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WO2025075699A1 - Formulation de copolymère de silicone- (méth)acrylate et ses procédés de préparation et d'utilisation - Google Patents

Formulation de copolymère de silicone- (méth)acrylate et ses procédés de préparation et d'utilisation Download PDF

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Publication number
WO2025075699A1
WO2025075699A1 PCT/US2024/039474 US2024039474W WO2025075699A1 WO 2025075699 A1 WO2025075699 A1 WO 2025075699A1 US 2024039474 W US2024039474 W US 2024039474W WO 2025075699 A1 WO2025075699 A1 WO 2025075699A1
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WO
WIPO (PCT)
Prior art keywords
group
alternatively
independently selected
carbon atoms
subscript
Prior art date
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PCT/US2024/039474
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English (en)
Inventor
Matthew JELETIC
Michael TELGENHOFF
Barbara CRESSMAN
Yusei SAKURAI
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dow Global Technologies LLC
Rohm and Haas Co
Dow Silicones Corp
Original Assignee
Dow Global Technologies LLC
Rohm and Haas Co
Dow Silicones Corp
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Publication of WO2025075699A1 publication Critical patent/WO2025075699A1/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1818—C13or longer chain (meth)acrylate, e.g. stearyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
    • C09D143/04—Homopolymers or copolymers of monomers 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
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/07—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof
    • D06M11/11—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof with halogen acids or salts thereof
    • D06M11/26—Halides of elements of Groups 7 of the Periodic Table
    • 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
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/48—Oxides or hydroxides of chromium, molybdenum or tungsten; Chromates; Dichromates; Molybdates; Tungstates
    • D06M11/485—Oxides or hydroxides of manganese; Manganates
    • 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
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/152—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen having a hydroxy group bound to a carbon atom of a six-membered aromatic ring
    • 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
    • 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 composition including a silicone - (meth)acrylate copolymer, a manganese ion source, and a phenolic compound, and methods for its preparation and use are provided.
  • the composition is useful for treating textiles to impart durable water repellency thereto.
  • R 1 has 16 to 24 carbon atoms.
  • R 1 may have 16 to 22 carbon atoms, alternatively 18 to 24 carbon atoms, and alternatively 18 to 22 carbon atoms.
  • R 1 may be selected from the group consisting of stearyl, eicosyl, and behenyl. Alternatively, R 1 may be stearyl.
  • each R 3 is a group of formula OSi(R 4 )a; 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 DSiR ,; with the proviso that R 4 , R 5 , and R 6 are selected such that the silicone - (meth)acrylate macromonomer unit with subscript x has at least 6 silicon atoms.
  • 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.
  • subscript w may be at least 80, alternatively at least 81, alternatively at least 82, alternatively at least 83, alternatively at least 84, and alternatively at least 85.
  • subscript w may be up to 98.75, alternatively up to 98, alternatively up to 97, alternatively up to 96, alternatively up to 97, alternatively up to 96, alternatively up to 95, alternatively up to 94, alternatively up to 93, alternatively up to 92, alternatively up to 91, and alternatively up to 90.
  • subscript w may be 80 to 98, alternatively 81 to 97, alternatively 82 to 96, alternatively 82 to 95, and alternatively 85 to 90.
  • Subscript x has a value of 0.25 to 15.
  • subscript x is at least 0.25, alternatively at least 0.5, alternatively at least 0.75, alternatively at least 1, alternatively at least 2, alternatively at least 3, alternatively at least 4, alternatively at least 5.
  • subscript x may be up to 15, alternatively up to 14, alternatively up to 13, alternatively up to 12, alternatively up to 11, and alternatively up to 10.
  • subscript x may be 1 to 14, alternatively 2 to 13, alternatively 3 to 12, alternatively 4 to 11, alternatively 5 to 10, alternatively 5 to 15; and alternatively 10.
  • Subscript y has a value of 1 to 5.
  • subscript y may be at least 1, alternatively at least 1.25, alternatively at least 1.5, alternatively at least 2, and alternatively at least 1.75.
  • subscript y may be up to 5, alternatively up to 4, alternatively up to 3, alternatively up to 2.75, alternatively up to 2.5, and alternatively up to 2.25.
  • subscript y may be 1 to 3, alternatively 1 to 2, alternatively 1.5 to 2.5, alternatively 1.75 to 2.25, and alternatively 2.
  • subscript zl may be 0 to 18.75, alternatively > 0 to 18.75, alternatively 0.5 to 7, alternatively 1 to 6, and alternatively 2 to 5.
