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WO2025122684A1 - Compositions de tensioactif d'éther d'aryle partiellement fluoré et procédés d'utilisation - Google Patents

Compositions de tensioactif d'éther d'aryle partiellement fluoré et procédés d'utilisation Download PDF

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WO2025122684A1
WO2025122684A1 PCT/US2024/058568 US2024058568W WO2025122684A1 WO 2025122684 A1 WO2025122684 A1 WO 2025122684A1 US 2024058568 W US2024058568 W US 2024058568W WO 2025122684 A1 WO2025122684 A1 WO 2025122684A1
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chf
group
formula
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reactor
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Andrii Matsnev
Kätchen K. Lachmayr
Peter A. Morken
Phan Linh Tang
John Christopher Sworen
Alexander Borisovich Shtarov
Vincent FRANCO
Cameron PARRISH
Adam Paul Smith
Axel Hans-Joachim Herzog
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Chemours Co FC LLC
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    • 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
    • C08F14/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F14/18—Monomers containing fluorine
    • C08F14/26—Tetrafluoroethene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/01—Sulfonic acids
    • C07C309/28—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C309/41—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing singly-bound oxygen atoms bound to the carbon skeleton
    • C07C309/42—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing singly-bound oxygen atoms bound to the carbon skeleton having the sulfo groups bound to carbon atoms of non-condensed six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/01—Sulfonic acids
    • C07C309/28—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C309/45—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton
    • C07C309/51—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton at least one of the nitrogen atoms being part of any of the groups, X being a hetero atom, Y being any atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C65/00—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
    • C07C65/21—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing ether groups, groups, groups, or groups
    • 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
    • C08F14/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F14/18—Monomers containing fluorine
    • C08F14/22—Vinylidene fluoride
    • 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
    • C08F14/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F14/18—Monomers containing fluorine
    • C08F14/28—Hexafluoropropene
    • 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
    • C08F16/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F16/12—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
    • C08F16/14—Monomers containing only one unsaturated aliphatic radical
    • C08F16/24—Monomers containing halogen

Definitions

  • the present disclosure relates to the field of surfactants. More specifically, the present disclosure relates to partially fluorinated aryl ether surfactants and their use in emulsion polymerization and polymer dispersions.
  • a conventional process for the aqueous emulsion polymerization of fluorinated monomer includes feeding fluorinated monomer to a heated reactor containing a fluorosurfactant and deionized water.
  • Paraffin wax is employed in the reactor as a stabilizer for some polymerizations, e.g., polytetrafluoroethylene (PTFE) homopolymers.
  • PTFE polytetrafluoroethylene
  • a free-radical initiator solution is employed and, as the polymerization proceeds, additional fluorinated monomer is added to maintain the pressure.
  • a chain transfer agent is employed in the polymerization of some polymers, e.g., melt-processible TFE copolymers to control melt viscosity. After several hours, the feeds are stopped, the reactor is vented and purged with nitrogen, and the raw dispersion in the vessel is transferred to a cooling vessel.
  • fluoropolymer polymerizations have utilized perfluorinated or highly fluorinated surfactants as process aids.
  • perfluorinated or highly fluorinated surfactants As process aids.
  • fluoropolymer polymerization processes are very sensitive to chain transfer reactions with hydrocarbons and are not amenable to non-fluorinated surfactant technology.
  • an aqueous fluoropolymer emulsion polymerization composition includes an aqueous solvent; at least one monomer selected from the group consisting of tetrafluoroethylene (TFE), hexafluoropropylene, vinylidene fluoride, perfluoroalkyl vinyl ether (PAVE), and combinations thereof; and a partially fluorinated aryl ether surfactant of Formula 1 :
  • Ri includes a terminal group selected from the group consisting of CO2X, SO3X, and PO(OX)2.
  • X is selected from the group consisting of H, Li, Na, K, Cs, NH4, 1 / 2 Mg, ! Ca, and 1 / 2 Ba.
  • R2, R3, R4, R5, and Re are independently selected from the group consisting of H, halogen, C1.8 linear or branched alkyl, C1-4 alkoxy that is partially or fully halogenated and may further include an ether, Formula 2, and Formula 3:
  • Y is selected from the group consisting of -O-, -C(O)NH-, -C(O)O-, -S-, -S(O)-, -SO2-, -SO2NH-, -OC(O)O-, -C(O)-, phosphonate, phosphate, -C(CHs)2-, -C(CF 3 )2-, and -C(CF 2 H) 2 -.
  • R7, Rs, R9, Rio, and Rn are independently selected from the group consisting of H, halogen, and C1-4 alkoxy that is partially or fully halogenated and may further include an ether.
  • At least one of R2, R3, R4, Rs, and Re is selected from the group consisting of C1-3 alkoxy that is partially or fully halogenated and may further include an ether, Formula 2, and Formula 3 and is not -O-CF2-CHF-CF3.
  • At least two of R2, R3, R4, Rs, and Re are selected from the group consisting of H and halogen.
  • the halogen is fluorine and the halogenated is fluorinated.
  • R1 consists of the terminal group selected from the group consisting of CO2X, SO3X, and PO(OX)2.
  • R1 is SO3X.
  • R1 is CO2X.
  • R1 is PO(OX)2.
  • At least one of R2, R3, R4, Rs, and Re is C1-4 linear or branched alkyl.
  • At least one of R2, R3, R4, Rs, and Re is C1-3 alkoxy that is partially or fully halogenated and may further include an ether.
