Method of recycling homogenous platinum-group metal catalyst

Abstract

A method of recycling a homogeneous platinum-group metal catalyst is disclosed. The method comprises disposing an oxidized anode in an electrically non-conductive media comprising the homogenous platinum-group metal catalyst to adsorb the homogenous platinum-group metal catalyst to a surface of the oxidized anode to form a coated anode in a first mixture. The coated anode is disposed in an electrically conductive media, a reduction potential is applied to the anode to release the homogenous catalyst into the electrically conductive media to form a second mixture. The second mixture and a precipitation agent are combined to precipitate out an electrolyte from the second mixture to yield a third mixture including a recycled solution including the homogenous platinum-group metal and precipitated electrolyte. A recycled solution including a recycled homogenous platinum-group metal catalyst is also disclosed.

Description

Aty Ref.: 157928.216186-WO (86207) METHOD OF RECYCLING HOMOGENOUS PLATINUM-GROUP METAL CATALYST CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority to and al advantages of U.S. Provisional Patent Application No.63 / 680,834 filed on 08 August 2024, the content of which is incorporated herein by reference. FIELD OF THE INVENTION

[0002] The present disclosure generaly relates to a method of recycling a catalyst and, more specificaly, to a method of recycling a homogenous platinum-group metal catalyst. The present disclosure also relates to a recycled solution comprising a recycled homogenous platinum-group metal catalyst and related methods. DESCRIPTION OF THE RELATED ART

[0003] Hydrosilylation reactions are generaly known in the art and involve an addition reaction between silicon-bonded hydrogen and aliphatic unsaturation. Hydrosilylation reactions are utilized in various applications. For example, curable compositions may rely on hydrosilylation reactions for purposes of curing or crosslinking components of the curable compositions. Hydrosilylation reactions may also be utilized to prepare individual components or compounds, e.g. components for inclusion in curable compositions. Given the excelent and desirable properties of silicones and other silicon-based materials, hydrosilylation reactions are utilized in myriad industries.

[0004] Hydrosilylation reactions are caried out in the presence of a catalyst, which typicaly includes a platinum-group metal due to its excelent catalytic activity. Metal complexes can also be utilized to catalyze hydrosilylation reactions. These catalysts are expensive and can be chalenging to separate out from hydrosilylation media for efective reuse. BRIEF SUMMMARY

[0005] The present disclosure provides a method of recycling a homogenous platinum-group metal catalyst. The method comprises disposing an oxidized anode in an electricaly non- conductive media comprising the homogenous platinum-group metal catalyst to adsorb the homogenous platinum-group metal catalyst to a surface of the oxidized anode to form a coated anode in a first mixture. The electricaly non-conductive media is substantialy free from an electrolyte.

[0006] The method also comprises removing the coated anode from the first mixture and disposing the coated anode in an electricaly conductive media comprising an electrolyte. A reduction potential or reduction current is applied to the coated anode to release the homogenous platinum-group metal catalyst from the coated anode into the electricaly conductive media to form a second mixture.Aty Ref.: 157928.216186-WO (86207)

[0007] The method also comprises combining a precipitation agent and the second mixture to cause precipitation of the electrolyte to yield a third mixture comprising a recycled solution comprising the homogenous platinum-group metal catalyst and precipitated electrolyte.

[0008] A recycled solution comprising the homogenous platinum-group metal catalyst formed in accordance with the method is also provided. Brief Description of the Drawings

[0009] Various advantages and aspects of this disclosure may be understood in view of the folowing detailed description when considered in connection with the accompanying drawing, wherein:

[0010] Figure 1a depicts the percentage and amount (mgPt / gadsorbent) of platinum uptake as a function of time (in minutes) for a neutral PVF-CNT electrode and an oxidized PVF-CNT electrode as described in the Examples;

[0011] Figure 1b depicts the platinum recovery percentage with and without removal of the excess electrolyte from a pre-oxidized PVF-CNT electrode using a rinsing solvent as described in the Examples;

[0012] Figure 2 depicts platinum regeneration eficiency and turnover number (TON) retention after the release of the platinum in an electricaly conductive media with no ligand and with norbornene as described in the Examples;

[0013] Figure 3 depicts platinum regeneration eficiency and TON retention for the release step with varying mol percentages of norbornene as described in the Examples;

[0014] Figure 4 depicts the accumulated TON until deactivation of the platinum catalyst for an electricaly non-conductive hydrosilylation solution containing norbornene. 1,3- divinyltetramethyldisiloxane (DVSi), or no ligand, as described in the Examples;

[0015] Figure 5 depicts the accumulated TON until deactivation of the platinum catalyst for an electricaly conductive media comprising acetone, THF, chloroform, DCM, or toluene as described in the Examples;

[0016] Figure 6 depicts a ratio of the TOF of a second reaction using a recycled catalyst to the TOF of a first reaction using a pristine catalyst at diferent reaction start times for solutions with no ligand added, norbornene added, or DVSi added, as described in the Examples; and

[0017] Figure 7 depicts platinum regeneration percentage after the release in conductive media under reduction potential as described in the Examples. DETAILED DESCRIPTION OF THE DISCLOSURE

[0018] The present disclosure provides a method of recycling a homogenous platinum-group metal catalyst (“the method”). The method alows for the recovery of a homogenous platinum- group catalyst with excelent eficiency and regeneration. Thus, the disclosure alows for repeated use of such homogenous platinum-group metal catalysts, e.g. in successive hydrosilylation reactions, thus providing cost reductions.Aty Ref.: 157928.216186-WO (86207)

[0019] The method comprises disposing an oxidized anode in an electricaly non-conductive media comprising the homogenous platinum-group metal catalyst to adsorb the homogenous platinum-group metal catalyst to a surface of the oxidized anode to form a coated anode in a first mixture. The electricaly non-conductive media is substantialy free of an electrolyte. By “substantialy free” with reference to the electricaly non-conductive media being substantialy free of an electrolyte, it is meant that the electricaly non-conductive media can comprise an electrolyte in an amount that does not make the electricaly non-conductive media electricaly conductive. For example, the electricaly non-conductive media may comprise an electrolyte in an amount of less than 4, alternatively less than 3, alternatively less than 2, alternatively less than 1, alternatively 0, weight percent based on the total weight of the electricaly non-conductive media. The first mixture is distinguished from the electricaly non-conductive media simply by virtue of the reduction of the homogenously platinum-group metal catalyst from the electricaly non- conductive media when forming the coated anode. If desired, other compounds or components may be added in or to the first mixture, although typicaly that is not the case.

[0020] The coated anode need not be fuly coated with the homogenous platinum-group metal catalyst; the coated anode may be continuously or discontinuously coated, or partialy coated in any patern, random or otherwise. The coated anode is removed from the first mixture and disposed in an electricaly conductive media comprising an electrolyte. A reduction potential or a reduction curent is applied to the coated anode to release the homogenous catalyst from the coated anode into the electricaly conductive media to form a second mixture. The second mixture and a precipitation agent are combined to cause precipitation of the electrolyte to yield a third mixture comprising a recycled solution comprising the homogeneous platinum-group metal catalyst and precipitated electrolyte.

[0021] In certain embodiments, the method further comprises preparing the electricaly non- conductive media. In such embodiments, the method may further comprise the step of contacting (A) an unsaturated compound and (B) a silicon hydride compound in the presence of the homogenous platinum-group metal catalyst to give a hydrosilylation reaction product. The electricaly non-conductive media may comprise, alternatively consist essentialy of, alternatively consist of a hydrosilylation reaction product. Generaly, the step of disposing an anode in the electricaly non-conductive media is preceded by the step of contacting (A) an unsaturated compound and (B) a silicon hydride compound. Suitable examples of the unsaturated compound (A) and the silicone hydride compound (B) are described in greater detail below.

[0022] Typicaly, the electricaly non-conductive media is a flowable liquid at room temperature and atmospheric pressure, i.e., the electricaly non-conductive media has a measurable viscosity at room temperature and atmospheric pressure. In certain embodiments, when the electricaly non-conductive media comprises the reaction product, the reaction product itself is a flowable liquid at room temperature and atmospheric pressure. In other embodiments, the electricaly non-Aty Ref.: 157928.216186-WO (86207) conductive media further comprises a vehicle for carrying or solubilizing the reaction product in the electricaly non-conductive media. For example, in such embodiments, the reaction product may be a solid at room temperature in the absence of any vehicle, and the vehicle is utilized to give the electricaly non-conductive media in flowable liquid form.

[0023] In some embodiments, the electricaly non-conductive media further comprises a catalyst stabilizing agent comprising an aliphatic unsaturated moiety. The catalyst stabilizing agent may be referred to herein as a ligand. The catalyst stabilizing agent may comprise a hydrocarbon comprising an aliphaticaly unsaturated group or an organosiloxane comprising a silicon-bonded aliphaticaly unsaturated group. In specific embodiments, the catalyst stabilizing agent comprises the hydrocarbon, and the hydrocarbon comprises a cyclic hydrocarbon. Non-limiting examples of the catalyst stabilizing agent include methacrylate, cycloolefins (e.g., cyclohexane, cycloheptane, cyclooctene, norbornene, cyclododecene), and quinones (e.g., benzoquinone, hydroquinone, anthraquinone, chloranil). In certain embodiments, the catalyst stabilizing agent comprises, alternatively consists essentialy of norbornene (NB). In specific embodiments, the catalyst stabilizing agent comprises, alternatively consists essentialy of, alternatively consists of 1,3- divinyltetramethyldisiloxane (DVSi).

[0024] The homogeneous platinum-group metal catalyst may be any homogenous catalyst comprising a platinum-group metal atom (i.e., Pt, Pd, Rh, Ru, Ir, Os).

[0025] In specific embodiments, the homogeneous platinum-group metal catalyst comprises platinum. In these embodiments, the homogeneous platinum-group metal catalyst is exemplified by, for example, platinum black, compounds such as chloroplatinic acid, chloroplatinic acid hexahydrate, a reaction product of chloroplatinic acid and a monohydric alcohol, platinum bis(ethylacetoacetate), platinum bis(acetylacetonate), platinum chloride, and complexes of such compounds with olefins or organopolysiloxanes, as wel as platinum compounds microencapsulated in a matrix or core-shel type compounds.

