Hydroxyl – functional aminosiloxane ester copolymer and methods for its preparation

Abstract

A hydroxyl-functional aminosiloxane ester copolymer, an emulsion containing said copolymer, and methods for making said copolymer and said emulsion are provided. The hydroxyl-functional aminosiloxane ester copolymer, and the emulsion containing said copolymer, may be useful as an alternative to conventional aminosiloxane polymers, and emulsions thereof, for various end use applications.

Description

HYDROXYL - FUNCTIONAL AMINOSILOXANE ESTER COPOLYMER AND METHODSFOR ITS PREPARATIONCROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefits of U.S. Provisional Patent Application No. 63 / 559891 filed 1 March 2024 under 35 U.S.C. §119 (e) and Indian Patent Application No. 202541010563 filed 7 February 2025 under 35 U.S.C. §119 (a)-(d) and 35 U.S.C.§365(a). Indian Patent Application No. 202541010563 and U.S. Provisional Patent Application No. 63 / 559891 are hereby incorporated by reference.TECHNICAL FIELD

[0002] This invention relates to a hydroxyl - functional aminosiloxane ester copolymer (copolymer) and method for its preparation. The invention further relates to an emulsion containing the copolymer and method for making the emulsion.INTRODUCTION

[0003] Amino-functional polyorganosiloxanes, such as amine-terminated polydiorganosiloxanes are useful in various applications. Amine-terminated polydiorganosiloxanes made by condensation may suffer from the drawback of instability as shown by viscosity changes and / or development of an ammonia odor after aging, which is undesirable for certain applications. Traditionally, primary amine terminated polyorganosiloxanes are expensive to make by equilibration as they require costly starting materials and catalysts and require multiple process steps to complete.

[0004] Another method for making amine-terminated polyorganosiloxanes uses allylamine-or a derivative that hydrolyzes into allylamine. These are used to do hydrosilylation chemistry with SiH terminated polymers to form the amine-terminated polyorganosiloxanes; however, this method suffers from the drawback that the amine-terminated polyorganosiloxane product may contain at least trace amounts of either SiH or allylamine, either of which would have to be removed before the product can be used in certain applications.

[0005] Another method of making amine-terminated polyorganosiloxanes is by ammonolysis of chloropropyl terminated siloxanes. This costly, multi-step method may suffer from the drawback of leaving residual salt (i.e., ammonium chloride) in the amine-terminated polyorganosiloxane product that may require extensive washing to remove, which is cost ineffective and poorly sustainable. Also, any residual ammonium chloride may produce a foul smell, which is undesirable for certain applications.

[0006] Acryl functional silicone compounds and methods to prepare them have been disclosed in U.S. Patent 4,697,026 to Lee, et al. Lee discloses the acryl functional silicon compounds canbe prepared by intimately mixing an amino functional silicon compound having at least one primary amine or secondary amine group with an acryl functional compound having at least two acrylate, methacrylate, acrylamide, or methacrylamide groups per molecule. When amine compound and acryl compound are mixed, there is a reaction which produces an acryl functional silicon compound. This reaction is known as the Michael-type addition. Without wishing to be bound by theory, it is thought that the compounds described by Lee et al. would be unsuitable for use in certain applications because the acrylate functionalities of those compounds can be skin sensitizers and irritants, rendering them unsuitable for applications where contact with the consumer’ s skin and potentially accidental contact with the eye can occur.

[0007] US Patent Application Publication 2024-0180813 to Rekken, et al. discloses an aminosiloxane ester copolymer and methods for its preparation and use. However, the aminosiloxane ester copolymer has limited functionality. The amino groups in the backbone of the polymer are limited to NH. This may limit the potential uses for the aminosiloxane ester copolymer.SUMMARY

[0008] A hydroxyl - functional aminosiloxane ester copolymer (copolymer) comprises formula:, where each R1is an independently selected monovalent hydrocarbon group of 1 to 12 carbon atoms, each REis an independently selected amino-functional group of formula R zN-RA-, where each R3is independently selected from the group consisting of H and a hydroxyl- functional group of formulaR4is H or OH, andR5is OH or H,with the provisos that when R4is H, then R5is OH; and when R4is OH, then R5is H; and per molecule, at least one R is the hydroxyl-functional group, each RAis an independently divalent hydrocarbon group of 1 to 12 carbon atoms, each R2is independently selected from the group consisting of hydrogen and methyl, each RDis an independently selected divalent hydrocarbon group of 2 to 20 carbon atoms, each subscript a independently has a value such that 0 < a < 150; and subscript b has a value such that 1 < b < 100.

[0009] A process for preparing the copolymer comprises: combining, under conditions to effect reaction, starting materials comprising(i) an aminosiloxane ester copolymer terminated with primary amino-functional groups prepared as described in US Patent Application Publication 2024-0180813 to Rekken, et al.,(ii) glycidol, and optionally (iii) a solvent.

[0010] An emulsion comprises: (I) a liquid continuous phase comprising water, and (II) a discontinuous phase dispersed in the liquid continuous phase, where the discontinuous phase comprises the copolymer described above.DETAILED DESCRIPTION

[0011] The hydroxyl - functional aminosiloxane ester copolymer (copolymer) comprises formula:, where each R1is an independently selected monovalent hydrocarbon group of 1 to 12 carbon atoms, each REis independently selected from the group consisting of an amino-functional group of formula R32N-RA-, whereeach R3is independently selected from the group consisting of H and a hydroxyl- functional group of formulaR4is H or OH, and R5is OH or H, with the provisos that when R4is H, then Rsis OH; when R4is OH, then R5is H; and per molecule, at least one R3is the hydroxyl-functional group, each RAis an independently divalent hydrocarbon group of 1 to 12 carbon atoms, each R2is independently selected from the group consisting of hydrogen and methyl, each RDis an independently selected divalent hydrocarbon group of 2 to 20 carbon atoms, each subscript a independently has a value such that 0 < a < 150; and subscript b has a value such that 1 < b < 100.

[0012] Suitable monovalent hydrocarbon groups for R1include alkyl, alkenyl, aryl, and combinations thereof (e.g., aralkyl and aralkenyl). For example, suitable alkyl groups include methyl, ethyl, propyl (including iso-propyl and n-propyl), butyl (including iso-butyl, n-butyl, sec-butyl, and tert-butyl), pentyl (including linear pentyl and / or cyclopentyl) and branched alkyl groups with 5 carbon atoms, hexyl (including linear hexyl and / or cyclohexyl) and branched alkyl groups with 6 carbon atoms), octyl (including linear octyl and / or cyclooctyl), branched alkyl groups with 8 carbon atoms), decyl (including linear decyl and / or cyclodecyl) and branched alkyl groups with 10 carbon atoms, and dodecyl (including linear dodecyl and / or cyclododecyl) and branched alkyl groups with 12 carbon atoms. Alternatively, the alkyl group for R1may be selected from the group consisting of methyl and ethyl, alternatively methyl. Suitable alkenyl groups for R1include vinyl, allyl and hexenyl; alternatively vinyl or allyl; and alternatively vinyl. Suitable aryl groups for R1may include cyclopentadienyl, phenyl, naphthyl, and anthracenyl. Suitable aralkyl groups for R1include tolyl, xylyl, benzyl, 1 -phenylethyl, and 2- phenylethyl. Alternatively, the aryl group for R1may be phenyl. Aralkyl groups such as benzyl, 1 -phenylethyl, and 2-phenylethyl, and aralkenyl groups such as styryl, may also be used for R1. Alternatively, each R1may be selected from the group consisting of methyl and phenyl. Alternatively, each R1may be methyl.

[0013] Each R2is independently selected from the group consisting of hydrogen and methyl. Alternatively, each R2may be hydrogen.

[0014] Each RDis an independently selected divalent hydrocarbon group of 2 to 20 carbon atoms, alternatively 2 to 12 carbon atoms, alternatively 3 to 12 carbon atoms, alternatively 4 to 12 carbon atoms, and alternatively 4 to 10 carbon atoms. The divalent hydrocarbon groups for RDmay be linear, branched, cyclic, or combinations thereof. Suitable divalent hydrocarbon groups for RDinclude alkylene groups, arylene groups, and combinations thereof. Alternatively, each RDmay be an alkylene group such as propylene, butylene, hexylene, octylene, decylene, or dodecylene; alternatively, each RDmay be butylene, hexylene, or decylene. Alternatively, RDmay be a branched alkylene group. The arylene group for RDmay be arylene group such as phenylene. Alternatively, RDmay be a dialkylarylene group such as:each subscript u is independently 1 to 6, alternatively 1 to 2.

[0015] Each REis an independently selected amino-functional group of formula R32N-RA-, where RAis a divalent hydrocarbon group. Each RAis an independently selected divalent hydrocarbon group of 1 to 12 carbon atoms, alternatively 2 to 12 carbon atoms, alternatively 2 to 5 carbon atoms, and alternatively 2 to 3 carbon atoms. The divalent hydrocarbon groups for RAmay be linear, branched, or cyclic, or combinations thereof. Suitable divalent hydrocarbon groups for RAinclude alkylene groups, arylene groups, and combinations thereof (e.g., dialkylarylene groups). The alkylene group is exemplified by ethylene, propylene, or butylene. The arylene group for RAmay be arylene group such as phenylene. Alternatively, RAmay be a dialkylarylene group such as:each subscript u is independently 1 to 6, alternatively 1 to 2. Alternatively, each RAmay be an alkylene group such as ethylene, propylene, or butylene; alternatively ethylene. Alternatively, each REmay be a secondary amino-functional group (i.e.,in each amino-functional group of formula R32N-RA-, one R3is H and the other is the hydroxyl- functional group). Alternatively, each REmay be a tertiary amino-functional group (i.e., in each amino-functional group of formula R32N-RA-, each R3is the hydroxyl-functional group).

