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WO2025090190A1 - Traitement textile pour conférer une hydrophobie comprenant l'utilisation d'un copolymère de silicone-(méth)acrylate et d'un uréthane - Google Patents

Traitement textile pour conférer une hydrophobie comprenant l'utilisation d'un copolymère de silicone-(méth)acrylate et d'un uréthane Download PDF

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Publication number
WO2025090190A1
WO2025090190A1 PCT/US2024/045246 US2024045246W WO2025090190A1 WO 2025090190 A1 WO2025090190 A1 WO 2025090190A1 US 2024045246 W US2024045246 W US 2024045246W WO 2025090190 A1 WO2025090190 A1 WO 2025090190A1
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WIPO (PCT)
Prior art keywords
group
meth
silicone
alternatively
independently selected
Prior art date
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PCT/US2024/045246
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English (en)
Inventor
Anirudha BANERJEE
Ericka BRUSKE
Devin FERGUSON
Matthew JELETIC
Douglas HASSO
Brian Macdonald
Jodi Mecca
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Dow Silicones Corp
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Dow Silicones Corp
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Publication of WO2025090190A1 publication Critical patent/WO2025090190A1/fr
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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/356—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms
    • D06M15/3568—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms containing silicon
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10—Repellency against liquids
    • D06M2200/11—Oleophobic properties
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10—Repellency against liquids
    • D06M2200/12—Hydrophobic properties

Definitions

  • a textile treatment emulsion contains a silicone - (meth)acrylate copolymer and a urethane compound.
  • the emulsion is useful for imparting oil repellency to textiles.
  • PFAS Per- and Polyfluorinated Substances
  • W02023019044 discloses a silicone - (meth)acrylate copolymer emulsion that can impart water repellency to textiles. However, this publication does not address oil repellency.
  • a method for making a textile treatment emulsion comprises: I) mixing starting materials comprising i) an aqueous copolymer emulsion comprising a silicone - (meth)acrylate copolymer, a surfactant, and water; and ii ) an aqueous composition comprising an alkyl urethane, a surfactant, and water; wherein starting material i ) the aqueous copolymer emulsion and starting material ii) the aqueous composition are used in amounts sufficient to provide a weight ratio of the silicone - (meth) acrylate copolymer : the alkyl urethane of 1: ⁇ 9.
  • the aqueous copolymer emulsion comprising the silicone - (meth) acrylate copolymer, the surfactant, and water may be prepared as described in US Provisional Patent Application Number 63/593716, which is hereby incorporated by reference.
  • the silicone - (meth)acrylate copolymer comprises unit formula: each R 1 is an independently selected monovalent hydrocarbon group of 1 to 12 carbon atoms; each D 2 is an independently selected divalent hydrocarbon group of 2 to 12 carbon atoms; and each R 2 is independently selected from the group consisting of H and methyl; each R 3 is a group of formula OSi(R 4 h; where each R 4 is independently selected from the group consisting of R and DSi(R 5 )3, where each R is an independently selected monovalent hydrocarbon group of 1 to 12 carbon atoms, and each D is independently selected from the group consisting of an oxygen atom, a (poly)alkylene oxide group of 1 to 12 units, and a divalent hydrocarbon group of 2 to 4 carbon atoms; each R 5 is independently selected from the group consisting of R and DSi(R 6 )3; where each R 6 is independently selected from the group consisting of R and DSi
  • a quantity (a + bl + b2) 1 based on combined weights of the macromonomers used to prepare the copolymer, as described below.
  • the silicone - (meth)acrylate copolymer prepared as described above may have a weight average molecular weight measured by GPC of > 181,000 g/mol.
  • silicone - (meth)acrylate copolymer 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; and alternatively up to 750,000 g/
  • the silicone - (meth) acrylate copolymer 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.
  • silicone - (meth) acrylate copolymer (copolymer) above may be prepared by radical polymerization, via a method as described below, and that this method would form a terminal moiety for the copolymer.
  • the copolymer 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.