  • the C1-3 alkoxy that is partially or fully halogenated and may further include an ether is partially halogenated.
  • At least one of R2, R3, R4, Rs, and Re is selected from the group consisting of -O-CH2F, -O-CHF2, -O-CF3, -O-CH2-CHF2, -O-CF2-CH3, -O-CF2-CHF2, -O-CH(CH 2 F) 2 , -O-CF(CH 2 F) 2 , -O-CH(CHF 2 ) 2 , -O-CHF-CHF-O-CF3, -O-CF2-CH2-O-CF2H, -O-CF2-CH2-O-CF3, and -O-CF2-CHF-O-CF3.
  • At least two of R2, R3, R4, Rs, and Re are independently selected from the group consisting of -O-CH2F, -O-CHF2, -O-CF 3 , -O-CH2-CHF2, -O-CF2-CH3, -O-CF2-CHF2, -O-CH(CH 2 F) 2 , -O-CF(CH 2 F) 2 , -O-CH(CHF 2 )2, -0-CHF-CHF-0-CF3, -O-CF2-CH2-O-CF2H, -O-CF2-CH2-O-CF3, and -O-CF2-CHF-O-CF3.
  • At least one of R7, Rs, Rg, R10, and R11 is the C1-4 alkoxy that is partially or fully halogenated and may further include an ether.
  • a compound has Formula 1.
  • R1 includes a terminal group selected from the group consisting of CO2X, SO3X, and PO(OX)2.
  • X is selected from the group consisting of H, Li, Na, K, Cs, NH4, 1 XMg, 1 /2Ca, and 2 Ba.
  • R2, R3, R4, Rs, and Re are independently selected from the group consisting of H, halogen, Ci-s linear or branched alkyl, C1-4 alkoxy that is partially or fully halogenated and may further include an ether, Formula 2, and Formula 3:
  • Y is selected from the group consisting of -O-, -C(O)NH-, -C(O)O-, -S-, -S(O)-, -SO2-, -SO2NH-, -OC(O)O-, -C(O)-, phosphonate, phosphate, -C(CH 3 )2-, -C(CF 3 ) 2 -, and -C(CF 2 H) 2 -.
  • R7, Rs, R9, Rio, and Rn are independently selected from the group consisting of H, halogen, and C1-4 alkoxy that is partially or fully halogenated and may further include an ether.
  • At least one of R2, R3, R4, Rs, and Re is selected from the group consisting of C1-3 alkoxy that is partially or fully halogenated and may further include an ether, Formula 2, and Formula 3 and is not -O-CF2-CHF-CF3.
  • At least two of R2, R3, R4, Rs, and Re are selected from the group consisting of H and halogen.
  • R1 is CO2H
  • R2, R3, R4, Rs, and Re are not, in combination, H, -O- CHF2, -O-CHF2, H, and H, respectively.
  • the halogen is fluorine and the halogenated is fluorinated.
  • R1 consists of the terminal group selected from the group consisting of CO2X, SO3X, and PO(OX)2.
  • R1 is SO3X.
  • R1 is CO2X
  • R1 is PO(OX)2.
  • Re is C1-4 linear or branched alkyl.
  • At least one of R2, R3, R4, Rs, and Re is C1-3 alkoxy that is partially or fully halogenated and may further include an ether.
  • the C1-3 alkoxy that is partially or fully halogenated and may further include an ether is partially halogenated.
  • At least one of R2, R3, R4, Rs, and Re is selected from the group consisting of -O-CH2F, -O-CHF2, -O-CF3, -O-CH2-CHF2, -O-CF2-CH3, -O-CF2-CHF2, -O-CH(CH 2 F) 2 , -O-CF(CH 2 F) 2 , -O-CH(CHF 2 )2, -O-CHF-CHF-O-CF3, -O-CF2-CH2-O-CF2H, -O-CF2-CH2-O-CF3, and -O-CF2-CHF-O-CF3.
  • R 2 , R3, R 4 , Rs, and Re are independently selected from the group consisting of -O-CH2F, -O-CHF2, -0-CF3, -0-CH2-CHF2, -O-CF 2 -CH 3 , -O-CF 2 -CHF 2 , -O-CH(CH 2 F) 2 , -O-CF(CH 2 F)2, -O-CH(CHF 2 ) 2 , -0-CHF-CHF-0-CF3, -O-CF 2 -CH 2 -O-CF 2 H, -O-CF 2 -CH 2 -O-CF 3 , and -O-CF2-CHF-O-CF3.
  • At least one of R7, Rs, R9, R10, and R11 is the C1-4 alkoxy that is partially or fully halogenated and may further include an ether.
  • partially fluorinated aryl ether surfactants compositions containing partially fluorinated aryl ether surfactants, and methods of forming and using partially fluorinated aryl ether surfactants.
  • the partially fluorinated aryl ether surfactant has the chemical structure of Formula 1 :
  • R1 includes a terminal group of CO 2 X, SO3X, or PO(OX) 2 , where X may be H, Li, Na, K, Cs, NH 4 , 1 / 2 Mg, 1 / 2 Ca, or 1 / 2 Ba.
  • R 2 , R3, R 4 , Rs, and Re are independently H, a halogen, a C1.8 linear or branched alkyl, or a Ci- 4 alkoxy that is partially or fully halogenated and may further include an ether.
