Partially fluorinated ARYL ether surfactant compositions and methods of use

Abstract

A partially fluorinated aryl ether surfactant has Formula 1. Formula 1 R1 includes a terminal group selected from CO2X, SO3X, and PO(OX)2. X is selected from H, Li, Na, K, Cs, NH4, ½Mg, ½Ca, and ½Ba. R2, R3, R4, R5, and R6 are independently selected from 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: Formula 2 Formula 3 Y is -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-, or -C(CF2H)2-. R7, R8, R9, R10, and R11 are independently selected from 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, R5, and R6 is selected from 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, R5, and R6 are selected from H and halogen.

Description

TITLE OF THE INVENTIONPARTIALLY FLUORINATED ARYL ETHER SURFACTANT COMPOSITIONS AND METHODS OF USECROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of priority of U.S. Provisional Application No. 63 / 606,767 filed December 6, 2023, the disclosure of which is incorporated herein by reference in its entirety.FIELD

[0002] 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.BACKGROUND

[0003] 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. 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.

[0004] Conventionally, fluoropolymer polymerizations have utilized perfluorinated or highly fluorinated surfactants as process aids. There is emerging technology which enables the use of non-fluorinated hydrocarbon surfactants; however some fluoropolymer polymerization processes are very sensitive to chain transfer reactions with hydrocarbons and are not amenable to non-fluorinated surfactant technology.

[0005] There is a need for lightly fluorinated surfactants which enable robust fluoropolymers and are compliant with emerging regulations which require fewer fluorine atoms in molecules.SUMMARY

[0006] In one embodiment, 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 :Formula 1

[0007] 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 / 2Mg, ! Ca, and1 / 2Ba.

[0008] 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:Formula 2 Formula 3

[0009] 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(CF3)2-, and -C(CF2H)2-.

[0010] 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.

[0011] 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.

[0012] At least two of R2, R3, R4, Rs, and Re are selected from the group consisting of H and halogen.

[0013] In one embodiment of the composition, the halogen is fluorine and the halogenated is fluorinated.

[0014] In another embodiment of the composition, R1 consists of the terminal group selected from the group consisting of CO2X, SO3X, and PO(OX)2.

[0015] In another embodiment of the composition, R1 is SO3X.

[0016] In another embodiment of the composition, R1 is CO2X.

[0017] In another embodiment of the composition, R1 is PO(OX)2.

[0018] In another embodiment of the composition, at least one of R2, R3, R4, Rs, and Re is C1-4 linear or branched alkyl.

[0019] In another embodiment of the composition, 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.

[0020] In another embodiment of the composition, the C1-3 alkoxy that is partially or fully halogenated and may further include an ether is partially halogenated.

[0021] In another embodiment of the composition, 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(CH2F)2, -O-CF(CH2F)2, -O-CH(CHF2)2, -O-CHF-CHF-O-CF3, -O-CF2-CH2-O-CF2H, -O-CF2-CH2-O-CF3, and -O-CF2-CHF-O-CF3.

[0022] In another embodiment of the composition, at least two of R2, R3, R4, Rs, and Re are independently selected from the group consisting of -O-CH2F, -O-CHF2,-O-CF3, -O-CH2-CHF2, -O-CF2-CH3, -O-CF2-CHF2, -O-CH(CH2F)2, -O-CF(CH2F)2, -O-CH(CHF2)2, -0-CHF-CHF-0-CF3, -O-CF2-CH2-O-CF2H, -O-CF2-CH2-O-CF3, and -O-CF2-CHF-O-CF3.

[0023] In another embodiment of the composition, 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.

[0024] In another embodiment, a compound has Formula 1.Formula 1

[0025] 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, NH4,1XMg,1 / 2Ca, and 2 Ba.

[0026] 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:Formula 2 Formula 3

[0027] 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(CH3)2-, -C(CF3)2-, and -C(CF2H)2-.

[0028] 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.

[0029] 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.

[0030] At least two of R2, R3, R4, Rs, and Re are selected from the group consisting of H and halogen.

[0031] When R1 is CO2H, R2, R3, R4, Rs, and Re are not, in combination, H, -O- CHF2, -O-CHF2, H, and H, respectively.

[0032] In one embodiment of the compound, the halogen is fluorine and the halogenated is fluorinated.

[0033] In another embodiment of the compound, R1 consists of the terminal group selected from the group consisting of CO2X, SO3X, and PO(OX)2.

[0034] In another embodiment of the compound, R1 is SO3X.

[0035] In another embodiment of the compound, R1 is CO2X.

[0036] In another embodiment of the compound, R1 is PO(OX)2.

[0037] In another embodiment of the compound, at least one of R2, R3, R4, Rs, andRe is C1-4 linear or branched alkyl.

[0038] In another embodiment of the compound, 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.

[0039] In another embodiment of the compound, the C1-3 alkoxy that is partially or fully halogenated and may further include an ether is partially halogenated.

[0040] In another embodiment of the compound, 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(CH2F)2, -O-CF(CH2F)2, -O-CH(CHF2)2, -O-CHF-CHF-O-CF3, -O-CF2-CH2-O-CF2H, -O-CF2-CH2-O-CF3, and -O-CF2-CHF-O-CF3.

[0041] In another embodiment of the compound, at least two of R2, R3, R4, Rs, and Re are independently selected from the group consisting of -O-CH2F, -O-CHF2, -0-CF3, -0-CH2-CHF2, -O-CF2-CH3, -O-CF2-CHF2, -O-CH(CH2F)2, -O-CF(CH2F)2, -O-CH(CHF2)2, -0-CHF-CHF-0-CF3, -O-CF2-CH2-O-CF2H, -O-CF2-CH2-O-CF3, and -O-CF2-CHF-O-CF3.

