Polyorganosiloxane emulsion and methods for its preparation and use

Abstract

A polyorganosiloxane emulsion has a discontinuous phase dispersed in a continuous phase, wherein the discontinuous phase includes a hydrosilylation reaction curable polyorganosiloxane composition, and the continuous phase comprises water. The emulsion is useful for forming a coated article in which a substrate has a polyorganosiloxane release coating on its surface. The coated article is useful for food contact applications.

Description

POLYORGANOSILOXANE EMULSION AND METHODS FOR ITS PREPARATION AND USE CROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of U.S. Provisional Patent Application Serial No. 63 / 688,418 filed on 29 August 2024 under 35 U.S.C. §119 (e). U.S. Provisional Patent Application Serial No.63 / 688,418 is hereby incorporated by reference. FIELD

[0002] A polyorganosiloxane emulsion comprises a discontinuous phase dispersed in a continuous phase, wherein the discontinuous phase comprises a curable polyorganosiloxane composition and the continuous phase comprises water. The emulsion is useful for forming a coated article comprising a polyorganosiloxane release coating on a substrate. The coated article is suitable for use in food contact applications. INTRODUCTION

[0003] Oleophobic (e.g., greaseproof) properties are desirable for different articles such as paper or paperboard of different grammage in a wide range of applications including food applications like packaging or baking but also in composite filter for extractor or filter hoods as well as in any applications were anti-staining or anti-fingerprint protection is required.

[0004] Paper is typically a material in thin form obtained or derived from fibres of cellulose pulp from wood and other plant sources. Paper is usually available in thin sheets, bags or other containers. Paper can contain additives and / or can be treated to improve its properties such as resistance to various chemicals, resistance to harsh environments, or increased printability. Treated papers or special grades papers are useful in food related applications.

[0005] For example, baking paper (also called parchment paper or bakery release paper) is typically made of paper that has at least one non-stick surface that resists to cooking temperatures. The heat resistant, non-stick surface is obtained, for example, by treating the paper with sulphuric acid and with a silicone coating. Sulphuric acid paper treatment provides mechanical strength, low permeability and greaseproofness. Alternatively, the paper can be treated with a silicone composition to provide a silicone coating that enables water barrier and anti-adhesive performances for improved cold or warm food release.

[0006] Greaseproof papers permit packing food or wrapping fatty food (e.g., butter) in sheets, wrappers and other containers. They can be used as interleavers for sliced food like sliced cheese, bacon, deli meat, salmon, cookie dough or other food. Greaseproof papers withstand oil and fatty food from permeating the paper and soiling it. It may be desirable for the greaseproof paper to also have release properties such as non-tackiness to prevent food from sticking to the paper at ambient temperature (anti-adhesive properties) and / or after use at high temperature(microwaving or baking release properties). The greaseproof paper also desirably has water repellent properties useful for steam cooked food like dumplings, or for frozen food to prevent breakage upon de-freezing, piercing, or any damage to the paper packaging.

[0007] Greaseproof papers can be made of special grades of papers, such as glassine, where cellulose fibres are treated to obtain a very low porosity, impeding grease and oil to penetrate in the paper. The paper can be treated with wax (e.g., paraffinic wax), starch, alginate or cellulose gum to fill pores thereby hindering fatty products to penetrate the paper. However, these treatments may be inefficient, and may detrimentally impact water barrier and food release properties. Manufacturing such types of papers requires appropriate processes, such as calendaring or supercalendering, demanding further investments in the paper making process line that can add significantly to the cost price of the finished greaseproof paper.

[0008] Alternatively, greaseproof papers may be obtained by treating papers with compounds forming an oil- and grease repellent layer on the paper. A known treatment is based on fluorinated compounds that are able to provide some non-stick properties by forming a film having low surface energy, which is resistant to chemical agents thereby providing oil, fat and water repellence to the treated paper. However, the current trend is to restrict use of fluorinated compounds by various regulations, especially in the food packaging area. Another approach has been to treat papers with a mixture of polyvinyl alcohol and a chromate-fatty acid complex. However the use of heavy metal such as chromium also raises environmental and health concerns in food packaging related uses. Other treatments permit to confer some oleophobicity to the paper but they often require relatively high amounts of material to be effective and form a thick coating on the paper, which may be detrimental to the mechanical properties and durability upon creasing or folding of the paper and is not cost effective.

[0009] US Patent 10723891 discloses “an aqueous coating composition and a greaseproof article comprising a substrate bearing a coating formed by curing the composition. The substrate is made of paper, acrylic material or polyethylene terephthalate or paper / plastics laminate material. The article is used for food packaging. The aqueous coating composition is able to form a coating on a substrate upon curing by hydrosilylation.” This aqueous coating composition may suffer from various drawbacks including being expensive due to the use of a platinum group metal hydrosilylation reaction catalyst. SUMMARY

[0010] A polyorganosiloxane emulsion comprises a discontinuous phase dispersed in a continuous phase, wherein the continuous phase comprises water, the discontinuous phase comprises a curable polyorganosiloxane composition, and wherein the emulsion further comprises a surfactant. A method for preparing the polyorganosiloxane emulsion is provided.A method for using the polyorganosiloxane emulsion to prepare a coated paper substrate suitable for use in food contact applications is also provided. DETAILED DESCRIPTION

[0011] The curable polyorganosiloxane composition (composition), introduced above, comprises: (A) an aldehyde-functional polyorganosiloxane, (B) a polyorganohydrogensiloxane, and (C) a catalyst composition. The composition may optionally further comprise an additional starting material, e.g., (D) an antioxidant. (A) Aldehyde-Functional Polyorganosiloxane

[0012] Starting material (A) is an aldehyde-functional polyorganosiloxane. Aldehyde- functional polyorganosiloxanes suitable for use herein are known and may be made by known methods, such as those described in US Patent 5021601 to Frances et al.; US Patent 5739246 to Graiver et al.; US Patent 7696294 to Asirvatham; and US Patent 7999053 to Sutton et al.; European Patent Application Publication EP 0392948 A1 to Frances, and PCT Patent Application Publication WO2006027074 to Kühnle et al.

[0013] Alternatively, the aldehyde-functional polyorganosiloxane may be prepared by a hydroformylation process. This hydroformylation process comprises 1) combining, under conditions to catalyze hydroformylation reaction, starting materials comprising a gas comprising hydrogen and carbon monoxide, an alkenyl-functional polyorganosiloxane, and a hydroformylation reaction catalyst such as a rhodium / ligand complex, wherein the ligand may be a bisphosphite, a phosphoramidite, or a phosphine or phosphine amine. Step 1) of the hydroformylation process produces a hydroformylation reaction product comprising the aldehyde-functional polyorganosiloxane. The hydroformylation process (or any other process in the references cited above for making the aldehyde-functional polyorganosiloxane) may further comprise one or more additional steps such as: 2) recovering the aldehyde-functional polyorganosiloxane and removing the catalyst (e.g., rhodium / ligand complex from the hydroformylation reaction) from the aldehyde-functional polyorganosiloxane. Removing the catalyst may be performed by methods known in the art, including but not limited to adsorption (e.g., by contacting with an adsorbent such as activated carbon for a time sufficient to adsorb all or at least a portion of the catalyst) with subsequent filtration to remove the adsorbent, and / or membrane separation (e.g., nanofiltration). Suitable recovery methods are as described, for example, in US Patents 5681473 to Miller, et al.; 8748643 to Priske, et al.; and 10155200 to Geilen, et al. The hydroformylation process for making aldehyde-functional polyorganosiloxanes may be as described, for example, in US Patent Application Publication US20230242711 and PCT Patent Application Publication WO2023200934, both of which are hereby incorporated by reference for the purpose of disclosing suitable aldehyde-functionalpolyorganosiloxanes.

[0014] The aldehyde-functional polyorganosiloxane has at least two aldehyde-functional groups per molecule. Each aldehyde-functional group is bonded to a silicon atom in the polyorganosiloxane and may have , wherein G is a divalent hydrocarbyl group of 2 to 8 carbon atoms aliphatic unsaturation. G may be linearor branched. Examples of divalent hydrocarbyl groups for G include alkane-diyl groups of empirical formula -CuH2u-, where subscript u is 2 to 8. The alkane-diyl group may be a linear alkane-diyl, e.g., -CH2-CH2-, -CH2-CH2-CH2-, -CH2-CH2-CH2-CH2-, or -CH2-CH2-CH2-CH2-CH2-CH2-, or a branched alkane-diyl, or. Alternatively, each G may be an alkane-diyl group of 2 to 6 carbon atoms;2, 3, or 6 carbon atoms; and alternatively 2 carbon atoms.

[0015] The aldehyde-functional polyorganosiloxane may comprise unit formula (A1): (R73SiO1 / 2)c(R72R8SiO1 / 2)d(R72SiO2 / 2)e(R7R8SiO2 / 2)f(R7SiO3 / 2)g(R8SiO3 / 2)h(SiO4 / 2)i(ZO1 / 2)j; wherein each R7is a monovalent hydrocarbyl group free of aliphatic unsaturation, e.g., each R7may 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; each R8is the aldehyde-functional group of formula , wherein G is the divalent hydrocarbon group free of aliphatic8 carbon atoms described above; each Z is independently selected from the group consisting of a hydrogen atom, an alkyl group of 1 to 18 carbon atoms, and an aryl groups of 6 to 18 carbon atoms; subscripts c, d, e, f, g, h, and i are integers each representing an average number of siloxane units per molecule, and subscripts c, d, e, f, g, h, and i have values such that: c ≥ 0, d ≥ 0, e ≥ 0, f ≥ 0, g ≥ 0, h ≥ 0, a quantity (d + f + h) ≥ 2, i ≥ 0, and 10,000 ≥ (c + d + e + f + g + h + i) ≥ 2, and subscript j has a value such that 1.5 > j / (g + h + i) > 0.