  • Subscript z2 may be 0.
  • subscript z2 may be at least 0.5, alternatively at least 1, and alternatively at least 2; while at the same time, subscript z2 may be up to 8, alternatively up to 7, alternatively up to 6, alternatively up to 5, and alternatively up to 4.
  • subscript z2 may be 0 to 8, alternatively > 0 to 8, alternatively 0.5 to 7, alternatively 1 to 6, and alternatively 2 to 5.
  • the copolymer may be prepared by any convenient means such as that disclosed in PCT Patent Application Publication WO2022/197350 to Jeletic et al. by using the manganese ion source and the phenolic compound described herein as inhibitors, instead of the inhibitor described therein.
  • the copolymer may be prepared as described in U.S. Patent 10,047,199 to limura et al. by varying appropriate starting materials and their amounts.
  • PCT Patent Application Publication WO2022/197350 and U.S. Patent 10,047,199 are hereby incorporated by reference.
  • composition according to this invention may be prepared via a process comprising:
  • the starting materials used in the process to prepare the composition may optionally further comprise (H) a chain transfer agent; (J) an additional non- crystallizable monomer that is distinct from each of (A), (B) and (C); and a combination of both (H) and (J).
  • Copolymerizing may comprise preparing the copolymer described above by a method comprising dissolving one or more of starting materials (A), (B), (C), and when present (H) and/or (J), with (K) the manganese ion source and (L) the phenolic compound in a solvent (e.g., an organic solvent such as a monohydric alcohol).
  • a solvent e.g., an organic solvent such as a monohydric alcohol
  • the resulting composition comprises (F) the copolymer, (K) the manganese ion source, and (L) the phenolic compound.
  • An aqueous emulsion may be prepared by a process comprising emulsifying said composition by mixing, under shear, the composition described above and additional starting materials comprising (D) a surfactant and (E) water.
  • the resulting aqueous emulsion comprises (F) the silicone - (meth)acrylate copolymer, (K) the manganese ion source, (L) the phenolic compound, (D) the surfactant, and (E) the water.
  • D 3 is a divalent hydrocarbon group of 1 to 12 carbons
  • D 4 is a divalent group of 2 to 4 carbon atoms
  • subscript v is 0 to 12
  • R 8 is a crosslinkable group, each as described above; where amounts of starting materials (A), (B), and (C) total 100 weight% based on combined amounts of starting materials (A), (B), and (C); and starting materials (A), (B), and (C) arc copolymerized in an emulsion further comprising
  • the emulsion polymerization process described above may comprise forming an emulsion comprising starting materials (A), (B), (C), (D), (E), (H), (K), and (L) (and optionally
  • starting material (A) is a solid at RT
  • the starting materials may be heated to a temperature and for a time sufficient to melt starting material (A), e.g., 30 °C to 50 °C for 5 minutes to 15 minutes.
  • the resulting starting materials may be mixed under shear to form the aqueous 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 sonicators, homogenizers, microfluidizers, and speedmixers are known in the art and are commercially available.
  • Copolymerizing may be performed in a batch process with a residence time of 15 minutes to 24 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 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.
  • a process for preparing the emulsion formulation suitable for treating the textile may comprise practicing step 1) of the process described above, thereby preparing the aqueous emulsion, and 2) combining the aqueous emulsion prepared in step 1) and an additional starting material comprising (G) a water dispersible crosslinker.
  • Step 2) may optionally further comprise adding a further additional starting material, which may be selected from the group consisting of (M) a wax, (N) a biocide, (O) additional water (which may be the same as starting material (E)), (P) a flame retardant, (Q) a wrinkle reducing agent, (R) an antistatic agent, (S) a penetrating agent and a combination of two or more of starting materials (M), (N), (O), (P),(Q), (R) and (S).
  • Step 2) of this process may optionally further comprise adding additional (D) surfactant.
  • Step 2) of the process described above may be performed by any convenient means, such as mixing using in 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. The starting materials used in the processes described above are further described below.
  • Starting material (A) is a crystallizable monomer of formula (A-l): , where R 1 and R 2 are as described above.
  • crystallizable monomers for starting material (A) include stearyl (meth)acrylate, eicosyl (meth)acrylate, behenyl (meth)acrylate, and combinations thereof.
  • R 2 is hydrogen
  • starting material (A) may be an acrylate selected from stearyl acrylate, eicosyl acrylate, behenyl acrylate, and combinations thereof.