[0042] In another embodiment of the compound, 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.DETAILED DESCRIPTION

[0043] Provided are partially fluorinated aryl ether surfactants, compositions containing partially fluorinated aryl ether surfactants, and methods of forming and using partially fluorinated aryl ether surfactants.

[0044] It has been surprisingly found that certain partially fluorinated aryl ethers can be tolerated very well as surfactants in certain sensitive fluoropolymer polymerization processes.

[0045] In some embodiments, the partially fluorinated aryl ether surfactant has the chemical structure of Formula 1 :Formula 1

[0046] R1 includes a terminal group of CO2X, SO3X, or PO(OX)2, where X may be H, Li, Na, K, Cs, NH4,1 / 2Mg,1 / 2Ca, or1 / 2Ba.

[0047] In some embodiments, R2, R3, R4, Rs, and Re are independently H, a halogen, a C1.8 linear or branched alkyl, or a Ci-4alkoxy that is partially or fully halogenated and may further include an ether.

[0048] In some embodiments, at least one of R2, R3, R4, Rs, and Re is a C1-3 alkoxy that is partially or fully halogenated and may further include an ether and isnot -O-CF2-CHF-CF3, and at least two of R2, R3, R4, R5, and Re are independently H or halogen.

[0049] In exemplary embodiments, R2, R3, R4, Rs, and Re include no more than two contiguous fluorinated carbon atoms.

[0050] In some embodiments, the partially fluorinated aryl ether surfactant has a structure selected from the following:where R1 is CO2X, SO3X, or PO(OX)2, where X is H, Li, Na, K, Cs, NH4, Wig, Wa, or Wa.

[0051] In some embodiments, when R1 is CO2H, R2, R3, R4, Rs, and Re are not, in combination, H, -O-CHF2, -O-CHF2, H, and H, respectively.

[0052] In some embodiments, at least one of R2, R3, R4, Rs, and Re has the chemical structure of Formula 2:Formula 2 where 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.

[0053] In some embodiments, the partially fluorinated aryl ether surfactant has a structure selected from:where R1 is CO2X, SO3X, or PO(OX)2, where X is H, Li, Na, K, Cs, NH4, Wig , Wa, or Ba.

[0054] In some embodiments, at least one of R2, R3, R4, Rs, and Re has the chemical structure of Formula 3:where Y is -O-, -C(O)NH-, -C(O)O-, -S-, -S(O)-, -SO2-, -SO2NH-, -OC(O)O-, -C(O)-, phosphonate, phosphate, -C(CH3)2-, -C(CP3)2-, or -C(CF2H)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.

[0055] In some embodiments, the partially fluorinated aryl ether surfactant has a structure selected from:where Ri is CO2X, SO3X, or PO(OX)2, where X is H, Li, Na, K, Cs, NH4,1 / 2Mg,1 / 2Ca, or Ba.

[0056] In some embodiments, the halogen is fluorine and the halogenated is fluorinated.

[0057] In some embodiments, the R1 is SO3X.

[0058] In some embodiments, the R1 is CO2X.

[0059] In some embodiments, the R1 is R1 is PO(OX)2.

[0060] In some embodiments, the Ci-3alkoxy that is partially or fully halogenated and may further include an ether is partially halogenated.

[0061] In some embodiments, 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(CH2F)2, -O-CF(CH2F)2, -O-CH(CHF2)2, -O-CHF-CHF-O-CF3, -O-CF2-CH2-O-CF2H, -O-CF2-CH2-O-CF3, or -O-CF2-CHF-O-CF3.

[0062] In some embodiments, at least two of R2, R3, R4, Rs, and Re are independently -O-CH2F, -O-CHF2, -O-CF3, -O-CH2-CHF2, -O-CF2-CH3, -O-CF2-CHF2, -O-CH(CH2F)2, -O-CF(CH2F)2, -O-CH(CHF2)2, -O-CHF-CHF-O-CF3, -O-CF2-CH2-O-CF2H, -O-CF2-CH2-O-CF3, or -O-CF2-CHF-O-CF3.

[0063] In some embodiments, 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.

[0064] In some embodiments, the partially fluorinated aryl ether surfactant has a structure selected from:

[0065] In some embodiments, 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.

[0066] In some embodiments, a partially fluorinated aryl ether surfactant aids in an aqueous fluoropolymer emulsion polymerization.

[0067] In some embodiments, a partially fluorinated aryl ether surfactant aids in formation or stabilization of a fluoropolymer emulsion.

[0068] In other embodiments, a partially fluorinated aryl ether surfactant is a dispersant of solid particles in a fluoropolymer melt.

[0069] In other embodiments, a partially fluorinated aryl ether surfactant provides anti-inflammatory and / or antiviral properties.

[0070] In other embodiments, a partially fluorinated aryl ether surfactant is part of a fire-fighting composition, such as in a fire-fighting foam.

[0071] In other embodiments, a partially fluorinated aryl ether surfactant is part of a grease, paint, coating, lubricant, herbicidal, insecticidal, ink, cleaner, anti-fogging, or metalworking composition.

[0072] In some embodiments, the fluoropolymer is a polymer formed from monomers of tetrafluoroethylene (TFE), hexafluoropropylene (HFP), vinylidene fluoride, or perfluoroalkyl vinyl ether (PAVE). In some embodiments, 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).

[0073] In some embodiments, a partially fluorinated aryl ether surfactant is formed by adding a phenol to a fluorinated alkene or vinyl ether.

[0074] In some embodiments, the phenol is sulfonated in which case the phenol addition step creates the surfactant, as shown in Scheme 1.Scheme 1

[0075] In some embodiments, the phenol is first added to a fluorinated alkene or vinyl ether followed by a sulfonation step, as shown in Scheme 2.Scheme 2

[0076] Appropriate groups for R in Scheme 1 and Scheme 2 may include, but are not limited to, -F, -H, or -O-CF3.

[0077] In some embodiments, the alkene in Scheme 1 or Scheme 2 includes one or more hydrogens in place of fluorine atoms.