[0016] In the formula for the copolymer, at least one R is the hydroxyl-functional group. Alternatively, at least two R3, per molecule, are hydroxyl-functional groups of the formula shown above. Alternatively, at least 50 mol %, alternatively 50 mol % to 100 mol %, alternatively 60 mol % to 100 mol %, alternatively 70 mol % to 100 mol %, alternatively 80 mol % to 100 mol %, alternatively 90 mol % to 100 mol %, alternatively 95 mol % to 100 mol %, alternatively 90 mol % to 99 mol % of all R3are hydroxyl-functional groups.

[0017] Subscript a has a value such that 0 < a < 150. Alternatively, subscript a may have a value of 2 to 150, alternatively 2 to 145, alternatively 2 to 143, alternatively 2 to 142, alternatively 14 to 86, alternatively 14 to 45, and alternatively, 40 to 86. Alternatively, subscript a may be 44 to 145, alternatively 44 to 90, alternatively 44 to 85, alternatively 75 to 90, and alternatively 75 to 85.

[0018] Subscript b has a value such that 1 < b < 100. Alternatively, subscript b may have a value of 2 to 20, and alternatively 2 to 10.

[0019] The copolymer described above may have a number average molecular weight (Mn) of at least 769 g / mol, alternatively 769 g / mol to 250,000 g / mol, alternatively > 1,000 g / mole to 250,000 g / mole measured by GPC according to the test method described hereinbelow.Alternatively, the copolymer may have a Mn of > 1,244 g / mol, alternatively 4,000 g / mole to 250,000 g / mole, alternatively 4,000 g / mole to 100,000 g / mole, measured by GPC.

[0020] Alternatively, the copolymer described above may have a weight average molecular weight (Mw) of 2,000 g / mol to 400,000 g / mol. Alternatively, Mw may be 10,000 g / mol to 390,000 g / mol; alternatively 12,000 g / mol to 200,000 g / mol; alternatively 15,000 g / mol to 185,000 g / mol; alternatively 19,000 g / mol to 175,000 g / mol; alternatively 20,000 g / mol to 100,000 g / mol; alternatively 21,000 g / mol to 80,000 g / mol; alternatively 22,000 g / mol to 75,000 g / mol; alternatively 25,000 g / mol to 65,000 g / mol; alternatively 30,000 g / mol to 60,000 g / mol; alternatively 35,000 g / mol to 55,000 g / mol; and alternatively 40,000 g / mol to 50,000 g / mol.PROCESS FOR MAKING THE HYDROXYL-FUNCTIONAL AMINOSILOXANE ESTER COPOLYMER

[0021] The copolymer described above may be prepared by a process comprising:1) combining starting materials comprising: (i) an aminosiloxane ester copolymer terminated with primary amino-functional groups, (ii) glycidol, and optionally (iii) a solvent. The aminosiloxane ester copolymer terminated with primary amino-functional groups is known in the art and may be prepared as described in US Patent Application Publication 2024-0180813.The aminosiloxane ester copolymer terminated with primary amino-functional groups comprises formula:, where each R1is an independently selected monovalent hydrocarbon group of 1 to 12 carbon atoms, each RAis an independently divalent hydrocarbon group of 1 to 12 carbon atoms, each R2is independently selected from the group consisting of hydrogen and methyl, each RDis an independently selected divalent hydrocarbon group of 2 to 20 carbon atoms, each subscript a independently has a value such that 0 < a < 150; and subscript b has a value such that 1 < b < 100, each as described above, and each REis independently a group of formula H2N-RA-, where RAis as described above.

[0022] The process for preparing the copolymer described herein comprises: / ) combining starting materials comprising (i) the aminosiloxane ester copolymer with terminal primary amino-functional groups; (ii) glycidol, and optionally (iii) a solvent. Glycidol has generalformula glycidol , which is commercially available from various sources such as Millipore Sigma of St. Louis, Missouri, USA.

[0023] Starting material (i) the aminosiloxane ester copolymer terminated with primary aminofunctional groups, and starting material (ii) the glycidol, are added in amounts to provide a molar ratio of NH / epoxy groups, where N-H content is calculated as N-H on the terminal primary amino-functional polyorganosiloxane minus the moles of acrylate on the bis-acryloyloxy-alkane used for preparing the aminosiloxane ester copolymer terminated with primary amino-functional groups (i.e., N-H / Epoxy mol ratio) >1 / 1, alternatively > 1 / 1, and alternatively at least 1.3 / 1; while at the same time N-H / Epoxy mol ratio may be up to 2 / 1, alternatively up to 1.5 / 1, and alternatively up to 1.3 / 1. The reactants may be heated at a temperature of 50 °C to 100 °C, alternatively 60 °C to 70 °C.

[0024] Alternatively, the starting materials may be mixed and / or heated during step 1 ). The method may optionally further comprise adding starting material (iii), a solvent. The solvent may optionally be added, e.g., with mixing and before heating, to facilitate mixing of (i) theaminosiloxane ester copolymer terminated with primary amino-functional groups and (ii) the glycidol. The process may further comprise mixing the aminosiloxane ester copolymer and / or the glycidol with (iii) the solvent, e.g., for a time sufficient to dissolve the aminosiloxane ester copolymer terminated with primary amino-functional groups and / or the glycidol in the solvent before heating. The solvent may be a monohydric alcohol, e.g., methanol, ethanol, propanol including isopropanol, and / or butanol; or a polyhydric alcohol such as diethylene glycol butyl ether (butyl carbitol). Optionally, a co-solvent may be used with the solvent. The co-solvent may comprise isododecane (IDD), dipropylene glycol dimethyl ether, or a combination thereof. The method may optionally further comprise: 2) recovering the copolymer prepared herein, by any convenient means, such as stripping and / or distillation to remove unreacted starting materials, side products, and / or solvent, when used.

[0025] Alternatively, the hydroxyl-functional aminosiloxane ester copolymer described above may be prepared by a process comprising:I) combining starting materials comprising(A) a terminal primary amino-functional polyorganosiloxane of formula, wherein R1, RA, and subscript a are as described above;(B) a bis-acryloyloxy-alkane of formula, wherein RDis as described above; wherein starting material (A) and starting material (B) are present in amounts such that a molar ratio of (A):(B) ranges from 2: 1 to 1 : 1.1 ; and(ii) glycidol. Alternatively, the molar ratio of (A):(B) may be 2:1 to 1 : 1.05; alternatively 2:1 to 1 :1. Alternatively, the molar ratio of (A):(B) may be at least 1 :1, alternatively at least 1.1:1, and alternatively at least 1.3:1, while at the same time said ratio may be up to 2: 1, alternatively up to 1.8:1, alternatively up to 1.5: 1.

[0026] The process described above may optionally further comprise adding, during step I), an additional starting material selected from the group consisting of: (C) a catalyst, (D) asolvent, (E) an acrylate polymerization inhibitor, and a combination of two or more of (C), (D), and (E).£0027] Step I) comprises mixing the starting materials, optionally with heating. Mixing in step I) may be performed for 1 to 48 hours, alternatively 4 to 24 hours, and alternatively 6 to 15 hours. The temperature during step I) may be 0 °C to 180 °C, alternatively 20 °C to 160 °C, alternatively 60 °C to 150 °C, and alternatively 80 °C to 120 °C. Mixing (and heating) may be performed by any convenient means, such as loading the starting materials into a vessel such as an agitated, jacketed batch reactor or reactive distillation apparatus having a jacketed reboiler, which jackets can be heated and cooled by passing steam / water or heat transfer fluid through the jacket. Step I) may be performed under inert conditions, such as less than 3% oxygen, by purging the reactor with an inert gas, such as nitrogen. For example, step I) may be performed under an atmosphere containing < 3% oxygen when operated above 60 °C. Alternatively, before heating in step I), the process may optionally further comprise mixing the starting materials at RT for up to 60 minutes, alternatively 5 minutes to 30 minutes, and alternatively 15 minutes to 30 minutes. Without wishing to be bound by theory, it is thought that mixing at RT may facilitate coalescence of the starting materials into one phase and begin reacting (A) the terminal primary amino-functional polyorganosiloxane and (B) the bis-acryloyloxy-alkane. Furthermore, it is thought that this additional mixing step may prevent or minimize polymerization of the acrylate groups.

[0026] Starting material (A) used in the process described above is the terminal primary amino-functional polyorganosiloxane of formula, where R1, RA, and subscript a are as described above. Suitable terminal primary aminofunctional polyorganosiloxanes are exemplified by bis-3-aminopropyl-terminated polydimethylsiloxanes, which are commercially available, e.g., under the tradename SiVance from Milliken Chemical of Spartanburg, South Carolina, USA. Terminal primary aminofunctional polyorganosiloxanes may be made by known methods, such as those disclosed in U.S. Patent Application Publication 2004 / 0210074 to Hupfield, et al.; U.S. Patent 11,028,229 to Suthiwangcharoen, et al.; U.S. Patent 11,028,233 to Suthiwangcharoen, et al.; U.S. Patent 7,238,768 to Hupfield and U.S. Patent 8,796,198 to Henning, et al.