  • Crystallizable monomers suitable for starting material (A) are commercially available, e.g., from Millipore Sigma of St. Louis, Missouri, USA and from BASF SE of Ludwigshafen, Germany. Crystallizable means that the monomer has a melting point) > 25 °C ⁇ 5 °C.
  • Starling material (A) is used in an amount of 80% to 98.75%, based on combined weights of starting materials (A), (B), and (C), and when present (J).
  • the amount of starting material (A) may be at least 80%, alternatively at least 81%, alternatively at least 82%, alternatively at least 83%, alternatively at least 84%, and alternatively at least 85% on the same basis.
  • the amount of starting material (A) may be up to 98.75%, alternatively up to 98.5%, alternatively up to 98%, alternatively up to 97%, alternatively up to 96%, alternatively up to 95%, alternatively up to 94%, alternatively up to 93%, alternatively up to 92%, alternatively up to 91%, alternatively up to 90%, and alternatively up to 89%, on the same basis.
  • the amount of starting material (A) may be 80% to 98%, alternatively 81% to 97%, alternatively 82% to 96%, alternatively 82% to 95%, alternatively 85% to 90%; on the same basis.
  • Starting material (B) is a silicone - (meth)acrylate macromonomer of formula (B- 1 ): are as described above.
  • starting material (B) may comprise formula (B-2): are as described above.
  • starting material (B) may comprise a macromonomer selected from the group consisting of:
  • Starting material (C) is a crosslinkablc (mcth)acrylatc monomer.
  • the crosslinkablc is a crosslinkablc (mcth)acrylatc monomer.
  • (meth)acrylate monomer may have formula ( where R 2 , R 7 , D 3 , R 8 , and subscript v are as described above.
  • suitable crosslinkable (meth)acrylates for starting material (C) include (2-acetoacetoxy)ethyl methacrylate, hydroxybutyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxyethylcaprolactone (mcth)acrylatc, hydroxypropyl (mcth)acrylatc, urcido (mcth)acrylatc, glycidyl (mcth)acrylatc (GMA), poly(ethylene glycol) (meth)acrylate (PEGMA), and combinations thereof.
  • the ureido (meth)acrylate monomer may have formula (C-2): oxygen atom or an NH moiety.
  • C-2 formula (C-2): oxygen atom or an NH moiety.
  • Examples of ureido monomers are known in the art and are disclosed, for example, in U.S. Patent 9,212,292 to Pressley, et al.
  • Other crosslinkable (meth)acrylate monomers are known in the ail and are commercially available, e.g., from BASF SE.
  • Other crosslinkable (meth)acrylates are commercially available as Sipomer WAM1 and 2.
  • the crosslinkable (meth) acrylate monomer may be (C-3) (meth)acrylic acid.
  • Acrylic acid and methacrylic acid are commercially available from Sigma-Aldrich, Inc. of St. Louis, Missouri, USA.
  • Stalling 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.
  • Monoalkyl trimethyl ammonium salts can be used and are represented by formula (D- 1-3): 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), hexadeclyltrimethyl ammonium chloride, didodecyldimethyl ammonium bromide, dihexadecyldimethyl ammonium chloride, dihexadecyldimethyl ammonium bromide, dioctadecyldimethyl ammonium chloride, dieicosyldimethyl ammonium chloride, and didocosyldimethyl ammonium chloride.
  • LTAC dodecyltrimethyl ammonium chloride/lauryltrimethyl ammonium chloride
  • CTAC cetyltrimethyl ammonium chloride
  • hexadeclyltrimethyl ammonium chloride didodecyldimethyl ammonium bromide
  • quaternary ammonium salts are commercially available under trademarks such as ADOGENTM, ARQUADTM, TOMAHTM, and VARIQUATTM.
  • 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 ARQUADTM T27 W, ARQUADTM 16-29, by Akzo Nobel Chemicals Inc., Chicago, Illinois; and Ammonyx Cetac-30 by the Stepan Company, Northfield, Illinois, USA.
  • 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.
  • Such silicone-based surfactants may be used to form such aqueous emulsions and are known in the art, and have been described, for example, in U.S. Patent 4,122,029 to Gee et al., U.S. Patent 5,387,417 to Rentsch, and U.S. Patent 5,811,487 to Schulz et al.
  • 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 process described above. Additional water may be added after step 1).
  • the aqueous emulsion prepared as described above may be diluted with additional water to achieve a desired amount of starting materials before treating a textile with the emulsion formulation.