[0078] In some embodiments, one or more of the aryl hydrogens in Scheme 1 or Scheme 2 are substituted with fluorine atoms.

[0079] There are multiple ways of including a difluoromethylether (-O-CHF2) as an R-group for a partially fluorinated aryl ether surfactant. One of the most practical 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). For example, using thermal decomposition of a chemical such as a chloro / iodo / bromo difluoromethylacetate (CICF2CO2Na, for example), or base catalyzed dehydrohalogenation of chlorodifluoromethane or trifluoromethane.

[0080] There are multiple ways of including a trifluoromethylether (-O-CF3) as an R-group for a partially fluorinated aryl ether surfactant (see, for example, J. Am. Chem. Soc., Vol. 144, pp. 10438-10445 (2002) and Beilstein J. Org. Chem., Vol. 4, No. 13 (2008)). An anisole derivatives may be chlorinated, then the ensuing trichloromethyl ether may be subjected to a fluoride exchange reaction. Phenols may be treated with CCIVHF / cat. BF3 in a pressure vessel. Electrophilic trifluoromethylating reagents may also be employed. Additionally a commercially available trifluoromethoxyarene with further functionalization may be used as building blocks to prepare inventive surfactants. For example 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.

[0081] In some embodiments, -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).

[0082] In some embodiments, -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.

[0083] In some embodiments, -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)).

[0084] In some embodiments, -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. jScheme 3

[0085] In some embodiments, -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 (2018); or Angew. Chem. Int. Ed., Vol. 55, pp. 11726(2016)) then sulfonated to afford M+’OSO3-ArOCF2CH2OCF3.Scheme 4

[0086] In some embodiments, -O-CF2CH3 is included as an R-group for a partially fluorinated aryl ether surfactant by Scheme 5. ArOCF2CHs can be prepared by treating ethynyl ethers with HF-Pyridine (see, for example, Org. Biomol. Chem., Vol. 16, pp. 1113-1117 (2018)); ArOC(=S)OCHs with tetrabutylammonium dihydrogentrifluoride and N-bromosuccinimide (see, for example Synlett, 251-252 (1994)), phenol acetates with XeF2 (see, for example, Tetrahedron Lett., Vol. 50, pp. 5452-5455 (2009)), or phenol with 2-bromo-1 ,1-difluoroethene, followed by hydrogenolysis (see, for example, Org. Lett., Vol. 14, pp. 3944-3947 (2012)).Scheme 5

[0087] In some embodiments, -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)).

[0088] In some embodiments, -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 OrganicheskoiKhimii, Vol. 18, pp. 2321-7 (1982)) with subsequent selective electrochemical fluorination or treatment with diluted fluorine gas at low temperature in an inert solvent. Alternatively, the ether obtained from the perfluorinated aromatic molecule and the precursor alcohol may undergo dehydrofluorination with subsequent addition of fluorine to a double bond. Other methods and starting materials may also lead to the aforementioned compound with -O-CF(CH2F)2 included as an R-group.

[0089] In some embodiments, -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)).TEST METHODSRaw Dispersion Particle Size (RDPS) Measurements

[0090] 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. Approximately 1 .5 ml_ of water was placed in the cuvette, then the cuvette was capped, shaken, and uncapped. Water was poured out of the cuvette thus assuring the cuvette was free of particles. Approximately 2.5 gm of filtered water was placed in the cuvette. One drop of the fluoropolymer dispersion to be analyzed was added to the cuvette. The cuvette was capped and shaken to completely mix the fluoropolymer particles in the water. The sample was placed in the Nano-ZS for determination of Dv(50). 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 (Tm) Measurements

[0091] The Tmof the PTFE homopolymer was measured by a differential scanning calorimeter (DSC). 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.Moving Die Rheometer (MDR) Measurements

[0092] Curing characteristics were measured on fluoroelastomer curing compositions of about 8 grams following ASTM D5289 on an MDR-2000 Rheometer (Alpha Technologies, Bellingham, WA). The curing temperature was 177°C, and the curing time was 12 minutes. The moving die frequency was 1 .66 Hz, and the oscillation amplitude was 0.5°.

[0093] 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.Percent Solids Measurements

[0094] The reported weight percent of fluoropolymer solids in aqueous dispersions was measured using an MB45 Moisture Analyzer (Ohaus Corporation, Parsippany, NJ). The measurement was carried out as follows. A clean glass fiber pad was placed on the instrument balance and tared. A two-gram dispersion sample was pipetted on the glass fiber pad. The drying process was started by pushing the start button. The integral halogen dryer was programed to reach 175 °C. During the drying process, water vaporized, and upon completion, the results were displayed as wt% solids. Typical drying times were about 5 minutes.Fluoroelastomer Property Measurements

[0095] Compression set resistances were determined on the fluoroelastomers with a compression device that compressed fluoroelastomer samples to 25% deflectionfollowing 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).

[0096] Hardness was determined for 1 second following ASTM D2240.

[0097] Tensile properties were determined on the unaged fluoroelastomers at 23°C by the ISO 37:2005 C or 1 2008 testing protocol. Prior to the tensile testing, the fluoroelastomer was post-cured for 4 hours at 232°C. Measured tensile properties included the tensile strength in MPa, the elongation at break in %, and the elastic modulus at 100% in MPa.EXAMPLESSynthesis of Partially Fluorinated Aryl Ether Surfactants

[0098] Table 1 shows the chemical structures of the Inventive Examples 1-15 (IE1- IE15) of partially fluorinated aryl ether surfactants described herein.Table 1

[0099] Nine Comparative Examples (CE1-CE9) are also described herein.Comparative Example 1 is C6F13-CH2-CH2-SO3H, available under the trade designation Capstone™ 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 availableunder the trade designation Dowfax™ 2A1 solution surfactant (The Dow ChemicalCompany, Midland, Ml). 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:

[0100] The following representative syntheses of specific Inventive Examples are provided.Preparation of sodium 3,4-bis(difluoromethoxy)benzoate (Inventive Example 14)

[0101] 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.