  • At least one of R 2 , R3, R 4 , Rs, and Re is a C1-3 alkoxy that is partially or fully halogenated and may further include an ether and is not -O-CF2-CHF-CF3, and at least two of R2, R3, R4, R5, and Re are independently H or halogen.
  • R2, R3, R4, Rs, and Re include no more than two contiguous fluorinated carbon atoms.
  • the partially fluorinated aryl ether surfactant has a structure selected from the following: where R1 is CO 2 X, SO 3 X, or PO(OX) 2 , where X is H, Li, Na, K, Cs, NH 4 , Wig, Wa, or Wa.
  • R1 is CO 2 H
  • R 2 , R3, R 4 , Rs, and Re are not, in combination, H, -O-CHF 2 , -O-CHF 2 , H, and H, respectively.
  • At least one of R 2 , R3, R 4 , Rs, and Re has the chemical structure of Formula 2:
  • R?, Rs, R9, R10, and Rn are independently H, a halogen, or a C1-4 alkoxy that is partially or fully halogenated and may further include an ether.
  • the partially fluorinated aryl ether surfactant has a structure selected from: where R1 is CO2X, SO 3 X, or PO(OX) 2 , where X is H, Li, Na, K, Cs, NH 4 , Wig , Wa, or Ba.
  • At least one of R 2 , R3, R 4 , Rs, and Re has the chemical structure of Formula 3:
  • Y is -O-, -C(O)NH-, -C(O)O-, -S-, -S(O)-, -SO 2 -, -SO 2 NH-, -OC(O)O-, -C(O)-, phosphonate, phosphate, -C(CH3) 2 -, -C(CP3) 2 -, or -C(CF 2 H) 2 - and R7, Rs, R9, R10, and Rn are independently H, a halogen, or a C1-4 alkoxy that is partially or fully halogenated and may further include an ether.
  • the partially fluorinated aryl ether surfactant has a structure selected from: where Ri is CO 2 X, SO 3 X, or PO(OX) 2 , where X is H, Li, Na, K, Cs, NH 4 , 1 / 2 Mg, 1 / 2 Ca, or Ba.
  • the halogen is fluorine and the halogenated is fluorinated.
  • the R1 is SO3X.
  • the R1 is CO 2 X.
  • the R1 is R1 is PO(OX) 2 .
  • the Ci- 3 alkoxy that is partially or fully halogenated and may further include an ether is partially halogenated.
  • At least one of R2, R3, R4, Rs, and Re is -O-CH2F, -O-CHF2, -O-CF3, -O-CH2-CHF2, -O-CF2-CH3, -O-CF2-CHF2, -O-CH(CH 2 F) 2 , -O-CF(CH 2 F) 2 , -O-CH(CHF 2 ) 2 , -O-CHF-CHF-O-CF3, -O-CF2-CH2-O-CF2H, -O-CF 2 -CH 2 -O-CF 3 , or -O-CF 2 -CHF-O-CF 3 .
  • R2, R3, R4, Rs, and Re are independently -O-CH 2 F, -O-CHF 2 , -O-CF 3 , -O-CH2-CHF2, -O-CF 2 -CH 3 , -O-CF2-CHF2, -O-CH(CH 2 F) 2 , -O-CF(CH 2 F) 2 , -O-CH(CHF 2 ) 2 , -O-CHF-CHF-O-CF3, -O-CF2-CH2-O-CF2H, -O-CF2-CH2-O-CF3, or -O-CF2-CHF-O-CF3.
  • At least one of R7, Rs, R9, R10, and Rn is a C1-4 alkoxy that is partially or fully halogenated and may further include an ether.
  • the partially fluorinated aryl ether surfactant has a structure selected from:
  • an aqueous fluoropolymer emulsion polymerization composition includes the partially fluorinated aryl ether surfactant, an aqueous solvent, and tetrafluoroethylene (TFE), hexafluoropropylene, vinylidene fluoride, perfluoroalkyl vinyl ether (PAVE), or a combination thereof.
  • TFE tetrafluoroethylene
  • PVAVE perfluoroalkyl vinyl ether
  • a partially fluorinated aryl ether surfactant aids in an aqueous fluoropolymer emulsion polymerization.
  • a partially fluorinated aryl ether surfactant aids in formation or stabilization of a fluoropolymer emulsion.
  • a partially fluorinated aryl ether surfactant is a dispersant of solid particles in a fluoropolymer melt.
  • a partially fluorinated aryl ether surfactant provides anti-inflammatory and/or antiviral properties.
  • a partially fluorinated aryl ether surfactant is part of a fire-fighting composition, such as in a fire-fighting foam.
  • a partially fluorinated aryl ether surfactant is part of a grease, paint, coating, lubricant, herbicidal, insecticidal, ink, cleaner, anti-fogging, or metalworking composition.
  • the fluoropolymer is a polymer formed from monomers of tetrafluoroethylene (TFE), hexafluoropropylene (HFP), vinylidene fluoride, or perfluoroalkyl vinyl ether (PAVE).
  • the fluoropolymer is polytetrafluoroethylene (PTFE), a perfluoroalkoxy alkane (PFA) copolymer of TFE and PAVE, a fluorinated ethylene propylene (FEP) copolymer of TFE and HFP, or polyvinylidene fluoride (PVDF).
  • a partially fluorinated aryl ether surfactant is formed by adding a phenol to a fluorinated alkene or vinyl ether.
  • the phenol is sulfonated in which case the phenol addition step creates the surfactant, as shown in Scheme 1.