  • the copolymer may be prepared via a method comprising:
  • R 2 is selected from the group consisting of H and methyl; D 2 is a divalent hydrocarbon group of 2 to 12 carbon atoms, and each R 3 is a group of formula OSi(R 4 h; where each R 4 is independently selected from the group consisting of R and DSi(R 5 )3, where each R is an independently selected monovalent hydrocarbon group of 1 to 12 carbon atoms, and each D is independently selected from the group consisting of an oxygen atom, a (poly)alkylene oxide group of 1 to 12 units, and a divalent hydrocarbon group of 2 to 4 carbon atoms; each R 5 is independently selected from the group consisting of R and DSi(R 6 )3; where each R 6 is independently selected from the group consisting of R and DSiRs; with the proviso that R 4 , R 5 , and R 6 are selected such that the silicone - (meth)acrylate co-macromonomer of formula (B-2) has at least 5 silicon atoms per molecule; wherein starting material (
  • Step 1) of the method for making the copolymer may comprise an emulsion polymerization reaction.
  • the additional starting materials used in this emulsion polymerization method further comprise (D) a surfactant and (E) water.
  • 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.
  • 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 copolymer during copolymerization in step 1). These starting materials may be mixed under shear to form i) the 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.
  • 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 copolymer, thereby forming starting material z) the aqueous copolymer emulsion, which comprises (F) the silicone - (meth) acrylate copolymer, (D) the surfactant, and (E) the water, and optionally (I) manganese ion source and (J) the phenolic compound (when used).
  • 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
  • the method described herein may optionally further comprise one or more additional steps.
  • 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.
  • the starting materials comprising (A) the silicone - (meth)acrylate macromonomer and (B) the silicone -
  • step 1) combining the starting materials and copolymerizing 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.
  • Copolymerizing 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.
  • aerobic or anaerobic conditions means that oxygen is not required to be present in the gas in the headspace of the reactor where copolymerizing takes place, or dissolved in the liquid where copolymerizing 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.
  • the silicone - (meth)acrylate copolymer 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, (1) the manganese ion source, and (J) the phenolic compound, in an organic solvent (such as a monohydric alcohol) and copolymerizing 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.
  • the starting materials such as (A) the silicone - (meth)acrylate macromonomer, and optionally one or more of (B) the silicone - (meth)acrylate co-
  • the resulting copolymer 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 copolymer may be emulsified using (D) the surfactant and (E) the water.
  • the product prepared in step 1) is starting material i) the aqueous copolymer emulsion, which comprises (F) the silicone - (meth) acrylate copolymer, (D) the surfactant, and (E) the water.
  • Starting material i ) the aqueous copolymer 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 copolymer emulsion are further described below.
  • Starting material (A) used herein is a silicone - (meth) acrylate macromonomer.
  • the silicone - (meth)acrylate macromonomer has formula (A-l): each R 1 is an independently selected monovalent hydrocarbon group of 1 to 12 carbon atoms; D 2 is a divalent hydrocarbon group of 2 to 12 carbon atoms; and R 2 is selected from the group consisting of H and methyl.
  • each R 1 is an independently selected monovalent hydrocarbon group of 1 to 12 carbon atoms.
  • the monovalent hydrocarbon group for R 1 may be an alkyl group, such as an alkyl group of 1 to 6 carbon atoms.
  • the alkyl groups may have 1 to 3 carbon atoms, alternatively 1 to 2 carbon atoms.
  • each R 1 group may be methyl.
  • D 2 is a divalent hydrocarbon group of 2 to 12 carbon atoms.
  • D 2 may have 2 to 10, alternatively 3 to 5, and alternatively 3 carbon atoms.
  • the divalent hydrocarbon group for D 2 may be exemplified by an alkylene group such as ethylene, propylene, or butylene.
  • the divalent hydrocarbon group for D 2 may be propylene.
  • D 2 may be linear, e.g., -(CFh) - or -(CFh -.
  • D 2 may be -(CHip-.
  • starting material (A) comprises formula (A-2): described above.
  • Starting material (A) may comprise 3-(l,l,l,5,5,5-hexamethyl-3- ((trimethylsilyl)oxy)trisiloxan-3-yl)propyl methacrylate of formula
  • Starting material (A) may be prepared by known methods, such as those disclosed in PCT Publication WO2020/142388 and U.S. Patent 6,420,504.