[0016] In unit formula (A1), each R7may be independently selected from the group consistingof an alkyl group of 1 to 18 carbon atoms and an aryl group of 6 to 18 carbon atoms. Suitable alkyl groups for R7may be linear, branched, cyclic, or combinations of two or more thereof. The alkyl groups are exemplified by propyl (including n-propyl and / or isopropyl), butyl (including n-butyl, tert-butyl, sec-butyl, and / or isobutyl); pentyl, hexyl, heptyl, octyl, decyl, dodecyl, undecyl, and octadecyl (and branched isomers having 5 to 18 carbon atoms), and the alkyl groups are further exemplified by cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. Alternatively, the alkyl group for R7may be selected from the group consisting of methyl and ethyl. Alternatively, the alkyl group for R7may be methyl. Suitable aryl groups for R7may be monocyclic or polycyclic and may have pendant hydrocarbyl groups. For example, the aryl groups for R7include phenyl, tolyl, xylyl, and naphthyl and further include aralkyl groups such as benzyl, 1-phenylethyl and 2-phenylethyl. Alternatively, the aryl group for R7may be monocyclic, such as phenyl, tolyl, or benzyl; alternatively the aryl group for R7may be phenyl. Alternatively, each R7may be independently selected from the group consisting of an alkyl group of 1 to 12 carbon atoms and an aryl group of 6 to 12 carbon atoms. Alternatively, each R7may be independently selected from the group consisting of an alkyl group of 1 to 6 carbon atoms and an aryl group of 6 to 10 carbon atoms. Alternatively, each R7may be selected from methyl and phenyl. Alternatively, each R7may be methyl.

[0017] In unit formula (A1), each Z is independently selected from the group consisting of H and an alkyl group of 1 to 18 carbon atoms, which may be as described above with respect to R7. Alternatively, each Z may be hydrogen or an alkyl group of 1 to 6 carbon atoms. Alternatively, each Z may be hydrogen or methyl.

[0018] In unit formula (A1), each R8is the aldehyde-functional group described above.

[0019] Alternatively, the aldehyde-functional polyorganosiloxane may comprise (A2) a linear polydiorganosiloxane having, per molecule, at least one aldehyde-functional group; alternatively at least two aldehyde-functional groups (e.g., when in the unit formula (A1) for the aldehyde- functional polyorganosiloxane above, subscripts g = h = i = 0). For example, said aldehyde- functional polydiorganosiloxane may comprise unit formula (A3): (R73SiO1 / 2)c(R8R72SiO1 / 2)d(R72SiO2 / 2)e(R7R8SiO2 / 2)f, where R7and R8are as described above, subscript c is 0, 1, or 2; subscript d is 0, 1, or 2, subscript e ≥ 0, subscript f ≥ 0, with the provisos that a quantity (d + f) ≥ 1, a quantity (c + d) = 2, and a quantity (c + d + e + f) ≥ 2. Alternatively, in the unit formula (A3) for the linear aldehyde-functional polyorganosiloxane, above, the quantity (c + d + e + f) may be at least 3, alternatively at least 4, and alternatively > 50. At the same time said formula, the quantity (a + b + c + d) may be less than or equal to 10,000; alternatively less than or equal to 4,000; alternatively less than or equal to 2,000; alternatively less than or equal to 1,000; alternatively less than or equal to 500; alternatively less than or equalto 250; and alternatively less than or equal to 200.

[0020] Alternatively, (A) the aldehyde-functional polyorganosiloxane may be branched. For example, (A4) the branched aldehyde-functional polyorganosiloxane may comprise a Q branched polyorganosiloxane of unit formula (A5): (R7SiO ) (R7 R8SiO )(R7 3 1 / 2 q 2 1 / 2 r 2SiO2 / 2)s(SiO4 / 2)t, wherein R7and R8are as described above, and subscripts q, r, s, and t have average values such that 2 ≥ q ≥ 0, 4 ≥ r ≥ 0, 995 ≥ s ≥ 4, t = 1, (q + r) = 4, and (q + r + s + t) has a value sufficient to impart a viscosity > 170 mPa·s measured by rotational viscometry (as described below with the test methods) to the branched polyorganosiloxane. Alternatively, viscosity may be > 170 mPa·s to 1000 mPa·s, alternatively > 170 to 500 mPa·s, alternatively 180 mPa·s to 450 mPa·s, and alternatively 190 mPa·s to 420 mPa·s.

[0021] Alternatively, (A5) the Q branched aldehyde-functional polyorganosiloxane may 7 7 78 7 7 8comprise formula (A6): [R R Si-(O-SiR ) -O] -Si-[O-(R Si-O) -SiR ] , where R and R2 2 n (4-m) 2 v 3 m are as described above; and subscripts v, m, and n have values such that 200 ≥ v ≥ 1, 2 ≥ m ≥ 0, and 200 ≥ n ≥ 1.

[0022] Alternatively, (A4) the branched aldehyde-functional polyorganosiloxane may comprise a T branched polyorganosiloxane (silsesquioxane) of unit formula (A7): 77 8 7 8 7 7 7 8(R3SiO1 / 2)aa(R R2SiO1 / 2)bb(R2SiO2 / 2)cc(R R SiO2 / 2)ee(R SiO3 / 2)dd, where R and R are as described above, subscript aa ≥ 0, subscript bb > 0, subscript cc is 15 to 995, subscript dd > 0, and subscript ee ≥ 0. Subscript aa may be 0 to 14, alternatively 0 to 10. Alternatively, subscript aa may have a value such that: 12 ≥ aa ≥ 0; alternatively 10 ≥ aa ≥ 0; alternatively 7 ≥ aa ≥ 0; alternatively 5 ≥ aa ≥ 0; and alternatively 3 ≥ aa ≥ 0. Alternatively, subscript bb ≥ 1. Alternatively, subscript bb ≥ 3. Alternatively, subscript bb may have a value such that: 12 ≥ bb > 0; alternatively 12 ≥ bb ≥ 3; alternatively 10 ≥ bb > 0; alternatively 7 ≥ bb > 1; alternatively 5 ≥ bb ≥ 2; and alternatively 7 ≥ bb ≥ 3. Alternatively, subscript cc may have a value such that: 800 ≥ cc ≥ 15; and alternatively 400 ≥ cc ≥ 15. Alternatively, subscript ee may have a value such that: 800 ≥ ee ≥ 0; 800 ≥ ee ≥ 15; and alternatively 400 ≥ ee ≥ 15. Alternatively, subscript ee may b 0. Alternatively, a quantity (cc + ee) may have a value such that 995 ≥ (cc + ee) ≥ 15. Alternatively, subscript dd ≥ 1. Alternatively, subscript dd may be 1 to 10. Alternatively, subscript dd may have a value such that: 10 ≥ dd > 0; alternatively 5 ≥ dd > 0; and alternatively dd = 1. Alternatively, subscript dd may be 1 to 10, alternatively subscript dd may be 1 or 2. Alternatively, when subscript dd = 1, then subscript bb may be 3 and subscript cc may be 0. The values for subscript bb may be sufficient to provide the silsesquioxane of unit formula (A7) with an aldehyde content of 0.1% to 1%, alternatively 0.2% to 0.6%, based on the weight of the silsesquioxane.

[0023] Alternatively, (A) the aldehyde-functional polyorganosiloxane may comprise (A8) an aldehyde-functional polyorganosiloxane resin, such as (A9) an aldehyde-functional polyorganosilicate resin and / or (A10) an aldehyde-functional silsesquioxane resin. Such resins may be prepared, for example, by hydroformylating an alkenyl-functional polyorganosiloxane resin, as described in the references cited above. The aldehyde-functional polyorganosilicate resin comprises monofunctional units (“M” units) of formula RM’3SiO1 / 2 and tetrafunctional silicate units (“Q” units) of formula SiO4 / 2, where each RM’may be independently selected from the group consisting of R7and R8as described above. Alternatively, each RM’may be selected from the group consisting of an alkyl group, an aldehyde-functional group of the formula shown above, and an aryl group. Alternatively, each RM’may be selected from methyl, (propyl- aldehyde) and phenyl. Alternatively, at least one-third, alternatively at least two thirds of the RM’groups are methyl groups. Alternatively, the M’ units may be exemplified by (Me3SiO1 / 2), (Me2PhSiO1 / 2), and (Me2RPr-AldSiO1 / 2). The polyorganosilicate resin is soluble in solvents such as those described herein as starting material (C)(ii), exemplified by liquid hydrocarbons, such as benzene, ethylbenzene, toluene, xylene, and heptane, or in liquid non-functional organosilicon compounds such as low viscosity linear and cyclic polydiorganosiloxanes.

[0024] When prepared, the polyorganosilicate resin comprises the M’ and Q units described above, and the polyorganosiloxane further comprises units with silicon bonded hydroxyl groups, and / or hydrolyzable groups, described by moiety (ZO1 / 2), above, and may comprise neopentamer of formula Si(OSiRM’3)4, where RM’is as described above, e.g., the neopentamer may be tetrakis(trimethylsiloxy)silane.29Si NMR and13C NMR spectroscopies may be used to measure hydroxyl and alkoxy content and molar ratio of M’ and Q units, where said ratio is expressed as {M’(resin)} / {Q(resin)}, excluding M’ and Q units from the neopentamer. M’ / Q ratio represents the molar ratio of the total number of triorganosiloxy groups (M’ units) of the resinous portion of the polyorganosilicate resin to the total number of silicate groups (Q units) in the resinous portion. M’ / Q ratio may be 0.5 / 1 to 1.5 / 1, alternatively 0.6 / 1 to 0.9 / 1.

[0025] The Mn of the polyorganosilicate resin depends on various factors including the types of hydrocarbon groups represented by RM’that are present. The Mn of the polyorganosilicate resin refers to the number average molecular weight measured using GPC, when the peak representing the neopentamer is excluded from the measurement. The Mn of the polyorganosilicate resin may be 1,500 Da to 30,000 Da, alternatively 1,500 Da to 15,000 Da; alternatively >3,000 Da to 8,000 Da. Alternatively, Mn of the polyorganosilicate resin may be 3,500 Da to 8,000 Da.

[0026] Alternatively, the polyorganosilicate resin may comprise unit formula (A11): (R73SiO 7 1 / 2)mm(R 2R8SiO1 / 2)nn(SiO4 / 2)oo(ZO1 / 2)j, where Z, R7, and R8, and subscript j are asdescribed above and subscripts mm, nn and oo have average values such that mm ≥ 0, nn > 0, oo > 0, and 0.5 < (mm + nn) / oo < 4. Alternatively, 0.6 < (mm + nn) / oo < 4; alternatively 0.7 < (mm + nn) / oo < 4, and alternatively 0.8 < (mm + nn) / oo < 4.

