Textile treatment with silicone – (METH)acrylate (CO)polymer, poly[poly(alkylene glycol) (METH)acrylate], and blocked isocyanate

Abstract

A textile treatment emulsion includes a combination of actives; namely a silicone – (meth)acrylate copolymer, a poly(alkylene glycol (meth)acrylate copolymer), and a blocked isocyanate. The textile treatment emulsion can be applied to fabric and dried to impart oil repellency to the fabric.

Description

TEXTILE TREATMENT WITH SILICONE - (METH)ACRYLATE (CO)POLYMER, POLY[POLY( ALKYLENE GLYCOL) (METH) ACRYLATE], AND BLOCKED ISOCYANATECROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority under 35 USC § 1 19(e) to US Provisional Patent Application Number 63 / 593716 filed on 27 October 2023, US Provisional Patent Application Number 63 / 674322 filed on 23 July 2024; US Provisional Patent Application Number 63 / 674323 filed on 23 July 2024, US Provisional Patent Application Number 63 / 674325 filed on 23 July 2024, US Provisional Patent Application Number 63 / 674328 filed on 23 July 2024, and US Provisional Patent Application Number 63 / 674329 filed on 23 July 2024. US Provisional Patent Application Numbers 63 / 593716, 63 / 674322, 63 / 674323, 63 / 674325, 63 / 674328, and 63 / 674329 are hereby incorporated by reference.FIELD

[0002] A textile treatment emulsion contains a combination of actives comprising a silicone - (meth)acrylate (co)polymer, a poly[poly(alkylene glycol) (meth) acrylate], and a blocked isocyanate. The emulsion is useful for imparting oil repellency to textiles.INTRODUCTION

[0003] Per- and Polyfluorinated Substances (PFAS) dominated the textile coating market for many years; however, customers and regulatory bodies desire the elimination of PFAS due to environmental regulations. There is an ongoing need in the textiles industry to find an alternative to PFAS that imparts oil repellency to textiles and that is compatible with the current capital infrastructure because plasma treatments and engineered surface structures typically cannot be done at mills with existing equipment.

[0004] W02023019044 discloses a silicone - (meth)acrylate copolymer emulsion that can impart water repellency to textiles. However, this publication does not address oil repellency.SUMMARY

[0005] A textile treatment emulsion comprises a silicone - (meth)acrylate (co)polymer, a poly[poly(alkylene glycol) (meth)acrylate], a blocked isocyanate, a surfactant, and water. The textile treatment emulsion can be applied to fabric and dried to impart oil repellency to the fabric.DETAILED DESCRIPTION

[0006] The textile treatment emulsion introduced above comprises a combination of actives, i.e., the silicone - (meth)acrylate (co)polymer, the poly[poly(alkylene glycol) (meth)acrylate], and the blocked isocyanate. The silicone - (meth) acrylate (co)polymer and thepoly | poly (alkylene glycol) (meth)acrylatel may be discrete molecules, or may be copolymerized together, or may be a combination of both. For example, discrete molecules may be combined by physically mixing an aqueous emulsion comprising the silicone - (meth)acrylate (co)polymer and an aqueous composition comprising the poly[poly(alkylene glycol) (meth) aery late]. For example, the silicone - (meth)acrylate (co)polymer may comprise unit formula:, wherein each R1is an independently selected monovalent hydrocarbon group of 1 to 12 carbon atoms; each D2is an independently selected divalent hydrocarbon group of 2 to 12 carbon atoms; each R2is independently selected from the group consisting of H and methyl; subscripts a and b represent weight fractions of units in the silicone - (meth)acrylate (co)polymer, and subscripts a and b have values such that 0.25 < a < 1, and 0 < b < 0.75. A quantity (a + b) = 1, based on combined weights of the macromonomers used to prepare the silicone - (meth)acrylate (co)polymer, as described below. The silicone - (meth)acrylate (co)polymer may have a weight average molecular weight measured by GPC of > 181,000 g / mol. Alternatively, the silicone - (meth)acrylate (co)polymer may have a weight average molecular weight measured by GPC of at least 200,000 g / mol, alternatively at least 210,000 g / mol, alternatively at least 212,000 g / mol, alternatively at least 225,000 g / mol, alternatively at least 230,000 g / mol, and alternatively at least 234,000 g / mol; while at the same time, weight average molecular weight may be up to 2,000,000 g / mol; alternatively up to 1,000,000 g / mol; alternatively up to 950,000 g / mol; alternatively up to 925,000 g / mol; alternatively up to 912,000 g / mol, alternatively up to 900,000 g / mol, alternatively up to 850,000 g / mol; alternatively up to 800,000 g / mol; alternatively up to 750,000 g / mol; and alternatively up to 721,000 g / mol. Alternatively, the silicone - (meth)acrylate (co)polymer may have a weight average molecular weight of 212,000 g / mol to 912,000 g / mol, measured by GPC. The samples for GPC analysis may be prepared in THF eluent at concentration 10 mg / mL copolymer. The solution may be shaken on a flat-bed shaker at ambient temperature for 2 hours. The solution may then be filtered through a 0.45 m PTFE syringe filter prior to injection. A Waters e2695 LC pump and autosampler, equipped with two 5 uM Agilent PLG gel Mixed C columns in series and Shodex RI501 differential refractive index detector was used to analyze the samples. The instrument was equilibrated for 30 min at 1 mL / min and samples were run at 1 mL / min. AgilentGPC software Cirrus version 3.3 may be used for data collection and for data reduction. A total of 16 PS linear narrow molecular weight standards from Agilent having Mp values from 3750 to 0.58 kg / mol may be used for molecular weight calibration. A 3rdorder polynomial was used for calibration curve fitting. Thus, all molecular weight averages, distributions and references to molecular weight provided in this report are polystyrene equivalent values.

[0007] One skilled in the art would recognize that the silicone - (meth) acrylate (co)polymer above may be prepared by radical polymerization, via a method as described below, and that this method would form a terminal moiety for the silicone - (meth)acrylate (co)polymer. The silicone - (meth)acrylate (co)polymer with the unit formula above further comprises a terminal moiety which may be derived from an initiator, a chain transfer agent, or both, as described, for example in Odian, George (2004). Principles of Polymerization (4th ed.). New York: Wiley- Interscience. ISBN 978-0-471-27400-1.

[0008] The silicone - (meth)acrylate (co)polymer may be prepared via a method comprising:1) polymerizing starting materials comprising: (A) a silicone - (meth) acrylate macromonomer of formulaeach R1is an independently selected monovalent hydrocarbon group of 1 to 12 carbon atoms; D2is a divalent hydrocarbon group of 2 to 12 carbon atoms; and R2is selected from the group consisting of H and methyl; and optionally (B) a silicone - (meth) acrylate co-macromonomer of formulaeach R1is an independently selected monovalent hydrocarbon group of 1 to 12 carbon atoms; D2is a divalent hydrocarbon group of 2 to 12 carbon atoms; and R2is selected from the group consisting of H and methyl.

[0009] To make the silicone - (meth)acrylate (co)polymer, starting material (A) is present in an amount of > 25 weight % to 100 weight %, based on combined weights of starting materials (A) and (B); and starting material (B) is present in an amount of 0 to < 75 weight %, based on combined weights of starting materials (A) and (B). Starting materials (A) and (B) are polymerized in the presence of an additional starting material, wherein the additional starting material comprises (C) an initiator. The additional starting material used in step 1) mayoptionally further comprise one or more of (H) a chain transfer agent; (I) a manganese ion source; (J) a phenolic compound; and a chelating agent.

[0010] Step 1) of the method for making the silicone - (meth)acrylate (co)polymer may comprise an emulsion polymerization reaction. The additional starting materials used in this emulsion polymerization method further comprise (D) a surfactant and (E) water. In step 1), the emulsion polymerization described above may comprise forming an emulsion comprising starting material (A) the silicone - (meth)acrylate macromonomer, (B) the silicone - (meth)acrylate co-macromonomer (when present), (D) the surfactant, (E) water, and optionally one or more of (H) the chain transfer agent, (I) the manganese ion source, and (J) the phenolic compound and thereafter adding (C) the initiator and copolymerizing. Optionally, the poly [poly (alkylene glycol) (meth)acrylate], which is described further below, may also be present, e.g., the poly[poly(alkylene glycol) (meth)acrylate] may be dissolved in the water used for the emulsion polymerization to make the silicone - (meth) acrylate (co)polymer. Alternatively, the poly(alkylene glycol) (meth) acrylate macromonomer, which is described further below, may also be present, e.g., the poly(alkylene glycol) (meth)acrylate macromonomer may be dissolved in the water used for the emulsion polymerization to make the silicone - (meth)acrylate (co)polymer, and optionally the poly(alkylene glycol) (meth)acrylate macromonomer may be polymerized during the formation of the silicone - (meth)acrylate (co)polymer. Without wishing to be bound by theory, it is thought that during processing to combine and emulsify (A) the silicone - (meth)acrylate macromonomer, (D) the surfactant, and(E) the water, and when present (B) the silicone - (meth)acrylate co-macromonomer, (H) the chain transfer agent, and / or the poly [poly (alkylene glycol) (meth)acrylate] ; starting materials (I) the manganese ion source and / or (J) the phenolic compound may inhibit formation of acrylic radicals that can impact the formation of the silicone - (meth)acrylate (co)polymer during copolymerization in step 1). These starting materials may be mixed under shear to form i) an aqueous copolymer emulsion. Mixing under shear may be performed by any convenient means for forming an aqueous emulsion, such as sonication and with subsequent microfluidization. Equipment for mixing under shear, such as rotor-stators, sonolators, sonicators, homogenizers, microfluidizers, and speedmixers are known in the art and are commercially available. Without wishing to be bound by theory, it is thought that mixing under shear may be used to obtain a submicron particle size in the emulsion. In step 1), starting materials comprising (A) the silicone - (meth)acrylate macromonomer, (B) the silicone - (meth) acrylate co-macromonomer (when present), (C) the initiator (and when present (H) the chain transfer agent) copolymerize to form(F) the silicone - (meth)acrylate (co)polymer, thereby forming starting material z) an aqueous copolymer emulsion, which comprises (F) the silicone - (meth)acrylate (co)polymer, (D) thesurfactant, and (E) the water, and optionally (1) manganese ion source and (J) the phenolic compound (when used), and optionally the poly[poly(alkylene glycol) (meth)acrylate] and / or the poly (alkylene glycol) (meth)acrylate macromonomer (when present).