[0102] 3,4-Bis(difluoromethoxy)benzoic acid was prepared from 100g (0.42 mol) of 3,4 -bis(difluoromethoxy)benzaldehyde following the procedure from J. Chem.Pharm. Res., 2015, 7(6):301-311. The obtained material was recrystallized from ethyl acetate to give 78g (73% yield) of 3,4-bis(difluoromethoxy)benzoic acid; mp.: 104-106°C; white crystalline solid. The structure was confirmed by1H NMR. The acid may be used as a partially fluorinated aryl ether surfactant or converted to a carboxylate salt.

[0103] 1H NMR (DMSO-cfe, 400 MHz): 5 7.33 (t, 1 H, J = 73 Hz), 7.36 (t, 1 H, J = 73 Hz), 7.47 (d, 1 H, J = 8.5 Hz), 7.83 (s, 1 H), 7.89 (d, 1H, J = 8.5 Hz), 13.38 (bs, 1 H).19F NMR (DMSO-cfe, 377 MHz): 5 -82.8 (d, 1 F, J = 73 Hz), -82.5 (d, 1 F, J = 73 Hz).

[0104] The 78g of 3,4-bis(difluoromethoxy)benzoic acid was dissolved in 300m L of 3% NaOH solution and reacidified. The filtered solid was washed with deionized (DI) water until constant pH and the resulting solid was dried at 90-100°C for 2hrs in a vacuum oven at 200-250mmHg. The white material obtained was neutralized with 10% NaOH solution until pH=7.1. Water was removed by blowing nitrogen and theresulting solid was dried at 80°C and 200-250mmHg until the product became crystalline. Then, the material was placed in a desiccator where it was dried over P2O5 to obtain 78g (Yield:92%) of Inventive Example 14.1H NMR (DMSO-cfe, 400 MHz): 5 7.22 (t, 1 H, J = 73 Hz), 7.26 (t, 1 H, J = 73 Hz), 7.26 (d, 1 H, J = 8.3 Hz), 7.86 (d, 1 H, J = 8.3 Hz), 7.89 (s, 1 H).19F NMR (DMSO-cfe, 377 MHz): 5 -81.8 (d, 1 F, J = 73 Hz), -81.7 (d, 1 F, J = 73 Hz).Preparation of sodium 3',6-difluoro-4'-(trifluoromethoxy)[1 , 1 '-biphenyl]-3-sulfonate (Inventive Example 12)

[0105] 1-Bromo-3-fluoro-4-trifluoromethoxy-benzene (25.0g, 96.5 mmol), 2-fluoro- phenylboronic acid (33.7g, 241 mmol), potassium carbonate (33.7g), Pd(PPh3)4 (0.22g, 0.2mol%), water (1 12g), toluene (142g), were stirred and refluxed under nitrogen during 16 hours reaching 74% conversion of aryl bromide by GC. The resulting top toluene layer was separated, washed two times with water and dried over MgSC Toluene removed by distillation and the resulting 4-CF3O-3-F-C6H3- C6H4F was distilled under vacuum. To the portion of obtained 4-CF3O-3-F-C6H3- C6H4F (9.9g) in dichloromethane (36 g), chlorosulfonic acid (4.35g, 1 .03 eq.) was added at -2-0°C and warmed to room temperature over 2 hours and quenched with water (0.86g). The crude product in acid form was precipitated, filtered and washed with dichloromethane. The acid dissolved in water at 25%, and converted to sodium salt by neutralization with NaOH solution at 35-45°C, cooled to 0°C, and precipitated sodium 3',6-difluoro-4'-(trifluoromethoxy)[1 ,1'-biphenyl]-3-sulfonate was filtered out and dried in vacuum to obtain a white solid (5.75g) of Inventive Example 12.1H NMR (500 MHz, acetone-d6): 5=6.88 (t, J=9.5 Hz, 1 H), 7.41-7.49 (m, 3 H), 7.85 (m, 1 H), 8.05 (dm, J=7.3 Hz, 1 H).19F NMR (470.2 MHz, acetone-d6): 5= -59.63 (m, J=5 Hz, 3 F), -117.74 (m, 1 F), -130.62 (m, 1 F).Preparation of sodium 3,5-bis(1 , 1 ,2,2-tetrafluoroethoxy)benzenesulfonate (Inventive Example 2)

[0106] Sodium 3,5-dihydroxybenzenesulfonate dihydrate (9.98g, 40.2 mmol), potassium hydroxide (2.47g, 44.1 mmol), acetonitrile 38.8g and DI water 100.7g were placed in a shaker tube. The tube was frozen and evacuated, then (50g, 500mmol) of tetrafluoroethylene (TFE) were charged to the reactor. The mixture was warmed to 130-135°C gradually while shaking and the heating continued for 14hrs.Then the tube was cooled to an ambient temperature and vented. Content of the tube was moved to a round bottom flask and dried. Crude material was redissolved in 15mL of water and acidified with concentrated HCI. Upon cooling, the acid form of the product was filtered off, it was washed with ice-cold DI water and briefly dried, then it was mixed with 10mL of DI water and treated with 20% aqueous NaOH solution till pH=8-9. The product was filtered off, washed with ice-cold DI water to pH=7 (pH paper) and dried. Obtained 5.3g (29.4%). NMR and IC analysis of the smaller sample suggested that this material contained up to 12.1 % of water. From aqueous fractions, additional 13.3g of material were isolated, that brought the total yield of Inventive Example 2 to 90%.1H NMR (DMSO-cfe, 400 MHz): 5 6.85 (t, 2H, J = 52 Hz), 7.20 (s, 1 H), 7.47 (s, 2H).19F NMR (DMSO-cfe, 376 MHz): 6 -137.8 (dt, 4F, J = 52 Hz, J = 6 Hz), -87.9 (bm, 4F).Preparation of ammonium 4-(1 ,1 ,2-trifluoro-2- (trifluoromethoxy)ethoxy)benzenesulfonate (Inventive Example 3)

