Preparation of methacryl-functional organosilicon compounds

Abstract

A composition and method for production of a methacryloxyalkyl-functional organosilicon compound, such as a methacryloxyalkyl-functional organosiloxane polymer with at least one silicon bonded hydrogen atom per molecule or a methacryloxyalkyl-functional organosiloxane polymer with at least one silicon bonded alkenyl group per molecule, is provided. A new inhibitor package provides the ability to produce the methacryloxyalkyl-functional organosilicon compound on a commercial scale, with heating under anaerobic conditions while avoiding gelation.

Description

PREPARATION OF METHACRYL-FUNCTIONAL ORGANOSILICON COMPOUNDS CROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of U.S. Provisional Patent Application Serial No. 63 / 626088 filed on 29 January 2024 under 35 U.S.C. §119 (e). U.S. Provisional Patent Application Serial No.63 / 626088 is hereby incorporated by reference. FIELD

[0002] A composition and method for production of a methacryl-functional organosilicon compound on a commercial scale is provided. More particularly, the methacryl-functional organosilicon compound can be prepared with minimized gelation under anaerobic conditions. The methacryl-functional organosilicon compound may be useful in a two-step curable silicone composition, which cures via hydrosilylation reaction and via radical initiated reaction and is suitable for use on uneven surfaces. INTRODUCTION

[0003] (Meth)acryl-functional organosilicon compounds find use in a myriad of end use applications. For example, an organopolysiloxane having a viscosity of at least 100 mPa.s at 25° C. and having both SiC-bonded acryloxyalkyl groups and Si-bonded hydrogen atoms in the same molecule have been prepared as described in US Patent 4554339. Hydrogenpolysiloxanes having a (meth)acryloxypropyl group on a side chain are disclosed in US Patent 5256754. Other methacryloxy group- or acryloxy group-containing polyorganosiloxanes are disclosed in US Patent 9018332 to Okawa et al., US Patent 9051428 to Davio, et al., US Patent 12163068 to Yook, et al. and US Patent Publication 20210122769. SUMMARY

[0004] A method for preparing a methacryl-functional organosilicon compound comprises heating the methacryl-functional organosilicon compound under anaerobic conditions in the presence of an inhibitor comprising a manganese ion source and a phenolic compound. A composition comprises the methacryl-functional organosilicon compound, the manganese ion source, and the phenolic compound. DETAILED DESCRIPTION

[0005] The method for preparing the methacryl-functional organosilicon compound introduced above comprises heating a methacryl-functional organosilicon compound under anaerobic conditions in the presence of the inhibitor comprising the manganese ion source and the phenolic compound. The methacryl-functional organosilicon compound may be heated under anaerobic conditions during formation, after formation, or both. A composition comprising the methacryl-functional organosilicon compound, the manganese ion source, and the phenolic compound is formed.

[0006] The methacryl-functional organosilicon compound prepared as described herein may comprise a silicon bonded methacryloxyalkyl- group of , wherein R5is an alkylene group having 2 to 6 carbon atoms.or branched. Examples of the alkylene groups for R5include ethylene, propylene, methylethylene, butylene, pentylene, and hexylene groups. Alternatively, R5may be propylene, methylethylene, or a combination thereof. Alternatively, R5may be propylene. The methacryl- functional organosilicon compound may be, for example, a methacryloxyalkyl-functional silane, a methacryloxyalkyl-functional organosiloxane polymer, or a methacryloxyalkyl-functional silazane.

[0007] The methacryl-functional organosilicon compound may be a methacryloxyalkyl- functional organosiloxane polymer. The methacryloxyalkyl-functional organosiloxane polymer may be linear, cyclic, branched, resinous, or combinations thereof. The methacryloxyalkyl- functional organosiloxane polymer may comprise unit formula (R3SiO1 / 2)g(R2SiO2 / 2)h(RSiO3 / 2)i(SiO4 / 2)j(ZO1 / 2)k, where each R is independently selected from the group consisting of H, a monovalent hydrocarbon group, and the methacryloxyalkyl- group of the formula described above, with the proviso that at least one R per molecule is the methacryloxyalkyl group; each Z is independently selected from hydrogen or an alkyl group of 1 to 6 carbon atoms; and subscripts g, h, i, j, and k represent average numbers of each unit per molecule and have values such that g ≥ 0, h ≥ 0, i ≥ 0, j ≥ 0, k ≥ 0, 10,000 ≥ (g + h + i + j) ≥ 2, and (g + h + i) ≥ 1. Subscript k represents the number of silicon bonded hydroxyl or alkoxy groups per molecule and may have a value = 0. The monovalent hydrocarbon groups for R are exemplified by alkyl, alkenyl, and aryl.

[0008] The alkyl group for R may be branched, unbranched, or cyclic. Examples of alkyl groups include methyl, ethyl, propyl (including n-propyl and / or iso-propyl), butyl (including iso- butyl, n-butyl, tert-butyl, and / or sec-butyl), pentyl (including, iso-pentyl, neopentyl, and / or tert- pentyl); and hexyl, heptyl, octyl, nonyl, and decyl, as well as branched saturated monovalent hydrocarbon groups of 6 or more carbon atoms; and cyclic alkyl groups such as cyclopentyl or cyclohexyl.

[0009] The alkenyl group for R has a double bond and may be branched or unbranched.Alkenyl groups have at least 2 carbon atoms. Alternatively, alkenyl groups may have 2 to 12 carbon atoms, alternatively 2 to 10 carbon atoms, alternatively 2 to 6 carbon atoms, alternatively 2 to 4 carbon atoms, and alternatively 2 carbon atoms. Suitable alkenyl groups include, but are not limited to vinyl, allyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, and dodecenyl; alternatively vinyl, allyl and hexenyl; and alternatively vinyl.

[0010] Suitable aryl groups for R may have 6 to 12 carbon atoms, and are exemplified by phenyl, tolyl, xylyl, naphthyl, benzyl, and phenethyl groups. Alternatively, the aryl group may be phenyl.

[0011] Alternatively, the methacryloxyalkyl-functional organosiloxane polymer may be selected from the group consisting of: Component B1) a polyorganosiloxane having at least 2 silicon bonded alkenyl groups and at least one methacryloxyalkyl-functional group per molecule; Component B2) a polyorganosiloxane having at least 2 silicon bonded hydrogen atoms and at least one methacryloxyalkyl-functional group per molecule; and Component B3) a mixture of both component B1) and component B2).

[0012] Component B1) may comprise unit formula (B1): (R2R62SiO1 / 2)2(R62SiO2 / 2)n(R6R3SiO2 / 2)m, where each R2is an independently selected alkenyl group, each R6is independently selected from the group consisting of an alkyl group and an aryl group, and each R3is the methacryloxyalkyl group of , where R5is as described above. In the unit formulas herein,selected alkyl group, as described and exemplified above. Alternatively, R1may be methyl or ethyl; alternatively each R1may be methyl. Each R2is an independently selected alkenyl group, as described and exemplified above. Alternatively, each R2may be independently selected from vinyl, allyl, and hexenyl; alternatively, vinyl. Each R6may independently selected from the group consisting of an alkyl group as and an aryl group, each as described and exemplified above. Alternatively, in unit formula (B1), each R6may be alkyl or aryl. Alternatively, each R6may be alkyl, alternatively methyl.

[0013] In unit formula (B1), subscripts m and n represent average numbers of each difunctional siloxane unit per molecule in the unit formula (B1). Subscript m is an integer of 1 to 500, n is an integer of 1 to 1000, and 0.01 ≤ m / (n+m) ≤ 0.5. Alternatively, subscript m may be at least 1, alternatively at least 10, alternatively at least 15, alternatively at least 25, and alternatively at least 50, while at the same time subscript m may be up to 1000, alternatively upto 500, alternatively up to 400, alternatively up to 300, and alternatively up to 275. Subscript m may have any range that combines the upper and lower limits described above.

[0014] Alternatively, in formula (B1) subscript n may be at least 1, alternatively at least 2, alternatively at least 3, alternatively at least 4, alternatively at least 5, alternatively at least 6, alternatively at least 7, and alternatively at least 8; while at the same time subscript n may be up to 500, alternatively up to 400, alternatively up to 300, alternatively up to 200, alternatively up to 100, alternatively up to 50, alternatively up to 25, alternatively up to 10, alternatively up to 9, and alternatively up to 8. Subscript n may have any range that combines the upper and lower limits described above.

[0015] Examples of methacryloxyalkyl-functional polydiorganosiloxanes of unit formula (B1) have average unit formulas B1-1) to B1-9), as follows: B1-1) (ViMe2SiO1 / 2)2(MaMeSiO2 / 2)8(Me2SiO2 / 2)272, B1-2) (ViMe2SiO1 / 2)2(MaMeSiO2 / 2)10(Me2SiO2 / 2)1000, B1-3) (ViMe2SiO1 / 2)2(MaMeSiO2 / 2)2(Me2SiO2 / 2)15, B1-4) (ViMe2SiO1 / 2)2(MaMeSiO2 / 2)2(Me2SiO2 / 2)2, B1-5) (ViMe2SiO1 / 2)2(MaMeSiO2 / 2)4(Me2SiO2 / 2)25, B1-6) (ViMe2SiO1 / 2)2(MaMeSiO2 / 2)4(Me2SiO2 / 2)24, B1-7) (ViMe2SiO1 / 2)2(MaMeSiO2 / 2)2(Me2SiO2 / 2)25, B1-8) (ViMe2SiO1 / 2)2(MaMeSiO2 / 2)2, and B1-9) (ViMe2SiO1 / 2)2(MaMeSiO2 / 2)16(Me2SiO2 / 2)265. In these average unit formulas, Vi represents vinyl, Me represents methyl, Ma represents methacryloxypropyl, and the subscripts after each unit represent average number of that unit per molecule.

[0016] Component B2) may comprise unit formula (B2): (HR62SiO1 / 2)2(R62SiO2 / 2)n(R6R3SiO2 / 2)m, where R3, R6, and subscripts m and n are as described above for formula (B1) for component B1).