[0011] The method described herein may optionally further comprise one or more additional steps. For example, before step 1) the starting materials comprising (A) the silicone - (meth)acrylate macromonomer and, when present, (B) the silicone - (meth)acrylate co- macromonomer and / or (H) the chain transfer agent may be combined under aerobic or anaerobic conditions, optionally with heating for extended times. For example, the starting materials comprising (A) the silicone - (meth) acrylate macromonomer and (B) the silicone - (meth) acrylate co-macromonomer, and when present one or more of (H) the chain transfer agent, (I) manganese ion source, and / or (J) the phenolic compound, may be emulsified with (D) the surfactant and (E) the water before adding (C) the initiator and polymerizing in step 1). In step 1), combining the starting materials and polymerizing in the method described above may be performed on a commercial scale under anaerobic or aerobic conditions optionally at elevated temperature, e.g., up to 100 °C, alternatively 25 °C to 60 °C, alternatively 40 °C to 80 °C, and alternatively 45 °C to 50 °C. Polymerizing may be performed in a batch process with a residence time of 15 minutes to 48 hours, alternatively 30 minutes to 12 hours, alternatively 40 minutes to 8 hours, and alternatively 40 minutes to 2 hours. For purposes of this application, aerobic or anaerobic conditions means that oxygen is not required to be present in the gas in the headspace of the reactor where polymerizing takes place, or dissolved in the liquid where polymerizing takes place. The balance of the gas in the headspace could be an inert gas such as nitrogen or argon. Anaerobic conditions means that the gas in the headspace contains no more than 2% oxygen.

[0012] Alternatively, the silicone - (meth)acrylate (co)polymer described above may be prepared by a method comprising dissolving one or more of the starting materials, such as (A) the silicone - (meth) acrylate macromonomer, and optionally one or more of (B) the silicone - (meth) acrylate co-macromonomer, (H) the chain transfer agent, (I) the manganese ion source, and (J) the phenolic compound, in an organic solvent (such as a monohydric alcohol) and polymerizing starting materials (A) the silicone - (meth) acrylate macromonomer and when present (B) the silicone - (meth) acrylate co-macromonomer and (H) the chain transfer agent in a method such as that disclosed in US Patent 10047199 to limura et al. by varying appropriate starting materials and their amounts. The resulting silicone - (meth) acrylate (co)polymer may be solvent borne. All or a portion of the solvent may be removed by any convenient means, such as by stripping or distillation with heat and optionally reduced pressure. The resulting silicone - (meth)acrylate (co)polymer may be emulsified using (D) the surfactant and (E) the water.

[0013] Regardless of the method used to make the silicone - (meth)acrylate (co)polymer, e.g. , either via emulsion polymerization or by emulsifying the silicone - (meth)acrylate (co)polymer prepared in solvent (after solvent removal), the product prepared in step 1) is starting material i) the aqueous copolymer emulsion, which comprises (F) the silicone - (meth)acrylate (co)polymer, (D) the surfactant, and (E) the water. Starting material i) the aqueous (co)polymer emulsion may optionally further comprise (I) the manganese ion source and / or (J) the phenolic compound. The starting materials used in the method for making z ) the aqueous (co)polymer emulsion are further described below.

[0014] Starting material (A) used herein is a silicone - (meth) acrylate macromonomer. The silicone - (meth)acrylate macromonomer has formula (A-l):each R1is an independently selected monovalent hydrocarbon group of 1 to 12 carbon atoms; D2is a divalent hydrocarbon group of 2 to 12 carbon atoms; and R2is selected from the group consisting of H and methyl.

[0015] In formula (A-l), each R1is an independently selected monovalent hydrocarbon group of 1 to 12 carbon atoms. The monovalent hydrocarbon group for R1may be an alkyl group, such as an alkyl group of 1 to 6 carbon atoms. Alternatively, the alkyl groups may have 1 to 3 carbon atoms, alternatively 1 to 2 carbon atoms. Alternatively, each R1group may be methyl.

[0016] In formula (A-l), D2is a divalent hydrocarbon group of 2 to 12 carbon atoms. Alternatively, D2may have 2 to 10, alternatively 3 to 5, and alternatively 3 carbon atoms. The divalent hydrocarbon group for D2may be exemplified by an alkylene group such as ethylene, propylene, or butylene. Alternatively, the divalent hydrocarbon group for D2may be propylene. Alternatively, D2may be linear, e.g., -(CH2)2- or -(CH2)3-. Alternatively, D2may be (CH2)3-. Alternatively, when D2comprises -(CHifs-, starting material (A) comprises formula (A-2):described above.

[0017] Starting material (A) may comprise 3-(l,l,l,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl methacrylate of formulaStarting material (A) may be prepared by known methods, such as those disclosed in US Patent Application Publication US20220112322 and US Patent 6420504, both of which are hereby incorporated by reference.

[0018] Starting material (B) is a silicone - (meth) aery late co-macromonomer (co- macromonomer) that may optionally be copolymerized with (A) the silicone - (meth)acrylate macromonomer described above. Starting material (B), the co-macromonomer may comprise formula, wherein each R1is an independently selected monovalent hydrocarbon group of 1 to 12 carbon atoms; D2is a divalent hydrocarbon group of 2 to 12 carbon atoms; and R2is selected from the group consisting of H and methyl, each as described and exemplified above for formula (A-l). Alternatively, when D2comprises -(CH213-, the co-macromonomer may comprise:are as described above. Alternatively, the co-macromonomer may comprise 3-(l, 1, 1,3, 5,5,5- heptamethyltrisiloxan-3-yl)propyl methacrylate of formula

[0019] Starting material (A) the silicone - (meth)acrylate macromonomer, and starting material (B) the silicone - (meth)acrylate co-macromonomer are used in the following amounts when making the silicone - (meth)acrylate (co)polymer: starting material (A) is used in an amount of 25 weight % to 100 weight %, based on combined weights of starting materials (A)and (B); and starting material (B) is used in an amount of 0 to 75 weight %, based on combined weights of starting materials (A) and (B). Alternatively, starting material (A) may be used in an amount > 25 %, alternatively at least 40 %, alternatively at least 50%, alternatively at least 63%, and alternatively at least 75%, based on combined weights of starting materials (A) and (B); while at the same time the amount of starting material (A) may be up to 100%, alternatively up to 99%, alternatively up to 95%, alternatively up to 75%, alternatively up to 63%, alternatively up to 50%, and alternatively up to 40%, on the same basis. Alternatively, the amount of starting material (A) may be 100%, and the amount of starting material (B) may be 0. Alternatively, starting material (B) may be present, and the amount of starting material (B) may be > 0%, alternatively at least 1%, alternatively up to 5%, alternatively up to 10%, alternatively up to 15%, alternatively up to 20%, and alternatively at least 25%; while at the same time the amount of starting material (B) may be up to 60%, alternatively up to 50%, alternatively up to 37%, and alternatively up to 25%, on the same basis.

[0020] The starting materials used to make the silicone - (meth)acrylate (co)polymer may optionally be free of crosslinkable groups, for example, the starting materials that polymerize in step 1) of the method described herein may be free of crosslinkable (meth)acrylate monomers such as organic (meth) acrylate monomers having crosslinkable groups. For example, the starting materials used in step 1) may be free of crosslinkable (meth)acrylate monomers such as organic (meth)acrylate monomers having crosslinkable groups exemplified by (2- acetoacetoxy)ethyl methacrylate, hydroxybutyl (meth) acrylate, hydroxyethyl (meth)acrylate, hydroxyethylcaprolactone (meth)acrylate, hydroxypropyl (meth)acrylate, ureido (meth)acrylate, glycidyl (meth)acrylate (GMA). The starting materials used in step 1) may be free of organosilyl monomers having crosslinkable groups, such as alkenyltrialkoxysilanes (e.g., 3- (trimethoxysilyl)propyl (meth)acrylate, vinyltriethoxysilane and vinyltrimethoxysilane).

[0021] Alternatively, the starting materials used in the method described herein, which forms the silicone - (meth) acrylate (co)polymer may optionally include a crosslinkable (meth)acrylate monomer such as a poly(alkylene glycol) (meth)acrylate macromonomer, as described further below.

[0022] Starting material (A), and when present starting material (B) are polymerized in the presence of an additional starting material. The additional starting material comprises (C) an initiator. Alternatively, the starting materials that polymerize in step 1) may consist of starting materials (A) the macromonomer, (B) the co-macromonomer, and (C) the initiator, and when present (H) the chain transfer agent. Alternatively, the starting materials used in step 1) may consist essentially of, or may consist of, (A) the macromonomer, (B) the co-macromonomer, (C) the initiator, (D) the surfactant, and (E) the water, and when present (H) the chain transfer agent,(1) the manganese ion source, and (J) the phenolic compound, and these starting materials are described further below.

[0023] Starting material (C), the initiator, is also added in step 1) of the method for making the silicone - (meth) acrylate (co)polymer described above. Suitable initiators include azo compounds and peroxide compounds. For example, the azo compound may be an aliphatic azo compound such as 1 -t-amylazo-1- cyanocyclohexane, azo-bis-isobutyronitrile and 1-t-butylazo- cyanocyclohexane, 2,2’-azo- bis-(2-methyl)butyronitrile, 2,2’-azobis(2-methylpropionitrile), 2,2’-azobis(2-methylpropionamidine) dihydrochloride, 2,2’-azobis(cyanovaleric acid), or a combination of two or more thereof. Azo compounds are known in the art and are commercially available, e.g., under the tradename VAZO™ WSP from The Chemours Company of Wilmington, Delaware, USA. The peroxide compound may be a peroxide or a hydroperoxide, such as t-butylperoctoate, t-butyl perbenzoate, dicumyl peroxide, di-t-butyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, di-t-amyl peroxide and combinations of two or more thereof. Additionally, di-peroxide initiators may be used alone or in combination with other initiators. Such di -peroxide initiators include, but are not limited to, l,4-bis-(t-butyl peroxycarbo)cyclohexane, 1 ,2-di(t-butyl peroxy)cyclohexane, and 2,5-di(t-butyl peroxy)-3- hexyne. Suitable peroxide compounds are known in the art and are commercially available from various sources, such as Sigma-Aldrich, Inc. of St. Louis, Missouri, USA. Alternatively, the initiator may comprise isoascorbic acid.

[0024] An initiator may be used alone as starting material (C). Alternatively, starting material (C) may be a redox pair, which comprises an initiator as the oxidizing component and a reducing component. Alternatively, a redox pair including isoascorbic acid and an organic hydroperoxide such as t-amyl hydroperoxide or t-butyl hydroperoxide may be used as starting material (C). Examples of suitable initiators and / or redox pairs for starting material (C) are disclosed in US Patent 6576051 to Bardman et al., beginning at col. 11, line 16. How the initiator is added depends on various factors including whether the initiator is water soluble and the type of initiator (e.g., whether a thermal initiator or a redox pair is used). Typically, when a thermal initiator is used, all the initiator is added at once at the beginning of step 1). Alternatively, when a redox pair is used, it may be metered in over time.