[0107] Phenol (67.6 g, 718 mmol, 1 equiv), potassium carbonate (23.2 g, 168 mmol, 0.23 equiv), and tetrahydrofuran (731 mL) were charged to a 1 L pressure reactor. The reactor was cooled, evacuated, then charged with PMVE (182 g, 1100 mmol, 1.5 equiv). The reactor was heated to 60°C for 12 hours. The reaction mixture was filtered and concentrated by rotary evaporation. The product was distilled, bp 57°C 125 torr, to afford 165 g (88% Yield) of (1 ,1 ,2-trifluoro-2- (trifluoromethoxy)ethoxy)benzene. Product structure was confirmed by NMR.1H NMR (DMSO-cfe, 400 MHz): 6 7.17 m, 1 H), 7.26 (m, 2H), 7.34 (m, 1 H), 7.47 (m, 2H).19F NMR (DMSO-de, 376 MHz): 6 -146.7 (m, 1 F), -85.9 (m, 2F), -58.8 (m, 3F).

[0108] (1 ,1 ,2-trifluoro-2-(trifluoromethoxy)ethoxy)benzene (32.9 g, 126 mmol, 1 equiv) was dissolved in 1 ,2-dichloroethane (170 mL) in a round-bottom flask with N2 atmosphere and magnetic stirring bar. Chlorosulfonic acid (16.7 g, 143 mmol, 1.1 equiv) was added slowly, and the mixture stirred at room temperature for 24 hours. The reaction was then cooled to -5°C and quenched by the addition of water (3 mL, 166 mmol, 1 .3 equiv). The mixture was then further cooled to -20°C and the precipitated solids were collected by filtration and rinsed with cold hexane. The resulting solids were suspended in water (53 mL) and pH was adjusted to 7 by the addition of NH4OH (19.3 g, 28 wt% NH3, 317 mmol, 2.5 equiv). The mixture was thenfiltered, and the filtrated was lyophilized. The solids were purified by trituration with refluxing hexane followed by hot filtration. The solid was then dried in vacuo to give Inventive Example 3 (20 g, 44% yield). Product structure was confirmed by NMR.1H NMR (DMSO-de, 400 MHz): 5 7.13 (m, 1 H), 7.24 (m, 2H), 7.70 (m, 2H).19F NMR (DMSO-cfe, 376 MHz): 5 -146.3 (m, 1 F), -85.6 (m, 2F), -58.2 (m, 3F).Preparation of ammonium 2, 4, 6-tris(2, 2-difluoroethoxy)-3, 5-difluorobenzoate (Inventive Example 13)

[0109] To a dry 250m L three neck flask equipped with reflux condenser, thermometer, stir bar and gas inlet under nitrogen atmosphere 60% sodium hydride (7.0g, 175.0 mmol) and 100mL of anhydrous THF were added. The reaction mixture was cooled to -55 to -60°C and stirred for 15min at that temperature. Then 2,2- difluoroethanol (14g, 170.1 mmol) was added dropwise and the reactor was allowed to warm up to room temperature slowly and stirred until gas evolution stopped. The reactor was cooled again to -50 to -55°C and methyl pentafluorobenzoate (10g, 44.2 mmol) was added. Reaction mixture was allowed to warm to room temperature and kept stirring overnight. Then, 100mL of 5% HCI was added to the reactor, the mixture was extracted 5x50mL of dichloromethane. Combined organic phase was washed with 50m L of water and dried over magnesium sulphate for 3 hours with periodic shaking. Solution was filtered and solvent was evaporated. The product obtained was hydrolyzed with a mixture of 20% aqueous potassium hydroxide solution (40mL) and 50mL of dioxane at room temperature initially and then at 50°C until no more water insoluble material can be observed. Solvent was evaporated, product was redissolved in 80mL of water and acidified with concentrated hydrochloric acid. The resulting material was filtered, washed with water, and dried in desiccator over the weekend at ambient temperature. Then it was converted into ammonium salt with ammonium hydroxide. After drying, obtained 9g of Inventive Example 13 (49% yield).1H NMR (D2O, 400 MHz): 6 4.27 (tm, 4H, J = 14 Hz), 4.40 (tm, 2H, J = 14 Hz), 5.96- 6.29 (m).19F NMR (D2O, 376 MHz): 6 -148.4 (s, 2F), -127.8 (dt, J = 54 Hz, Hz, J = 14 Hz), -127.1 (dt, J = 54 Hz, Hz, J = 14 Hz).Synthesis of FluoropolymerExample 1

[0110] 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. After removal of trace oxygen, 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. To start the polymerization, 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. As the reactor pressure dropped, a mixture of 50 wt% TFE and 50 wt% PMVE was fed to the reactor to maintain a 2.1 MPa pressure. After a total of 333 g incremental major monomer was fed, corresponding to a total of 16.4 ml or 0.43 mM initiator solution, and 3.0 hours of polymerization, monomer and initiator fed were discontinued. The reactor was cooled and the pressure in the reactor reduced to atmospheric pressure. The total fluoropolymer dispersion has a total of 1359 g, a solids content of 25.0 wt% solids, a pH of 4.6, and a volume average particle size [Dv(50)J of 114 nm.