[0026] Complexes of platinum with organopolysiloxanes suitable for use as the homogeneous platinum-group metal catalyst include 1,3-diethenyl-1,1,3,3-tetramethyldisiloxane complexes with platinum. These complexes may be microencapsulated in a resin matrix. Alternatively, the homogeneous platinum-group metal catalyst can comprise 1,3-diethenyl-1,1,3,3- tetramethyldisiloxane complex with platinum. The homogeneous platinum-group metal catalyst may be prepared by a method comprising reacting chloroplatinic acid with an aliphaticaly unsaturated organosilicon compound such as divinyltetramethyldisiloxane, or alkene-platinum- silyl complexes. Alkene-platinum-silyl complexes may be prepared, for example by mixing 0.015 mole (COD)PtCl2 with 0.045 mole COD and 0.0612 moles HMeSiCl2.

[0027] The homogeneous platinum-group metal catalyst may also, or alternatively, be a photoactivatable hydrosilylation-reaction catalyst, which may initiate curing via iradiation and / or heat. The photoactivatable hydrosilylation-reaction catalyst can be any hydrosilylation-reactionAty Ref.: 157928.216186-WO (86207) catalyst that comprises a platinum-group metal and is capable of catalyzing a hydrosilylation reaction, particularly upon exposure to radiation having a wavelength of from 150 to 800 nanometers (nm).

[0028] Specific examples of photoactivatable hydrosilylation-reaction catalysts suitable for the homogeneous platinum-group metal catalyst include, but are not limited to, platinum(I) β- diketonate complexes such as platinum(I) bis(2,4-pentanedioate), platinum(I) bis(2,4- hexanedioate), platinum(I) bis(2,4-heptanedioate), platinum(I) bis(1-phenyl-1,3-butanedioate, platinum(I) bis(1,3-diphenyl-1,3-propanedioate), platinum(I) bis(1,1,1,5,5,5-hexafluoro-2,4- pentanedioate); (^-cyclopentadienyl)trialkylplatinum complexes, such as (Cp)trimethylplatinum, (Cp)ethyldimethylplatinum, (Cp)triethylplatinum, (chloro-Cp)trimethylplatinum, and (trimethylsilyl- Cp)trimethylplatinum, where Cp represents cyclopentadienyl; triazene oxide-transition metal complexes, such as Pt[C6H5NNNOCH3]4, Pt[p-CN-C6H4NNNOC6H11]4, Pt[p- H3COC6H4NNNOC6H11]4, Pt[p-CH3(CH2)x-C6H4NNNOCH3]4, 1,5-cyclooctadiene.Pt[p-CN- C6H4NNNOC6H11]2, 1,5-cyclooctadiene.Pt[p-CH3O-C6H4NNNOCH3]2, [(C6H5)3P]3Rh[p- CN-C6H4NNNOC6H11], and Pd[p-CH3(CH2)x—C6H4NNNOCH3]2, where x is 1, 3, 5, 11, or 17; (^-diolefin)(^-aryl)platinum complexes, such as1,5-cyclooctadienyl)diphenylplatinum, ^4-1,3,5,7-cyclooctatetraenyl)diphenylplatinum,2,5-norboradienyl)diphenylplatinum,1,5-cyclooctadienyl)bis-(4-dimethylaminophenyl)platinum, (^4-1,5-cyclooctadienyl)bis-(4- acetylphenyl)platinum, and (^4-1,5-cyclooctadienyl)bis-(4-trifluormethylphenyl)platinum. Typicaly, the photoactivatable hydrosilylation-reaction catalyst is a Pt(I) β-diketonate complex and more typicaly the catalyst is platinum(I) bis(2,4-pentanedioate).

[0029] Non-limiting examples of platinum-group metal catalysts include rhodium chloride, rhodium acetate, ruthenium chloride, iridium chloride, osmium tetroxide, platinum (I) chloride diphosphine, platinum (0) tetraphenylphosphine, platinum (I) chloride diphenylphosphinoferrocene, platinum (I) chloride diphosphine, platinum (I) chloride cyclooctadiene, and platinum (I) ammonia chloride. In some embodiments, the platinum-group metal catalyst is selected from the group consisting of Speier’s catalyst, Karstedt’s catalyst, Marko’s catalyst, and combinations thereof. Speier’s catalyst is disclosed in U.S. Patent No. 2,823,218. Karstedt’s catalyst is disclosed in U.S. Patent No.3,814,730. Marko’s catalyst is disclosed in U.S. Patent No.6,803,440. In specific embodiments, the platinum-group metal catalyst comprises, alternatively consists essentialy of, alternatively consists of, Karstedt’s catalyst.

[0030] In some embodiments, the method further comprises the step of disposing an anode in an electricaly conductive oxidation media comprising an oxidation electrolyte and applying an oxidation potential or an oxidation curent to form the oxidized anode. In one embodiment, anAty Ref.: 157928.216186-WO (86207) oxidation potential is applied. In a diferent embodiment, an oxidation current is applied. The anode can be any suitable material for application of an oxidation potential or oxidation current so long as the anode is capable of forming a coated anode with the homogenous platinum-group metal. In certain embodiments, the anode may comprise, alternatively consist essentialy of, alternatively consist, of polyvinyl ferrocene (PVF) and / or multi-waled carbon nanotubes (CNT). In some embodiments, the anode is washed with a polar solvent (e.g., chloroform) for a washing time (e.g., 5 to 20 minutes) before the anode is disposed in the electricaly non-conductive media. The anode can have any shape or dimension, and may have selectively controled surface-area to volume ratios for influencing formation of the coated anode. The electricaly conductive oxidation media may comprise the electricaly conductive media and the oxidation electrolyte may comprise the oxidation electrolyte.

[0031] The oxidation potential may be applied from 0.01 to 5 V, alternatively 0.1 to 2 V, alternatively 0.1 to 1 V, alternatively 0.2 to 0.8 V, alternatively 0.4 to 0.6 V. In certain embodiments, the oxidation curent is applied in an amount of 0.1 to 200 mA / cm2, alternatively 1 to 150 mA / cm2, alternatively 10 to 100 mA / cm2, alternatively 20 to 80 mA / cm2, alternatively 40 to 60 mA / cm2.

[0032] The method also comprises the step of removing the coated anode from the first mixture. After removal, the coated anode is disposed in an electricaly conductive media comprising an electrolyte. The electricaly conductive media may comprise the electrolyte in a solubilized form or the electricaly conductive media may otherwise cary the electrolyte in a polar vehicle. In certain embodiments, the polar vehicle is a polar solvent.

[0033] Non-limiting examples of polar vehicles include ethyl acetate, acetonitrile, dimethylforamide (DMF), dimethylsulfoxide (DMSO), N-methyl-2-pyrrolidone (NMP) methanol, ethanol, isopropanol, water, propylene carbonate, butanone, hexafluoroisopropanol, 1,4- dioxane, N,N-dimethylacetamide, 1,2-dichloroethane, cyclohexanone, formamide, glycol ethers, and pyridine. In some embodiments, the polar vehicle is selected from the group consisting of chloroform, dichloromethane, acetone, tetrahydrofuran, and combinations thereof. In specific embodiments, the polar vehicle is chloroform or tetrahydrofuran.

[0034] The electricaly conductive media further comprises an electrolyte. Non-limiting examples of electrolytes include sodium chloride (NaCl), potassium chloride (KCl), calcium chloride (CaCl₂), magnesium sulfate (MgSO₄), sodium bicarbonate (NaHCO₃), potassium nitrate (KNO₃), calcium nitrate (Ca(NO₃)₂), lithium chloride (LiCl), ammonium chloride (NH₄Cl), sodium sulfate (Na₂SO₄), magnesium chloride (MgCl₂), aluminum sulfate (Al₂(SO₄)₃), potassium carbonate (K₂CO₃), sodium phosphate (Na₃PO₄), potassium bromide (KBr), calcium carbonate (CaCO₃), sodium iodide (NaI), zinc sulfate (ZnSO₄), iron(ii) chloride (FeCl₃), copper(i) sulfate (CuSO₄), acetic acid (CH₃COOH), citric acid (C₆H₈O₇), formic acid (HCOOH), lactic acid (C₃H₆O₃), tartaric acid (C₄H₆O₆), sodium citrate (Na₃C₆H₅O₇), potassium phthalate (KHP).Aty Ref.: 157928.216186-WO (86207)

[0035] In certain embodiments the electrolyte comprises, alternatively consists essentialy of, alternatively consists of a quaternary ammonium salt. Examples of quaternary ammonium salts include tetramethylammonium chloride (TMA-Cl), tetramethylammonium hydroxide (TMA-OH), tetramethylammonium bromide (TMA-Br), tetramethylammonium iodide (TMA-I), trimethylphenylammonium chloride (TMPA-Cl), trimethylbenzylammonium chloride (TMB-A-Cl), dimethyldodecylammonium chloride (DDAC), dimethylstearylbenzylammonium chloride (DMSBAC), dodecyltrimethylammonium bromide (DTAB), cetyltrimethylammonium bromide (CTAB), cetyltrimethylammonium chloride (CTAC), hexadecyltrimethylammonium bromide (HTAB), hexadecyltrimethylammonium chloride (HTAC), lauryltrimethylammonium chloride (LTAC), octyltrimethylammonium chloride (OTAC), n-butylpyridinium chloride (NBPC), n- ethylpyridinium chloride (NEPC), n-methylpyridinium chloride (NMPC), n-propylpyridinium chloride (NPPC), n-butyltrimethylammonium bromide (NBTAB), n-ethyltrimethylammonium chloride (NETAC), n-methyltrimethylammonium chloride (NMTAC), n-propyltrimethylammonium chloride (NPTAC), n,n-dimethyldodecylamine (DDA), n,n-dimethylhexadecylamine (DDA), n,n,n- trimethyl-1-octylammonium chloride (TMOAC), n,n,n-trimethyl-1-decylammonium chloride (TMDAC), n,n,n-trimethyl-1-dodecylammonium bromide (TMDAB), and n,n,n-trimethyl-1- tetradecylammonium chloride (TMTAC). In specific embodiments, the electrolyte comprises, alternatively consists essentialy of, alternatively consists of tetra-n-butylammonium hexafluorophosphate (TBAPF6).

[0036] The electricaly conductive media may comprise the electrolyte in a concentration of between 0.001 to 2 M, alternatively 0.01 to 1 M, alternatively 0.025 to 0.5 M, alternatively 0.025 to 0.1 M, alternatively 0.025 to 0.075 M.

[0037] In some embodiments, the electricaly conductive media further comprises a catalyst stabilizing agent comprising an aliphatic unsaturated moiety. The catalyst stabilizing agent may be referred to herein as a ligand. The catalyst stabilizing agent may comprise a hydrocarbon comprising an aliphaticaly unsaturated group or an organosiloxane comprising a silicon-bonded aliphaticaly unsaturated group. In specific embodiments, the hydrocarbon is a cyclic hydrocarbon. Non-limiting examples of the catalyst stabilizing agent include methacrylate, cycloolefins (e.g., cyclohexane, cycloheptane, cyclooctene, norbornene, cyclododecene), and quinones (e.g., benzoquinone, hydroquinone, anthraquinone, chloranil). In certain embodiments, the catalyst stabilizing agent comprises, alternatively consists essentialy of norbornene (NB). In specific embodiments, the catalyst stabilizing agent comprises, alternatively consists essentialy of, alternatively consists of 1,3-divinyltetramethyldisiloxane (DVSi).