[0027] Starting material (B) used in the process described above is the bis-acryloyloxy-alkane of formuladescribed above.Examples of suitable bis-acryloyloxy-alkanes include 1,3 -butanediol diacrylate; 1 ,4-butanediol diacrylate; 1,6-hexanediol diacrylate [also named l,6-bis(acryloyloxy)hexane]; 1,9- bis(acryloyloxy)nonane; 1,10-decanediol diacrylate; and a combination thereof. Suitable bis- acryloyloxy-alkanes are known in the art and are commercially available, e.g., from various sources including Sigma- Aldrich, Inc. of St. Louis, Missouri, USA.

[0028] Starting material (ii) is glycidol, as described and exemplified above. The amount of glycidol may be sufficient to provide the amount as described above based on the amount of aminosiloxane ester copolymer prepared by reaction of starting materials comprising (A) and (B).

[0029] Starting material (C) is a catalyst that may optionally be added during the process described above. Without wishing to be bound by theory, it is thought that the catalyst may accelerate synthesis of the copolymer. When used, the catalyst is present in an amount of > 0 to < 90 weight % based on weights of starting materials (A) and (B) combined. The exact amount of solvent depends on the type of catalyst selected. For example, when the catalyst is an alcohol, which can also be used as a solvent, as described below, the amount of catalyst may be higher than if a different catalyst is used. For example, alcohols may be used in an amount up to 90% on the basis above, while other the other catalysts described herein may be used in an amount > 0 to < 5 weight % based on weights of starting materials (A) and (B) combined.

[0030] The catalyst may comprise an alcohol, a tertiary amine, pyridine, a pyridine derivative, or another aromatic heterocycle. Suitable alcohols include methanol, ethanol, isopropanol, butanol, n-propanol, and isofol- 12 (2-butyl-octanol), isofol-20 (2-octyl-l -dodecanol; and INCI: Octyldodecanol. Without wishing to be bound by theory, it is thought that the longer chain alcohols, e.g., isofol-12 (2-butyl-octanol), isofol-20 (2-octyl-l -dodecanol; INCI: Octyldodecanol may act as cosolvents for the copolymer produced and may be formulated into personal care compositions. These alcohols are commercially available from Sasol of Sandton, South Africa.

[0031] Suitable tertiary amines include trimethylamine; triethylamine; tributylamine; tetramethylethylenediamine; l,8-diazabicyclo[5.4.0]undec-7-ene (DBU); 1 ,5- diazabicyclo[4.3.0]non-5-ene (DBN); l,4-diazabicyclo[2.2.2]octane (DABCO); 1,5,7- triazabicyclo[4.4.0]dec-5-ene (AKA l,3,4,6,7,8-Hexahydro-2H-pyrimido[l,2,-a]pyrimidine)(TBD); 7-methyl- 1,5, 7-triazabicyclo| 4.4.0 |dec-5-ene (mTBD); N-(2-hydroxyethyl)piperazine; tetramethyl guanidine (TMG); 1 ,2,2,6,6-pentamethylpiperidine; N-methylmorpholine (NMP); 2,2,6,6-tetramethylpiperidine (TMP); and 1 - azabicyclo[2.2.2]octane. Suitable pyridine derivatives include dimethyl pyridine, e.g., 2,6-dimethylpyridine (aka 2,6-lutidine), and trimethyl pyridine. The catalysts described above are commercially available from various sources including Sigma Aldrich, Inc. and Fisher Scientific of Hampton, New Hampshire, USA.

[0032] Starting material (D) is a solvent that may optionally be added during the process described above. Suitable solvents include polydialkylsiloxanes, alcohols, aromatic hydrocarbons, aliphatic hydrocarbons, ethers, or a combination thereof. Polydialkylsiloxanes with suitable vapor pressures may be used as the solvent, and these include hexamethyldisiloxane, octamethyltrisiloxane, hexamethylcyclotrisiloxane, dodecamethylcyclohexasiloxane, tetradecamethylcycloheptasiloxane and other low molecular weight polyalkylsiloxanes, such as 0.5 to 1.5 cSt DOWSIL™ 200 Fluids and DOWSIL™ OS FLUIDS, which are commercially available from DSC.

[0033] Alternatively, starting material (D) may comprise an organic solvent. The organic solvent can be an alcohol such as methanol, ethanol, isopropanol, butanol, n-propanol, and isofol- 12 (2-butyl-octanol), isofol-20 (2-octyl-l -dodecanol; and INCI: Octyldodecanol; an aromatic hydrocarbon such as benzene, toluene, or xylene; an aliphatic hydrocarbon such as heptane, hexane, octane, or isododecane; or a combination thereof. Suitable organic solvents are commercially available from various sources including Sigma Aldrich, Inc. of St. Louis, Missouri, USA.

[0034] The solvent in this process is optional. When present, the amount of solvent will depend on various factors including the type of solvent selected and the amount and type of other starting materials selected for use in the process. However, when used, the amount of solvent may be > 0% to 90%, based on combined weights of all starting materials used in step I). The solvent may be added, for example, to aid mixing and delivery of one or more starting materials. For example, the catalyst may be delivered in a solvent. All or a portion of the solvent may optionally be removed after step I).

[0035] Starting material (E) is an acrylate polymerization inhibitor that may optionally be added during the process described above. When present, starting material (E), the inhibitor, may be used in an amount > 0 to < 0.01% based on weights of starting materials (A) and (B) combined alternatively > 0 to < 10,000 ppm, alternatively 1 ppm to 2,000 ppm, alternatively 10 ppm to 500 ppm, on the same basis. Suitable inhibitors are commercially available, and include, for example, nitrobenzene, butylated hydroxyl toluene (BHT), diphenyl picryl hydrazyl (DPPH), p-methoxyphenol, 4-methoxy-phenol (MEHQ), 4-hydroxyphenol (HQ), 2,4-di-t-butyl catechol,phenothiazine, N,N-diethylhydroxylamine, salts of N-nitroso phenylhydroxylamine, (2, 2,6,6- tetramethylpiperidin- 1 -yl)oxidanyl (TEMPO), and 4-hydroxy-(2,2,6,6-tetramethylpiperidin-l- yl)oxidanyl (4-hydroxy TEMPO), phenothiazine (PTZ).

[0036] One skilled in the art would recognize that certain starting materials may have more than one function. For example, the alcohol described above may function as both a catalyst and a solvent Longer chain alcohols, such as, isofol- 12 (2-butyl-octanol), isofol-20 (2-octyl-l - dodecanol; and INCI: Octyldodecanol may functional as both solvents and emollient when the copolymer is formulated into a personal care product.

[0037] Alternatively, the hydroxyl-functional aminosiloxane ester copolymer described above may be prepared by a process comprising: i) combining starting materials comprising:(B) the bis-acryloyloxy-alkane as described above;(F) a bis-silanol-terminated polydiorganosiloxane of formula:subscript a are as described above; and(G) a cyclic siloxazane of formulac is 0 or 1 , each R8is an independently selected monovalent hydrocarbon group of 1 to 18 carbon atoms, and each R9is independently selected from the group consisting of hydrogen and an alkyl group of 1 to 15 carbon atoms. This process may optionally further comprise adding, during step 1), an additional starting material selected from the group consisting of: (C) the catalyst, (D) the solvent, (E) the acrylate polymerization inhibitor, each as described above, and a combination of two or more of (C), (D), and(E); and(ii) glycidol, as described above.One skilled in the art would recognize that the glycidol and the cyclic siloxazane have potential to react with one another. Therefore, the starting mateirals in step i) may be combined in any order so as to minimize or eliminate such a side reaction. For example, (F) the bis-silanol- terminated polydiorganosiloxane and (G) the cyclic siloxazane may be first be combined to form a terminal aminosiloxane before adding (B) the bis-acryloyloxy-alkane and the glycidol. Alternatively, (F) the bis-silanol-terminated polydiorganosiloxane, (G) the cyclic siloxazane, and (B) the bis-acryloyloxy-alkane may first be combined and reacted to form an aminosiloxane ester copolymer before addition of the glycidol.

[0038] Step i) comprises mixing the starting materials, optionally with heating. Mixing in step i) may be performed for 1 to 48 hours, alternatively 4 to 24 hours, and alternatively 6 to 15 hours. The temperature during step i) may be 0 °C to 180 °C, alternatively 20 to 160, alternatively 60 °C to 180 °C, and alternatively 60 °C to 150 °C. Mixing (and heating) may be performed by any convenient means, such as loading the starting materials into a vessel such as an agitated, jacketed batch reactor or reactive distillation apparatus having a jacketed reboiler, which jackets can be heated and cooled by passing steam / water or heat transfer fluid through the jacket. Step i) may be performed under inert conditions, such as less than 3% oxygen, by purging the reactor with an inert gas, such as nitrogen. For example, step i) may be performed under an atmosphere containing < 3% oxygen when operated above 60 °C.

