WO2010009191A2 - Fluorinated ether compounds and methods of using the same - Google Patents

Fluorinated ether compounds and methods of using the same Download PDF

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Publication number
WO2010009191A2
WO2010009191A2 PCT/US2009/050627 US2009050627W WO2010009191A2 WO 2010009191 A2 WO2010009191 A2 WO 2010009191A2 US 2009050627 W US2009050627 W US 2009050627W WO 2010009191 A2 WO2010009191 A2 WO 2010009191A2
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chf
group
ocf
independently
compound according
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PCT/US2009/050627
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French (fr)
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WO2010009191A3 (en
Inventor
Rudolf J. Dams
Michael S. Terrazas
Klaus Hintzer
Zai-Ming Qiu
Miguel A. Guerra
Andreas R. Maurer
Harald Kaspar
Kai H. Lochhaas
Michael JÜRGENS
Tilman C. Zipplies
Werner Schwertfeger
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3M Innovative Properties Company
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Priority to MX2011000702A priority Critical patent/MX2011000702A/en
Priority to EA201100053A priority patent/EA201100053A1/en
Priority to CN2009801355732A priority patent/CN102149674A/en
Priority to EP09790431A priority patent/EP2318357A2/en
Priority to US13/054,601 priority patent/US8633288B2/en
Priority to JP2011518865A priority patent/JP2011528659A/en
Priority to BRPI0915955A priority patent/BRPI0915955A2/en
Publication of WO2010009191A2 publication Critical patent/WO2010009191A2/en
Publication of WO2010009191A3 publication Critical patent/WO2010009191A3/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C235/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms
    • C07C235/02—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton
    • C07C235/04—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C235/10—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton being acyclic and saturated having the nitrogen atom of at least one of the carboxamide groups bound to an acyclic carbon atom of a hydrocarbon radical substituted by nitrogen atoms not being part of nitro or nitroso groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/01—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms
    • C07C211/02—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C07C211/09—Diamines
    • C07C211/11—Diaminopropanes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/01—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms
    • C07C211/02—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C07C211/14—Amines containing amino groups bound to at least two aminoalkyl groups, e.g. diethylenetriamines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C291/00—Compounds containing carbon and nitrogen and having functional groups not covered by groups C07C201/00 - C07C281/00
    • C07C291/02—Compounds containing carbon and nitrogen and having functional groups not covered by groups C07C201/00 - C07C281/00 containing nitrogen-oxide bonds
    • C07C291/04—Compounds containing carbon and nitrogen and having functional groups not covered by groups C07C201/00 - C07C281/00 containing nitrogen-oxide bonds containing amino-oxide bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/01—Sulfonic acids
    • C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
    • C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C07C309/13—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton
    • C07C309/14—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton containing amino groups bound to the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
    • C07C69/67—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids
    • C07C69/708—Ethers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/09—Esters of phosphoric acids
    • C07F9/091—Esters of phosphoric acids with hydroxyalkyl compounds with further substituents on alkyl
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se)
    • C07F9/3804—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se) not used, see subgroups
    • C07F9/3808—Acyclic saturated acids which can have further substituents on alkyl
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/002—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds
    • C08G65/005—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens
    • C08G65/007—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens containing fluorine

Definitions

  • Fluorochemicals have been used in a variety of applications for many years.
  • fluorinated surfactants have been added to a variety of formulations (e.g., coatings and foams).
  • the addition of a fluorinated surfactant to a formulation may enhance the properties of the formulation by improving, for example, wetting behavior, leveling properties, and stability (e.g., with respect to phase separation or foam half-life).
  • fluorochemicals have been used to provide properties such as hydrophobicity and oleophobicity to various materials (e.g., ceramics, metals, fabrics, plastics, and porous stones).
  • fluorinated surfactants and repellents include long-chain perfluoroalkyl groups, (e.g., perfluorooctyl groups). Recently, however, there has been an industry trend away from using perfluorooctyl fluorinated surfactants, which has resulted in a desire for new types of surfactants which may be used in a variety of applications.
  • the present disclosure provides compounds that have partially fluorinated polyether groups and/or fully fluorinated polyether groups with a low number (e.g., up to 4) continuous perfluorinated carbon atoms.
  • the compounds may be useful, for example, as surfactants or surface treatments.
  • the compounds disclosed herein unexpectedly lower the surface tension of water to an extent comparable to or higher than fully fluorinated surfactants having a greater number of perfluorinated carbon atoms.
  • the compounds disclosed herein unexpectedly raise the contact angle versus water and/or hexadecane to an extent comparable to treatment compositions having a greater number of perfluorinated carbon atoms.
  • the present disclosure provides a compound represented by formula:
  • Rf is selected from the group consisting of: Rf-(O) r -CHF-(CF 2 ) n -; [R ⁇ -(OVC(L)H-CF 2 -O] 1n -W-;
  • Q is selected from the group consisting of a bond, -C(O)O - + NH(R') 2 -, -C(O)-N(R')-, and -C(O)-O-, wherein R' is selected from the group consisting of hydrogen and alkyl having from 1 to 4 carbon atoms;
  • X is selected from the group consisting of alkylene, arylalkylene, and poly(alkyleneoxy) wherein alkylene and arylalkylene are each optionally interrupted by at least one functional group independently selected from the group consisting of ether, amine, ester, amide, carbamate, and urea;
  • Z is selected from the group consisting of an ammonium group, an amine- oxide group, an amine, a carboxylate, a sulfonate, a sulfate, phosphate, a phosphonate, and an amphoteric group, with the proviso that when X is alkylene having at least 10 carbon atoms, Z may also be hydrogen, and with the further proviso that when X is poly(alkyleneoxy), Z may also be selected from the group consisting of hydroxyl and alkoxy;
  • Rf and Rf* 3 independently represent a partially or fully fluorinated alkyl group having from 1 to 10 carbon atoms and optionally interrupted with at least one oxygen atom;
  • L is selected from the group consisting of F and CF 3 ;
  • W is selected from the group consisting of alkylene and arylene;
  • r is 0 or 1, wherein when r is 0, then Rf is interrupted with at least one oxygen atom;
  • s is 1 or 2, wherein when s is 2, then Z is selected from the group consisting of an ammonium group, a phosphate, a sulfate, and a phosphonate;
  • t is O or l;
  • m is 1, 2, or 3;
  • n is 0 or 1 ; each p is independently a number from 1 to 6; and
  • z is a number from 2 to 7.
  • the present disclosure provides a composition
  • a composition comprising a compound disclosed herein and at least one of solvent or water.
  • the composition further comprises a non-fluorinated polymer.
  • the present disclosure provides a method comprising treating a surface with a composition comprising a compound disclosed herein and at least one of solvent or water.
  • the surface comprises at least one of a polymer, ceramic (i.e., glasses, crystalline ceramics, glass ceramics, and combinations thereof), stone such as natural stone (e.g., sandstone, limestone, marble, and granite) or manmade or engineered stone, concrete, laminate, metal, or wood.
  • Z is a phosphate or phosphonate group.
  • the present disclosure provides an article having a surface, wherein at least a portion of the surface is in contact with a compound disclosed herein.
  • the surface comprises at least one of a polymer, ceramic (i.e., glasses, crystalline ceramics, glass ceramics, and combinations thereof), stone such as natural stone (e.g., sandstone, limestone, marble, and granite) or manmade or engineered stone, concrete, laminate, metal, or wood.
  • Z is a phosphate or phosphonate group.
  • the present disclosure provides a method of reducing the surface tension of a liquid, the method comprising combining at least the liquid with an amount of a compound disclosed herein sufficient to reduce the surface tension of the liquid.
  • the present disclosure provides methods of making a foam, the method comprising combining at least a liquid, a gas, and a compound according to the present disclosure to make the foam.
  • the liquid is water.
  • the liquid is a hydrocarbon liquid.
  • alkyl group and the prefix “alk-” are inclusive of both straight chain and branched chain groups and of cyclic groups. In some embodiments, alkyl groups have up to 30 carbons (in some embodiments, up to 20, 15, 12, 10, 8, 7, 6, or 5 carbons) unless otherwise specified. Cyclic groups can be monocyclic or polycyclic and, in some embodiments, have from 3 to 10 ring carbon atoms.
  • Alkylene is the divalent form of the “alkyl” groups defined above.
  • Arylalkylene refers to an “alkylene” moiety to which an aryl group is attached.
  • aryl as used herein includes carbocyclic aromatic rings or ring systems, for example, having 1, 2, or 3 rings and optionally containing at least one heteroatom (e.g., O, S, or N) in the ring.
  • heteroatom e.g., O, S, or N
  • aryl groups include phenyl, naphthyl, biphenyl, fluorenyl as well as furyl, thienyl, pyridyl, quinolinyl, isoquinolinyl, indolyl, isoindolyl, triazolyl, pyrrolyl, tetrazolyl, imidazolyl, pyrazolyl, oxazolyl, and thiazolyl.
  • Rf is selected from the group consisting of: Rf-(O) r -CHF-(CF 2 ) n - I;
  • Rf is selected from the group consisting of
  • Rf is selected from the group consisting of CF 3 -(O-CF 2 ) Z - and CF 3 -O-(CF 2 ) 3 -O-CF 2 -.
  • Rf has a molecular weight of up to 600 grams per mole (in some embodiments, up to 500, 400, or even up to 300 grams per mole).
  • Rf and Rf* 3 independently represent a partially or fully florinated alkyl group having from 1 to 10 carbon atoms and optionally interrupted with at least one oxygen atom.
  • Rf and Rf* 3 include linear and branched alkyl groups. In some embodiments, Rf and/or Rf* 3 is linear.
  • Rf and Rf* 3 independently represent a fully fluorinated (i.e., perfluorinated) alkyl group having up to 6 (in some embodiments, 5, 4, 3, 2, or 1) carbon atoms.
  • Rf and Rf* 3 independently represent a fully fluorinated alkyl group interrupted with at least one oxygen atom, of which the alkyl groups between oxygen atoms have up to 6 (in some embodiments, 5, 4, 3, 2, or 1) carbon atoms, and wherein the terminal alkyl group has up to 6 (in some embodiments, 5, 4, 3, 2, or 1) carbon atoms.
  • Rf and Rf* 3 independently represent a partially fluorinated alkyl group having up to 6 (in some embodiments, 5, 4, 3, 2, or 1) carbon atoms and up to 2 hydrogen atoms.
  • Rf and Rf independently represent a partially fluorinated alkyl group having up 2 hydrogen atoms interrupted with at least one oxygen atom, of which the alkyl groups between oxygen atoms have up to 6 (in some embodiments, 5, 4, 3, 2, or 1) carbon atoms, and wherein the terminal alkyl group has up to 6 (in some embodiments, 5, 4, 3, 2, or 1) carbon atoms.
  • Rf and Rf* 3 are independently represented by formula
  • R f 1 is a perfluorinated alkyl group having from 1 to 6 (in some embodiments, 1 to 4) carbon atoms.
  • Rf 2 and Rf 3 are each independently perfluorinated alkylene having from 1 to 4 carbon atoms, x and y are each independently numbers from 0 to 4, and the sum of x and y is at least 1. In some of these embodiments, t is 1 , and r is 1.
  • Rf and Rf* 3 are independently represented by formula
  • Rf 4 is a perfluorinated alkyl group having from 1 to 6 (in some embodiments, 1 to 4) carbon atoms.
  • R f 5 and R/ are each independently perfluorinated alkylene having from 1 to 4 carbon atoms, a and b are each independently numbers from 0 to 4. In some of these embodiments, t is 0, and r is 0.
  • Rf and Rf* 3 are independently represented by formula Rf 7 -(OCF2) P -, wherein p is from 1 to 6 (in some embodiments, 1 to 4), and Rf 7 is selected from the group consisting of a partially fluorinated alkyl group having 1, 2, 3, 4, 5, or 6 carbon atoms and 1 or 2 hydrogen atoms and a fully fluorinated alkyl group having 1, 2, 3 or 4 carbon atoms.
  • Rf and Rf* 3 are independently represented by formula Rf 8 -O-(CF2) P -, wherein p is from 1 to 6 (in some embodiments, 1 to 4) and R f 8 is selected from the group consisting of a partially fluorinated alkyl group having 1, 2, 3, 4, 5, or 6 carbon atoms and 1 or 2 hydrogen atoms and a fully fluorinated alkyl group having 1, 2, 3 or 4 carbon atoms.
  • L is selected from the group consisting of F and CF 3 . In some embodiments of Formula II, L is F. In other embodiments, L is CF 3 .
  • W is selected from the group consisting of alkylene and arylene.
  • Alkylene includes linear, branched, and cyclic alkylene groups having from 1 to 10 (in some embodiments, 1 to 4) carbon atoms.
  • W is methylene.
  • W is ethylene.
  • Arylene includes groups having 1 or 2 aromatic rings, optionally having at least one heteroatom (e.g., N, O, and S) in the ring, and optionally substituted with at least one alkyl group or halogen atom.
  • W is phenylene.
  • t is 0 or 1.
  • t is 1.
  • t is
  • Rf is typically interrupted by at least one oxygen atom.
  • n 1, 2, or 3. In some embodiments, m is 1.
  • n is 0 or 1. In some embodiments, n is 0. In some embodiments, n is 1. In Formulas III, p is a number from 1 to 6 (i.e., 1, 2, 3, 4, 5, or 6). In some embodiments, p is 1, 2, 5, or 6. In some embodiments, p is 3. In some embodiments, p is 1 or 2. In some embodiments, p is 5 or 6.
  • z is a number from 2 to 7 (i.e., 2, 3, 4, 5, 6, or 7). In some embodiments, z is a number from 2 to 6, 2 to 5, 2 to 4, or 3 to 4.
  • compounds according to the present disclosure have an Rf group represented by Formula III (i.e., CFsCFH-O-(CF 2 ) P -). In some of these embodiments Rf is selected from the group consisting of CF 3 CFH-O-(CF 2 )3- and CF 3 CFH-O-(CF 2 ) S -.
  • compounds according to the present disclosure have an Rf group represented by Formula I.
  • Rf is selected from the group consisting of:
  • Rf is selected from the group consisting of:
  • Rf is selected from the group consisting of:
  • Rf is selected from the group consisting of:
  • Rf is selected from the group consisting of: CF 3 -O-CF 2 CF 2 -CF 2 -O-CHF-;
  • compounds according to the present disclosure have an Rf group represented by Formula II.
  • L is F
  • m is 1
  • W is alkylene.
  • Rf is selected from the group consisting of:
  • Rf is represented by formula
  • Rf is selected from the group consisting of:
  • compounds according to the present disclosure have an Rf group represented by Formula IV (i.e., CF 3 -(O-CF 2 ) Z -).
  • Rf group represented by Formula IV i.e., CF 3 -(O-CF 2 ) Z -.
  • z is a number from 2 to 6, 2 to 5, 2 to 4, 3 to 5, or 3 to 4. .
  • compounds according to the present disclosure have an Rf represented by Formula V (i.e., CF 3 -O-(CF 2 ) 3 -O-CF 2 -).
  • Q is selected from the group consisting of a bond, -C(0)0 ⁇ + NH(R) 2 -, -C(O)-N(R')-, and -C(O)-O-, wherein R is hydrogen or alkyl having 1 to 4 carbon atoms (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or sec- butyl).
  • R is hydrogen or alkyl having 1 to 4 carbon atoms (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or sec- butyl).
  • Q is selected from the group consisting of -C(O)-N(R')- and -C(O)-O-.
  • Q is selected from the group consisting of a bond and -C(O)-N(R')-. In some embodiments, Q is -C(O)-N(R')-. In some embodiments, Q is -C(O)O - 4 NH(R) 2 -. In some embodiments, R is hydrogen or methyl. In some embodiments, R' is hydrogen. It should be understood that when Q is a bond, a compound represented by Formula (Rf-Q-X) 8 -Z can also be represented by Formula (Rf-X) 8 -Z.
  • X is selected from the group consisting of alkylene and arylalkylene, wherein alkylene and arylalkylene are each optionally interrupted by at least one functional group independently selected from the group consisting of ether (i.e., -0-), amine (i.e., -N(R)-), ester, (i.e., -0-C(O)- or -C(O)-O-), amide (i.e., -N(R')-C(0)- or -C(O)-N(R')-), carbamate (i.e., -N(R')-C(0)-0- or -0-C(O)-N(R')- ), and urea (i.e., -N(R')-C(0)-N(R')-), wherein in any of these functional groups, R is as defined in any of the above embodiments.
  • X is alkylene having up to 5 carbon atoms. In some embodiments, X is alkylene having at least 10 (e.g., at least 12, 15, 18, 20, 22, 25, 28, or 30) carbon atoms. In some embodiments, X is alkylene that is optionally interrupted by at least one ether group. In some of these embodiments, X is a poly(alkyleneoxy) group.
  • X is -[EO]f-[R 2 O] g -[EO]f- or -[R 2 O] g -[EO]r[R 2 O] g -, wherein EO represents -CH 2 CH 2 O-; each R 2 O independently represents -CH(CH 3 )CH 2 O-, -CH 2 CH(CH 3 )O-, -CH(CH 2 CH 3 )CH 2 O-, -CH 2 CH(CH 2 CH 3 )O-, or -CH 2 C(CH 3 ) 2 O- (in some embodiments, -CH(CH 3 )CH 2 O-, or -CH 2 CH(CH 3 )O-); each f is independently from 1 to 150 (in some embodiments, from 7 to about 150, 14 to about 125, 5 to 15, or 9 to 13); and each g is independently from O to 55 (in some embodiments, from about 21 to about 54, 15 to 25, 9 to about 25, or 19 to 23).
  • Z is selected from the group consisting of an ammonium group, an amine-oxide group, an amine, a carboxylate (i.e., -CO 2 Y), a sulfonate (i.e., -SO 3 Y), a sulfate (i.e., -0-SO 3 Y or (-O) 2 -SO 2 Y), phosphate (i.e., -0-P(O)(OY) 2 or (-O) 2 -P(O)OY), a phosphonate (i.e., -P(O)(OY) 2 ), and an amphoteric group, with the proviso that when X is alkylene having at least 10 carbon atoms, Z may also be hydrogen, and with the further proviso that when X is poly(alkyleneoxy), Z may also be a hydroxyl (i.e., -OH) or alkoxy (i
  • Ammonium groups include those represented by formula -[N(R) 3 ] M , wherein each R is independently hydrogen, alkyl, or aryl, wherein alkyl and aryl are optionally substituted by at least one halogen, alkoxy, nitro, or nitrile group and aryl may additionally be optionally substituted by alkyl, and wherein M " is a counter anion.
  • Ammonium groups also include ring systems having one or two aromatic or saturated rings and a positively charged nitrogen atom (e.g., pyrrolium, pyrimidinium, pyrazolium, isoxazolium, oxazolium, thiazolium, isothiazolium, pyridinium, pyrazinium, pyridazinium, imidazolium, isoindolium, indolium, purinium, quinolinium, isoquinolinium, naphthyridinium, quinoxalinium, quinazolinium, phthalazinium, indazolium, pyrrolidinium, piperidinium, azepinium, or piperazinium).