[0038] The method also includes the step of applying a reduction potential or reduction curent to the coated anode to release the homogenous platinum-group metal catalyst from the coated anode into the electricaly conductive media to form a second mixture. The reduction potential may be applied from 0.01 to 5 V, alternatively 0.1 to 2 V, alternatively 0.1 to 1 V, alternatively 0.1Aty Ref.: 157928.216186-WO (86207) to 0.8 V, alternatively 0.2 to 0.6 V. In certain embodiments, the reduction current is applied in an amount of 0.1 to 200 mA / cm2, alternatively 1 to 150 mA / cm2, alternatively 10 to 100 mA / cm2, alternatively 20 to 80 mA / cm2, alternatively 40 to 60 mA / cm2.

[0039] The method further includes the step of combining a precipitation agent and the second mixture to cause precipitation of the electrolyte to yield a third mixture comprising a recycled solution comprising the homogenous platinum-group metal catalyst and precipitated electrolyte. The precipitation agent and the second mixture can be combined in any manner and in any order of addition, optionaly under mixing or shear. Generaly, the precipitation agent is more non-polar than components of the second mixture. In certain embodiments, the precipitation agent is a reaction mixture comprising (A) an unsaturated compound and (B) a silicon hydride compound or a hydrosilylation reaction product of the (A) unsaturated compound and the (B) silicon hydride compound. Alternatively, the precipitation agent may be a distinct compound, diferent from the reaction mixture or the hydrosilylation reaction product. For example, the precipitation agent may comprise, alternatively consist essentialy of, alternatively consist of an unsubstituted hydrocarbon. Non-limiting examples of unsubstituted hydrocarbons include butane, pentane, hexane, heptane, octane, nonane, decane, cyclohexane, cyclopentane, cyclobutane, cyclooctane, cyclododecane, cyclopropane, cyclobutene, cyclopentene, and cyclohexene. In specific embodiments, the precipitation agent comprises, alternatively consists essentialy of, alternatively consists of cyclohexane.

[0040] The method may further include isolating the recycled solution comprising the homogenous platinum-group metal catalyst from the precipitated electrolyte. Methods of isolating the recycled solution from the precipitated electrolyte include decantation, suction filtration, gravity filtration, centrifugal filtration, liquid-liquid extraction, pressure filtration, and recrystalization. The separated precipitated electrolyte may be disposed of or recycled for further use in another round of the method.

[0041] The method may additionaly comprise the step of combining the recycled solution with hydrosilylation component(s). In some embodiments, the recycled homogenous platinum-group metal catalyst within the recycled solution wil act as a hydrosilylation catalyst for the hydrosilylation component(s).

[0042] A recycled solution comprising the homogenous platinum-group metal catalyst formed in accordance with the method is also provided herein. The recycled homogenous platinum-group metal catalyst demonstrates excelent catalytic functionality, comparable to that of the pristine homogenous platinum-group metal catalyst.

[0043] As introduced above, the electricaly non-conductive media is generaly a reaction product from a hydrosilylation reaction. In addition, the recycled solution can be combined with hydrosilylation component(s). The components utilized to form the reaction product of the electricaly non-conductive media may be the same as or diferent from the component(s) of theAty Ref.: 157928.216186-WO (86207) hydrosilylation component(s) which utilizes the recycled solution. The method may be performed multiple times, such that the same homogenous platinum-group metal catalyst can be reused in multiple distinct hydrosilylation reactions in a recycling process. Components of a hydrosilylation reaction are described below, which equaly apply to the components utilized to prepare the reaction product of the electricaly non-conductive media and the hydrosilylation-curable reaction, which are described colectively below but independently selected.

[0044] The description below, which applies to both the components utilized to prepare the reaction product of the electricaly non-conductive media and the hydrosilylation components, is directed to the “composition” for clarity. The composition can be the composition utilized to prepare the reaction product of the electricaly non-conductive media, or the hydrosilylation component(s) utilizing the recycled solution, or both. Reference to the composition also applies to the hydrosilylation components.

[0045] The composition comprises (A) an unsaturated compound. The (A) unsaturated compound includes at least one aliphaticaly unsaturated group per molecule, which may alternatively be refered to as ethylenic unsaturation. The (A) unsaturated compound is not limited and may be any unsaturated compound having at least one aliphaticaly unsaturated group. In certain embodiments, the (A) unsaturated compound comprises an organic compound. In other embodiments, the (A) unsaturated compound comprises a siloxane. In yet other embodiments, the (A) unsaturated compound comprises a silicone-organic hybrid, or an organosilicon compound. Various embodiments and examples of the (A) unsaturated compound are disclosed below.

[0046] In certain embodiments, the (A) unsaturated compound includes an average of at least two aliphaticaly unsaturated groups per molecule. In such embodiments, the (A) unsaturated compound is capable of polymerization or curing beyond single cure-site hydrosilylation. The aliphaticaly unsaturated groups of the (A) unsaturated compound may be terminal, pendent, or in both locations in the (A) unsaturated compound.

[0047] For example, the aliphaticaly unsaturated group may be an alkenyl group and / or an alkynyl group. “Alkenyl group” means an acyclic, branched or unbranched, monovalent hydrocarbon group having one or more carbon-carbon double bonds. The alkenyl group may have from 2 to 30 carbon atoms, alternatively from 2 to 24 carbon atoms, alternatively from 2 to 20 carbon atoms, alternatively from 2 to 12 carbon atoms, alternatively from 2 to 10 carbon atoms, alternatively from 2 to 6 carbon atoms. Alkenyl groups are exemplified by, but not limited to, vinyl, alyl, propenyl, and hexenyl. “Alkynyl group” means an acyclic, branched or unbranched, monovalent hydrocarbon group having one or more carbon-carbon triple bonds. The alkynyl group may have from 2 to 30 carbon atoms, alternatively from 2 to 24 carbon atoms, alternatively from 2 to 20 carbon atoms, alternatively from 2 to 12 carbon atoms, alternatively from 2 to 10Aty Ref.: 157928.216186-WO (86207) carbon atoms, alternatively from 2 to 6 carbon atoms. Alkynyl is exemplified by, but not limited to, ethynyl, propynyl, and butynyl.

[0048] In specific embodiments, the (A) unsaturated compound has the formula R2—Z—R2, where Z is a divalent linking group, which may be a divalent hydrocarbon, a polyoxyalkylene, a polyalkylene, a polyisoalkylene, a hydrocarbon-silicone copolymer, a siloxane, or mixtures (in block or randomized form) thereof. Z may be linear or branched. In these specific embodiments, R2 is independently selected and includes aliphatic unsaturation, i.e., each R2 is independently selected from alkenyl groups and alkynyl groups.

[0049] In these specific embodiments, the (A) unsaturated compound includes two aliphaticaly unsaturated groups represented by R2.

[0050] In one embodiment of the (A) unsaturated compound, Z is a divalent hydrocarbon. The divalent hydrocarbon Z may contain 1 to 30 carbons, either as aliphatic or aromatic structures, and may be branched or unbranched. Alternatively, the linking group Z may be an alkylene group containing 1 to 12 carbons. In these embodiments, the (A) unsaturated compound may be selected from α, ω-unsaturated hydrocarbons. The α, ω-unsaturated hydrocarbons may alternatively be refered to as olefins.

[0051] For example, the (A) unsaturated compound may be any diene, diyne or ene-yne compound. With reference to the formula above, in these embodiments, R2 may be, for example, independently selected from CH2=CH—, CH2=CHCH2—, CH2=CH(CH2)4—, CH2=C(CH3)CH2— or and similar substituted unsaturated groups such as H2C=C(CH3)—, and HC=C(CH3)—. In such embodiments, the (A) unsaturated compound may be referred to as an α,ω-unsaturated hydrocarbon. The α,ω-unsaturated hydrocarbon may be, for example, an α,ω- diene of the formula CH2=CH(CH2)bCH=CH2, an α,ω-diyne of the formula CH≡C(CH2)bC≡CH, an α,ω-ene-yne of the formula CH2=CH(CH2)bC≡CH, or mixtures thereof, where b is independently from 0 to 20, alternatively from 1 to 20.

[0052] Specific examples of suitable diene, diyne or ene-yne compounds include 1,4-pentadiene, 1,5-hexadiene; 1,6-heptadiene; 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,11- dodecadiene, 1,13-tetradecadiene, and 1,19-eicosadiene, 1,3-butadiyne, 1,5-hexadiyne (dipropargyl), and 1-hexene-5-yne.

[0053] However, the (A) unsaturated compound may alternatively have the formula R2-Z,́ where R2 is defined above and Z’ is a monovalent hydrocarbon group (or silyl or siloxane group). In these specific embodiments, the (A) unsaturated compound includes one aliphaticaly unsaturated group represented by R2.

[0054] When the (A) unsaturated compound includes only one aliphaticaly unsaturated group, the (A) unsaturated compound may be referred to as an unsaturated hydrocarbon, and may beAty Ref.: 157928.216186-WO (86207) any -ene or -yne compound. In such embodiments, the (A) unsaturated compound may be an acyclic alkene and / or an acyclic alkyne. However, the (A) unsaturated compound may include aryl groups so long as the (A) unsaturated compound also includes the at least one aliphaticaly unsaturated group independent from any aryl groups, e.g. pendent therefrom.

[0055] In another embodiment, the (A) unsaturated compound comprises, alternatively is, a polyether. In these embodiments, the (A) unsaturated compound comprises a polyoxyalkylene group having the formula (CaH2aO), wherein a is from 2 to 4 inclusive. With reference to the general formula above, Ź is the polyoxyalkylene group. In these embodiments, the (A) unsaturated compound may be refered to as the polyoxyalkylene.

[0056] The polyoxyalkylene may comprise oxyethylene units (C2H4O), oxypropylene units (C3H6O), oxybutylene or oxytetramethylene units (C4H8O), or mixtures thereof, which may be in block form or randomized in the (A) unsaturated compound.