[0039] The copolymer produced by this process has terminal groups shown by REin the formula above. The selection of the terminal groups depends on the amounts of starting materials used in the process. Where more than two molar equivalents of (G) the cyclic siloxazane, per mole of (F) the bis-silanol-terminated polydiorganosiloxane, then each REmay be the amino-functional group of formula R32N-RA-, as described above. Alternatively, the copolymer produced by this process may have one instance of REbeing the amino-functional group and one instance of REbeing the hydroxyl group in the same molecule.

[0040] Starting material (F), the bis-silanol-terminated polydiorganosiloxane, and starting material (B), the bis-acryloyloxy-alkane, are present in amounts such that a molar ratio of (F):(B) ranges from 2: 1 to 1 : 1.1 ; alternatively 2: 1 to 1 :1.05; alternatively 2: 1 to 1:1. Alternatively, the molar ratio of (F):(B) may be at least 1 :1, alternatively at least 1.1 :1, and alternatively at least 1.3:1, while at the same time said ratio may be up to 2: 1 , alternatively up to 1.8:1, alternatively up to 1.5:1.

[0041] Starting material (F) is the bis-silanol-terminated polydiorganosiloxane of formula:subscript a are as described above.Examples of starting material (F) include bis-silanol terminated polydimethylsiloxanes, which are known in the art and are commercially available, for example under the tradename XIAMETER™ OHX from DSC. Bis-silanol terminated polydiorganosiloxanes suitable for use as starting material (F) may be prepared by methods known in the art, such as hydrolysis and condensation of the corresponding organohalosilanes or equilibration of cyclic polydiorganosiloxanes.

[0042] Starting material (G) is the cyclic siloxazane of formula:where subscript c is 0 or 1 , each R8is an independently selected monovalent hydrocarbon group of 1 to 18 carbon atoms, and each R9is independently selected from the group consisting of hydrogen and an alkyl group of 1 to 15 carbon atoms. Each R9is independently selected from the group consisting of hydrogen and an alkyl group of 1 to 15 carbon atoms, alternatively 1 to 12 carbon atoms, and alternatively 1 to 6 carbon atoms. Suitable alkyl groups are exemplified by methyl, ethyl, propyl (e.g., iso-propyl and / or n-propyl), butyl (e.g., isobutyl, n-butyl, tertbutyl, and / or sec-butyl), pentyl (e.g., isopentyl, neopentyl, and / or tert-pentyl), hexyl, heptyl, octyl, nonyl, and decyl, as well as branched saturated monovalent hydrocarbyl groups of 6 or more carbon atoms including cycloalkyl groups such as cyclopentyl and cyclohexyl. Alternatively, each alkyl group for R9may be methyl. Alternatively, each R9may be a hydrogen atom. Alternatively, at least one R9per molecule may be an alkyl group such as methyl.

[0043] Each R8is an independently selected monovalent hydrocarbon group of 1 to 18 carbon atoms. The monovalent hydrocarbon group is exemplified by an alkyl group, an aryl group, and an aralkyl group. Alternatively, the monovalent hydrocarbon group may be an alkyl group, s for Rsare exemplified by those described above for R9.

[0044] Examples of suitable cyclic siloxazanes include:1 ,1 ,3,3,-tetramethyl-2-oxa-7-aza-l ,3 -disilacycloheptane of formulaand l,l,3,3,5,5-hexamethyl-2,4-di-oxa-9-aza-l,3,5-trisilacyclononane of formula

[0045] The cyclic siloxazane may be prepared by a hydrosilylation reaction of an allyl- functional amine and an SiH-terminated siloxane oligomer in the presence of a hydrosilylation reaction catalyst and a hydrosilylation reaction promoter, as described in U.S. Patent 11760839 to Rekken, et al., which is hereby incorporated by reference.

[0046] Starting material (ii) in the process described above is glycidol, as described above. The amount of glycidol in this process may be sufficient to provide the amount as described above based on the amount of aminosiloxane ester copolymer prepared by reaction of starting materials comprising (B), (F), and (G).

[0047] In the process described above, (B) bis-acryloyloxy-alkane, (F) the bis-silanol- terminated polydiorganosiloxane, (G) the cyclic siloxazane, and (ii) the glycidol may be combined concurrently, or in any order, in step i). Without wishing to be bound by theory, it is thought that when starting materials (B), (F), (G), and (ii) are combined concurrently, (G) the cyclic siloxazane will first react with the silanol groups of starting material (B) to form a terminal primary amino-functional polydiorganosiloxane in situ, which will subsequently undergo an aza-Michael addition with the (B) the bis-acryloyloxy-alkane. The inventors surprisingly found that (B) the bis-acryloyloxy-alkane did not readily react with the secondary amine functionality of the cyclic siloxazane. Alternatively, in step i), starting material (G), the cyclic siloxazane, and starting material (F), the bis-silanol-terminated polydiorganosiloxane, may be combined to form an amino-functional polyorganosiloxane, and thereafter startingmaterial (B), the bis-acryloyloxy-alkane, may be added. Without wishing to be bound by theory, it is thought that (G) the cyclic siloxazane does not readily react with (B) the bis-acryloyloxy- alkane. The process may comprise forming (A) the terminal primary amino-functional polyorganosiloxane by a process comprising i) combining starting materials comprising: (G) the cyclic polysiloxazane described above, (F) the bis-silanol-terminated polydiorganosiloxane described above, and optionally ii ) recovering (A) the primary amino-functional polyorganosiloxane. This process may be performed as described in U.S. Patent 11760839 to Rekken, et al., by selecting a bis-silanol-terminated polydiorganosiloxane corresponding to starting material (F) above for use in the process. Thereafter, the other starting materials may be combined with (a) the primary amino-functional polyorganosiloxane.

[0048] Step i) (combining starting materials comprising (G) and (F)) in the process for forming (A) the primary amino-functional polyorganosiloxane may be performed by any convenient means, such as mixing, optionally with heating. Mixing and heating may be performed using any convenient means, such as loading the starting materials into a vessel such as an agitated, jacketed batch reactor or reactive distillation apparatus having a jacketed reboiler, which jackets can be heated and cooled by passing steam / water or heat transfer fluid through the jacket. The process may be performed at a temperature of at least 50 °C, alternatively at least 85 °C, and alternatively at least 90 °C. Alternatively, heating in step i) may be performed at 50 °C to 150 °C, alternatively 85 °C to 150 °C, and alternatively 90 °C to 150 °C. The process is performed for a time sufficient to form (A) the terminal primary amino-functional polyorganosiloxane. In step i), one of (G) the cyclic siloxazane and (F) the bis-silanol-terminated polydiorganosiloxane may be added continuously or in increments into a vessel containing the other of (F) and (G). Such addition may be performed manually or using metering equipment. The process for forming (A) the primary amino-functional polyorganosiloxane described above may optionally further comprise one or more additional steps. This process may optionally further comprise step Hi) adding one or more additional starting materials to the reaction mixture in step i). Alternatively, step Hi) may be performed during and / or after step i) and before step ii). The additional starting material may be selected from the group consisting of an acid precatalyst, an aminoalkyl-functional alkoxysilane, an endblocker, a solvent as described above for starting material (D), and a combination of two or more of thereof, as described in U.S. Patent11760839 to Rekken, et al. The resulting primary amino-functional polyorganosiloxane may be used in the process as described above to make the hydroxyl-functional aminosiloxane ester copolymer described above.

[0049] In the process for making the hydroxyl-functional aminosiloxane ester copolymer described above, the process may optionally comprise one or more additional steps. Theprocesses may further comprise: II) recovering the hydroxyl-functional aminosiloxane ester copolymer (during and / or after step II). Recovery may be performed by any convenient means, such as stripping and / or distillation with heating and optionally with reduced pressure; and / or removing (C) the catalyst, e.g., by stripping and / or distillation, neutralization, when catalyst is used, and / or adsorption. Furthermore, one skilled in the art would recognize that in the process described above, when (G) the cyclic siloxazane is used, an alcohol is not used as (C) the catalyst and (D) the solvent when (G) the cyclic siloxazane is present, so as to avoid reaction of the alcohol with the cyclic siloxazane to generate an alkoxy-functional aminofunctional alkoxysilane or siloxane.EMULSION COMPRISING THE HYDROXY-FUNCTIONAL AMINOSILOXANE ESTER COPOLYMER

[0050] The hydroxy-functional aminosiloxane ester copolymer (copolymer) described above may be formulated in an emulsion. The emulsion may comprise: (I) a liquid continuous phase comprising water, and (II) a discontinuous phase dispersed in the liquid continuous phase, where the discontinuous phase comprises the copolymer described above. The emulsion further comprises a surfactant. The amount of copolymer added to the emulsion can vary and is not limited. However, the amount typically may range from a weight ratio of copolymer / emulsion of 1 to 70%, alternatively 2 to 60%. Water (and additional starting materials, if present) may constitute the balance of the emulsion to 100%.Water

[0051] The water is not generally limited, and may be utilized neat (i.e., absent any carrier vehicles / sol vents), 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 making the emulsion described herein. 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). Alternatively, the water may be purified before use to make the emulsion.(H) Surfactant