[0027] Alternatively, (A) the aldehyde-functional polyorganosiloxane may comprise (A10) the aldehyde-functional silsesquioxane resin, i.e., a resin containing trifunctional (T’) units. The aldehyde-functional silsesquioxane resin may have unit formula (A12): (R77 3SiO1 / 2)c(R 2R8SiO1 / 2)d(R7 2SiO2 / 2)e(R7R8SiO2 / 2)f(R7SiO3 / 2)g(R8SiO3 / 2)h(ZO1 / 2)j; where R7and R8are as described above, subscript h > 1, 2 < (g + h) < 10,000; 0 < (c + d) / (g + h) < 3; 0 < (e + f) / (g + h) < 3; and 0 < j / (g + h) < 1.5. Alternatively, the aldehyde-functional silsesquioxane resin may comprise unit formula (A13): (R7SiO3 / 2)g(R8SiO3 / 2)h(ZO1 / 2)j, where R7, R8, Z, and subscripts g, h, and j are as described above. Alternatively, the alkenyl-functional silsesquioxane resin may further comprise difunctional (D’) units of formulae (R72SiO2 / 2)e(R7R8SiO2 / 2)f in addition to the T’ units described above, i.e., a D’T’ resin, where subscripts e and f are as described above. Alternatively, the aldehyde-functional silsesquioxane resin may further comprise monofunctional (M’) units of formulae (R73SiO ) (R7 1 / 2 c 2R8SiO1 / 2)d, i.e., an M’D’T’ resin, where subscripts c and d are as described above for unit formula (A1).

[0028] One aldehyde-functional polyorganosiloxane may be used in the curable polyorganosiloxane composition of this invention. Alternatively, two or more aldehyde- functional polyorganosiloxanes that differ from one another may be used. For example, the aldehyde-functional polyorganosiloxanes may differ in at least one property such as structure, molecular weight, type of aldehyde-functional group, and selection of groups for R7. For example, a branched aldehyde-functional polyorganosiloxane may be used as starting material (A). Alternatively, a combination of a linear aldehyde-functional polyorganosiloxane and a resinous aldehyde-functional polyorganosiloxane may be used in addition to, or instead of, the branched aldehyde-functional polyorganosiloxane. (B) Polyorganohydrogensiloxane

[0029] Starting material (B) in the curable polyorganosiloxane composition is a polyorganohydrogensiloxane having, per molecule, at least two silicon bonded hydrogen atoms. The polyorganohydrogensiloxane comprises two or more siloxane units selected from, HR92SiO1 / 2, R93SiO1 / 2, HR9SiO2 / 2, R92SiO2 / 2, R9SiO3 / 2, HSiO3 / 2and SiO4 / 2units, with the proviso that at least two units per molecule have a silicon bonded hydrogen atom. In the preceding formulae, each R9is an independently selected monovalent hydrocarbyl group as described and exemplified above for R7. Monovalent halogenated hydrocarbyl groups are exemplified by the hydrocarbyl groups described above, but having one or more hydrogen atoms replaced with a halogen atom, such as Cl or F. Examples of suitable monovalent halogenated hydrocarbongroups include, but are not limited to, chlorinated alkyl groups such as chloromethyl and chloropropyl groups; fluorinated alkyl groups such as 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; chlorinated cycloalkyl groups such as 2,2-dichlorocyclopropyl, 2,3-dichlorocyclopentyl; and fluorinated cycloalkyl groups such as 2,2-difluorocyclopropyl, 2,3-difluorocyclobutyl, 3,4-difluorocyclohexyl, and 3,4- difluoro-5-methylcycloheptyl. The polyorganohydrogensiloxane may be linear, branched, cyclic, resinous, or a combination thereof. Alternatively, the polyorganohydrogensiloxane may be linear or branched. Alternatively, the polyorganohydrogensiloxane may be linear.

[0030] Alternatively, (B) the polyorganohydrogensiloxane, may comprise unit formula (B1): (R99 3SiO1 / 2)w(R 2HSiO1 / 2)x(R9 2SiO2 / 2)y(R9HSiO2 / 2)z, wherein R9is as described above; subscripts w, x, y, and z are integers representing average numbers of siloxane units per molecule, and subscripts w, x, y, and z have values such that: w is 0, 1, or 2, x is 0, 1, or 2, a quantity (w + x) has an average value of 2; y ≥ 0, z ≥ 0, a quantity (x + z) ≥ 2, and 10,000 ≥ (w + x + y + z) ≥ 2. Alternatively each R9may 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 R9may be methyl or phenyl. Alternatively, each R9in unit formula (B1) may be methyl.

[0031] In unit formula (B1) above, subscript y may have an average value ranging from 0 to 2,000, and subscript z may an average value ranging from 0 to 2,000. Alternatively, subscript y may be 0 to 1,000, alternatively 0 to 500, alternatively 0 to 250, alternatively 0 to 100, alternatively 0 to 50, and alternatively 0 to 25. Alternatively, subscript z may be 0 to 1,000; alternatively 2 to 500, alternatively 2 to 250, alternatively 2 to 100, and alternatively 3 to 50. Alternatively, a quantity (y + z) may be 2 to 1,000, alternatively 3 to 900, and alternatively 4 to 800.

[0032] Polyorganohydrogensiloxanes for starting material B-2) are exemplified by: a) dimethylhydrogensiloxy-terminated polydimethylsiloxane, b) dimethylhydrogensiloxy-terminated poly(dimethylsiloxane / methylhydrogensiloxane), c) dimethylhydrogensiloxy-terminated polymethylhydrogensiloxane, d) trimethylsiloxy-terminated poly(dimethylsiloxane / methylhydrogensiloxane), e) trimethylsiloxy-terminated polymethylhydrogensiloxane, f) a resin consisting essentially of H(CH3)2SiO1 / 2 units and SiO4 / 2 units, and g) a combination thereof.

[0033] Polyorganohydrogensiloxanes are also commercially available, such as those available from Gelest, Inc. of Morrisville, Pennsylvania, USA, for example, HMS-H271, HMS-071, HMS-993; HMS-301 and HMS-301 R, HMS-031, HMS-991, HMS-992, HMS-993, HMS-082,HMS-151, HMS-013, HMS-053, HAM-301, HPM-502, and HMS-HM271. Other polyorganohydrogensiloxanes include DOWSIL™ 6-3570 Polymer, DOWSIL™ SH1107 Fluid, SYL-OFF™ 7048 Crosslinker, SYL-OFF™ 7678 Crosslinker, SYL-OFF™ 7682-000 Crosslinker, SYL-OFF™ 7682-055 Crosslinker, SYL-OFF™ SL 8 Crosslinker, SYL-OFF™ SL 9 Crosslinker, SYL-OFF™ SL 11 Crosslinker, SYL-OFF™ SL 12 Crosslinker, XIAMETER™ MHX-11007 Fluid, and XIAMETER™ OFS-5057 Fluid, all of which are commercially available from The Dow Chemical Company of Midland, Michigan, USA. Methods of preparing linear, branched, and cyclic organohydrogenpolysiloxanes suitable for use herein, such as hydrolysis and condensation of organohalosilanes, are well known in the art, see for example US Patent 3957713 to Jeram et al. and US Patent 4329273 to Hardman, et al. Methods of preparing organohydrogenpolysiloxane resins suitable for use herein are exemplified, e.g., in US Patents 5310843; 4370358; and 4707531. And, US Patent 2823218 to Speier, et al., discloses organohydrogensiloxane oligomers and linear polymers, e.g., 1,1,3,3-tetramethyldisiloxane; 1,1,1,3,3-pentamethyldisiloxane; 1,1,1,3,5,5,5-heptamethyltrisiloxane; bis-trimethylsiloxy- terminated polymethylhydrogensiloxane homopolymer; bis-trimethylsiloxy-terminated poly(dimethyl / methylhydrogen)siloxane copolymer; and cyclic polymethylhydrogensiloxanes.

[0034] Starting material (A) the aldehyde-functional polyorganosiloxane and starting material (B) the polyorganohydrogensiloxane are selected such that in the curable polyorganosiloxane composition, when the aldehyde-functional polyorganosiloxane has only two silicon bonded aldehyde-functional groups per molecule, then the polyorganohydrogensiloxane has at least three silicon bonded hydrogen atoms per molecule; and when the polyorganohydrogensiloxane has only two silicon bonded hydrogen atoms per molecule, then the aldehyde-functional polyorganosiloxane has at least three silicon bonded aldehyde-functional groups per molecule.

[0035] Amounts of and selections of starting materials (A) and (B) are provided to make the composition capable of curing. The amounts and selections of starting materials (A) and (B) may be such that a molar ratio of silicon bonded hydrogen atoms in starting material (B) to silicon bonded aldehyde groups in starting material (A) (the “SiH / Aldehyde ratio”) is 1:1 to 1:10, alternatively 1: 1.05 to 1:10. Without wishing to be bound by theory, it is thought that when the SiH / Aldehyde ratio is 1 : > 1, then this minimizes the amount of unreacted silicon bonded hydrogen atoms after curing. (C) Catalyst Composition

[0036] Starting material (C) is a catalyst composition, which catalyzes hydrosilylation reaction of the aldehyde groups and silicon bonded hydrogen atoms. The catalyst composition comprises starting material (i) the halogenated arylborane Lewis acid. The halogenated arylborane Lewis Acid has general formula BR1R2R3, wherein R1, R2, and R3are each independently selected fromthe group consisting of halogen atoms, aryl groups, and halogenated aryl groups, with the proviso that at least one of R1, R2, and R3is a halogenated aryl group; alternatively at least two of R1, R2, and R3are halogenated aryl groups; and alternatively all three of R1, R2, and R3may be halogenated aryl groups. Suitable halogen atoms include Cl and F, alternatively F. Suitable aryl groups include phenyl, tolyl, and xylyl. Suitable halogenated aryl groups are exemplified by the aryl groups described above, wherein at least one hydrogen atom is replaced by a halogen atom. The halogenated aryl groups are exemplified by groups of empirical formula (C6HaX(5-a)), wherein subscript a is an integer with a value of 0, 1, 2, 3, or 4; and each X is selected from the group consisting of a halogen atom and a halogenated alkyl group. The halogen atom for X may be F, Cl, or I; alternatively F or Cl, and alternatively F. The halogenated alkyl group may have empirical formula (CbX’(2b+1)), where X’ is a halogen atom as described above and subscript b is an integer with a value of 1 to 9, alternatively 1 to 4, and alternatively 1 to 3. Alternatively, the halogenated aryl group may be selected from the group consisting of: , 2),). Alternatively, the halogenated arylborane Lewis acid may ane such as B(C6F5)3, which is commercially available from, e.g., Sigma-Aldrich, Inc. of St. Louis, Missouri, USA. Halogenated arylboranes may also be prepared by known methods, such as those disclosed in PCT Patent Application Publication WO2019 / 055740 by varying appropriate starting materials. Optional Catalyst Composition Components