  • the phenol is first added to a fluorinated alkene or vinyl ether followed by a sulfonation step, as shown in Scheme 2.
  • R in Scheme 1 and Scheme 2 may include, but are not limited to, -F, -H, or -O-CF3.
  • the alkene in Scheme 1 or Scheme 2 includes one or more hydrogens in place of fluorine atoms.
  • one or more of the aryl hydrogens in Scheme 1 or Scheme 2 are substituted with fluorine atoms.
  • difluoromethylether (-O-CHF2) as an R-group for a partially fluorinated aryl ether surfactant.
  • a base catalyzed addition of difluorocarbene to the corresponding alcohol is a base catalyzed addition of difluorocarbene to the corresponding alcohol.
  • Difluorocarbene can be generated in multiple ways (see, for example, Chemical Reviews, Vol. 96, pp. 1585-1632 (1996); Bioorganic & Medicinal Chemistry Letters, Vol. 23, pp. 3857-3863 (2013); or Tetrahedron, Vol. 99, 132458 (2021), and references cited therein).
  • a chemical such as a chloro/iodo/bromo difluoromethylacetate (CICF2CO2Na, for example), or base catalyzed dehydrohalogenation of chlorodifluoromethane or trifluoromethane.
  • CICF2CO2Na chloro/iodo/bromo difluoromethylacetate
  • CF3O-Ar-B(OH)2 and/or CFsO-Ar-Br(l) may be employed in Pd-catalyzed coupling reactions to prepare intermediates which can be sulfonated with common sulfonating agents to generate inventive surfactants.
  • CFsO-Ar-OH can be used in an Ullman coupling reaction to prepare CFsO-Ar-O-Ar intermediates which can be sulfonated with common sulfonating agents to generate inventive surfactants.
  • -O-CF2-CHF2 is included as an R-group for a partially fluorinated aryl ether surfactant by base-catalyzed addition of phenol to tetrafluoroethylene (TFE), followed by sulfonation with a common electrophilic sulfonating agent, such as sulfur trioxide, oleum, or chlorosulfonic acid (see, for example, US Patent No. 7,531 ,700).
  • TFE tetrafluoroethylene
  • -O-CF2-CHF-O-CF3 is included as an R-group for a partially fluorinated aryl ether surfactant by catalyzed addition of phenol to perfluoromethylvinyl ether (PMVE) (see, for example, US Patent No. 6,136,836), followed by sulfonation with a common electrophilic sulfonating agent, such as sulfur trioxide, oleum, or chlorosulfonic acid.
  • PMVE perfluoromethylvinyl ether
  • -O-CH2-CHF2 is included as an R-group for a partially fluorinated aryl ether surfactant by nucleophilic substitution of a polyfluorinated aromatic molecule with a corresponding alcohol (see, for example, Science of Synthesis, Vol. 31a, pp. 21-78 (2007); Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry, Vol. 12, pp. 2845-50 (1972-1999) (1980); Zhurnal Organicheskoi Khimii, Vol. 18, pp. 2321-7 (1982)).
  • -O-CF2-CH2-O-CHF2 is included as an R-group for a partially fluorinated aryl ether surfactant by Scheme 3. Phenol is reacted with ethylbromodifluoroacetate and a base to provide the ester, which can be subsequently reduced to ArOCF2CH2OH. The alcohol can be converted to ArOCF2CH2OCF2H using the same strategies described for phenols. j
  • -O-CF2-CH2-O-CF3 is included as an R-group for a partially fluorinated aryl ether surfactant by Scheme 4. Phenol is reacted with ethylbromodifluoroacetate and a base to provide the ester which can be subsequently reduced to ArOCF2CH2OH. The alcohol can be converted to ArOCF2CH2OCF3 using many different chemical sequences (see, for example, Angew. Chem. Int. Ed., Vol. 57, pp.292 -295 (2016); or Angew. Chem. Int. Ed., Vol. 55, pp. 11726(2016)) then sulfonated to afford M + ’OSO3-ArOCF2CH2OCF3.
  • -O-CF2CH3 is included as an R-group for a partially fluorinated aryl ether surfactant by Scheme 5.
  • -O-CH(CH2F)2 is included as an R-group for a partially fluorinated aryl ether surfactant by nucleophilic substitution of a polyfluorinated aromatic molecule with the corresponding alcohol (see, for example, Science of Synthesis, Vol. 31a, pp. 21-78 (2007); Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry, Vol. 12, pp. 2845-50 (1972-1999) (1980); or Zhurnal Organicheskoi Khimii, Vol. 18, pp. 2321-7 (1982)).
  • -O-CF(CH2F)2 is included as an R-group for a partially fluorinated aryl ether surfactant by nucleophilic substitution of a polyfluorinated aromatic molecule with the corresponding precursor alcohol HO- CH(CH2F)2 (see, for example, Science of Synthesis, Vol. 31a, pp. 21-78 (2007); Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry, Vol. 12, pp. 2845-50 (1972-1999) (1980); or Zhurnal Organicheskoi Khimii, Vol. 18, pp.
  • -O-CH(CHF2)2 is included as an R-group for a partially fluorinated aryl ether surfactant by nucleophilic substitution of a polyfluorinated aromatic molecule with the corresponding alcohol (see, for example, Science of Synthesis, Vol. 31a, pp. 21-78 (2007); Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry, Vol. 12, pp. 2845-50 (1972-1999) (1980); or Zhurnal Organicheskoi Khimii, Vol. 18, pp. 2321-7 (1982)).