[0052] The surfactant may be anionic, cationic, nonionic, or amphoteric, or a combination of two or more thereof. The amount of surfactant may be 2 % to 25 % based on combined weights of all starting materials in the emulsion. The anionic surfactant may selected from alkali metal sulfosuccinates, sulfonated glyceryl esters of fatty acids, salts of sulfonated monovalent alcohol esters, amides of amino sulfonic acids, sulfonated products of fatty acids nitriles, sulfonated aromatic hydrocarbons, condensation products of naphthalene sulfonic acids with formaldehyde,sodium octahydroanthracene sulfonate, sodium lauryl sulfate, alkali metal alkyl sulfates, alkyl ether sulfates having at least 8 carbon atoms, alkyl aryl ether sulfates, alkylarylsulfonates having at least 8 carbon atoms, alkylbenzenesulfonic acids, salts of alkylbenzenesulfonic acids, sulfuric esters of polyoxyethylene alkyl ether, amine salts or sodium salts or potassium salts of alkylnaphthylsulfonic acid, and combinations thereof. Suitable anionic surfactants are commercially available from various sources including sodium lauryl sulfate, which is available from Pilot under the tradename CALIMULSE™ SLS. Other anionic surfactants commercially available from TDCC, include alkyldiphenyloxide disulfonate salts, which are available under the tradename DOWFAX™; dioctyl sulfosuccinates, which are available under the tradename TRITON™ GR; phosphate esters, which are available under the tradename TRITON™ H-55, Id- 65, QS-44, OR XQS-20; sulfates and sulfonates, which are available under the tradename TRITON™ QS-15 and TRITON™ XN-45S.

[0053] The cationic surfactant may be selected from dodecylamine acetate, octadecylamine acetate, acetates of the amines of tallow fatty acids, homologues of aromatic amines having fatty acids, fatty amides derived from aliphatic diamines, fatty amides derived from aliphatic diamines, fatty amides derived from disubstituted amines, derivatives of ethylene diamine, quaternary ammonium compounds, salts of quaternary ammonium compounds, alkyl trimethylammonium hydroxides, dialkyldimethylammonium hydroxides, coconut oil, methylpolyoxyethylene cocoammonium chloride, dipalmitoylethyl hydroxyethylmonium methosulfate, amide derivatives of amino alcohols, amine salts of long chain fatty acids, and combinations thereof. Cationic surfactants are commercially available from various sources including dialkylmethyl quaternary ammonium compounds (e.g., cetrimonium chloride) under the tradename ARQUAD™ from Akzo Nobel; ADOGEN™ cationic surfactants from Evonik; TOMAH™ cationic surfactants from Tomah Products, Inc. of Milton, Wisconsin, USA; and VARIQUAT™ cationic surfactants from Sea-Land Chemical Company of Westlake, Ohio, USA.

[0054] The nonionic surfactant may be selected from alkylphenol alkoxylates, ethoxylated and propoxylated fatty alcohols, alkyl polyglucosides and hydroxyalkyl polyglucosides, sorbitan derivatives, N- alkylglucamides, alkylene oxide block copolymers, such as block copolymers of ethylene oxide, propylene oxide and / or butylene oxide, fatty alcohol poly glycolethers, polyhydroxy and polyalkoxy fatty acid derivatives, amine oxides, silicone polyethers, various polymeric surfactants. Nonionic surfactants are commercially available, for example, alkylphenol alkoxylates are available under the tradename ECOSURF™ EH; secondary alcohol ethoxylates, nonylphenol ethoxylates, and ethylene oxide / propylene oxide copolymers are commercially available under the tradename TERGITOL™; and specialty alkoxylates such asamine ethoxylates and octylphenol ethoxylates are available under the tradename TRITON ™, all from TDCC. Alternatively, the nonionic surfactant may be, e.g., trideceth-6 or trideceth-12, which are available under the tradename SYNPERONIC™ from Croda or LUTENSOL™ from BASF. Alternatively, the nonionic surfactant may be e.g., a fatty alcohol polyglycol ether such as GENAPOL™ UD 050, and GENAPOL™ UDI 10, which are commercially available from Clariant of Frankfurt, Germany.

[0055] The nonionic surfactant may also be a silicone polyether (SPE). The silicone poly ether as an emulsifier may have a rake type structure wherein the polyoxyethylene or polyoxyethylene-polyoxypropylene copolymeric units are grafted onto the siloxane backbone, or the SPE can have an ABA block copolymeric structure wherein A represents the polyether portion and B the siloxane portion of an ABA structure. Suitable silicone polyethers include Dow Silicones™ 5329 from DSC. Alternatively, the nonionic surfactant may be selected from polyoxyalky lene-substituted silicones, silicone alkanolamides, silicone esters and silicone glycosides. Such silicone-based surfactants 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.

[0056] Suitable amphoteric surfactants include betaines such as alkyl(C12-14)betaine, cocoamidopropylbetaine, cocoamidopropyldimethyl-hydroxysulphobetaine, dodecylbetaine, hexadecylbetaine, and tetradecylbetaine; sultaines such as cocamidopropylhydroxysultaine; lecithin; hydrogenated lecithin; cocoamphodiacetates; cocoiminodipropionate; and dodecyliminodipropionate.

[0057] The emulsion may be formed as a water-in-oil emulsion (w / o), which contains a water- in-oil surfactant, which may subsequently inverted by addition of more aliquots of water to form the oil-in-water (o / w) emulsion. The water-in-oil surfactant may be nonionic and may be selected from polyoxyalkylene-substituted silicones, silicone alkanolamides, silicone esters and silicone glycosides, as described above. Alternatively, when the emulsion is an o / w emulsion, it may include nonionic surfactants known in the art to prepare o / w emulsions. Suitable nonionic surfactants for this embodiment are exemplified by the polyoxyethylene alkyl ethers, polyoxyethylene alkylphenol ethers, polyoxyethylene lauryl ethers, polyoxyethylene sorbitan monooleates, polyoxyethylene alkyl esters, polyoxyethylene sorbitan alkyl esters, polyethylene glycol, polypropylene glycol, diethylene glycol, ethoxylated trimethylnonanols, and polyoxyalkylene glycol modified polysiloxane surfactants, as described above.Additional Starting Materials

[0058] In addition to the copolymer, water, and surfactant, the emulsion described above may further comprise an additional starting material selected from the group consisting of a (I) anacid compound, (J) an acid anhydride, (K) a thickener, (L) a stabilizer, (M) a preservative, (N) a solvent, and a combination of two or more of (H), (I), (J), (K), (L), (M), and (N). Alternatively, when the emulsion will be used in a method for treating a textile, the emulsion described above may further comprise an additional starting material selected from the group consisting of an amino-functional polydiorganosiloxane, a co-solvent, an acid compound, an acid anhydride, a thickener, a stabilizer, a preservative, a brightener, a perfume, a perfume delivery system, a pH adjuster (other than the acid compound introduced above and described in detail below), a solvent (other than the co-solvents described above), a dispersant, a catalytic material, a fabric softener, a processing aid, and a combination of two or more thereof. Suitable additional starting materials are known in the art and are described, for example, as additional ingredients in US Patent 10752864 beginning at col. 7, line 20 and in PCT Patent Publication WO2023278918.

[0059] The acid compound may optionally be added to the emulsion described herein for adjusting pH. Suitable acids include acetic acid, formic acid, propionic acid, and combinations thereof. Suitable acids for adjusting pH are disclosed, for example, in US Patent 6180117 to Berthiaume et al.

[0060] The solvent used in the emulsion, when present, may be a solvent as described above used in the method of making the hydroxyl - functional aminosiloxane ester copolymer. The solvent may be present in the emulsion due to its presence with the hydroxyl - functional aminosiloxane ester copolymer during manufacture of the copolymer. Alternatively, the solvent may be added to the emulsion (after formation of the hydroxyl - functional aminosiloxane ester copolymer). Alternatively, the solvent in the emulsion may comprise butyl carbitol. The amount of solvent in the emulsion may be up to 10%, alternatively 1% to 5%, alternatively up to 3% based on combined weights of all starting materials in the emulsion. The solvent may be selected (type and amount) so that it does not detrimentally impact stability of the emulsion.Amino-Functional Polydiorganosiloxane

[0061] The amino-functional polydiorganosiloxane produced as described herein may comprise unit formula: (R43SiOi / 2)a(R42SiO2 / 2MR8R4SiO2 / 2)c(R8R42SiOi / 2U, where each R4is independently selected from a monovalent hydrocarbon group and a monovalent halogenated hydrocarbon group; each R8is independently selected from an endblocking group and an amino-functional group, with the proviso that at least one R8per molecule is the aminofunctional group; and subscripts a, b, c, and d represent average numbers of each unit in the unit formula.