  • the water may be added in an amount of 20% 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.
  • starting materials (D) and (E) copolymerize with starting materials (A), (B), and (C), but 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), (B), (C), and (I).
  • Diols include, for example, 1,2-propanediol; 1,3- propanediol; 1 ,2-butanediol; 1,3-butanediol; 1,4-butanediol; 2,3-butanediol; 2-methyl- 1 ,2- propanediol; 1,5 -pentanediol; 2-methyl-2,3-butanediol; 1,6-hexanediol; 1,2-hexanediol; 2,5- hexanediol; 2-methyl-2,4-pentanediol; 2,3-dimethyl-2,3-butanediol; 2-ethylhexanediol; 1,2- octanediol; 1,2-decanediol; 2,2,4-trimethylpentanediol; 2-butyl-2-ethyl-l,3-propanedio
  • crosslinker (G) examples include U.S. Patent Application 2017/0204558 to Knaup; U.S. Patent 9,777,105 to Hamajima et al., beginning at col. 11, line 54, which are hereby incorporated by reference for the purpose of describing suitable crosslinkers.
  • the exact amount of crosslinker (G) depends on various factors including the type and amount of (F) silicone - (meth) acrylate copolymer formed in step 1) and the textile to be treated, however, the weight of the crosslinker (G) may 0.25% to 3.75% on fabric weight, alternatively 0.25% to 1%, and alternatively 0.25% to 0.5%, on the same basis.
  • An additional starting material that may be added in step 1) of the process 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, GASF Sau AG, Basel, Switzerland, Encyclopedia of Radicals in Chemistry, Biology and Materials, Online ⁇ 2012 John Wiley & Sons, Ltd.
  • Stalling material (I), an initiator is also added in step 1) described above.
  • Suitable initiators include azo compounds and peroxide compounds.
  • the azo compound may be an aliphatic azo compound such as 1-t-amylazo-l- cyanocyclohexane, azo-bis- isobutyronitrile and 1-t-butylazo-cy anocyclohexane, 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.
  • (I) may be a redox pair, which comprises an initiator as the oxidizing component and a reducing component.
  • a redox pair including isoascorbic acid and a hydrophobic organic hydroperoxide such as t-amyl hydroperoxide or t-butyl hydroperoxide may be used as starting material (I).
  • suitable initiators and/or redox pairs for stalling material (I) are disclosed in U.S. Patent 6,576,051 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.
  • Stalling material (J) is an optional additional monomer that may be added in step 1).
  • Starting material (J) is a non-crystallizable monomer that is distinct from starting materials (A), (B), and (C), described above.
  • the additional monomer when present, may be used in an amount of > 0 to 18.75 weight % based on weight of (F) the silicone - (meth)acrylate copolymer.
  • the additional monomer may be present in an amount of at least 0.5%, alternatively at least 1%, and alternatively at least 2%; while at the same time the additional monomer may be present in an amount up to 18.75%, alternatively up to 15%, alternatively up to 10%, alternatively up to 8%, and alternatively up to 5%, on the same basis.
  • the amount of (I) the additional monomer may be > 0 to 18.75%, alternatively 0.5% to 7%, alternatively 1 % to 6%, and alternatively 2% to 5%, on the same basis.
  • Starting material (K) is a manganese ion source, which may be a manganese (II) compound.
  • Suitable manganese compounds include manganese (II) acetate, manganese (II) nitrite, manganese (II) propionate, manganese (II) oxide, manganese (II) hydroxide, manganese (II) chloride, manganese (II) phosphate, manganese (II) perchlorate, hydrates thereof (e.g., manganese (II) tetrahydrate) and combinations thereof.
  • the manganese ion source may comprise manganese (II) acetate or manganese (II) 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 stalling materials (A), (B), and (C).
  • 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 the emulsion formulation for treating the textile.
  • suitable waxes include paraffin waxes (e. ., n-paraffins, iso-paraffins, and/or cycloparaffins), silicone waxes such as silicone wax with long chain alkyl groups (e.g., alkyl methyl silicone wax) and/or amino-silicone wax, and a combination of two or more thereof.
  • Suitable waxes are disclosed, for example, in U.S. Patent Application 2017/0204558 to Knaup and U.S. Patent 10,844,151 to Probst, et al.
  • Waxes may be delivered as water-based dispersions, for example Michelman wax 743 and others from Michelman of Cincinnati, Ohio, U.S.A.