[0057] For example, the (A) unsaturated compound as the polyoxyalkylene may have the folowing general formula: R2O—[(C2H4O)c(C3H6O)d(C4H8O)e]—R2 wherein each R2 is independently selected and defined above; c is from 0 to 200, d is from 0 to 200, and e is from 0 to 200, with the proviso that c, d and e are not simultaneously 0. In specific embodiments, c is from 0 to 50, alternatively from 0 to 10, alternatively from 0 to 2. In these or other embodiments, d is from 0 to 100, alternatively 1 to 100, alternatively 5 to 50. In these or other embodiments, e is from 0 to 100, alternatively 0 to 50, alternatively 0 to 30. In various embodiments, the ratio of (d+e) / (c+d+e) is greater than 0.5, alternatively greater than 0.8, or alternatively greater than 0.95.

[0058] This polyoxyalkylene is terminated at each molecular chain end (i.e. alpha and omega positions) with R2, which is independently selected and described above. Additional examples of R2 include H2C=C(CH3)CH2—H2C=CHCH2CH2—, H2C=CHCH2CH2CH2—, and H2C=CHCH2CH2CH2CH2—, HC≡C—, HC≡CCH2—, HC≡CCH(CH3)—, HC≡CC(CH3)2—, HC≡CC(CH3)2CH2—. However, the polyoxyalkylene set forth above is merely one exemplary example of a suitable polyoxyalkylene.

[0059] In specific embodiments, the polyoxyalkylene group comprises only oxypropylene units (C3H6O). Representative, non-limiting examples of polyoxypropylene-containing polyoxyalkylenes include: H2C=CHCH2O[C3H6O]dCH2CH=CH2, H2C=CHO[C3H6O]dCH=CH2, H2C=C(CH3)CH2O[C3H6O]dCH2C(CH3)=CH2, HC≡CCH2O[C3H6O]dCH2C=CH, and HC≡CC(CH3)2O[C3H6O]dC(CH3)2C≡CH, where d is as defined above.Aty Ref.: 157928.216186-WO (86207)

[0060] Representative, non-limiting examples of polyoxybutylene or poly(oxytetramethylene) containing polyoxyalkylenes include: H2C=CHCH2O[C4H8O]eCH2CH=CH2, H2C=CHO[C4H8O]eCH=CH2, H2C=C(CH3)CH2O[C4H8O]eCH2C(CH3)=CH2, HC≡CCH2O[C4H8O]eCH2C≡CH, and HC≡CC(CH3)2O[C4H8O]eC(CH3)2C≡CH, where e is as defined above.

[0061] The examples of polyoxyalkylenes suitable for (A) the unsaturated compound include two aliphaticaly unsaturated groups. However, the polyoxyalkylene suitable for (A) the unsaturated compound may include only one aliphaticaly unsaturated group. For example, the polyoxyalkylene suitable for (A) the unsaturated compound may alternatively have the folowing general formula: R2O—[(C2H4O)c(C3H6O)d(C4H8O)e]— R3 where R2, c, d, and e are defined above, and R3 is H or an alkyl group, such as CH3. Any description or examples above also apply to this embodiment as wel. One of skil in the art readily understands how the examples of polyoxyalkylenes above with two aliphaticaly unsaturated groups may alternatively include but one aliphaticaly unsaturated group.

[0062] The polyoxyalkylene may be prepared by, for example, the polymerization of ethylene oxide, propylene oxide, butylene oxide, 1,2-epoxyhexane, 1,2-epoxyoctance, and / or cyclic epoxides, such as cyclohexene oxide or exo-2,3-epoxynorborane. The polyoxyalkylene moiety of the polyoxyalkylene may comprise oxyethylene units (C2H4O), oxypropylene units (C3H6O), oxybutylene units (C4H8O), or mixtures thereof. Typicaly, the polyoxyalkylene group comprises a majority of oxypropylene or oxybutylene units, as defined on a molar basis and indicated in the above formula by the c, d, and e subscripts.

[0063] In another embodiment, Z of the general formula R2—Z—R2 or Z’ or the formula R2-Ź of the (A) unsaturated compound comprises a polyalkylene group. The polyalkylene group may comprise from C2 to C6 alkylene units or their isomers. One specific example is polyisobutylene group, which is a polymer including isobutylene units. For example, the (A) unsaturated compound may be a di-alyl terminated polyisobutylene or an alyl-terminated polyisobutylene. The molecular weight of the polyisobutylene group may vary, but typicaly ranges from 100 to 10,000 g / mole.

[0064] In certain embodiments, the (A) unsaturated compound comprises an organopolysiloxane. The organopolysiloxane is not limited and may be any organopolysiloxane including at least one silicon-bonded aliphaticaly unsaturated group per molecule. For example, the organopolysiloxane may be linear, branched, partly branched, cyclic, resinous (i.e., have a three-dimensional network), or may comprise a combination of diferent structures. When the (A)Aty Ref.: 157928.216186-WO (86207) unsaturated compound comprises the organopolysiloxane, the aliphaticaly unsaturated group is silicon-bonded (e.g. as silicon-bonded alkenyl and / or silicon-bonded alkynyl).

[0065] In certain embodiments when the (A) unsaturated compound comprises an organopolysiloxane, the organopolysiloxane has the folowing average formula: R4fSiO(4-f) / 2 wherein each R4 is an independently selected substituted or unsubstituted hydrocarbyl group with the proviso that in each molecule, at least one, alternatively at least two, R4 groups is an aliphaticaly unsaturated group, and wherein f is selected such that 0 < f ≤ 3.2.

[0066] The average formula above for the organopolysiloxane may be alternatively writen as (R43SiO1 / 2)w(R42SiO2 / 2)x(R4SiO3 / 2)y(SiO4 / 2)z, where R4 and its proviso is defined above, and w, x, y, and z are independently from ≥0 to ≤1, with the proviso that w+x+y+z=1. One of skil in the art understands how such M, D, T, and Q units and their molar fractions influence subscript f in the average formula above. T and Q units, indicated by subscripts y and z, are typicaly present in silicone resins, whereas D units, indicated by subscript x, are typicaly present in silicone polymers (and may also be present in silicone resins).

[0067] Each R4 is independently selected, as introduced above, and may be linear, branched, cyclic, or combinations thereof. In general, hydrocarbyl groups suitable for R4 may independently be linear, branched, cyclic, or combinations thereof. Cyclic hydrocarbyl groups encompass aryl groups as wel as saturated or non-conjugated cyclic groups. Cyclic hydrocarbyl groups may independently be monocyclic or polycyclic. Linear and branched hydrocarbyl groups may independently be saturated or unsaturated. One example of a combination of a linear and cyclic hydrocarbyl group is an aralkyl group. General examples of hydrocarbyl groups include alkyl groups, aryl groups, alkenyl groups, halocarbon groups, and the like, as wel as derivatives, modifications, and combinations thereof. Examples of suitable alkyl groups include 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), hexyl, hexadecyl, octadecyl, as wel as branched saturated hydrocarbon groups having from 6 to 18 carbon atoms. Examples of suitable non-conjugated cyclic groups include cyclobutyl, cyclohexyl, and cycyloheptyl groups. Examples of suitable aryl groups include phenyl, tolyl, xylyl, naphthyl, benzyl, and dimethyl phenyl. Examples of suitable alkenyl groups include vinyl, alyl, propenyl, isopropenyl, butenyl, isobutenyl, pentenyl, heptenyl, hexenyl, hexadecenyl, octadecenyl and cyclohexenyl groups. Examples of suitable monovalent halogenated hydrocarbon groups (i.e., halocarbon groups, or substituted hydrocarbon groups) include halogenated alkyl groups, aryl groups, and combinations thereof. Examples of halogenated alkyl groups include the alkyl groups described above where one or more hydrogen atoms is replaced with a halogen atom such as F or Cl.Aty Ref.: 157928.216186-WO (86207) Specific examples of halogenated alkyl groups include fluoromethyl, 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, 2,2-difluorocyclopropyl, 2,3- difluorocyclobutyl, 3,4-difluorocyclohexyl, and 3,4-difluoro-5-methylcycloheptyl, chloromethyl, chloropropyl, 2-dichlorocyclopropyl, and 2,3-dichlorocyclopentyl groups, as wel as derivatives thereof. Examples of halogenated aryl groups include the aryl groups described above where one or more hydrogen atoms is replaced with a halogen atom, such as F or Cl. Specific examples of halogenated aryl groups include chlorobenzyl and fluorobenzyl groups.

[0068] In certain embodiments, the organopolysiloxane is substantialy linear, alternatively is linear. In these embodiments, the substantialy linear organopolysiloxane may have the average formula: R4fŚiO(4-f) / ́2 wherein each R4 and its proviso are defined above, and wherein f ís selected such that 1.9 ≤ f́ ≤ 2.2.

[0069] In these embodiments, at a temperature of 25 °C, the substantialy linear organopolysiloxane is typicaly a flowable liquid or is in the form of an uncured rubber. Generaly, the substantialy linear organopolysiloxane has a viscosity of from 10 to 30,000,000 mPa·s, alternatively from 10 to 10,000 mPa·s, alternatively from 100 to 1,000,000 mPa·s, alternatively from 100 to 100,000 mPa·s, at 25 °C. Viscosity may be measured at 25 °C via a Brookfield LV DV-E viscometer, as understood in the art.

[0070] In specific embodiments in which the organopolysiloxane is substantialy linear or linear, the organopolysiloxane may have the average formula: (R43SiO1 / 2)m(́R42SiO2 / 2)n(Ŕ4SiO3 / 2)o, wherein each R4 is independently selected and defined above (including the proviso that in each molecule, at least one R4 is an aliphaticaly unsaturated group), and m≥́2, n≥́0, and o≥2. In specific embodiments, ḿ is from 2 to 10, alternatively from 2 to 8, alternatively from 2 to 6. In these or other embodiments, n ís from 0 to 1,000, alternatively from 1 to 500, alternatively from 1 to 200. In these or other embodiments, o is from 2 to 500, alternatively from 2 to 200, alternatively from 2 to 100.