  • Starting material (B) is a silicone - (meth) acrylate 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 (B-l), where formula ( each R 1 is an independently selected monovalent hydrocarbon group of 1 to 12 carbon atoms; D 2 is a divalent hydrocarbon group of 2 to 12 carbon atoms; and R 2 is selected from the group consisting of H and methyl, each as described and exemplified above for formula (A-l).
  • formula (B-l) may comprise: are as described above.
  • formula (B-2) may comprise 3-(l, 1,1, 3,5,5, 5-heptamethyltrisiloxan-3- yl)propyl methacrylate of formula
  • the co-macromonomer may comprise a silicone - (meth)acrylate co-macromonomer of formula ( divalent hydrocarbon group of 2 to 12 carbon atoms; and R 2 is selected from the group consisting of H and methyl, each as described above for formula (A-l).
  • each R 3 is a group of formula OSi(R 4 )3; each R 4 is independently selected from the group consisting of R and DSi(R 5 h, where each R is an independently selected monovalent hydrocarbon group of 1 to 12 carbon atoms; each D is independently selected from the group consisting of an oxygen atom, a (poly)alkylene oxide group of 1 to 12 units, and a divalent hydrocarbon group of 2 to 4 carbon atoms; each R 5 is independently selected from the group consisting of R and DSi(R 6 )3; where each R 6 is independently selected from the group consisting of R and DSiRs; with the proviso that R 4 , R 5 , and R 6 are selected such that the co-macromonomer of formula (B-2) has at least 6 silicon atoms per molecule.
  • R 4 , R 5 , and R 6 are selected such that the unit has at least 5 silicon atoms, alternatively at least 6 silicon atoms, alternatively 6 to 20 silicon atoms, alternatively 7 to 19 silicon atoms, alternatively 8 to 18 silicon atoms, alternatively 9 to 17 silicon atoms, and alternatively 10 to 16 silicon atoms, per molecule.
  • each R is a monovalent hydrocarbon group of 1 to 12 carbon atoms.
  • the monovalent hydrocarbon group for R may be an alkyl group, such as an alkyl group of 1 to 6 carbon atoms.
  • the alkyl groups may have 1 to 3 carbon atoms, alternatively 1 to 2 carbon atoms.
  • each R group may be methyl.
  • each D is independently selected from the group consisting of an oxygen atom, a (poly)alkylene oxide group of 1 to 12 units, and a divalent hydrocarbon group of 2 to 4 carbon atoms.
  • the divalent hydrocarbon group for D may be exemplified by an alkylene group such as ethylene, propylene, or butylene; an arylene group such as phenylene, or an alkylarylene group such as: each subscript u is independently 1 to 6, alternatively 1 to 2.
  • the divalent hydrocarbon group for D may be alkylene, and alternatively the divalent hydrocarbon group for D may be ethylene.
  • the (poly) alkylene oxide group for D may have 2 to 4 carbon atoms per unit, e.g., have formula D 5 (OD 6 ) V -OR, where D 5 is an alkylene group of 2 to 4 carbon atoms, D 6 is an alkylene group of 2 to 4 carbon atoms, R is as described above, and subscript v’ is 0 to 12. Alternatively subscript v’ may be 0 or 1. Alternatively, subscript v’ may be 0. Examples of (poly) alkylene oxide groups include ethyleneoxide-propyleneoxide.
  • each D may be selected from an oxygen atom and a divalent hydrocarbon group.
  • each divalent hydrocarbon group for D may be an alkylene group such as ethylene.
  • each D may be oxygen.
  • some instances of D may be oxygen and other instances of D may be alkylene, e.g. , ethylene, in the same unit.
  • formula (B-2) may comprise formula (B-2-1): are as described above.
  • formula (B-2) may comprise formula (B-2-2): are as described above.
  • formula (B-2) may comprise formula (B-2-3):
  • formula (B-2) may comprise a co-macromonomer selected from the group consisting of: 3-(5-((l,l,l,3,5,5,5-heptamethyltrisiloxan-3-yl)oxy)-l,l,l,3,7,9,9,9- octamethyl-3,7-bis((trimethylsilyl)oxy)pentasiloxan-5-yl)propyl methacrylate of formula
  • 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 copolymer: 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).
  • 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.