  • a positively charged nitrogen atom e.g., pyrrolium, pyrimidinium, pyrazolium, isoxazolium, oxazolium, thiazolium, isothiazolium, pyridinium, pyrazinium
  • Amine-oxide groups include those represented by formula -N(O)(R. 1 ) ⁇ wherein each R 1 is independently hydrogen, alkyl, or aryl, wherein alkyl and aryl are optionally substituted as described above for R, and ring systems having one or two aromatic or saturated rings and an N- oxide (e.g., an N-oxide of pyrrolium, pyrimidinium, pyrazolium, isoxazolium, oxazolium, thiazolium, isothiazolium, pyridinium, pyrazinium, pyridazinium, imidazolium, isoindolium, indolium, purinium, quinolinium, isoquinolinium, naphthyridinium, quinoxalinium, quinazolinium, phthalazinium, indazolium, pyrrolidinium, piperidinium, azepinium, or piperazinium).
  • Amines include those represented by formula -NR 2 , wherein each R is independently hydrogen, alkyl, or aryl, wherein alkyl and aryl are optionally substituted as described above, or two R groups may join to form a 5 to 7-membered ring optionally containing at least one O, N, or S and optionally substituted by alkyl having 1 to 6 carbon atoms.
  • Amphoteric groups include those having both an ammonium group and either a carboxylate, a sulfonate, a sulfate, phosphate, or a phosphonate group.
  • Z is selected from the group consisting of an ammonium group, an amine-oxide group, a carboxylate, a sulfonate, a sulfate, phosphate, a phosphonate, and an amphoteric group. In some embodiments, Z is selected from the group consisting of an ammonium group, an amine-oxide group, and an amphoteric group. In some embodiments, Z is selected from the group consisting of a carboxylate, a sulfonate, a sulfate, phosphate, and a phosphonate.
  • Z is selected from the group consisting of -[N(R) 3 ] + M ⁇ , -N(O)(R 1 ) 2 , -N + (R) 2 -X ⁇ SO 3 A, and -N + (R) 2 -X ⁇ CO 2 A.
  • Z is -[N(R) 3 ] + M ⁇ .
  • Z is -N(O)(R 1 ) 2 , -N + (R) 2 -X ⁇ SO 3 A, or -N + (R) 2 -X ⁇ CO 2 A.
  • each R is independently selected from the group consisting of hydrogen and alkyl having from 1 to 6 carbon atoms (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, n-pentyl, isopentyl, neopentyl, or n- hexyl).
  • each R is independently hydrogen or methyl.
  • each R 1 is independently selected from the group consisting of hydrogen and alkyl having from 1 to 6 carbon atoms (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, n-pentyl, isopentyl, neopentyl, or n- hexyl), wherein alkyl is optionally substituted by at least one halogen, alkoxy, nitro, or nitrile group, or two R 1 groups may join to form a 5 to 7-membered ring optionally containing at least one O, N, or S and optionally substituted by alkyl having 1 to 6 carbon atoms.
  • each R 1 is independently hydrogen or methyl.
  • each X 1 is selected from the group consisting of alkylene and arylalkylene, wherein alkylene and arylalkylene are each optionally interrupted by at least one ether linkage. In some embodiments, X 1 is alkylene having up to 5 carbon atoms.
  • M " is a counter anion.
  • Typical counter anions include halides (i.e., fluoride, chloride, bromide, and iodide), organic acid salts (e.g., formate, acetate, propionate, lactate, laurate, palmitate, stearate, or citrate), organic sulfonic or sulfuric acid salts (e.g., alkyl sulfates or alkanesulfonates), nitrate, and tetrafluoroborate.
  • the organic acid salts and sulfonic acid salts may be partially fluorinated or perfluorinated.
  • the acid salt is RfC(O)O " , wherein Rf is as defined in any of the above embodiments.
  • M " is chloride, bromide, or iodide (i.e., Cl-, Br-, or I-). In some embodiments, M " is selected from the group consisting of chloride, acetate, iodide, bromide, methylsulfate, ethylsulfate, and formate.
  • A is selected from the group consisting of hydrogen and a free anion.
  • Z is selected from the group consisting of -P(O)(OY) 2 , -0-P(O)(OY) 2 , -SO 3 Y, -0-SO 3 Y, and
  • Y is a counter cation.
  • Exemplary Y counter cations include alkali metal (e.g., sodium, potassium, and lithium), alkaline earth metal (e.g., calcium and magnesium), ammonium, alkyl ammonium (e.g., tetraalkylammonium), and five to seven membered heterocyclic groups having a positively charged nitrogen atom (e.g, a pyrrolium ion, pyrazolium ion, pyrrolidinium ion, imidazolium ion, triazolium ion, isoxazolium ion, oxazolium ion, thiazolium ion, isothiazolium ion, oxadiazolium ion, oxatri
  • alkali metal e.g., sodium, potassium, and lithium
  • alkaline earth metal e.g., calcium and magnesium
  • ammonium alkyl ammonium (e.g.
  • Z is -[N(R) 3 J + M " , wherein each R and is independently hydrogen or methyl, and wherein M- is selected from the group consisting of chloride, acetate, iodide, bromide, methylsulfate, ethylsulfate, and formate.
  • Q is
  • X is alkylene having up to 5 (e.g., 1, 2, 3, 4, 5) carbon atoms.
  • Q is -C(O)O- NH(R) 2 -
  • X is selected from the group consisting of alkylene having up to 5 carbon atoms, -[EOMR 2 O] g -[EO]f-, and-[R 2 O] g -[EOHR 2 O] g -, wherein EO represents -CH 2 CH 2 O-; each R 2 O independently represents -CH(CH 3 )CH 2 O-, -CH 2 CH(CH 3 )O-,
  • each f is independently a number from 1 to 150 (in some embodiments, from 7 to about 150, 14 to about 125, 5 to 15, or 9 to 13); and each g is independently a number from O to 55 (in some embodiments, from about 21 to about 54, 15 to 25, 9 to about 25, or 19 to 23).
  • the compound is represented by a formula selected from the group consisting of [Rf-C(O)O + NH(R') 2 -X] 2 -NH(R) + RfC(O)O " and
  • Z is -N(0)(R 1 ) 2 , -N + (R) 2 -X ⁇ SO 3 A, or -N + (R) 2 -X ⁇ CO 2 A, wherein each R and R*are independently hydrogen or methyl, and wherein X 1 is alkylene having up to 5 carbon atoms.
  • X-Z is selected from the group consisting of:
  • EO represents -CH 2 CH 2 O-; each R 2 O independently represents -CH(CH 3 )CH 2 O-, -CH 2 CH(CH 3 )O-, -CH(CH 2 CH 3 )CH 2 O-, -CH 2 CH(CH 2 CH 3 )O-, or
  • R 3 is hydrogen or alkyl having up to 4 carbon atoms (e.g., methyl, ethyl, n- propyl, isopropyl, n-butyl, sec-butyl, or isobutyl); each f is independently from 1 to 150 (in some embodiments, from 7 to about 150, 14 to about 125, 5 to 15, or 9 to 13); and each g is independently from 0 to 55 (in some embodiments, from about 21 to about 54, 15 to 25, 9 to about 25, or 19 to 23). In some embodiments, each g is 0.
  • each g is 0.
  • Compounds represented by Formula (Rf-Q-X) 8 -Z can be prepared, for example, starting with a partially or fully fluorinated carboxylic acid, a salt thereof, a carboxylic acid ester, or a carboxylic acid halide.
  • a partially or fully fluorinated carboxylic acid, a salt thereof, a carboxylic acid ester, or a carboxylic acid halide Partially and fully fluorinated carboxylic acids and salts thereof, carboxylic acid esters, and carboxylic acid halides can be prepared by known methods.
  • starting materials represented by formula Rf -(O) r -CHF-(CF 2 ) n -C(O)G or [Rf-(O) 1 -C(L)H-CF 2 -O] 1n -W-C(O)G, wherein G represents -OH, -O-alkyl (e.g., having from 1 to 4 carbon atoms), or -F and Rf, Rf 1 , n, m, L, t, r, and W are as defined in any of the embodiments above, can be prepared from fluorinated olefins of Formula VI or VII:
  • Numerous compounds of Formula VI or VII are known (e.g., perfluorinated vinyl ethers and perfluorinated allyl ethers), and many can be obtained from commercial sources (e.g., 3M Company, St. Paul, MN, and E.I. du Pont de Nemours and Company, Wilmington, DE). Others can be prepared by known methods; (see, e.g., U. S. Pat. Nos. 5,350,497 (Hung et al.) and 6,255,536 (Worm et al.)).
  • Compounds of formula Rf-(O) r -CHF-(CF 2 ) n -C(O)G, wherein n is O, can be prepared, for example, by reacting a fluorinated olefin of Formula VII with a base (e.g., ammonia, alkali metal hydroxides, and alkaline earth metal hydroxides).
  • a base e.g., ammonia, alkali metal hydroxides, and alkaline earth metal hydroxides.
  • a fluorinated olefin of Formula VII can be reacted with an aliphatic alcohol (e.g., methanol, ethanol, n-butanol, and t-butanol) in an alkaline medium, and the resulting ether can be decomposed under acidic conditions to provide a fluorinated carboxylic acid of formula Rf -(O) r -CHF-(CF 2 ) n -C(O)G, wherein n is 0.
  • an aliphatic alcohol e.g., methanol, ethanol, n-butanol, and t-butanol
  • Rf-(O) 1 -CHF-(CF 2 )D-C(O)G wherein n is 1, can be prepared, for example, by a free radical reaction of the fluorinated olefin of Formula VII with methanol followed by an oxidation of the resulting reaction product using conventional methods. Conditions for these reactions are described, for example, in U. S. Pat. App. Pub. No. 2007/0015864 (Hintzer et al.), the disclosure of which, relating to the preparation of compounds of formula Rf -(O) r -CHF-(CF 2 ) n -C(O)G, is incorporated herein by reference.
  • Fluorinated vinyl ethers of Formulas VI or VII, wherein r and/or t is 1, can be oxidized (e.g., with oxygen) in the presence of a fluoride source (e.g., antimony pentafluoride) to carboxylic acid fluorides of formula Rf-O-CF 2 C(O)F according to the methods described in U. S. Pat. No. 4,987,254 (Schwertfeger et al.), in column 1, line 45 to column 2, line 42, the disclosure of which is incorporated herein by reference.
  • a fluoride source e.g., antimony pentafluoride
  • CF 3 -(CF 2 ) 2 -O-CF 2 -C(O)-CH 3 and CF 3 -O-(CF 2 )S-O-CF 2 -C(O)-CH 3 which are described in U. S. Pat. App. Pub. No. 2007/0015864 (Hintzer et al.), the disclosure of which, relating to the preparation of these compounds, is incorporated herein by reference. These methods may be useful, for example, for providing structurally pure compounds (e.g., free of other compounds containing other fluorinated segments). In some embodiments, compounds according to the present disclosure are at least 95% (e.g., 96, 97, 98, or 99%) pure.
  • Rf* 3 and t are as defined above
  • m is 1, 2, or 3
  • W is alkylene or arylene
  • G is as defined above.
  • G represents -O-alkyl (e.g., having from 1 to 4 carbon atoms in the alkyl group).
  • Compounds of Formula VIII can be obtained, for example, from commercial sources or can be prepared by known methods. The reaction can be carried out, for example, under conditions described in U. S. Pat. App. Pub. No. 2007/0015864
  • Fluorinated carboxylic acids and their derivatives according to formula CF 3 CFH-O-(CF 2 ) P -C(O)G can be prepared, for example, by decarbonylation of difunctional perfluorinated acid fluoride according to the reaction:
  • the reaction is typically carried out at an elevated temperature in the presence of water and base (e.g., a metal hydroxide or metal carbonate) according to known methods; see, e.g., U. S. Pat. No. 3,555,100 (Garth et al.), the disclosure of which, relating to the decarbonylation of difunctional acid fluorides, is incorporated herein by reference.
  • base e.g., a metal hydroxide or metal carbonate
  • Compounds of Formula IX are available, for example, from the coupling of perfluorinated diacid fluorides of Formula X and hexafluoropropylene oxide according to the reaction:
  • Compounds represented by Formula (Rf-Q-X) 8 -Z can be prepared, for example, from a partially or fully fluorinated carboxylic acid or salt thereof, an acid fluoride thereof, or a carboxylic acid ester (e.g., Rf-C(O)-OCHs) using a variety of conventional methods.
  • a methyl ester can be treated with an amine having formula NH 2 -X-Z according to the following reaction sequence.
  • Rf, X, and Z are as defined in any of the above embodiments.
  • Some amines having formula NH 2 -X-Z are commercially available, such as, amino acids (e.g., sarcosine, 7-aminoheptanoic acid, 12-aminododecanoic acid, and 3- aminopropylphosphonic acid), aliphatic amines (e.g., dodecylamine and hexadecylamine), and difunctional amines (e.g., 3-(dimethylamino)propylamine).
  • amino acids e.g., sarcosine, 7-aminoheptanoic acid, 12-aminododecanoic acid, and 3- aminopropylphosphonic acid
  • aliphatic amines e.g., dodecylamine and hexadecylamine
  • difunctional amines e.g., 3-(dimethylamino)propyl
  • the reaction may be carried out, for example, at an elevated temperature (e.g., up to 80 0 C, 70 0 C, 60 0 C, or 50 0 C), and may be carried out neat or in a suitable solvent.
  • a compound represented by formula Rf-C(O)-NH-X-Z can also be subjected to functional group transformations of the Z group using conventional techniques.
  • quaternary ammonium compounds according to the present disclosure can be prepared by using an amine having formula NH 2 -X-NR 2 (e.g., 3-(dimethylamino)propylamine) in the first step to provide an amino-functionalized amide, which can then be quaternized by reaction with an acid (e.g., hydrochloric acid or acetic acid) or alkylating agents (e.g., diethylsulfate, propane sultone, iodomethane, bromobutane, or chloromethane).
  • an acid e.g., hydrochloric acid or acetic acid
  • alkylating agents e.g., diethylsulfate, propane sultone, iodomethane, bromobutane, or chloromethane.
  • the reaction with an acid or an alkylating agent may be carried out at room temperature or at an elevated temperature (e.g., up to 60 0 C or 50 0 C).
  • the amino-functionalized amide can be treated with hydrogen peroxide or a peracid (e.g., perbenzoic acid or peracetic acid) optionally at an elevated temperature (e.g., 60 0 C to 70 0 C) and in a suitable solvent (e.g., ethanol) to provide a compound of formula wherein Z is an amine oxide group.
  • a peracid e.g., perbenzoic acid or peracetic acid
  • a suitable solvent e.g., ethanol
  • Compounds represented by Formula (Rf-Q-X) 8 -Z can also be prepared, for example, by reaction of a carboxylic acid ester (e.g., Rf-C(O)-OCHs) with an amino alcohol having formula NH2-X"-0H (e.g., ethanolamine) to prepare hydroxyl-substituted Rf-(CO)NHX” OH as shown in the following reaction sequence, wherein Rf is as defined in any of the above embodiments, s is 1 or 2, and X" is a precursor to X, wherein X is as defined in any of the above embodiments.
  • a carboxylic acid ester e.g., Rf-C(O)-OCHs
  • an amino alcohol having formula NH2-X"-0H e.g., ethanolamine
  • the conditions for the reaction with NH 2 -X-Z, described above, can be used for the reaction with NH 2 -X"-0H.
  • the hydroxyl-substituted compound Rf-(C0)NHX"0H can then be treated with, for example, phosphonoacetic acid, phosphonopropionic acid, or phosphorous (V) oxychloride to provide phosphonates or phosphates according to the present disclosure.
  • the reaction with phosphonoacetic acid or phosphonopropionic acid can be carried out, for example, in a suitable solvent (e.g., methyl isobutyl ketone or methyl ethyl ketone), optionally in the presence of a catalyst (e.g., methanesulfonic acid) and optionally at an elevated temperature (e.g., up to the reflux temperature of the solvent).
  • a suitable solvent e.g., methyl isobutyl ketone or methyl ethyl ketone
  • a catalyst e.g., methanesulfonic acid
  • an elevated temperature e.g., up to the reflux temperature of the solvent.
  • the reaction of the hydroxyl-substituted compound represented by formula Rf-C(0)-NH-X"-0H with phosphorous (V) oxychloride can be carried out, for example, in a suitable solvent (e.g., toluene), optionally at an elevated temperature (
  • One or two equivalents of the hydroxyl-substituted compound can be used provide compounds having formula (Rf-C(O)-NH-X) 8 -Z, wherein Z is a phosphate, and s is 1 or 2. If one equivalent of the hydroxyl-substituted compound is used, an equivalent of water or alcohol may be added.
  • Compounds represented by Formula Rf-Q-X-Z can also be prepared, for example, by reducing an ester of formula Rf-C(O)-OCH 3 or a carboxylic acid of formula Rf-C(O)-OH using conventional methods (e.g., hydride, such as sodium borohydride, reduction) to a hydroxyl-substituted compound of formula Rf-CH 2 OH as shown in the following reaction sequence, wherein Rf, X, and Z are as defined in any of the above embodiments.
  • conventional methods e.g., hydride, such as sodium borohydride, reduction
  • the hydroxyl-substituted compound of formula Rf-CH 2 OH can then be converted, for example, to a phosphate or phosphonate using any of the techniques described above.
  • Compounds according to the present disclosure can also be prepared, for example, by reaction of a carboxylic acid represented by formula Rf-C(O)-OH with an epoxide or mixture of epoxides according to the following reaction sequence, wherein Rf, f, g, and R 3 are as defined in any of the above embodiments and R 4 is hydrogen, methyl, ethyl, or a combination thereof.
  • the reaction can be carried out, for example, in the presence of Lewis Acid catalysts such as complexes of boron trifluoride (e.g., boron trifluoride etherate, boron trifluoride tetrahydropyran, and boron trifluoride tetrahydrofuran), phosphorous pentafluoride, antimony pentafluoride, zinc chloride, and aluminum bromide.
  • Lewis Acid catalysts such as complexes of boron trifluoride (e.g., boron trifluoride etherate, boron trifluoride tetrahydropyran, and boron trifluoride tetrahydrofuran), phosphorous pentafluoride, antimony pentafluoride, zinc chloride, and aluminum bromide.
  • the reaction can also be carried out in the presence of (CFsSO 2 ) 2 CH 2 .
  • Ring-opening polymerizations can be carried out neat or in a suitable solvent such as a hydrocarbon solvent (e.g., toluene) or a halogenated solvent (e.g., dichloromethane, carbon tetrachloride, trichloroethylene, or dichloroethane).
  • a suitable solvent such as a hydrocarbon solvent (e.g., toluene) or a halogenated solvent (e.g., dichloromethane, carbon tetrachloride, trichloroethylene, or dichloroethane).
  • the reactions can be carried out at or near room temperature or below (e.g., in a range from about 0 0 C to 40 0 C).
  • the reactions can also be carried out above room temperature (e.g, up to 40 0 C, 60 0 C, 70 0 C, 90 0 C, or up to the reflux temperature of the solvent).
  • carboxylic acid and diamine or triamine can be adjusted to provide, mono-salts, di-salts, or tri-salts.
  • a carboxylic acid represented by formula Rf-C(O)-OH may be reacted with one equivalent of a diamine to provide a compound having formula Rf-Q-X-Z, wherein Q is -C(O)O- NH(R) 2 -, and Z is an amine (e.g., a primary, secondary, or tertiary amine).
  • Two equivalents of a carboxylic acid represented by formula Rf-C(O)-OH may also be reacted with a diamine to provide a compound, for example, having formula Rf-Q-X-Z, wherein Q is-C(O)O NH(R') 2 -, and Z is an ammonium group having formula -[NH(R) 2 ] RfC(O)O " .