[0017] Examples of methacryloxyalkyl-functional polydiorganosiloxanes of unit formula (B2) have average unit formulas B2-1 to B2-9), as follows: B2-1) (HMe2SiO1 / 2)2(MaMeSiO2 / 2)2(Me2SiO2 / 2)15, B2-2) (HMe2SiO1 / 2)2(MaMeSiO2 / 2)4(Me2SiO2 / 2)25, B2-3) (HMe2SiO1 / 2)2(MaMeSiO2 / 2)8(Me2SiO2 / 2)272, B2-4) (HMe2SiO1 / 2)2(MaMeSiO2 / 2)2(Me2SiO2 / 2)2, B2-5) (HMe2SiO1 / 2)2(MaMeSiO2 / 2)10(Me2SiO2 / 2)1000, B2-6) (HMe2SiO1 / 2)2(MaMeSiO2 / 2)4(Me2SiO2 / 2)24, B2-7) (HMe2SiO1 / 2)2(MaMeSiO2 / 2)2(Me2SiO2 / 2)25,B2-8) (HMe2SiO1 / 2)2(MaMeSiO2 / 2)16(Me2SiO2 / 2)265, and B2-9) (HMe2SiO1 / 2)2(MaMeSiO2 / 2)1. In these average unit formulas, Me represents methyl, Ma represents methacryloxypropyl, and the subscripts after each unit represent average number of that unit per molecule.

[0018] The inhibitor used herein comprises a manganese ion source and a phenolic compound. The manganese ion source used herein may be a manganese (III) compound or a manganese (II) compound. Suitable manganese (III) compounds include manganese (III) acetylacetonate. Alternatively, the manganese ion source may be a manganese (II) compound. Suitable manganese compounds include manganese (II) acetate, manganese (II) nitrite, manganese (II) propionate, manganese (II) oxide, manganese (II) hydroxide, manganese (II) chloride, manganese (II) phosphate, manganese (II) perchlorate, manganese (II) ethylhexanoate; hydrates thereof (e.g., manganese (II) acetate tetrahydrate); and combinations thereof. Alternatively, the manganese ion source may comprise manganese (II) acetate or manganese (II) acetate tetrahydrate, or a combination thereof; mangaese (II) ethyl hexanoate; manganese (III) acetylacetonate; or a combination thereof. Alternatively, the manganese ion source may comprise manganese (II) acetate or manganese (II) acetate tetrahydrate, or a combination thereof. Suitable manganese ion sources are commercially available from Millipore Sigma of St. Louis, Missouri, USA, Fisher Scientific of Waltham, Massachusetts, USA, and City Chemical LLC of Connecticut, USA. The amount of manganese ion source depends on various factors including the selections and amounts of starting materials used in the method, whether a methacryl-functional starting material or the methacryl-functional organosilicon compound to be produced, or both, will be heated under anaerobic conditions, and the time and temperature for heating. However the amount of manganese ion source may be 0.1 ppm to 5,000 ppm, alternatively 0.1 ppm to 1,000 ppm, based on combined weights of all starting materials used in the methods described herein to make the methacryl-functional organosilicon compound, excluding solvent, if used. Alternatively, the amount of the manganese ion source may be > 0 ppm, alternatively at least 0.1 ppm, alternatively at least 0.5 ppm, alternatively at least 1 ppm, alternatively at least 1.5 ppm; while at the same time, the amount of manganese ion source may be up to 5,000 ppm, alternatively up to 1,000 ppm, alternatively up to 100 ppm, alternatively up to 10 ppm, alternatively up to 5 ppm, alternatively up to 4 ppm, and alternatively up to 3 ppm, and alternatively up to 2 ppm, on the same basis. The amount of manganese ion source may have any range that combines the upper and lower limits described above.

[0019] The phenolic compound used herein has one or more phenolic groups per molecule. Suitable phenolic compounds include hydroquinone (HQ), dihydroxybenzene (catechol), resorcinol, dihydroxyxylene, methoxyphenols such as guaiacol, p-methoxyphenol (also calledmethyl ether of hydroquinone or MeHQ), tert-butyl hydroquinone (tBuHQ), pyrogallol, methylpyrogallol, cresol, phenol, xylenols, and combinations thereof. Alternatively, the phenolic compound may be selected from the group consisting of HQ, MeHQ, tBuHQ, and a combination of two or more thereof. Suitable phenolic compounds are commercially available, e.g., from Millipore Sigma of St. Louis, Missouri, USA. The amount of phenolic compound source depends on various factors including the selections and amounts of other starting materials used to make component (B), however the amount may be 5 ppm to 5,000 ppm based on combined weights of all starting materials used in the methods described herein to make component (B), excluding solvent, if used. Alternatively, the amount of the phenolic compound may be at least 5 ppm, alternatively at least 50 ppm, alternatively at least 100 ppm, alternatively at least 150 ppm; while at the same time, the amount of phenolic compound may be up to 500 ppm, alternatively up to 400 ppm, alternatively up to 350 ppm, and alternatively up to 320 ppm, on the same basis. The amount of the phenolic compound may have any range that combines the upper and lower limits described above. Alternatively, when the methacryl-functional organosilicon compound to be produced has a silicon bonded hydrogen atom, then the amount of the phenolic compound may be at least 100 ppm, alternatively 100 ppm to 500 ppm, based on combined weights of all starting materials used in the methods described herein. Alternatively, when the methacryl-functional organosilicon compound to be produced does not include any silicon bonded hydrogen atom, then the amount of the phenolic compound may be at least 5 ppm, alternatively 5 ppm to 500 ppm, based on combined weights of all starting materials used in the methods described herein. General Method for Preparing the Methacryl-functional Organosilicon Compound

[0020] A general method for preparing the methacryl-functional organosilicon compound described above may comprise: 1) combining, under conditions to effect a chemical reaction, starting materials comprising: i) a methacryl-functional reactant having a first reactive moiety, and ii) a second reactant having a second reactive moiety, wherein at least one of starting materials i) and ii) is an organosilicon raw material, and wherein the chemical reaction occurs between the first reactive moiety and the second reactive moiety to form a reaction product comprising the methacryl-functional organosilicon compound; and optionally 2) recovering the methacryl-functional organosilicon compound from the reaction product; wherein at least one of step 1) and, when present, step 2) comprises heating themethacryl-functional organosilicon compound under anaerobic conditions in the presence of iii) the manganese ion source described above and iv) the phenolic compound described above. Heating under anaerobic conditions may be performed during step 1), e.g., during formation of the methacryl-functional organosilicon compound. Alternatively, heating under anaerobic conditions may be performed during step 2), when step 2) is present. Alternatively, heating under anaerobic conditions may be performed during both steps 1) and 2). One or more additional starting materials may be used during the method, such as v) a catalyst, and vi) a solvent to facilitate mixing of the starting materials.

[0021] For purposes of this application, “anaerobic” conditions means that no more than 2% oxygen, alternatively less than 2%, is present in the gas in the headspace of a vessel (used to perform the method described herein), or dissolved in the liquid where the reaction to form the methacryl-functional organosilicon compound takes place or where recovering is performed, when step 2) is present. The balance of the gas in the headspace could be an inert gas such as nitrogen or argon. Alternatively, “anaerobic” includes performing one or more method steps under an inert gas sweep in the vessel used to perform step 1) of the method for preparing the methacryl-functional organosilicon compound described herein, alternatively to recover the methacryl-functional organosilicon compound when step 2) is present, or both. Heating under anaerobic conditions may be performed by any convenient means and may be continuous or intermittent. For example, during the general method, heating under anaerobic conditions may be performed at a temperature of at least 40 °C, alternatively at least 45 °C; while at the same time temperature may be up to 100 °C, alternatively < 100 °C, alternatively up to 95 °C, and alternatively up to 90 °C. Heating under anaerobic conditions may be performed for at least 1, alternatively at least 2 hours; while at the same time heating under anaerobic conditions may be performed for up to 48, alternatively up to 24, alternatively up to 12, and alternatively up to 9 hours. All or a portion of the heating under anaerobic conditions may be performed during formation of the methacryl-functional organosilicon compound, e.g., during step 1). Alternatively, all or a portion of the heating under anaerobic conditions may be performed during recovery of the methacryl-functional organosilicon compound, e.g., during step 2), when step 2) is present.

[0022] When step 2) is present, recovering may be performed by any convenient means such as stripping, distillation, filtration, and a combination thereof. Alternatively, recovering may be performed via means that do not remove iii) the manganese ion source and iv) the phenolic compound from the methacryl-functional organosilicon compound. The reaction product prepared in step 1), and / or the methacryl-functional organosilicon compound recovered in step2) may have the form of a composition comprising the methacryl-functional organosilicon compound and one or both of iii) the manganese ion source and iv) the phenolic compound. For example, in step 2) an unreacted starting material, such as an excess of one of starting materials i) or ii) may be removed; a catalyst or solvent, if used, may be removed; and / or a side product and / or any neutralization product, if present, may be removed from the reaction product prepared in step 1). Alternatively, the composition prepared by the method may comprise: the methacryl-functional organosilicon compound, the manganese ion source, and the phenolic compound. The methacryl-functional organosilicon compound and / or the composition described herein may find use in a myriad of end use applications. For example, the methacryl-functional organosilicon compound, or the composition comprising the methacryl-functional organosilicon compound, the manganese ion source, and the phenolic compound may be used in addition to, or instead of, the methacryl-functional siloxane described in any of US Patents 4554339, 5256754, 9018332, 9051428, and 12163068, and US Patent Publication 20210122769. Alternatively, when the methacryl-functional organosilicon compound is a methacryloxyalkyl-functional organosiloxane polymer, said polymer may be used as component (B) in a two-step curable silicone composition, as described in US Provisional Patent Application 63 / 520106 filed on 17 August 2023, which is hereby incorporated by reference. Alternatively, the composition described above comprising the manganese ion source and the phenolic compound, in addition to the methacryloxyalkyl-functional organosiloxane polymer, may be used in place of component (B) the methacryloxyalkyl-functional organosiloxane polymer, and component (I), the free radical scavenger, in the two-step curable silicone composition of US Provisional Patent Application 63 / 520106.

[0023] In one embodiment, the general method described above may be used to prepare a methacryloxy-alkyl functional silazane as described, for example, in US Patent Publication 20140203323, which is hereby incorporated by reference particularly at paragraph

[0049] , describing a method for making a silazane compound with one or more silazane bonds and one or more methacryloxyalkyl groups, per molecule, by adding the manganese ion source and the phenolic compound thereto. For example, in this embodiment, i) the methacryl-functional reactant having the first reactive moiety may be a chlorosilane having a methacryloxyalkyl- group, and ii) the second reactant may comprise ammonia gas, which may be heated under anaerobic conditions in the presence of iii) the manganese ion source and iv) the phenolic compound, described above, thereby producing a reaction product comprising the methacryloxy- alkyl functional silazane. The methacryloxy-alkyl functional silazane may be recovered in step 2) by any convenient means, such as stripping and / or distillation. Alternatively, the manganeseion source and the phenolic compound may be omitted during step 1) to form the reaction product, and the manganese ion source and the phenolic compound may be introduced in step 2), for example, when recovering the methacryloxy-alkyl functional silazane from the reaction product comprises heating under anaerobic conditions.