  • the amount of starting material (A) may be 100%, and the amount of starting material (B) may be 0.
  • 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.
  • the starting materials used to make the copolymer may optionally be free of crosslinkable groups, for example, the starting materials that copolymerize 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.
  • 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, and glycidyl (meth) acrylate (GMA).
  • 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)
  • 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).
  • alkenyltrialkoxysilanes e.g., 3- (trimethoxysilyl)propyl (meth)acrylate, vinyltriethoxysilane and vinyltrimethoxysilane.
  • the additional starting material comprises (C) an initiator.
  • the starting materials that copolymerize 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.
  • 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, (I) the manganese ion source, and (J) the phenolic compound, and these starting materials are described further below.
  • Starting material (C), the initiator, is also added in step 1) of the method for making the copolymer described above.
  • Suitable initiators include azo compounds and peroxide compounds.
  • 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.
  • 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.
  • diperoxide 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.
  • the initiator may comprise isoascorbic acid.
  • An initiator may be used alone as starting material (C).
  • starting material (C) may be a redox pair, which comprises an initiator as the oxidizing component and a reducing component.
  • 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.
  • 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.
  • 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 copolymer.
  • 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 of both 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): R 12 R 13 R 14 R 15 N + X’ _ where R 12 to R 15 are 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.
  • 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): R 16 R 17 N + (CH3)2X’ _ where R 16 and R 17 are 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): R 18 N + (CH3)3X”‘ where R 18 is 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.
  • 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 ADOGENTM, ARQUADTM, TOMAHTM, and VARIQUATTM.
  • 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.
  • cationic surfactants that are commercially available include compositions sold under the names ARQUADTM T27 W, ARQUADTM 16-29, by Akzo Nobel Chemicals Inc., Chicago, Illinois; and Ammonyx Cetac-30 by the Stepan Company, Northfield, Illinois, USA.
  • the amount of (D-l) the cationic surfactant may be 0.1% to 5%, based on weight of the silicone - (meth) acrylate copolymer in i) the aqueous copolymer emulsion.
  • 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.
  • 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.
  • Starting material (D-2) is a nonionic surfactant.
  • suitable nonionic surfactants which 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 TERGITOLTM TMN-6 and TERGITOLTM TMN-10; (ii) the Cl 1-15 secondary alkyl polyoxyethylene ethers sold under the names TERGITOLTM 15-S-7, TERGITOLTM 15-S- 9, TERGITOLTM 15-S-15, TERGITOLTM 15-S-30, and TERGITOLTM 15-S-40, by the Dow Chemical Company, of Midland, Michigan, USA; octylphenyl polyoxyethylene (40) ether sold under the name TRITONTM X405 by the Dow Chemical Company; (iii) nonylphenyl polyoxyethylene (10) ether sold under the name MAKONTM 10 by the Stepan Company; (iv) ethoxylated alcohols sold under the name Trycol 5953 by Henkel Corp./Emery Group,
  • alkyl-oxo alcohol polyglycol ethers such as GENAPOLTM UD 050, and GENAPOLTM UDI 10
  • alkyl polyethylene glycol ether based on ClO-Guerbet alcohol and ethylene oxide such as LUTENSOLTM XP 79.
  • 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 (polypropylene 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 PLURONICTM, such as PLURONICTM L61, L62, L64, L81, P84.
  • 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.
  • 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 TERGITOLTM TMN-6 and TERGITOLTM TMN-10; alkyleneoxy polyethylene oxyethanol (Cn-15 secondary alcohol ethoxylates 7EO, 9EO, and 15EO) sold under the trademarks TERGITOLTM 15-S-7, TERGITOLTM 15-S-9, TERGITOLTM 15-S-15; other Cn-15 secondary alcohol ethoxylates sold under the trademarks TERGITOLTM 15-S-12, 15-S-20, 15-S-3O, 15-S-40; octylphenoxy polyethoxy ethanol (40EO) sold under the trademark TRITONTM X-405 ; and alcohol ethoxylates with tradename ECOSURFTM EH, such as ECOSURFTM EH-40. All of these surfactants are sold by 6EO
  • nonylphenoxy polyethoxy ethanol 10EO
  • MAKONTM 10 polyoxyethylene 23 lauryl ether
  • RENEXTM 30 a polyoxyethylene ether alcohol available from Fisher Scientific.