  • three equivalents of a carboxylic acid represented by formula Rf-C(O)-OH may be reacted with a triamine to provide a compound, for example, having formula (Rf-Q-X) 2 -Z, wherein each Q is -C(O)O " + NH(R') 2 -, and Z is an ammonium group having formula (-) 2 [NHR] + RfC(O)O ⁇ .
  • the salts can be prepared, for example, by stirring a carboxylic acid and a diamine or triamine at room temperature or optionally at an elevated temperature and optionally in a suitable solvent (e.g., ethanol).
  • a suitable solvent e.g., ethanol
  • Compounds according to the present disclosure may be formulated into concentrates (e.g., in at least one of water or organic solvent), wherein the compound is present in an amount of at least 10, 20, 30, or even at least 40 percent by weight, based on the total weight of the concentrate. Techniques for preparing concentrates are known in the art.
  • the present disclosure provides a composition comprising at least one of water or a water-miscible organic solvent and a compound according to the present disclosure.
  • Z is selected from the group consisting of an ammonium group, an amine-oxide group, an amine, a hydroxyl, an alkoxy, a carboxylate, a sulfonate, a sulfate, phosphate, a phosphonate, and an amphoteric group.
  • compositions according to and/or useful for practicing methods according to the present disclosure may comprise water and a non-fluorinated polymer. These aqueous compositions may be useful, for example, for coatings (e.g., floor finishes, varnishes, automotive coatings, marine coatings, sealers, hard coats for plastic lenses, coatings for metal cans or coils, and inks).
  • compounds according to the present disclosure can be formulated into an aqueous solution or dispersion at a final concentration, for example, of about 0.001 to about 1 weight percent (wt. %), about 0.001 to about 0.5 wt. %, or about 0.01 to about 0.3 wt. %, based on the weight of the solution or dispersion.
  • compounds according to the present disclosure may enhance wetting and/or leveling of a coating (e.g., an aqueous coating) on a substrate surface and may provide better dispersability of a component (e.g., a thickening agent or pigment) within the coating composition.
  • aqueous compositions comprising compounds according to the present disclosure include at least one non-fluorinated polymer, typically a film-forming polymer.
  • suitable polymers include acrylic polymers, (e.g., poly(methyl methacrylate-co-ethyl acrylate) or poly(methyl acrylate-co- acrylic acid)); polyurethanes, (e.g., reaction products of aliphatic, cycloaliphatic or aromatic diisocyanates with polyester glycols or polyether glycols); polyolef ⁇ ns, (e.g., polystyrene); copolymers of styrene with acrylate(s) (e.g., poly(styrene-co-butyl acrylate); polyesters, (e.g, polyethylene terephthalate, polyethylene terephthalate isophthalate, or polycaprolactone); polyamides, (e.g., polyhexam
  • the non-fluorinated polymer is at least one of an acrylic polymer, a polyurethane, a polystyrene, or a styrene-acrylate copolymer.
  • aqueous compositions comprising compounds according to the present disclosure may contain one or more water-miscible solvents (e.g., coalescing solvents) including ethers of polyhydric alcohols (e.g., ethylene glycol monomethyl (or monoethyl) ether, diethylene glycol methyl (or ethyl) ether, triethylene glycol monomethyl (or monoethyl) ether, 2-butoxyethanol (i.e., butyl cellusolve), or di(propylene glycol) methyl ether (DPM)); alkylene glycols and polyalkylene glycols (e.g., ethylene glycol, propylene glycol, butylene glycol, triethylene glycol, hexylene glycol, diethylene glycol, polyethylene glycol, polypropylene glycol); and 2,2,4-trimethyl-l,3-pentanediol monoisobutyrate (an ester alcohol available, for example, from Eastman Chemical Company
  • Other water- miscible organic solvents that may be added to a composition include alcohols having 1 to 4 carbon atoms (e.g., methanol, ethanol, isopropanol, or isobutanol); amides and lactams, (e.g., N,N-dimethylformamide, N,N-dimethylacetamide, or N-methylpyrrolidone); ketones and ketoalcohols (e.g., acetone, cyclohexanone, methyl isobutyl ketone, diacetone alcohol); ethers (e.g., tetrahydrofuran or dioxane); l,3-dimethyl-2-imidazolidinone; and combinations thereof.
  • alcohols having 1 to 4 carbon atoms e.g., methanol, ethanol, isopropanol, or isobutanol
  • amides and lactams e.g., N,N-dimethylformamide,
  • aqueous compositions comprising compounds according to the present disclosure may also include at least one additive (e.g., biocides, fillers, additional leveling agents, emulsif ⁇ ers, defoamers, anticorrosive agents, dispersants, and rust inhibitors).
  • the aqueous compositions may also optionally contain at least one pigment.
  • a surface e.g., in coating applications
  • water and solvent typically evaporate, and the polymer particles coalesce to form a continuous film.
  • the aqueous composition can be applied to a surface, dried, and optionally heated, leaving the surface with a solid coating.
  • the addition of compounds according to the present disclosure may improve the film forming properties of some compositions by improving the ability of the coating to wet the substrate and/or by allowing for even evaporation of the water (i.e., leveling) during film formation.
  • Aqueous compositions that may be improved by the addition of compounds according to the present disclosure include floor polishes and finishes, varnishes for a variety of substrates (e.g., wood floors), aqueous gels applied in the manufacture of photographic film, automotive or marine coatings (e.g., primers, base coats, or topcoats), sealers for porous substrates (e.g., wood, concrete, or natural stone), hard coats for plastic lenses, coatings for metallic substrates (e.g., cans, coils, electronic components, or signage), inks (e.g, for pens or gravure, screen, or thermal printing), and coatings used in the manufacture of electronic devices (e.g., photoresist inks).
  • the aqueous compositions may be clear or pigmented.
  • aqueous compositions comprising compounds according to some embodiments of the present disclosure and a non-fluorinated polymer may be useful as alkaline waterborne coating compositions, for example, amine-stabilized floor finish compositions.
  • the compound comprises at least one of a carboxylate, a sulfonate, a sulfate, phosphate, or a phosphonate group.
  • Methods comprising treating a surface according to the present disclosure can be carried out using a variety of application methods known to one of skill in the art (e.g., brushing, mopping, padding, bar coating, spraying (e.g., with a spray bottle), dip coating (i.e., immersing the substrate in a formulation), gravure coating, roll coating, spin-coating, flow coating, vacuum coating, painting, and wiping (e.g., with a sponge or cloth).
  • application methods e.g., brushing, mopping, padding, bar coating, spraying (e.g., with a spray bottle), dip coating (i.e., immersing the substrate in a formulation), gravure coating, roll coating, spin-coating, flow coating, vacuum coating, painting, and wiping (e.g., with a sponge or cloth).
  • knife-coating or bar-coating may be used to ensure uniform coatings on a substrate.
  • the surface is a flooring surface comprising at least one of vinyl composition tiles, vinyl sheet flooring, linoleum, rubber sheeting, rubber tile, cork, synthetic sports flooring and vinyl asbestos tile, and non-resilient flooring substrates such as terrazzo, concrete, wood flooring, bamboo, wood laminate, engineered wood products (e.g., wood epoxy blends, permanently coated substrates such as those available from Pergo, Raleigh, NC, under the trade designation "PERGO” and from DIAN, Gardena, CA, under the trade designation "PARQUET BY DIAN”), stone, marble, slate, ceramic tile, grout, and dry shake flooring.
  • terrazzo concrete, wood flooring, bamboo, wood laminate
  • engineered wood products e.g., wood epoxy blends, permanently coated substrates such as those available from Pergo, Raleigh, NC, under the trade designation "PERGO” and from DIAN, Gardena, CA, under the trade designation "PARQUET BY DIAN”
  • stone, marble, slate, ceramic tile, grout under the trade designation "PARQUET BY D
  • compositions according to the present disclosure may also be useful as additives in cleaning solutions and may provide improved wetting of the surface and/or the contaminants to be removed.
  • methods comprising treating a surface according to the present disclosure include cleaning a surface.
  • a cleaning solution is typically formulated to include about 0.001 to about 1 wt. %, or about 0.001 to about 0.5 wt. % of a compound according to the present disclosure, based on the total weight of the solution.
  • an aqueous solution comprising a compound according to the present disclosure is sprayed (e.g., from a spray bottle) or otherwise applied to a hard surface such as window glass, a mirror, or ceramic tile, and the surface is wiped clean with a paper or fabric wipe.
  • the contaminated part may also be immersed or dipped into the aqueous solution.
  • the cleaning solution is typically placed in a bath, and electronic parts are either dipped or run through the bath on a conveyor belt.
  • the composition further comprises at least one gas (i.e., the composition is a foam).
  • X is alkylene having at least 10 (e.g., at least 12, 15, 18, 20, 22, 25, 28, or 30) carbon atoms. These compounds may be useful, for example, to reduce the surface tension of compositions containing hydrocarbon solvents.
  • Suitable hydrocarbon solvents include crude oil; refined hydrocarbons (e.g., gasoline, kerosene, and diesel); paraff ⁇ nic and isoparaffmic hydrocarbons (e.g., pentanes, hexanes, heptanes, higher alkanes, and isoparaffmic solvents obtained from Total Fina, Paris, France, under trade designations "ISANE IP 130" and “ISANE IP 175" and from Exxon Mobil Chemicals, Houston, TX, under the trade designation "ISOPAR”); mineral oil; ligroin; naphthenes; aromatics (e.g., xylenes and toluene); natural gas condensates; and combinations (either miscible or immiscible) thereof.
  • compositions comprising a hydrocarbon solvent and a compound according to the present disclosure further comprise at least one gas (i.e., the composition is a foam).
  • compositions e.g., aqueous or hydrocarbon foams
  • aqueous or hydrocarbon foams include from at least 0.01, 0.015, 0.02, 0.025, 0.03, 0.035, 0.04, 0.045, 0.05, 0.055, 0.06, 0.065, 0.07, 0.075, 0.08, 0.085, 0.09, 0.095, 0.1, 0.15, 0.2, 0.25, 0.5, 1, 1.5, 2, 3, 4, or 5 percent by weight, up to 5, 6, 7, 8, 9, or 10 percent by weight of at least one compound according to the present disclosure, based on the total weight of the composition.
  • the amount of a compound according to the present disclosure in a foam may be in a range of from 0.01 to 10, 0.1 to 10, 0.1 to 5, 1 to 10, or from 1 to 5 percent by weight, based on the total weight of the composition.
  • Lower and higher amounts of the compound in the composition e.g., a foam
  • Forming gas bubbles e.g., nitrogen, carbon dioxide, and air
  • a composition comprising a liquid (e.g., water or a solvent) and a compound according to the present disclosure
  • a variety of mechanisms e.g., mechanical and chemical mechanisms.
  • Useful mechanical foaming mechanisms include agitating (e.g., shaking, stirring, and whipping) the composition, injecting gas into the composition (e.g., inserting a nozzle beneath the surface of the composition and blowing gas into the formulation) and combinations thereof.
  • Useful chemical foaming mechanisms include producing gas in situ through a chemical reaction, decomposition of a component of the composition (e.g., a component that liberates gas upon thermal decomposition), evaporating a component of the composition (e.g., a liquid gas, and volatilizing a gas in the composition by decreasing the pressure on the composition or heating the composition).
  • Foams according to and/or prepared by methods according to the present disclosure comprise gas bubbles at volume fractions ranging from 10% to 90% of the total foam volume.
  • Compounds according to the present disclosure may be useful additives, for example, in foams for delivering oil- and/or water-repellent treatments to substrates (including fibrous substrates, e.g., textile, non-woven, carpet, and leather).
  • substrates including fibrous substrates, e.g., textile, non-woven, carpet, and leather.
  • compounds according to the present disclosure may provide repellent properties to a variety of surfaces and improve the ability to clean these surfaces.
  • Articles according to the present disclosure, having a surface treated with a compound according to the present disclosure may be at least one of non-staining, stain-releasing with simple washing methods, oil resistant (e.g., resistant to fingerprints), resistant to lime deposits, or resist being worn-off due to wear and abrasion from use, cleaning, and the elements.
  • Z is a phosphate or phosphonate group.
  • compounds according to the present disclosure can be used individually or in combination with a non-fluorinated surfactant (e.g., a hydrocarbon or silicone surfactant) to produce the desired surface tension reduction or wetting improvement.
  • a non-fluorinated surfactant e.g., a hydrocarbon or silicone surfactant
  • useful auxiliary surfactants may be found, for example, in Industrial Applications Of Surfactants, D.R. Karsa, Ed., Royal Society of Chemistry, London, and M. Rosen, Surfactants and Interfacial Phenomena, Wiley-Interscience, New York.
  • the compounds disclosed herein which have partially fluorinated polyether groups and/or have fully fluorinated polyether groups with a low number (e.g., up to 4) continuous perfluorinated carbon atoms, are herein demonstrated to have useful surfactant properties and may provide a lower-cost alternative to surfactants having a larger number of continuous perfluorinated carbon atoms.
  • the compounds disclosed herein may be useful, for example, as nonionic, anionic, cationic, or zwitterionic surfactants. For some applications that require rapid spraying and wetting processes (e.g., painting of car bodies, metal working, paper making, and textile manufacturing), it is advantageous to use highly dynamic surfactants that can reduce the surface tension within milliseconds.
  • the present disclosure provides dynamic surfactants (e.g., compounds represented by formula [Rf-C(O)O + NH(R)-X] 2 -NH(R) + RfC(O)O " or Rf-C(O)O + NH(R)-X-NH(R) 2 + RfC(O)O " ) that rival the performance of the best known dynamic surfactants (see, e.g., U.S. Pat. No. 5,503,967 column 21, line 10 and the perfluoropolyether salts in U.S. Pat. Nos. 5,453,539 and 5,536,425).
  • dynamic surfactants e.g., compounds represented by formula [Rf-C(O)O + NH(R)-X] 2 -NH(R) + RfC(O)O " or Rf-C(O)O + NH(R)-X-NH(R) 2 + RfC(O)O "
  • the surface tension of the liquid is reduced by at least 10% (in some embodiments, at least 20%, 30%, 40%, 50%, 60%, or even 70%). In some embodiments, the surface tension of the liquid is reduced to an extent not less than when an equivalent liquid is combined with an amount of a surfactant, wherein the surfactant is the same as the compound except Rf is replaced with a group represented by formula CsF 7 -O-CF(CFs)-, and wherein the amount by weight of the surfactant is the same as the amount by weight of the compound.
  • a surfactant refers to a liquid that is the same in all respects except for the identity of the surfactant.
  • Example 1 CF 3 OCF 2 CF 2 CF 2 OCF 2 C(O)NHCH 2 CH 2 CH 2 N + (CH 3 ) 2 H OC(O)CH 3 Part A
  • Example 3 CF 3 OCF 2 CF 2 CF 2 OCHFCF 2 C(O)NHCH 2 CH 2 CH 2 N + (CH 3 ) 2 H OC(O)CH 3
  • Example 4 CF 3 OCF 2 CF 2 CF 2 OCHFCF 2 C(O)NHCH 2 CH 2 CH 2 N(CH 3 ) 2 O
  • Example 2 The method of Example 2 was followed except using 19.6 grams of
  • Part B The method of Part B of Example 1 was followed except using 16.3 grams of CF 3 CF 2 CF 2 OCHFCF 2 COOCH 3 instead Of CF 3 OCF 2 CF 2 CF 2 OCF 2 C(O)OCH 3 .
  • Example 6 CF 3 CF 2 CF 2 OCHFCF 2 C(O)NHCH 2 CH 2 CH 2 N(CH 3 ) 2 O
  • the method of Example 2 was followed except using 16.3 grams of
  • Example 7 CF 3 OCF 2 OCF 2 OCF 2 C(O)NHCH 2 CH 2 CH 2 N + (CH 3 ) 2 H OC(O)CH 3 Part A
  • Example 8 CF 3 OCF 2 OCF 2 OCF 2 C(O)NHCH 2 CH 2 CH 2 N(CH 3 ) 2 O The method of Example 2 was followed except using 16.4 grams of
  • Part B The method of Part B of Example 1 was followed except using 19.6 grams of CF 3 OCF 2 OCF 2 OCF 2 COOCH 3 instead Of CF 3 OCF 2 CF 2 CF 2 OCF 2 C(O)OCH 3 .
  • Example 10 CF 3 OCF 2 OCF 2 OCF 2 OCF 2 C(O)NHCH 2 CH 2 CH 2 N(CH 3 ) 2 O The method of Example 2 was followed except using 19.6 grams of
  • Example 12 CF 3 OCF 2 CF 2 CF 2 OCHFC(O)NHCH 2 CH 2 CH 2 N(CH 3 ) 2 O The method of Example 2 was followed except using 18 grams of
  • Example 13 CF 3 CF 2 CF 2 OCHFC(O)NHCH 2 CH 2 CH 2 N + (CH 3 ) 2 H OC(O)CH 3 Part A
  • Example 14 CF3CF2CF2OCHFC(O)NHCH2CH2CH2N(CH3)2O
  • Example 2 The method of Example 2 was followed except using 13.8 grams of CF 3 CF 2 CF 2 OCHFCOOCH 3 , prepared as described in Part A of Example 13, instead of CF 3 OCF 2 CF 2 CF 2 OCF 2 C(O)OCH 3 .
  • Example 15 CF 3 OCF 2 OCF 2 OCF 2 OCF 2 C(O)NHCH 2 CH 2 CH 2 N + (CH 3 ) 2 CH 2 CH 2 CH 2 SO 3
  • Example 16 CF 3 OCF 2 CF 2 CF 2 OCHFCF 2 C(O)NHCH 2 CH 2 CH 2 N + (CH 3 ) 2 CH 2 CH 2 CH 2 SO 3
  • Example 15 The method of Example 15 was followed except using 19.6 grams of CF 3 O(CF 2 ) 3 OCHFCF 2 COOCH 3 , prepared as described in Part A of Example 3, instead of CF 3 OCF 2 OCF 2 OCF 2 OCF 2 COOCH 3 .
  • Example 17 CF 3 OCF 2 CF 2 CF 2 OCF 2 C(O)O(CH 2 CH 2 O) n H
  • ammonium salt was treated with sulfuric acid, and the lower phase was separated and distilled.
  • Example 18 CF 3 OCF 2 OCF 2 OCF 2 OCF 2 C(O)O(CH 2 CH 2 O) n H The method of Example 17 was followed except using 18.9 grams of perfluoro-
  • Example 19 CF 3 OCF 2 CF 2 CF 2 OCF 2 C(O)N(CH 3 )CH 2 C(O)O- K+
  • a stirrer, thermometer, and condenser were placed 18 grams (0.05 mole) Of CF 3 OCF 2 CF 2 CF 2 OCF 2 C(O)OCH 3 , prepared in Example 1, Part A, and dry sarcosine (4.5 grams, 0.05 mole).
  • the reaction mixture was heated under nitrogen at 60 0 C using a heating mantle for 48 hours and then cooled to about 30 0 C.
  • Example 20 CF 3 OCF 2 OCF 2 OCF 2 OCF 2 C(O)N(CH 3 )CH 2 C(O)O- K+
  • Example 19 The method of Example 19 was followed except using 19.6 grams of CF 3 OCF 2 OCF 2 OCF 2 OCF 2 COOCH 3 , prepared as described in Part A of Example 9, instead of CF 3 OCF 2 CF 2 CF 2 OCF 2 C(O)OCH 3 .