[0071] When the organopolysiloxane is substantialy linear, alternatively is linear, the silicon- bonded aliphaticaly unsaturated group(s) may be pendent, terminal or in both pendent and terminal locations. As a specific example of the organopolysiloxane having pendant silicon- bonded aliphaticaly unsaturated groups, the organopolysiloxane may have the average formula: (CH3)3SiO[(CH3)2SiO]n [́(CH3)ViSiO]mŚi(CH3)3Aty Ref.: 157928.216186-WO (86207) where n ánd ḿ are defined above, and Vi indicates a vinyl group. With regard to this average formula, one of skil in the art knows that any methyl group may be replaced with a vinyl or a substituted or unsubstituted hydrocarbyl group, and any vinyl group may be replaced with any ethylenicaly unsaturated group, so long as at least two aliphaticaly unsaturated groups are present per molecule. Alternatively, as a specific example of the organopolysiloxane having terminal silicon-bonded aliphaticaly unsaturated groups, the organopolysiloxane may have the average formula: Vi(CH3)2SiO[(CH3)2SiO]nŚi(CH3)2Vi where ń and Vi are defined above. The dimethyl polysiloxane terminated with silicon-bonded vinyl groups may be utilized alone or in combination with the dimethyl, methyl-vinyl polysiloxane disclosed immediately above. With regard to this average formula, one of skil in the art knows that any methyl group may be replaced with a vinyl or a substituted or unsubstituted hydrocarbyl group, and any vinyl group may be replaced with any ethylenicaly unsaturated group, so long as at least two aliphaticaly unsaturated groups are present per molecule. Because the at least two silicon-bonded aliphaticaly unsaturated groups may be both pendent and terminal, the (A) organopolysiloxane may have the average formula: Vi(CH3)2SiO[(CH3)2SiO]n[(́CH3)ViSiO]mŚiVi(CH3)2 where n,́ ḿ and Vi are defined above.

[0072] The substantialy linear organopolysiloxane can be exemplified by a dimethylpolysiloxane capped at both molecular terminals with dimethylvinylsiloxy groups, a methylphenylpolysiloxane capped at both molecular terminals with dimethylvinylsiloxy groups, a copolymer of a methylphenylsiloxane and dimethylsiloxane capped at both molecular terminals with dimethylvinylsiloxy groups, a copolymer of a methylvinylsiloxane and a methylphenylsiloxane capped at both molecular terminals with dimethylvinylsiloxy groups, a copolymer of a methylvinylsiloxane and diphenylsiloxane capped at both molecular terminals with dimethylvinylsiloxy groups, a copolymer of a methylvinylsiloxane, methylphenylsiloxane, and dimethylsiloxane capped at both molecular terminals with dimethylvinylsiloxy groups, a copolymer of a methylvinylsiloxane and a methylphenylsiloxane capped at both molecular terminals with trimethylsiloxy groups, a copolymer of a methylvinylsiloxane and diphenylsiloxane capped at both molecular terminals with trimethylsiloxy groups, and a copolymer of a methylvinylsiloxane, methylphenylsiloxane, and a dimethylsiloxane capped at both molecular terminals with trimethylsiloxy groups.

[0073] In these or other embodiments, the (A) organopolysiloxane may be a resinous organopolysiloxane. In these embodiments, the resinous organopolysiloxane may have the average formula: R4fŚiO(4-f)́ / 2Aty Ref.: 157928.216186-WO (86207) wherein each R4 and its provisos are defined above, and wherein f́ is selected such that 0.5 ≤ f ≤́ 1.7.

[0074] The resinous organopolysiloxane has a branched or a three dimensional network molecular structure. At 25 °C, the resinous organopolysiloxane may be in a liquid or in a solid form, optionaly dispersed in a carrier, which may solubilize and / or disperse the resinous organopolysiloxane therein.

[0075] In specific embodiments, the resinous organopolysiloxane may be exemplified by an organopolysiloxane that comprises only T units, an organopolysiloxane that comprises T units in combination with other siloxy units (e.g. M, D, and / or Q siloxy units), or an organopolysiloxane comprising Q units in combination with other siloxy units (i.e., M, D, and / or T siloxy units). The resinous organopolysiloxane comprises T and / or Q units. A specific example of the resinous organopolysiloxane is a vinyl functional silsesquioxane, or a vinyl functional MQ resin.

[0076] The organopolysiloxane may comprise a combination or mixture of diferent organopolysiloxanes, including those of diferent structures.

[0077] Alternatively, the (A) unsaturated compound may be a silicone-organic hybrid. For example, the (A) unsaturated compound may comprise the hydrosilylation reaction product of organopolysiloxanes (or of one or more organopolysiloxanes with one or more organic compounds), in which case the backbone of the (A) unsaturated compound may include organic divalent linking groups. As another example, organohydrogensiloxanes may be reacted with other organopolysiloxanes, or with organic compounds, to give the (A) unsaturated compound.

[0078] For example, the (A) unsaturated compound may be the reaction product of (a1) at least one Si-H compound and (b1) at least one compound having ethylenic unsaturation. In these embodiments, a molar excess of ethylenic unsaturated groups of the (b1) compound are utilized as compared to Si-H groups of the (a1) Si-H compound such that the (A) unsaturated compound includes at least one, alternatively an average of at least two, silicon-bonded aliphaticaly unsaturated groups.

[0079] The reaction product of the (a1) Si-H compound and the (b1) compound having ethylenic unsaturation may be referred to as an (AB)n type copolymer, with the (a1) Si-H compound forming units A and the (b1) compound having ethylenic unsaturation forming units B. Combinations of diferent (a1) Si-H compounds may be utilized, and combinations of diferent (b1) compounds having ethylenic unsaturation may be utilized, such that the resulting (b) crosslinking agent comprises distinct units but may not be an (AB)n type copolymer. The distinct units may be randomized or in block form.

[0080] Alternatively stil, the (A) unsaturated compound may comprise an organosilicon- compound, but not an organopolysiloxane. For example, the (A) unsaturated compound may comprise a silane, a disilane, or a siloxane (for example a disiloxane), while not constituting an organopolysiloxane.Aty Ref.: 157928.216186-WO (86207)

[0081] One example of a suitable silane is that of formula R5z'ŚiR64-z,́ where each R5 independently is an aliphaticaly unsaturated group, R6 is independently a substituted or unsubstituted hydrocarbyl group, and 1 ≤ z’ ≤ 4. One example of a siloxane is tetramethyldivinyldisiloxane. One of skil in the art understands how to prepare or obtain such compounds for use as the (A) unsaturated compound.

[0082] The (A) unsaturated compound can be a single unsaturated compound or a combination comprising two or more diferent silicon hydride compounds.

[0083] The composition and (A) unsaturated compound are subject to at least one of the folowing two provisos: (1) the (A) unsaturated compound also includes at least one silicon- bonded hydrogen atom per molecule; and / or (2) the composition further comprises (B) a silicon hydride compound including at least one silicon-bonded hydrogen atom per molecule.

[0084] In a first embodiment, the proviso (1) is true such that the (A) unsaturated compound also includes at least one silicon-bonded hydrogen atom per molecule. In a second embodiment, the proviso (2) is true such that the composition further comprises (B) a silicon hydride compound including at least one silicon-bonded hydrogen atom per molecule. Finaly, in a third embodiment, both proviso (1) and proviso (2) are true such that the (A) unsaturated compound also includes at least one silicon-bonded hydrogen atom per molecule, and that the composition further comprises (B) a silicon hydride compound including at least one silicon-bonded hydrogen atom per molecule.

[0085] In the first embodiment, the proviso (1) is true and the (A) unsaturated compound includes at least one silicon-bonded hydrogen atom per molecule in addition to the aliphaticaly unsaturated group. In these embodiments, the (A) unsaturated compound may be any compound including at least one silicon-bonded hydrogen atom and at least one aliphaticaly unsaturated group. In these embodiments, the (A) unsaturated compound is typicaly an organosilicon compound and / or an organopolysiloxane.

[0086] One of skil in the art readily understands how to prepare or obtain such unsaturated compounds. For example, organosilicon compounds including both aliphatic unsaturated and silicon-bonded hydrogen may be prepared from the unsaturated organic compounds disclosed above. As but one example, an α,ω-diene of the formula CH2=CH(CH2)bCH=CH2 may be reacted with a silane of formula H2Si(CH3)2 in the presence of a hydrosilylation catalyst to give an unsaturated compound of formula CH2=CH(CH2)bCH2CH2Si(CH3)2H, which includes one aliphaticaly unsaturated group and one silicon-bonded hydrogen atom. The organosilicon compound may also be a silane, disilane, siloxane, etc. For example, the organosilicon compound may be ofand R6 are independently selected and defined above, b́ is 1, 2, or 3, ć is 1, 2, or 3, with the proviso that 2≤ (b+́c)́ ≤4.Aty Ref.: 157928.216186-WO (86207)

[0087] When the (A) unsaturated compound comprises the organopolysiloxane having both aliphatic unsaturation and silicon-bonded hydrogen, the organopolysiloxane may have the formula R4dH́eŚiO(4-d-́e)́ / 2, where R4 is independently selected and defined above (stil subject to the proviso that at least one R4 is the aliphaticaly unsaturated group), and é and f áre each greater than 0 such that 0 < (d+́e)́ ≤ 3.2.

[0088] Alternatively, when the (A) unsaturated compound comprises the organopolysiloxane having both aliphatic unsaturation and silicon-bonded hydrogen, the silicon-bonded aliphaticaly unsaturated group(s) and the silicon-bonded hydrogen atom(s) may be present in any M, D, and / or T siloxy unit present in the organopolysiloxane, and may be bonded to the same silicon atom (in the case of M and / or D siloxy units). The organopolysiloxane may comprise, for example, as M siloxy units: (R43SiO1 / 2), (R42HSiO1 / 2), (R4H2SiO1 / 2), and / or (H3SiO1 / 2). The organopolysiloxane may comprise, for example, as D siloxy units: (R42SiO2 / 2), (R4HSiO2 / 2), and / or (H2SiO2 / 2). The organopolysiloxane may comprise, for example, as T siloxy units: (R4SiO3 / 2) and / or (HSiO3 / 2). Such siloxy units may be combined in any manner, optionaly along with Q siloxy units, to give an organopolysiloxane having at least one silicon-bonded aliphaticaly unsaturated group designated by R4 and at least one silicon-bonded hydrogen atom.

[0089] For example, the organopolysiloxane may have any one of the folowing formulas: (R42HSiO1 / 2)w(́R42SiO2 / 2)x(́R4SiO3 / 2)y(́SiO4 / 2)z,́ (R4H2SiO1 / 2)w(́R42SiO2 / 2)x(́R4SiO3 / 2)y(́SiO4 / 2)z,́ (R43SiO1 / 2)w(́R4HSiO2 / 2)x(́R4SiO3 / 2)y(́SiO4 / 2)z,́ (R4H2SiO1 / 2)w(́R4HSiO2 / 2)x(́R4SiO3 / 2)y(́SiO4 / 2)z,́ (R43SiO1 / 2)w(́R42SiO2 / 2)x(́HSiO3 / 2)y(́SiO4 / 2)z,́ (R43SiO1 / 2)w(́R4HSiO2 / 2)x(́R4SiO3 / 2)y(́SiO4 / 2)z,́ and / or (R4H2SiO1 / 2)w(́R4HSiO2 / 2)x(́HSiO3 / 2)y(́SiO4 / 2)z,́ etc., where each R4 is independently selected and defined above (with at least one R5 being an aliphaticaly unsaturated group), and w,́ x,́ y,́ and z áre independently from ≥0 to ≤1, with the proviso that w+́x+́y+́z=́1.