[0037] Starting material (ii) is an optional inhibitor for (i) the halogenated arylborane Lewis acid. Starting material (ii) comprises a Lewis basic amine. The Lewis basic amine may be a primary amine, a secondary amine, or a tertiary amine. The Lewis basic amine may have formula: R4R5R6N, wherein R4, R5, and R6are each independently selected from the group consisting of H and an alkyl group of 1 to 6 carbon atoms. Alternatively, each R4, R5, and R6may be alkyl, alternatively ethyl. Examples of suitable Lewis basic amines include trialkyl amines exemplified by triethylamine, tripropylamine, tributylamine, tripentylamine, and trihexylamine, all of which are known in the art and are commercially available, e.g., from Sigma-Aldrich, Inc. When present, the amount of (ii) the Lewis basic amine is sufficient to provide at least 1.0 molar equivalents of amine with respect to (i) the halogenated arylborane Lewis acid. Alternatively, the amount of of (ii) the Lewis basic amine may be sufficient to provide ≥ 1.0 molar equivalents, alternatively > 1.0 molar equivalents, alternatively at least 1.05 molar equivalents, of amine with respect to (i) the halogenated arylborane Lewis acid. At the same time, the amount of (ii) the Lewis basic amine may be sufficient to provide up to 1.5 molar equivalents, alternatively up to 1.25 molar equivalents, of amine with respect to (i) the halogenated arylborane Lewis acid. Alternatively, when the Lewis basic amine is used, the amount may be 1.0 to 1.5, alternatively 1.05 to 1.5, molar equivalents of Lewis basic amine with respect to borane in (i) the halogenated arylborane Lewis acid.

[0038] Starting material (iii) is a solvent that may optionally be used in preparation of (C) the catalyst composition. When (ii) the Lewis basic amine is used, the catalyst composition may be prepared by a process comprising combining (i) the halogenated arylborane Lewis acid and (ii) the Lewis basic amine. Combining may be performed by any convenient means, such as dissolving the (i) the halogenated arylborane Lewis acid and (ii) the Lewis basic amine in (iii)the solvent with mixing. Mixing may be performed by any convenient means, such as mixing in a batch vessel at room temperature or with heating, e.g., to a temperature less than boiling point of the solvent, when used. Without wishing to be bound by theory, it is thought that (i) the halogenated arylborane Lewis acid and (ii) the Lewis basic amine may form a physical mixture or a complex, or a combination thereof. The solvent may optionally be removed after combining (i) the halogenated arylborane Lewis acid and (ii) the Lewis basic amine. For example, all or a portion of the solvent may be removed by evaporation or stripping with heat and optionally reduced pressure.

[0039] Starting material (iii), the solvent, may be selected from the group consisting of aromatic hydrocarbons, aliphatic hydrocarbons, halogenated aromatic hydrocarbons, halogenated aliphatic hydrocarbons, or a combination thereof. The halogenated hydrocarbons may be any one or more of the above aromatic hydrocarbons and / or aliphatic hydrocarbons, wherein at least one hydrogen atom is replaced with a halogen atom, such as Cl or F. Alternatively, the solvent may be selected from the group consisting ofaromatic hydrocarbons, aliphatic hydrocarbons, and a combination thereof. The aromatic hydrocarbon may be benzene, toluene, xylene, or a combination thereof. The aliphatic hydrocarbon may be heptane, hexane, octane, or a combination thereof. The glycol ether may be propylene glycol methyl ether, dipropylene glycol methyl ether, propylene glycol n-butyl ether, propylene glycol n-propyl ether, ethylene glycol n-butyl ether, or a combination thereof. The amount of solvent is not critical, and may be sufficient to dissolve (i) the halogenated arylborane Lewis acid and (ii) the inhibitor.

[0040] The (C) catalyst composition comprising: (i) the halogenated arylborane Lewis acid and optionally (ii) the Lewis basic amine, described above, may be free of conventional hydrosilylation reaction catalysts (which include platinum). The catalyst composition may also be free of conventional hydrosilylation reaction inhibitors such as those described, for example, in US Patent 10774217. Without wishing to be bound by theory, it is thought that conventional hydrosilylation reaction inhibitors, such as alkyne alcohols (or acetylenic alcohols), cycloalkenylsiloxanes, ketones, ene-yne compounds, triazoles, phosphines, mercaptans, hydrazines, sulphoxides, phosphates, nitriles, hydroperoxides, amines (other than (ii) the Lewis basic amine described for use in (C) the catalyst composition), ethylenically unsaturated isocyanates, fumarates, maleates, and alkenes are not needed, e.g., to control bath life when the catalyst described above is used in a curable polyorganosiloxane composition suitable for making a release coating instead of a conventional platinum hydrosilylation reaction catalyst for a composition including an alkenyl-functional polyorganosiloxane and a polyorganohydrogensiloxane. (D) Antioxidant

[0041] In the curable polyorganosiloxane composition, starting material (D) the antioxidant, introduced above, comprises a phenolic antioxidant, which is optional. Suitable antioxidants include phenolic antioxidants and combinations of phenolic antioxidants with stabilizers. Phenolic antioxidants include fully sterically hindered phenols and partially hindered phenols. Suitable phenolic antioxidants are commercially available and are exemplified by those with the tradename IRGANOX™ from BASF Corporation of Florham Park, New Jersey, USA. These include 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene (IRGANOX™ 1330); pentaerythritol tetrakis(3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate) (IRGANOX™ 1010). Others include octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate; butylated hydroxytoluene (BHT); and 2,5,7,8-tetramethyl-2-(4,8,12-trimethyltridecyl)chroman-6-ol (which is also known as (±)-α-Tocopherol or vitamin E). Antioxidants are known in the art and are commercially available from various sources, including Sigma-Aldrich, Inc. The amount of antioxidant, when used, depends on various factors including the type of antioxidant selected and the aldehyde content of starting material (A), however, when used, the amount of antioxidant may be at least 500 ppm, alternatively at least 1,000 ppm; while at the same time the amount of antioxidant may be up to 10,000 ppm, alternatively up to 5,000 ppm, and alternatively up to 2,500 ppm; and alternatively 1,000 ppm to 5,000 ppm, each based on weight of (A) the aldehyde-functional polyorganosiloxane. Without wishing to be bound by theory, it is thought that the antioxidant may minimize or prevent oxidation of the aldehyde functional groups of starting material (A), when exposed to air, but if starting material (A), and / or the emulsion, is stored under high purity argon or nitrogen, the oxidation will also be avoided even without the antioxidant. (E) Water

[0042] Starting material (E) is water, which is not generally limited, and may be utilized neat (i.e., without any solvents), and / or pure (i.e., free of minerals and / or other impurities). For example, the water may be processed or unprocessed prior to its combination with other starting materials in the emulsion. Examples of processes that may be used for purifying the water include distilling, filtering, deionizing, 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). The water may be utilized in any amount, which will be selected by one of skill in the art, depending on various factors, including the desired dilution of the emulsion. However, the amount of water may be 20% to 99%, alternatively 20% to 95%, alternatively 50% to 90%, and alternatively 80% to 90%, based on combined weights of all starting materials in the emulsion.Surfactant

[0043] Starting material (F) is a surfactant. The surfactant may be a non-ionic surfactant. The surfactant may comprise a polyvinyl alcohol (PVA). The polyvinyl alcohol compound is an example of a non-ionic surfactant. Polyvinyl alcohol compounds are known in the art and are disclosed, for example in US Patent Application Publication 20070099007 at paragraphs

[0172] and

[0173] . Polyvinyl alcohol compounds may be made by saponification of polyvinylacetate, so up to 15 % of polyvinylacetate may remain in the polyvinyl alcohol compound used herein. Alternatively, the polyvinyl alcohol compound may be 88% to 92% polyvinyl alcohol (with the balance being 12% to 8 % polyvinylacetate). The polyvinyl alcohol compound may have a minimum viscosity of 5 cP at 4 % aqueous solution at 20 °C. The polyvinyl alcohol may be delivered in an aqueous solution at 10% PVA with the balance being water. Suitable polyvinyl alcohol surfactants for use in the polyorganosiloxane emulsion herein are commercially available under the name PVA 40 TAD from BIM Kemi AB. The amount of PVA added to the emulsion (actives basis, not including the water when the PVA is delivered in an aqueous solution) may be > 0 to 1.5%, alternatively 0.01% to 1%, and alternatively 0.035 % to 0.35%, based on combined weights of all starting material used in the polyorganosiloxane emulsion.

[0044] Starting material (F) may optionally further comprise a co-surfactant in addition to, or instead of, the PVA. The co-surfactant may be a non-ionic surfactant. Some suitable non-ionic surfactants which can be used herein as the co-surfactant include polyoxyethylene alkyl ethers (such as, lauryl, cetyl, stearyl or octyl), polyoxyethylene alkyl phenol ethers, alkylglycosides, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitan monooleates, polyoxyethylene alkyl esters, polyoxyethylene sorbitan alkyl esters, polyethylene glycol (such as polyethylene glycol having 23 ethylene-oxide units), polypropylene glycol, diethylene glycol, ethoxylated trimethylnonanols, tristyrylphenol ethers (TSP’s), distyryl phenol ethers (DSP’s), and polyoxyalkylene glycol modified polysiloxane surfactants.