  • the nonionic surfactant may also be a silicone polyether (SPE).
  • SPE silicone polyether
  • 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 DOWSILTM OFX-5329 Fluid from The Dow Chemical Company.
  • 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.
  • the nonionic surfactant may be delivered in a dilution, and the amount used may be sufficient to provide 0.1% to 10% of the surfactant, based on weight of the silicone - (meth)acrylate copolymer in the aqueous copolymer emulsion.
  • 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.
  • 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.
  • 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 copolymer in the aqueous copolymer emulsion.
  • 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 be unprocessed (e.g., may be tap water, i.e., provided by a municipal water system or well water, used without further purification). The amount of water is sufficient to form an aqueous emulsion for emulsion polymerization in step 1) of the method for making the copolymer described above. Additional water may be added after step 1).
  • the aqueous copolymer 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).
  • 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.
  • the silicone - (meth) acrylate copolymer, (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.
  • the silicone - (meth)acrylate copolymer is 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).
  • the silicone - (meth)acrylate copolymer is a reaction product of starting materials consisting of starting materials (A) and (C), (and, when present, (B) and/or (H)).
  • 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 copolymerization.
  • starting materials (D) and/or (E), or any other starting material added during the method may participate in the copolymerization reaction of starting materials comprising (A) and (C), and any optional starting materials (e.g., starting materials (B) and/or (H)), when present.
  • 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 a combination of two or more thereof.
  • Step 2) of this method may optionally further comprise adding additional (D) surfactant.
  • 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.
  • 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 Sau 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).
  • the chain transfer agent may be used in an amount of 0.5% to 0.6% on the same basis.
  • 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.
  • 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).
  • 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 copolymer emulsion.
  • 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.
  • hydroquinone HQ
  • 2-methylhydroquinone 2-t-butylhydroquinone
  • 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).
  • 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 copolymer emulsion.
  • 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.
  • DPPH 2,2-diphenyl-l-picrylhydrazyl
  • TEMPO 2,2,6,6-tetramethylpiperidin- l-yl)oxidanyl
  • 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 z ) the aqueous copolymer 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.
  • the aqueous copolymer emulsion may optionally further comprise starting material (P), a penetrating agent.
  • starting material P
  • penetrating agents are exemplified by glycol ethers, which are commercially available from The Dow Chemical Company and include DOWANOLTM DPM, TPM, PPh, EPh, Methyl CARBITOLTM, and Butyl CARBITOLTM.
  • the aqueous copolymer 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 alkylpoly siloxane of unit formula (R 19 3SiO)2(R 19 2SiO2/2)aa, wherein each R 19 is an independently selected monovalent saturated hydrocarbon group having 1 to 18 carbon atoms, and subscript aa has an average value of 20 to 300, 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 %,
  • each R 19 is 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 R 19 may be an alkyl group, alternatively an alkyl group of 1 to 6 carbon atoms.
  • the alkyl groups may have 1 to 3 carbon atoms, alternatively 1 to 2 carbon atoms.
  • each R 19 may be methyl.
  • Suitable alkylpolysiloxanes e.g., bis-trimethylsiloxy- terminated polydimethylsiloxanes, are known in the art and are commercially available, e.g., as XIAMETERTM 200 Fluids from The Dow Chemical Company.
  • the softening additive may comprise a (Q-2) combination comprising: 60 to 70 weight %, based on combined weights of all starting materials in (Q-2), the combination, of (Q-l) the alkylpolysiloxane described above, 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 1 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 amino-functional polyorganosiloxane per 1 mole of nitrogen atoms, and having a kinematic viscosity at 25 °C of 10 to 100,000 mm 2 /s measured by the method of
  • 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.
  • 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.
  • manganese (III) acetylacetonate (CAS No. 14284-89-0), zinc acetate hydrate (CAS No. 16788-43-5), zinc (11) 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 the silicone - (meth)acrylate copolymer, 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), when used.
  • the aqueous copolymer emulsion prepared as describe ed 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.
  • starting materials to add to i ) the aqueous copolymer 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.
  • manganese (II) acetylacetonate may be an inhibitor or a condensation reaction catalyst.