[0111] The same polymerization procedure was repeated for other surfactants. Each surfactant was initially present at a concentration of 2.8 mM. CE1 served as a positive control. The results are shown in Table 2.Table 2

[0112] The results demonstrate that high solids amorphous perfluoropolymer batches with polymerization rates similar to a highly fluorinated control can be achieved with the inventive examples of partially fluorinated aryl ether surfactant. Non-fluorinated hydrocarbon surfactants (Comparative Examples 5, 6, and 7) were tested as well, and no polymerization occurred (data not shown).Example 2

[0113] To prepare a 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. To commence polymerization, 5.0 mL of 0.5% ammonium persulfate and 2.5% disodium phosphate heptahydrate was added to the reactor. A mixture of 50% vinylidene fluoride, 30% hexafluoropropene, and 20% tetrafluoroethylene was then set to feed the reactor in order to maintain a pressure of 320 psi. Additional initiator was fed to the reactor to continue the polymerization in increments of 0.0-0.4 mL every 30 minutes to achieve or maintain a monomer flow rate of 80 grams / hour. At the completion of the 5-hour batch time all feeds to the reactor were halted. The lack of polymerization processing aids was then evaluated based on total monomer fed during the 5-hour batch time, as well as resulting coagulum.

[0114] To prepare a VF2 / HFP / TFE fluoroelastomer by a semi-batch emulsion polymerization process with a polymerization processing aid (PPA), 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 to80 °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. To commence polymerization, 5.0 mL of 0.5% ammonium persulfate and 2.5% disodium phosphate heptahydrate was added to the reactor. A mixture of 50% vinylidene fluoride, 30% hexafluoropropene, and 20% tetrafluoroethylene was then set to feed the reactor in order to maintain a pressure of 320 psi. Additional initiator was fed to the reactor to continue the polymerization in increments of 0.0-0.4 mL every 30 minutes to achieve or maintain a monomer flow rate of 80 grams / hour. At the completion of the 5-hour batch time all feeds to the reactor were halted. Polymerization processing aids were then evaluated based on total monomer fed during the 5-hour batch time, as well as resulting coagulum.

[0115] The reaction conditions are shown in Table 3. Comparative Examples 1-3 and Inventive Examples 1-3 were tested as PPAs and a negative control included no PPA.Table 3

[0116] 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.Example 3

[0117] In a semi-batch emulsion polymerization process for making polytetrafluoroethylene (PTFE), a high concentration of a dispersing agent (DA) waspre-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.

[0118] For each run, 210 g of paraffin wax was added to a 3-gallon, jacketed, horizontal, stainless-steel reactor, fitted with a two-blade agitator. The autoclave was sealed and placed under vacuum, then approximately 6000 g of deionized, deaerated water, the primary dispersive agent and 3 g of the perfluororionomer nucleating additive (20% active) was added to the autoclave, followed by a flush of 200 g of deionized, deaerated water. 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. 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.

[0119] 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. For Runs 5-8, the DSP solution included 30 g of DSP in 970 g of deionized, deaerated water and 300 mL were used.

[0120] Kick-off of the polymerization was assumed to have occurred with a 10-psi drop, which marked time zero and the effective start of the polymerization, and the TFE feed count began from zero. The autoclave pressure was brought back to 400 psig with TFE and maintained at 400 psig for the duration of the polymerization by continuous addition of TFE. At kick-off, simultaneous addition of a maintenance initiator solution, using the same DSP stock solution as for initiation wascommenced. The maintenance initiator solution was fed at a rate of 0.6 mL / min feed rate until the end of batch. Runs 3-4 had a maintenance initiator solution fed at a rate of 1.2 mL / min. Run 10-13 failed to kick-off.

[0121] After a total of 3000 g of TFE had been fed to the reactor after kick-off, the agitator was stopped, establishing the completion of the polymerization reaction. After the agitator was stopped, the reactor was vented to atmospheric pressure, was cooled to 80 °C and the dispersion was discharged from the autoclave. Upon cooling, the solid wax was separated from the dispersion, and the dispersion was filtered to remove undispersed solids. The reactor was opened, and all adhered polymer was removed from the reactor. The reactor cleanout was combined with the filtered solids, and the total mass was recorded as the total wet coagulum.

[0122] 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 (Tm) by differential scanning calorimetry (DSC) heating at 2 °C / min, and the coagulum amount.Table 4

[0123] 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 subtractingthe 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.

[0124] 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.

[0125] Interestingly, 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. However, 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.

[0126] The melting points for Runs 1 and 3-7 were slightly lower than for Run 9, which can indicate lower molecular weights. However, Runs 2 and 8 deviate from this trend, with melting points approximately 1 °C higher than Run 9.Example 4

[0127] In 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. All dispersive agents were added to the pre-charge, or before kick-off of the polymerization. Fluoropolyether acid nucleating additive of the type disclosed in U.S. Patent No. 7,897,682 was used as the nucleating agent in the following polymerization procedures. All runs listed in Table 5, contained 72 g of ammonium (2,3,3,3-tetrafluoro-2-(heptafluoropropoxy)propanoate (70.5% active). Runs 1-3 contained an additional dispersive agent, whereas Run 4 only contains the ammonium (2,3,3,3-tetrafluoro-2-(heptafluoropropoxy)propanoate as the sole dispersive agent (DA) for comparison. For the selected dispersive agents listed in Table 5, the following polymerization procedure is used unless otherwise noted.

[0128] For each run, 210 g of paraffin wax was added to a 3 gallon, jacketed, horizontal, stainless-steel reactor, fitted with a two-blade agitator. The autoclave was sealed and placed under vacuum, then approximately 6000 g of deionized, deaerated water, the primary dispersive agent was added to the autoclave, followed by a flush of 100 g of deionized, deaerated water. Then 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 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.

[0129] 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, andthe 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. Autoclave pressure was brought back to 400 psig with TFE and maintained at 400 psig for the duration of the polymerization by continuous addition of TFE. At kick-off, the simultaneous addition of a maintenance initiator solution, 10 g DSP in 990 g deionized, and deaerated water, at a rate of 0.6 mL / min feed rate was commenced until the end of batch.