[0045] Non-ionic surfactants which are commercially available include compositions such as (i) 2,6,8-trimethyl-4-nonyloxy polyethylene oxyethanols (6EO) and (10EO) sold under the names TERGITOL™ TMN-6 and TERGITOL™ TMN-10; (ii) the C11-15 secondary alkyl polyoxyethylene ethers (e.g., C11-15secondary alcohol ethoxylates 7EO, 9EO, and 15EO sold under the names TERGITOL™ 15-S-7, TERGITOL™ 15-S-9, and TERGITOL™ 15-S-15, which has HLB value 15.4), other C11-15secondary alcohol ethoxylates sold under the tradenames ECOSURF™ EH-40 and TERGITOL™ 15-S-12, TERGITOL™ 15-S-30, and TERGITOL™ 15-S-40, by The Dow Chemical Company of Midland, Michigan, USA; octylphenyl polyoxyethylene (40) ether sold under the name TRITON™ X405 by The DowChemical Company; (iii) nonylphenyl polyoxyethylene (10) ether sold under the name MAKON™ 10 by the Stepan Company; (iv) ethoxylated alcohols sold under the name Trycol 5953 by Henkel Corp. / Emery Group, of Cincinnati, Ohio, USA; (v) ethoxylated alcohols sold under the name BRIJ™ L23 (with HLB value of 16.9) and BRIJ™ L4 (with HLB value of 9.7) by Croda Inc. of Edison, New Jersey, USA, (vi) polyoxyethylene 23 lauryl ether (Laureth-23) sold commercially under the trademark BRIJ™ 23 by ICI Surfactants, Wilmington, Delaware; and RENEX™ 30, a polyoxyethylene ether alcohol sold by ICI Surfactants, Wilmington, Delaware, USA; (vii) alkyl-oxo alcohol polyglycol ethers such as GENAPOL™ UD 050 (with HLB value of 11.4), and GENAPOL™ UD110 (with HLB value of 14.4), (viii) alkyl polyethylene glycol ether based on C10-Guerbet alcohol and ethylene oxide such as LUTENSOL™ XP 79, and (ix) alkyl polyglycosides, such as those sold under the trade name Glucopon™ by BASF, and alkyl glucosides such as decyl glucoside, lauryl glucoside, and coco- glucoside, which are sold under the trade name EcoSenseTMby The Dow Chemical Company. Other commercially available nonionic surfactants include TERGITOL™ 15-S-5, also from The Dow Chemical Company, which has an HLB value of 10.5; Lutensol XP 50 with an HLB value of 10, and Lutensol XP 140 with an HLB value of 16. Other commercially available nonionic surfactants include isotrideceth-12 or Poly(oxy-1,2-ethanediyl) with an isotridecyl alcohol (iso- C13), with CAS # 69011-36-5, which is available under the name ROKAnol™ IT12 from PCC Group.

[0046] Suitable non-ionic surfactants also include poly(oxyethylene)-poly(oxypropylene)- poly(oxyethylene) tri-block copolymers. Poly(oxyethylene)-poly(oxypropylene)- poly(oxyethylene) tri-block copolymers are also commonly known as Poloxamers. They are nonionic triblock copolymers composed of a central hydrophobic chain of polyoxypropylene (poly(propylene oxide)) flanked by two hydrophilic chains of polyoxyethylene (poly(ethylene oxide)). Poly(oxyethylene)-poly(oxypropylene)-poly(oxyethylene) tri-block copolymers are commercially available from BASF of Florham Park, New Jersey, USA, and are sold under the tradename PLURONIC™, such as PLURONIC™ L61, L62, L64, L81, P84.

[0047] The non-ionic surfactant may also be a silicone polyether (SPE). The silicone polyether as a surfactant may have a rake type structure wherein the polyoxyethylene or polyoxyethylene-polyoxypropylene copolymeric units are grafted onto the siloxane backbone, or the SPE can have an ABA block copolymeric structure wherein A represents the polyether portion and B the siloxane portion of an ABA structure. Alternatively, the SPE may have a resinous structure, such as a polyorganosilicate resin having polyether groups bonded to silicon atoms therein. Suitable SPE’s include DOWSIL™ OFX-5329 Fluid from The Dow Chemical Company. Alternatively, the non-ionic surfactant may be selected from polyoxyalkylene-substituted silicones, silicone alkanolamides, silicone esters and silicone glycosides. Such silicone-based surfactants may be used to form such aqueous emulsions and are known in the art, and have been described, for example, in US Patent 4122029 to Gee et al., US Patent 5387417 to Rentsch, and US Patent 5811487 to Schulz et al. Other silicone polyether surfactants are known in the art and are also commercially available, e.g., DOWSIL™ 502W and DOWSIL™ 67 Additive are commercially available from The Dow Chemical Company.

[0048] The co-surfactant is optional. The amount of co-surfactant may be 0 to 5 %, alternatively > 0 to 1%, alternatively 0.01% to 0.1%, and alternatively 0.04% based on combined weights of all starting materials used to make the polyorganosiloxane emulsion.

[0049] The polyorganosiloxane emulsion described above may comprise starting materials (A), (B), (C), (E), and (F). Alternatively, the emulsion may consist essentially of starting materials (A), (B), (C), (E), and (F). Alternatively, the emulsion may consist of starting materials (A), (B), (C), (E), and (F). The polyorganosiloxane emulsion described above may comprise starting materials (A), (B), (C), (D), (E), and (F). Alternatively, the emulsion may consist essentially of starting materials (A), (B), (C), (D), (E), and (F). Alternatively, the emulsion may consist of starting materials (A), (B), (C), (D), (E), and (F). Optional Additional Starting Materials

[0050] Alternatively, in addition to starting materials (A), (B), (C), (E), and (F) (and when present (D)), the polyorganosiloxane emulsion may further comprise an optional additional starting material. Examples of suitable additional starting materials are disclosed, for example, in US Patent Application Publication 20070099007 at paragraphs

[0177] to

[0184] and BfR36 XXXVI-Paper-and-Board-for-Food-Contact.pdf (bund.de). The additional starting material may be selected from the group consisting of a hydrosilylation reaction inhibitor; a pH buffer; a biocide; an antifoam; a wax; a flame retardant; an antistatic agent; a wetting agent; a wet strength agent; a filler; a pigment; a surface refining and coating agent; and a combination of two or more thereof. (G) Hydrosilylation Reaction Inhibitor

[0051] Starting material (G) is a hydrosilylation reaction inhibitor that may optionally be used herein, e.g., when the curable polyorganosiloxane composition contains residual platinum group metal catalyst from the process of making a starting material. Starting material (G) may be selected from the group consisting of (G1) an acetylenic alcohol, (G2) a silylated acetylenic alcohol, (G3) an ene-yne compound, (G4) a triazole, (G5) a phosphine, (G6) a mercaptan, (G7) a hydrazine, (G8) an amine, (G9) a fumarate, (G10) a maleate, (G11) an ether, (G12) carbon monoxide, (G13) an alkenyl-functional siloxane oligomer, and (G14) a combination of two or more thereof. Alternatively, the hydrosilylation reaction inhibitor may be selected from thegroup consisting of (G1) an acetylenic alcohol, (G2) a silylated acetylenic alcohol, and a combination thereof.

[0052] Acetylenic alcohols are exemplified by 3,5-dimethyl-1-hexyn-3-ol, 1-butyn-3-ol, 1- propyn-3-ol, methyl butynyls such as 2-methyl-3-butyn-2-ol and 3-methyl-1-butyn-3-ol, 3- methyl-1-pentyn-3-ol, 3-phenyl-1-butyn-3-ol, 4-ethyl-1-octyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, and ethynyl cyclohexanols such as 1-ethynyl-1-cyclohexanol, and a combination thereof. Acetylenic alcohols are known in the art and are commercially available from various sources, see for example, US Patent 3445420 to Kookootsedes, et al. Alternatively, the hydrosilylation reaction inhibitor may be a silylated acetylenic compound. Without wishing to be bound by theory, it is thought that adding a silylated acetylenic compound reduces yellowing of the reaction product prepared from hydrosilylation reaction as compared to a reaction product from hydrosilylation of starting materials that do not include a silylated acetylenic compound or that include an organic acetylenic alcohol inhibitor, such as those described above. The silylated acetylenic compound is exemplified by (3-methyl-1-butyn-3-oxy)trimethylsilane, ((1,1- dimethyl-2-propynyl)oxy)trimethylsilane, bis(3-methyl-1-butyn-3-oxy)dimethylsilane, bis(3- methyl-1-butyn-3-oxy)silanemethylvinylsilane, bis((1,1-dimethyl-2- propynyl)oxy)dimethylsilane, methyl(tris(1,1-dimethyl-2-propynyloxy))silane, methyl(tris(3- methyl-1-butyn-3-oxy))silane, (3-methyl-1-butyn-3-oxy)dimethylphenylsilane, (3-methyl-1- butyn-3-oxy)dimethylhexenylsilane, (3-methyl-1-butyn-3-oxy)triethylsilane, bis(3-methyl-1- butyn-3-oxy)methyltrifluoropropylsilane, (3,5-dimethyl-1-hexyn-3-oxy)trimethylsilane, (3- phenyl-1-butyn-3-oxy)diphenylmethylsilane, (3-phenyl-1-butyn-3-oxy)dimethylphenylsilane, (3-phenyl-1-butyn-3-oxy)dimethylvinylsilane, (3-phenyl-1-butyn-3-oxy)dimethylhexenylsilane, (cyclohexyl-1-ethyn-1-oxy)dimethylhexenylsilane, (cyclohexyl-1-ethyn-1- oxy)dimethylvinylsilane, (cyclohexyl-1-ethyn-1-oxy)diphenylmethylsilane, (cyclohexyl-1- ethyn-1-oxy)trimethylsilane, and combinations thereof. The silylated acetylenic compound useful as the hydrosilylation reaction inhibitor herein may be prepared by methods known in the art, for example, US Patent 6677407 to Bilgrien, et al. discloses silylating an acetylenic alcohol described above by reacting it with a chlorosilane in the presence of an acid receptor.