[0024] Alternatively, the general method described above can be used to prepare a methacryloxyalkyl-functional organosiloxane polymer having an aliphatically unsaturated group, such as B1) the polyorganosiloxane having at least 2 silicon bonded alkenyl groups and at least one methacryloxyalkyl-functional group per molecule, described above. This embodiment of the method may be performed by adding the manganese ion source and the phenolic inhibitor in a method described, for example, in US Patent 12163068 to Yook, et al., which is hereby incorporated by reference. In this embodiment, in the general method, the chemical reaction may comprise equilibration and condensation reaction, starting material ii) may comprise a silanol-terminated polydiorganosiloxane, starting material i) may comprise a methacryl- functional dialkoxysilane, and the starting materials used in step 1) may further comprise an endblocker and an acid catalyst. To prepare the methacryloxyalkyl-functional organosiloxane polymer that also has an aliphatically unsaturated group, such as an alkenyl group (e.g., component B1)), this equilibration / condensation method may comprise: 1) combining, under conditions to effect equilibration and condensation reaction, starting materials comprising: ii) a silanol-terminated polydiorganosiloxane, i) a methacryl-functional dialkoxysilane, and an endblocker, in the presence of iii) the manganese ion source, iv) the phenolic compound, andv) an acid catalyst; and 2) removing water and alcohol.

[0025] In step 1), the silanol-terminated polydiorganosiloxane may be selected from the group consisting of hydroxy-terminated polydimethylsiloxane (CAS# 70131-67-8), hydroxy- terminated vinylmethylsiloxane-dimethylsiloxane copolymer (CAS# 67923-19-7), hydroxy- terminated polyvinylmethylsiloxane (CAS# 68083-20-5), hydroxy-terminated polyphenylmethylsiloxane (CAS# 80801-30-5), diphenylsilanediol (CAS# 947-42-2), and combinations of two or more thereof. When preparing component B1), at least one of the hydroxy-terminated polydiorganosiloxanes may include aliphatically unsaturated groups, e.g., alkenyl groups such as vinyl, allyl, or hexenyl, particularly when the endblocker does not include an aliphatically unsaturated group. The methacryl-functional dialkoxysilane can be selected from 3-[dimethoxy(methyl)silyl]propyl methacrylate (CAS#14513-34-9) and 3- [dimethoxy(methyl)silyl]propyl acrylate (CAS# 13732-00-8). The endblocker may be selected from hexamethyldisiloxane (CAS# 107-46-0), 1,3-divinyltetramethyldisiloxane (CAS# 2626-95- 4), dimethylvinylsiloxy-terminated polydimethylsiloxane (CAS# 68083-19-2), and combinationsthereof. Additionally, dialkoxy- or dichloro- silane, such as dimethoxydiphenylsilane (CAS# 6843-66-9), dimethoxymethylvinylsilane (CAS# 16753-62-1), dichlorodiphenylsilane (CAS# 80-10-4), 3-mercpatopropylmethyldimethoxysilane (CAS# 31001-77-1), dimethoxy(methyl)(3,3,3-trifluoropropyl)silane (CAS# 358-67-8), diethoxy(methyl)phenylsilane (CAS#775-56-4), diethoxymethylsilane (CAS# 2031-62-1), dimethoxymethylsilane (CAS# 16881-77-9), may optionally be added as co-reactants. In addition, if a branched or resinous methacryloxyalkyl functional organosiloxane polymer is desired, a trialkoxysilane and / or a tetraalkoxysilane such as trimethoxy(methyl)silane (CAS# 1185-55-3), 3- (trimethoxysilyl)propyl methacrylate (CAS# 2530-85-0), 3-(triethoxysilyl)propyl methacrylate (CAS# 21142-29-0), tetramethyl orthosilicate (CAS# 681-84-5) can be added to obtain T” and Q branched structures. Typical catalysts for condensation reaction are summarized in US Patent 8076411 to Dessilly, et al., which is hereby incorporated by reference.

[0026] In this method, water may optionally be added as an additional starting material in step 1), and a solvent such as heptane or toluene may be added to facilitate removal of the water and alcohol via azeotropic distillation in step 2). The acid catalyst may be triflic acid. Alternatively, the acid catalyst may be added with the water, for example an aqueous solution of HCl may be used in step 1) of this method. The catalyst may be neutralized at the end of the method, e.g., by adding a neutralizing agent such as calcium carbonate and / or calcium bicarbonate. In addition to removing water and alcohol, step 2) in this method may further comprise filtration to remove solids formed by neutralizing the catalyst.

[0027] Alternatively, the methacryloxyalkyl-functional organosiloxane polymer, such as B1) the polyorganosiloxane having at least 2 silicon bonded alkenyl atoms and at least one methacryloxyalkyl-functional group per molecule, described above, may be prepared by a method described in US Patent 9051428 to Davio, et al. with the manganese ion source and the phenolic compound added. In the general method described above, the chemical reaction may comprise equilibration and condensation reaction, starting material ii) may comprise a polydiorganosiloxane with a hydroxyl group or a hydrolyzable group bonded to silicon, starting material i) may comprise a methacryl-functional dialkoxysilane, and the starting materials in step 1) may further comprise v) a phosphazene catalyst. This embodiment of the method comprises: 1) combining, under conditions to effect equilibration and condensation reaction, starting materials comprising: i) a polydiorganosiloxane with a hydroxyl group or a hydrolyzable group bonded to silicon, and ii) the methacryl-functional dialkoxysilane, as described herein, in the presence of iii) the manganese ion source, as described above, iv) the phenolic compound, as described above, and v) a phosphazene catalyst; thereby preparing an equilibrium andcondensation reaction product comprising the methacryloxyalkyl-functional organosiloxane polymer, and 2) recovering the methacryloxyalkyl-functional organosiloxane polymer by a technique comprising removing water and alcohol, and neutralizing the phosphazene catalyst. A solvent such as toluene can be used to reduce the viscosity and facilitate the water and methanol removal by azeotropic distillation in step 2). After reaction is completed, a neutralizer such as a trialkylamine and / or a disilazane derivative may be used to neutralize the catalyst. Any solid side product formed by neutralizing the catalyst may then be filtered out after treatment, wherein step 2) further comprises filtering.

[0028] Alternatively, the general method described above may be used to prepare a methacryloxyalkyl-functional organosiloxane polymer, such as B2) the polyorganosiloxane having at least 2 silicon bonded hydrogen atoms and at least one methacryloxyalkyl-functional group per molecule, described above. In this embodiment of the method, the chemical reaction comprises hydrolysis and subsequent condensation / equilibration, starting material ii) may comprise water, and starting material i) may comprise a methacryl-functional alkoxysilane, such as a methacryl-functional dialkoxysilane. This method comprises: 1) combining, under conditions to effect hydrolysis, starting materials comprising: the methacryl-functional alkoxysilane, and water, in the presence of iii) the manganese ion source, and iv) the phenolic compound, and optionally v) an acid such as HCl; thereby preparing a hydrolysis product, and thereafter combining, under conditions to effect condensation and equilibration, starting materials comprising the hydrolysis product, a polydiorganosiloxane (which may be linear and / or cyclic), and a silyl hydride functional polydiorganosiloxane, and an acid condensation reaction catalyst (such as trifluoromethane sulfonic acid); thereby preparing a condensation and equilibration reaction product comprising the methacryloxyalkyl- functional organosiloxane polymer. The method may optionally further comprise 2) recovering the resulting methacryloxyalkyl-functional organosiloxane polymer by stripping or distillation to remove volatiles, optionally under vacuum, and optionally with neutralization of the acid catalyst with a neutralizing agent, as described above. When solids are present, such as solids formed from the neutralization, step 2) may further comprise filtering to remove the solids. Inthis embodiment, method step 1) conditions to effect hydrolysis may comprise heating the starting materials at a temperature of 50 °C to < 100 °C, alternatively 75 °C to 90 °C, for an amount of time sufficient to form the hydrolysis product. Conditions to effect condensation and equilibration may comprise heat at a temperature of at least 40 °C, alternatively 40 °C to < 100 °C, and alternatively 40 °C to 80 °C, for a time sufficient to form the methacryloxyalkyl- functional organosiloxane polymer. Any one or more of hydrolysis, condensation, and equilibration, and when present step 2), may be performed with heating under anaerobic conditions.

[0029] In this embodiment of the method, the methacryl-functional alkoxysilane may have formula: R3R9xSi(OR8)3-x, where R3 is the methacryloxyalkyl- group as defined above; each R8is an independently selected alkyl group of 1 to 6, alternatively 1 to 4, and alternatively 1 to 2 carbon atoms; each R9is an independently selected alkyl group of 1 to 12, alternatively 1 to 6, alternatively 1 to 4, and alternatively 1 to 2 carbon atoms; and subscript x is 0 or 1, alternatively 1. Examples of suitable methacryl-functional alkoxysilanes include 3- methacryloxypropylmethyldimethoxysilane (CAS # 14513-34-9), commercially available from TCI, Tokyo Chemical Industry Co., Ltd.

[0030] The water used for hydrolysis is not generally limited, and may be utilized neat (i.e., absent any carrier vehicles and / or solvents), and / or pure (i.e., free from, or substantially free from, minerals and / or other impurities). For example, the water may be processed or unprocessed prior to the reaction with the methacryl-functional alkoxysilane. Examples of processes that may be used for purifying the water include distilling, filtering, deionizing, reverse osmosis, and combinations of two or more thereof, such that the water may be deionized, distilled, and / or filtered. Alternatively, the water may be unprocessed (e.g., may be tap water, i.e., provided by a municipal water system or well water, used without further purification). Alternatively, the water may be purified before reaction with the methacryl-functional alkoxysilane. The water may be utilized in any amount, which will be selected by one of skill in the art, depending on various factors, e.g., the particular methacryl-functional alkoxysilane selected, the reaction parameters employed, the scale of the reaction (e.g., total amount of methacryl-functional alkoxysilane to be hydrolyzed).

[0031] The polydiorganosiloxane used for condensation and equilibration reaction in this method may be linear, cyclic, or a combination thereof. The linear polydiorganosiloxane may comprise unit formula (R103SiO1 / 2)2(R102SiO2 / 2)y, where each R10is an independently selected monovalent hydrocarbyl group, such as an alkyl or aryl group, and subscript y has an average value of 1 to 10. The cyclic polydiorganosiloxane may comprise unit formula (R102SiO2 / 2)z,where R10is as described above and subscript z has an average value of 3 to 15, alternatively 4 to 12, alternatively 4 to 6. Suitable alkyl groups for R10are as described above for R1, and suitable aryl groups for R10are as described above for R6. Examples of suitable linear polydiorganosiloxanes include polydimethylsiloxanes, which are commercially available from Dow under the tradename XIAMETER™ PMX-200 Silicone Fluid with different viscosities. Alternatively, the polydiorganosiloxane may be cyclic, and is exemplified by octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, and combinations of two or more thereof, all of which are commercially available from Dow.