[0025] Alternatively, the initiator may optionally further comprise iron(II) sulfate heptahydrate, potassium persulfate, or a combination thereof. The initiator (C) may be used in an amount sufficient to provide 0.01% to 3%, alternatively 0.1% to 1.5%, based on weight of (F) the silicone - (meth) acrylate (co)polymer.

[0026] Starting material (D) is a surfactant. The surfactant may be selected from the group consisting of (D-l) a cationic surfactant, (D-2) a nonionic surfactant, and (D-3) a combination ofboth the cationic surfactant and the nonionic surfactant. Cationic surfactants useful herein include compounds containing quaternary ammonium hydrophilic moieties in the molecule which are positively charged, such as quaternary ammonium salts, which may be represented by formula (D-l-1): R12R13R14R1SN+X’_where R12to R15are alkyl groups containing 1-30 carbon atoms, or alkyl groups derived from tallow, coconut oil, or soy; and X’ is a halogen, e.g., chlorine or bromine. Alternatively, the quaternary ammonium compounds may be alkyl trimethylammonium and dialkyldimethylammonium halides, or acetates, having at least 8 carbon atoms in each alkyl substituent. Dialkyl dimethyl ammonium salts can be used and are represented by formula (D-l-2): R16R17N+(CH3)2X’_where R16and R17are alkyl groups containing 12-30 carbon atoms or alkyl groups derived from tallow, coconut oil, or soy; and X’ is halogen. Monoalkyl trimethyl ammonium salts can be used and are represented by formula (D-l-3): R18N+(CH3 3X”‘ where R18is an alkyl group containing 12-30 carbon atoms or an alkyl group derived from tallow, coconut oil, or soy; and X” is halogen or acetate.

[0027] Representative quaternary ammonium halide salts are dodecyltrimethyl ammonium chloride / lauryltrimethyl ammonium chloride (LTAC), cetyltrimethyl ammonium chloride (CTAC), hexadecyltrimethyl ammonium chloride, didodecyldimethyl ammonium bromide, dihexadecyldimethyl ammonium chloride, dihexadecyldimethyl ammonium bromide, dioctadecyldimethyl ammonium chloride, dieicosyldimethyl ammonium chloride, and didocosyldimethyl ammonium chloride. These quaternary ammonium salts are commercially available under trademarks such as ADOGEN™, ARQUAD™, TOMAH™, and VARIQUAT™.

[0028] Other suitable cationic surfactants which can be used include fatty acid amines and amides and their salts and derivatives, such as aliphatic fatty amines and their derivatives. Such cationic surfactants that are commercially available include compositions sold under the names ARQUAD™ T27 W, ARQUAD™ 16-29, by Akzo Nobel Chemicals Inc., Chicago, Illinois; and Ammonyx Cetac-30 by the Stepan Company, Northfield, Illinois, USA.

[0029] The amount of (D-l) the cationic surfactant may be 0.1% to 5%, based on weight of the silicone - (meth)acrylate (co)polymer in i) the aqueous (co)polymer emulsion. Alternatively, the amount of cationic surfactant may be at least 0.1%, alternatively at least 0.2%, alternatively at least 0.3%, alternatively at least 0.4%, alternatively at least 0.5%; while at the same time the amount of cationic surfactant may be up to 5%, alternatively up to 4%, alternatively up to 3%, alternatively up to 2%, alternatively up to 1%, on the same basis. Alternatively, the amount of cationic surfactant may be 0.2% to 4%, alternatively 0.3% to 3%, alternatively 0.4% to 2.5%, and alternatively 0.5% to 2%; on the same basis.

[0030] Starting material (D-2) is a nonionic surfactant. Some suitable nonionic surfactantswhich can be used include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, alkylglucosides, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, and polyoxyethylene sorbitan fatty acid esters. Nonionic surfactants which are commercially available include compositions such as (i) 2,6,8-trimethyl-4-nonyl polyoxyethylene ether sold under the names TERGITOL™ TMN-6 and TERGITOL™ TMN-10; (ii) the Cl 1-15 secondary alkyl polyoxyethylene ethers sold under the names TERGITOL™ 15-S-7, TERGITOL™ 15-S- 9, TERGITOL™ 15-S-15, TERGITOL™ 15-S-30, and TERGITOL™ 15-S-40, by the Dow Chemical Company, of Midland, Michigan, USA; octylphenyl polyoxyethylene (40) ether sold under the name TRITON™ X405 by the Dow Chemical 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 and BRIJ™ L4 by Croda Inc. of Edison, New Jersey, USA, (vi) alkyl-oxo alcohol poly glycol ethers such as GENAPOL™ UD 050, and GENAPOL™ UDI 10, and (vii) alkyl polyethylene glycol ether based on ClO-Guerbet alcohol and ethylene oxide such as LUTENSOL™ XP 79.

[0031] Suitable nonionic surfactants also include poly(oxyethylene)-poly(oxypropylene)- poly (oxy ethylene) 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.

[0032] Other suitable nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenol ethers, polyoxyethylene lauryl ethers, 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, and polyoxyalkylene glycol modified polysiloxane surfactants. Commercially available nonionic surfactants which can be used include compositions such as 2,6,8-trimethyl-4-nonyloxy polyethylene oxyethanols (6EO) and (10EO) sold under the trademarks TERGITOL™ TMN-6 and TERGITOL™ TMN-10; alkyleneoxy polyethylene oxyethanol (Ci 1-15 secondary alcohol ethoxylates 7EO, 9EO, and 15EO) sold under the trademarks TERGITOL™ 15-S-7, TERGITOL™ 15-S-9, TERGITOL™ 15-S-15; other C ii-i5 secondary alcohol ethoxylates sold under the trademarks TERGITOL^^ 15-S-12, 15-S-20, 15-S-3O, 15-S-40; octylphenoxy polyethoxy ethanol (40EO) sold under thetrademark TRITON™ X-405; and alcohol ethoxylates with tradename ECOSURF™ EH, such as ECOSURF™ EH-40. All of these surfactants are sold by the Dow Chemical Company.

[0033] Other useful commercial nonionic surfactants are nonylphenoxy polyethoxy ethanol (10EO) sold under the trademark MAKON™ 10 by Stepan Company; polyoxyethylene 23 lauryl ether (Laureth-23) sold commercially by Sigma Aldrich, Inc.; and RENEX™ 30, a polyoxyethylene ether alcohol available from Fisher Scientific.

[0034] The nonionic surfactant may also be a silicone polyether (SPE). The silicone polyether as an emulsifier may have a rake type structure wherein the polyoxyethylene or polyoxyethylene-polyoxypropylene copolymeric units are grafted onto the siloxane backbone, or the SPE can have an ABA block copolymeric structure wherein A represents the polyether portion and B the siloxane portion of an ABA structure. Suitable SPE’s include DOWSIL™ OFX-5329 Fluid from The Dow Chemical Company. Alternatively, the nonionic 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 copolymer 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.

[0035] Starting material (D-2) the nonionic surfactant may be delivered in a dilution, and the amount used may be sufficient to provide 0.1% to 12% of the surfactant, based on weight of the silicone - (meth)acrylate (co)polymer in i) the aqueous (co)polymer emulsion. Alternatively, the amount of nonionic surfactant may be at least 0.1%, alternatively at least 0.2%, alternatively at least 0.3%, alternatively at least 0.4%, alternatively at least 0.5%, alternatively at least 1%, alternatively at least 2%, alternatively at least 3%, alternatively at least 4%; while at the same time the amount of nonionic surfactant may be up to 10%, alternatively up to 9%, alternatively up to 8%, alternatively up to 7%, alternatively up to 5%, alternatively up to 4%, alternatively up to 3%, alternatively up to 2%, alternatively up to 1%, on the same basis. Alternatively, the amount of nonionic surfactant may be 1% to 10%, alternatively 2% to 10%, alternatively 3 to 10%, alternatively 5% to 9%, alternatively 6% to 8%, and alternatively 7%; on the same basis. Alternatively, starting materials (D-l) the cationic surfactant and (D-2) the nonionic surfactant may be present in combined amounts < 10%, based on weight of the silicone - (meth)acrylate (co)polymer in the i ) aqueous (co)polymer emulsion.

[0036] Starting material (E) is water. The water is not generally limited, for example, the water may be processed or unprocessed. 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 beunprocessed (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 contain the poly[poly(alkylene glycol) (meth) aery late], prepared as described below, when the poly[poly(alkylene glycol) (meth)acrylate] is prepared before the silicone - (meth)acrylate (co)polymer is formed. The amount of water is sufficient to form an aqueous emulsion for emulsion polymerization in step 1) of the method for making the silicone - (meth)acrylate (co)polymer described above. Additional water may be added after step 1). For example, the aqueous (co)polymer emulsion prepared as described above may be diluted with additional water to achieve a desired amount of starting materials. The water may be added in an amount of 10% to 97%, alternatively 30% to 90%, alternatively 40% to 80%, alternatively 50% to 97%, alternatively 50% to 90%, and alternatively 60% to 80%; based on combined weights of all starting materials in step 1). Alternatively, the water may be added in an amount of at least 20%, alternatively at least 30%, alternatively at least 40%, alternatively at least 50%, and alternatively at least 60%; while at the same time the amount of water may be up to 97%, alternatively up to 96%, alternatively up to 95%, and alternatively up to 80%, on the same basis.

[0037] The silicone - (meth) acrylate (co)polymer, (F), may be prepared by emulsion polymerization of starting materials comprising (A) the macromonomer and (C) the initiator (and optionally (B) the co-macromonomer) described above. Alternatively, the silicone - (meth) acrylate (co)polymer may be a reaction product of starting materials consisting essentially of starting materials (A) the macromonomer and (C) the initiator (and when present, (B) the co- macromonomer and / or (H) the chain transfer agent). Alternatively, the silicone - (meth)acrylate (co)polymer may be a reaction product of starting materials consisting of starting materials (A) and (C), (and, when present, (B) and / or (H)). Without wishing to be bound by theory, it is thought that none of starting materials (D) the surfactant, (E) the water, (I) the manganese ion source, and (J) the phenolic compound, copolymerize with starting materials (A) and (C), (and when present (B) and / or (H)), but that starting materials (D) and (E) merely serve as a vehicle for polymerization. However, nothing herein shall exclude the possibility that a portion of one or more of starting materials (D) and / or (E), or any other starting material added during the method, may participate in the polymerization reaction of starting materials comprising (A) and (C), and any optional starting materials (e.g., starting materials (B) and / or (H)), when present.

[0038] The method described above may optionally comprise step 2) adding an additional starting material. The additional starting material may be selected from the group consisting of (K) a biocide, (L) additional water (which may be the same as starting material (E)), (M) a flame retardant, (N) a wrinkle reducing agent, (O) an antistatic agent, (P) a penetrating agent, (Q) an additive such as a softening agent, (R) a catalyst, such as a condensation reaction catalyst, and acombination of two or more thereof. Step 2) of this method may optionally further comprise adding additional (D) surfactant.