  • Example 21 CF 3 OCF 2 CF 2 CF 2 OCF 2 C(O)NHCH 2 CH 2 OC(O)CH 2 P(O)(OH) 2 Part A
  • Example 22 CF 3 OCF 2 OCF 2 OCF 2 OCF 2 C(O)NHCH 2 CH 2 OC(O)CH 2 P(O)(OH) 2
  • Example 22 was prepared using the method of Example 21 except using the methyl ester described in Part A of Example 9 in Part A and using 4.2 grams of
  • Example 2 The method of Example 2 was followed except using 16.3 grams of
  • Examples 1 to 20 were diluted with deionized water to the concentrations given in Table 1 (below). Surface tensions were measured for the solutions containing Examples 1 to 20 using a Kruss K- 12 tensiometer (obtained from Kruss GmbH, Hamburg, Germany) using the Du Nouy ring method at 20 0 C. The results are summarized in Table 1 (below).
  • CF 3 CFH-O-(CF 2 ) 5 COOH (426 grams, 1.0 mole), which was prepared according to the method described in Example 3 of U.S. Pat. App. Pub. No. 2007/0276103, was esterified at 65 0 C with methanol (200 grams, 6.3 moles) and concentrated sulfuric acid (200 grams, 2.0 moles). The reaction mixture was washed with water and distilled at 172 0C to give 383 grams of CF 3 CFH-O-(CF 2 ) 5 COOCH 3 , which was combined with material from a repeat run and used in Part B. Part B
  • a portion of the material from Part C (2.5 grams) was diluted with 7.5 grams of water, and the pH was adjusted to about 9 using 5% aqueous ammonia. The resulting solution was diluted with isopropyl alcohol to 150 grams total to provide a 2% by weight solution.
  • FC(O)CF(CF 3 )-O-(CF 2 ) 3 COF 503 grams, 1.4 mole
  • sodium carbonate 387 grams, 3.7 moles
  • diglyme 650 grams
  • the reaction liberated carbon dioxide gas.
  • Distilled water 35 grams, 1.9 mole was added at 85 0 C, and then the reaction mixture was heated to 165 0 C and maintained at that temperature for 30 minutes. The reaction was allowed to cool, and sulfuric acid (250 grams, 2.6 moles) in 1250 grams of water was added.
  • CF 3 -CFH-O-(CF 2 ) 3 -CH 2 -OH was prepared according to the method of Example 23, Part B, except 200 grams (0.6 mole) of CF 3 -CFH-O-(CF 2 )S-C(O)O-CH 3 was reduced with 30 grams (0.79 mole) of sodium borohydride in 0.2 L of 1,2-dimethoxyethane. At the end of the reaction 150 grams of concentrated sulfuric acid in 0.3 L of water were added, and 115 grams of CF 3 -CFH-O-(CF 2 ) 3 -CH 2 -OH, having a boiling point of 130 0 C, were obtained. Part C
  • Example 25 (CF 3 OCF 2 OCF 2 OCF 2 C(O)O ) 2 + NH 3 CH 2 CH 2 CH 2 N + H(CHs) 2
  • Example 26 (CF 3 OCF 2 OCF 2 OCF 2 C(O)O ) 2 +NH 3 CH(CH 3 )CH 2 (OCH 2 CH(CH 3 )) X (OCH 2 CH 2 ) 9 (OCH 2 CH(CH 3 )) 3 6 .
  • Example 26 was prepared according to the method of Example 25 except 30 grams of a polyetheramine obtained from Huntsman Corporation, The Woodlands, TX, under the trade designation "JEFFAMINE ED-600" were used instead of DMAPA.
  • Example 27 was prepared according to the method of Example 25 except 37.8 grams of perfluoro-3,5,7,9-tetraoxadecanoic acid (obtained from Anles Ltd.) were used instead of perfluoro-3,5,7-trioxaoctanoic acid.
  • Example 28 was prepared according to the method of Example 25 except 37.8 grams of perfluoro-3,5,7,9-tetraoxadecanoic acid (obtained from Anles Ltd.) were used instead of perfluoro-3,5,7-trioxaoctanoic acid, and 30 grams of a polyetheramine obtained from Huntsman Corporation under the trade designation "JEFFAMINE ED-600" were used instead of DMAPA.
  • Example 29 CF 3 OCF 2 OCF 2 OCF 2 C(O)O + NH 3 CH 2 CH 2 CH 2 N(CH 3 ) 2
  • Example 29 was prepared according to the method of Example 25 except 10.2 grams (0.1 mole) of DMAPA were used.
  • Example 30 was prepared according to the method of Example 25 except 3.4 grams (0.03 mole) of diethylenetriamine were used instead of DMAPA.
  • Example 31 was prepared according to the method of Example 25 except 37.8 grams of perfluoro-3,5,7,9-tetraoxadecanoic acid (obtained from Anles Ltd.) were used instead of perfluoro-3,5,7-trioxaoctanoic acid, and 10.2 grams (0.1 mole) of DMAPA were used.
  • Example 32 (CF 3 OCF 2 OCF 2 OCF 2 OCF 2 C(O)O ) 3 + NH 3 CH2CH2 + NH2CH2CH2N + H 3
  • Example 32 was prepared according to the method of Example 25 except 37.8 grams of perfluoro-3,5,7,9-tetraoxadecanoic acid (obtained from Anles Ltd.) were used instead of perfluoro-3,5,7-trioxaoctanoic acid, and 3.4 grams (0.03 mole) of diethylenetriamine were used instead of DMAPA.
  • Example 33 was prepared according to the method of Example 25 except 34.1 grams of 2-H-perfluoro-3,7-dioxaoctanoic acid were used instead of perfluoro-3,5,7- trioxaoctanoic acid.
  • 2-H-Perfluoro-3,7-dioxaoctanoic acid was prepared was prepared from CF 3 OCF 2 CF 2 CF 2 OCHFC(O)ONH 4 , which was prepared according to the method described in U. S. Pat. App. Pub. No. 2007/0015864 (Hintzer et al.) in the Preparation of Compound 12, the disclosure of which preparation is incorporated herein by reference.
  • the ammonium salt was treated with sulfuric acid, and the lower phase was separated and distilled.
  • Example 34 was prepared according to the method of Example 25 except 39.2 grams of 3-H-perfluoro-4,8-dioxanonanoic acid were used instead of perfluoro-3,5,7- trioxaoctanoic acid.
  • 3-H-Perfluoro-4,8-dioxanonanoic acid was prepared was prepared from CF 3 OCF 2 CF 2 CF 2 OCHFCF 2 C(O)ONH 4 , which was prepared according to the method described in U. S. Pat. App. Pub. No. 2007/0015864 (Hintzer et al.) in the Preparation of Compound 11, the disclosure of which preparation is incorporated herein by reference.
  • the ammonium salt was treated with sulfuric acid, and the lower phase was separated and distilled.
  • Examples 25 to 34 were diluted with deionized water to the concentrations given in Table 4 (below). Surface tensions were measured for the solutions containing Examples 25 to 34 using a Kruss tensiometer (obtained from Kruss GmbH under the trade designation "KRUSS BUBBLE PRESSURE TENSIOMETER BP2") using the maximum bubble pressure technique and different surface ages at 22 0 C. The results are summarized in Table 4 (below) for a surface age of 100 milliseconds.

Abstract

Compounds represented by formula (Rf-Q-X)s-Z. Each Rf is independently a partially fluorinated or fully fluorinated group selected from Rfa-(O)r-CHF-(CF2)n-; [Rfb-(O)t-C(L)H-CF2-O]m-W-; CF3CFH-O-(CF2)p-; CF3-(O-CF2)z-; and CF3-O-(CF2)3-O-CF2-. Methods of reducing surface tension of a liquid, making foams, and treating a surface using the compounds are also disclosed.

Description

FLUORINATED ETHER COMPOUNDS AND METHODS OF USING THE SAME
CROSS-REFERENCE TO RELATED APPLICATIONS
This application claims priority to U.S. Provisional Application Serial No. 61/081942, filed July 18, 2008, the disclosure of which is herein by reference.
BACKGROUND
Fluorochemicals have been used in a variety of applications for many years. For example, fluorinated surfactants have been added to a variety of formulations (e.g., coatings and foams). The addition of a fluorinated surfactant to a formulation (e.g., a coating formulation) may enhance the properties of the formulation by improving, for example, wetting behavior, leveling properties, and stability (e.g., with respect to phase separation or foam half-life). In other applications, fluorochemicals have been used to provide properties such as hydrophobicity and oleophobicity to various materials (e.g., ceramics, metals, fabrics, plastics, and porous stones).
Traditionally, many widely used fluorinated surfactants and repellents include long-chain perfluoroalkyl groups, (e.g., perfluorooctyl groups). Recently, however, there has been an industry trend away from using perfluorooctyl fluorinated surfactants, which has resulted in a desire for new types of surfactants which may be used in a variety of applications.
SUMMARY
The present disclosure provides compounds that have partially fluorinated polyether groups and/or fully fluorinated polyether groups with a low number (e.g., up to 4) continuous perfluorinated carbon atoms. The compounds may be useful, for example, as surfactants or surface treatments. In some embodiments, the compounds disclosed herein unexpectedly lower the surface tension of water to an extent comparable to or higher than fully fluorinated surfactants having a greater number of perfluorinated carbon atoms. In some embodiments, the compounds disclosed herein unexpectedly raise the contact angle versus water and/or hexadecane to an extent comparable to treatment compositions having a greater number of perfluorinated carbon atoms.
In one aspect, the present disclosure provides a compound represented by formula:
(Rf-Q-X)8-Z; wherein
Rf is selected from the group consisting of: Rf-(O)r-CHF-(CF2)n-; [R^-(OVC(L)H-CF2-O]1n-W-;
Figure imgf000003_0001
CF3-(O-CF2),-; and
Figure imgf000003_0002
Q is selected from the group consisting of a bond, -C(O)O- +NH(R')2-, -C(O)-N(R')-, and -C(O)-O-, wherein R' is selected from the group consisting of hydrogen and alkyl having from 1 to 4 carbon atoms;
X is selected from the group consisting of alkylene, arylalkylene, and poly(alkyleneoxy) wherein alkylene and arylalkylene are each optionally interrupted by at least one functional group independently selected from the group consisting of ether, amine, ester, amide, carbamate, and urea; Z is selected from the group consisting of an ammonium group, an amine- oxide group, an amine, a carboxylate, a sulfonate, a sulfate, phosphate, a phosphonate, and an amphoteric group, with the proviso that when X is alkylene having at least 10 carbon atoms, Z may also be hydrogen, and with the further proviso that when X is poly(alkyleneoxy), Z may also be selected from the group consisting of hydroxyl and alkoxy;
Rf and Rf*3 independently represent a partially or fully fluorinated alkyl group having from 1 to 10 carbon atoms and optionally interrupted with at least one oxygen atom;
L is selected from the group consisting of F and CF3; W is selected from the group consisting of alkylene and arylene; r is 0 or 1, wherein when r is 0, then Rf is interrupted with at least one oxygen atom; s is 1 or 2, wherein when s is 2, then Z is selected from the group consisting of an ammonium group, a phosphate, a sulfate, and a phosphonate; t is O or l; m is 1, 2, or 3; n is 0 or 1 ; each p is independently a number from 1 to 6; and z is a number from 2 to 7.
In another aspect, the present disclosure provides a composition comprising a compound disclosed herein and at least one of solvent or water. In some embodiments, the composition further comprises a non-fluorinated polymer.
In another aspect, the present disclosure provides a method comprising treating a surface with a composition comprising a compound disclosed herein and at least one of solvent or water. In some embodiments, the surface comprises at least one of a polymer, ceramic (i.e., glasses, crystalline ceramics, glass ceramics, and combinations thereof), stone such as natural stone (e.g., sandstone, limestone, marble, and granite) or manmade or engineered stone, concrete, laminate, metal, or wood. In some of these embodiments, Z is a phosphate or phosphonate group.
In another aspect, the present disclosure provides an article having a surface, wherein at least a portion of the surface is in contact with a compound disclosed herein. In some embodiments, the surface comprises at least one of a polymer, ceramic (i.e., glasses, crystalline ceramics, glass ceramics, and combinations thereof), stone such as natural stone (e.g., sandstone, limestone, marble, and granite) or manmade or engineered stone, concrete, laminate, metal, or wood. In some of these embodiments, Z is a phosphate or phosphonate group. In another aspect, the present disclosure provides a method of reducing the surface tension of a liquid, the method comprising combining at least the liquid with an amount of a compound disclosed herein sufficient to reduce the surface tension of the liquid.
In another aspect, the present disclosure provides methods of making a foam, the method comprising combining at least a liquid, a gas, and a compound according to the present disclosure to make the foam. In some of these embodiments, the liquid is water. In some of these embodiments, the liquid is a hydrocarbon liquid. In this application:
The terms "a", "an", and "the" are used interchangeably with the term "at least one". The phrase "at least one of followed by a list refers to any one of the items in the list and any combination of two or more items in the list. "Alkyl group" and the prefix "alk-" are inclusive of both straight chain and branched chain groups and of cyclic groups. In some embodiments, alkyl groups have up to 30 carbons (in some embodiments, up to 20, 15, 12, 10, 8, 7, 6, or 5 carbons) unless otherwise specified. Cyclic groups can be monocyclic or polycyclic and, in some embodiments, have from 3 to 10 ring carbon atoms.
"Alkylene" is the divalent form of the "alkyl" groups defined above.
"Arylalkylene" refers to an "alkylene" moiety to which an aryl group is attached.
The term "aryl" as used herein includes carbocyclic aromatic rings or ring systems, for example, having 1, 2, or 3 rings and optionally containing at least one heteroatom (e.g., O, S, or N) in the ring. Examples of aryl groups include phenyl, naphthyl, biphenyl, fluorenyl as well as furyl, thienyl, pyridyl, quinolinyl, isoquinolinyl, indolyl, isoindolyl, triazolyl, pyrrolyl, tetrazolyl, imidazolyl, pyrazolyl, oxazolyl, and thiazolyl.
"Arylene" is the divalent form of the "aryl" groups defined above.
In this application, all numerical ranges are inclusive of their endpoints and non- integral values between the endpoints unless otherwise stated.
DETAILED DESCRIPTION
For compounds represented by formula (Rf-Q-X)8-Z, Rf is selected from the group consisting of: Rf-(O)r-CHF-(CF2)n- I;
[R^-(OVC(L)H-CF2-O]1n-W- II;
Figure imgf000005_0001
CF3-O-(CF2)S-O-CF2- V. In some embodiments of Formula (Rf-Q-X)8-Z, Rf is selected from the group consisting of
Rf-(O)1-CHF-(CF2V, [Rfb-(O),-C(L)H-CF2-O]m-W-, and CF3CFH-O-(CF2)P-. In some embodiments of Formula (Rf-Q-X)8-Z, Rf is selected from the group consisting of CF3-(O-CF2)Z- and CF3-O-(CF2)3-O-CF2-.
In some embodiments of Formula (Rf-Q-X)8-Z, Rf has a molecular weight of up to 600 grams per mole (in some embodiments, up to 500, 400, or even up to 300 grams per mole). In Formulas I and II, Rf and Rf*3 independently represent a partially or fully florinated alkyl group having from 1 to 10 carbon atoms and optionally interrupted with at least one oxygen atom. Rf and Rf*3 include linear and branched alkyl groups. In some embodiments, Rf and/or Rf*3 is linear. In some embodiments, Rf and Rf*3 independently represent a fully fluorinated (i.e., perfluorinated) alkyl group having up to 6 (in some embodiments, 5, 4, 3, 2, or 1) carbon atoms. In some embodiments, Rf and Rf*3 independently represent a fully fluorinated alkyl group interrupted with at least one oxygen atom, of which the alkyl groups between oxygen atoms have up to 6 (in some embodiments, 5, 4, 3, 2, or 1) carbon atoms, and wherein the terminal alkyl group has up to 6 (in some embodiments, 5, 4, 3, 2, or 1) carbon atoms. In some embodiments, Rf and Rf*3 independently represent a partially fluorinated alkyl group having up to 6 (in some embodiments, 5, 4, 3, 2, or 1) carbon atoms and up to 2 hydrogen atoms. In some embodiments, Rf and Rf independently represent a partially fluorinated alkyl group having up 2 hydrogen atoms interrupted with at least one oxygen atom, of which the alkyl groups between oxygen atoms have up to 6 (in some embodiments, 5, 4, 3, 2, or 1) carbon atoms, and wherein the terminal alkyl group has up to 6 (in some embodiments, 5, 4, 3, 2, or 1) carbon atoms.
In some embodiments of Formulas I and II, Rf and Rf*3 are independently represented by formula
Figure imgf000006_0001
Rf 1 is a perfluorinated alkyl group having from 1 to 6 (in some embodiments, 1 to 4) carbon atoms. Rf2 and Rf3 are each independently perfluorinated alkylene having from 1 to 4 carbon atoms, x and y are each independently numbers from 0 to 4, and the sum of x and y is at least 1. In some of these embodiments, t is 1 , and r is 1. In some embodiments of Formulas I and II, Rf and Rf*3 are independently represented by formula
Rf 4-[ORf 5]a-[ORf 6]b-O-CF2-.
Rf4 is a perfluorinated alkyl group having from 1 to 6 (in some embodiments, 1 to 4) carbon atoms. Rf 5 and R/ are each independently perfluorinated alkylene having from 1 to 4 carbon atoms, a and b are each independently numbers from 0 to 4. In some of these embodiments, t is 0, and r is 0. In some embodiments of Formulas I and II, Rf and Rf*3 are independently represented by formula Rf7-(OCF2)P-, wherein p is from 1 to 6 (in some embodiments, 1 to 4), and Rf7 is selected from the group consisting of a partially fluorinated alkyl group having 1, 2, 3, 4, 5, or 6 carbon atoms and 1 or 2 hydrogen atoms and a fully fluorinated alkyl group having 1, 2, 3 or 4 carbon atoms.
In some embodiments of Formulas I and II, Rf and Rf*3 are independently represented by formula Rf8-O-(CF2)P-, wherein p is from 1 to 6 (in some embodiments, 1 to 4) and Rf 8 is selected from the group consisting of a partially fluorinated alkyl group having 1, 2, 3, 4, 5, or 6 carbon atoms and 1 or 2 hydrogen atoms and a fully fluorinated alkyl group having 1, 2, 3 or 4 carbon atoms.
In Formula II, L is selected from the group consisting of F and CF3. In some embodiments of Formula II, L is F. In other embodiments, L is CF3.
In Formula II, W is selected from the group consisting of alkylene and arylene. Alkylene includes linear, branched, and cyclic alkylene groups having from 1 to 10 (in some embodiments, 1 to 4) carbon atoms. In some embodiments, W is methylene. In some embodiments, W is ethylene. Arylene includes groups having 1 or 2 aromatic rings, optionally having at least one heteroatom (e.g., N, O, and S) in the ring, and optionally substituted with at least one alkyl group or halogen atom. In some embodiments, W is phenylene. In Formulas II, t is 0 or 1. In some embodiments, t is 1. In some embodiments, t is
0. In embodiments wherein t is 0, Rf is typically interrupted by at least one oxygen atom.
In Formula II, m is 1, 2, or 3. In some embodiments, m is 1.