[0062] The monovalent hydrocarbon group for R4may be as described above for R1, e.g., alkyl, alkenyl, aryl, and combinations thereof (such as aralkyl and aralkenyl). For purposes ofthis application, “halogenated hydrocarbon group’’ means a hydrocarbon where one or more hydrogen atoms bonded to a carbon atom have been formally replaced with a halogen atom. Monovalent halogenated hydrocarbon groups include haloalkyl groups, halogenated aryl groups, and haloalkenyl groups. Haloalkyl groups include fluorinated alkyl groups such as trifluoromethyl (CF3), fluoromethyl, trifluoroethyl, 2-fhioropropyl, 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, 8,8,8,7,7-pentafluorooctyl, 2,2-difluorocyclopropyl, 2,3-difluorocyclobutyl, 3,4-difluorocyclohexyl, and 3,4-difhioro-5-methylcycloheptyl; and chlorinated alkyl groups such as chloromethyl, 3-chloropropyl 2,2-dichlorocyclopropyl, 2,3-dichlorocyclopentyl. Haloalkenyl groups include chloroallyl. Alternatively, each R4may be selected from alkyl and aryl. Alternatively, each R4may be selected from methyl and phenyl. Alternatively, at least 80% of all R4groups are methyl. Alternatively, each R4is methyl.

[0063] The subscripts a, b, c, and d have values such that: 2 > a > 0, 4000 > b > 0, 4000 > c > 0, and 2 > d > 0, with the provisos that a quantity (a + d) = 2, a quantity (c + d) > 2, and a quantity 4 < (a + b + c + d) < 8000. Alternatively, 4 < (a + b + c + d) < 4000. Alternatively, 10 < (a + b + c + d) < 100. Alternatively, 1000 > b > 0. Alternatively, 1000 > c > 0.

[0064] The amino-functional group for R8has formula:subscript q is 0 to 4; R is hydrogen, an alkyl group, or a hydroxyalkyl group having 1 to 4 carbon atoms; and A and A’ are each independently a linear or branched alkylene group having 1 to 6 carbon atoms and optionally containing an ether linkage. In this formula, R3and Rsare each independently a group -OR’ or an optionally substituted alkyl or aryl group. Alternatively, the group R3may be an alkyl group such as methyl and the group R3may have the formula -OR’, such as methoxy or ethoxy, where R’ is an alkyl or alkoxyalkyl group having 1 to 6 carbon atoms, for example, methyl, ethyl, butyl or methoxyethyl. Alternatively, 80% to 100% of all groups R8are amino- functional groups of the formula shown above. Without wishing to be bound by theory, when an endblocker is not used for preparing the amino-functional polydiorganosiloxane, all or substantially all of groups R8are amino-functional groups of the formula shown above. Alternatively, one or more of groups R8may have a formula derived from the endblocker, when it is used. For example, when a monoalkoxysilane is used as endblocker during preparation of the amino-functional polydiorganosloxane, some of groups R8may have formula R9sSiO-, where each R9isindependently a monovalent organic group unreactive with silanol functionality. And, when a silazane is used as endblocker, some of R8may have formula R10R] 12SiO-, where each R10is independently selected from the group consisting of a monovalent hydrocarbon group and a monovalent halogenated hydrocarbon group, each R11is an independently selected monovalent hydrocarbon group of 1 to 6 carbon atoms, where monovalent hydrocarbon groups and monovalent halogenated hydrocarbon groups are as described above for R4.

[0065] Alternatively, in the formula for the amino-functional group above, R may be hydrogen; q may be 0 or 1 ; and A and A’ (if present) each contain 2 to 4 carbon atoms. Examples of suitable amino-functional groups for R8above include -O(CH3)2Si-(CH2)3NH2, - O(CH3)2Si-(CH2)4NH2, -O(CH3)2Si-(CH2)3NH(CH2)2NH2, -O(CH3)2Si- CH2CH(CH3)CH2NH(CH2)2NH2, -O(CH3)2Si-(CH2)3NHCH2CH2NH(CH2)2NH2, -O(CH3)2Si- CH2CH(CH3)CH2NH(CH2)3NH2, -O(CH3)2Si-(CH2)3NH(CH2)4NH2, and -O(CH3)2Si- (CH2)3O(CH2)2NH2.

[0066] Suitable amino-functional polydiorganosiloxanes are known in the art and may be prepared by known methods, such as those described, for example, in US Patents 7238768, 11028229, and 11028233. Suitable amino-functional polydiorganosiloxanes are known in the art and are commercially available. For example, XIAMETER™ OFX-8040 Fluid, DOWSIL™ AP-8041 Fluid, XIAMETER™ OFX-8630 Fluid, and XIAMETER™ OFX-8822 Fluid are all commercially available from The Dow Chemical Company of Midland, Michigan, USA. The amount of amino-functional polydiorganosiloxane that may be added to the emulsion described herein depends on various factors including the amount of aminosiloxane ester copolymer in the emulsion, however the amount of the amino-functional polydiorganosiloxane may be 0 to 50% based on weight of (A) the aminosiloxane ester copolymer, alternatively > 0, alternatively at least 1%, alternatively at least 5%, while at the same time, the amount may be up to 50%, alternatively up to 40%, alternatively up to 30%, alternatively up to 20%, alternatively up to 10%, on the same basis.Co-Solvent

[0067] The co-solvent is optional, and may be present, for example, when the hydroxyfunctional aminosiloxane ester copolymer is prepared in the co-solvent. The co-solvent may be a hydrophilic glycol ether, a monohydric alcohol, or a combination thereof. Examples of suitable glycol ethers include Butyl CARBITOL™ glycol ether and Butyl CELLOSOLVE™ Solvent, which are commercially available from Dow. Examples of suitable monohydric alcohols include ethanol and isopropanol. The amount of co-solvent in the emulsion depends on various factors including the content of aminosiloxane ester copolymer in the emulsion, however, the amount of co-solvent may be 0 to 10%, alternatively > 0, alternatively at least 1%,based on combined weights of all starting materials in the emulsion; while at the same time the amount of co-solvent may be up to 10%, alternatively up to 8%, and alternatively up to 5%, on the same basis.Acid Compound

[0068] The acid compound may optionally be added to the emulsion for adjusting pH. Suitable acids include acetic acid, formic acid, propionic acid, and combinations thereof. Suitable acids for adjusting pH are disclosed, for example, in US Patent 6180117.

[0069] When selecting starting materials for use in the emulsion described above, there may be overlap between types of starting materials because certain starting materials described herein may have more than one function. When adding additional starting materials to the emulsion, the additional starting materials are distinct from one another and from the hydroxy-functioanl aminosiloxane ester copolymer, the surfactant, and the water.Method for Making the Emulsion

[0070] Emulsions may be prepared in a batch, semi-continuous, or continuous process using conventional equipment. For example, mixing the starting materials to form the emulsion may occur, for example using, batch equipment with high-shear and high-speed dispersers include those made by Charles Ross & Sons (NY), Hockmeyer Equipment Corp. (NJ); batch mixing equipment such as those sold under the tradename Speedmixer™; batch equipment with high shear actions include Banbury-type (CW Brabender Instruments Inc., NJ) and Henschel type (Henschel mixers America, TX). Illustrative examples of continuous mixers / compounders include extruders, such as single-screw, twin-screw, and multi-screw extruders, co-rotating extruders, such as those manufactured by Krupp Werner & Plleiderer Corp (Ramsey, NJ), and Leistritz (NJ); twin-screw counterrotating extruders, two-stage extruders, twin-rotor continuous mixers, dynamic or static mixers or combinations of these equipment.

[0071] The starting materials described above may be combined under any suitable conditions for forming an emulsion. For example, to simplify the mixing process and keep the emulsion viscosity low while handling, any acid compound may be added at the end of the method, i.e., once the desired dilution level is reached. However, when an optional additional starting material is used, the optional additional starting material may be added by any convenient means. Certain additional starting materials, such as the co-solvent, may be emulsified with the hydroxy-functional aminosiloxane ester copolymer, for example, when the hydroxy-functional aminosiloxane ester copolymer is prepared with the co-solvent. Other additional starting materials may be combined by mixing with the emulsion comprising the hydroxy-functional aminosiloxane ester copolymer after formation of the emulsion, e.g., when an amino-functional polydiorganosiloxane is used, the amino-functional polydiorganosiloxane may be emulsified,and the resulting emulsion may be mixed with an emulsion comprising the hydroxy-functional aminosiloxane ester copolymer, as described above. For example, 90% ± 5% of the emulsion comprising the hydroxy-functional aminosiloxane ester copolymer and 10% ± 5% of an aqueous emulsion comprising the amino-functional polydiorganosiloxanes, a surfactant, and water may be combined by mixing to form the emulsion to be used in the method for treating textiles.Method for Treating Textiles

[0072] The emulsion described above may be used in a process for treating textiles, e.g., fibers and / or fabrics. The process comprises: i) applying the emulsion described above to a textile, and ii) drying the textile.

[0073] In step i), the emulsion may be applied to the textile by any convenient method. For example, the emulsion may be applied by padding, dipping, spraying or exhausting. The emulsion may be applied to the textile during making the fiber or fabric, or later such as during laundering the textile.

[0074] The amount of emulsion applied to the textile depends on various factors including the type of textile and the amount of aminosiloxane ester copolymer in the emulsion. However, the amount of the emulsion applied to the textile may be sufficient to provide 0.2 % to 15 % of the emulsion on the textile, based on dry weight of the textile, alternatively 0.2 % to 5 %, on the same basis. Alternatively, the amount of the emulsion applied to the textile may be sufficient to deliver 0.1 % to 15 % of the hydroxy-functional aminosiloxane ester copolymer on the textile, based on dry weight of the textile. Without wishing to be bound by theory, it is thought that the amount of hydroxy-functional aminosiloxane ester copolymer to be applied on the textile depends on various factors including the desired benefit to the textile. For example, when softening is the desired benefit, the amount of the hydroxy-functional aminosiloxane ester copolymer on the textile may be 0.1 % to 0.5 %, based on dry weight of the textile. Alternatively, when oil stain release is desired, the amount of the hydroxy-functional aminosiloxane ester copolymer on the textile may be 2 % to 15 %, alternatively 2 % to 10 %, and alternatively 5 % to 10 %, each based on dry weight of the textile. Oil stain release may be measured as described in the test methods for oil stain release described in the EXAMPLES below.