[0090] In the second embodiment, the proviso (2) is true and the composition further comprises (B) a silicon hydride compound including at least one silicon-bonded hydrogen atom per molecule. In these embodiments, the (B) silicon hydride compound may be any compound including at least one silicon-bonded hydrogen atom. Depending on a structure of the (B) silicon hydride compound, the (B) silicon hydride compound may be a silane compound, an organosilicon compound, an organohydrogensilane, an organohydrogensiloxane, etc.Aty Ref.: 157928.216186-WO (86207)

[0091] The (B) silicon hydride compound can be linear, branched, cyclic, resinous, or have a combination of such structures. In acyclic polysilanes and polysiloxanes, the silicon-bonded hydrogen atom(s) can be located at terminal, pendant, or at both terminal and pendant positions. Cyclosilanes and cyclosiloxanes typicaly have from 3 to 12 silicon atoms, alternatively from 3 to 10 silicon atoms, alternatively from 3 to 4 silicon atoms.

[0092] In certain embodiments, the (B) silicon hydride compound is of formula R74-sSiHs, where R7 is independently selected and may be any silicon-bonded group, and s is selected such that 1 ≤ s ≤ 4. Typicaly, s is 1, 2, or 3, alternatively 1 or 2. Each R7 is typicaly independently a substituted or unsubstituted hydrocarbyl group, suitable examples of which are described above. However, R7 can be any silicon-bonded group so long as the (B) silicon hydride is stil capable of undergoing hydrosilylation via its silicon-bonded hydrogen atom. For example, R7 can be a halogen. When the (B) silicon hydride is a silane compound, the (B) silicon hydride can be a monosilane, disilane, trisilane, or polysilane.

[0093] In these or other embodiments, the (B) silicon hydride compound may be an organosilicon compound of formula: HgŔ83-gŚi-R9-SiR82H, wherein each R8 is an independently selected substituted or unsubstituted hydrocarbyl group, ǵ is 0 or 1, and R9 is a divalent linking group. R9 may be a siloxane chain (including, for example, -R82SiO-, -R8HSiO-, and / or -H2SiO- D siloxy units) or may be a divalent hydrocarbon group. Typicaly, the divalent hydrocarbon group is free of aliphatic unsaturation. The divalent hydrocarbon group may be linear, cyclic, branched, aromatic, etc., or may have combinations of such structures.

[0094] When ǵ is 1, and when R9 is a divalent hydrocarbon group, specific examples of the (B) silicon hydride compound include:.

[0095] In these or other embodiments, the (B) silicon hydride compound comprises an organohydrogensiloxane, which can be a disiloxane, trisiloxane, or polysiloxane. Examples ofAty Ref.: 157928.216186-WO (86207) organohydrogensiloxanes suitable for use as the (B) silicon hydride compound include, but are not limited to, siloxanes having the folowing formulae: PhSi(OSiMe2H)3, Si(OSiMe2H)4, MeSi(OSiMe2H)3, and Ph2Si(OSiMe2H)2, wherein Me is methyl, and Ph is phenyl. Additional examples of organohydrogensiloxanes that are suitable for purposes of the (B) silicon hydride compound include 1,1,3,3-tetramethyldisiloxane, 1,1,3,3-tetraphenyldisiloxane, phenyltris(dimethylsiloxy)silane, 1,3,5-trimethylcyclotrisiloxane, a trimethylsiloxy-terminated poly(methylhydrogensiloxane), a trimethylsiloxy-terminated poly(dimethylsiloxane / methylhydrogensiloxane), and a dimethylhydrogensiloxy-terminated poly(methylhydrogensiloxane).

[0096] When the (B) silicon hydride compound comprises an organohydrogensiloxane, the (B) silicon hydride compound may comprise any combination of M, D, T and / or Q siloxy units, so long as the (B) silicon hydride compound includes at least one silicon-bonded hydrogen atom. These siloxy units can be combined in various manners to form cyclic, linear, branched and / or resinous (three-dimensional networked) structures. The (B) silicon hydride compound may be monomeric, polymeric, oligomeric, linear, branched, cyclic, and / or resinous depending on the selection of M, D, T, and / or Q units.

[0097] Because the (B) silicon hydride compound includes at least one silicon-bonded hydrogen atom, with reference to the siloxy units set forth above, the (B) silicon hydride compound may comprise any of the folowing siloxy units including silicon-bonded hydrogen atoms, optionaly in combination with siloxy units which do not include any silicon-bonded hydrogen atoms: (R82HSiO1 / 2), (R8H2SiO1 / 2), (H3SiO1 / 2), (R8HSiO2 / 2), (H2SiO2 / 2), and / or (HSiO3 / 2), where R8 is independently selected and defined above.

[0098] In specific embodiments, for example when the (B) silicon hydride compound is substantialy linear, the (B) silicon hydride compound may comprise the average formula: (R103SiO1 / 2)e(́R82SiO2 / 2)f́(́R8HSiO2 / 2)g’(́HSiO3 / 2)h’(R8SiO3 / 2)i’, wherein each R10 is independently hydrogen or R8, each R8 is independently selected and defined above, and e≥́2, f́≥́0, and g≥́2. In specific embodiments, é is from 2 to 10, alternatively from 2 to 8, alternatively from 2 to 6. In these or other embodiments, f́́ is from 0 to 1,000, alternatively from 1 to 500, alternatively from 1 to 200. In these or other embodiments, ǵ is from 2 to 500, alternatively from 2 to 200, alternatively from 2 to 100. In these or other embodiments, h’ is from 0 to 20, alternatively 1 to 10, alternatively 1 to 8. In these or other embodiments, i’ is from 0 to 20, alternatively 1 to 10, alternatively 1 to 8.

[0099] In one embodiment, the (B) silicon hydride compound is linear and includes one or more pendent silicon-bonded hydrogen atoms. In these embodiments, the (B) silicon hydride compound may be a dimethyl, methyl-hydrogen polysiloxane having the average formula;Aty Ref.: 157928.216186-WO (86207) (CH3)3SiO[(CH3)2SiO]f́[́(CH3)HSiO]gŚi(CH3)3 where f́́ and ǵ are defined above.

[0100] In these or other embodiments, the (B) silicon hydride compound is linear and includes terminal silicon-bonded hydrogen atoms. In these embodiments, the (B) silicon hydride compound may be an SiH terminal dimethyl polysiloxane having the average formula: H(CH3)2SiO[(CH3)2SiO]f́Śi(CH3)2H where f́́ is as defined above. The SiH terminal dimethyl polysiloxane may be utilized alone or in combination with the dimethyl, methyl-hydrogen polysiloxane disclosed immediately above. Further, the SiH terminal dimethyl polysiloxane may have one trimethylsiloxy terminal such that the SiH terminal dimethyl polysiloxane may have only one silicon-bonded hydrogen atom. Alternatively stil, the (B) organohydrogensiloxane may include both pendent and terminal silicon- bonded hydrogen atoms.

[0101] In certain embodiments, the (B) silicon hydride compound may have one of the folowing average formulas: (R103SiO1 / 2)e(́R82SiO2 / 2)f́(́R8HSiO2 / 2)g(́R8SiO3 / 2)h, (R103SiO1 / 2)e(́R82SiO2 / 2)f́(́R8HSiO2 / 2)g(SiO4 / 2)i, (R103SiO1 / 2)e(́R82SiO2 / 2)f́(́R8HSiO2 / 2)g(́R8SiO3 / 2)h(SiO4 / 2)i, wherein each R11 and R9 is independently selected and defined above, e,̋ f́,̋ and g̋ are defined above, and h≥0, and i is ≥0. In each of the average formulas above, the sum of the subscripts is 1.

[0102] Some of the average formulas above for the (B) silicon hydride compound are resinous when the (B) silicon hydride compound includes T siloxy units (indicated by subscript h) and / or Q siloxy units (indicated by subscript i). When the (B) silicon hydride compound is resinous, the (B) silicon hydride compound is typicaly a copolymer including T siloxy units and / or Q siloxy units, in combination with M siloxy units and / or D siloxy units. For example, the organohydrogenpolysiloxane resin can be a DT resin, an MT resin, an MDT resin, a DTQ resin, an MTQ resin, an MDTQ resin, a DQ resin, an MQ resin, a DTQ resin, an MTQ resin, or an MDQ resin.

[0103] In various embodiments in which the (B) silicon hydride compound is resinous, or comprises an organopolysiloxane resin, the (B) silicon hydride compound typicaly has the formula: (R113SiO1 / 2)j(Ŕ112SiO2 / 2)k(Ŕ11SiO3 / 2)l(ŚiO4 / 2)m̋ (IV) wherein each R11 independently is H or a substituted or unsubstituted hydrocarbyl group, with the proviso that in one molecule, at least one R11 is H; and wherein 0≤j≤́1; 0≤k≤́1;0≤l≤1́;and 0≤ḿ≤1; with the proviso that j+́k+́l+ḿ́=1.Aty Ref.: 157928.216186-WO (86207)

[0104] In certain embodiments, the (B) silicon hydride compound may comprise an alkylhydrogen cyclosiloxane or an alkylhydrogen dialkyl cyclosiloxane copolymer, represented in general by the formulawhere R11 is independently selected and defined above, and where r ís an integer from 0-7 and ś is an integer from 3-10. Specific examples of suitable organohydrogensiloxanes of this type include (OSiMeH)4, (OSiMeH)3(OSiMeC6H13), (OSiMeH)2(OSiMeC6H13)2, and (OSiMeH)(OSiMeC6H13)3, where Me represents methyl (—CH3).

[0105] The (B) silicon hydride compound can be a single silicon hydride compound or a combination comprising two or more diferent silicon hydride compounds.

[0106] Finaly, in a third embodiment, both proviso (1) and proviso (2) are true such that the (A) unsaturated compound also includes at least one silicon-bonded hydrogen atom per molecule, and the composition further comprises (B) a silicon hydride compound including at least one silicon-bonded hydrogen atom per molecule. Examples of suitable unsaturated compounds and silicon hydride compounds for this third embodiment are set forth above.

[0107] The (A) unsaturated compound, as wel as the (B) silicon hydride compound, if present in the composition, may be disposed in a carier vehicle. Examples of carrier vehicles are described.