In Formula I, n is 0 or 1. In some embodiments, n is 0. In some embodiments, n is 1. In Formulas III, p is a number from 1 to 6 (i.e., 1, 2, 3, 4, 5, or 6). In some embodiments, p is 1, 2, 5, or 6. In some embodiments, p is 3. In some embodiments, p is 1 or 2. In some embodiments, p is 5 or 6.
In Formula IV, z is a number from 2 to 7 (i.e., 2, 3, 4, 5, 6, or 7). In some embodiments, z is a number from 2 to 6, 2 to 5, 2 to 4, or 3 to 4. In some embodiments, compounds according to the present disclosure have an Rf group represented by Formula III (i.e., CFsCFH-O-(CF2)P-). In some of these embodiments Rf is selected from the group consisting of CF3CFH-O-(CF2)3- and CF3CFH-O-(CF2)S-.
In some embodiments, compounds according to the present disclosure have an Rf group represented by Formula I. In some of these embodiments, Rf is selected from the group consisting of:
C3F7-O-CHF-;
CF3-O-CF2CF2-CF2-O-CHF-; CF3CF2CF2 -0-CF2CF2-CF2-O-CHF-;
CF3-O-CF2-CF2-O-CHF-; CF3-O-CF2-O-CF2-CF2-O-CHF-;
CF3-(O-CF2)2-O-CF2-CF2-O-CHF-; and
CF3-(O-CF2)3-O-CF2-CF2-O-CHF-. In other of these embodiments, Rf is selected from the group consisting of:
CF3-O-CHF-CF2-; CF3-O-CF2-CF2-O-CHF-CF2-;
CF3-CF2-O-CHF-CF2-;
CF3-O-CF2-CF2-CF2-O-CHF-CF2-;
CF3-O-CF2-O-CF2-CF2-O-CHF-CF2-;
CF3-(O-CF2)2-O-CF2-CF2-O-CHF-CF2-; and CF3-(O-CF2)3-O-CF2-CF2-O-CHF-CF2-.
In other of these embodiments, Rf is selected from the group consisting of:
CF3-O-CF2-CHF-; C3F7-O-CF2-CHF-; CF3-O-CF2-CF2-CF2-O-CF2-CHF-; CF3-O-CF2-O-CF2-CF2-O-CF2-CHF-;
CF3-(O-CF2)2-O-CF2-CF2-O-CF2-CHF-; and
CF3-(O-CF2)3-O-CF2-CF2-O-CF2-CHF-. In other of these embodiments, Rf is selected from the group consisting of:
CF3-O-CF2-CHF-CF2-; C2F5-O-CF2-CHF-CF2-;
C3F7-O-CF2-CHF-CF2-; CF3-O-CF2-CF2-CF2-O-CF2-CHF-CF2-; CF3-O-CF2-O-CF2-CF2-O-CF2-CHF-CF2-; CF3-(O-CF2)2-O-CF2-CF2-O-CF2-CHF-CF2-; and CF3-(O-CF2)S-O-CF2-CF2-O-CF2-CHF-CF2-.
In other of these embodiments, Rf is selected from the group consisting of: CF3-O-CF2CF2-CF2-O-CHF-;
CF3-O-CF2-CF2-CF2-O-CHF-CF2-; CF3-O-CF2-CF2-CF2-O-CF2-CHF-; and CF3-O-CF2-CF2-CF2-O-CF2-CHF-CF2-.
In some embodiments, compounds according to the present disclosure have an Rf group represented by Formula II. In some of these embodiments, L is F, m is 1, and W is alkylene. In some of these embodiments, Rf is selected from the group consisting of:
CF3-O-CHF-CF2-O-CH2-; CF3-O-CF2-CF2-CF2-O-CHF-CF2-O-CH2;
C3F7-O-CHF-CF2-O-CH2-; C3F7-O-CHF-CF2-O-CH2-CH2-;
C3F7-O-CF2-CF2-O-CHF-CF2-OCH2-; and C3F7-O-CF2-CF2-CF2-O-CHF-CF2-OCH2-. In other of these embodiments, Rf is represented by formula
C3F7-O-CF2-CHF-CF2-OCH2-. In other of these embodiments, Rf is selected from the group consisting of:
CF3-CHF-CF2-O-CH2-; and C3F7-CF2-CHF-CF2-OCH2-.
In some embodiments, compounds according to the present disclosure have an Rf group represented by Formula IV (i.e., CF3-(O-CF2)Z-). In some of these embodiments, z is a number from 2 to 6, 2 to 5, 2 to 4, 3 to 5, or 3 to 4. .
In some embodiments, compounds according to the present disclosure have an Rf represented by Formula V (i.e., CF3-O-(CF2)3-O-CF2-).
In Formula (Rf-Q-X)8-Z, Q is selected from the group consisting of a bond, -C(0)0~ +NH(R)2-, -C(O)-N(R')-, and -C(O)-O-, wherein R is hydrogen or alkyl having 1 to 4 carbon atoms (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or sec- butyl). In some embodiments, Q is selected from the group consisting of -C(O)-N(R')- and -C(O)-O-. In some embodiments, Q is selected from the group consisting of a bond and -C(O)-N(R')-. In some embodiments, Q is -C(O)-N(R')-. In some embodiments, Q is -C(O)O- 4NH(R)2-. In some embodiments, R is hydrogen or methyl. In some embodiments, R' is hydrogen. It should be understood that when Q is a bond, a compound represented by Formula (Rf-Q-X)8-Z can also be represented by Formula (Rf-X)8-Z. In Formula (Rf-Q-X)8-Z, X is selected from the group consisting of alkylene and arylalkylene, wherein alkylene and arylalkylene are each optionally interrupted by at least one functional group independently selected from the group consisting of ether (i.e., -0-), amine (i.e., -N(R)-), ester, (i.e., -0-C(O)- or -C(O)-O-), amide (i.e., -N(R')-C(0)- or -C(O)-N(R')-), carbamate (i.e., -N(R')-C(0)-0- or -0-C(O)-N(R')- ), and urea (i.e., -N(R')-C(0)-N(R')-), wherein in any of these functional groups, R is as defined in any of the above embodiments. In some embodiments, X is alkylene having up to 5 carbon atoms. In some embodiments, X is alkylene having at least 10 (e.g., at least 12, 15, 18, 20, 22, 25, 28, or 30) carbon atoms. In some embodiments, X is alkylene that is optionally interrupted by at least one ether group. In some of these embodiments, X is a poly(alkyleneoxy) group. In some of these embodiments, X is -[EO]f-[R2O]g-[EO]f- or -[R2O]g-[EO]r[R2O]g-, wherein EO represents -CH2CH2O-; each R2O independently represents -CH(CH3)CH2O-, -CH2CH(CH3)O-, -CH(CH2CH3)CH2O-, -CH2CH(CH2CH3)O-, or -CH2C(CH3)2O- (in some embodiments, -CH(CH3)CH2O-, or -CH2CH(CH3)O-); each f is independently from 1 to 150 (in some embodiments, from 7 to about 150, 14 to about 125, 5 to 15, or 9 to 13); and each g is independently from O to 55 (in some embodiments, from about 21 to about 54, 15 to 25, 9 to about 25, or 19 to 23). In Formula (Rf-Q-X)8-Z, Z is selected from the group consisting of an ammonium group, an amine-oxide group, an amine, a carboxylate (i.e., -CO2Y), a sulfonate (i.e., -SO3Y), a sulfate (i.e., -0-SO3Y or (-O)2-SO2Y), phosphate (i.e., -0-P(O)(OY)2 or (-O)2-P(O)OY), a phosphonate (i.e., -P(O)(OY)2), and an amphoteric group, with the proviso that when X is alkylene having at least 10 carbon atoms, Z may also be hydrogen, and with the further proviso that when X is poly(alkyleneoxy), Z may also be a hydroxyl (i.e., -OH) or alkoxy (i.e., -O-alkyl). Ammonium groups include those represented by formula -[N(R)3] M , wherein each R is independently hydrogen, alkyl, or aryl, wherein alkyl and aryl are optionally substituted by at least one halogen, alkoxy, nitro, or nitrile group and aryl may additionally be optionally substituted by alkyl, and wherein M" is a counter anion. Ammonium groups also include ring systems having one or two aromatic or saturated rings and a positively charged nitrogen atom (e.g., pyrrolium, pyrimidinium, pyrazolium, isoxazolium, oxazolium, thiazolium, isothiazolium, pyridinium, pyrazinium, pyridazinium, imidazolium, isoindolium, indolium, purinium, quinolinium, isoquinolinium, naphthyridinium, quinoxalinium, quinazolinium, phthalazinium, indazolium, pyrrolidinium, piperidinium, azepinium, or piperazinium). Amine-oxide groups include those represented by formula -N(O)(R.1)^ wherein each R1 is independently hydrogen, alkyl, or aryl, wherein alkyl and aryl are optionally substituted as described above for R, and ring systems having one or two aromatic or saturated rings and an N- oxide (e.g., an N-oxide of pyrrolium, pyrimidinium, pyrazolium, isoxazolium, oxazolium, thiazolium, isothiazolium, pyridinium, pyrazinium, pyridazinium, imidazolium, isoindolium, indolium, purinium, quinolinium, isoquinolinium, naphthyridinium, quinoxalinium, quinazolinium, phthalazinium, indazolium, pyrrolidinium, piperidinium, azepinium, or piperazinium). Amines include those represented by formula -NR2, wherein each R is independently hydrogen, alkyl, or aryl, wherein alkyl and aryl are optionally substituted as described above, or two R groups may join to form a 5 to 7-membered ring optionally containing at least one O, N, or S and optionally substituted by alkyl having 1 to 6 carbon atoms. Amphoteric groups include those having both an ammonium group and either a carboxylate, a sulfonate, a sulfate, phosphate, or a phosphonate group.
In some embodiments, Z is selected from the group consisting of an ammonium group, an amine-oxide group, a carboxylate, a sulfonate, a sulfate, phosphate, a phosphonate, and an amphoteric group. In some embodiments, Z is selected from the group consisting of an ammonium group, an amine-oxide group, and an amphoteric group. In some embodiments, Z is selected from the group consisting of a carboxylate, a sulfonate, a sulfate, phosphate, and a phosphonate. In some embodiments of compounds represented by formula (Rf-Q-X)8-Z, Z is selected from the group consisting of -[N(R)3]+M~, -N(O)(R1)2, -N+(R)2-X^SO3A, and -N+(R)2-X^CO2A. In some of these embodiments, Z is -[N(R)3]+M~. In other embodiments, Z is -N(O)(R1)2, -N+(R)2-X^SO3A, or -N+(R)2-X^CO2A.
In any of the above embodiments of Z, each R is independently selected from the group consisting of hydrogen and alkyl having from 1 to 6 carbon atoms (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, n-pentyl, isopentyl, neopentyl, or n- hexyl). In some embodiments, each R is independently hydrogen or methyl. In any of the above embodiments of Z, each R1 is independently selected from the group consisting of hydrogen and alkyl having from 1 to 6 carbon atoms (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, n-pentyl, isopentyl, neopentyl, or n- hexyl), wherein alkyl is optionally substituted by at least one halogen, alkoxy, nitro, or nitrile group, or two R1 groups may join to form a 5 to 7-membered ring optionally containing at least one O, N, or S and optionally substituted by alkyl having 1 to 6 carbon atoms. In some embodiments, each R1 is independently hydrogen or methyl.
In any of the above embodiments of Z, each X1 is selected from the group consisting of alkylene and arylalkylene, wherein alkylene and arylalkylene are each optionally interrupted by at least one ether linkage. In some embodiments, X1 is alkylene having up to 5 carbon atoms.
In any of the above embodiments of Z, M" is a counter anion. Typical counter anions include halides (i.e., fluoride, chloride, bromide, and iodide), organic acid salts (e.g., formate, acetate, propionate, lactate, laurate, palmitate, stearate, or citrate), organic sulfonic or sulfuric acid salts (e.g., alkyl sulfates or alkanesulfonates), nitrate, and tetrafluoroborate. The organic acid salts and sulfonic acid salts may be partially fluorinated or perfluorinated. In some embodiments, the acid salt is RfC(O)O", wherein Rf is as defined in any of the above embodiments. In some embodiments, M" is chloride, bromide, or iodide (i.e., Cl-, Br-, or I-). In some embodiments, M" is selected from the group consisting of chloride, acetate, iodide, bromide, methylsulfate, ethylsulfate, and formate.
In any of the above embodiments of Z, A is selected from the group consisting of hydrogen and a free anion.
In some embodiments of compounds represented by formula (Rf-Q-X)8-Z, Z is selected from the group consisting of -P(O)(OY)2, -0-P(O)(OY)2, -SO3Y, -0-SO3Y, and
-CO2Y. In some embodiments, s is 2, and Z is (-O)2-P(O)(OY). In some of these embodiments, Y is hydrogen. In other of these embodiments, Y is a counter cation. Exemplary Y counter cations include alkali metal (e.g., sodium, potassium, and lithium), alkaline earth metal (e.g., calcium and magnesium), ammonium, alkyl ammonium (e.g., tetraalkylammonium), and five to seven membered heterocyclic groups having a positively charged nitrogen atom (e.g, a pyrrolium ion, pyrazolium ion, pyrrolidinium ion, imidazolium ion, triazolium ion, isoxazolium ion, oxazolium ion, thiazolium ion, isothiazolium ion, oxadiazolium ion, oxatriazolium ion, dioxazolium ion, oxathiazolium ion, pyridinium ion, pyridazinium ion, pyrimidinium ion, pyrazinium ion, piperazinium ion, triazinium ion, oxazinium ion, piperidinium ion, oxathiazinium ion, oxadiazinium ion, and morpholinium ion). Interconversions of Y groups can be carried out, for example, using conventional acid-base chemistry.
In some embodiments of compounds according to the present disclosure, Z is -[N(R)3J+M", wherein each R and is independently hydrogen or methyl, and wherein M- is selected from the group consisting of chloride, acetate, iodide, bromide, methylsulfate, ethylsulfate, and formate. In some embodiments of compounds according to the present disclosure, Q is
-C(O)-N(R')-, and wherein X is alkylene having up to 5 (e.g., 1, 2, 3, 4, 5) carbon atoms.
In some embodiments of compounds according to the present disclosure, Q is -C(O)O- NH(R)2-, and X is selected from the group consisting of alkylene having up to 5 carbon atoms, -[EOMR2O]g-[EO]f-, and-[R2O]g-[EOHR2O]g-, wherein EO represents -CH2CH2O-; each R2O independently represents -CH(CH3)CH2O-, -CH2CH(CH3)O-,
-CH(CH2CH3)CH2O-, -CH2CH(CH2CH3)O-, or -CH2C(CH3)2O- (in some embodiments, -CH(CH3)CH2O-, or -CH2CH(CH3)O-); each f is independently a number from 1 to 150 (in some embodiments, from 7 to about 150, 14 to about 125, 5 to 15, or 9 to 13); and each g is independently a number from O to 55 (in some embodiments, from about 21 to about 54, 15 to 25, 9 to about 25, or 19 to 23). In some of these embodiments, the compound is represented by a formula selected from the group consisting of [Rf-C(O)O +NH(R')2-X]2-NH(R)+ RfC(O)O" and
Rf-C(O)O +NH(R)2-X-NH(R)2 + RfC(O)O", wherein each R is independently selected from the group consisting of hydrogen and alkyl having from 1 to 6 (e.g., from 1 to 4, 1 to 3, or 1 to 2) carbon atoms.
In some embodiments of compounds according to the present disclosure, Z is -N(0)(R1)2, -N+(R)2-X^SO3A, or -N+(R)2-X^CO2A, wherein each R and R*are independently hydrogen or methyl, and wherein X1 is alkylene having up to 5 carbon atoms. In some embodiments of compounds represented by Formula (Rf-Q-X)8-Z, X-Z is selected from the group consisting of:
-[EOMR2O]8-[EO]^R3; and -[R2O]8-[EOMR2O]8-R3, wherein
EO represents -CH2CH2O-; each R2O independently represents -CH(CH3)CH2O-, -CH2CH(CH3)O-, -CH(CH2CH3)CH2O-, -CH2CH(CH2CH3)O-, or
-CH2C(CH3)2O- (in some embodiments, -CH(CH3)CH2O-, or -CH2CH(CH3)O-);
R3 is hydrogen or alkyl having up to 4 carbon atoms (e.g., methyl, ethyl, n- propyl, isopropyl, n-butyl, sec-butyl, or isobutyl); each f is independently from 1 to 150 (in some embodiments, from 7 to about 150, 14 to about 125, 5 to 15, or 9 to 13); and each g is independently from 0 to 55 (in some embodiments, from about 21 to about 54, 15 to 25, 9 to about 25, or 19 to 23). In some embodiments, each g is 0. Compounds represented by Formula (Rf-Q-X)8-Z can be prepared, for example, starting with a partially or fully fluorinated carboxylic acid, a salt thereof, a carboxylic acid ester, or a carboxylic acid halide. Partially and fully fluorinated carboxylic acids and salts thereof, carboxylic acid esters, and carboxylic acid halides can be prepared by known methods. For example, starting materials represented by formula Rf -(O)r-CHF-(CF2)n-C(O)G or [Rf-(O)1-C(L)H-CF2-O]1n-W-C(O)G, wherein G represents -OH, -O-alkyl (e.g., having from 1 to 4 carbon atoms), or -F and Rf, Rf1, n, m, L, t, r, and W are as defined in any of the embodiments above, can be prepared from fluorinated olefins of Formula VI or VII:
R^-(O)1-CF=CF2 VI, or Rf-(O)1-CF=CF2 VII, wherein Rf, Rf, and t are as defined above. Numerous compounds of Formula VI or VII are known (e.g., perfluorinated vinyl ethers and perfluorinated allyl ethers), and many can be obtained from commercial sources (e.g., 3M Company, St. Paul, MN, and E.I. du Pont de Nemours and Company, Wilmington, DE). Others can be prepared by known methods; (see, e.g., U. S. Pat. Nos. 5,350,497 (Hung et al.) and 6,255,536 (Worm et al.)).
Compounds of formula Rf-(O)r-CHF-(CF2)n-C(O)G, wherein n is O, can be prepared, for example, by reacting a fluorinated olefin of Formula VII with a base (e.g., ammonia, alkali metal hydroxides, and alkaline earth metal hydroxides). Alternatively, for example, a fluorinated olefin of Formula VII can be reacted with an aliphatic alcohol (e.g., methanol, ethanol, n-butanol, and t-butanol) in an alkaline medium, and the resulting ether can be decomposed under acidic conditions to provide a fluorinated carboxylic acid of formula Rf -(O)r-CHF-(CF2)n-C(O)G, wherein n is 0. Compounds of formula
Rf-(O)1-CHF-(CF2)D-C(O)G, wherein n is 1, can be prepared, for example, by a free radical reaction of the fluorinated olefin of Formula VII with methanol followed by an oxidation of the resulting reaction product using conventional methods. Conditions for these reactions are described, for example, in U. S. Pat. App. Pub. No. 2007/0015864 (Hintzer et al.), the disclosure of which, relating to the preparation of compounds of formula Rf -(O)r-CHF-(CF2)n-C(O)G, is incorporated herein by reference. These methods may be useful, for example, for providing structurally pure compounds (e.g., free of other compounds containing other fluorinated segments). In some embodiments, compounds according to the present disclosure are at least 95% (e.g., 96, 97, 98, or 99%) pure. Fluorinated vinyl ethers of Formulas VI or VII, wherein r and/or t is 1, can be oxidized (e.g., with oxygen) in the presence of a fluoride source (e.g., antimony pentafluoride) to carboxylic acid fluorides of formula Rf-O-CF2C(O)F according to the methods described in U. S. Pat. No. 4,987,254 (Schwertfeger et al.), in column 1, line 45 to column 2, line 42, the disclosure of which is incorporated herein by reference. Examples of compounds that can be prepared according to this method include
CF3-(CF2)2-O-CF2-C(O)-CH3 and CF3-O-(CF2)S-O-CF2-C(O)-CH3, which are described in U. S. Pat. App. Pub. No. 2007/0015864 (Hintzer et al.), the disclosure of which, relating to the preparation of these compounds, is incorporated herein by reference. These methods may be useful, for example, for providing structurally pure compounds (e.g., free of other compounds containing other fluorinated segments). In some embodiments, compounds according to the present disclosure are at least 95% (e.g., 96, 97, 98, or 99%) pure.
