of a (meth)acrylate- functional polyorganosiloxane and an organic (meth)acrylic compound, thereby forming a depleted mixture containing less of the volatile component than the mixture before sorbing and enriching the copolymer with sorbed volatile component thereby forming an enriched copolymer, 2) desorbing at least some of the sorbed volatile component from the enriched copolymer, thereby forming a desorbed volatile component and a regenerated copolymer containing less of the sorbed volatile component than the enriched copolymer before desorbing, and 3) using the regenerated copolymer as all or a portion of the copolymer in repeating step

1 ) ·

[0103] In a second embodiment, 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).

[0104] In a third embodiment, in the method of the first or second embodiment, the

(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.

[0105] In a fourth embodiment, in the method of any one of the first to third embodiments, 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.

[0106] In a fifth embodiment, in the method of any one of the first to fourth embodiments, the volatile component is a volatile organic compound.

[0107] In a sixth embodiment, in the method of any one of the first to fourth embodiments, 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.

[0108] In a seventh embodiment, in the method of any one of the first to sixth embodiments, 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.

[0109] In an eighth embodiment, in the method of any one of the first to seventh

embodiments, the mixture is a process vapor/gas stream and the depleted mixture is a depleted process vapor/gas.

[0110] In a ninth embodiment, in the method of any one of the first to eighth embodiments, the copolymer is prepared by a method comprising:

i) combining 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;

optionally, ii) 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

iv) optionally recovering the copolymer.

[0111] In a tenth embodiment, in the method for preparing the copolymer in the ninth embodiment, 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).

[0112] In an eleventh embodiment, starting material B) is selected from the group consisting of:

formula

formula

both B1 ) and B2), where 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.

[0113] In a twelfth embodiment, in the method for preparing the copolymer in any one of the ninth to eleventh embodiments, 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. [0114] In a thirteenth embodiment, in the method for preparing the copolymer in the twelfth embodiment, starting material C) is selected from the group consisting of i) (meth)acrylates and ii) (meth)acrylamides.

[0115] In a fourteenth embodiment, in the method for preparing the copolymer in the thirteenth embodiment, 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.

[0116] In a fifteenth embodiment, in the method for preparing the copolymer in any one of the ninth to fourteenth embodiments, starting material F) the solvent is used in step i).

[0117] In a sixteenth embodiment, in the method for preparing the copolymer in any one of the ninth to fifteenth embodiments, 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.

[0118] In a seventeenth embodiment, 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).

[0119] In an eighteenth embodiment, an apparatus 100 for depleting a volatile component in a mixture comprises:

a) 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,

optionally b) a collector in fluid communication with the outlet 104 of the contactor and configured for collecting the depleted mixture, and

optionally c) a recovery apparatus in fluid communication with the copolymer 102 and configured for collecting desorbed volatile component from the copolymer 102.

[0120] In a nineteenth embodiment, in the apparatus 101 of the eighteenth embodiment, 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.

[0121] In a twentieth embodiment, 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

(meth)acrylate-functional polyorganosiloxane and the organic (meth)acrylic compound, wherein during operation of the apparatus 100 the mixture comprising the volatile component and at least one other component enters the second contactor 201 through the second inlet 203, contacts the second copolymer 202 such that at least some of the volatile component is sorbed by the second copolymer 202, and a depleted mixture exits the second contactor 201 through the second outlet 204.

Claims

Claims:

1. A method for depleting a volatile component in a mixture comprising the volatile component and at least one other component, the method comprising

1 ) sorbing at least some of the volatile component by a copolymer of a (meth)acrylate- functional polyorganosiloxane and an organic (meth)acrylic compound, thereby forming a depleted mixture containing less of the volatile component than the mixture before sorbing and enriching the copolymer with sorbed volatile component thereby forming an enriched copolymer,

2) desorbing at least some of the sorbed volatile component from the enriched copolymer, thereby forming a desorbed volatile component and a regenerated copolymer containing less of the sorbed volatile component than the enriched copolymer before desorbing, and

3) using the regenerated copolymer as all or a portion of the copolymer in repeating step

1 ) ·

2. The method of claim 1 , further comprising 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).

3. The method of claim 1 or claim 2, where the (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.

4. The method of any one of claims 1 to 3, where the organic (meth)acrylic compound is selected from the group consisting of i) (meth)acrylate and ii) (meth)acryl amide compounds.

5. The method of claim 4, where 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.

6. The method of claim 4, where the (meth)acrylamide is selected from the group consisting of N-isopropylacrylamide and N-isopropylmethacrylamide.

7. The method of any one of claims 1 to 6, where the volatile component is a volatile organic compound.

8. The method of any one of claims 1 to 6, where 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.

9. The method of any one of claims 1 to 8, where 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.

10. The method of any one of claims 1 to 9, where the mixture is a process vapor/gas stream and the depleted mixture is a depleted process vapor/gas.

1 1 . The method of any one of the preceding claims, where the copolymer has a form selected from thin films, coated support materials, nanorods, nanospheres, beads, granules, powders, pellets, particulates, and fibers.

12. The method of any one of the preceding claims, where 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).

13. An apparatus for depleting a volatile component in a mixture, the apparatus comprising: a) a contactor defining an internal volumetric space and having an inlet and an outlet in fluid communication with the inlet 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, wherein during operation of the apparatus a mixture comprising the volatile component and at least one other component enters the contactor through the inlet, contacts the copolymer such that at least some of the volatile component is sorbed by the copolymer, and a depleted mixture exits the contactor through the outlet, optionally b) a collector in fluid communication with the outlet of the contactor and configured for collecting the depleted mixture, and

optionally c) a recovery apparatus in fluid communication with the copolymer and configured for collecting desorbed volatile component from the copolymer.

14. The apparatus of claim 13, where the contactor 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.

15. The apparatus of claim 14, further comprising a splitter or second mixture feed to a second inlet of a second contactor disposed with the apparatus for parallel flow of the mixture, where the second contactor defines a second internal volumetric space and has a second outlet in fluid communication with the second inlet via the second internal volumetric space, wherein the second internal volumetric space of the second contactor contains a second copolymer of a (meth)acrylate-functional polyorganosiloxane and an organic (meth)acrylic compound, which may be the same as or different from the copolymer of the (meth)acrylate-functional

polyorganosiloxane and the organic (meth)acrylic compound, wherein during operation of the apparatus the mixture comprising the volatile component and at least one other component enters the second contactor through the second inlet, contacts the second copolymer such that at least some of the volatile component is sorbed by the second copolymer, and a depleted mixture exits the second contactor through the second outlet.