[0032] Alternatively, when starting material i) in the general method described above comprises a methacrylic acid, an esterification reaction can be used as the chemical reaction, and the method can be used for preparing a methacryloxyalkyl-functional organosiloxane polymer with silyl hydride functionality, such as component B2) the polyorganosiloxane having at least 2 silicon bonded hydrogen atoms and at least one methacryloxyalkyl-functional group per molecule. This method may be performed according to US Patent 4554339 with the manganese ion source and the phenolic compound described herein added. This embodiment of the method may comprise: Pre-1) combining, under conditions to effect addition reaction, starting materials comprising an alkenyl-functional alcohol, and a diorganopolysiloxane having a silicon bonded hydrogen atom, in the presence of an addition reaction catalyst which promotes the addition of silicon bonded hydrogen to an aliphatic multiple bond; thereby preparing an addition reaction product comprising a diorganopolysiloxane having an OH group bonded to a silicon atom via a divalent hydrocarbon linker (derived from the alkenyl functional group of the alkenyl-functional alcohol); and 1) combining, under conditions to effect esterification reaction, starting materials comprising ii) the diorganopolysiloxane having the OH group bonded to the silicon atom via the divalent hydrocarbon linker, and i) a methacrylic acid, in the presence of v) an esterification reaction catalyst and iii) the manganese ion source, and iv) the phenolic compound; thereby preparing an esterification reaction product comprising a methacryloxyalkyl-functional organosiloxane polymer with silyl hydride functionality and at least one methacryloxyalkyl-functional group per molecule,the manganese ion source, and the phenolic compound; optionally 2) recovering a composition comprising the methacryloxyalkyl-functional organosiloxane polymer with silyl hydride functionality and at least one methacryloxyalkyl- functional group per molecule, the manganese ion source, and the phenolic compound; optionally 3) combining, under conditions to effect equilibration reaction, starting materials comprising the esterification reaction product or the composition, when step 2) is present, and a bis-hydroxyl-terminated polyorganohydrogensiloxane, optionally a bis-hydroxyl-terminated polydiorganosiloxane free of silicon bonded hydrogen atoms, optionally a cyclic polydiorganosiloxane, and optionally an acid catalyst which promotes equilibration; thereby preparing an equilibrium reaction product comprising B2) the polyorganosiloxane having at least 2 silicon bonded hydrogen atoms and at least one methacryloxyalkyl-functional group per molecule, the manganese ion source, and the phenolic compound.

[0033] Alternatively, in the general method described above, when starting material ii) comprises a hydroxyl-functional polydiorganosiloxane and starting material i) comprises a methacryloxyalkyl-functional polyorganosiloxane the general method described above may be a method for preparing a methacryloxyalkyl-functional organosiloxane polymer with silyl hydride functionality, such as component B2) the polyorganosiloxane having at least 2 silicon bonded hydrogen atoms and at least one methacryloxyalkyl-functional group per molecule according to US Patent 5256754, but with the manganese ion source and the phenolic compound added thereto. This embodiment of the method may comprise: 1) combining, under conditions to effect equilibration reaction, starting materials comprising: i) a 1,3-hydroxyl-1,1,3,3-tetraorganodisiloxane, a cyclic polydiorganosiloxane, ii) a methacryloxyalkyl-functional polyorganosiloxane, iii) the manganese ion source, and iv) the phenolic compound; and optionally an acid catalyst which promotes equilibration; thereby preparing an equilibrium reaction product comprising the methacryloxyalkyl- functional organosiloxane polymer with silicon bonded hydrogen atoms.

[0034] Alternatively, in the general method described above, when starting material ii) comprises an organohydrogensiloxane oligomer or polymer (e.g., a polyorganohydrogensiloxane) and starting material i) comprises an alkenyl-functional methacrylate compound, and a hydrosilylation reaction catalyst is present, the chemical reaction may be a hydrosilylation reaction for preparing the methacryloxyalkyl-functional organosiloxane polymer with silyl hydride functionality. This method may be performed as described in US Patent 9018332 and US Patent 10280265 to Eldred, et al., and European Patent 3387045B to Eldred, et al., except with adding the manganese ion source and the phenolic compound, as follows. This hydrosilylation reaction method comprises: 1) combining, under conditions to effect hydrosilylation reaction, starting materials comprising: ii) an organohydrogensiloxane oligomer or polymer, e.g., a polyorganohydrogensiloxane, and i) an alkenyl functional methacrylate compound, in the presence of iii) the manganese ion source, iv) the phenolic compound, and v) a hydrosilylation reaction catalyst; thereby preparing a hydrosilylation reaction product comprising methacryloxyalkyl-functional organosiloxane polymer with silyl hydride functionality.

[0035] The hydrosilylation reaction method may further comprise step 2), wherein recovering may comprise stripping and / or distillation to separate the methacryloxyalkyl-functional organosiloxane polymer with silyl hydride functionality from the hydrosilylation reaction catalyst and any unreacted starting material. Stripping and / or distillation may be performed under anaerobic conditions with heating under anaerobic conditions, optionally under vacuum. In this hydrosilylation reaction method embodiment, the alkenyl functional methacrylate compound may be an organic compound, such as a 1-alkenyloxypolyalkylene glycol methacrylate. The polyorganohydrogensiloxane, the alkenyl-functional methacrylate compound, and the hydrosilylation reaction catalyst may be as described in US Patent 9018332, and alternatively, the hydrosilylation reaction catalyst may be as described and exemplified below for component (E) in the two-step curable composition described below.

[0036] In an alternative embodiment of the hydrosilylation reaction method described above, ii) the organohydrogensiloxane oligomer may have formula (I):re each R11is independently an alkyl group of 1 to 6 arbon atoms, a halogenated alkyl group of 1 to 6 carbon atoms, or a halogenated aryl group of 6 to 10 carbon atoms, each R12is independently an alkyl group of 1 to 6 carbon atoms, an aryl group of 6 to 10 carbon atoms, a halogenated alkyl group of 1 to 6 carbon atoms, or a halogenated aryl group of 6 to 10 carbon atoms, and subscript aa is an integer up to 20. Suitable alkyl and aryl groups are as described and exemplified above for R. The halogenated alkyl and aryl groups may be any of the above described alkyl and aryl groups wherein at least one hydrogen atom is replaced by a halogen atoms, such as chlorine or fluorine. Alternatively, each R11and each R12may be alkyl. Alternatively, each R11and each R12may be methyl.

[0037] In this embodiment of the hydrosilylation reaction method, the i) methacrylate compound may be a carboxylic acid alkenyl ester of formula (II): alkylene group of 1 to 6 carbon atoms,atoms. In this embodiment of the hydrosilylation reaction method, the hydrosilylation reaction catalyst may be an iridium complex of formula (III) [Ir(R15)bb(R16)cc]dd, where subscript bb is 1 or 2, R15is a 1,5-cyclooctadiene ligand or a 2,5-norbornadiene ligand, subscript cc is 0, 1 or 2, R16is a ligand that can be activated off the complex at a temperature less than a boiling point of the organohydrogensiloxane oligomer, and subscript dd is 1 or 2.

[0038] In this embodiment, the hydrosilylation product comprises a methacryloxyalkyl- functional organohydrogensiloxane oligomer of formula (IV):=0, R13is -CH2-, and R14is methyl, then the methacryloxyalkyl-functional organohydrogensiloxane oligomer has formula: . when starting material ii)comprises an alkenyl-functional polyorganosiloxane and starting material i) comprises a methacrylate-functional silyl hydride compound, such as the methacryloxyalkyl-functional organohydrogensiloxane oligomer of formula (IV) above, and a hydrosilylation reaction catalyst is present, the chemical reaction may be a hydrosilylation reaction for preparing a methacryloxyalkyl-functional organosiloxane polymer. In this embodiment, the hydrosilylation reaction method may comprise: 1) combining, under conditions to effect hydrosilylation reaction, starting materials comprising: i) the methacryloxyalkyl-functional organohydrogensiloxane oligomer of formula (IV), ii) a polyorganosiloxane having at least one aliphatically unsaturated group per molecule, in the presence of iii) the manganese ion source, described above, iv) the phenolic compound, described above, and v) a hydrosilylation reaction catalyst, as described and exemplified herein for component (E) in the two – step curable silicone composition; thereby producing a hydrosilylation reaction product comprising a methacryloxyalkyl-functional organosiloxane polymer.

[0040] In this embodiment, the method may further comprise step 2), wherein recovering may comprise stripping and / or distillation to separate the methacryloxyalkyl-functional organosiloxane polymer from the hydrosilylation reaction catalyst and any unreacted starting material. Stripping and / or distillation may be performed under anaerobic conditions with heating under anaerobic conditions, optionally under vacuum.

[0041] In this embodiment, the polyorganosiloxane having at least one aliphatically unsaturated group per molecule may be as described in PCT Patent Publication WO2023 / 091868 to Han, et al., which is hereby incorporated by reference. For example, the polyorganosiloxane having at least one aliphatically unsaturated group per molecule may comprise unit formula: (R43SiO1 / 2)a(R42RASiO1 / 2)b(R42SiO2 / 2)c(R4RASiO2 / 2)d(R4SiO3 / 2)e(RASiO3 / 2)f(SiO4 / 2)g(ZO1 / 2)h; where each RAis an independently selected alkenyl group as described and exemplified above for R; each R4is independently selected from a hydrogen atom, an alkyl group, or an aryl group,as described and exemplified above for R; each Z is independently selected from hydrogen or an alkyl group of 1 to 6 carbon atoms, as described above, subscripts a, b, c, d, e, f, and g represent numbers of each unit in the above unit formula and have values such that subscript a ≥ 0, subscript b ≥ 0, subscript c ≥ 0, subscript d ≥ 0, subscript e ≥ 0, subscript f ≥ 0, and subscript g ≥ 0; a quantity (a + b + c + d + e + f + g) ≥ 2, and a quantity (b + d + f) ≥ 1, and subscript h has a value such that 0 ≤ h / (e + f + g) ≤ 1.5. At the same time, the quantity (a + b + c + d + e + f + g) may be ≤ 10,000. Alternatively, in this unit formula, each R4may be independently selected from the group consisting of a hydrogen atom, an alkyl group of 1 to 18 carbon atoms, and an aryl group of 6 to 18 carbon atoms. Alternatively, each R4may be independently selected from the group consisting of an alkyl group of 1 to 18 carbon atoms and an aryl group of 6 to 18 carbon atoms. Alternatively, each R4may be independently selected from the group consisting of methyl and phenyl. Alternatively, each Z may be hydrogen or an alkyl group of 1 to 6 carbon atoms. Alternatively, each Z may be hydrogen.. Alternatively, each Z may be hydrogen or an alkyl group of 1 to 6 carbon atoms. Alternatively, each Z may be hydrogen. Alternatively, in this embodiment of the method, the polyorganosiloxane having at least one aliphatically unsaturated group per molecule and the methacryloxyalkyl-functional organohydrogensiloxane oligomer of formula (IV), and the amounts of each, may be selected to form a polyorganosiloxane having at least 2 silicon bonded alkenyl groups and at least one methacryloxyalkyl-functional group per molecule, suitable for use as component B1) in the two – step curable silicone composition described below. Alternatively, in this embodiment of the method, when at least some instances of R4are hydrogen, then the polyorganosiloxane having at least one aliphatically unsaturated group per molecule and the methacryloxyalkyl-functional organohydrogensiloxane oligomer of formula (IV), and the amounts of each, may be selected to form a polyorganosiloxane having at least 2 silicon bonded hydrogen atoms and at least one methacryloxyalkyl-functional group per molecule, suitable for use as component B2) in the two – step curable silicone composition described below.