[0053] Alternatively, the hydrosilylation reaction inhibitor may be an ene-yne compound such as 3-methyl-3-penten-1-yne, 3,5-dimethyl-3-hexen-1-yne; and a combination thereof. Alternatively, the hydrosilylation reaction inhibitor may comprise a triazole, exemplified by benzotriazole. Alternatively, the hydrosilylation reaction inhibitor may comprise a phosphine. Alternatively, the hydrosilylation reaction inhibitor may comprise a mercaptan. Alternatively, the hydrosilylation reaction inhibitor may comprise a hydrazine. Alternatively, the hydrosilylation reaction inhibitor may comprise an amine. Amines are exemplified bytetramethyl ethylenediamine, 3-dimethylamino-1-propyne, n-methylpropargylamine, propargylamine, 1-ethynylcyclohexylamine, or a combination thereof. Alternatively, the hydrosilylation reaction inhibitor may comprise a fumarate. Fumarates include dialkyl fumarates such as diethyl fumarate, dialkenyl fumarates such as diallyl fumarate, and dialkoxyalkyl fumarates such as bis-(methoxymethyl)ethyl fumarate. Alternatively, the hydrosilylation reaction inhibitor may comprise a maleate. Maleates include dialkyl maleates such as diethyl maleate, dialkenyl maleates such as diallyl maleate, and dialkoxyalkyl maleates such as bis-(methoxymethyl)ethyl maleate. Alternatively, the hydrosilylation reaction inhibitor may comprise an ether.

[0054] Alternatively, the hydrosilylation reaction inhibitor may comprise carbon monoxide. Alternatively, the hydrosilylation reaction inhibitor may comprise an alkenyl-functional siloxane oligomer, which may be cyclic or linear such as methylvinylcyclosiloxanes exemplified by 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, 1,3,5,7-tetramethyl-1,3,5,7- tetrahexenylcyclotetrasiloxane, 1,3-divinyl-1,3-diphenyl-1,3-dimethyldisiloxanel; 1,3-divinyl- 1,1,3,3-tetramethyldisiloxane; and a combination of two or more thereof. The compounds useful as hydrosilylation reaction inhibitors described above are commercially available, e.g., from Sigma-Aldrich Inc. or Gelest, Inc., and are known in the art, for example, see US Patent 3989667 to Lee, et al. Suitable hydrosilylation reaction inhibitors for use herein are exemplified by those described as stabilizer E in US Patent Application Publication 2007 / 0099007 at paragraphs

[0148] to

[0165] .

[0055] The amount of hydrosilylation reaction inhibitor may be may be 0% to 1%, alternatively 0% to 5%, alternatively 0.001% to 1%, alternatively 0.01% to 0.5%, and alternatively 0.0025% to 0.025%, based on the weight of all starting materials in the polyorganosiloxane emulsion. (H) Buffer System

[0056] Starting material (H) is a buffer system (buffer) for maintaining a desired pH of the polyorganosiloxane emulsion. Starting material (H) may be any suitable buffer, which may comprise a mono or polyprotic acid and its conjugate base. For example, a buffer comprising HCO3- / CO32-and H2PO4- / HPO42-described as agent F in US Patent Application Publication 20070099007 at paragraphs

[0145] to

[0147] may be used herein. The buffer may comprise NaCO3 and NaHCO3; and / or citric acid and sodium hydroxide or a citrate salt such as potassium citrate or sodium citrate. The amount of the buffer, when used, may be > 0%, alternatively at least 0.01%, alternatively at least 0.025%, and alternatively at least 0.05% based on combined weights of all starting materials used in the polyorganosiloxane emulsion. At the same time, the amount of buffer may be up to 0.5%, alternatively up to 0.25%, and alternatively up to 0.1%, onthe same basis. (I) Biocide

[0057] Starting material (I) is an optional biocide that may be added to the polyorganosiloxane emulsion. Biocides are known in the art, for example, the biocide is exemplified by (I1) a fungicide, (I2) an herbicide, (I3) a pesticide, (I4) an antimicrobial agent, and a combination of two or more thereof. Exemplary biocides are disclosed, for example, in US Patent 9221041 to Brandstadt, et al. Exemplary biocides include quarternary ammonium compounds (QATs), sodium benzoate and phenoxyethanol and methylisothiazolinone, which are commercially available as Neolone PE Preservative, and other isothiazolones, and combinations thereof. For example, the biocide may comprise 5-chloro-2-methyl-2H-isothiazol-3-one; 2-methyl-2H- isothiazol-3-one; a bronopol based biocide; or a combination thereof. Biocides are commercially available, as exemplified by KATHON™ LXE and BIOBAN™ BP-30 both from Lanxess. When used, the biocide may be present in an amount > 0 to 1%, alternatively 0.01% to 0.05%, based on combined weights of all starting materials in the polyorganosiloxane emulsion. (J) Anti-Foam

[0058] The polyorganosiloxane emulsion may optionally further comprise starting material (J) an anti-foaming agent (anti-foam). The amount of (J) the anti-foam may be > 0% to 2%, alternatively 0.01% to 1.5%, and alternatively 0.025% to 0.1%, based on combined weights of all starting materials used in the polyorganosiloxane emulsion. Suitable anti-foams are exemplified by emulsions containing silica and polydimethylsiloxanes. Such anti-foams are commercially available from The Dow Chemical Company, e.g., under the tradenames DOWSIL™ AFE-1520, DOWSIL™ 1530, DOWSIL™ 7989, SYL-OFF™ EM 7989 ANTIFOAM, XIAMETER™ AFE-0100, XIAMETER™ AFE-1510, XIAMETER™ AFE- 1520, and XIAMETER™ AFE-1530. Method of Making the Polyorganosiloxane Emulsion

[0059] The polyorganosiloxane emulsion may be prepared by combining the starting materials described above, in the amounts described above, in any order of addition, optionally with a master batch, and optionally under shear. However, (A) the aldehyde-functional polyorganosiloxane and (D) the antioxidant may be combined separately, and later combined with the other starting materials of the curable polyorganosiloxane composition before forming the polyorganosiloxane emulsion. Without wishing to be bound by theory, it is thought that the antioxidant may prevent or minimize oxidation of the aldehyde groups into carboxylic acids before cure of the polyorganosiloxane composition. Alternatively, the emulsion may be formed by subjecting said starting materials to shear, for example in a mixer of the rotor and stator type or in an apparatus applying increased shear such as a high pressure homogenizer, microfluidizer,colloid mill, or sonolator (ultrasonic mixer). Equipment for mixing under shear, such as rotor- stators, sonolators, sonicators, homogenizers, microfluidizers, and speedmixers are known in the art and are commercially available. To avoid premature reaction during formation of the emulsion, some of the starting materials may be emulsified separately. For example, all or a portion of starting material (A) (and when present starting material (D) may be emulsified in the absence of starting material (B), starting material (B) being added subsequently. Alternatively, starting materials comprising (A) and (B) (and when present (D) may be emulsified in the absence of (C) the catalyst composition, with the catalyst composition being emulsified and added separately.

[0060] Alternatively, the emulsion described above may be provided in the form of a kit, e.g., with two or more separate parts that may be mixed together to form the emulsion described above. The kit may prevent hydrosilylation reaction of starting materials comprising (A) and (B) before use of the polyorganosiloxane emulsion (e.g., before coating the emulsion on a surface of a substrate). Typically, this is achieved by storing (B) the polyorganohydrogensiloxane in a separate part from (C) the catalyst composition. A kit for preparing the polyorganosiloxane emulsion described above may comprise: (I) a base emulsion comprising (B) the polyorganohydrogensiloxane and at least a portion of (A) the aldehyde-functional polyorganosiloxane, (E) the water, (F) the surfactant and when present one or more of (D) the antioxidant, (G) the hydrosilylation reaction inhibitor, (H) the buffer, and (I) the biocide; and (II) a curing agent emulsion comprising (C) the catalyst composition and at least a portion of (A) the aldehyde-functional polyorganosiloxane, (C) the catalyst composition, (E) the water, and (F) the buffer, and when present (G) the hydrosilylation reaction inhibitor; and optionally (III) a third part comprising (J) the anti-foam. The base emulsion and the curing agent emulsion (and when present, the third part comprising the anti-foam) may be combined, e.g., by mixing at ambient temperature to form the polyorganosiloxane emulsion described above just before use. The relative amounts of base emulsion and curing agent emulsion (weight ratio of base: curing agent) may be 50:1 to 1:1, alternatively 35:1 to 1:1, and alternatively 20:1.

[0061] The method for preparing the emulsion described above may optionally further comprise diluting the emulsion to a desired concentration of polyorgansiloxane composition in the discontinuous phase. The method described above may optionally further comprise diluting the emulsion with 60 weight parts to 900 weight parts of additional water, where the additional water is as described above as starting material (E). Method for Treating Paper

[0062] The polyorganosiloxane emulsion prepared as described above may be used for treating a substrate comprising paper. For example, a method for treating a substrate comprising paper comprises: I) coating the substrate with the polyorganosiloxane described above, and II) drying the substrate. Step I) may be performed by any convenient method, such as padding, dipping, or spraying the substrate with the paper treatment composition.

[0063] Step II) may be performed by any convenient method, such as heating the substrate. Step II) may be performed by placing the substrate in an oven. Heating the substrate may be performed to remove all or a portion of the water and / or cure the curable polyorganosiloxane composition. The exact temperature depends on various factors including the temperature sensitivity of the type of paper substrate selected, and the desired drying time. However, heating may be performed at a temperature > 100 °C to remove water. Alternatively, the temperature may be > 90 °C to 200 °C, alternatively 100 °C to 200 °C, alternatively 110 °C to 160 °C, alternatively 110 °C to 150 °C , and alternatively 120 °C to 150 °C for a time sufficient to remove all or a portion of the water and cure the curable polyorganosiloxane composition. The heating time may depend on various factors including the temperature selected and coating thickness, however the time may be up to 5 min, alternatively 2 seconds to < 5 min, alternatively 2 seconds to 1 min, alternatively 2 seconds to 20 seconds. It may be desirable for the coated substrate to have a coating weight or thickness of 0.3 g / m2to 0.6 g / m2.