[0130] After a total of 3000 g of TFE had been fed to the reactor (after kick-off), the agitator was stopped, establishing the completion of the polymerization reaction. After the agitator was stopped, the reactor was vented to atmospheric pressure and was cooled to 80 °C, and the dispersion was discharged from the autoclave. Upon cooling, the solid wax was separated from the dispersion and the dispersion was filtered to removed undispersed solids. The reactor was opened, and all adhered polymer was removed from the reactor. The reactor cleanout was combined with the filtered solid, and the total mass was recorded as the total wet coagulum.

[0131] 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 (Tm) by differential scanning calorimetry (DSC) heating at 2 °C / min, and the coagulum amount.Table 5

[0132] 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.Example 5

[0133] In 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.

[0134] For the selected dispersive agents listed in Table 6, the following polymerization procedure was used unless otherwise noted. Runs 1-7 included partially fluorinated aryl ether surfactants as the second dispersive agent, and 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.

[0135] For each run, 210 g of paraffin wax was added to a 3-gallon, jacketed, horizontal, stainless-steel reactor, fitted with a two-blade agitator. The autoclave was sealed and placed under vacuum, then approximately 6500 g of deionized, deaerated water, 3 g of perfluoroionomer particulate as the nucleating seed (20% in water), 77 g of dispersive agent (ammonium (2,3,3,3-tetrafluoro-2- (heptafluoropropoxy)propanoate, 70.5% in water, 21 .7 mM) were added to the autoclave, followed by a flush of 100 g of deionized, deaerated water. The autoclavewas 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.

[0136] After the addition of the pre-charge reagents, 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. Autoclave pressure was brought back to 400 psig with TFE and maintained at 400 psig for the duration of the polymerization by continuous addition of TFE. At kick-off, the simultaneous addition of a maintenance initiator solution, 10 g DSP in 990 g deionized, deaerated water, at a rate of 0.6 mL / min feed rate was commenced until the end of batch.

[0137] After 500 g of TFE had been fed, since kick-off, an aqueous solution made using deionized, deaerated water containing the dispersive agent listed in Table 6 was fed into the reactor at a rate of 80 mL / min until 300 mL had been delivered, follow by a 100 mL deionized, deaerated water flush.

[0138] After a total of 3000 g of TFE had been fed to the reactor after kick-off, the agitator was stopped, establishing the completion of the polymerization reaction. Runs 10 and 12 were terminated after a polymerization time of at least 110 minutes and fail to consume 3000 g TFE. After the agitator was stopped, the reactor was vented to atmospheric pressure and cooled to 80 °C, and the dispersion was discharged from the autoclave. Upon cooling, the solid wax was separated from the dispersion, and the dispersion was filtered to remove undispersed solids. The reactor was opened, and all adhered polymer was removed from the reactor. The reactor cleanout was combined with the filtered solid, and the total mass was recorded as the total wet coagulum.

[0139] 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 (Tm) by differential scanning calorimetry (DSC) heating at 2 °C / min, and the coagulum amount.Table 6

[0140] High solids batches that ran to 3000 g of TFE were able to achieve high solids, except for Runs 10 and 12, which were terminated early due to extremely slow polymerization rates. All other runs had solid % ranges consistent with Run 8, the positive control, or higher.

[0141] 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.Example 6

[0142] Fluoroelastomer was prepared by a semi-batch emulsion polymerization process, carried out at 80°C in a 40-liter, well-stirred reaction vessel.

[0143] As a comparative example, a solution of 100.5 g Capstone™ 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. 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. After 45 g of this monomer mixture was fed, 24.2 g of a mixture of 72.0 mol % 1 ,4-diiodoperfluorobutane, 22.7 mol % 1 ,6-diiodoperfluorohexane, 4.0 mol % 1 ,8-diiodoperfluorooctane, and 1.2 mol % 1 ,10-diiodoperfluorodecane was charged to the reactor. The reactor was continuously added 6 ml / hour initiator solution to maintain polymerization rate. After 2920 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 14 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 9.3 hours, monomer and initiator fed were discontinued. The reactor was cooled and the pressure in the reactor reduced to atmospheric. 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 contained36.5 wt% VF2, 36.7 wt% HFP, 26.5 wt% TFE and 0.219 wt% I.

[0144] As a first inventive example, a solution of 1.0 g perfluoroionomer particulate as disclosed in US Patent No. 6,916,853 and 42.0 g of Inventive Example 3 as the DA in 3957 g water was pumped into the reactor, followed by pumping a solution of23.6 g disodium phosphate heptahydrate in 17 liters of deionized, deoxygenated water. 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. The reactor was charged with 67 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. After 45 g of the monomer mixture was ted, 26.3 g of a mixture of 72.0 mol % 1 ,4-diiodoperfluorobutane, 22.7 mol % 1 ,6-diiodoperfluorohexane, 4.0 mol % 1 ,8-diiodoperfluorooctane, and 1.2 mol % 1 ,10-diiodoperfluorodecane was charged to the reactor. 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. 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 aluminumsulfate 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.

[0145] In a second inventive example, a solution of 1.5 g perfluoroionomer particulate as disclosed in US Patent No. 6,916,853 and 46.8 g Inventive Example 1 as the DA in 3953 g water was pumped into the reactor. The procedure was otherwise the same as with Inventive Example 3 as the DA. The resulting fluoroelastomer latex had a solids content of 27.4 wt% solids, and a pH of 4.0. 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.

[0146] 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. (Savannah, GA), 1 .5 parts 2,5- dimethyl-2,5-di-(tert-butyl peroxy) hexane (45% by weight) on calcium carbonate / silica carrier commercially available under the trade designation “Varox® DBPH-50” from Vanderbilt Chemicals LLC (Norwalk, CT).

[0147] Table 7 shows the curing characteristics and the compression set results on the cured compositions.Table 7

[0148] 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.

[0149] All above-mentioned references are hereby incorporated by reference herein.