  • RDPS was measured using laser light scattering with a Zetasizer Nano-ZS manufactured by Malvern Instruments. Samples for analysis were prepared in 10x10x45 mm polystyrene cuvettes, capped and placed in the device for analysis. Preparation of the sample was as follows. Water used to flush the cuvette and used to dilute the dispersion sample was rendered substantially free of particles by drawing deionized, deaerated water into a 10 cc glass hypodermic syringe with a locking tip. A Whatman 0.02 micron filter (Cat. No. 6809-2002) was fitted to the locking tip of the syringe and pressure was applied force water through the filter and into the cuvette.
  • a Whatman 0.02 micron filter Cat. No. 6809-2002
  • Dv(50) is the median particle size based on volumetric particle size distribution, i.e. the particle size below which 50% of the volume of the population resides. Melting Point (T m ) Measurements
  • the T m of the PTFE homopolymer was measured by a differential scanning calorimeter (DSC).
  • DSC differential scanning calorimeter
  • the unmelted PTFE homopolymer was heated from room temperature to 380°C at a heating rate of 2°C per minute and the melting temperature reported was the peak temperature of the endotherm on first melting.
  • Reported cure properties include the minimum S’ torque (ML) in dN m, the maximum S’ torque achieved during a specified time period (MH) in dN m, the (scorch) time to increase one unit of S’ torque from ML (ts1 ) in minutes, the (scorch) time to increase two units of S’ torque from ML (ts2) in minutes, the (cure) time to an increase of 50% of S’ torque from ML to MH (tso) in minutes, and the (cure) time to an increase of 90% of S’ torque from ML to MH (tgo) in minutes.
  • Compression set resistances were determined on the fluoroelastomers with a compression device that compressed fluoroelastomer samples to 25% deflection following ASTM D395, Test Method B. Prior to the compression set testing, the fluoroelastomer was post-cured for 4 hours at 232°C. The compression set resistance is reported as a percentage change in thickness after 70 hours at 200°C (CS1).
  • Table 1 shows the chemical structures of the Inventive Examples 1-15 (IE1- IE15) of partially fluorinated aryl ether surfactants described herein.
  • Comparative Example 1 is C6F13-CH2-CH2-SO3H, available under the trade designation CapstoneTM FS-10 (The Chemours Company FC, LLC, Wilmington, DE).
  • Comparative Example 2 is C6F5SO3H.
  • Comparative Example 3 is 3, 5-di-tert-butyl-4- methoxybenzenesulfonic acid.
  • Comparative Example 4 is ammonium 2- (heptafluoropropoxy)tetrafluoropropanoate.
  • Comparative Example 5 is available under the trade designation DowfaxTM 2A1 solution surfactant (The Dow Chemical
  • Comparative Example 6 is sodium dodecyl benzenesulfonate (SDBS). Comparative Example 7 is sodium dodecyl sulfate (SDS).
  • Comparative Example 8 is 3,4,5-trimethoxybenzoic acid. Comparative Example 9 has Formula 4:
  • 3,4-Bis(difluoromethoxy)benzaldehyde can be synthesized from 3,4- dihydroxybenzaldehyde and chlorodifluoromethane or sodium chlorodifluoroacetate in the presence of inorganic base, or it can be purchased commercially.
  • Fluoropolymer was prepared by a semi-batch emulsion polymerization process, carried out at 80°C in a 2-liter, well-stirred reaction vessel.
  • a solution of 0.5 g perfluoroionomer particulate as disclosed in US Patent No. 6,916,853 and 1.26 g of Inventive Example 1 (IE1) as the partially fluorinated aryl ether surfactant in 900 g water was pumped into the reactor, followed by pumping a solution of 0.5 g disodium phosphate heptahydrate in 100 g deionized, deoxygenated water. The reactor was heated to 80°C.
  • the reactor was pressurized with a mixture of 30 wt% tetrafluoroethylene (TFE) and 70 wt% perfluoromethyl ether (PMVE). At the end of pressurization, the reactor pressure was 2.1 MPa.
  • TFE tetrafluoroethylene
  • PMVE perfluoromethyl ether
  • the reactor pressure was 2.1 MPa.
  • the reactor was charged with 0.20 mM of ammonium persulfate (APS) based on total water in the reactor, or charged with 8.6 ml_ of an initiator solution of 0.6% ammonium persulfate and 1 .1 % disodium phosphate heptahydrate to start polymerization.
  • the reactor was continuously fed with 2.6 ml/hour of initiator solution.
  • VF2/HFP/TFE fluoroelastomer by a semi-batch emulsion polymerization process without a processing aid, a 4.0-liter reactor was charged with a solution containing 2.0 grams of disodium phosphate, and 2498 grams of deionized, deoxygenated water. No polymerization processing aid was added. The reactor was heated to 80 °C, agitated at 700 rpm, and pressurized with a mixture of 25.0 % vinylidene fluoride, 73% hexafluoropropene, and 2% tetrafluoroethylene to a pressure of 320 psi.
  • VF2/HFP/TFE fluoroelastomer by a semi-batch emulsion polymerization process with a polymerization processing aid (PPA)
  • PPA polymerization processing aid
  • a 4.0-liter reactor was charged with a solution containing 2.0 grams of disodium phosphate, 5.6 mmol of PPA (1-3 grams depending on molecular weight) and deionized, deoxygenated water for a total of 2,500 grams of solution.