[0042] The two-step curable silicone composition (Composition) of US Provisional Patent Application 63 / 520106, introduced above, comprises: (A) an organopolysiloxane resin represented by average unit formula: (R13SiO1 / 2)a(R2R12SiO1 / 2)b(SiO4 / 2)c(HO1 / 2)d, wherein each R1is an independently selected alkyl group; each R2is an independently selected alkenyl group; subscripts a, b, and c are mole fractions of each siloxy unit in the formula; subscript d represents the amount of silicon bonded hydroxyl groups in the formula; and subscripts a, b, c and d have values such that a ≥ 0, b > 0, 0.3 ≤ c ≤ 0.7, a quantity (a + b + c) = 1, and 0 ≤ d ≤ 0.05; (B) a methacryloxyalkyl-functional organosiloxane polymer selected from the group consisting of (B1)an organosiloxane polymer having two silicon atom-bonded alkenyl groups and at least one silicon atom-bonded methacryloxyalkyl group per molecule, (B2) an organosiloxane polymer having two silicon atom-bonded hydrogen atoms and at least one silicon atom-bonded methacryloxyalkyl group per molecule, and (B3) a mixture of components (B1) and (B2); (C) an organohydrogensiloxane oligomer having a viscosity at 25 °C of not more than 1,000 mPa·s, and having at least one silicon atom-bonded hydrogen atom and at least one silicon atom-bonded aryl group in a molecule; optionally (D) an alkenyl-functional organopolysiloxane free of silicon atom-bonded aryl groups and SiO4 / 2units; (E) a hydrosilylation reaction catalyst; (F) a photoradical initiator; (G) a hydrosilylation inhibitor; and optionally (H) a solvent.

[0043] Component (A) in the Composition is an organopolysiloxane resin represented by average unit formula (A1): (R13SiO1 / 2)a(R2R12SiO1 / 2)b(SiO4 / 2)c(HO1 / 2)d. In formula (A1), each R1is an independently selected alkyl group, as described and exemplified above for R. Alternatively, R1may be methyl or ethyl; alternatively each R1may be methyl.

[0044] In formula (A1), R2is an alkenyl group, as described above for R. Alternatively, each R2may be vinyl.

[0045] In formula (A1), subscripts a, b, and c represent mole fractions of the siloxane units in the molecule, and subscript d represents hydroxyl content. Subscripts a, b, c, and d are numbers satisfying the following conditions: a ≥ 0, b > 0, 0.3 ≤ c ≤ 0.7, a quantity (a + b + c) = 1, and 0 ≤ d ≤ 0.05. Alternatively, subscripts a, b, c, and d may have values such that 0.1 ≤ a ≤ 0.5, 0.01 ≤ b ≤ 0.2, 0.4 ≤ c ≤ 0.7, 0 ≤ d ≤ 0.05, or alternatively 0.2 ≤ a ≤ 0.5, 0.01 ≤ b ≤ 0.2, 0.4 ≤ c ≤ 0.7, 0 ≤ d ≤ 0.05. Without wishing to be bound by theory, it is thought that when subscripts a, b, c and d are numbers within the ranges mentioned above, a pre-cured product obtained by hydrosilylation reaction of the Composition will have appropriate hardness and mechanical strength.

[0046] Molecular weight of the organopolysiloxane resin for component (A) is not limited, however, its number average molecular weight (Mn) measured using GPC with with polystyrene standards may be at least 1,500 g / mol, alternatively at least 2,000 g / mol, or alternatively at least 3,000 g / mol; while at the same time Mn may be up to 6,000 g / mol; alternatively up to 5,500 g / mol. The Mn of component (A) can be any range that combines the upper and lower limits described above, e.g., 3,000 g / mol to 5,500 g / mol.

[0047] Examples of organopolysiloxane resins suitable for use as component (A) may be made by known methods, such as the methods for making the alkenyl-functional polyorganosilicate resins described in PCT Patent Publications WO2021225675 (corresponding to US Patent12163068) and WO2023091868, and the references cited therein. Suitable organopolysiloxane resins for component (A) include one or more of the following: A-1) (Me3SiO1 / 2)0.40(ViMe2SiO1 / 2)0.04(SiO4 / 2)0.56, A-2) (Me3SiO1 / 2)0.42(ViMe2SiO1 / 2)0.05(SiO4 / 2)0.53(OH)0.02, and A-3) (Me3SiO1 / 2)0.40(ViMe2SiO1 / 2)0.10(SiO4 / 2)0.50.

[0048] Component (A) is used in the Composition in an amount of < 82 mass %, alternatively up to 80 mass %, alternatively 55 mass % to 80 mass %, alternatively 55 mass % to 75 mass % based on a total mass of components (A), (B), (C), and (D). Alternatively, the amount of component (A) may be at least 59 mass %, alternatively at least 60 mass %, alternatively at least 61 mass %, and alternatively at least 62 mass %; while at the same time, the amount of component (A) may be up to 80 mass %, alternatively up to 75 mass %, alternatively up to 73 mass %, alternatively up to 72 mass %, and alternatively up to 70 mass %, on the same basis. The amount of component (A) can be any range that combines the upper and lower limits described above. Without wishing to be bound by theory, it is thought that if the amount of component (A) is equal to or above the lower limit of the range described above, a pre-cured product obtained by curing the Composition via hydrosilylation reaction will have low tack, or tack-free, surface and appropriate hardness and mechanical strength, whereas if the amount is equal to or below the upper limit of the range described above, the pre-cured product of the Composition has appropriate mechnical stength without brittlenss.

[0049] Component (B) may be a methacryloxy-alkyl functional organosiloxane polymer of formula (B1), formula (B2), or (B3) a mixture thereof, as described above. Component (B) is used in the Composition in an amount ranging from 10 mass % to 30 mass % based on the total mass of components (A), (B), (C), and (D). Alternatively, component (B) may be used in the Composition in an amount ranging from 12 mass % to 25 mass %, on the same basis. Without wishing to be bound by theory, it is thought that if the amount of component (B) is equal to or above the lower limit of the ranges described above, the pre-cured product of Composition will have good curability by irradiation with the active energy ray (as described below), and if the amount is equal to or below the upper limit of the ranges described above, the Composition will be stable when exposed to stress such as pressure or temperature. Alternatively, the amount of component (B) may be at least 10 mass %, alternatively at least 11 mass %, alternatively at least 12 mass %, alternatively at least 13 mass %, alternatively at least 14 mass %, alternatively at least 15 mass %, and alternatively at least 15.2 mass %; while at the same time the amount of component (B) may be up to 30 mass %, alternatively up to 29 mass %, alternatively up to 27 mass %, alternatively up to 25 mass %, alternatively up to 24 mass %, alternatively up to 23mass %, and alternatively up to 22.6 mass % on the same basis.

[0050] Alternatively, the amount of component B1) may be at least 10 mass %, alternatively at least 12 mass %, alternatively at least 14 mass %, alternatively at least 15 mass %, alternatively at least 16 mass %, alternatively at least 17 mass %, and alternatively at least 20 mass %; while at the same time the amount of component B1) may be up to 30 mass %, alternatively up to 27 mass %, alternatively up to 25 mass %, alternatively up to 24 mass %, alternatively up to 23 mass %, alternatively up to 22.6 mass %, and alternatively up to 22 mass %, on the same basis.

[0051] Alternatively, the amount of component B2) may be at least 10 mass %, alternatively at least 11 mass %, alternatively at least 13 mass %, alternatively at least 14 mass %, alternatively at least 15 mass %, alternatively at least 15.2 mass %, and alternatively at least 15.3 mass %; while at the same time the amount of component B2) may be up to 30 mass %, alternatively up to 25 mass %, alternatively up to 23 mass %, alternatively up to 22 mass %, alternatively up to 20 mass %, alternatively up to 15.7 mass %, and alternatively up to 15.3 mass %, on the same basis. The amount of component (B) can be any range that combines the upper and lower limits described above, provided that the total amount of components B1) and B2) is 10 mass % to 30 mass % based on the total mass of components (A), (B), (C), and (D).

[0052] Component (C) is an aryl-functional organohydrogensiloxane oligomer, which may be added to the Composition to impart a rigid property, and to impart a pre-cured product (obtained by hydrosilylation reaction of the Composition) with high glass transition temperature (i.e., Tg > 60 ⁰C). Molecular weight of component (C) is not limited, however, it may be ≤ 2,000 g / mol, alternatively ≤ 1,500 g / mol. Component (C) may have a viscosity ≤1,000 mPa·s, alternatively ≤ 500 mPa·s, or alternatively ≤ 100 mPa·s, where viscosity is measured using a type B viscometer according to ASTM D 1084 at 23 ± 2 °C.

[0053] Component (C) may also act as a chain extending agent or a crosslinking agent for the Composition. Component (C) may have, per molecule, at least one silicon atom-bonded hydrogen atom and at least one silicon atom-bonded aryl group. Alternatively, component (C) may have, per molecule, at least two silicon atom-bonded hydrogen atoms, and at least one silicon atom-bonded aryl group.

[0054] The organohydrogensiloxane oligomer for component (C) may comprise unit formula (C1): (HR72SiO1 / 2)2(R72SiO2 / 2)e, where each R7is independently selected from alkyl and aryl, where suitable alkyl and aryl groups are as described and exemplified above for R, with the proviso that at least one R7, per molecule, is an aryl group. Alternatively, at least one R7per molecule is phenyl. Subscript e represents average number of difunctional siloxane units per molecule, and subscript e is an integer with a value of 0 to 10, alternatively 0 to 5, alternatively 0to 3, and alternatively 0 or 1.