[0075] After the emulsion is applied to the textile, it can be dried in step ii) by any convenient means. Drying may be performed at ambient or elevated temperature (with heating). Alternatively, drying in step ii) may comprise heating.

[0076] Suitable fibers may have the form of threads, strands, filaments, tows, or yams, and suitable fabrics include woven and nonwoven materials such as webs, mats, loop-forminglyknitted or loop-drawingly knitted. Suitable fibers may be of any natural or synthetic origin. Examples textiles, which can be treated by the process of this invention, include those of natural origin such as cotton, hemp, linen, silk, and wool; synthetics such as polyester, polyamide, polyacrylonitrile, polyolefins such as polyethylene and polypropylene, polyvinyl alcohol; interpolymers of vinyl acetate, rayon, polyurethane; manmade and / or regenerated cellulosics; and combinations and blends of two or more thereof. The textile fabrics can be present in the form of fabric webs or garments or parts of garments.EXAMPLES

[0077] The following examples are intended to illustrate the invention and are not to be construed as limiting to the scope of the invention set forth in the claims. Certain starting materials used in the Examples are described in Table 1 below, followed by characterization and evaluation procedures also used in the Examples.Table 1 - Starting Materials

[0078] In this Reference Example 1 , hydroxyl-functional aminosiloxane ester copolymer samples were prepared as follows. A terminal primary amino-functional polyorganosiloxane (TAS) and 1 ,6-hexanediol diacrylate (HDD A) were combined at a mole ratio of 1 / 1 to 2 / 1 by the process described in US Patent Application Publication 2024-0180813 to Rekken, et al. The resulting sample of aminosiloxane ester copolymer (with terminal primary amino-functional groups) was mixed with glycidol at a mole ratio equal to or less than the number of moles of NH on the TAS minus the number of moles of acrylate from the diacrylate. A solvent shown below in Table 2, if used, was then (optionally) added. The resulting mixture was stirred at ambient temperature for 30 minutes to produce a clear solution and then heated for a time (heatingduration, hours) shown below in Table 2 to give the resulting dihydroxypropyl-functional aminosiloxane ester copolymer. NMR was used to verify the consumption of the glycidol and the formation of the new dihydroxypropyl-functional aminosiloxane ester copolymer.Table 2 - Preparation of AEC Copolymers according to Reference Example 11denotes this sample was stirred at ambient temperature for 16 hr prior to heating.

[0079] In this Example 2, the aminosiloxane ester copolymer was reacted with EXCESS Glycidol. To a 3-neck flask was added, an aminosiloxane ester copolymer made from the combination of a terminal aminosiloxane (TAS) (shown above in Table 1) and 1 ,6-hexanediol diacrylate (HDDA) at a mole ratio of 1 / 1 to 2 / 1 by the process described in Reference Example 1 . The resulting aminosiloxane ester copolymer was mixed with glycidol at a mole ratio greater than the number of moles of NH on TAS (moles of NH on the hydroxyl-functional aminosiloxane ester copolymer) minus the number of moles of acrylate from the diacrylate. Moles NH = 4 * Moles TAS — 2 * Moles Alkanediol Diacrylate = Moles Glycidol The mixture was stirred at ambient temperature for 30 minutes to produce a clear solution and then heated to 50-70 °C for a time shown below in Table 3 (heating duration, hours) to give the dihydroxypropyl-substituted aminosiloxane ester copolymer. NMR was used to verify the consumption of the glycidol and the formation of the new material. However, the use of excess glycidol resulted in the reverse formation of some of the acrylate under the conditions tested in this example. The target copolymer existed in the mixture, but the value of b decreased as the NH used to react with the acrylate reformed and released the acrylate, resulting in a shorter copolymer with exposed acrylate.Table 3 - Preparation of Copolymers in Example 2

[0080] Example 3. Synthesis of Hydroxyl-Functional Aminosiloxane Ester Copolymer Samples starting from a terminal aminosiloxane (TAS). To a reaction flask was added, an aminosiloxane ester copolymer made in situ from the combination of a terminal aminosiloxane (TAS) (Table 1) and an alkanediol diacrylate such as BDDA, HDDA, and DDDA at a mole ratio of 1 / 1 to 2 / 1 in the presence of a solvent. The mixture was stirred at ambient temperature for 30 minutes and then heated for a time (under temperature and time conditions shown as Heat 1 and Time 1 in Table 4) to give the aminosiloxane ester copolymer. After heating, the mixture was allowed to cool and stir at ambient temperature overnight. Glycidol was then added at a mole ratio equal to or less than the number of moles of NH on TAS minus the number of moles of acrylate from the alkanediol diacrylate. The mixture was stirred at ambient temperature for 30 minutes and then heated for a time (under temperature and time conditions shown as Heat 2 and Time 2 in Table 4) to give the dihydroxypropyl-substituted aminosiloxane ester copolymer. After the hold, material was heated to 70 °C for 2 hours.!H,13C, and29Si NMR was used to verify the consumption of the glycidol and the formation of the new dihydroxypropyl-functional aminosiloxane ester copolymer.Table 4 - Synthesis of AEC Copolymer Samples of Example 3* = material stirred at ambient temperature over 3 days after heating.**=material was not heated to ’’Heat 1” for two hours.Example 4. In a 500 mL round bottom flask with a magnetic stir bar inerted using N2 the following were combined at ambient temperature and mixed: TAS 3 and HDDA at a 1.2 to 1 ratio, a 75% molar equivalent of glycidol relative to the molar amount of N-H on the polymer after having subtracted by the moles acrylate in HDDA [Moles glycidol = 0.75*(Moles N-H - Moles Acrylate)], butyl carbitol and isopropanol so that they consist of 5% and 1% of the total mixture, respectively. The material was stirred at ambient temperature then heated to 40°C and held for 0.75 hours. The mixture was then heated to 80 °C for 6 hours.]H,13C, and29Si NMR was used to verify the consumption of the acrylate and glycidol and the formation of dihydroxypropyl -functional aminosiloxane ester copolymer similar to what is produced in Example 3m with a similar viscosity.

[0081] Comparative Example 5. In a round bottom flask with a magnetic stir bar, TAS 5 and HDDA were added at a mole ratio of 2 to 1 and combined with IPA so that the solvent consisted of 10% of the total mixture. The flask was inerted using N2 and mixed at ambient temperature for 2 hrs and then heated to 50°C for another 2 hours. The flask was cooled and then heated to 70 °C for 6 hrs to give the intermediate polymer as a clear fluid. The next day, a 25% molar equivalent of glycidol relative to the molar amount of N-H on the polymer was added to the reaction flask at ambient temperature and after 30 minutes, warmed to 30 °C and held for 2 hrs upon which the solution became hazy. Si29NMR revealed that none of the polymer was formed. Emulsion Data

[0082] In this Reference Example 6, a copolymer, surfactant, and water in step 1 were first added to a speed mixer cup and mixed at 3500 RPM for 30 seconds in a FlackTek DAC 330-100 SE SpeedMixer. At this point, a microemulsion was formed. Additional dilution water was added to the microemulsion in a stepwise manner (steps 2 and 3) with 30-second mixing at 3500 RPM in between each dilution step to lower the emulsion viscosity. Glacial acetic acid was added to emulsion El in step 4 to reduce the emulsion pH and further tune the emulsion clarity. To provide additional stability to the emulsion, a co-surfactant was added to emulsions E2, E3, E4 in step 5. All the microemulsions were completely transparent at this point. All the emulsions were stable for at least 2 weeks at room temperature as well as in a 50 °C oven. Emulsion E4 remained transparent and stable after heat aging in a 50 °C oven for 6 weeks. Emulsion Samples El to E5 are summarized below in Table 5. Additional emulsion samples E6 to El 1 were prepared as described above, and these are summarized below in Table 6. Additional emulsion samples E12 to El 6 were prepared as described above, and these are summarized below in Table 7.