  • the starting materials used in aqueous copolymer emulsion (prepared as described above) and in the textile treatment emulsion (prepared as described below) may be distinct from one another.
  • Step 2) of the method described above for making the aqueous copolymer 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 copolymer emulsion prepared in step 1) later.
  • the aqueous copolymer emulsion prepared as described above is used to prepare the textile treatment emulsion described herein.
  • the method for preparing the textile treatment emulsion comprises: step I) mixing starting materials comprising starting material i) and starting material ii), wherein starting material i) is the aqueous copolymer emulsion comprising (F) the silicone - (meth)acrylate copolymer, (D) the surfactant, and (E) the water, as described above; and starting material ii) is an aqueous composition comprising an alkyl urethane, a surfactant, and water; and wherein starting material i) and starting material ii) are used in amounts sufficient to provide a weight ratio of the silicone - (meth) acrylate copolymer : the alkyl urethane of 1: ⁇ 9.
  • the weight ratio may be 1:3 to 1: 1 (copolymer : alkyl urethane weight ratio).
  • the weight ratio represents the relative amounts of solids delivered by the emulsions, i.e., the weight of the silicone - (meth)acrylate copolymer delivered in starting material i) : the weight of alkyl urethane delivered in starting material ii ).
  • the aqueous copolymer emulsion for starting material i ) is as described above.
  • Starting material ii) the aqueous composition comprising the alkyl urethane, surfactant, and water is known in the art and may be made by known methods such as those disclosed in EP 3 198 072 Bl (corresponding to US Patent 10246608, which is hereby incorporated by reference).
  • the aqueous composition may comprise a hydrophobic compound e.g., alkyl urethane compound) having at least one linkage of Formula (I): -NHC(O)-X- (I), wherein the linkage of Formula (I) comprises 30 to 100% by mol of the total urethane linkages in the hydrophobic compound;
  • X is the residue of a cyclic or acyclic sugar alcohol which is substituted with at least two -R’ ; -C(O)R’ ; -(CH2CH2O)n(CH(CH3)CH2O) m C(O)R’ ; or mixtures thereof; where the cyclic or acyclic sugar alcohol is selected from glucose, glyceraldehyde, erythrose, arabinose, ribose, allose, altrose, mannose, xylose, lyxose, gulose, galactose, talose, fructose, ribulose,
  • This method may optionally further comprise one or more additional steps.
  • the method may further comprise step II) adding to the textile treatment emulsion, starting material iii ) an aqueous additive comprising a blocked isocyanate and water.
  • the method may further comprise step III) adding to the textile treatment emulsion an additional starting material selected from the group consisting of the biocide, additional water, the flame retardant, the wrinkle reducing agent, the antistatic agent, the penetrating agent, the softening agent, the catalyst (each as described above), and a combination of two or more thereof; wherein each of these additional starting materials is as described above and may be added in step III) of the method for making the textile treatment emulsion, e.g., if not added in step 2) of the method for making starting material i ) the aqueous copolymer emulsion described above.
  • order of addition of the starting materials is not critical.
  • Steps I), II) and III) may be done in any order.
  • step I) may be performed before step II) and step III).
  • one or more of the additional starting materials from step III) may be combined with i ) the aqueous copolymer emulsion or ii ) the aqueous composition before starting materials i ) and ii ) are mixed.
  • the aqueous additive comprising the blocked isocyanate and water is optional, and when used is added in step III) as described herein.
  • 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, or oximes.
  • Blocked isocyanates are commercially available, such as ARKOPHOBTM DAN and ARKOPHOBTM SR from Archroma of Pratteln, Switzerland; RUCOTM-GUARD WEB and RUCOTM-LINK XCR from Rudolf GmbH of Geretsreid, explanation, Germany, and PHOBOLTM EXTENDER UXN and PHOBOLTM EXTENDER XAN extender from Archroma.
  • the blocked isocyanate may be an oxime blocked isocyanate, such as PHOBOLTM EXTENDER XAN.
  • 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, H 6 XDI, MDI, and HDI.
  • the polyisocyanate may be an aliphatic isocyanate where the NCO group is not directly attached to an aromatic ring.
  • the polyisocyanate may be HDI or MDI.