[0108] The composition may comprise the (A) unsaturated compound and the (B) silicon hydride compound, when present, in varying amounts or ratios contingent on desired properties or end use application of the composition. In various embodiments when the composition comprises components (A) and (B), the composition comprises components (A) and (B) in an amount to provide a mole ratio of silicon-bonded hydrogen atoms to aliphaticaly unsaturated groups of from 0.3 to 5, alternatively from 0.6 to 3.

[0109] The composition further comprises (C) the homogenous platinum-group metal catalyst (“the catalyst”). The (C) catalyst is described above and may be any homogenous platinum-group metal catalyst. In certain embodiments, the (C) catalyst is a recycled catalyst recycled according to the method. The (C) catalyst is present in the composition in a catalytic amount, i.e., an amount or quantity suficient to promote a reaction or curing thereof at desired conditions. The catalytic amount of the (C) catalyst may be greater than 0.01 ppm, and may be greater than 1,000 ppm (e.g., up to 10,000 ppm or more). In certain embodiments, the typical catalytic amount of (C) catalyst is less than 5,000 ppm, alternatively less than 2,000 ppm, alternatively less than 1,000 ppm (but in any case greater than 0 ppm). In specific embodiments, the catalytic amount of the (C) catalyst may range from 0.01 to 1,000 ppm, alternatively 0.01 to 100 ppm, and alternatively 0.01 to 50 ppm of metal based on the weight of the composition. The ranges may relate solely to the metal content within the (C) catalyst.Aty Ref.: 157928.216186-WO (86207)

[0110] The composition may further comprise one or more optional components, including adhesion promoters, carrier vehicles, dyes, pigments, anti-oxidants, heat stabilizers, flame retardants, flow control additives, biocides, filers (including extending and reinforcing filers), surfactants, thixotroping agents, water, carier vehicles or solvents, pH bufers, etc. The composition may be in any form and may be incorporated into further compositions, e.g. as a component of a composition. For example, the composition may be in the form of, or incorporated into, an emulsion. The emulsion may be an oil-in-water emulsion, water-in-oil emulsion, silicone- in-oil emulsion, etc. The composition itself may be a continuous or discontinuous phase of such an emulsion.

[0111] The composition may be prepared by combining components (A), (B), (C) along with any optional components, in any order of addition, optionaly with a master batch, and optionaly under shear.

[0112] A method of preparing a hydrosilylation reaction product is also provided. The hydrosilylation reaction product is formed from the composition and may take a variety of forms depending on a section of the components in the composition.

[0113] The method comprises reacting an aliphaticaly unsaturated group and a silicon-bonded hydrogen atom in the presence of (C) a hydrosilylation catalyst to give the hydrosilylation reaction product. The (C) hydrosilylation catalyst is the (C) catalyst described above. The hydrosilylation reaction product is formed by an addition reaction between the silicon-bonded hydrogen atom and the aliphaticaly unsaturated group. As understood in the art, the hydrosilylation reaction can be generaly represented, in the case of a double bond and in the presence of the (C) hydrosilylation catalyst, -Si-H + C=C- ^ -Si-CH2-CH2-. The (C2) hydrosilylation catalyst and inventive method can be utilized in any hydrosilylation reaction, e.g. in lieu of or in addition to conventional hydrosilylation catalysts.

[0114] The aliphaticaly unsaturated group is present in the (A) unsaturated compound. At least one of the folowing two provisos applies: (1) the (A) unsaturated compound also includes at least one silicon-bonded hydrogen atom per molecule; and / or (2) the silicon-bonded hydrogen atom is present in the (B) silicon hydride compound separate from the (A) unsaturated compound. In a first embodiment, the proviso (1) is true such that the (A) unsaturated compound also includes at least one silicon-bonded hydrogen atom per molecule. In a second embodiment, the proviso (2) is true such that the composition further comprises (B) a silicon hydride compound including at least one silicon-bonded hydrogen atom per molecule. Finaly, in a third embodiment, both proviso (1) and proviso (2) are true such that the (A) unsaturated compound also includes at least one silicon-bonded hydrogen atom per molecule, and that the composition further comprises the (B) silicon hydride compound including at least one silicon-bonded hydrogen atom per molecule. These embodiments are described in detail above with respect to the composition itself.Aty Ref.: 157928.216186-WO (86207)

[0115] The hydrosilylation-reaction product prepared via the method is not limited and is generaly a function of the (A) unsaturated compound and, if utilized, the (B) silicon hydride compound. For example, the hydrosilylation-reaction product may be monomeric, oligomeric, polymeric, resinous, etc. The hydrosilylation-reaction product may comprise a fluid, an oil, a gel, an elastomer, a rubber, a resin, etc. The hydrosilylation-reaction product may take any form, as understood in the art, based on the selection of the (A) unsaturated compound and, if utilized, the (B) silicon hydride compound.

[0116] By way of example only, below are two reaction mechanisms that may be utilized via the inventive method. In these two reaction mechanisms, the method utilizes 1-octene as the (A) unsaturated compound and two diferent (B) silicon hydride compounds. The catalyst is the (C) catalyst described above, which can be utilized discretely or formed in situ from the redox- switchable catalyst system:

[0117] In the reaction mechanisms above, Ph is phenyl and Me is methyl. One of skil in the art understands how the (A) unsaturated compound and, if utilized, the (B) silicon hydride compound may be selected based on a desired target species of the hydrosilylation-reaction product.

[0118] The method may be utilized to prepare hydrosilylation-reaction products in the form of functionalized, e.g. olefin functionalization, silanes or siloxanes. Such functionalized silanes or siloxanes may be utilized in other end use applications, e.g. as a discrete component in another composition, including a curable composition, a personal care or cosmetic composition, etc.

[0119] The hydrosilylation-reaction product may also include various byproducts formed via the hydrosilylation reaction. For example, the hydrosilylation-reaction product typicaly includes a target species and various byproducts. The hydrosilylation-reaction product may also include other components, e.g. a carrier or solvent, if the method and reaction is caried out therein and / or if the composition includes such components. The method may further comprise isolating the target species, e.g. via any suitable purification method.

[0120] The folowing examples, ilustrating embodiments of this disclosure, are intended to ilustrate and not to limit the disclosure. Unless otherwise noted, al reactions are carried out under air, and al solvents, substrates, and reagents are purchased or otherwise obtained fromAty Ref.: 157928.216186-WO (86207) various commercial suppliers (e.g. Sigma-Aldrich, Thermo Scientific, Fisher Chemical, etc.) and utilized as received. Materials

[0121] A brief summary is provided in Table 1 below, seting forth information as to certain abbreviations, shorthand notations, and components utilized in the Examples, as wel as their sources.

[0122] Table 1: Components UtilizedGeneral Procedure 1

[0123] PVF was synthesized via free-radical polymerization of vinyl ferrocene. A PVF-CNT dispersion was prepared by combining PVF and vacuum-dried CNT in a 2:1 mass ratio (8 mgPVF / 4 mgCNT) to give a PVF-CNT mixture. The PVF-CNT mixture was combined with chloroform containing 0.4 mg 1,3-benzenedisulfonyl azide / mL as a crosslinker (10 wt. % with respect to CNT) to make a dispersion solution of 8 mg PVF and 4 mg CNT / mL chloroform. The dispersion solution was sonicated in an ice bath below 15 °C for 30 minutes. A volume of 75 µL of the dispersion solution was drop-casted using a pipete tip on each side of 1 cm2 of a carbon paper strip (1 × 3 cm) that was cut from a carbon sheet to give a wet PVF-CNT electrode. The wet PVF- CNT was dried at room temperature and put in an oven at 160 °C for 1.5 hours to crosslink the PVF, yielding 1.5 mg of PVF-CNT coating that contains 1 mg of PVF.Aty Ref.: 157928.216186-WO (86207)

[0124] 3D-printed polypropylene (PP) cels were used to oxidize and reduce PVF-CNT electrodes. A piece of carbon paper was used as a counter electrode (CE) and a silver wire contained in 10 mM AgNO30.1 M TBAPF6 was used as a reference electrode (RE). An electrolyte used was 0.5 M TBAPF6 in DCM. An electrochemical test was performed with a potentiostats (Admiral Squistat Prime). Cyclic voltammetry (CV) of the PVF-CNT electrode was run at a scan rate of 50 mV / s to find a half potential of the PVF-CNT electrode (E1 / 2, PVF-CNT). The half potential of PVF-CNT is calculatedCNT) / 2 where Eoxi and Ered are oxidation and reduction peak potentials, respectively. Chronoamperometry (CA) at 0.6 V vs. E1 / 2, PVF-CNT was applied for 15 minutes to fuly oxidize the PVF-CNT electrodes. Folowing pre-oxidation, the PVF-CNT electrode was rinsed and immersed in chloroform (used as a rinsing solvent) for 10 minutes to remove excess salt. The residual chloroform was dried at room temperature.

[0125] A hydrosilylation solution was formed by combining a volume of Unsaturated Compound and a volume of Silicon Hydride Compound in a Molar Ratio (as defined below in Table 2). Catalyst was added to the hydrosilylation solution (5 µL of Catalyst) along with a concentration of Ligand (as identified below) to give a mixture. The mixture was heated at Reaction Temperature for 1.5 hours to activate the Catalyst and give a reaction mixture. A sample of 1 mL of the reaction mixture with a conversion of >99 % was transferred to a 7 mL vial containing the pre-oxidized PVF-CNT. The 7 mL vial was placed in a mixer (VWR Analog Vortex Mixer) at 300 RPM for an Adsorption Time. A volume of 100 µL of the reaction mixture was sampled for ICP- OES (Agilent 5110 ICP-OES) measurement. Catalyst recovery (%) was calculated by measuring the Catalyst concentration change in the reaction mixture.

[0126] The reaction mixture and 8 mL of 50 mM Electrolyte in Electrolyte Vehicle were combined to give a conductive solution. The PVF-CNT electrode was transferred to a cel containing 1 mL of the conductive solution. A Reduction Potential was applied for a Reduction Time to release the adsorbed Catalyst. An amount of 200 µL of the conductive solution was taken before and after the application of the Reduction Potential for Catalyst concentration measurement using ICP-OES. The sample taken before the application of the Reduction Potential was taken for compensating the ICP-OES background signal. The regeneration (%) was calculated using the amount of the adsorbed Catalyst and the released Catalyst. The PVF- CNT electrode was removed from the conductive solution. A volume of 0.4 mL of the conductive solution was isolated. The volume of 0.4 mL of the conductive solution was combined with 1.2 mL of the hydrosilylation solution and the Electrolyte salt immediately precipitated out of the combined solution. The combined solution is centrifuged to give a recycled solution and the precipitated Electrolyte salt.Aty Ref.: 157928.216186-WO (86207)

[0127] The recycled solution was transfered to a 4 mL reaction vial with a stir bar and the 4 mL reaction vial was placed in a heat block. The recycled solution was heated at Reaction Temperature for a Reaction Time, using the recycled Catalyst within the recycled solution. NMR samples were taken to calculate the turnover frequency (TOF) of the recycled catalyst. The TOF of pristine Catalyst was obtained by adding a Catalyst solution into the conductive solution such that the concentration of Catalyst was identical to the concentration in the conductive solution containing the recycled Catalyst. The amount of active catalyst in the conductive solution was calculated by multiplying the regeneration percent by the TOF retention. Similarly to TOF retention, turnover number (TON) was calculated to compare the activity of the recycled Catalyst with that of the pristine or unrecycled Catalyst. Examples 1-10

[0128] Examples 1-10 were conducted in accordance with General Procedure 1. The various procedural distinctions and compounds used are presented in Tables 3 and 4 below.