[0083] Table 5Table 6Table 7.TEST METHODS FOR OIL STAIN RELEASE

[0084] To evaluate textile treatment performance of some of the emulsions prepared as described above, each emulsion sample was applied to lab standard polyester fabric using a padding process. The fabric was dried at 160 °C for 3 minutes. After conditioning in the lab for 24 hours, 3 drops each of DI water, olive oil, and artificial sebum were placed on the fabric with a pipette. Absorption times were monitored for each drop. The stained fabric was then washed following AATCC standards, with a 90 °F wash cycle followed by a hot tumble dry. The resulting fabric samples were then observed for staining and ranked according to the release of the artificial sebum. The fabric samples were then measured using a colorimeter to determine the color change in the stained areas compared to un-stained areas. The delta E values were recorded. The lower the delta E values, the better the performance. Equipment used were as follows:Padder: Mathis Lab Padder HVF-87718, Washer / Dryer: GE GUD27ESSMWW, and Colorimeter: BYK-Gardener Spectro-guide Cat. No. 6801, Ser. No. 1067004. Table 8TEST METHOD FOR SOFTNESS

[0085] Samples of the finished textile were given to panel participants. A blank (un-finished) sample was also given to the panel. Panel participants were asked to rank the sample fabric compared to the blank from 0 to 5, with a 0 score meaning the sample fabric was the same or not as soft as the blank and increasing to a 5 score meaning the sample was much softer than the blank. Scores across the panel were averaged and are shown in Table 9Table 9 Softness compared to BlankINDUSTRIAL APPLICABILITY

[0086] The hydroxyl -functional aminosiloxane ester copolymer described herein may have one or more of the following advantages: low cyclic polyorganosiloxane content (< 0.05 % octamethylcyclo tetrasiloxane), stability after aging as evidenced by low cyclics content after aging, little or no crosslinking, and potential for biodegradability. Furthermore, the aminosiloxane ester copolymer may be miscible with organic solvents and some oils. The copolymer described herein is useful various end use applications as a replacement for conventional aminosiloxanes. For example, the copolymer may be used as an additive in leather coatings.

[0087] The hydroxyl-functional aminosiloxane ester copolymer is useful for treating textiles to impart softness and / or oil stain release. Without wishing to be bound by theory, by selecting the species and amount of hydroxyl-functional aminosiloxane ester copolymer, oil stain release can be improved for different oils (e.g., olive oil and / or sebum). The examples above demonstrate that the method for treating textiles with the emulsion of the hydroxyl-functional aminosiloxane ester copolymer of the present invention provides a fluorine-free textile treatment that imparts softness and oil stain release to textiles. For example, copolymer 1.5-AEC-85-6-75G at 10 weight % on fabric provided good oil stain release for both olive oil and sebum. Copolymer 1.1- AEC-9-6-95G provided better oil stain release for olive oil than for sebum. Copolymer 2-AEC- 85-6-75G provided better oil stain release for sebum than for olive oil.DEFINITIONS AND USAGE OF TERMS

[0088] All amounts, ratios, and percentages 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 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., IL, and III. The use of “for example,” “e.g. ” “such as,” and “including” to list illustrative examples does not limit to only the listed examples. Thus, “for example” or “such as” means “for example, but not limited to” or “such as, but not limited to” and encompasses other similar or equivalent examples. The disclosure of ranges includes the range itself and also anything subsumed therein, as well as endpoints. Similarly, the disclosure of Markush groups includes the entire group and also any individual members and subgroups subsumed therein. For example, disclosure of the Markush group a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group, includes the member alkyl individually; the subgroup alkyl and aryl; and any otherindividual member and subgroup subsumed therein. Any feature or aspect of the invention may be used in combination with any other feature or aspect recited herein. Abbreviations are as defined below in Table A.Table A - Abbreviations

Claims

CLAIMS:

1. A hydroxyl-functional aminosiloxane ester copolymer, wherein said copolymer comprises formula:where each R1is an independently selected monovalent hydrocarbon group of 1 to 12 carbon atoms, each REis an independently selected amino-functional group of formula R3N-RA-, where each R3is independently selected from the group consisting of H and a hydroxyl- functional group of formulaR4is H or OH, andR5is OH or H, with the provisos that when R4is H, then R5is OH; and when R4is OH, then Rsis H; and per molecule, at least one R3is the hydroxyl-functional group, each RAis an independently divalent hydrocarbon group of 1 to 12 carbon atoms, each R2is independently selected from the group consisting of hydrogen and methyl, each RDis an independently selected divalent hydrocarbon group of 2 to 20 carbon atoms, each subscript a independently has a value such that 0 < a < 150; and subscript b has a value such that 1 < b < 100.

2. The copolymer of claim 1 , where one or more of conditions i) to viii) are satisfied, where: condition i) is that subscript a is 2 to 145;condition ii) is that subscript b is 2 to 20; condition iii) is that each RDhas 3 to 12 carbon atoms; condition iv) is that each R2is hydrogen; condition v) is that each R1is an alkyl group of 1 to 6 carbon atoms; condition vi) is that each RAis an alkyl group of 1 to 6 carbon atoms; condition vii) is that 1 mol% to 100 mol % of R3represent the hydroxyl-functional group; and condition viii) is that the copolymer has a number average molecular weight of > 1 ,000 g / mole to 250,000 g / mol measured by gel permeation chromatography.

3. The copolymer of claim 1 or claim 2, where: each R1is methyl, each R is -(CsHe)-, each hydroxyl group has formulaeach subscript a is independently 2 to 86, and each subscript b is independently 2 to 20.

4. A method for preparing the copolymer of any one of claims 1 to 3, wherein the method comprises:(1) combining, under conditions to effect epoxy ring opening reaction, starting materials comprising(i) an aminosiloxane ester copolymer with a terminal primary amino-functional group, wherein the aminosiloxane ester copolymer has formulawhere each R1is an independently selected monovalent hydrocarbon group of 1 to 12 carbon atoms, each RAis an independently divalent hydrocarbon group of 1 to 12 carbon atoms, each R2is independently selected from the group consisting of hydrogen and methyl,each RDis an independently selected divalent hydrocarbon group of 2 to 20 carbon atoms, each subscript a independently has a value such that 0 < a < 150; subscript b has a value such that 1 < b < 100; each REis independently a primary amino-functional group of formula H2N-RA-, where RAis as described above(ii) glycidol, and optionally (iii) a solvent, with the proviso that (i) the aminosiloxane ester copolymer with the terminal aminofunctional group and (ii) the epoxy-functional alcohol are used in amounts such that a molar ratio of N-H moieties on (i) the aminosiloxane ester copolymer to epoxy moieties on (ii) the epoxy-functional alcohol (N-H / Epoxy mol ratio) is > 1 / 1.

5. The method of claim 4, wherein in the formula for (i) the hydroxyl-functional aminosiloxane ester copolymer, one or more of conditions i) to vii) are satisfied, where condition i) is that each subscript a is independently 2 to 145; condition ii) is that subscript b is 2 to 20; condition iii) is that each RDhas 3 to 12 carbon atoms; condition iv) is that each R2is hydrogen; condition v) is that each R1is an alkyl group of 1 to 6 carbon atoms; condition vi) is that each RAis an alkyl group of 1 to 6 carbon atoms; and condition vii) is that each REis independently a primary amino-functional group of formula H2N-RA-, where RAin this primary amino-functional group is ethylene, propylene, or butylene.

6. The method of claim 4 or claim 5, further comprising: (2) recovering the hydroxyl- functional aminosiloxane ester copolymer during and / or after step (1).

7. An emulsion comprising:(I) a liquid continuous phase comprising water, and(II) a discontinuous phase dispersed in the liquid continuous phase, where the discontinuous phase comprises the hydroxyl-functional aminosiloxane ester copolymer of any one of claims 1 to 3.

8. The emulsion of claim 7, where the emulsion further comprises an additional starting material selected from the group consisting of (H) a surfactant, (I) an acid compound, (J) an acidanhydride, (K) a thickener, (L) a stabilizer, and a combination of two or more of (H), (I), (J), (K), and (L).

9. A method for preparing an emulsion, the method comprising: mixing under shear starting materials comprising the hydroxyl-functional aminosiloxane ester copolymer of any one of claims 1 to 3, water, and optionally one or more starting material selected from the group consisting of (H) a surfactant, (I) an acid compound, (J) an acid anhydride, (K) a thickener, (L) a stabilizer.

10. The emulsion of claim 7, wherein the emulsion further comprises an additional starting material selected from the group consisting of an amino-functional polydiorganosiloxane, a cosolvent, an acid compound, an acid anhydride, a thickener, a stabilizer, a preservative, a brightener, a perfume, a perfume delivery system, a pH adjuster, a solvent, a co-solvent, a dispersant, a catalytic material, a fabric softener, a processing aid, and a combination of two or more thereof.

11. A method for treating a textile, wherein the method comprises: i) applying the emulsion of any one of claims 7, 8, or 10 to a textile, and ii) drying the textile.

12. The method of claim 11, wherein the textile comprises polyester.

13. The method of claim 11 or claim 12, wherein the emulsion is applied to the textile in an amount sufficient to provide 2 weight % to 10 weight % of the hydroxyl-functional aminosiloxane ester copolymer on the textile, based on dry weight of the textile.

14. The method of any one of claims 11 to 13, wherein drying in step ii) comprises heating.

15. The method of any one of claims 1 1 to 14, wherein one or more of conditions i) to vii) are satisfied: condition i) is that subscript a is 8 to 90; condition ii) is that subscript b is 2 to 20; condition iii) is that each RDhas 3 to 12 carbon atoms; condition iv) is that each R2is hydrogen; condition v) is that each R1is an alkyl group of 1 to 6 carbon atoms; condition vi) is that each RAis an alkyl group of 1 to 6 carbon atoms;condition vii) is that 75 mol% to 95 mol % of R3represent the hydroxyl-functional group; and condition viii) is that the copolymer has a number average molecular weight of > 1 ,000 g / mole to 250,000 g / mol measured by gel permeation chromatography.

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