  • the N-heterocycle blocking agent may be2,6-dimethylpyrazine or a dimethylpyrazole, e.g., 3,5-dimethylpyrazole.
  • the aqueous additive for use herein may be free of oxime compounds.
  • the blocked 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).
  • 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 1. Table 1 - Commercially Available Aqueous Additives
  • the exact amount of the blocked isocyanate compound depends on various factors including the type and amount of (F) silicone - (meth) aery late copolymer, the type and amount of the alkyl urethane, 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 an aqueous dispersion with other components, e.g., water and optionally a surfactant.
  • other components e.g., water and optionally a surfactant.
  • the amount of starting material Hi) that may be mixed with starting materials i) and ii) may be sufficient to provide a weight ratio of silicone - (meth)acrylate copolymer and alkyl urethane combined : blocked isocyanate of 16:1 to 1:1; alternatively 16:1 to 2: 1; and alternatively 16:1 to 4:1.
  • the catalyst, described above as starting material (R) may also be used in the textile treatment emulsion.
  • Step III) of the method for preparing the textile treatment emulsion may be performed during or after step I).
  • the additional starting material may be mixed with i) the aqueous copolymer emulsion before step II).
  • the additional starting material may be added during or after mixing starting materials i) and ii).
  • Steps II) and III) of the process 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. Step II) and step III) may be performed concurrently or sequentially in the same vessel. Alternatively, steps II) and step III) may be performed in different equipment. Step II) may be performed at RT or elevated temperature, e.g., up to 100 °C, alternatively RT to 80 °C, and alternatively RT.
  • the textile treatment emulsion prepared as described above may be used for treating a textile.
  • a method for treating a textile comprises: 1 ) contacting the textile with the textile treatment emulsion described above, and 2 ) heating the textile.
  • Step I ) may be performed by any convenient method, such as padding, exhausting, dipping, or spraying the textile with the textile treatment emulsion.
  • the method should be sufficient to deliver a sufficient amount of the silicone - (meth)acrylate copolymer and the alkyl urethane 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 silicone - (meth)acrylate copolymer and the alkyl urethane combined, based on weight of the textile.
  • 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 the silicone - (meth)acrylate copolymer.
  • 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 (when the blocked isocyanate is used), and/or cure the silicone - (meth)acrylate copolymer.
  • 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.
  • silicone - (meth)acrylate copolymer 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 3. 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.
  • 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
  • a silicone - (meth)acrylate copolymer emulsion was prepared as follows. The following monomers, water, surfactant, and inhibitors were added to a widemouth jar (-400 mL): 3.38 g of EH40, 85.13 g of water, 9.06 g of 3MT-ALMA, 27.19 g of Sil6, 0.36 g of 4-methoxyphenol solution (2.5 % in water), 0.0046 g of hydroquinone, 0.10 g of Manganese (II) acetate tetrahydrate solution (0.7 % in water).
  • 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 to 40 °C with slow stirring before pouring off. This material was Emulsion 3, which is summarized below in Table 3.
  • aqueous compositions were prepared as follows. First, solutions A, B, and C were prepared. Solution A preparation: Added 0.0566 g of t- butylhydroperoxide (70% in water) and then enough water to make a 10 g solution. Solution B preparation: Added 0.0773 g of isoascorbic acid and then enough water to make a 10 g solution. Solution C preparation: Added 6 mg iron (II) sulfate heptahydrate and then enough water to make a 10 g solution.
  • Solution A preparation Added 0.0566 g of t- butylhydroperoxide (70% in water) and then enough water to make a 10 g solution.
  • Solution B preparation Added 0.0773 g of isoascorbic acid and then enough water to make a 10 g solution.
  • Solution C preparation Added 6 mg iron (II) sulfate heptahydrate and then enough water to make a 10 g solution.
  • the resulting coarse emulsion was then passed through a microfluidizer (Microfluidics Microfluidizer 110Y) and set to 5,000 psi, twice.
  • the resulting emulsion was then transferred to a 1 L 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 60 °C. After reaching temperature, Solution C was added (1.74 grams of prepared Solution C) and a redox initiator was then fed into the flask at 0.25 mL/min (Solutions A+B, prepared as described above in separate feeds). The reaction was run for 45 min. The resulting material was then allowed to cool to 30 to 40 °C with slow stirring before pouring off. This material was Emulsion 4, which is summarized below in Table 3.