[0039] An additional starting material that may be added in step 1) of the method described above comprises (H) a chain transfer agent. Suitable chain transfer agents include mercaptans such as alkyl mercaptans, e.g., n-octyl mercaptan, n-dodecyl mercaptan, dodecyl mercaptan (dodecane thiol), and / or 2,2-dimethyldecyl mercaptan. Alternatively, the chain transfer agent may be water soluble, such as mercaptoacetic acid and / or 2-mercaptoethanol. Suitable chain transfer agents are known in the art and have been disclosed, for example, in “Radical Polymerization in Industry” by Peter Nesvadba, Performance Chemical Research, BASF Schweiz AG, Basel, Switzerland, Encyclopedia of Radicals in Chemistry, Biology and Materials, Online © 2012 John Wiley & Sons, Ltd. Starting material (H) is optional and may be added in an amount of 0 to 1%, based on combined weights of starting material (A), and when present starting material (B). Alternatively, (H) the chain transfer agent may be used in an amount of 0.5% to 0.6% on the same basis.

[0040] Starting material (I) is an optional manganese ion source, which may be a manganese (III) compound or a manganese (II) compound. Alternatively, starting material (I) may be a manganese (II) compound. Suitable manganese (II) compounds include manganese (II) acetate, manganese (II) nitrite, manganese (II) propionate, manganese (II) oxide, manganese (II) hydroxide, manganese (II) chloride, manganese (II) phosphate, manganese (II) perchlorate, hydrates thereof e.g., manganese (II) acetate tetrahydrate) and combinations thereof. Alternatively, the manganese ion source may comprise manganese (II) acetate or manganese (II) acetate tetrahydrate, or a combination thereof. Suitable manganese ion sources are commercially available from Millipore Sigma of St. Louis, Missouri, USA, Fisher Scientific of Waltham, Massachusetts, USA, and City Chemical LLC of Connecticut, USA. The amount of manganese ion source depends on various factors including the selections and amounts of other starting materials used, however the amount may be 0.1 ppm to 5,000 ppm based on combined weights of starting material (A), and when present starting material (B). Alternatively, the amount of the manganese ion source may be > 0 ppm, alternatively at least 0.5 ppm, alternatively at least 1 ppm, alternatively at least 1.5; while at the same time, the amount of manganese ion source may be up to 10 ppm, alternatively up to 5 ppm, alternatively up to 4 ppm, and alternatively up to 3 ppm, and alternatively up to 2 ppm, based on combined weights of all starting materials in starting material i ) the aqueous (co)polymer emulsion.

[0041] Starting material (J) is an optional phenolic compound. Suitable phenolic compounds include hydroquinone (HQ), 2-methylhydroquinone, 2-t-butylhydroquinone, dihydroxybenzene (catechol), 4-di-t-butyl dihydroxybenzene (4-di-t-butyl catechol), resorcinol, dihydroxyxylene,methoxyphenols such as guaiacol, p-methoxyphenol (also called methyl ether of hydroquinone or MeHQ), tert-butyl hydroquinone (tBuHQ), pyrogallol, methylpyrogallol, cresol, phenol, xylenols, butylated hydroxyl toluene, N-nitroso phenylhydroxylamine, butylated hydroxy anisole, and combinations thereof. Alternatively, the phenolic compound may be selected from the group consisting of HQ, MeHQ, tBuHQ, and a combination of two or more thereof. Suitable phenolic compounds are commercially available, e.g., from Millipore Sigma. The amount of phenolic compound source depends on various factors including the selections and amounts of other starting materials used, however the amount may be 5 ppm to 5,000 ppm based on combined weights of starting material (A) and when present starting material (B). Alternatively, the amount of the phenolic compound may be at least 5 ppm, alternatively at least 50 ppm, alternatively at least 100 ppm, alternatively at least 150 ppm; while at the same time, the amount of phenolic compound may be up to 500 ppm, alternatively up to 400 ppm, alternatively up to 350 ppm, and alternatively up to 320 ppm, based on combined weights of all starting materials in starting material i ) the aqueous (co)polymer emulsion.

[0042] Alternatively, another inhibitor may be used in addition to, or instead of, (I) the manganese ion source and (J) the phenolic compound described above. For example, the inhibitor may comprise, or may be, nitrobenzene; 2,2-diphenyl-l-picrylhydrazyl (DPPH); phenothiazine; N,N-diethylhydroxylamine; (2,2,6,6-tetramethylpiperidin- l-yl)oxidanyl (TEMPO); 4-hydroxy-(2,2,6,6-tetramethylpiperidin-l-yl)oxidanyl (4-hydroxy TEMPO); or a combination of two or more thereof.

[0043] Starting material (K) is an optional biocide. The amount of biocide will vary depending on factors including the type of biocide selected and the benefit desired. However, when used, the amount of biocide may be > 0% to 5% based on the combined weights of all starting materials in i) the aqueous (co)polymer emulsion. Starting material (K) is exemplified by (K-l) a fungicide, (K-2) an herbicide, (K-3) a pesticide, (K-4) an antimicrobial agent, or a combination thereof. Suitable biocides are disclosed, for example, in US Patent 9480977.

[0044] The aqueous (co)polymer emulsion may optionally further comprise starting material (P), a penetrating agent. Suitable penetrating agents are exemplified by glycol ethers, which are commercially available from The Dow Chemical Company and include DOW ANOL™ DPM, TPM, PPh, EPh, Methyl CARBITOL™, and Butyl CARBITOL™.

[0045] The aqueous (co)polymer emulsion may optionally further comprise an amount sufficient to impart softness to a textile without significantly decreasing water and / or oil repellency of (Q) a softening additive selected from (Q-l) an alkylpolysiloxane of unit formula (R193SiO)2(R192SiO2 / 2)aa, wherein each R19is an independently selected monovalent saturated hydrocarbon group having 1 to 18 carbon atoms, and subscript aa has an average value of 20 to300, or (Q-2) a combination comprising 60 to 70 weight %, based on combined weights of all starting materials in (Q-2), the combination, of (Q-l) the alkylpolysiloxane, 29 to 39 weight %, based on combined weights of all starting materials in (Q-2), the combination, of (Q-2-1) a silicone resin having a hardness > 20 measured by Type A durometer according to JIS K 6249:2003, and 0 to 2 weight %, based on combined weights of all starting materials in (Q-2), the combination, of (Q-2-2) an amino-functional polyorganosiloxane having a functional group equivalent of 100 to 20,000 g / mol, wherein the equivalent means molecular weight of the aminofunctional polyorganosiloxane per 1 mole of nitrogen atoms, and having a kinematic viscosity at 25 °C of 10 to 100,000 mm2 / s measured by the method of JIS K 2283:2000. Alternatively, (Q- 2-2) the amino-functional polyorganosiloxane may be present in an amount of 1% to 2%, on the same basis.

[0046] In the (Q-l) alkylpolysiloxane of the formula shown above, each R19is an independently selected monovalent saturated hydrocarbon group having 1 to 18 carbon atoms, and subscript aa has an average value of 20 to 300. The monovalent saturated hydrocarbon group for R19may be an alkyl group, alternatively an alkyl group of 1 to 6 carbon atoms. Alternatively, the alkyl groups may have 1 to 3 carbon atoms, alternatively 1 to 2 carbon atoms. Alternatively, each R19may be methyl. Suitable alkylpoly siloxanes, e.g., bis-trimethylsiloxy- terminated polydimethylsiloxanes, are known in the art and are commercially available, e.g., as XIAMETER™ 200 Fluids from The Dow Chemical Company.

[0047] Alternatively, (Q) the softening additive may comprise a (Q-2) combination comprising: 60% to 70%, based on combined weights of all starting materials in (Q-2), the combination, of (Q-l) the alkylpolysiloxane described above, 29% to 39%, based on combined weights of all starting materials in (Q-2), the combination, of (Q-2-1) a silicone resin having a hardness > 20 measured by Type A durometer according to JIS K 6249:2003, and 1% to 2%, based on combined weights of all starting materials in (Q-2), the combination, of (Q-2-2) an amino-functional polyorganosiloxane having a functional group equivalent of 100 to 20,000 g / mol, wherein the equivalent means molecular weight of the amino-functional polyorganosiloxane per 1 mole of nitrogen atoms, and having a kinematic viscosity at 25 °C of 10 to 100,000 mm2 / s measured by the method of JIS K 2283:2000.

[0048] Starting material (Q) the softening additive may be delivered in an additional aqueous emulsion, which comprises (Q) the softening additive, (D’) a surfactant (which may be as described above for starting material (D) the surfactant) and (E’) water (which may be as described above for starting material (E)). The additional aqueous emulsion may be prepared by known methods, such as those described in US Patent Application Publication 20200332148, by varying the types and amounts of starting materials as described herein.

[0049] Starting material (R) is an optional catalyst. The catalyst comprises a metal complex, which may be a metal carboxylate (e.g., a metal acetate or a metal acetylacetonate), wherein the metal is selected from the group consisting of manganese (Mn), zinc (Zn), and zirconium (Zr). Alternatively, the metal may be Zn or Zr, and alternatively Zn. Suitable catalysts include manganese (II) acetate (CAS No. 638-38-0), manganese (II) acetate tetrahydrate (CAS No. 6156-78-1), manganese (II) acetylacetonate (CAS No. 14024-58-9), manganese (III) acetylacetonate (CAS No. 14284-89-0), zinc acetate hydrate (CAS No. 16788-43-5), zinc (II) acetate (CAS No. 557-34-6), zinc (II) acetate dihydrate (CAS No. 5970-45-6), zinc(II) acetylacetonate (CAS No. 14024-63-6), zinc (II) acetylacetonate hydrate (CAS No. 108503-47- 5), zirconium acetate (CAS No. 7585-20-8), and zirconium (IV) acetylacetonate (CAS No. 17501-44-9), all of which are commercially available from Sigma Aldrich, Inc. The amount of starting material (R) depends on various factors including the types and amounts of silicone - (meth)acrylate (co)polymer, whether a blocked isocyanate is used, and the types and amounts of other optional additional starting materials, however, the amount of the catalyst may be > 0 to 10%, alternatively 0.5% to 7.5%, alternatively > 0.5% to < 7.5%, and alternatively 1% to 5%, based on weight of metal complex to amount of blocked isocyanate (solids). Alternatively, the aqueous (co)polymer emulsion prepared as described above, or the textile treatment emulsion prepared as described below, may comprise 0.001 % to 0.1 %, of (R) the catalyst, based on combined weights of all starting materials used.