  • Other waxes are also commercially available, for example, from Sasol Wax of Hamburg, Germany, and silicone waxes, such as DOWSILTM AMS-C30, are available from Dow Silicones Corporation of Midland, Michigan, U.S.A.
  • Starting material (S) is a penetrating agent. Suitable 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 emulsion formulation may optionally further comprise an additional starting material selected from the group consisting of (M) the wax, (N) the biocide, (O) additional water, (P) the flame retardant, (Q) the wrinkle reducing agent, (R) the antistatic agent, (S) the penetrating agent, and a combination of two or more of starting materials (M), (N), (O), (P), (Q), (R) and (S).
  • additional starting materials and their amounts are as described above.
  • the emulsion formulation described herein may be formulated with starting materials that are fluorocarbon-free.
  • the emulsion formulation may be free of any starting material that contains a fluorine atom covalently bonded to a carbon atom.
  • the method may be sufficient to deliver on fabric weight of 0.25 weight % to 10 weight % of (F), the silicone - (meth)acrylate copolymer, and on fabric weight of 0.1 weight % to 3.75 weight %, alternatively 0.25% to 1 %, of (G), the water dispersible crosslinker, both based on weight of the textile.
  • 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 emulsion formulation described herein is suitable for use on textiles in any form, e.g., woven fabrics, knitted fabrics, or nonwoven textiles.
  • Example Bl did not have any 50 °C holds between passes, and the total residence time was 12 min to complete 3 passes through the homogenizer for this example only.
  • textile treatment emulsions were prepared as follows: 3 separate solutions were prepared (A) 1.053g 70%tBHP in 40 g of DI water (B) 1.44 g Isoascorbic acid in 40 g of water (C) 47 mg of Iron(II) sulfate heptahydrate in 15 g of water. [0078] 940 g of a monomer emulsion mix 1 from Table 2 above, was added to a 4 neck flask.
  • Sample II (working example according to this invention) contained manganese (II) acetate, HQ, and MEHQ and had the best face rating at each time tested.
  • Sample B 1 contained MEHQ and 4-hydroxyTEMPO as inhibitors, but initially failed the face rating test even with only 4 minutes processing time at high temperature.
  • Sample Cl contained the same inhibitors as sample Bl, but was exposed to high temperature for extended time. Sample Cl failed the face rating test after 20 washes.
  • Sample C2 contained MEHQ as inhibitor (but without Mn(II)), and sample C2 failed the face rating test after 1, 10, and 20 washes.
  • Sample C3 contained MEHQ and 4-hydroxyTEMPO as inhibitors and Sample C3 failed the face rating test after 10 and 20 washes.
  • the emulsion formulation and process described herein can produce a fabric having durable water repellency as measured by the Bundesmann test described herein. More specifically, the fabric can have Bundesmann face rating > 4.5 after initial treatment and can maintain the face rating > 4.5 after 1, 5, 10, and 20 washes.
  • any ranges and subranges relied upon in describing the present invention independently and collectively fall within the scope of the appended claims and are understood to describe and contemplate all ranges including whole and/or fractional values therein, even if such values are not expressly written herein.
  • One of skill in the art readily recognizes that the enumerated ranges and subranges sufficiently describe and enable various embodiments of the present invention, and such ranges and subranges may be further delineated into relevant halves, thirds, quarters, fifths, and any other subrange subsumed within the range.
  • a range of “16 to 24” may be further delineated into a lower third, i.e.. 16 to 18, a middle third, i.e..
  • the range “16 to 24” includes the subrange “18 to 22”, each which individually and collectively are within the scope of the appended claims, and may be relied upon individually and/or collectively and provide adequate support for specific embodiments within the scope of the appended claims.
  • the language which defines or modifies a range such as “at least,” “greater than,” “less than,” “no more than,” and the like, it is to be understood that such language includes subranges and/or an upper or lower limit.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
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  • Life Sciences & Earth Sciences (AREA)
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  • Wood Science & Technology (AREA)
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Abstract

Une composition comprend un copolymère de silicone-(méth)acrylate, une source d'ions manganèse et un composé phénolique. L'invention concerne des procédés de préparation et d'utilisation de la composition. La composition peut être émulsifiée, et la formulation d'émulsion aqueuse résultante peut être utilisée pour traiter un textile afin de conférer un caractère hydrofuge.
PCT/US2024/039474 2023-10-05 2024-07-25 Formulation de copolymère de silicone- (méth)acrylate et ses procédés de préparation et d'utilisation Pending WO2025075699A1 (fr)

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