  • the * denotes 0.4 g of a 2.5 % water solution of 4-methoxyphenol, 0.006 g of hydroquinone and 0. 12 g of 0.7 % water solution of Mn(II)acetate tetrahydrate were used.
  • textile treatment emulsions were prepared by mixing the starting materials in the amounts shown below in Table 4, as follows: Each starting material was added into a 125 g Nalgene plastic bottle, and the bottle was inverted twice to mix.
  • the weight ratio means the weight of copolymer delivered in the aqueous copolymer emulsion (from Table 3) : the weight of alkyl urethane solids in Zelan R3.
  • Examples 1-7 showed that under the conditions tested, mixing Zelan R3 and an aqueous copolymer emulsion of a silicone - (meth)acrylate copolymer made with 3MT-ALMA afforded a textile treatment emulsion that imparted durable oil repellency to textiles.
  • Examples 1 and 4 showed that a blocked isocyanate additive was not necessary to impart oil repellency to textiles under the conditions tested.
  • Examples 2, 3, and 5-7 showed that a blocked isocyanate could be added to the textile treatment emulsion, and the resulting treated textiles had durable oil repellency under the conditions tested.
  • Comparative 1 demonstrated the Zelan R3 did not provide durable oil repellency to textiles without the silicone - (meth) acrylate copolymer.
  • Comparative 2 showed that under the conditions tested, a weight ratio of silicone -
  • (meth) acrylate copolymer alkyl urethane 1 : ⁇ 9 provided durable oil repellency. Comparative 4 showed that an emulsion prepared including a copolymer of 3MT-ALMA and stearyl acrylate did not impart oil repellency under the conditions tested.
  • 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.
  • 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 NaHCCL (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.
  • the procedure for comparative examples 5 and 6 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.
  • Ludox HS silica 5 g of a 40% solution of Ludox HS-40 colloidal silica and 35 g of DI water
  • 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.
  • 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.
  • Ludox HS silica 5 g of a 40% solution of Ludox HS-40 colloidal silica and 35 g of DI water
  • Comparative Examples 5 and 6 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 to 7 in Table 5, above) had superior oil repellency using the modified AATCC method 118 described herein. Comparative Examples 7 and 8 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.
  • Comparative Example 11 shows a pretreatment method of the blocked isocyanate (XAN) additive similarly described in example 2 in US Patent Publication US20230038369 (Comparative Examples 5 and 6 above). This comparative example 11 did not pass the modified AATCC method 118 after 10 sec and had worse oil repellency than Comparative Examples 5 and 6 at 10 sec.
  • XAN blocked isocyanate
  • 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.
  • 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 1) to reapply the textile treatment emulsion in order to impart oil repellency.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

Une émulsion de traitement textile peut être obtenue par mélange d'une émulsion aqueuse d'un copolymère de silicone-(méth)acrylate et d'une émulsion aqueuse d'un alkyluréthane. L'émulsion de traitement textile peut être appliquée sur un tissu et chauffée, ce qui permet d'augmenter le caractère oléofuge du tissu.
PCT/US2024/045246 2023-10-27 2024-09-05 Traitement textile pour conférer une hydrophobie comprenant l'utilisation d'un copolymère de silicone-(méth)acrylate et d'un uréthane Pending WO2025090190A1 (fr)

Applications Claiming Priority (10)

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US202363593716P 2023-10-27 2023-10-27
US63/593,716 2023-10-27
US202463674323P 2024-07-23 2024-07-23
US202463674322P 2024-07-23 2024-07-23
US202463674325P 2024-07-23 2024-07-23
US202463674328P 2024-07-23 2024-07-23
US63/674,322 2024-07-23
US63/674,328 2024-07-23
US63/674,323 2024-07-23
US63/674,325 2024-07-23

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PCT/US2024/045246 Pending WO2025090190A1 (fr) 2023-10-27 2024-09-05 Traitement textile pour conférer une hydrophobie comprenant l'utilisation d'un copolymère de silicone-(méth)acrylate et d'un uréthane

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