[0050] When selecting starting materials to add to z ) the aqueous (co)polymer emulsion prepared as described above in step 1), and when present step 2), described above, there may be overlap between types of starting materials because certain starting materials described herein may have more than one function. For example, manganese (II) acetylacetonate may be an inhibitor or a condensation reaction catalyst. The starting materials used in aqueous (co)polymer emulsion (prepared as described above) and in the textile treatment emulsion (prepared as described below) may be distinct from one another.

[0051] Step 2) of the method described above for making the aqueous (co)polymer emulsion may be performed by any convenient means, such as mixing using a jacketed vessel equipped with an agitator. Step 1) and step 2), and any optional and / or additional steps as described above may be performed sequentially in the same vessel. Alternatively, step 1) and step 2) may be performed in different equipment. Step 2) may be performed at RT or elevated temperature, e.g., up to 100 °C, alternatively 40 °C to 80 °C. Alternatively, heating may be performed in step 1), and step 2) may be performed at RT. Alternatively, step 2) may be performed at lower temperatures and elevated pressures, such as up to 5 atmospheres. Alternatively, step 2) may be absent and any additional starting materials may be combined with the aqueous (co)polymeremulsion prepared in step 1) later.Poly[poly(alkylene glycol) (meth)acrylatel

[0052] The textile treatment emulsion described herein further comprises a poly[poly(alkylene glycol) (meth)acrylate]. The poly [poly (alkylene glycol) (meth)acrylate] comprises unit formula:, wherein each R3is independently selected from the group consisting of H and methyl; each D3is independently selected from the group consisting of an ethylene group and a propylene group; each R4is independently selected from the group consisting of H and an alkyl group of 1 to 4 carbon atoms; subscript m is sufficient to give each unit a number average molecular weight of > 200 g / mol to 5,000 g / mol; and subscript n is a weight fraction, and n = 1. Alternatively, each D3may be an ethylene group. Alternatively, the alkyl group for R4may be methyl or ethyl. Alternatively, each R4may be methyl. Alternatively, the poly[poly(alkylene glycol) (meth)acrylate] may have one or more of the following conditions: each R3is methyl; each R4is the alkyl group; and subscript m is sufficient to give each unit a number average molecular weight of 300 g / mol to 2,000 g / mol. Alternatively, the poly [poly (alkylene glycol) (meth)acrylate] may have one or more of the following conditions: each R3is methyl; each R4is H; and subscript m is sufficient to give each unit a number average molecular weight of 360 g / mol to 2,000 g / mol. Alternatively, the poly [poly (alkylene glycol) (meth)acrylate] may have Mn, Mw, and Mz measured by GPC as described below in the EXAMPLES, Method C. Number average molecular weight, Mn, for the poly[poly(alkylene glycol) (meth)acrylate] may be at least 2,000 g / mol; alternatively at least 2,358 g / mol; alternatively at least 5,000 g / mol; alternatively at least 8,000 g / mol; and alternatively at least 8,620 g / mol; while at the same time, Mn may be up to 100,000 g / mol; alternatively up to 80,000 g / mol; alternatively up to 76,000 g / mol; alternatively up to 50,000 g / mol; alternatively up to 25,000 g / mol; alternatively up to 18,000 g / mol; and alternatively up to 17,555 g / mol. Weight average molecular weight of the poly[poly(alkylene glycol) (meth)acrylate] may be at least 20,000 g / mol; alternatively at least 25,000 g / mol; alternatively at least 29,000 g / mol; alternatively at least 29,803 g / mol; alternatively at least 50,000 g / mol; alternatively at least 100,000 g / mol; alternatively at least 107,703 g / mol; while at the same time, Mw may be up to 200,000 g / mol; alternatively up to 175,000 g / mol; alternatively up to 166,615 g / mol; alternatively up to 150,000 g / mol; and alternatively up to 130,628 g / mol. The samples for GPCanalysis may be prepared in a 20 mM Phosphate buffer in MilliQ HPLC Water, pH ~7.0 eluent at concentration 2 mg / mL polymer. The solution may be shaken on a flat-bed shaker at ambient temperature for a couple of hours. The solution may then be filtered through a 17 mm 0.45 pm PTFE syringe filter prior to injection. A Waters UPLC system with isocratic pump, vacuum degasser, variable injection size autosampler, and column heater equipped with two TOSOHBioscience TSKgel 7.8 mm ID X 30 cm 7 pm and 13 pm columns in series and Waters UPLC refractive index detector was used to analyze the samples. The samples were run at 1 mL / min. Empower, Version 3 may be used for data collection and for data reduction. Standards of sodium salts of poly(acrylic acid) with Mp 216 to Mp 1,100,000 and Mp 900 to Mp 1,100,000 from American Polymer Standards were tested. A 2ndorder polynomial was used for calibration curve fitting. Thus, all molecular weight averages, distributions and references to molecular weight provided in this report are poly(acrylic acid) equivalent values.

[0053] The poly[poly(alkylene glycol) (meth)acrylate] described above may be prepared by a method comprising: polymerizing a poly(alkylene glycol) (meth)acrylate macromonomer of formula, wherein R3, D3, R4, and subscript m are as described above, wherein the poly(alkylene glycol) (meth)acrylate macromonomer is polymerized in the presence of an additional starting material, wherein the additional starting material comprises (C) an initiator; (E) water; optionally a chain transfer agent; optionally a manganese ion source; and optionally a phenolic compound; and wherein the product of this method is an aqueous solution comprising the poly [poly (alkylene glycol) (meth)acrylate] and water. Examples of suitable poly(alkylene glycol) (meth)acrylate macromonomers are commercially available and are exemplified by poly(ethylene glycol) methacrylate with number average molecular weight of 360 g / mol or 500 g / mol each with CAS No. 25736-86-1; poly(ethylene glycol) methyl ether methacrylate with number average molecular weight of 300 g / mol, 500 g / mol, 950 g / mol, or 2,000 g / mol each with CAS No. 26915-72-0; and poly(propylene glycol) (meth) acrylate with number average molecular weight of 375 g / mol and CAS No. 39420-45-6; all of which are commercially available from Sigma- Aldrich. Each of these poly(alkylene glycol) (meth) acrylate macromonomers may be delivered with an inhibitor, as described and exemplified above. Alternatively, the poly (alkylene glycol) (meth)acrylate macromonomer may be prepared by known methods such as that described in Chinese patent publication CN104774327A, which describes how to make high molecular weight polyethylene glycol ether methacrylate.

[0054] The starting materials and reaction conditions for making the poly[poly(alkyleneglycol) (meth) aery late | may be as described above for preparing the silicone - (meth) acrylate (co)polymer described above. The product prepared by polymerizing the poly(alkylene glycol) (meth) acrylate macromonomer may be an aqueous solution of the poly [poly (alkylene glycol) (meth)acrylate], which may be soluble in the water. The textile treatment emulsion herein may be prepared by a method comprising mixing i ) the aqueous (co)polymer emulsion and ii ) the aqueous solution under ambient conditions.

[0055] Alternatively, the method for making the textile treatment emulsion may comprise preparing the aqueous (co)polymer emulsion as described above, and thereafter polymerizing the poly(alkylene glycol) (meth)acrylate macromonomer in said aqueous (co)polymer emulsion. Alternatively, the method for making the textile treatment emulsion may comprise polymerizing the poly(alkylene glycol) (meth) acrylate macromonomer in water, thereby forming an aqueous solution comprising the poly[poly(alkylene glycol) (meth)acrylate] in water, and thereafter using the aqueous solution for preparing the aqueous (co)polymer emulsion described above. Without wishing to be bound by theory, it is thought that the resulting products described above (when either the silicone - (meth) acrylate macromonomer is copolymerized in the presence of the poly [poly (alkylene glycol) (meth)acrylate], or when the poly(alkylene glycol) (meth) acrylate macromonomer is polymerized in the presence of the silicone - (meth) acrylate macromonomer) may comprise a block copolymer with a block of the silicone - (meth) acrylate (co)polymer described above and a block of the poly[poly(alkylene glycol) (meth)acrylate] described herein. Alternatively, if the silicone - (meth)acrylate (co)polymer and the poly(alkylene glycol) (meth)acrylate macromonomer do not copolymerize, then the textile treatment emulsion will comprise the silicone - (meth)acrylate (co)polymer, the poly[poly(alkylene glycol) (meth) acrylate], the surfactant, and water, as described above.

[0056] Regardless of how the silicone - (meth) acrylate (co)polymer and the poly [poly (alkylene glycol) (meth)acrylate] are combined, the amounts of each may be sufficient to provide a weight ratio of the silicone - (meth) acrylate (co)polymer : the poly[poly(alkylene glycol) (meth) acrylate] of 19:1 to 1: 19, alternatively 9:1 to 1:9, and alternatively 3: 1 to 1:3 in the textile treatment emulsion.Blocked Isocyanate

[0057] The textile treatment emulsion described herein further comprises a blocked isocyanate, which may be delivered in an aqueous additive, which comprises the blocked isocyanate and water. The term “blocked isocyanate” encompasses mono-, di- and polyisocyanates in which an isocyanate group has been reacted with a blocking agent, which upon heating, release the isocyanate and the blocking agent. Suitable blocking agents are known in the art such as amines, amides, compounds having an active hydrogen atom, alcohols, N-heterocyclic compounds, oroximes. Blocked isocyanates are commercially available, such as ARKOPHOB™ DAN and ARKOPHOB™ SR from Archroma of Pratteln, Switzerland; RUCO™-GUARD WEB and RUCO™-LINK XCR from Rudolf GmbH of Geretsreid, Bayern, Germany, and PHOBOL™ EXTENDER UXN and PHOBOL™ EXTENDER XAN from Archroma. Alternatively, the blocked isocyanate may be an oxime blocked isocyanate, such as PHOBOL™ EXTENDER XAN. Alternatively, the blocked isocyanate may comprise a nitrogen containing heterocycle (N-heterocycle) - blocked isocyanate. The N-heterocycle-blocked isocyanate comprises an isocyanate compound and an N-heterocycle-blocking agent. The isocyanate compound may be monomeric or polymeric. The isocyanate compound may comprise, or maybe, a unit selected from the group consisting of IPDI, HnMDI, TMXDI, TMI, XDI, H6XDI, MDI, and HDI. Alternatively, the polyisocyanate may be an aliphatic isocyanate where the NCO group is not directly attached to an aromatic ring. Alternatively, the polyisocyanate may be HDI or MDI. The N-heterocycle blocking agent may be caprolactam, 2,6-dimethylpyrazine or a dimethylpyrazole, e.g., 3,5-dimethylpyrazole. Alternatively, the aqueous additive for use herein may be free of oxime compounds. Without wishing to be bound by theory, it is thought that theblocked isocyanate may be free of species that may interfere with the performance of the isocyanate in the textile treatment emulsion, such as silicones and amines (that are not within the blocking group). And, without wishing to be bound by theory, it is thought that the blocked isocyanate may be delivered in an emulsion or dispersion that is free of anionic surfactant. Suitable aqueous additives are commercially available and may be delivered in aqueous dispersions, and examples thereof are shown below in Table 0.Table 0 - Commercially Available Aqueous Additives

[0058] The exact amount of the blocked isocyanate compound depends on various factors including the type and amount of silicone - (meth)acrylate copolymer, poly(alkylene glycol) meth)acrylate, and the textile to be treated, however, the weight of the blocked isocyanate may be sufficient to provide 0.1% to 3.75% of solids on fabric weight, alternatively 0.1% to 0.75%, alternatively 0.25% to 1%, and alternatively 0.25% to 0.5%, on the same basis; wherein solids refers to the amount of blocked isocyanate that may be delivered in the aqueous additive, whichfurther comprises another component, e.g., water and optionally a surfactant. Alternatively, the amount of the aqueous additive that may be used may be sufficient to provide a weight ratio of silicone - (meth)acrylate (co)polymer and poly[poly(alkylene glycol) (meth)acrylate] combined : blocked isocyanate (weight ratio of actives) of 16:1 to 1:1, alternatively the weight ratio of actives may be 16: 1 to 2: 1, alternatively 16: 1 to 4: 1, and alternatively 16:1 to 8: 1.