Compounds of formula [Rfb-(O),-C(L)H-CF2-O]m- W-C(O)G can be prepared, for example, by reaction of a fluorinated olefin of Formula VI with a hydroxyl compound of Formula VIII according to the reaction:
RfMO)1-CF=CF2 + (HO)1n-W-C(O)G *- [Rf°-(O)t-CFH-CF2-O]m-W-C(O)G VI vm wherein Rf*3 and t are as defined above, m is 1, 2, or 3, W is alkylene or arylene, and G is as defined above. Typically, G represents -O-alkyl (e.g., having from 1 to 4 carbon atoms in the alkyl group). Compounds of Formula VIII can be obtained, for example, from commercial sources or can be prepared by known methods. The reaction can be carried out, for example, under conditions described in U. S. Pat. App. Pub. No. 2007/0015864
(Hintzer et al.), the disclosure of which, relating to the preparation of compounds of formula [Rfb-(O),-C(L)H-CF2-O]m- W-C(O)G, is incorporated herein by reference.
Fluorinated carboxylic acids and their derivatives according to formula CF3CFH-O-(CF2)P-C(O)G can be prepared, for example, by decarbonylation of difunctional perfluorinated acid fluoride according to the reaction:
FCOCF(CF3)-O-(CF2)PC(O)F → CF3-CHF-O-(CF2)PC(O)G. IX
The reaction is typically carried out at an elevated temperature in the presence of water and base (e.g., a metal hydroxide or metal carbonate) according to known methods; see, e.g., U. S. Pat. No. 3,555,100 (Garth et al.), the disclosure of which, relating to the decarbonylation of difunctional acid fluorides, is incorporated herein by reference. Compounds of Formula IX are available, for example, from the coupling of perfluorinated diacid fluorides of Formula X and hexafluoropropylene oxide according to the reaction:
O FC(O)-(CF2)p l-C(O)F + (CF3)-FC-CF2 *" FCOCF(CF3)-O-(CF2)pC(O)F
X «
Compounds of Formula X are available, for example, by electrochemical fluorination or direct fluorination of a difunctional ester of formula CH3OCO(CH2)P-1COOCH3 or a lactone of formula:
Figure imgf000016_0001
General procedures for carrying out electrochemical fluorination are described, for example, in U. S. Pat. No. 2,713,593 (Brice et al.) and International App. Pub. No. WO 98/50603, published November 12, 1998. General procedures for carrying out direct fluorination are described, for example, in U. S. Pat. No. 5,488,142 (Fall et al.). Some carboxylic acids and carboxylic acid fluorides useful for preparing compounds represented by formula (Rf-Q-X)8-Z are commercially available. For example, carboxylic acids of formula CFs-[O-CF2] i_3C(O)OH are available from Anles
Ltd., St. Petersburg, Russia.
Compounds represented by Formula (Rf-Q-X)8-Z can be prepared, for example, from a partially or fully fluorinated carboxylic acid or salt thereof, an acid fluoride thereof, or a carboxylic acid ester (e.g., Rf-C(O)-OCHs) using a variety of conventional methods. For example, a methyl ester can be treated with an amine having formula NH2-X-Z according to the following reaction sequence.
Rf-C(O)-OCH3 + NH2-X-Z → Rf-C(O)-NH-X-Z
In this sequence, Rf, X, and Z are as defined in any of the above embodiments. Some amines having formula NH2-X-Z are commercially available, such as, amino acids (e.g., sarcosine, 7-aminoheptanoic acid, 12-aminododecanoic acid, and 3- aminopropylphosphonic acid), aliphatic amines (e.g., dodecylamine and hexadecylamine), and difunctional amines (e.g., 3-(dimethylamino)propylamine). The reaction may be carried out, for example, at an elevated temperature (e.g., up to 80 0C, 70 0C, 60 0C, or 50 0C), and may be carried out neat or in a suitable solvent. A compound represented by formula Rf-C(O)-NH-X-Z can also be subjected to functional group transformations of the Z group using conventional techniques. For example, quaternary ammonium compounds according to the present disclosure, including compounds that contain an amphoteric group, can be prepared by using an amine having formula NH2-X-NR2 (e.g., 3-(dimethylamino)propylamine) in the first step to provide an amino-functionalized amide, which can then be quaternized by reaction with an acid (e.g., hydrochloric acid or acetic acid) or alkylating agents (e.g., diethylsulfate, propane sultone, iodomethane, bromobutane, or chloromethane). The reaction with an acid or an alkylating agent may be carried out at room temperature or at an elevated temperature (e.g., up to 60 0C or 50 0C). Or the amino-functionalized amide can be treated with hydrogen peroxide or a peracid (e.g., perbenzoic acid or peracetic acid) optionally at an elevated temperature (e.g., 60 0C to 70 0C) and in a suitable solvent (e.g., ethanol) to provide a compound of formula wherein Z is an amine oxide group. Compounds represented by Formula (Rf-Q-X)8-Z can also be prepared, for example, by reaction of a carboxylic acid ester (e.g., Rf-C(O)-OCHs) with an amino alcohol having formula NH2-X"-0H (e.g., ethanolamine) to prepare hydroxyl-substituted Rf-(CO)NHX" OH as shown in the following reaction sequence, wherein Rf is as defined in any of the above embodiments, s is 1 or 2, and X" is a precursor to X, wherein X is as defined in any of the above embodiments.
Rf-C(O)-OCH3 + NH2-X" -OH → Rf-C(0)-NH-X"-0H → (Rf-C(O)-NH-X)8-Z The conditions for the reaction with NH2-X-Z, described above, can be used for the reaction with NH2-X"-0H. The hydroxyl-substituted compound Rf-(C0)NHX"0H can then be treated with, for example, phosphonoacetic acid, phosphonopropionic acid, or phosphorous (V) oxychloride to provide phosphonates or phosphates according to the present disclosure. The reaction with phosphonoacetic acid or phosphonopropionic acid can be carried out, for example, in a suitable solvent (e.g., methyl isobutyl ketone or methyl ethyl ketone), optionally in the presence of a catalyst (e.g., methanesulfonic acid) and optionally at an elevated temperature (e.g., up to the reflux temperature of the solvent). The reaction of the hydroxyl-substituted compound represented by formula Rf-C(0)-NH-X"-0H with phosphorous (V) oxychloride can be carried out, for example, in a suitable solvent (e.g., toluene), optionally at an elevated temperature (e.g., the reflux temperature of the solvent). One or two equivalents of the hydroxyl-substituted compound can be used provide compounds having formula (Rf-C(O)-NH-X)8-Z, wherein Z is a phosphate, and s is 1 or 2. If one equivalent of the hydroxyl-substituted compound is used, an equivalent of water or alcohol may be added.
Compounds represented by Formula Rf-Q-X-Z can also be prepared, for example, by reducing an ester of formula Rf-C(O)-OCH3 or a carboxylic acid of formula Rf-C(O)-OH using conventional methods (e.g., hydride, such as sodium borohydride, reduction) to a hydroxyl-substituted compound of formula Rf-CH2OH as shown in the following reaction sequence, wherein Rf, X, and Z are as defined in any of the above embodiments.
Rf-C(O)-OCH3 → Rf-CH2OH → Rf-X-Z The hydroxyl-substituted compound of formula Rf-CH2OH can then be converted, for example, to a phosphate or phosphonate using any of the techniques described above. Compounds according to the present disclosure can also be prepared, for example, by reaction of a carboxylic acid represented by formula Rf-C(O)-OH with an epoxide or mixture of epoxides according to the following reaction sequence, wherein Rf, f, g, and R3 are as defined in any of the above embodiments and R4 is hydrogen, methyl, ethyl, or a combination thereof.
Rf-C(O)-OH + Rf-C(O)-O-(CH2-CHR4-O)f+g-R3
Figure imgf000019_0001
The reaction can be carried out, for example, in the presence of Lewis Acid catalysts such as complexes of boron trifluoride (e.g., boron trifluoride etherate, boron trifluoride tetrahydropyran, and boron trifluoride tetrahydrofuran), phosphorous pentafluoride, antimony pentafluoride, zinc chloride, and aluminum bromide. The reaction can also be carried out in the presence of (CFsSO2)2CH2. Ring-opening polymerizations can be carried out neat or in a suitable solvent such as a hydrocarbon solvent (e.g., toluene) or a halogenated solvent (e.g., dichloromethane, carbon tetrachloride, trichloroethylene, or dichloroethane). The reactions can be carried out at or near room temperature or below (e.g., in a range from about 0 0C to 40 0C). The reactions can also be carried out above room temperature (e.g, up to 40 0C, 60 0C, 70 0C, 90 0C, or up to the reflux temperature of the solvent).
Compounds according to the present disclosure can also be prepared, for example, by reaction of a carboxylic acid represented by formula Rf-C(O)-OH, wherein Rf is defined as in any of the above embodiments, with a diamine or triamine (e.g., 3-
(dimethylamino)propylamine or diethylenetriamine). The equivalents of carboxylic acid and diamine or triamine can be adjusted to provide, mono-salts, di-salts, or tri-salts. For example, a carboxylic acid represented by formula Rf-C(O)-OH may be reacted with one equivalent of a diamine to provide a compound having formula Rf-Q-X-Z, wherein Q is -C(O)O- NH(R)2-, and Z is an amine (e.g., a primary, secondary, or tertiary amine).
Two equivalents of a carboxylic acid represented by formula Rf-C(O)-OH may also be reacted with a diamine to provide a compound, for example, having formula Rf-Q-X-Z, wherein Q is-C(O)O NH(R')2-, and Z is an ammonium group having formula -[NH(R)2] RfC(O)O". In a further example, three equivalents of a carboxylic acid represented by formula Rf-C(O)-OH may be reacted with a triamine to provide a compound, for example, having formula (Rf-Q-X)2-Z, wherein each Q is -C(O)O" +NH(R')2-, and Z is an ammonium group having formula (-)2[NHR]+RfC(O)O~.
The salts can be prepared, for example, by stirring a carboxylic acid and a diamine or triamine at room temperature or optionally at an elevated temperature and optionally in a suitable solvent (e.g., ethanol). Compounds according to the present disclosure may be formulated into concentrates (e.g., in at least one of water or organic solvent), wherein the compound is present in an amount of at least 10, 20, 30, or even at least 40 percent by weight, based on the total weight of the concentrate. Techniques for preparing concentrates are known in the art. In some embodiments, the present disclosure provides a composition comprising at least one of water or a water-miscible organic solvent and a compound according to the present disclosure. In some these embodiments, Z is selected from the group consisting of an ammonium group, an amine-oxide group, an amine, a hydroxyl, an alkoxy, a carboxylate, a sulfonate, a sulfate, phosphate, a phosphonate, and an amphoteric group. In some embodiments, compositions according to and/or useful for practicing methods according to the present disclosure may comprise water and a non-fluorinated polymer. These aqueous compositions may be useful, for example, for coatings (e.g., floor finishes, varnishes, automotive coatings, marine coatings, sealers, hard coats for plastic lenses, coatings for metal cans or coils, and inks). When used in aqueous compositions (e.g., for coatings) compounds according to the present disclosure can be formulated into an aqueous solution or dispersion at a final concentration, for example, of about 0.001 to about 1 weight percent (wt. %), about 0.001 to about 0.5 wt. %, or about 0.01 to about 0.3 wt. %, based on the weight of the solution or dispersion. In some embodiments, compounds according to the present disclosure may enhance wetting and/or leveling of a coating (e.g., an aqueous coating) on a substrate surface and may provide better dispersability of a component (e.g., a thickening agent or pigment) within the coating composition.
In some embodiments, aqueous compositions comprising compounds according to the present disclosure (e.g., for coatings) include at least one non-fluorinated polymer, typically a film-forming polymer. Examples of suitable polymers include acrylic polymers, (e.g., poly(methyl methacrylate-co-ethyl acrylate) or poly(methyl acrylate-co- acrylic acid)); polyurethanes, (e.g., reaction products of aliphatic, cycloaliphatic or aromatic diisocyanates with polyester glycols or polyether glycols); polyolefϊns, (e.g., polystyrene); copolymers of styrene with acrylate(s) (e.g., poly(styrene-co-butyl acrylate); polyesters, (e.g, polyethylene terephthalate, polyethylene terephthalate isophthalate, or polycaprolactone); polyamides, (e.g., polyhexamethylene adipamide); vinyl polymers, (e.g., poly( vinyl acetate/methyl acrylate), poly(vinylidene chloride/vinyl acetate); polydienes, (e.g., poly(butadiene/styrene)); cellulosic derivatives including cellulose ethers and cellulose esters, (e.g., ethyl cellulose, or cellulose acetate/butyrate), urethane-acrylate copolymers, and combinations thereof. Methods and materials for preparing aqueous emulsions or latexes of such polymers are well known, and many are widely available from commercial sources. In some embodiments, the non-fluorinated polymer is at least one of an acrylic polymer, a polyurethane, a polystyrene, or a styrene-acrylate copolymer. In some embodiments, aqueous compositions comprising compounds according to the present disclosure may contain one or more water-miscible solvents (e.g., coalescing solvents) including ethers of polyhydric alcohols (e.g., ethylene glycol monomethyl (or monoethyl) ether, diethylene glycol methyl (or ethyl) ether, triethylene glycol monomethyl (or monoethyl) ether, 2-butoxyethanol (i.e., butyl cellusolve), or di(propylene glycol) methyl ether (DPM)); alkylene glycols and polyalkylene glycols (e.g., ethylene glycol, propylene glycol, butylene glycol, triethylene glycol, hexylene glycol, diethylene glycol, polyethylene glycol, polypropylene glycol); and 2,2,4-trimethyl-l,3-pentanediol monoisobutyrate (an ester alcohol available, for example, from Eastman Chemical Company, Kingsport, TN, under the trade designation "TEXANOL"). Other water- miscible organic solvents that may be added to a composition include alcohols having 1 to 4 carbon atoms (e.g., methanol, ethanol, isopropanol, or isobutanol); amides and lactams, (e.g., N,N-dimethylformamide, N,N-dimethylacetamide, or N-methylpyrrolidone); ketones and ketoalcohols (e.g., acetone, cyclohexanone, methyl isobutyl ketone, diacetone alcohol); ethers (e.g., tetrahydrofuran or dioxane); l,3-dimethyl-2-imidazolidinone; and combinations thereof.
Depending on the application, aqueous compositions comprising compounds according to the present disclosure may also include at least one additive (e.g., biocides, fillers, additional leveling agents, emulsifϊers, defoamers, anticorrosive agents, dispersants, and rust inhibitors). The aqueous compositions may also optionally contain at least one pigment. When an aqueous composition comprising a non-fluorinated polymer and a compound according to the present disclosure is applied to a surface (e.g., in coating applications), water and solvent typically evaporate, and the polymer particles coalesce to form a continuous film. The aqueous composition can be applied to a surface, dried, and optionally heated, leaving the surface with a solid coating. The addition of compounds according to the present disclosure may improve the film forming properties of some compositions by improving the ability of the coating to wet the substrate and/or by allowing for even evaporation of the water (i.e., leveling) during film formation.
Aqueous compositions that may be improved by the addition of compounds according to the present disclosure include floor polishes and finishes, varnishes for a variety of substrates (e.g., wood floors), aqueous gels applied in the manufacture of photographic film, automotive or marine coatings (e.g., primers, base coats, or topcoats), sealers for porous substrates (e.g., wood, concrete, or natural stone), hard coats for plastic lenses, coatings for metallic substrates (e.g., cans, coils, electronic components, or signage), inks (e.g, for pens or gravure, screen, or thermal printing), and coatings used in the manufacture of electronic devices (e.g., photoresist inks). The aqueous compositions may be clear or pigmented.
In some embodiments, aqueous compositions comprising compounds according to some embodiments of the present disclosure and a non-fluorinated polymer may be useful as alkaline waterborne coating compositions, for example, amine-stabilized floor finish compositions. In some of these embodiments, the compound comprises at least one of a carboxylate, a sulfonate, a sulfate, phosphate, or a phosphonate group.
Methods comprising treating a surface according to the present disclosure can be carried out using a variety of application methods known to one of skill in the art (e.g., brushing, mopping, padding, bar coating, spraying (e.g., with a spray bottle), dip coating (i.e., immersing the substrate in a formulation), gravure coating, roll coating, spin-coating, flow coating, vacuum coating, painting, and wiping (e.g., with a sponge or cloth). When treating flat substrates of appropriate size, knife-coating or bar-coating may be used to ensure uniform coatings on a substrate. In some embodiments of methods comprising treating a surface according to the present disclosure, the surface is a flooring surface comprising at least one of vinyl composition tiles, vinyl sheet flooring, linoleum, rubber sheeting, rubber tile, cork, synthetic sports flooring and vinyl asbestos tile, and non-resilient flooring substrates such as terrazzo, concrete, wood flooring, bamboo, wood laminate, engineered wood products (e.g., wood epoxy blends, permanently coated substrates such as those available from Pergo, Raleigh, NC, under the trade designation "PERGO" and from DIAN, Gardena, CA, under the trade designation "PARQUET BY DIAN"), stone, marble, slate, ceramic tile, grout, and dry shake flooring.
Compounds according to the present disclosure may also be useful as additives in cleaning solutions and may provide improved wetting of the surface and/or the contaminants to be removed. In some embodiments, methods comprising treating a surface according to the present disclosure include cleaning a surface. A cleaning solution is typically formulated to include about 0.001 to about 1 wt. %, or about 0.001 to about 0.5 wt. % of a compound according to the present disclosure, based on the total weight of the solution. For hard-surface cleaning, an aqueous solution comprising a compound according to the present disclosure is sprayed (e.g., from a spray bottle) or otherwise applied to a hard surface such as window glass, a mirror, or ceramic tile, and the surface is wiped clean with a paper or fabric wipe. The contaminated part may also be immersed or dipped into the aqueous solution. For methods of cleaning used in the manufacture of electronic materials, the cleaning solution is typically placed in a bath, and electronic parts are either dipped or run through the bath on a conveyor belt. In some embodiments of composition comprising at least one of water or a water- miscible solvent and a compound according to the present disclosure, the composition further comprises at least one gas (i.e., the composition is a foam).