[0055] Examples of suitable organohydrogensiloxane oligomers for component (C) may be selected from C-1): H(CH3)2SiO(C6H5)2SiOSi(CH3)2H, C-2): H(CH3)2SiO(C6H5)(CH3)SiOSi(CH3)2H, C-3): H(CH3)(C6H5)SiOSi(CH3)(C6H5)H, and C-4): a mixture of two or more of C-1), C-2), and C-3). Alternatively, component (C) may be one or both of C-1) and C-2).

[0056] Component (C) is used in an amount ranging from 0.1 mass % to 10 mass %, based on the total mass of components (A), (B), (C), and (D). Without wishing to be bound by theory, it is thought that when the Composition contains at least 0.1 mass % of component (C), the Composition will have good handleability, and a pre-cured product of the Composition will have a tack-free or low tack surface, and when the amount of component (C) in the Compsition is 10 mass % or less, the pre-cured product has high glass transition temperature. Alternatively, the amount of component (C) may be at least 0.1 mass %, alternatively at least 0.2 mass %, alternatively at least 0.3 mass %, alternatively at least 0.4 mass %, alternatively at least 0.5 mass %, alternatively at least 1 mass %, alternatively at least 1.2 mass %, alternatively at least 1.3 mass %, alternatively at least 1.4 mass %, alternatively at least 1.5 mass %, alternatively at least 2 mass %; while at the same time, the amount of component (C) may be up to 10 mass%, alternatively up to 9 mass %, alternatively up to 8 mass %, alternatively up to 7 mass %, alternatively up to 6 mass %, alternatively up to 5.5 mass %, alternatively up to 5.1 mass %, alternatively up to 5 mass %, alternatively up to 4.5 mass %, and alternatively up to 3 mass %, on the same basis. The amount of component (C) can be any range that combines the upper and lower limits described above.

[0057] Component (D) is optional and may be used in the Composition to facilitate coating the Composition on a substrate. Component (D) is an alkenyl-functional organopolysiloxane, which is free of silicon atom-bonded aryl groups and free of tetrafunctional units of formula SiO4 / 2. Component (D) may have a substantially linear, alternatively linear, structure.

[0058] Component (D) may have unit formula: (R2R11 2SiO1 / 2)2(R 2SiO2 / 2)f, where R1is an alkyl group and R2is an alkenyl group, as described and exemplified above for component (A), and subscript f represents average number of difunctional siloxane units per molecule, and subscript f is an integer ranging from 10 to 10,000.

[0059] Examples of such component (D) include dimethylpolysiloxanes capped at both molecular chain terminals with dimethylvinylsiloxy groups. Component (D) may have a viscosity ranging from 10 mPa·s to 1,000,000 mPa·s measured using a type B viscometer according to ASTM D 1084 at 23 ± 2 °C.

[0060] Component (D) is used in the Composition in an amount ranging from 0 to 25 mass %, based on a total mass of components (A), (B), (C), and (D). If a mixture of components (A), (B), and (C) can be fully cured, component (D) may be omitted. Alternatively, by considering an application method, an addition of component (D) might be helpful to facilitate coating on a substrate (e.g., a base film). Alternatively, when component (D) is included in the Composition, the amount may be at least 10 mass %, alternatively at least 10.5 mass %, alternatively at least 11 mass %, alternatively at least 11.6 mass %; while at the same time the amount of component (D) may be up to 25 mass %, alternatively up to 23 mass %, alternatively up to 22.9 mass %, on the same basis described above. The amount of component (D) can be any range that combines the upper and lower limits described above.

[0061] Components (A), (B), (C), and (D) are used in amounts in the Composition sufficient to provide a molar ratio of silicon atom-bonded hydrogen atoms (SiH) to silicon atom-bonded alkenyl, e.g., vinyl groups (Vi) sufficient to effect hydrosilylation reaction when heating the Composition to form a pre-cured product (e.g., to react the Composition via hydrosilylation reaction to form the pre-cured product, which is deformable and has a low tack or tack-free surface. A molar ratio ("SiH / Vi ratio") of all silicon atom-bonded hydrogen atoms relative to all silicon atom-bonded alkenyl groups in components (A), (B), (C), (D), and (E) is 0.29 / 1 to < 0.9 / 1. Alternatively, SiH / Vi ratio may be at least 0.29 / 1 alternatively at least 0.3 / 1, alternatively at least 0.4 / 1, alternatively at least 0.44 / 1, alternatively at least 0.5 / 1, and alternatively at least 0.57 / 1, while at the same time, SiH / Vi ratio may be up to 0.9 / 1, alternatively up to 0.7 / 1, alternatively up to 0.69 / 1, alternatively up to 0.58 / 1, and alternatively up to 0.57 / 1. Without wishing to be bound by theory, it is thought that if the SiH / Vi molar ratio is equal to or above the lower limit of the range described above, the Composition can be properly pre-cured by heating to effect hydrosilylation reaction, and the pre-cured product will have appropriate hardness and a low tack or tack-free surface, and when the molar ratio is equal to or below the upper limit of the range described above, the pre-cured product has deformable property.

[0062] Component (E) is a hydrosilylation reaction catalyst used to facilitate thermal curing of the Composition. Hydrosilylation reaction catalysts suitable for component (E) are known in the art and commercially available. Suitable hydrosilylation catalysts comprise a platinum group metal such as platinum, rhodium, ruthenium, palladium, osmium, or iridium metal or an organometallic compound and / or complex. Alternatively, component (E) may comprise a platinum-based catalyst. Examples of the platinum-based catalysts include a platinum fine powder, chloroplatinic acid, an alcohol solution of chloroplatinic acid, a platinum- alkenylsiloxane complex, a platinum-olefin complex and a platinum-carbonyl complex.Alternatively, component (E) may comprise a platinum-alkenylsiloxane complex such as 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complexes with platinum. These complexes may be microencapsulated in a resin matrix. Examples of suitable hydrosilylation reaction catalysts for component (E) are described in, for example, US Patent 12195593 to Guo, et al., and the references cited therein. Hydrosilylation reaction catalysts are commercially available, for example, SYL-OFF™ 4000 Catalyst and SYL-OFF™ 2700 are available from Dow.

[0063] Component (E) is used in the Composition in an effective quantity for facilitating thermal cure via hydrosilylation reaction. The amount of component (E) is sufficient to provide an amount of the platinum group metal ranging from 0.01 ppm to 500 ppm, alternatively 0.01 ppm to 100 ppm, alternatively 0.01 ppm to 50 ppm, and alternatively 0.1 ppm to 10 ppm, by mass relative to 100 parts by mass of components (A), (B), (C), and (D) combined. Alternatively, the amount of component (E) may be sufficient to provide at least 0.01 ppm, alternatively at least 0.1 ppm, alternatively at least 1 ppm, alternatively at least 2 ppm, and alternatively at least 5 ppm of the platinum group metal, while at the same time the amount of component (E) may be up to 500 ppm, alternatively up to 250 ppm, alternatively up to 100 ppm, alternatively up to 50 ppm, alternatively up to 25 ppm, and alternatively up to 10 ppm of the platinum group metal, on the same basis. The amount of component (E) can be any range that combines the upper and lower limits described above.

[0064] Component (F) in the Composition is a photoradical initiator. Component (F) is added to the Composition to effect curing by irradiating the Composition with an active energy ray. Suitable photoradical initiators include UV initiators which are known in the art and are commercially available. For example, photoradical initiators suitable for use herein include 2,6- bis(4-azido benzylidene)cyclohexanone, 2,6-bis(4-azido benzylidene)-4-methylcyclohexanone, 1-hydroxy-cyclohexyl-phenyl-ketone (IRGACURE™ 184), 2-methyl-1[4-(methylthio)phenyl]- 2-morpholinopropane-1-one (IRGACURE™ 907); 2-hydroxy-2-methyl-1-phenyl-propane-1-one (DAROCUR™ 1173); a mixed initiator (IRGACURE™ 500) of 50% of IRGACURE™ 184C and 50% of benzophenone; a mixed initiator (IRGACURE™ 1000) of 20% of IRGACURE™ 184C and 80% of DAROCUR™ 1173; 2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methyl-1- propanone (IRGACURE™ 2959); methylbenzoylformate (DAROCUR™ MBF); alpha, alpha- dimethoxy-alpha-phenylacetophenone (IRGACURE™ 651); 2-benzyl-2-(dimethylamino)-1-[4- (4-morpholinyl)phenyl]-1-butanone (IRGACURE™ 369); a mixed initiator (IRGACURE™ 1300) of 30% of IRGACURE™ 369 and 70% of IRGACURE™ 651; Diphenyl(2,4,6- trimethylbenzoyl)phosphine oxide (IRGACURE™ TPO), Ethyl (2,4,6-trimethylbenzoyl) phenyl phosphinate (IRGACURE™ TPO-L), propriety oxime ester compounds (N-1919, NCI-831,NCI-930, NCI-730, and NCI-100 supplied from Adeka Corporation), thioxanthen-9-one; 10- methylphenothiazine; isopropyl-9H-thioxanthen-9-one; 2,4-diethyl-9H-thioxanthen-9-one; 2- chlorothioxanthen-9-one; 1-chloro-4-propoxy-9H-thioxanthen-9-one; or a combination of two or more thereof. The photoradical initiators with the DAROCUR™ and IRGACURE™ brands are commercially available from BASF SE of Ludwigshafen, Germany. Alternatively, the photoradical initiator may be selected from the group consisting of F-1) 2-benzyl-2- dimethylamino-1-(4-morpholinophenyl)-butanone-1, F-2) benzophenone, F-3) a substituted benzophenone compound, F-4) acetophenone, F-5) a substituted acetophenone compound, F-6) benzoin, F-7) an alkyl ester of benzoin, F-8) a substituted phosphine oxide compound, F-9) xanthone, F-10) a substituted xanthone; and F-11) a combination of two or more of F-1) to F- 10). The type of photoradical initiator is not specifically restricted, however, some photoradical initiators, such as those containing thioether groups, phosphinate groups, or phosphine oxide groups, may inhibit the hydrosilylation reaction catalyst, therefore, when such a photoradical initiator will be included, the appropriate amount of (E) hydrosilylation reaction catalyst may need to be controlled and / or heating temperature / time may need to be adjusted.

[0065] The amount of (F) the photoradical initiator in the Composition will depend on various factors including the desired reaction rate, the photoinitiator used, and the selection and amount of component (B) and its methacryl- content, however, the amount may be 0.1 part by mass to 10 parts by mass, alternatively 0.1 part by mass to 5 parts by mass, relative to 100 parts by mass of components (A), (B), (C), and (D) combined.