[0059] The textile treatment emulsion described above may be prepared by a method comprising:I) polymerizing starting materials comprising(A) a silicone - (meth) acrylate macromonomer of formula, wherein each R1is an independently selected monovalent hydrocarbon group of 1 to 12 carbon atoms; D2is a divalent hydrocarbon group of 2 to 12 carbon atoms; and R2is selected from the group consisting of H and methyl; optionally (B) a silicone - (meth) acrylate co-macromonomer of formula, wherein each R1is an independently selected monovalent hydrocarbon group of 1 to 12 carbon atoms; D2is a divalent hydrocarbon group of 2 to 12 carbon atoms; and R2is selected from the group consisting of H and methyl; wherein starting material (A) is present in an amount of 25 weight % to 100 weight %, based on combined weights of starting materials (A) and (B); and wherein starting material (B) is present in an amount of 0 to 75 weight %, based oncombined weights of starting materials (A) and (B); and where starting materials (A) and (B) are copolymerized in the presence of an additional starting material, wherein the additional starting material comprises(C) an initiator; optionally (H) a chain transfer agent; optionally (I) a manganese ion source; and optionally (J) a phenolic compound; and wherein one of conditions (i) or (ii) is met, wherein condition (i) is that step I) further comprises adding a solvent before or during step I), removing the solvent after forming the silicone - (meth)acrylate copolymer, and forming an aqueous emulsion comprising the silicone - (meth) aery late copolymer, the surfactant, and water; and wherein condition (ii) is that step I) comprises an emulsion polymerization reaction; the additional starting materials further comprise the surfactant and water; and wherein the product of step I) comprises an aqueous copolymer emulsion comprising the silicone - (meth) acrylate copolymer, the surfactant, and the water;II) polymerizing a poly(alkylene glycol) (meth)acrylate macromonomer of formula, wherein R , D , R , and subscript m are as described above, wherein the poly(alkylene glycol) (meth) acrylate macromonomer is polymerized in the presence of an additional starting material, wherein the additional starting material comprises(C) an initiator;(E) water; optionally a chain transfer agent; optionally a manganese ion source; and optionally a phenolic compound; and wherein the product of step II) is an aqueous solution;III) combining materials comprising the product of step I), the product of step II), and the blocked isocyanate, and optionally IV) combining, with the product of step 111), an additional starting material, where the additional starting material, when present, is selected from the group consisting of a biocide, additional water, a flame retardant, a wrinkle reducing agent, an antistatic agent, a penetrating agent, a softening agent, a condensation reaction catalyst, and a combination of twoor more thereof. The order of the steps in this method is not critical. For example, step 1) and step II) may be performed sequentially in any order. Alternatively, step I) and step II) may be performed concurrently. Alternatively, at least a portion of (A) the silicone - (meth)acrylate macromonomer (and optionally at least a portion of (B) the silicone - (meth)acrylate co- macromonomer, when present and at least a portion of the poly(alkylene glycol) (meth)acrylate macromonomer may copolymerize when steps I) and II) are performed concurrently. Alternatively, the product of step I) (i.e. , the aqueous (co)polymer emulsion) and the product of step II) (i.e., the aqueous solution) may be prepared separately. Steps I) and II) may be performed before step III), and the product of step I), the product of step II), and the blocked isocyanate (e.g., delivered in the aqueous additive described above) may be combined by mixing.

[0060] Alternatively, step I) may performed before step II), and during step II), the poly(alkylene glycol) (meth)acrylate macromonomer is polymerized in the product of step I), and step III) is performed thereafter. This is the method as described above for polymerizing the poly(alkylene glycol) (meth)acrylate macromonomer in the presence of the silicone - (meth) acrylate (co)polymer in the aqueous (co)polymer emulsion.

[0061] Step III) of the method for preparing the textile treatment emulsion may be performed during or after step I). Step IV) is optional. The additional starting material may be mixed with the product of step I) or the product of step II), or both. Alternatively, the additional starting material may be incorporated into the product of step I) and / or the product of step II) in the methods for preparing the silicone - (meth)acrylate (co)polymer and / or the poly[poly(alkylene glycol) (meth)acrylate], as described above. Alternatively, one or more additional starting materials may be incorporated into the product of step I) and / or the product of step II) in the methods for preparing the silicone - (meth) aery late (co)polymer and / or the poly[poly(alkylene glycol) (meth) acrylate] (or a copolmerization product prepared when step I) and II) are performed concurrently) and / or one or more other additional starting materials may be added separately. The additional starting materials may be selected from the group consisting of a biocide, additional water, a flame retardant, a wrinkle reducing agent, an antistatic agent, a penetrating agent, a softening agent, a condensation reaction catalyst, and a combination of two or more thereof; as described above.

[0062] The method described above for making the textile treatment emulsion may be performed by any convenient means, such as mixing using a jacketed vessel equipped with an agitator. One or more of the steps may be performed concurrently or sequentially in the same vessel. Alternatively, different steps may be performed in different equipment. Each step may be performed at RT or elevated temperature, e.g., up to 100 °C, alternatively RT to 80 °C, andaltematively RT.Method of Use

[0063] The textile treatment emulsion prepared as described above may be used for treating a textile. For example, a method for treating a textile comprises: 1 ) contacting the textile with the textile treatment emulsion described above, and 2 ) heating the textile. Step J ) may be performed by any convenient method, such as padding, exhausting, dipping, or spraying the textile with the textile treatment emulsion. However, the method should be sufficient to deliver a sufficient amount of the actives (i.e., the silicone - (meth)acrylate (co)polymer, the poly[poly(alkylene glycol) (meth)acrylate], and / or the copolymerization products thereof, and the blocked isocyanate sufficient to impart durable oil resistance properties to the textile, according to the methods described herein. The method may be sufficient to deliver on fabric weight of 0.25 weight % to 10 weight % of the actives combined, based on weight of the textile.

[0064] Step 2 ) may be performed by any convenient method, such as placing the textile in an oven. Heating the textile may be performed to remove all or a portion of the water and optionally to cure one or more of the actives. The exact temperature depends on various factors including the temperature sensitivity of the type of textile selected and the desired drying time. However, heating may be performed at a temperature > 100 °C to remove water. Alternatively, the temperature may be > 100 °C to 200 °C for a time sufficient to remove all or a portion of the water, de-block the blocked isocyanate, and / or cure one or more of the actives.

[0065] The textile to be treated is not specifically restricted. Suitable textiles include naturally derived textiles such as fabrics of cotton, silk, linen, and / or wool; textiles derived from synthetic sources such as rayon, acetate, polyesters, polyamides (such as Nylons), polyacrylonitriles, and polyolefins such as polyethylenes and / or polypropylenes, and combinations of two or more thereof (e.g. , blends such as polyester / cotton blend). The form of the textile is also not specifically restricted. The textile treatment emulsion described herein is suitable for use on textiles in any form, e.g., woven fabrics, knitted fabrics, or nonwoven textiles.EXAMPLES

[0066] The following examples are provided to illustrate the invention to one skilled in the art and are not to be interpreted to limit the scope of the invention set forth in the claims. Starting materials used in these examples are summarized below in Table 1.Table 1. Starting Materials

[0067] In Table 1 above, 3-(l,5-bis(2-(l,l,l,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)ethyl)-3-(((2-(l,l,l,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)ethyl)dimethylsilyl)oxy)-l,l,5,5-tetramethyltrisiloxan-3- yl)propyl methacrylate has formula

[0068] Preparation of the Emulsions and Solutions were performed as follows:

[0069] In this Method A, silicone - (meth) acrylate (co)polymer emulsions were prepared as follows. All monomers, water and surfactant were added to a widemouth jar (400 mL) in selections and amounts shown below in Table 2. A sonicator was used to make an emulsion(Fisherbrand Model 705 sonic dismembrator, amplitude 50, Power ~62 W, for 2 min). The aqueous emulsion was then transferred to a reactor and heated to 65 °C. After the aqueous emulsion came to temperature, 2,2’-Azobis(2-methylpropionamidine) dihydrochloride was added (0.26 g), and the reactor contents were stirred for 6 h. The reactor contents were then cooled down to room temperature and the resulting aqueous (co)polymer emulsions were each poured into a bottle. The aqueous (co)polymer emulsions prepared as described above are summarized below in Table 2. Amounts of each starting material in Table 2 are in grams.

[0070] In this Method B, silicone - (meth)acrylate (co)polymer emulsions were prepared as follows. All monomers, water and surfactant were added to a widemouth jar (400 mL) in selections and amounts shown below in Table 2. In addition, the emulsions were inhibited with Hydroquinone (50 ppm based on monomer), Mn(II) acetate*4H2O (1.5 ppm based on monomer) and methyletherhydroquinone (150 ppm based on monomer). The resulting material was sonicated at an amplitude of 50 for two minutes using a sonicator (Fisher Brand Sonic Dismembrator) to create an emulsion. The resulting emulsion was then transferred to a 500 mL 4 neck flask equipped with a reflux condenser, nitrogen inlet, overhead stirrer (IKA RW20) and thermocouple probe. This emulsion was stirred at 250 RPM using a Teflon blade and heated to 65 °C. After reaching temperature 0.25 g of 2,2’ Azobis(2-methylpropionamidine dichloride was added and the reaction was run for 6 hours. The resulting material was then allowed to cool to 30 °C to 40 °C with slow stirring before pouring off. The aqueous (co)polymer emulsions prepared as described above are summarized below in Table 2. Amounts of each starting material in Table 2 are in grams.