[0064] The method may optionally further comprise one or more additional steps, such as repeating steps I) and II) to increase thickness of the coating on the substrate, and / or contacting the coated substrate with a material to be packaged, e.g., food. For example, the method described above may produce a paper substrate having a coating with a thickness of > 0 to < 1 μm, alternatively > 0 to 0.9 μm, alternatively > 0 to 0.75 μm, alternatively > 0 to 0.5 μm, alternatively > 0 to 0.25 μm, alternatively > 0 to 0.2 μm. However, other thicknesses are contemplated, e.g., of > 0 to < 10 μm, alternatively 0.1 μm to 10 μm; alternatively 0.15 μm to 5 μm; alternatively 0.2 μm to 2 μm; and alternatively 0.2 μm to 1 μm. Alternatively, when the substrate is a plastic coated paper wherein the surface of the substrate with the film thereon comprises the plastic, the film may have a thickness of 0.05 μm to < 1 μm, alternatively 0.05 μm to 0.9 μm, alternatively 0.05 μm to 0.8 μm. Alternatively, when the substrate is paper, the coating may have a thickness of 0.2 μm to < 1 μm, alternatively 0.2 μm to 0.9 μm, alternatively 0.2 μm to 0.8 μm, alternatively 0.2 μm to 0.7 μm, alternatively 0.2 μm to 0.6 μm; alternatively 0.2 μm to 0.5 pm; and alternatively 0.2 μm to 0.3 μm. Paper Substrate

[0065] The substrate to which the polyorganosiloxane emulsion is applied comprises paper and may further comprise an additional material. Substrates comprising paper (paper substrates) areexemplified by Kraft paper, parchment paper (e.g., bakery paper), paperboard, cardboard, and corrugated cardboard. The paper may be glazed or unglazed, calendared or un-calendared. Other paper substrates include glassine paper, super calender paper, or clay coated Kraft paper. Alternatively, the substrate may be a laminate of paper and plastic, such as polyethylene coated Kraft paper. Paper substrates are known in the art and are commercially available, such as bakery paper (2094) and general packaging paper (313), both from Metsä. For the sake of convenience the term paper has been used in the present description because the substrate used herein comprises paper as described above. One skilled in the art would recognize that the polyorganosiloxane emulsion described herein is applied to paper, e.g., when the substrate comprises paper and an additional material. For example, if a substrate comprises paper coated on one side with plastic, the opposite (paper) side may be coated with the polyorganosiloxane emulsion of the present invention. The paper substrate treated with the polyorganosiloxane emulsion, described above, may be utilized in various applications, as described above, such as food contact applications. EXAMPLES

[0066] The following examples are provided to illustrate the invention to one skilled in the art and are not to be construed so as to limit the scope of the invention set forth in the appended claims. Starting materials used in these examples are summarized below in Table 1. Starting Description Source Material dStarting Description Source Material Aldh d b hd l ldhd f ti l S th i d d d s h e

[0067] In this Reference Example 1, a Q-branched propyl aldehyde-functional polyorganosiloxane with unit formula [(C2H4CHO)(CH3)2SiO1 / 2]4[(CH3)2SiO2 / 2]160(SiO4 / 2), where C2H4CHO represents a propyl aldehyde group was prepared as described in PCT Publication WO2022081444 via hydroformylation of the Vinyl Polymer in Table 1 using arhodium bisphosphite ligand catalyst. The resulting Q-branched propyl aldehyde-functional polyorganosiloxane was divided into samples. To make Aldehyde Polymer 5 in Table 1, 1000 ppm of Antioxidant 2 was combined with a sample of the Q-branched propyl aldehyde- functional polyorganosiloxane.

[0068] To carbon treat a sample of Q-branched propyl aldehyde-functional polyorganosiloxane prepared as described in PCT Publication WO2022081444, 15 g of activated carbon and 50 g of toluene were combined, added to the Q-branched propyl aldehyde-functional polyorganosiloxane, and the resulting mixture was stirred overnight. After this, the mixture was filtered through a 0.2 micrometer membrane, and the toluene was removed by sparging the sample with nitrogen gas. The resulting carbon treated Q-branched propyl aldehyde-functional polyorganosiloxane was combined with 1000 ppm of Antioxidant 2.

[0069] In this Reference Example 2, catalyst solution f was prepared as follows: In air, a 30 mL vial was charged with BCF (5 g), TEA (1g), and toluene (50 g) to afford a colorless solution.

[0070] In this Reference Example 3, catalyst solution g was prepared as follows: In air, a 30 mL vial was charged with BCF (1 g) and toluene (5 g) to afford a colorless solution.

[0071] In this Reference Example 4, a base emulsion (Part A) was prepared as follows: First prepare an aqueous buffer solution by blending the water, citric acid and sodium hydroxide components together. Weigh out separately the Vinyl Polymer or the Aldehyde Polymer and SiH Polymer components in a dental cup and mix them separately in a dental mixer from e.g., Hauschild SpeedMixer™ – DAC 150.1FV at 3500 rpm for 30 seconds to form a polymer mix. The dental cup containing the polymer mix is further mixed with an IKA T25 Easy Clean Control ULTRA-TURRAX™ Homogenizer while adding slowly the PVA Surfactant, the Co- Surfactant, the Linear Olefinic Polyether, the buffer and the water to form a surfactant mix for one minute. The Dv0.9 particle size (that is, 90% of the particles have sizes below this value) is measured using laser diffraction spectroscopy with a Malvern Mastersizer 3000 instrument. The blend is further mixed for every subsequent one minute, and the particle size remeasured, until the Dv0.9 between 1.0 and 40 micrometers, alternatively between 1.2 and 15 micrometers, and alternatively between 1.5 and 3.0 micrometers. To the emulsion the inhibitor and Biocide 1 and Biocide 2 components are further added and gently mixed.

[0072] To the resulting Base Emulsion add the Catalyst Emulsion prepared and emulsified similarly as the Base Emulsion at a concentration ratio of 95:5 where the concentration ratio is based on relative weight of Base Emulsion to Catalyst Emulsion. Dilute the resulting mixture with a solution of water containing the Antifoam. The resulting Bath composition of 40 g to 60 g contains 74.95 wt% water, 23.75 wt% Base Emulsion, 1.25 wt% Catalyst Emulsion and 0.05 wt% Antifoam. The Bath contains between 9 wt% and 10 wt% siloxane content.

[0073] Table 2 provides the composition of the Base Emulsion (Part A) with amounts in weight-percent (wt%) relative to the base emulsion composition weight. The starting materials and amounts for the catalyst emulsion (Part B), as well as the antifoam and additional water are shown below in Table 2. Table 2 – Emulsion Samples Prepared According to Reference Example 5 Component C1 C2 1 2 3 Part A 23.75 23.75 23.75 23.75 23.75 98 48 43 0 87 75 25 40 18 19 12 25 22 03 02 0 40 0 04 75 02 01 01 05 95 00Table 3 – Additional Emulsion Samples Prepared According to Reference Example 5 Component C3 4 5 6 7 75 98 48 43 69 94 25 40 18 19 12Component C3 4 5 6 7 Part B (Total) 1.25 1.25 1.25 1.25 1.25 t 7 1 722 770 03 02 65 0 0 31 75 02 01 01 05 95 00an Automatic Film Applicator 4340M1 from Braive Instruments. The coat weight is controlled from 0.3 to 0.6 micrometers using a Meyer bar.

[0075] The coating was cured and dried in an oven at 150 °C for 5 minutes and completed at 170 °C for 30 min. The coated paper was then tested for: silicon coat weight, cure extractables, water resistance or Cobb (water uptake), grease resistance (KIT test), anchorage or abrasion resistance, anti-adhesiveness or bakery release.

[0076] Silicon coat weight was measured as follows: Silicon coat weights were measured by X-ray Fluorescence using an Oxford lab-x3500 XRF Analyzer after silicon elemental calibration with samples’ standards. An XRF measure of a blank substrate was performed prior to 3 measures of coated-paper samples leading to an average silicon coat weight or thickness expressed in g / m2. A silicon coat weight of 0.3 to 0.6 g / m2is preferred.

[0077] The cure performance of a sample composition is evaluated by determining the percent coat weight lost after immersion in methyl isobutyl ketone (MIBK). A sample composition is coated, cured and dried in an oven at 150 °C for 5 minutes and completed at 170 °C for 30 min. The coated substrate is then immediately cut into three sample discs (die cutter, 1.375 inch (3.49 cm)) handled only by tweezers to minimize contamination and / or damage. Each sample disc is analyzed via XRF to determine an initial coat weight (Wis) before being placed in an individual bottle (100-mL, covered with a lid) containing solvent (methyl isobutyl ketone, 40 mL) and allowed to rest on a bench to soak for 30 minutes. Each sample disc is then removed from the bottle, placed coated-side-up on a clean surface (tissue paper) to allow residual solvent to evaporate (without blotting / wiping), and analyzed via XRF to determine a final coat weight (Wfs). The extractable % of each sample is the percent change in coat weight from the solventsoak, i.e., is calculated using the formula: [(Wis - Wfs) / Wis] x 100%). The extractable % indicates the amount of non-cured components of the sample (e.g., non-crosslinked silicone) extractable from the coated substrate, such as a lower extractable % indicates a higher / better cure performance. For the present invention it is desirable to have an extractable % value of less than 25%.

[0078] The water resistance of paper substrates was tested by the conventional absorption test known as Cobb test described in TAPPI 441 om-04 test method. Samples were exposed to water for 45 seconds and the amount of water absorbed after a total of 60 seconds was measured by the weight. The ‘’Cobb value’’ represented the mass of absorbed water expressed in g / m2. The lower the Cobb value, the higher the water resistance of the substrate. A Cobb60 of less than 15 g / m2is desired.

[0079] Grease resistance test for paper substrates was evaluated following 3M KIT test described in TAPPI 559 cm-12 procedure: ‘Grease Resistance Test for Paper and Paperboard’. A drop of a fresh KIT solution (KIT number 1 to 12 from least to most aggressive) made from a combination of Castor oil, n-heptane and toluene at various ratios, was contacted with the substrate. After wiping off with a clean tissue, the area was immediately examined. A failure was denoted by a darkening or staining of the area. The procedure was repeated using a less aggressive solution until no stain was observed being considered as a “pass’’. Oil repellency of the paper was recorded by the maximum KIT number for which the drop did not penetrate the paper. The greater the KIT number, the better the oil repellency. A KIT number of greater than or equal to 4 is desired.

[0080] The bakery release or baking test measured the quantity of food left on a substrate after oven baking and release. Coated paper samples were folded into moulds and weighed. Cakes containing 4 eggs, 80 g of sugar, 80 g of potato flour, 85 g of wheat flour, and 5.5 g of baking powder were processed at room temperature with a universal kitchen machine and placed into the moulds prior to oven baking. The finished baked products were cooled down. The coated paper to be tested was then removed from the baked product and the quantity of baked product still adhering to the paper was weighed and converted in g / m2. The lower the bakery release values the better. A bakery release of below 35 g / m2is desired.