In some embodiments of compounds according to the present disclosure, X is alkylene having at least 10 (e.g., at least 12, 15, 18, 20, 22, 25, 28, or 30) carbon atoms. These compounds may be useful, for example, to reduce the surface tension of compositions containing hydrocarbon solvents. Suitable hydrocarbon solvents include crude oil; refined hydrocarbons (e.g., gasoline, kerosene, and diesel); paraffϊnic and isoparaffmic hydrocarbons (e.g., pentanes, hexanes, heptanes, higher alkanes, and isoparaffmic solvents obtained from Total Fina, Paris, France, under trade designations "ISANE IP 130" and "ISANE IP 175" and from Exxon Mobil Chemicals, Houston, TX, under the trade designation "ISOPAR"); mineral oil; ligroin; naphthenes; aromatics (e.g., xylenes and toluene); natural gas condensates; and combinations (either miscible or immiscible) thereof. In some embodiments, compositions comprising a hydrocarbon solvent and a compound according to the present disclosure further comprise at least one gas (i.e., the composition is a foam).
Typically, compositions (e.g., aqueous or hydrocarbon foams) according to and/or prepared by the present disclosure include from at least 0.01, 0.015, 0.02, 0.025, 0.03, 0.035, 0.04, 0.045, 0.05, 0.055, 0.06, 0.065, 0.07, 0.075, 0.08, 0.085, 0.09, 0.095, 0.1, 0.15, 0.2, 0.25, 0.5, 1, 1.5, 2, 3, 4, or 5 percent by weight, up to 5, 6, 7, 8, 9, or 10 percent by weight of at least one compound according to the present disclosure, based on the total weight of the composition. For example, the amount of a compound according to the present disclosure in a foam may be in a range of from 0.01 to 10, 0.1 to 10, 0.1 to 5, 1 to 10, or from 1 to 5 percent by weight, based on the total weight of the composition. Lower and higher amounts of the compound in the composition (e.g., a foam) may also be used, and may be desirable for some applications.
Forming gas bubbles (e.g., nitrogen, carbon dioxide, and air) in a composition comprising a liquid (e.g., water or a solvent) and a compound according to the present disclosure can be carried out using a variety of mechanisms (e.g., mechanical and chemical mechanisms). Useful mechanical foaming mechanisms include agitating (e.g., shaking, stirring, and whipping) the composition, injecting gas into the composition (e.g., inserting a nozzle beneath the surface of the composition and blowing gas into the formulation) and combinations thereof. Useful chemical foaming mechanisms include producing gas in situ through a chemical reaction, decomposition of a component of the composition (e.g., a component that liberates gas upon thermal decomposition), evaporating a component of the composition (e.g., a liquid gas, and volatilizing a gas in the composition by decreasing the pressure on the composition or heating the composition). Foams according to and/or prepared by methods according to the present disclosure comprise gas bubbles at volume fractions ranging from 10% to 90% of the total foam volume.
Compounds according to the present disclosure may be useful additives, for example, in foams for delivering oil- and/or water-repellent treatments to substrates (including fibrous substrates, e.g., textile, non-woven, carpet, and leather).
In some embodiments, compounds according to the present disclosure may provide repellent properties to a variety of surfaces and improve the ability to clean these surfaces. Articles according to the present disclosure, having a surface treated with a compound according to the present disclosure may be at least one of non-staining, stain-releasing with simple washing methods, oil resistant (e.g., resistant to fingerprints), resistant to lime deposits, or resist being worn-off due to wear and abrasion from use, cleaning, and the elements. In some of these embodiments, Z is a phosphate or phosphonate group.
In any of the aforementioned embodiments of compounds according to and/or useful in practicing the present disclosure (e.g., coating or cleaning solution compositions and foams), compounds according to the present disclosure can be used individually or in combination with a non-fluorinated surfactant (e.g., a hydrocarbon or silicone surfactant) to produce the desired surface tension reduction or wetting improvement. Useful auxiliary surfactants may be found, for example, in Industrial Applications Of Surfactants, D.R. Karsa, Ed., Royal Society of Chemistry, London, and M. Rosen, Surfactants and Interfacial Phenomena, Wiley-Interscience, New York.
The compounds disclosed herein, which have partially fluorinated polyether groups and/or have fully fluorinated polyether groups with a low number (e.g., up to 4) continuous perfluorinated carbon atoms, are herein demonstrated to have useful surfactant properties and may provide a lower-cost alternative to surfactants having a larger number of continuous perfluorinated carbon atoms. The compounds disclosed herein may be useful, for example, as nonionic, anionic, cationic, or zwitterionic surfactants. For some applications that require rapid spraying and wetting processes (e.g., painting of car bodies, metal working, paper making, and textile manufacturing), it is advantageous to use highly dynamic surfactants that can reduce the surface tension within milliseconds. In some embodiments, the present disclosure provides dynamic surfactants (e.g., compounds represented by formula [Rf-C(O)O +NH(R)-X]2-NH(R)+RfC(O)O" or Rf-C(O)O +NH(R)-X-NH(R)2 +RfC(O)O") that rival the performance of the best known dynamic surfactants (see, e.g., U.S. Pat. No. 5,503,967 column 21, line 10 and the perfluoropolyether salts in U.S. Pat. Nos. 5,453,539 and 5,536,425).
Compounds according to the present disclosure reduce the surface tension of a liquid with which they are combined. In some embodiments, the surface tension of the liquid is reduced by at least 10% (in some embodiments, at least 20%, 30%, 40%, 50%, 60%, or even 70%). In some embodiments, the surface tension of the liquid is reduced to an extent not less than when an equivalent liquid is combined with an amount of a surfactant, wherein the surfactant is the same as the compound except Rf is replaced with a group represented by formula CsF7-O-CF(CFs)-, and wherein the amount by weight of the surfactant is the same as the amount by weight of the compound. The term "equivalent liquid" refers to a liquid that is the same in all respects except for the identity of the surfactant.
Embodiments of this disclosure are further illustrated by the following non- limiting examples, but the particular materials and amounts thereof recited in these examples, as well as other conditions and, details, should not be construed to unduly limit this disclosure.
EXAMPLES
In the following examples, all reagents were obtained from Sigma-Aldrich, St. Louis, MO or Bornem, Belgium unless indicated otherwise. All percentages and ratios reported are by weight unless indicated otherwise.
Example 1 : CF3OCF2CF2CF2OCF2C(O)NHCH2CH2CH2N+(CH3)2H OC(O)CH3 Part A
The methyl ester of perfluoro-3,7-dioxaoctanoic acid (CF3OCF2CF2CF2OCF2C(O)OCH3) was prepared according to the method described in U. S. Pat. App. Pub. No. 2007/0015864 (Hintzer et al.) in the Preparation of Compound 1, the disclosure of which preparation is incorporated herein by reference. Part B
In a three-necked 100-mL flask fitted with a stirrer, thermometer, and condenser were placed 18 grams (0.05 mole) of the methyl ester from Part A and dimethylaminopropylamine (DMAPA) (5.1 grams, 0.05 mole). The reaction mixture was heated under nitrogen at 50 0C using a heating mantle for three hours. Methanol was then removed under reduced pressure. Acetic acid (3 grams, 0.05 mole) was added, and the resulting mixture was stirred for two hours under nitrogen at 30 0C. A clear, yellow, slightly viscous liquid was obtained, which was identified to be
CF3OCF2CF2CF2OCF2C(O)NHCH2CH2CH2N+(CH3)2H OC(O)CH3 using proton and 19fluorine nuclear magnetic resonance (NMR) spectroscopy. Example 2: CF3OCF2CF2CF2OCF2C(O)NHCH2CH2CH2N(CH3)2O
In a three-necked 100-mL flask fitted with a stirrer, thermometer, and condenser were placed 18 grams (0.05 mole) of the methyl ester from Example 1, Part A and DMAPA (5.1 grams, 0.05 mole). The reaction mixture was heated under nitrogen at 50 0C using a heating mantle for three hours. Methanol was then removed under reduced pressure. Ethanol (24 grams) and 8.4 grams (0.075 mole) of 30% hydrogen peroxide in water were added, and the mixture was heated at 70 0C for six hours. A clear, slightly amber solution Of CF3OCF2CF2CF2OCF2C(O)NHCH2CH2CH2N(CHs)2O was obtained.
Example 3: CF3OCF2CF2CF2OCHFCF2C(O)NHCH2CH2CH2N+(CH3)2H OC(O)CH3
Part A
The methyl ester of 3-H-perfluoro-4,8-dioxanonanoic acid
(CF3O(CF2)3OCHFCF2COOCH3) was prepared according to the method described in the synthesis of compound 2 in U. S. Pat. App. Pub. No. 2007/0142541 (Hintzer et al); the disclosure of this synthesis is incorporated herein by reference.
Part B
The method of Part B of Example 1 was followed except using 19.6 grams of
CF3O(CF2)3OCHFCF2COOCH3 instead Of CF3OCF2CF2CF2OCF2C(O)OCH3.
Example 4: CF3OCF2CF2CF2OCHFCF2C(O)NHCH2CH2CH2N(CH3)2O
The method of Example 2 was followed except using 19.6 grams of
CF3O(CF2)3OCHFCF2COOCH3, prepared as described in Part A of Example 3, instead of
CF3OCF2CF2CF2OCF2C(O)OCH3.
Example 5: CF3CF2CF2OCHFCF2C(O)NHCH2CH2CH2N+(CH3)2H OC(O)CH3
Part A
The methyl ester of 3-H-perfluoro-4-oxaheptanoic acid (C3F7OCHFCF2COOCH3) was prepared according to the method described in the synthesis of compound 4 in U. S. Pat. App. Pub. No. 2007/0142541 (Hintzer et al.); the disclosure of this synthesis is incorporated herein by reference.
Part B The method of Part B of Example 1 was followed except using 16.3 grams of CF3CF2CF2OCHFCF2COOCH3 instead Of CF3OCF2CF2CF2OCF2C(O)OCH3.
Example 6: CF3CF2CF2OCHFCF2C(O)NHCH2CH2CH2N(CH3)2O The method of Example 2 was followed except using 16.3 grams of
CF3CF2CF2OCHFCF2COOCH3, prepared as described in Part A of Example 5, instead of CF3OCF2CF2CF2OCF2C(O)OCH3.
Example 7: CF3OCF2OCF2OCF2C(O)NHCH2CH2CH2N+(CH3)2H OC(O)CH3 Part A
The methyl ester of perfluoro-3,5,7-trioxaoctanoic acid (obtained from Anles Ltd., St. Petersburg, Russia) was prepared by esterifϊcation in methanol using 50% aqueous sulfuric acid. Flash distillation of the reaction mixture resulted in a two-phase distillate. The lower phase was fractionally distilled to provide CF3OCF2OCF2OCF2COOCH3. Part B
The method of Part B of Example 1 was followed except using 16.4 grams of CF3OCF2OCF2OCF2COOCH3 instead Of CF3OCF2CF2CF2OCF2C(O)OCH3.
Example 8: CF3OCF2OCF2OCF2C(O)NHCH2CH2CH2N(CH3)2O The method of Example 2 was followed except using 16.4 grams of
CF3OCF2OCF2OCF2COOCH3, prepared as described in Part A of Example 7, instead of CF3OCF2CF2CF2OCF2C(O)OCH3.
Example 9: CF3OCF2OCF2OCF2OCF2C(O)NHCH2CH2CH2N+(CH3)2H OC(O)CH3 Part A
The methyl ester of perfluoro-3,5,7,9-tetraoxadecanoic acid (obtained from Anles
Ltd., St. Petersburg, Russia) was prepared by esterifϊcation in methanol using 50% aqueous sulfuric acid. Flash distillation of the reaction mixture resulted in a two-phase distillate. The lower phase was fractionally distilled to provide CF3OCF2OCF2OCF2OCF2COOCH3.
Part B The method of Part B of Example 1 was followed except using 19.6 grams of CF3OCF2OCF2OCF2OCF2COOCH3 instead Of CF3OCF2CF2CF2OCF2C(O)OCH3.
Example 10: CF3OCF2OCF2OCF2OCF2C(O)NHCH2CH2CH2N(CH3)2O The method of Example 2 was followed except using 19.6 grams of
CF3OCF2OCF2OCF2OCF2COOCH3, prepared as described in Part A of Example 9, instead of CF3OCF2CF2CF2OCF2C(O)OCH3.
Example 11 : CF3OCF2CF2CF2OCHFC(O)NHCH2CH2CH2N+(CH3)2H OC(O)CH3 Part A
The methyl ester of 2-H-perfluoro-3,7-dioxaoctanoic acid
(CF3OCF2CF2CF2OCHFCOOCH3) was prepared according to the method described in the synthesis of compound 3 (paragraph [0062]) in U. S. Pat. App. Pub. No. 2007/0142541 (Hintzer et al.); the disclosure of this synthesis is incorporated herein by reference. Part B
The method of Part B of Example 1 was followed except using 18 grams of CF3OCF2CF2CF2OCHFCOOCH3 instead Of CF3OCF2CF2CF2OCF2C(O)OCH3.
Example 12: CF3OCF2CF2CF2OCHFC(O)NHCH2CH2CH2N(CH3)2O The method of Example 2 was followed except using 18 grams of
CF3OCF2CF2CF2OCHFCOOCH3, prepared as described in Part A of Example 11, instead of CF3OCF2CF2CF2OCF2C(O)OCH3.
Example 13: CF3CF2CF2OCHFC(O)NHCH2CH2CH2N+(CH3)2H OC(O)CH3 Part A
The methyl ester of 2-H-perfluoro-3-oxahexanoic acid
(CF3CF2CF2OCHFCOOCH3) was prepared according to the method described in the synthesis of compound 5 in U. S. Pat. App. Pub. No. 2007/0142541 (Hintzer et al.); the disclosure of this synthesis is incorporated herein by reference. Part B
The method of Part B of Example 1 was followed except using 13.8 grams of CF3CF2CF2OCHFCOOCH3 instead Of CF3OCF2CF2CF2OCF2C(O)OCH3. Example 14: CF3CF2CF2OCHFC(O)NHCH2CH2CH2N(CH3)2O
The method of Example 2 was followed except using 13.8 grams of CF3CF2CF2OCHFCOOCH3, prepared as described in Part A of Example 13, instead of CF3OCF2CF2CF2OCF2C(O)OCH3.
Example 15 : CF3OCF2OCF2OCF2OCF2C(O)NHCH2CH2CH2N+(CH3)2CH2CH2CH2SO3
In a three-necked 100-mL flask, fitted with a stirrer, thermometer, and condenser were placed 19.6 grams (0.05 mole) Of CF3OCF2OCF2OCF2OCF2COOCH3, prepared as described in Part A of Example 9, and DMAPA (5.1 grams, 0.05 mole). The reaction mixture was heated under a nitrogen atmosphere for three hours at 50 0C using a heating mantle. Methanol was then removed under reduced pressure. 1 ,3-Propanesultone (6.1 grams, 0.05 mole) was added, resulting in an exothermic reaction. The reaction mixture was further heated at 50 0C for three hours, and 15 grams ethanol and 15 grams of deionized water were added. A clear, amber solution of
CF3OCF2OCF2OCF2OCF2C(O)NHCH2CH2CH2N+(CH3)2CH2CH2CH2SO3 was obtained.
Example 16: CF3OCF2CF2CF2OCHFCF2C(O)NHCH2CH2CH2N+(CH3)2CH2CH2CH2SO3
The method of Example 15 was followed except using 19.6 grams of CF3O(CF2)3OCHFCF2COOCH3, prepared as described in Part A of Example 3, instead of CF3OCF2OCF2OCF2OCF2COOCH3.
Example 17: CF3OCF2CF2CF2OCF2C(O)O(CH2CH2O)nH
In a three-necked 100-mL flask, fitted with a stirrer, heating mantle, dry ice condenser, and thermometer, were placed 17.3 grams (0.05 mole)
CF3OCF2CF2CF2OCF2C(O)OH, which was heated to 80 0C. Ethylene oxide (2.2 grams, 0.05 mole) was added, and the reaction mixture was heated until no more condensation drops of ethylene oxide were observed. The mixture was cooled to 30 0C under nitrogen and then 0.2 gram boron trifluoride diethyl etherate was added. The mixture was heated to 80 0C, and additional ethylene oxide (8.8 grams, 0.2 mole) was added over about 30 minutes at a rate sufficient to maintain a gentle reflux of ethylene oxide. The heating was continued for three hours after the addition until refluxing was no longer observed. The reaction mixture was then concentrated under reduced pressure at 800C to provide a brown liquid.
CF3OCF2CF2CF2OCF2C(O)OH was prepared from
CF3OCF2CF2CF2OCF2C(O)ONH4, which was prepared according to the method described in U. S. Pat. App. Pub. No. 2007/0015864 (Hintzer et al.) in the Preparation of Compound
1, the disclosure of which preparation is incorporated herein by reference. The ammonium salt was treated with sulfuric acid, and the lower phase was separated and distilled.
Example 18: CF3OCF2OCF2OCF2OCF2C(O)O(CH2CH2O)nH The method of Example 17 was followed except using 18.9 grams of perfluoro-
3,5,7,9-tetraoxadecanoic acid (obtained from Anles Ltd., St. Petersburg, Russia) instead of CF3OCF2CF2CF2OCF2C(O)OH.
Example 19: CF3OCF2CF2CF2OCF2C(O)N(CH3)CH2C(O)O- K+ In a three-necked 100-mL flask fitted with a stirrer, thermometer, and condenser were placed 18 grams (0.05 mole) Of CF3OCF2CF2CF2OCF2C(O)OCH3, prepared in Example 1, Part A, and dry sarcosine (4.5 grams, 0.05 mole). The reaction mixture was heated under nitrogen at 60 0C using a heating mantle for 48 hours and then cooled to about 30 0C. Isopropanol (23 grams) and potassium hydroxide (2.8 grams, 0.05 mole) were added to provide a solution of CF3OCF2CF2CF2OCF2C(O)N(CH3)CH2C(O)O- K+.
Example 20: CF3OCF2OCF2OCF2OCF2C(O)N(CH3)CH2C(O)O- K+
The method of Example 19 was followed except using 19.6 grams of CF3OCF2OCF2OCF2OCF2COOCH3, prepared as described in Part A of Example 9, instead of CF3OCF2CF2CF2OCF2C(O)OCH3.
Example 21 : CF3OCF2CF2CF2OCF2C(O)NHCH2CH2OC(O)CH2P(O)(OH)2 Part A
CF3OCF2CF2CF2OCF2C(O)OCH3, prepared in Example 1, Part A, was treated with ethanolamine according to the method described on column 16, lines 37-62 of U. S. Pat. No. 7,094,829 (Audenaert et al.), the disclosure of which method is incorporated herein by reference. Part B
In a three-necked 100-mL flask fitted with a stirrer, thermometer, condenser, and Dean-Stark trap were placed 3.9 grams (0.01 mole) of the material from Part A, 2- phosphonoacetic acid (1.4 gram, 0.01 mole), methyl isobutyl ketone (26 grams), and methanesulfonic acid (0.05 gram). The reaction mixture was heated at reflux for about six hours. Throughout the course of the reaction, about 0.2 gram of water was collected in the Dean-Stark trap. CF3OCF2CF2CF2OCF2C(O)NHCH2CH2OC(O)CH2P(O)O(OH)2 was obtained as a brown liquid solution in methyl isobutyl ketone.