[0071] In this Method C, a solution comprising polyPEGMA and water was prepared asfollows. In the synthesis of Solution 4, the water was added to a widemouth jar (400 mL) followed by the monomer in amounts according to Table 2. The monomer was stirred in water until fully dissolved. Afterwards, the solution was transferred to a 250 mL two-neck roundbottom flask equipped with a large stir bar, reflux condenser, nitrogen inlet, and thermocouple probe. The reaction was heated to 65 °C and 0.046 g of 2,2’Azobis(2-methylpropionamidine dichloride was added, and the reaction was allowed to stir at temperature for 4 hours. The reaction was then cooled down to room temperature and poured into a bottle. The aqueous copolymer solutions prepared as described above are summarized below in Table 3. Amounts of each starting material in Table 3 are in grams. Molecular weights (Mn, Mw, and Mz for the samples prepared according this Method C were analyzed on aqueous GPC, wherein Samples were prepared at 2 mg / mL in 20 mM phosphate buffer (pH 7), polyacrylic acid (PAA) standards were used for calibration, and Tosoh TSKgel GMPWxl couple to TSKgel G2500PWxl columns were used.

[0072] In this Method D, the silicone - (meth)acrylate (co)polymer was prepared in the presence of polyPEGMA. In this method, an aqueous (co (polymer emulsion was prepared as follows. All monomers, water, Solution 8 (prepared as described in Method C and summarized below in Table 3), and surfactant were added to a widemouth jar (400 mL) in selections and amounts shown below in Table 4. The emulsion was inhibited with Hydroquinone (50 ppm based on monomer), Mn(II) acetate*4H2O (1.5 ppm based on monomer) and methyletherhydroquinone (150 ppm based on monomer). The resulting material was sonicated at an amplitude of 50 for two minutes using a sonicator (Fisher Brand Sonic Dismembrator) to create an emulsion. The resulting emulsion was then transferred to a 500 mL 4 neck flask equipped with a reflux condenser, nitrogen inlet, overhead stirrer (IKA RW20) and thermocouple probe. This emulsion was stirred at 250 RPM using a Teflon blade and heated to 65 °C. After reaching temperature 0.25 g of 2,2’ Azobis(2-methylpropionamidine dichloride was added and the reaction was run for 6 hours. The resulting material was then allowed to cool to 30 °C with slow stirring before pouring off. The aqueous (co (polymer emulsion prepared as described above is summarized below in Table 4. In Table 4, Solution 8 is as described in Table 3. Amounts of each starting material in Table 4 are in grams.

[0073] In this Method E, silicone - (meth)acrylate and poly(alkylene glycol) (meth)acrylate (co (polymer emulsions were prepared as follows. All monomers, water and surfactant were added to a widemouth jar (400 mL) in selections and amounts shown below in Table 5. The Mn950 PEGMA was melted before addition. The emulsions were inhibited with Hydroquinone (50 ppm based on monomer), Mn(II) acetate*4H2O (1.5 ppm based on monomer) and methyletherhydroquinone (150 ppm based on monomer). The resulting material was sonicated atan amplitude of 50 for two minutes using a sonicator (Fisher Brand Sonic Dismembrator) to create an emulsion. The resulting emulsion was then transferred to a 500 mL 4 neck flask equipped with a reflux condenser, nitrogen inlet, overhead stirrer (IKA RW20) and thermocouple probe. This emulsion was stirred at 250 RPM using a Teflon blade and heated to 65 °C. After reaching temperature 0.25 g of 2,2’ Azobis(2-methylpropionamidine dichloride was added and the reaction was run for 6 hours. The resulting material was then allowed to cool to 30 °C to 40 °C with slow stirring before pouring off. The aqueous (co)polymer emulsions prepared as described above are summarized below in Table 5. Amounts of each starting material in Table 5 are in grams.Table 2. Aqueous (Co)polymer Emulsion Preparation via PolymerizationTable 3. Aqueous polyPEGMA Solutions via PolymerizationTable 4. Aqueous Emulsion Preparation via PolymerizationTable 5. Aqueous (Co)polymer Emulsion Preparation via Polymerization

[0074] In Table 5, theAdenotes that the poly (ethylene glycol) methyl ether methacrylate and the silicone methacrylate macromonomers were polymerized concurrently, and without wishing to be bound by theory, it is thought that at least a portion of the 3MT-ALMA and PEGMA copolymerized.

[0075] In this Reference Example 1 , textile treatment emulsions were prepared by adding each component as listed in Table 5 into a 125 g Nalgene plastic bottle. After adding the bottle was inverted twice to mix the contents. Order of addition was not important. The samples prepared are summarized below in Table 6.Table 6. Textile Treatment Emulsions

[0076] In Table 6, the * denotes that Emulsion 9, shown in Table 4, was used for treating the textile, wherein the poly(ethylene glycol) methyl ether methacrylate was polymerized in theaqueous (co)polymer emulsion. In Table 6, the denotes that Emulsions 10-12, shown in Table 5, were used for treating the textile, wherein the poly(ethylene glycol) methyl ether methacrylate and the silicone methacrylate monomers were polymerized concurrently.

[0077] In this Reference Example 2, textiles were treated with the textile treatment emulsions in Table 5 according to the following procedure. All the textiles were washed / dried before coating. Each textile treatment emulsion as described above in Table 5 was poured into a beaker, and then dip coated and passed through a Werner Mathis AG Textilmaschinen padder (tension setting of 70) for coating. After passing through once, the sample was placed in a forced air Mathis LTF oven at 160 °C for 3 min.

[0078] In this Reference Example 3, oil repellency was tested using a modified version of AATCC 118, i.e., the face rankings of A, B, C, and D were used as described in AATCC 118 (and as shown in Figure 3 of “Fluorine-free low surface energy organic coating for anti-stain applications” by Lei, et al, Progress in Organic Coatings 103 (2017)182-192, 184). Face ranking of A denoted a clear, well-rounded bead of oil; B denoted a rounding drop with partial darkening; C denoted wick was apparent and / or complete wetting; and D denoted complete wetting. The modifications to this test method were that the oil used was olive oil, and the time was extended from 10 sec to 5 min. A relatively large olive oil drop was used for this test, i.e., at least 250 uL per drop. For purposes of this application, a sample was deemed to have durable oil repellency if it had a rating of A or B after 5 min. Face rating of C or D represented unacceptably high oil absorbance by the fabric. Results are shown below in Table 6. As part of this method, if an inconsistency in the performance was noted, the test was conducted three times and the result gained twice was noted. If even one of the tests failed, the coating was determined to be uneven, a negative result on the performance noted by an N in Table 7.Table 7. Oil Repellency and Coating Results

[0079] Examples 1-3 and 5-10 in the table showed that when methoxy terminated polyPEGMA within a concentration of 25 to 75 wt% was used; the silicone - (meth)acrylate (co)polymer was made using either 3MT-ALMA as the only macromonomer, or a 3:1 weight ratio of 3MT-ALMA : MDM-ALMA, and the blocked isocyanate was delivered in PHOBOL XAN additive, all samples tested showed oil repellency. Examples 4 and 11 showed Nylon can be rendered oil repellent using the textile treatment emulsion and method described herein. Example 12 showed that when polyPEGMA made from PEGMA monomers with Mn of at least 360 g / mol and with an alcohol end group could be used. When synthetic Method D was utilized to make the silicone - (meth)acrylate (co)polymer, there was no differentiation in performance as shown in Example 13 as compared to cold blending compositions prepared as described in Method A with Method C or Method B with Method C. In Example 14, a copolymer of MDM- ALMA and 3MT-ALMA could be used without loss in performance. Comparative 1 showed polyPEGMA at 100 % (i.e. , without a silicone - (meth)acrylate (co)polymer) did not impart durable oil repellency under the conditions tested. Comparatives 3, 4, and 5 show that without the blocked isocyanate additive, the coating was uneven and oil repellency performance was greatly depleted at different concentrations and monomer molecular weight. Comparative 6 and Example 9 showed that a textile treatment emulsion containing a copolymer of 3MT-ALMA and Si 16 did not impart oil repellency under the conditions tested as compared to a textile treatment emulsion that did impart oil repellency, where the difference in the textile treatment emulsionswas that a polymer made with 3MT-ALMA was used instead of the copolymer of 3MT-ALMA and Sil6.

[0080] In this Synthesis Example 1, PDMS resin 1 (as described in Example 1 of US Patent Publication 20230038369 was prepared as follows: 0.88 g (10 mmol) of 3MT-ALMA, 0.31 g (1 mmol) of vinyl trimethoxysilane and 0.033g (0.1 mmol) of azobisisobutyronitrile were added to a round bottom flask with 47.95 g of dry xylenes at room temperature. The round bottom flask was equipped with a condenser, nitrogen inlet, overhead stirrer and thermocouple probe. The system was purged with nitrogen for 5 min and then the solution was heated up to 65°C and then held for 24 h.

[0081] In this Synthesis Example 2, PDMS resin 2 was prepared as follows: An 80 DP amino terminated PDMS (30 g, 10 mmol), bisphenol A (2.28 g, 10 mmol) and paraformaldehyde (1.2 g, 40 mmol) were dissolved in 150 mL of chloroform in a 500 mL round bottom flask. The mixture was heated under reflux for 6 h to give a light yellow solution. After removing the solvent under vacuum, the residue was dissolved in 75 mL of methylene chloride. The material was washed with a saturated solution of NaHCOs (75 mL x 5). The water was then distilled off leaving a light yellow liquid product. PDMS resin 2 gelled by the next day, so this resin could not be coated on a textile.

[0082] The procedure for these comparative examples 7 and 8, which included pre-treatment of fabric then treatment with the PDMS resin 1, was as follows: A Ixlcm PES or Nylon fabric was washed with 200 proof ethanol and then dried in an oven 80 °C for 10 min. Then a silica sol was prepared by hydrolysis of tetraethoxysilane (2.08 g, 10 mmol) in 60 mL of ethanol / 15 mL of DI water in the presence of ammonium hydroxide (2.75 mL). The fabric was dipped into the sol for 5 min and dried at room temperature (~30 min). This process was repeated 2 more times. The fabric was then soaked in a 5% suspension of Ludox HS silica (5 g of a 40% solution of Ludox HS-40 colloidal silica and 35 g of DI water) until saturated (~4 sec) and then dried overnight at 80 °C. The pretreated 1x1 cm PES or nylon fabric samples were dip coated 3 times into PDMS resin 1. The samples were cured for 1 h at 200 °C.

[0083] The procedure for these comparative examples 9 and 10 was as follows: A 1x1 cm PES or nylon fabric sample was dip coated 3 times into synthesis PDMS resin 1. The samples were cured for 1 h at 200 °C.