[0066] Component (G) is a hydrosilylation reaction inhibitor that may be added to adjust the hydrosilylation reaction rate of the silicon atom-bonded hydrogen atoms and the silicon atom- bonded alkenyl groups of the components (e.g., components (A) to (D)) in the Composition. Component (G) includes, without limitation, an alkyne alcohol; a cyclic alkenyl functional siloxane; a maleate; a fumarate; or a triazole. Alternatively, the inhibitor may comprise a silylated alkyne alcohol such as those disclosed in US Patent 6677407 to Bilgrien, et al.

[0067] Component (G) may be used in the Composition in an amount ranging from 1 ppm to 5,000 ppm, alternatively 10 ppm to 2,000 ppm by mass relative to mass of components (A), (B), (C), and (D) combined. Without wishing to be bound by theory, it is thought that when the amount of component (G) is greater than or equal to the lower limit of the aforementioned range, storage stability of the Composition is good, and when the amount of component (G) is less than or equal to the upper limit of the aforementioned range, curability via hydrosilylation reaction of the Composition at low temperatures is good.

[0068] Component (H) is a solvent that may optionally be added to the Composition. Thesolvent may be added during preparation of the Composition, for example, to aid mixing and delivery of one or more components and / or the solvent may be added after preparation of the Composition, e.g., to facilitate coating the on a substrate, as described hereinbelow. When preparing the Composition, certain components may be delivered in solvent, such as component (A) or (D). Suitable solvents include organic liquids exemplified by, but not limited to, aromatic hydrocarbons, aliphatic hydrocarbons, ketones, esters, ethers, glycols, and glycol ethers. Polyalkylsiloxanes with suitable vapor pressures may be used as the solvent, and polyalkylsiloxanes, such as 0.5 to 1.5 cSt polydimethylsiloxanes are known in the art and commercially available as DOWSIL™ 200 Fluids and DOWSIL™ OS FLUIDS, which are commercially available from Dow. Alternatively, the solvent may be selected from the group consisting of an aliphatic hydrocarbon, an aromatic hydrocarbon, an ether, an ester, and a solvent having both ether and ester moieties. Alternatively, the solvent may be selected from the group consisting of an aliphatic hydrocarbon and an aromatic hydrocarbon.

[0069] The amount of solvent will depend on various factors including the type of solvent selected and the amounts and types of other components in the Composition. Alternatively, the amount of solvent may be 0 to 300 parts by weight, per 100 parts by weight of all components in the Composition. Alternatively, the amount of solvent may be 5 parts by weight to 300 parts by weight, alternatively 10 parts by weight to 300 parts by weight, and alternatively 5 parts by weight to 200 parts by weight, on the same basis. EXAMPLES

[0070] The following examples are provided to illustrate the invention to one of ordinary skill in the art and are not to be interpreted as limiting the scope of the invention set forth in the claims. The components used in these examples are summarized below in Table 1. Table 1 – Components Component Chemical Description Source APMDMS 3 l l th ldi th il G l tComponent Chemical Description Source MviMvi1,1,3,3-tetramethyl-1,3-divinyl disiloxane Dow BHT DAE N icmethacryloxypropylmethyldimethoxysilane, 0.01N HCl, and an inhibitor according to Table 1 above were mixed in the amounts shown below in Tables 2 and 3 using a rotary evaporator at room temperature for 5 minutes before pulling vacuum (0 – 30 mmhg) at 80 °C for 2 hours to remove methanol and H2O. The resulting hydrolyzed product, decamethylcyclopentasiloxane, and 1,1,3,3-tetramethyldisiloxane were then added to a 4-neck round bottom flask and heated to 40 °C before adding trifluoromethanesulfonic acid (1000 ppm) to catalyze the equilibration and condensation reaction.

[0072] The temperature in the flask was then raised to 87-88 °C and stirred for at least 2 hours while under an N2, 2% O2 in N2 or Air sweep. The heating block was then removed, and CaCO3 was added at 80 °C. The temperature in the flask dropped to 24 °C after at least 3 hours and CaCO3 was filtered out with a 0.45 μm membrane. Volatiles were then removed by evaporation using a rotary evaporator at 100 – 120 °C at 2-4 torr for 2 hours. Each final sample was clear and colorless, and the composition thereof was analyzed by1H and29Si NMR. Table 2: amounts (g) of starting materials used to prepare a methacrylate functional polyorganosiloxane by condensation / equilibration Example No. I II III IV V e)Example No. I II III IV V / Starting (comparative) (comparative) (working) (comparative) (comparative) M t ri lInhibitor I II III IV V (comparative) (comparative) (working) (comparative) (comparative)Table 4: Results of Synthesis Example 1 Example Reaction Continuous Gelation Final Product Atmosphere Stripping Viscosity (cP)

[0073] Comparative Example I showed very rapid gelation times during stripping under typical manufacturing conditions for the preparation a polyorganosiloxane having at least 2 silicon bonded hydrogen atoms and at least one methacryloxyalkyl-functional group per molecule. The inhibitor package in this example was unable to prevent polymerization during the stripping conditions of this example despite a 2% O2 in N2 feed (which is the maximum oxygen content suitable for handling of materials with silicon bonded hydrogen atoms in commercial scale production). Comparative Example II showed reactor gelation during polymerization under an N2atmosphere (most commonly used for commercial scale production). Comparative Examples I and II demonstrated that BHT alone was not sufficient as an inhibitor for the production of methacryloxyalkyl-functional polyorganosiloxanes on a commercial scale under the conditions tested. Working Example III showed a methacryloxyalkyl-functional polyorganohydrogensiloxane was successfully prepared under anaerobic conditions suitable for commercial scale production. Without wishing to be bound by theory, it is thought that Working Example III demonstrates that the process for making methacryloxyalkyl-functionalorganosilicon compounds in which the Mn / HQ inhibitor package described herein is used successfully prevents gelation during polymerizations under N2 and during stripping conditions suitable for commercial scale production of methacryloxyalkyl-functional organosilicon compounds, including those with silicon bonded hydrogen atoms. Working Example III compared to Comparative Examples IV and V demonstrated the unique synergistic nature of the Mn / HQ inhibitor package, as gelation or large viscosity increases that would be expected to impact downstream applications were observed when either Mn(II)ACTH or HQ (but not both) was used under anaerobic conditions.

[0074] In this Synthesis Example 2, the procedure in Synthesis Example 1 was repeated, but instead using the starting materials and amounts shown below in Table 5, and reaction atmosphere shown below in Table 6. The results are shown below in Table 7. Table 5: amounts (g) of starting materials used to prepare a methacrylate functional polyorganosiloxane by condensation / equilibration Starting VII V terial VI ( III IX X Ma working) (working) (working) (comparative) (comparative)Table 6: Amouunts of Inhibitors (ppm) in the reaction product and reaction atmosphere used Inhibitor VI VII VIII (w rkin ) (w rkin ) (w rkin ) IX (comparative) X (comparative)Table 7 – Results of Synthesis Example 2 Example Reaction Continuous Stripping Gelation Final ProductExample Reaction Continuous Stripping Final Product Atmosphere Time Gelation Viscosity (cP)compound could be used in combination with the manganese ion source for the production of methacryloxyalkyl-functional polyorganosiloxanes on a commercial scale under the conditions tested. These methacryloxyalkyl-functional polyorganosiloxanes also contained silicon bonded hydrogen atoms, and examples VI, VII, and IX showed that 100 ppm of phenolic compound in combination with the Mn ion source was sufficient, however 50 ppm was not under the conditions tested, when making a methacryloxyalkyl-functional polyorganosiloxane that also contained silicon bonded hydrogen atoms. Comparative example X showed that tBuHQ was insufficient when making a methacryloxyalkyl-functional polyorganosiloxane that also contained silicon bonded hydrogen atoms in the absence of the Mn ion source, under the conditions tested.

[0076] In this Synthesis Example 3, the procedure in Synthesis Example 1 was repeated, but instead using the starting materials and amounts shown below in Table 8, and reaction atmosphere used are shown below in Table 9. The results are shown below in Table 10. Table 8: amounts (g) of starting materials used to prepare a methacrylate functional polyorganosiloxane by condensation / equilibration Starting Material XI (working) XII (working) XIII (working) XIV (working) MAPMDMS 54 59 54 5.4 .7 .9 .7 2 5 1 0 0 3Table 9: Amounts of inhibitor (ppm) in final polymerization and reaction atmosphere used Inhibitor XI (working) XII (working) XIII (working) XIV (working)Table 10: Results of Synthesis Example 3 Example Reaction Continuous Stripping Final Product Atmosphere Time Gelation Viscosity (cP)source can be successfully used in the method described herein. Working Example XIV demonstrated that a manganese (III) ion source can be used instead of a manganese (II) ion source.

[0078] In this Synthesis Example 4, the procedure in Synthesis Example 1 was repeated, but instead using the starting materials and amounts shown below in Table 11, and reaction atmosphere used are shown below in Table 12. In this Synthesis Example 4, 1,1,3,3- tetramethyl-1,3-divinyl disiloxane was used instead of 1,1,3,3-tetramethyldisiloxane in these examples. In comparative example XX, an acryloxy-functional silane was used instead of a methacryloxy-functional silane. The results are shown below in Table 13. Table 11: amounts (g) of starting materials used to prepare a methacrylate functional polyorganosiloxane that also has vinyl groups by condensation / equilibration Starting XV XVI XVII XVIII XIX XX Mat’l (working) (working) (working) (working) (working) (comparative)Table 12 – Inhibitors and reaction atmosphere for Synthesis Example 4 Inhibitor XV XVI XVII XVIII XIX XX e)Table 13 – Results of Synthesis Example 4 Example Reaction Continuous Final Product Atmosphere Stripping Time Gelation Viscosity (cP)d the phenolic compound could be successfully used to prepare a methacryloxypropyl-functional polyorganosiloxane that also had silicon bonded vinyl groups. Working Examples XVII and XIX showed that the amount of phenolic compound could be 5 ppm to 500 ppm when the methacryloxypropyl-functional polyorganosiloxane also had silicon bonded vinyl groups but did not have silicon bonded hydrogen atoms. Working examples XV to XIX and comparative example XX showed that when an acryloxy-functional silane was used instead of a methacryloxy-functional silane, the combination of Mn ion source and phenolic compound did not prevent gelation under the conditions tested. Problem to be Addressed

[0080] Commercial scale production of methacryl-functional organosilicon compounds can be challenging, particularly when the methacryl-functional organosilicon compound to be produced, or when a starting material used in the production, has silicon bonded hydrogen atoms (SiH). SiH compounds must be handled under anaerobic conditions for safety reasons. However, conventional free radical scavengers and methacrylate polymerization inhibitors are sometimes unsuitable for use with organosilicon compounds because they can create problems, such as poisoning hydrosilylation reaction catalysts used to prepare the methacryl-functional organosilicon compounds (e.g., in step 1) of embodiments of the method described above) and / or when residual inhibitor is present with the methacryl-functional organosilicon compounds after their production (e.g., when the method herein is used to prepare a methacryloxyalkyl- functional organosiloxane polymer for use in the two-step curable silicone composition, described above).