[0129] Table 3: Examples 1-5Aty Ref.: 157928.216186-WO (86207)Comparative Examples 1-3

[0131] Comparative Examples 1-3 were generaly conducted in accordance with General Procedure 1. However, Comparative Example 1 excluded the step of applying a potential to the PVF-CNT electrode. The PVF-CNT electrode of Comparative Example 1 was therefore neutral. Additionaly, Comparative Example 2 excluded the step of combining 0.4 mL of cyclohexane with the 0.4 mL of the conductive solution. Therefore, the Electrolyte salt was not precipitated out of the conductive solution. Al other procedural distinctions and compounds used are presented in Table 3 below.

[0132] Table 5: Comparative Examples 1-3Aty Ref.: 157928.216186-WO (86207)NMR

[0133] For al NMR samples, 50 µL of solution was taken and transferred in 650 µL CDCl3.1H NMR was measured using a 500 MHz NMR instrument. Inductively Coupled Plasma – Optical Emission Spectroscopy (ICP-OES) for Platinum Quantification

[0134] Al ICP-OES samples (100 µL for adsorption tests and 200 µL for desorption tests) taken from hydrosilylation solutions or conductive solutions, respectively, were dried at 120 °C in a vacuum oven for 1 hour. An amount of 1 mL of aqua regia made from commercial hydrochloric acid (37 %) and nitric acid (60 %) was added to a dried sample, folowed by digestion overnight. Platinum standard samples were made from a commercial platinum standard product (1000 ppm in 5 % HCl). Potentiostat

[0135] SP-200 Potentiostat (BioLogic, France) was used for cyclic voltammetry with iR compensation at 30%. Squidstat Prime with four channels (Admiral Instruments, USA) was used for the catalyst recovery process steps including OCP, oxidation, and reduction of PVF-CNT. iR compensation was skipped as Ru of our cel setup using electrolytes (0.45-0.5 M TBAPF6 DCM or chloroform) was below 100 Ω.

[0136] Figure 1a depicts the percentage and amount (mgPt / gadsorbent) of platinum uptake as a function of time (in minutes) for a neutral PVF-CNT electrode and an oxidized PVF-CNT electrode. For both the neutral and the oxidized PVF-CNT electrodes the platinum uptake increases as time increases. Notably, the oxidized PVF-CNT electrode has a substantialy higher uptake of platinum at almost any time than the control PVF-CNT electrode, demonstrating the criticality of oxidizing the PVF-CNT electrode to the recycling process. The oxidized PVF-CNT electrode adsorbed 78 % of platinum (3.2 mgPt / gadsorbent) in a solution comprising 5 ppm platinum while only 18 % of platinum (0.74 mgPt / gadsorbent) was adsorbed by a neutral PVF-CNT.

[0137] Figure 1b depicts the platinum recovery percentage with and without removal of the excess electrolyte from a pre-oxidized PVF-CNT electrode using a rinsing solvent. Without the removal of excess electrolyte, the platinum recovery is about 5.5 % while removal of the excess electrolyte yields a substantialy higher platinum recovery of 29.2 %.Aty Ref.: 157928.216186-WO (86207)

[0138] Platinum uptake (mgPt / mgPVF-CNT) from a hydrosilylation media and turnover frequency (TOF) retention of the recycled catalyst in the hydrosilylation media with and without the presence of a norbornene ligand was determined. With the norbornene the platinum uptake was 32.0 %, and without the norbornene the platinum uptake was 35.9 % after 60 minutes of adsorption. Activity retention was measured as being 100% with the inclusion of norbornene. Turnover frequency and turnover frequency retention are calculated according to the folowing equations. [^^^^^^^] [^^] ^^^= ^^^^^^^^ ^^^^ ^^^^^^^^^^ ^^^^^^^^^ ( ^ ^^ ^^^ %)= ×100 % ^^^^^^^^^^^ !

[0139] Figure 2 depicts platinum regeneration eficiency and turnover number (TON) retention after the release of the platinum in an electricaly conductive media with no ligand and with norbornene. The turnover number retention is 100% with the inclusion of norbornene turnover number and turnover number retention are calculated according to the folowing equations. ^^^^^^^^]'^^%^ ×100 %

[0140] Figure 3 depicts platinum regeneration eficiency and TON retention for the release step with varying mol percentages of norbornene. The more norbornene included, the greater the platinum regeneration. However, the addition of norbornene results in a substantial reduction of activity retention.

[0141] Figure 4 depicts the accumulated TON until deactivation of the platinum catalyst for an electricaly non-conductive hydrosilylation solution containing norbornene. 1,3- divinyltetramethyldisiloxane (DVSi), or no ligand. The TON is highest for the solution containing no ligand, slightly lower for the solution containing norbornene, and the lowest for the solution containing DVSi.

[0142] Figure 5 depicts the accumulated TON until deactivation of the platinum catalyst for an electricaly conductive media comprising acetone, THF, chloroform, DCM, or toluene. The TON is highest for the solution containing the non-conductive toluene. Acetone had the lowest TON, folowed by THF. Chloroform and DCM had moderate TONs, intermediate between acetone and THF with the low TONs, and toluene with the high TON.

[0143] Figure 6 depicts a ratio of the TOF of a second reaction using a recycled catalyst to the TOF of a first reaction using a pristine catalyst at diferent reaction start times for solutions with no ligand added, norbornene added, or DVSi added. For the solutions without ligands, the TOF of the used catalyst in the second reaction decreases by 66 % and 96 % after 20 minutes and 10Aty Ref.: 157928.216186-WO (86207) hours, respectively. It is believed this reduction is the result of aggregation after the completion of the first reaction. Catalysts in the solutions containing norbornene or DVSi, however, maintain activity after the first reaction substantialy beter. For the solutions comprising norbornene, TOF of the used catalyst in the second reaction is 83 % of the first reaction TOF for a reactant addition time of 3 hours. For the solutions comprising DVSi, TOF of the used catalyst is maintained near 100 % of the pristine catalyst for at least up to 10 hours after the first reaction. Without wishing to be bound by any theory, it is believed that the platinum stabilizing efect of the ligands is a result of the ligands slowing platinum nanoparticle formation.

[0144] Figure 7 depicts platinum regeneration percentage after the release in conductive media under reduction potential of PVF-CNT (-0.8 V, -0.6 V, -0.4 V, -0.2 V, and open circuit potential). Applying -0.4 V vs. E1 / 2,PVF-CNT results in 91 % regeneration of the adsorbed platinum, more than any other reduction potential.

Claims

Aty Ref.: 157928.216186-WO (86207) CLAIMS What is claimed is:

1. A method of recycling a homogenous platinum-group metal catalyst, the method comprising: disposing an oxidized anode in an electricaly non-conductive media comprising the homogenous platinum-group metal catalyst to adsorb the homogenous platinum-group metal catalyst to a surface of the oxidized anode to form a coated anode in a first mixture, the electricaly non-conductive media being substantialy free from an electrolyte; removing the coated anode from the first mixture; disposing the coated anode in an electricaly conductive media comprising an electrolyte; applying a reduction potential or reduction curent to the coated anode to release the homogenous platinum-group metal catalyst from the coated anode into the electricaly conductive media to form a second mixture; and combining a precipitation agent and the second mixture to cause precipitation of the electrolyte to yield a third mixture comprising a recycled solution comprising the homogenous platinum-group metal catalyst and precipitated electrolyte.

2. The method of claim 1, further comprising isolating the recycled solution comprising the homogenous platinum-group metal catalyst from the precipitated electrolyte.

3. The method of claim 2, further comprising combining the recycled solution with hydrosilylation components.

4. The method of any one preceding claim, wherein the non-conductive media and the electricaly conductive media each comprise a catalyst stabilizing agent comprising an aliphatic unsaturated moiety.

5. The method of claim 4, wherein the catalyst stabilizing agent of the non-conductive media and / or the electricaly conductive media comprises a cyclic hydrocarbon comprising an aliphaticaly unsaturated group or an organosiloxane comprising a silicon-bonded aliphaticaly unsaturated group.

6. The method of any one preceding claim, wherein the electricaly non-conductive media comprises a hydrosilylation reaction product, and wherein the method further comprises the step of contacting (A) an unsaturated compound and (B) a silicon hydride compound in the presence of the homogenous platinum-group metal catalyst to give the non-conductive media.Aty Ref.: 157928.216186-WO (86207) 7. The method of any one preceding claim, wherein the platinum-group metal catalyst is selected from the group consisting of Speier’s catalyst, Karstedt’s catalyst, Marko’s catalyst, and combinations thereof.

8. The method of any one preceding claim, wherein the platinum-group metal catalyst is Karstedt’s catalyst.

9. The method of any one preceding claim, wherein the electrolyte comprises a quaternary ammonium salt.

10. The method of any one preceding claim, wherein the electricaly conductive media comprises the electrolyte dissolved in a polar vehicle.

11. The method of claim 10, wherein the polar vehicle is selected from the group consisting of chloroform, dichloromethane, acetone, tetrahydrofuran, and combinations thereof.

12. The method of any one preceding claim, wherein the precipitation agent comprises an unsubstituted hydrocarbon.

13. The method of any one preceding claim, wherein the electricaly conductive media comprises the electrolyte in a concentration of between 0.001 to 2 M.

14. The method of any one preceding claim, wherein the oxidized anode is provided by disposing an anode in an electricaly conductive oxidation media comprising an oxidation electrolyte and applying an oxidation potential of from 0.1 to 2 V or an oxidation curent of from 1 to 150 mA / cm2.

15. The method of any one preceding claim, wherein the reduction potential is from 0.1 to 3 V or the reduction potential is from 1 to 150 mA / cm2.

16. A recycled solution comprising the homogenous platinum-group metal catalyst formed in accordance with the method of any one preceding claim.

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