[0084] The procedure for these comparative examples 11 and 12 was as follows:A Ixlcm PES or Nylon fabric was washed with 200 proof ethanol and then dried in an oven 80 °C for 10 min. Then a silica sol was prepared by hydrolysis of tetraethoxysilane (2.08 g, 10 mmol) in 60 mL of ethanol / 15 mL of DI water in the presence of ammonium hydroxide (2.75 mL). The fabric was dipped into the sol for 5 min and dried at room temperature (-30 min).This process was repeated 2 more times. The fabric was then soaked in a 5% suspension of Ludox HS silica (5 g of a 40% solution of Ludox HS-40 colloidal silica and 35 g of DI water) until saturated (~4 sec) and then dried overnight at 80 °C.Table 7 - Results for Comparative Examples 7 to 12

[0085] Comparative Examples 7 and 8 correspond to example 2 disclosed in US Patent Publication US20230038369. These received a failing oil repellency grade after 5 min in the modified AATCC method 118. In contrast, the present invention, (e.g., as shown in Examples 1-14 in Table 6, above) had superior oil repellency using the AATCC method 118. Comparative Examples 9 and 10 removed the sol gel and nanoparticle treatment and tested the 3MT- ALMA / vinyl trimethoxysilane copolymer, and these examples also failed the modified AATCC method 118 after 5 min.

[0086] In this Comparative Examplel3, the PES fabric was treated with 2 separate emulsions in 2 separate steps. First the fabric was coated with an emulsion of PhoboLXAN (0.69 g XAN + 74.31 g DI water), described in the coating / curing methods in Reference Example 2, above. In a second step the fabric was treated with an emulsion (in which 5.75 g of Emulsion 1 from Table 2 was combined with 69.25 g DI water) using the same coating and curing methods described above in Reference Example 2.

[0087] Comparative example 13 shows a pretreatment method of the blocked isocyanate (XAN) additive similarly described in example 2 in US Patent Publication US20230038369. This comparative example 13 did not pass the modified AATCC method 118 after 10 sec and had worse oil repellency Comparative Examples 7 and 8 at 10 sec.

[0088] In this Comparative Example 14, 3.83 g of Emulsion 1 described above in Table 2 and 1.59 g of DOWSIL™ IE-8749, a 70% solids silicone durable water repellent that is commercially available from The Dow Chemical Company, were added into a 125 g Nalgene plastic bottle. The bottle was then inverted twice to mix the contents. Fabric was coated and oil repellency was measured as described above in Reference Example 3. The fabric had a C rating after 10 s and a D rating after 30 s. Comparative 14 showed that a silicone material (the active in IE-8749) blended with a copolymer of 3MT-ALMA failed the oil repellency test herein after30 s.

[0089] In this Comparative Example 15, 2.25 g of Daikin XF-5100 (available in the United States instead of XF-5003, 3%), 4.5 g of RUCODRY Eco Plus (6%) and 1.875 g of RUCO- LINK XCR (2.5%), both from Rudolf Group, with 66.125 g of water. The resulting sample was coated on PES according to the method of Reference Example 2 and evaluated via the modified AATCC 1 18 test in Reference Example 3. The treated fabric failed the oil repellency test at 30 sec.INDUSTRIAL APPLICABILITY

[0090] The examples above demonstrate that the textile treatment emulsion and method of the present invention impart durable oil repellency to textiles. Without wishing to be bound by theory, it is thought that the textile treatment emulsion of the present invention can impart both water repellency and oil repellency to textiles. The method for imparting oil repellency to a textile comprises: step 1 ) applying to a textile, the textile treatment emulsion prepared as described above; and step 2) drying the textile, thereby removing all or a portion of the water. However, this method may consist essentially of, or consist of, step 1 ) and step 2) because this invention provides the added benefit that only one application of the textile treatment emulsion is required, e.g., it is not necessary to repeat step 7) to reapply the textile treatment emulsion in order to impart oil repellency.DEFINITIONS AND USAGE OF TERMS

[0091] All amounts, ratios, and percentages herein are by weight, unless otherwise indicated. The SUMMARY and ABSTRACT are hereby incorporated by reference. The articles, “a”, “an”, and “the” each refer to one or more, unless otherwise indicated by the context of the specification. The 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 symbol “<” denotes “less than”, the symbol “>” denotes “greater than”, the symbol “<” denotes “less than or equal to”, and the symbol “>” denotes “greater than or equal to”. The abbreviations used herein have the definitions in Table 8.Table 8 - Abbreviations

Claims

CLAIMS:

1. A method for preparing a textile treatment emulsion, wherein the method comprises:I) polymerizing starting materials comprising(A) a silicone - (meth) acrylate macromonomer of formulaindependently selected monovalent hydrocarbon group of 1 to 12 carbon atoms; D2is a divalent hydrocarbon group of 2 to 12 carbon atoms; and R2is selected from the group consisting of H and methyl; optionally (B) a silicone - (meth) aery late co-macromonomer of formulawherein each R1is an independently selected monovalent hydrocarbon group of 1 to 12 carbon atoms; D2is a divalent hydrocarbon group of 2 to 12 carbon atoms; and R2is selected from the group consisting of H and methyl; wherein starting material (A) is present in an amount of > 25 weight % to 100 weight %, based on combined weights of starting materials (A) and (B); and wherein starting material (B) is present in an amount of 0 to < 75 weight %, based on combined weights of starting materials (A) and (B); and where starting materials (A) and (B) are copolymerized in the presence of an additional starting material, wherein the additional starting material comprises(C) an initiator; optionally (H) a chain transfer agent; optionally (I) a manganese ion source; and optionally (J) a phenolic compound; and wherein one of conditions (i) or (ii) is met, wherein condition (i) is that step I) further comprises adding a solvent before orduring step 1), removing the solvent after forming a silicone - (meth)acrylate (co)polymer, and forming an aqueous (co)polymer emulsion comprising the silicone - (meth) acrylate (co)polymer, a surfactant, and water; and wherein condition (ii) is that step I) comprises an emulsion polymerization reaction; the additional starting materials further comprise the surfactant and water; and wherein the product of step I) comprises the aqueous (co)polymer emulsion comprising the silicone - (meth) acrylate (co)polymer, the surfactant, and the water;II) polymerizing a poly(alkylene glycol) (meth)acrylate macromonomer of formula, wherein each R3is independently selected from the group consisting of H and methyl; each D3is independently selected from the group consisting of an ethylene group and a propylene group; each R4is independently selected from the group consisting of H and an alkyl group of 1 to 4 carbon atoms; and subscript m is sufficient to provide the poly(alkylene glycol) (meth)acrylate macromonomer with a number average molecular weight of > 200 g / mol to 5,000 g / mol, wherein the poly(alkylene glycol) (meth)acrylate macromonomer is polymerized in the presence of an additional starting material, wherein the additional starting material comprises(C) an initiator;(E) water; optionally a chain transfer agent; optionally a manganese ion source; and optionally a phenolic compound; and wherein the product of step II) is an aqueous solution ;III) combining materials comprising the product of step I), the product of step II), and a blocked isocyanate, and optionally IV) adding an additional starting material, where the additional starting material, when present, is selected from the group consisting of a biocide, additional water, a flame retardant, a wrinkle reducing agent, an antistatic agent, a penetrating agent, a softening agent, a condensation reaction catalyst, and a combination of two or more thereof.

2. The method of claim 1, wherein steps I) and II) are performed separately and before stepIII); and step III) comprises mixing the aqueous (co)polymer emulsion formed in step I), the aqueous solution formed in step II), and an aqueous additive comprising the blocked isocyanate and water.

3. The method of claim 1, wherein step II) is performed before step I), and wherein during step I), the silicone - (meth)acrylate macromonomer polymerizes in the presence of the aqueous solution formed in step II).

4. The method of claim 1, wherein step I) and step II) are performed concurrently, and wherein at least a portion of the silicone - (meth)acrylate macromonomer and at least a portion of the poly(alkylene glycol) (meth)acrylate macromonomer copolymerize.

5. The method of any one of claims 1 to 4, wherein(A) the silicone - (meth)acrylate macromonomer has one or more of: each R1is methyl, each R2is methyl, and each D2is propyl; and when (B) the silicone - (meth)acrylate co-macromonomer is present, (B) the silicone - (meth) acrylate co-macromonomer of has one or more of: each R1is methyl, each R2is methyl, and each D2is propyl.

6. The method of any one of claims 1 to 5, wherein the poly(alkylene glycol) (meth)acrylate macromonomer has one or more of: each R3is methyl; each R4is the alkyl group; and subscript m is sufficient to provide the poly(alkylene glycol) (meth) acrylate macromonomer with a number average molecular weight of 300 g / mol to 2,000 g / mol.

7. The method of any one of claims 1 to 5, wherein the poly (alkylene glycol) (meth)acrylate macromonomer has one or more of: each R3is methyl; each R4is H; and subscript m is sufficient to provide the poly(alkylene glycol) (meth)acrylatemacromonomer with a number average molecular weight of 360 g / mol to 2,000 g / mol.

8. The method of any one of claims 1 to 7, wherein the silicone - (meth)acrylate (co)polymer and a poly [poly (alkylene glycol) (meth) acrylate] are present in the textile treatment emulsion in amounts such that a weight ratio of the silicone - (meth)acrylate (co)polymer : the poly[poly(alkylene glycol) (meth)acrylate] is 19:1 to 1 :19.

9. The method of claim 8, wherein the weight ratio is 9:1 to 1:9.

10. The method of any one of claims 1 to 9, wherein the blocked isocyanate comprises an oxime blocked isocyanate or an N-heterocycle blocked isocyanate.

11. The method any one of claims 1 to 10, wherein the silicone - (meth) acrylate (co)polymer, the poly[poly(alkylene glycol) (meth)acrylate], and the blocked isocyanate are present in amounts such that a weight ratio of the silicone - (meth)acrylate (co)polymer and the poly [poly (alkylene glycol) (meth)acrylate] combined : the blocked isocyanate is 16:1 to 1:1.

12. The method of any one of claims 1 to 11, wherein the surfactant is a nonionic surfactant.

13. A textile treatment emulsion prepared by the method of any one of claims 1 to 12.

14. A method for imparting oil repellency to a textile, wherein the method comprises: step 1 ) applying to a textile, the textile treatment emulsion of claim 13, and step 2 ) drying the textile, thereby removing all or a portion of the water.

15. The method of claim 14, wherein the method consists of step 1 ) and step 2).

16. An oil repellent textile prepared by the method of claim 14 or claim 15.

17. The method of any one of claims 1 to 12, wherein the silicone - (meth) acrylate (co)polymer has a weight average molecular weight > 181,000 g / mol measured by gel permeation chromatography.

18. The method of claim 17, wherein the weight average molecular weight is 212,000 g / mol to 2,000,000 g / mol.

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