[0081] Without wishing to be bound by theory, it is thought that the present invention addresses these problems by providing an inhibitor package comprising a manganese ion sourceand a phenolic compound, that, when used in combination, allow for commercial scale production of methacryl-functional organosilicon compounds that may be suitable for use in hydrosilylation reaction systems. DEFINITIONS AND USAGE OF TERMS

[0082] All amounts, ratios, and percentages herein are by weight, unless otherwise indicated. The SUMMARY and ABSTRACT are hereby incorporated by reference. The articles, “a”, “an”, and “the” each refer to one or more, unless otherwise indicated by the context of the specification. The abbreviations used herein have the definitions in Table Z. Table Z – Abbreviations Abbreviation Definition H

[0083] The invention has been described in an illustrative manner, and it is to be understood that the terminology which has been used is intended to be in the nature of words of description rather than of limitation. With respect to any Markush groups relied upon herein for describing particular features or aspects, different, special, and / or unexpected results may be obtained fromeach member of the respective Markush group independent from all other Markush members. Each member of a Markush group may be relied upon individually and or in combination and provides adequate support for specific embodiments within the scope of the appended claims.

[0084] Furthermore, any ranges and subranges relied upon in describing the present invention independently and collectively fall within the scope of the appended claims, and are understood to describe and contemplate all ranges including whole and / or fractional values therein, even if such values are not expressly written herein. One of skill in the art readily recognizes that the enumerated ranges and subranges sufficiently describe and enable various embodiments of the present invention, and such ranges and subranges may be further delineated into relevant halves, thirds, quarters, fifths, and any other subrange subsumed within the range.

Claims

CLAIMS:

1. A composition comprising: (I) a methacryl-functional organosilicon compound, having per molecule at least one silicon bonded methacryloxyalkyl group of , wherein R5is an alkylene group having 2 to 6 carbon atoms;(II) a manganese ion source, and (III) a phenolic compound.

2. The composition of claim 1, wherein the methacryl-functional organosilicon compound comprises a methacryloxyalkyl-functional organosiloxane polymer, wherein the methacryloxyalkyl-functional organosiloxane polymer is selected from the group consisting of component B1), component B2), and a mixture of both, wherein component B1) comprises unit formula: (R2R62SiO 6 1 / 2)2(R 2SiO2 / 2)n(R6R3SiO2 / 2)m, wherein each R2is an independently selected alkenyl group; each R6is independently selected from the group consisting of an alkyl group and an aryl group; each R3is the methacryloxyalkyl group of formula: , wherein R5is as described above; andaverage numbers of each difunctional siloxane unit per molecule in the unit formula for B1), wherein subscript m is an integer of 1 to 500, subscript n is an integer of 1 to 1000, and 0.01 ≤ m / (n+m) ≤ 0.5; and component B2) comprises unit formula: (HR62SiO1 / 2)2(R62SiO2 / 2)n(R6R3SiO2 / 2)m, wherein each R6is independently selected from the group consisting of an alkyl group and an aryl group;each R3is a methacryloxyalkyl group of formul , wherein R5is an alkylene group having 2 to 6 carbon atoms; and subscripts m and n represent average numbers each difunctional siloxane unit per molecule in the unit formula for B1), wherein subscript m is an integer of 1 to 500, subscript n is an integer of 1 to 1000, and 0.01 ≤ m / (n+m) ≤ 0.

5.

3. The composition of claim 1 or claim 2, wherein the manganese ion source comprises manganese (II) acetate, manganese (II) acetate tetrahydrate, or a combination thereof.

4. The composition of any one of claims 1 to 3, wherein the phenolic compound is selected from the group consisting of hydroquinone, monomethyl ether of hydroquinone, tert- butylhydroquinone, and a combination of two or more thereof.

5. The composition of any one of claims 2 to 4, wherein the composition contains > 0 ppm to 10 ppm of the manganese ion source, 5 ppm to 500 ppm of the phenolic compound, and a balance to 100 weight % of the methacryloxyalkyl-functional organosiloxane polymer.

6. The composition of any one of claims 1 to 4, wherein the composition is free of any methacrylate polymerization inhibitor other than the manganese ion source and the phenolic compound.

7. A method for preparing a composition of any one of claims 1 to 6, wherein the method comprises: 1) combining, under conditions to effect a chemical reaction, starting materials comprising: i) a methacryl-functional reactant comprising a first reactive moiety, ii) a second reactant comprising a second reactive moiety, with the proviso that at least one of starting materials i) and ii) is an organosilicon compound, andwherein the first reactive moiety and the second reactive moiety undergo the chemical reaction with each other to form the methacryl-functional organosilicon compound, in the presence of iii) the manganese ion source, and iv) the phenolic compound; thereby preparing a reaction product comprising the methacryl-functional organosilicon compound; and optionally 2) recovering the methacryl-functional organosiloxane compound from the reaction product; wherein at least one of step 1), and, when present, step 2), comprises heating under anaerobic conditions.

8. The method of claim 7, wherein the starting materials used in step 1) further comprise: v) a catalyst, vi) a solvent, and a combination thereof.

9. A method for preparing a composition of any one of claims 1 to 6, wherein the method comprises: 1) combining, under conditions to effect hydrolysis, starting materials comprising: a methacryloxyalkyl-functional alkoxysilane, and water, in the presence of the manganese ion source, and the phenolic compound, and optionally an acid such as HCl; wherein conditions to effect hydrolysis comprise heating the starting materials at a temperature of 50 °C to < 100 °C, under anaerobic conditions; thereby preparing a hydrolysis product, and thereafter combining, under conditions to effect condensation and equilibration, starting materials comprising the hydrolysis product, a polydiorganosiloxane, and a silyl hydride functional diorganosiloxane, and an acid condensation reaction catalyst, wherein conditions to effect condensation and equilibration comprise heating at a temperature of 40 °C to < 100 °C under anaerobic conditions, thereby forming a condensationand equilibration reaction product comprising a methacryloxyalkyl-functional organosiloxane polymer; and 2) recovering the methacryloxyalkyl-functional organosiloxane polymer.

10. A two-step curable silicone composition comprising: (A) an organopolysiloxane resin represented by average unit formula: (R13SiO1 / 2)a(R2R12SiO1 / 2)b(SiO4 / 2)c(HO1 / 2)d, wherein each R1is an independently selected alkyl group; each R2is an independently selected alkenyl group; and subscripts a, b, and c are mole fractions of each siloxy unit in the formula; subscripts a, b, c and d have values such that a ≥ 0, b > 0, 0.3 ≤ c ≤ 0.7, and a quantity (a + b + c) = 1; and subscript d represents the amount of silicon bonded hydroxyl groups in the formula and has a value such that 0 ≤ d ≤ 0.05; the composition of claim 2; (C) an organohydrogensiloxane oligomer having at least one silicon atom-bonded hydrogen atom and at least one silicon atom-bonded aryl group per molecule and a viscosity less than or equal to 1,000 mPa·s measured using a type B viscometer according to ASTM D 1084 at 23 ± 2 °C; optionally (D) an alkenyl-functional organopolysiloxane free of silicon atom-bonded aryl groups and SiO4 / 2 units; (E) a hydrosilylation reaction catalyst; (F) a photoradical initiator; (G) a hydrosilylation inhibitor; optionally (H) a solvent; the manganese ion source; and the phenolic compound; and where component (A) is present in an amount ranging from 55 mass % to 75 mass % based on a total mass of components (A), (B) the methacryloxyalkyl-functional organosiloxane polymer, (C), and (D);component (B) the methacryloxyalkyl-functional organosiloxane polymer is present in an amount ranging from 10 mass % to 30 mass % based on the total mass of components (A), (B), (C), and (D); component (C) is present in an amount ranging from 0.1 mass % to 10 mass % based on the total mass of components (A), (B), (C), and (D); component (D) is present in an amount ranging from 0 to 25 mass % based on the total mass of components (A), (B), (C), and (D); component (E) is present in an amount sufficient to provide 0.1 ppm to 500 ppm of a platinum group metal by mass relative to 100 parts by mass of components (A), (B), (C), and (D) combined; component (F) is present in an amount ranging from 0.01 to 10 parts by mass relative to 100 parts by mass of components (A), (B), (C), and (D) combined; component (G) is present in an amount ranging from 1 ppm to 5,000 ppm by mass relative to mass of components (A), (B), (C), and (D) combined; component (H) is present in an amount ranging from 0 to 300 parts by mass relative to 100 parts by mass of components (A), (B), (C), and (D) combined; and with the provisos that a molar ratio of silicon atom-bonded hydrogen atoms relative to silicon atom bonded-alkenyl groups in components (A) to (E) is 0.29 / 1 to less than 0.9 / 1; and the composition comprising the methacryloxyalkyl-functional organosiloxane polymer is used in an amount such that a content of the methacryloxyalkyl group is 5 mmol / 100 g or more relative to a total mass of components (A), (B), (C), and (D).

11. The method of claim 10, wherein > 0 ppm to 10 ppm of the manganese ion source is used, 100 ppm to 500 ppm of the phenolic compound is used, and the methacryl-functional organosilicon compound has at least one silicon bonded hydrogen atom per molecule 12. The composition of any one of claims 2 to 4, wherein the composition contains > 0 ppm to 10 ppm of the manganese ion source, 100 ppm to 500 ppm of the phenolic compound, and a balance to 100 weight % of the methacryloxyalkyl-functional organosiloxane polymer, wherein the methacryloxyalkyl-functional organosiloxane polymer has at least one silicon bonded hydrogen atom per molecule.

13. The method of any one of claims 7 to 9, wherein > 0 ppm to 10 ppm of the manganeseion source is used, 100 ppm to 500 ppm of the phenolic compound is used, and the methacryl- functional organosilicon compound has at least one silicon bonded hydrogen atom per molecule.

14. The composition of claim 1, wherein (I) the methacryl-functional organosilicon compound is free of silicon bonded hydrogen atoms, (II) the manganese ion source is present in an amount > 0 ppm to 10 ppm, and (III) the phenolic compound is present in an amount of 5 ppm to 500 ppm.

15. The composition of claim 14, wherein (I) the methacryl-functional organosilicon compound further comprises at least one silicon bonded hydrogen atom per molecule, (II) the manganese ion source is present in an amount of > 0 ppm to 10 ppm, and (III) the phenolic compound is present in an amount of 100 ppm to 500 ppm,

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