[0150] While the invention has been described with reference to a preferred embodiment, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the inventionwithout departing from the essential scope thereof. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed as the best mode contemplated for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims.

Claims

CLAIMSWhat is claimed is:1 . An aqueous fluoropolymer emulsion polymerization composition comprising: 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 surfactant of Formula 1 :Formula 1 wherein R1 comprises a terminal group selected from the group consisting of CO2X, SO3X, and PO(OX)2, wherein X is selected from the group consisting of H, Li, Na, K, Cs, NH4, %Mg, ! Ca, and %Ba; and wherein R2, R3, R4, Rs, and Re are independently selected from the group consisting of H, halogen, Ci-a linear or branched alkyl, C1-4 alkoxy that is partially or fully halogenated and may further include an ether, Formula 2, and Formula 3:Formula 2 Formula 3 wherein 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(CH3)2-, -C(CF3)2-, and-C(CF2H)2- and wherein R7, Rs, R9, R10, 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; with the proviso that at least one of R2, R3, R4, Rs, and Rs 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; and with the proviso that at least two of R2, R3, R4, Rs, and Re are selected from the group consisting of H and halogen.

2. The composition of claim 1 , wherein the halogen is fluorine and the halogenated is fluorinated.

3. The composition of claim 1 or claim 2, wherein R1 consists of the terminal group selected from the group consisting of CO2X, SO3X, and PO(OX)2.

4. The composition of claim 3, wherein R1 is SO3X.

5. The composition of claim 3, wherein R1 is CO2X.

6. The composition of claim 3, wherein R1 is PO(OX)2.

7. The composition of any of claims 1-6, wherein at least one of R2, R3, R4, Rs, and Re is C1-4 linear or branched alkyl.

8. The composition of any of claims 1-6, wherein 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.

9. The composition of any of claims 1-8, with the proviso that the C1-3 alkoxy that is partially or fully halogenated and may further include an ether is partially halogenated.

10. The composition of any of claims 1 -9, wherein at least one of R2, R3, R4, Rs, and Re is selected from the group consisting of -0-CH2F, -O-CHF2, -O-CF3, -O-CH2-CHF2, -O-CF2-CH3, -O-CF2-CHF2, -O-CH(CH2F)2, -O-CF(CH2F)2, -O-CH(CHF2)2, -O-CHF-CHF-O-CF3, -O-CF2-CH2-O-CF2H, -O-CF2-CH2-O-CF3, and -O-CF2-CHF-O-CF3.11 . The composition of claim 10, wherein at least two of R2, R3, R4, R5, and Re are independently selected from the group consisting of -O-CH2F, -O-CHF2, -O-CF3, -O-CH2-CHF2, -O-CF2-CH3, -O-CF2-CHF2, -O-CH(CH2F)2, -O-CF(CH2F)2, -O-CH(CHF2)2, -O-CHF-CHF-O-CF3, -O-CF2-CH2-O-CF2H, -O-CF2-CH2-O-CF3, and -O-CF2-CHF-O-CF3.

12. The composition of any of claims 1-11 , with the proviso that at least one of R7, Rs, R9, R10, and Rn is the C1-4 alkoxy that is partially or fully halogenated and may further include an ether.

13. A compound of Formula 1 :Formula 1 wherein R1 comprises a terminal group selected from the group consisting of CO2X, SO3X, and PO(OX)2, wherein X is selected from the group consisting of H, Li, Na, K, Cs, NFL, %Mg, ! Ca, and %Ba; and wherein R2, R3, R4, Rs, 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:Formula 2 Formula 3wherein 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(CH3)2-, -C(CF3)2-, and -C(CF2H)2- and wherein R7, Rs, R9, R10, 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; with the proviso that at least one of R2, R3, R4, R5, 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; with the proviso that at least two of R2, R3, R4, Rs, and Re are selected from the group consisting of H and halogen; and with the proviso that when R1 is CO2H, R2, R3, R4, Rs, and Re are not, in combination, H, -O-CHF2, -O-CHF2, H, and H, respectively.

14. The compound of claim 13, wherein the halogen is fluorine and the halogenated is fluorinated.

15. The compound of claim 13 or claim 14, wherein R1 consists of the terminal group selected from the group consisting of CO2X, SO3X, and PO(OX)2.

16. The compound of claim 15, wherein R1 is SO3X.

17. The compound of claim 15, wherein R1 is CO2X.

18. The compound of claim 15, wherein R1 is PO(OX)2.

19. The compound of any of claims 13-18, wherein at least one of R2, R3, R4, Rs, and Re is C1-4 linear or branched alkyl.

20. The compound of any of claims 13-18, wherein 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.21 . The compound of any of claims 13-20, with the proviso that the C1-3 alkoxy that is partially or fully halogenated and may further include an ether is partially halogenated.

22. The compound of any of claims 13-21 , wherein 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-CHF2I-O-CH(CH2F)2, -O-CF(CH2F)2, -O-CH(CHF2)2, -0-CHF-CHF-0-CF3, -O-CF2-CH2-O-CF2H, -O-CF2-CH2-O-CF3, and -O-CF2-CHF-O-CF3.

23. The compound of claim 22, wherein at least two of R2, R3, R4, Rs, and Re are independently selected from the group consisting of -O-CH2F, -O-CHF2, -O-CF3, -O-CH2-CHF2, -O-CF2-CH3, -O-CF2-CHF2, -O-CH(CH2F)2, -O-CF(CH2F)2, -O-CH(CHF2)2, -0-CHF-CHF-0-CF3, -O-CF2-CH2-O-CF2H, -O-CF2-CH2-O-CF3, and -O-CF2-CHF-O-CF3.

24. The compound of any of claims 13-23, with the proviso that at least one of R7, Rs, R9, R10, and Rn is the C1-4 alkoxy that is partially or fully halogenated and may further include an ether.

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