  • the reactor was heated to 80 °C, agitated at 700 rpm, and pressurized with a mixture of 25.0 % vinylidene fluoride, 73% hexafluoropropene, and 2% tetrafluoroethylene to a pressure of 320 psi.
  • Table 3 shows that Inventive Examples 1-3 performed significantly better as judged by monomer feed than Comparative Examples 2-3, which gave similar results to no PPA being present. Inventive Example 2 performed almost as well as Comparative Example 1 , the positive control.
  • a semi-batch emulsion polymerization process for making polytetrafluoroethylene (PTFE) a high concentration of a dispersing agent (DA) was pre-charged, and tetrafluoroethylene (TFE) monomer was fed in an amount to produce 25-30 wt% solids batches. All the dispersive agent was added to the precharge before kick-off of the polymerization.
  • Perfluoroionomer particulate as disclosed in US Patent No. 6,916,853 was employed as a nucleating additive. Thirteen different runs were completed, eight with different partially fluorinated aryl ether surfactants as the dispersing agent (DA) and five with different comparative dispersing agents. The dispersing agents are listed in Table 4.
  • the autoclave pressure was raised to 30 psig with nitrogen and vented to atmospheric pressure.
  • the autoclave was pressurized with nitrogen and vented two more times.
  • the pressure-vent cycle was repeated three times using TFE.
  • the reactor was heated to 65 °C with no agitation. Once the reactor temperature reached 65 °C, the agitator speed was set to 75 RPM, and the reactor was heated to the operating temperature or 84 °C.
  • the reactor temperature was held at the operating temperature, with agitation at 75 RMP.
  • the reaction was pressurized with 400 psig with TFE, and the initiator solution, for Runs 1-2 and 9-13, was disuccinyl peroxide (DSP, 70% active) 10 g in 990 g of deionized, deaerated water, was added at rate of 80 mL/min, until 300 mL (360 ml_ for Runs 3-4), was used.
  • the DSP solution included 30 g of DSP in 970 g of deionized, deaerated water and 300 mL were used.
  • the results reported in Table 4 include the dispersing agent (DA), the polymerization time, the pre-charge initiator concentration, the average particle size (Dv(50)), the first melt melting point (T m ) by differential scanning calorimetry (DSC) heating at 2 °C/min, and the coagulum amount.
  • DA dispersing agent
  • Dv(50) average particle size
  • T m first melt melting point
  • DSC differential scanning calorimetry
  • the differential initiation-polymerization time was a comparative value used to approximate how the concentration of initiator used in the polymerization precharge can influence polymerization time. Generally, the more initiator used in the pre-charge, the faster the polymerization rate. To account for the different concentrations of DSP used in each run in Table 4, this comparative value was developed.
  • the first comparison value is initiation-polymerization time, which was determined by multiplying the polymerization time in minutes by the pre-charge initiator (mM), which is then divided by the lowest amount of pre-charge initiator used in Table 4, 1 .062 mM, which is the standard amount of pre-charge initiator for Runs 1-3.
  • the differential initiation-polymerization time was then determined by subtracting the initiation-polymerization time from polymerization time. This relationship between initiator and polymerization time increases the initiator-polymerization times with the same factor that the pre-charge concentration was increased, for example: 1X vs 3X.
  • Runs 1-2, and 9 had zero values for differential initiation-polymerization times, because they each use the lowest levels on pre-charge initiator. This indicates a good polymerization rate relative to the amount of pre-charge initiator used.
  • Run 8 had the highest differential initiator-polymerization values, had the longest polymerization time of 150.5 minutes, and used the highest concentration of precharge initiator. Although run 8 was a successful polymerization, producing 27% solids, it was the slowest run.
  • Runs 1-9 which all included inventive examples, were run to completion as marked by the consumption of 3000 g of TFE. In contrast, comparative examples I Q- 13 failed to kick-off, and as a result failed to polymerize TFE. High solids batches were also produced from Runs 2-4, 6, and 8-9, which also had low levels of coagulum, indicating good stabilization of the polymerization. Run 9, like many of the other examples, had high solids and low coagulum, however, it required greater than 7000 ppm of the dispersive agent, whereas inventive examples, Runs 2-4, 6, and 8 significantly less dispersive aged, amount to approximately 1000 - 4100 ppm of dispersive agent.
  • Run 13 used the sodium salt of 3,4,5-trimethoxybenzoic acid as the dispersive agent, which has similar chemical structure and concentration to the dispersive agent used in Run 2.
  • Run 13 failed to kick-off and polymerize TFE, whereas, Run 2 achieved high solids, with a good polymerization rate.
  • the difference in the chemical structure of the dispersive agent between Runs 13 and 2 is just three methoxy groups, in Run 13, compared to OCF2H functionalization, with Run 2, which resulted in remarkable different polymerization results.
  • the agitator speed was set to 75 RPM, and the second dispersive solution was added, containing 4.5 g of nucleating additive, (8% fluoropolyether acid nucleating additive, 79% dimer acid of hexafluoropropylene epoxide, and water), and 72 g of dispersive agent (ammonium (2,3,3,3-tetrafluoro-2-(heptafluoropropoxy)propanoate, 70.5% in water), followed by a flush of 100 g of deionized, deaerated water.
  • the autoclave pressure was raised to 30 psig with nitrogen and vented to atmospheric pressure.
  • the autoclave was pressurized with nitrogen and vented two more times.