[0081] The anchorage test provided a quantitative determination of the rub-off resistance of silicone release coating anchoring on the substrate after an abrasion test. The silicon content of a coated substrate was determined by XRF before and after rub-off with an abrasion tester and was expressed as a % of Si left after rub-off compared to 100% initially coated. The higher the Si % left after rub-off the higher the anchorage or abrasion resistance. A Si abrasion test result above 80% is desired.

[0082] The results of these tests on the coated paper substrates described above is shown below in Tables 4 and 5. Table 4 – Results of Coating and Testing Samples in Table 2 Test Performance target C1 C2 1 2 3 Si Coat Weight (g / m²) 0.3-0.6 0.60 0.51 0.39 0.40 0.44 9 .1 .5 .0ers, samples C1 and C2, lead to similar abrasion resistance, and water uptake. C2 (made with an aldehyde-functional polyorganosiloxane) had a higher extractables level, grease barrier and baking residues as compared to C1 (made with vinyl functional polyorganosiloxane). BCF- cured working examples 1, 2, and 3 gradually lead to lower extractables than Pt-cured sample C2, with a noticeable grease barrier improvement by increasing the H / CH=O ratio, while the abrasion resistance was similarly and favorably high, and the baking residues were passed the test for bakery parchment quality. Working Examples 1, 2, and 3 also provided the benefit of passing these tests to provide good quality coatings at lower coat weights than C1 and C2. Working Example 3 had the highest grease barrier and highest abrasion resistance, with the lowest extractables of the samples made with aldehyde-functional polyorganosiloxane tested. In addition, Working Examples 1, 2, and 3 were platinum free, but Comparative Examples C1 and C2 both contained platinum. Table 5 – Results of Coating and Testing Samples in Table 3 Performance Performance target C3 4 5 6 7 Si C t W i ht ( / m²) 03-06 046 039 036 044 054 .6 .3 .4

[0084] The data in Table 5 show results with samples made using the aldehyde-functional polyorganosiloxane that had been treated with activated carbon. By increasing the H / CH=O ratio, the Working Examples 4, 5 and 6 led to a reduction in the level of extractables and an increase in abrasion resistance and grease barrier; with equal to or superior grease barrier for working examples 5 and 6 to that for Comparative Example C3 (cured with Pt). A larger increase in BCF level without the use of TEA inhibitor for Working Example 7 vs. Working Example 4 at the same H / HC=O ratio further favorably reduced the level of extractables,reduced water uptake, and increased abrasion resistance. Example 7 had better (i.e., less) water uptake than Comparative Example C3. Example 7 showed that TEA was not required to produce a suitable release coating under the conditions tested. Industrial Applicability

[0085] The inventors surprisingly found that the emulsion described herein may be platinum- free and cure to form a coating with low extractables (< 25% according to the test method in the EXAMPLES, above), high abrasion resistance (> 80% according to the test method in the EXAMPLES, above), low water update via the Cobb test (< 15 g / m2), effective grease barrier properties via the KIT test (≥ 4), and low baking residues (< 35 g / m2according to the test method described above in the EXAMPLES). Definitions and Usage of Terms

[0086] All amounts, ratios, and percentages herein are by weight, unless otherwise indicated by the context of the specification. The articles ‘a’, ‘an’, and ‘the’ each refer to one or more, unless otherwise indicated by the context of specification. The singular includes the plural unless otherwise indicated by the context of the specification. The SUMMARY and ABSTRACT are hereby incorporated by reference. The amounts of all starting materials in a composition or an emulsion total 100%. The transitional phrases “comprising”, “consisting essentially of”, and “consisting of” are used as described in the Manual of Patent Examining Procedure Ninth Edition, Revision 08.2017, Last Revised January 2018 at section §2111.03 I., II., and III. Any feature or aspect of the invention may be used in combination with any other feature or aspect recited herein. The abbreviations used herein have the definitions in Table 6. Table 6 - Abbreviations Abbreviation Definitions °C de rees Celsius

Claims

CLAIMS:

1. A polyorganosiloxane emulsion comprises a discontinuous phase dispersed in a continuous phase, wherein the continuous phase comprises water, the discontinuous phase comprises a curable polyorganosiloxane composition, wherein the curable polyorganosiloxane composition comprises (A) an aldehyde-functional polyorganosiloxane having, per molecule, at least two silicon bonded aldehyde-functional groups of , wherein G is a divalent hydrocarbon group free of aliphatic8 carbon atoms; (B) a polyorganohydrogensiloxane having, per molecule, at least two silicon bonded hydrogen atoms; with the provisos that when the aldehyde-functional polyorganosiloxane has only two silicon bonded aldehyde-functional groups per molecule, then the polyorganohydrogensiloxane has at least three silicon bonded hydrogen atoms per molecule; and when the polyorganohydrogensiloxane has only two silicon bonded hydrogen atoms per molecule, then the aldehyde-functional polyorganosiloxane has at least three silicon bonded aldehyde-functional groups per molecule; (C) a catalyst composition comprising (i) a halogenated arylborane Lewis acid; and wherein the emulsion further comprises a surfactant.

2. The emulsion claim 1, wherein (C) the catalyst composition further comprises (ii) a Lewis basic amine, and optionally (iii) a solvent.

3. The composition of claim 2, wherein (C)(ii) the Lewis basic amine comprises trialkyl amine and is present in an amount sufficient to provide 1.05 to 1.5 molar equivalents of amine with respect to (i) the halogenated arylborane Lewis acid.

4. The emulsion of any one of claims 1 to 3, further comprising an additional starting material selected from the group consisting of: a phenolic antioxidant; a hydrosilylation reaction inhibitor; a pH buffer; a biocide; an antifoam; a wax; a flame retardant; an antistatic agent; a wetting agent; a wet strength agent; a filler; a pigment; a surface refining and coating agent; and a combination of two or more thereof.

5. The emulsion of any one of claims 1 to 4, wherein (A) the aldehyde-functional polyorganosiloxane comprises unit formula: (R77 7 3SiO1 / 2)c(R 2R8SiO1 / 2)d(R 2SiO2 / 2)e(R7R8SiO2 / 2)f(R7SiO2 / 2)g(R8SiO2 / 2)h(SiO4 / 2)i(ZO1 / 2)j; wherein each R7is an independently selected alkyl group of 1 to 12 carbon atoms; each R8is the aldehyde-functional group of , wherein G is as described above;each Z is independently selected from the group consisting of a hydrogen atom and an alkyl group of 1 to 12 carbon atoms; subscripts c, d, e, f, g, h, and i are integers representing average number of units per molecule, and subscripts c, d, e, f, g, h, and i have values such that: c ≥ 0; d ≥ 0; e ≥ 0; f ≥ 0; g ≥ 0; h ≥ 0; a quantity (d + f + h) ≥ 2; i ≥ 0, and 10,000 ≥ (c + d + e + f + g + h + i) ≥ 2, and subscript j has a value such that 1.5 > j / (g + h + i) > 0.

6. The emulsion of any one of claims 1 to 5, wherein (A) the aldehyde-functional polyorganosiloxane comprises unit formula: (R73SiO 7 1 / 2)q(R 2R8SiO1 / 2)r(R7 2SiO2 / 2)s(SiO4 / 2)t, where R7and R8are as described above, and subscripts q, r, s, and t have average values such that 2 ≥ q ≥ 0, 4 ≥ r ≥ 0, 995 ≥ s ≥ 4, t = 1, (q + r) = 4, and (q + r + s + t) has a value sufficient to impart a viscosity > 170 mPa·s measured by rotational viscometry at 25 °C.

7. The emulsion of any one of claims 1 to 6, wherein (B) the polyorganohydrogensiloxane comprises unit formula: (R93SiO1 / 2)w(R9 2HSiO1 / 2)x(R9 2SiO2 / 2)y(R9HSiO2 / 2)z, wherein each R9is an independently selected monovalent hydrocarbyl group of 1 to 12 carbon atoms; subscripts w, x, y, and z are integers representing average number of units per molecule, and subscripts w, x, y, and z have values such that: w is 0, 1, or 2; x is 0, 1, or 2; a quantity (w + x) has an average value of 2; y ≥ 0; z ≥ 0; a quantity (x + z) ≥ 2, and 10,000 ≥ (w + x + y + z) ≥ 2.

8. The emulsion of any one of claims 1 to 7, wherein (C) (i) the halogenated arylborane Lewis acid comprises tris(pentafluorophenyl)borane.

9. The emulsion of any one of claims 1 to 8, wherein the emulsion is free of platinum.

10. A method for preparing the emulsion of any one of claims 4 to 9, wherein the method comprises:1) preparing a base part by a method comprising combining starting materials comprising (B) the polyorganohydrogensiloxane and at least a portion of (A) the aldehyde-functional polyorganosiloxane, the surfactant, the water, and optionally one or more of the buffer, the hydrosilylation reaction inhibitor and the biocide; 2) preparing a curing agent part by a method comprising combining starting materials comprising (C)(i) the halogenated arylborane Lewis acid and at least a portion of the surfactant and the water, and optionally (A) the aldehyde-functional polyorganosiloxane, the surfactant, water, the biocide, and the buffer; and 3) mixing the base part and the curing agent part.

11. The method of claim 10, further comprising mixing (C)(i) the halogenated arylborane Lewis acid, (ii) the Lewis basic amine, and optionally (iii) the solvent, before step 2).

12. The method of claim 10 or claim 11, further comprising preparing a third part by a method comprising mixing an anti-foam and water, and mixing the third part with the base part and the curing agent part during or after step 3).

13. A method for preparing a coated article, wherein the method comprises: I) practicing the method of any one of claims 10 to 12, thereby preparing the polyorganosiloxane emulsion; II) coating the polyorganosiloxane emulsion on a substrate; III) removing all or a portion of the water; and IV) heating the curable polyorganosiloxane composition to form a cured polyorganosiloxane coating on the substrate, thereby preparing the coated article.

14. The method of claim 13, wherein the substrate comprises paper.

15. The method of claim 13 or claim 14, wherein the coated article is used for a food contact application.

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