  • the pressurevent cycle was repeated three times using TFE.
  • the reactor was heated to 65 °C with no agitation. Once the reactor temperature reached 65 °C, the agitator speed was set to 75 RPM, and the reactor was heated to the operating temperature of 84 °C.
  • the reactor temperature was held at the operating temperature of 84 °C, with agitation at 75 RMP.
  • the reaction was pressurized with 400 psig with TFE, and the initiator solution, disuccinyl peroxide (DSP, 70% active) 10 g in 990 g of deionized, deaerated water, was added at rate of 80 mL/min, until 300 mL had been delivered to the autoclave.
  • Kick-off of the polymerization was assumed to have occurred with a 10-psi drop, which marked time-zero (the start of the polymerization), and the TFE feed count began from zero.
  • the results reported in Table 5 include the dispersing agent (DA), the polymerization time, the average particle size (Dv(50)), the first melt melting point (T m ) by differential scanning calorimetry (DSC) heating at 2 °C/min, and the coagulum amount.
  • DA dispersing agent
  • Dv(50) average particle size
  • T m first melt melting point
  • DSC differential scanning calorimetry
  • Runs 1-4 High solids batches were produced from all Runs 1-4. Furthermore, melting point, and particle size (RDPS, Dv(50)) were consistent between all runs, given the stabilizing effect of the secondary dispersive agent, ammonium (2,3,3,3-tetrafluoro-2- (heptafluoropropoxy)propanoate. Runs 1-3 had polymerization times within 1-3 minutes of Run 4, the control polymerization. Runs 1-3 had slightly increase melting points relative to Run 4, indicating good molecular weights with the addition of the second dispersive agent.
  • RDPS melting point, and particle size
  • a semi-batch emulsion polymerization process for making polytetrafluoroethylene (PTFE) a high concentration of a dispersing agent was precharged, and tetrafluoroethylene (TFE) monomer was fed in an amount to produce 25-30 wt% solids batches.
  • the first dispersive agent, ammonium (2,3,3,3-tetrafluoro- 2-(heptafluoropropoxy)propanoate was added at a mass of 77 g (70.5% active content), in the polymerization pre-charge (before kick-off).
  • the remaining dispersive agent was fed into the reactor after the polymerization has started (after kick-off) at approximately the 500 g TFE monomer feed point.
  • the total concentration of all dispersive agents was 171 mmole, except for Run 5 at 162 mmole, Run 7 at 169 mmol, and Run 8 at 156 mmole.
  • Perfluoroionomer particulate as disclosed in US Patent No. 6,916,853 was employed as a nucleating additive.
  • Runs 1-7 included partially fluorinated aryl ether surfactants as the second dispersive agent
  • runs 8-12 are comparative examples, where Run 8 served as a control and is the only example to contain ammonium (2,3,3,3-tetrafluoro-2- (heptafluoropropoxy)propanoate as the single dispersive agent.
  • the autoclave was sealed and placed under vacuum.
  • the autoclave pressure was raised to 30 psig with nitrogen and vented to atmospheric pressure.
  • the autoclave was pressurized with nitrogen and vented two more times.
  • the pressure-vent cycle was repeated three time using TFE.
  • the reactor was heated to 65 °C with no agitation. Once the reactor temperature reached 65 °C, the agitator speed was set to 75 RPM, and reactor was heated to the operating temperature, 84 °C.
  • the reactor temperature was held at the operating temperature, with agitation at 75 RMP.
  • the reaction was pressurized to 400 psig with TFE, and the initiator solution, disuccinyl peroxide (DSP, 70% active) 10 g in 990 g of deionized, deaerated water, was added at rate of 80 mL/min, until 300 mL had been delivered to the autoclave.
  • Kick-off of the polymerization was assumed to have occurred with a 10-psi drop, which marked time zero (the start of the polymerization), and the TFE feed count began from zero.
  • the results reported in Table 6 include the dispersing agent (DA), the polymerization time, the average particle size (Dv(50)), the first melt melting point (T m ) by differential scanning calorimetry (DSC) heating at 2 °C/min, and the coagulum amount.
  • DA dispersing agent
  • Dv(50) average particle size
  • T m first melt melting point
  • DSC differential scanning calorimetry
  • Run 8 One indicator of the secondary dispersive agent’s success in polymerization was the polymerization time. Run 8, the control, was completed within 47 minutes. Only Runs 1 and 7 had a faster, or equal, polymerization rates to Run 8, which is a good indication of their high success as post-charge dispersive agents. Runs 2-3 were very close to the polymerization time of the control. Each of these runs was highly successful with good polymerization times. Runs 4-6 were still successful, achieving moderate polymerization times, still outperforming Runs 9-12. All runs, except 10-11 , achieved good particle size within 180-220 nm, where Run 11 had unusually large particle size of 240 nm, which is a potential indicator of poor polymerization stabilization. The melting points of all runs, except Runs 9-10, fell within an acceptable range. Run 9 with the lowest melting point indication unsuccessful polymerization, as radical chain-transfer interaction between the surfactant the TFE monomer were likely evident, resulting in the depressed melting point.
  • Fluoroelastomer was prepared by a semi-batch emulsion polymerization process, carried out at 80°C in a 40-liter, well-stirred reaction vessel.
  • a solution of 100.5 g CapstoneTM FS-10 and 23.6 g disodium phosphate heptahydrate in 25 L of water was pumped into the reactor.
  • the reactor was heated to 80°C. After removal of trace oxygen, the reactor was pressurized with a mixture of 4 wt% vinylidene fluoride (VF2), 86 wt% hexafluoropropylene (HFP), and 10 wt% tetrafluoroethylene (TFE). At the end of pressurization, the reactor pressure was 2.2 MPa.
  • VF2 vinylidene fluoride
  • HFP 86 wt% hexafluoropropylene
  • TFE 10 wt% tetrafluoroethylene
  • the reactor was charged with 58 ml of an initiator solution of 1 % ammonium persulfate and 7.5% disodium phosphate heptahydrate to start polymerization. As the reactor pressure drops, a mixture of 35 wt% VF2, 37 wt% HFP, and 28 wt% TFE was fed to the reactor to maintain a 2.2 MPa pressure.
  • the resulting fluoroelastomer latex had a solids content of 25.8 wt% solids, and a pH of 3.1.
  • the latex was coagulated with aluminum sulfate solution, washed with deionized water, and dried.
  • the fluoroelastomer had an inherent viscosity of 0.51 dl/g, a Mooney viscosity at 121 °C, ML (1 + 10), of 69 and contained
  • the reactor was continuously added 3.4 ml/hour initiator solution to maintain polymerization rate. After 2922 g of the monomer mixture was added, 4-iodo-3,3,4,4-tetrafluorobutene-1 (ITFB) was introduced to the reactor at a feed rate of 4.83 g ITFB per 1000 g monomer. After 3700 g of the monomer mixture was added, an extra 33 ml initiator solution was added to the reactor. The reactor was continuously added 16.6 ml/hour initiator solution to maintain polymerization rate. After a total of 8333 g incremental major monomer was fed, corresponding to a total of 166 ml initiator solution, 20.4 g ITFB and 14.4 hours, monomer and initiator fed were discontinued.
  • ITFB 4-iodo-3,3,4,4-tetrafluorobutene-1
  • the reactor was cooled and the pressure in the reactor reduced to atmospheric pressure.
  • the resulting fluoroelastomer latex had a solids content of 24.4 wt% solids, and a pH of 3.5.
  • the latex was coagulated with aluminum sulfate solution, washed with deionized water, and dried.
  • the fluoroelastomer had an inherent viscosity of 0.54 dl/g, a Mooney viscosity at 121 °C, ML (1 + 10), of 64 and contained 37.8 wt% VF2, 36.3 wt% HFP, 25.8 wt% TFE and 0.182 wt% I.
  • the fluoroelastomer had an inherent viscosity of 0.50 dl/g, a Mooney viscosity at 121 °C, ML (1 + 10), of 69 and contained 36.8 wt% VF2, 36.7 wt% HFP, 26.2 wt% TFE and 0.223 wt% I.
  • Fluoroelastomer curing compositions included 100 parts by weight of the comparative or inventive fluoroelastomer as the peroxide-curable fluoroelastomer, 30 parts by weight medium thermal carbon black (MT Black, commercially available under the trade designation “Corax® N990” from Orion Engineered Carbons LLC, Kingwood, TX) as a filler, 3 parts by weight powdered ZnO (Zoco 102, commercially available under the trade designation “Zoco Grade 102” from Zochem LLC (Dickson, TN)) as a heat stabilizer, and 3.1 parts 1 ,3,5-triallyl-1 ,3,5-triazine-2,4,6(1 H,3H,5H)- trione (72% by weight) on silica carrier commercially available under the trade designation “TAIC DLC®-A 72%” from Natrochem Inc.
  • MT Black medium thermal carbon black
  • Zoco 102 commercially available under the trade designation “Zoco Grade 102” from Zochem LLC
  • Table 7 shows the curing characteristics and the compression set results on the cured compositions.
  • Table 7 shows that the polymers prepared with inventive surfactants had curing characteristics very similar to the comparative example made with highly fluorinated Comparative Example 1. Table 7 also shows the physical properties of crosslinked parts with the inventive examples having hardness, tensile properties, and compression set similar to the CE1 control.

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Abstract

L'invention concerne un tensioactif d'éther d'aryle partiellement fluoré de formule 1. Formule 1, R1 comprend un groupe terminal choisi parmi CO2X, SO3X et PO(OX)2. X est choisi parmi H, Li, Na, K, Cs, NH4, ½Mg, ½Ca et ½Ba. R2, R3, R4, R5 et R6 sont indépendamment choisis parmi H, halogène, alkyle en C1-8 linéaire ou ramifié, alcoxy en C1-4 qui est partiellement ou totalement halogéné et peut en outre comprendre un éther, formule 2 et formule 3 : Formule 2, formule 3, Y est -O-, -C(O)NH-, -C(O)O-, -S-, -S(O)-, -SO2-, -SO2NH-, -OC(O)O-, -C(O)-, phosphonate, phosphate, -C(CH3)2-, -C(CF3)2- ou -C(CF2H)2-. R7, R8, R9, R10 et R11 sont indépendamment choisis parmi H, halogène et alcoxy en C1-4 qui est partiellement ou totalement halogéné et peut en outre comprendre un éther. Au moins l'un de R2, R3, R4, R5 et R6 est choisi parmi alcoxy en C1-3 qui est partiellement ou totalement halogéné et peut en outre comprendre un éther, formule 2 et formule 3 et n'est pas -O-CF2-CHF-CF3. Au moins deux parmi R2, R3, R4, R5 et R6 sont choisis parmi H et halogène.
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