Example 22: CF3OCF2OCF2OCF2OCF2C(O)NHCH2CH2OC(O)CH2P(O)(OH)2
Example 22 was prepared using the method of Example 21 except using the methyl ester described in Part A of Example 9 in Part A and using 4.2 grams of
CF3OCF2OCF2OCF2OCF2C(O)NHCH2CH2OH instead of
CF3OCF2CF2CF2OCF2C(O)NHCH2CH2OH in Part B of Example 21.
Comparative Example A:
The method of Part B of Example 1 was followed except using 16.3 grams of
CF3CF2CF2OCF(CF3)COOCH3 (obtained from Hoechst AG, Germany) instead of
CF3OCF2CF2CF2OCF2C(O)OCH3.
Comparative Example B:
The method of Example 2 was followed except using 16.3 grams of
CF3CF2CF2OCF(CF3)COOCH3 (obtained from Hoechst AG , Germany) instead of
CF3OCF2CF2CF2OCF2C(O)OCH3.
Comparative Example C:
Perfluorohexanoic acid (obtained from ABCS GmBh Germany) (3.1 grams, 0.01 mole) was neutralized with potassium hydroxide (0.6 gram, 0.01 mole) in 5 grams of deionized water and 5 grams of isopropanol. A clear solution resulted after 30 minutes stirring at room temperature. Surface Tension Measurement
Examples 1 to 20 were diluted with deionized water to the concentrations given in Table 1 (below). Surface tensions were measured for the solutions containing Examples 1 to 20 using a Kruss K- 12 tensiometer (obtained from Kruss GmbH, Hamburg, Germany) using the Du Nouy ring method at 20 0C. The results are summarized in Table 1 (below).
Table 1
Figure imgf000033_0001
Figure imgf000034_0001
Dynamic Contact Angle on Glass
Dynamic advancing and receding contact angles were measured on flat glass (obtained from Aqua Production, France) using a Kruss DSA 100 (obtained from Kruss GmbH). Examples 21 and 22 were diluted to 20% solids in methyl isobutyl ketone. They were applied with a K Hand Coater Bar nr 3 (obtained from RK Print Coat Ltd, UK) at room temperature, leaving a 24 micron wet film deposited, and the coatings were dried at room temperature. The advancing and receding contact angles were measured after 1 hour at room temperature. For the purposes of comparison, a fluorochemical polymeric glass coating was obtained from 3M Company, St. Paul, MN, under the trade designation "ECC-4000" and was used as Comparative Example D (Comp. Ex. D). Comp. Ex. D was spray applied at 0.1% concentration. The results are summarized in Table 2 (below).
Table 2
Figure imgf000035_0001
Example 23: (CF3CFH-O-(CF2)5CH2O)2P(O)O-+NH4 Part A
CF3CFH-O-(CF2)5COOH (426 grams, 1.0 mole), which was prepared according to the method described in Example 3 of U.S. Pat. App. Pub. No. 2007/0276103, was esterified at 65 0C with methanol (200 grams, 6.3 moles) and concentrated sulfuric acid (200 grams, 2.0 moles). The reaction mixture was washed with water and distilled at 172 0C to give 383 grams of CF3CFH-O-(CF2)5COOCH3, which was combined with material from a repeat run and used in Part B. Part B
A 5 -L round-bottom flask equipped with a mechanical stirrer and nitrogen bubbler was charged with 1 L of 1 ,2-dimethoxyethane and sodium borohydride (76 grams, 2.0 moles) and heated to 80 0C. CF3CFH-O-(CF2)5COOCH3 (713 grams, 1.67 mole), prepared as described in Part A, was added to the stirred slurry over a period of one hour. A mixture of concentrated sulfuric acid (198 grams) and water (1.0 L) was added to the reaction mixture. The lower phase was separated, and the solvent was removed by distillation. Further distillation provided 506 grams of CF3CFH-O-(CF2)5CH2OH (boiling point 173 0C), the structure of which was confirmed by Fourier Transform Infrared Spectroscopy (FTIR) and 1H and 19F Nuclear Magnetic Resonance (NMR) Spectroscopy. Part C
A 100-mL three-necked flask equipped with a magnetic stir bar, thermometer, and a cooling water condenser connected to nitrogen was charged with phosphorous(V) oxy chloride (3.1 grams, 20 mmol) and six grams of toluene. The solution was cooled to 0 0C with an ice-water bath, and water (0.36 gram, 20 mmol) was added to the solution slowly with a syringe while maintaining the temperature below 5 0C. The reaction mixture was stirred at about 0 0C for one hour. Then a solution of a portion of the material from Part B (15.9 grams, 0.040 mole) in 16 grams of toluene was added. The solution was heated at 110 0C for 24 hours and then allowed to cool to room temperature. The solvent was removed under reduced pressure. Part D
A portion of the material from Part C (2.5 grams) was diluted with 7.5 grams of water, and the pH was adjusted to about 9 using 5% aqueous ammonia. The resulting solution was diluted with isopropyl alcohol to 150 grams total to provide a 2% by weight solution.
Example 24: (CF3CFH-O-(CF2)3CH2O)2P(O)O-+NH4 Part A
FC(O)CF(CF3)-O-(CF2)3COF (503 grams, 1.4 mole), prepared as described in U.S. Pat. App. Pub. No. 2004/0116742, was added over a period of two hours to a stirred mixture of sodium carbonate (387 grams, 3.7 moles) and diglyme (650 grams) at 78 0C. The reaction liberated carbon dioxide gas. Distilled water (35 grams, 1.9 mole) was added at 85 0C, and then the reaction mixture was heated to 165 0C and maintained at that temperature for 30 minutes. The reaction was allowed to cool, and sulfuric acid (250 grams, 2.6 moles) in 1250 grams of water was added. Two layers formed, and the top layer was washed with 33% sulfuric acid and then esterifϊed at 65 0C with methanol (200 grams, 6.3 moles) and concentrated sulfuric acid (200 grams, 2.0 moles). The reaction mixture was washed with water and distilled at 52 0C at 15 mmHg (2.0 x 10 Pa) to give 258 grams of CF3CFH-O-(CF2)3COOCH3. Part B
CF3-CFH-O-(CF2)3-CH2-OH was prepared according to the method of Example 23, Part B, except 200 grams (0.6 mole) of CF3-CFH-O-(CF2)S-C(O)O-CH3 was reduced with 30 grams (0.79 mole) of sodium borohydride in 0.2 L of 1,2-dimethoxyethane. At the end of the reaction 150 grams of concentrated sulfuric acid in 0.3 L of water were added, and 115 grams of CF3-CFH-O-(CF2)3-CH2-OH, having a boiling point of 130 0C, were obtained. Part C
(CF3CFH-O-(CF2)SCH2O)2P(O)O^NH4 was prepared according to the methods of Example 23, Parts C and D, except five grams of toluene were used, and a solution of the material from Part B (12.7 grams, 40 mmol) in 13 grams of toluene were added. After cooling to room temperature, the solvent was removed under reduced pressure to give 11.6 grams of liquid. A portion of the liquid (3 grams) was diluted with 7 grams of water, and the pH was adjusted to about 9 with 5% aqueous ammonia. The resulting solution was diluted with isopropyl alcohol to 150 grams total to provide a 2% by weight solution.
Surface Tension Measurement
Surface tension was determined for Examples 23 to 24 using a Kruss Kl 2 Tensiometer, purchased from Kruss USA, Charlotte, NC. For each Example the 2% solution in isopropanol/water was added dropwise to water, and the surface tension of the resulting solution was measured at room temperature. The results are shown in Table 3, below.
Table 3
Figure imgf000037_0001
Example 25: (CF3OCF2OCF2OCF2C(O)O )2 +NH3CH2CH2CH2N+H(CHs)2
Perfluoro-3,5,7-trioxaoctanoic acid (31.2 grams, 0.1 mole), obtained from Anles Ltd., and 31 grams of ethanol were added to a 250-mL three-necked flask fitted with a stirrer, a thermometer, and a condenser, and 5.1 grams (0.05 mole) of DMAPA was added dropwise with stirring over a period of about 15 minutes. The reaction mixture was stirred for about two hours after the addition at room temperature to provide a clear, slightly yellow solution of (CF3OCF2OCF2OCF2C(O)O )2 +NH3CH2CH2CH2N+H(CH3)2.
Example 26: (CF3OCF2OCF2OCF2C(O)O )2 +NH3CH(CH3)CH2(OCH2CH(CH3))X(OCH2CH2)9(OCH2CH(CH3))3 6.X +NH3
Example 26 was prepared according to the method of Example 25 except 30 grams of a polyetheramine obtained from Huntsman Corporation, The Woodlands, TX, under the trade designation "JEFFAMINE ED-600" were used instead of DMAPA.
Example 27: (CF3OCF2OCF2OCF2OCF2C(O)O )2 +NH3CH2CH2CH2N+H(CH3)2
Example 27 was prepared according to the method of Example 25 except 37.8 grams of perfluoro-3,5,7,9-tetraoxadecanoic acid (obtained from Anles Ltd.) were used instead of perfluoro-3,5,7-trioxaoctanoic acid.
Example 28: (CF3OCF2OCF2OCF2OCF2C(O)O )2
+NH3CH(CH3)CH2(OCH2CH(CH3))X(OCH2CH2)9(OCH2CH(CH3))3.6_X +NH3
Example 28 was prepared according to the method of Example 25 except 37.8 grams of perfluoro-3,5,7,9-tetraoxadecanoic acid (obtained from Anles Ltd.) were used instead of perfluoro-3,5,7-trioxaoctanoic acid, and 30 grams of a polyetheramine obtained from Huntsman Corporation under the trade designation "JEFFAMINE ED-600" were used instead of DMAPA.
Example 29: CF3OCF2OCF2OCF2C(O)O +NH3CH2CH2CH2N(CH3)2
Example 29 was prepared according to the method of Example 25 except 10.2 grams (0.1 mole) of DMAPA were used. Example 30: (CF3OCF2OCF2OCF2C(O)O )3 +NH3CH2CH2 +NH2CH2CH2N+H3
Example 30 was prepared according to the method of Example 25 except 3.4 grams (0.03 mole) of diethylenetriamine were used instead of DMAPA.
Example 31 : CF3OCF2OCF2OCF2OCF2C(O)O +NH3CH2CH2CH2N(CH3)2
Example 31 was prepared according to the method of Example 25 except 37.8 grams of perfluoro-3,5,7,9-tetraoxadecanoic acid (obtained from Anles Ltd.) were used instead of perfluoro-3,5,7-trioxaoctanoic acid, and 10.2 grams (0.1 mole) of DMAPA were used.
Example 32: (CF3OCF2OCF2OCF2OCF2C(O)O )3 +NH3CH2CH2+NH2CH2CH2N+H3 Example 32 was prepared according to the method of Example 25 except 37.8 grams of perfluoro-3,5,7,9-tetraoxadecanoic acid (obtained from Anles Ltd.) were used instead of perfluoro-3,5,7-trioxaoctanoic acid, and 3.4 grams (0.03 mole) of diethylenetriamine were used instead of DMAPA.
Example 33: (CF3OCF2CF2CF2OCHFC(O)O )2 +NH3CH2CH2CH2N+H(CH3)2
Example 33 was prepared according to the method of Example 25 except 34.1 grams of 2-H-perfluoro-3,7-dioxaoctanoic acid were used instead of perfluoro-3,5,7- trioxaoctanoic acid.
2-H-Perfluoro-3,7-dioxaoctanoic acid was prepared was prepared from CF3OCF2CF2CF2OCHFC(O)ONH4, which was prepared according to the method described in U. S. Pat. App. Pub. No. 2007/0015864 (Hintzer et al.) in the Preparation of Compound 12, the disclosure of which preparation is incorporated herein by reference. The ammonium salt was treated with sulfuric acid, and the lower phase was separated and distilled.
Example 34: (CF3OCF2CF2CF2OCHFCF2C(O)O )2 +NH3CH2CH2CH2N+H(CH3)2
Example 34 was prepared according to the method of Example 25 except 39.2 grams of 3-H-perfluoro-4,8-dioxanonanoic acid were used instead of perfluoro-3,5,7- trioxaoctanoic acid. 3-H-Perfluoro-4,8-dioxanonanoic acid was prepared was prepared from CF3OCF2CF2CF2OCHFCF2C(O)ONH4, which was prepared according to the method described in U. S. Pat. App. Pub. No. 2007/0015864 (Hintzer et al.) in the Preparation of Compound 11, the disclosure of which preparation is incorporated herein by reference. The ammonium salt was treated with sulfuric acid, and the lower phase was separated and distilled.
Dynamic Surface Tension Measurement
Examples 25 to 34 were diluted with deionized water to the concentrations given in Table 4 (below). Surface tensions were measured for the solutions containing Examples 25 to 34 using a Kruss tensiometer (obtained from Kruss GmbH under the trade designation "KRUSS BUBBLE PRESSURE TENSIOMETER BP2") using the maximum bubble pressure technique and different surface ages at 22 0C. The results are summarized in Table 4 (below) for a surface age of 100 milliseconds.
Table 4.
Figure imgf000041_0001
Various modifications and alterations of this disclosure may be made by those skilled in the art without departing from the scope and spirit of this disclosure, and it should be understood that this disclosure is not to be unduly limited to the illustrative embodiments set forth herein.

Claims

What is claimed is:
1. A compound represented by formula:
(Rf-Q-X)8-Z; wherein
Rf is selected from the group consisting of: Rf-(O)r-CHF-(CF2)n-; [R^-(OVC(L)H-CF2-O]1n-W-; CF3CFH-O-(CF2)P-;
Figure imgf000042_0001
CF3-O-(CF2)3-O-CF2-;
Q is selected from the group consisting of a bond, -C(O)O" +NH(R')2-, -C(O)-N(R')-, and -C(O)-O-, wherein R' is selected from the group consisting of hydrogen and alkyl having from 1 to 4 carbon atoms; X is selected from the group consisting of alkylene, arylalkylene, and poly (alky leneoxy), wherein alkylene and arylalkylene are each optionally interrupted by at least one functional group independently selected from the group consisting of ether, amine, ester, amide, carbamate, and urea;
Z is selected from the group consisting of an ammonium group, an amine- oxide group, an amine, a carboxylate, a sulfonate, a sulfate, phosphate, a phosphonate, and an amphoteric group, with the proviso that when X is alkylene having at least 10 carbon atoms, Z may also be hydrogen, and with the further proviso that when X is poly (alky leneoxy), Z may also be selected from the group consisting of hydroxyl and alkoxy; Rf and Rf*3 independently represent a partially or fully fluorinated alkyl group having from 1 to 10 carbon atoms and optionally interrupted with at least one oxygen atom;
L is selected from the group consisting of F and CF3; W is selected from the group consisting of alkylene and arylene; r is 0 or 1 , wherein when r is 0, then Kf is interrupted with at least one oxygen atom; s is 1 or 2, wherein when s is 2, then Z is selected from the group consisting of an ammonium group, a phosphate, and a phosphonate; t is 0 or 1 ; m is 1, 2, or 3; n is 0 or 1 ; each p is independently a number from 1 to 6; and z is a number from 2 to 7.
2. The compound according to claim 1, wherein Rf is selected from the group consisting of:
Rf-(O)r-CHF-(CF2)n-; [R^-(O)1-C(L)H-CF2-O]111-W-; and CF3CFH-O-(CF2)p-.
3. The compound according to claim 1 or 2, wherein t and r are each 1, and wherein
Rf a and Rf*3 are independently selected from the group consisting of: fully fluorinated aliphatic groups having from 1 to 6 carbon atoms; and fully fluorinated groups represented by formula:
Figure imgf000043_0001
wherein
Rf 1 is a perfluorinated aliphatic group having from 1 to 6 carbon atoms; Rf and Rf are each independently perfluorinated alkylene having from 1 to 4 carbon atoms; and x and y are each independently a number from 0 to 4, wherein the sum of x and y is at least 1.
4. The compound according to claim 1 or 2, wherein t and r are each 0, and wherein Rfa and Rf*3 are independently a fully fluorinated group represented by formula:
Rf 4-[ORf 5]a-[ORf 6]b-O-CF2-, wherein
Rf4 is a perfluorinated aliphatic group having from 1 to 6 carbon atoms; Rf5 and Rf6 are each independently perfluorinated alkylene having from 1 to 4 carbon atoms; and a and b are each independently numbers from 0 to 4.
5. The compound according to claim 1 or 2, wherein Rf is selected from the group consisting of:
C3F7-O-CHF-;
CF3-O-CF2CF2-CF2-O-CHF-; CF3CF2CF2 -0-CF2CF2-CF2-O-CHF-; CF3-O-CF2-CF2-O-CHF-;
CF3-O-CF2-O-CF2-CF2-O-CHF-; CF3-(O-CF2)2-O-CF2-CF2-O-CHF-; CF3-(O-CF2)3-O-CF2-CF2-O-CHF-;
CF3-O-CHF-CF2-; CF3-O-CF2-CF2-O-CHF-CF2-;
CF3-CF2-O-CHF-CF2-;
CF3-CF2-CF2-O-CHF-CF2-;
CF3-O-CF2-CF2-CF2-O-CHF-CF2-;
CF3-O-CF2-O-CF2-CF2-O-CHF-CF2-; CF3-(O-CF2)2-O-CF2-CF2-O-CHF-CF2-;
CF3-(O-CF2)3-O-CF2-CF2-O-CHF-CF2-;
CF3-O-CF2-CHF-;
C3F7-O-CF2-CHF-;
CF3-O-CF2-CF2-CF2-O-CF2-CHF-; CF3-O-CF2-O-CF2-CF2-O-CF2-CHF-;
CF3-(O-CF2)2-O-CF2-CF2-O-CF2-CHF-;
CF3-(O-CF2)3-O-CF2-CF2-O-CF2-CHF-;
CF3-O-CF2-CHF-CF2-;
C2F5-O-CF2-CHF-CF2-; C3F7-O-CF2-CHF-CF2-;
CF3-O-CF2-CF2-CF2-O-CF2-CHF-CF2-; CF3-O-CF2-O-CF2-CF2-O-CF2-CHF-CF2-; CF3-(O-CF2)2-O-CF2-CF2-O-CF2-CHF-CF2-; and CF3-(O-CF2)S-O-CF2-CF2-O-CF2-CHF-CF2-.
6. The compound according to claim 5, wherein Rf is selected from the group consisting of CF3-O-CF2CF2-CF2-O-CHF-; CF3-O-CF2-CF2-CF2-O-CF2-CHF-;
CF3-O-CF2-CF2-CF2-O-CHF-CF2-; and CF3-O-CF2-CF2-CF2-O-CF2-CHF-CF2-.
7. The compound according to claim 1 or 2, wherein Rf is selected from the group consisting of: CF3-O-CHF-CF2-O-CH2-;
CF3-O-CF2-CF2-CF2-O-CHF-CF2-O-CH2-;
C3F7-O-CHF-CF2-O-CH2-;
C3F7-O-CHF-CF2-O-CH2-CH2-;
C3F7-O-CF2-CF2-O-CHF-CF2-OCH2-; C3F7-O-CF2-CF2-CF2-O-CHF-CF2-OCH2-;
C3F7-O-CF2-CHF-CF2-OCH2-; CF3-CHF-CF2-O-CH2-; and C3F7-CF2-CHF-CF2-OCH2-.
8. The compound according to claim 1, wherein Rf is CF3CFH-O-(CF2)P-.
9. The compound according to claim 7, wherein Rf is selected from the group consisting of CF3CFH-O-(CF2)3- and CF3CFH-O-(CF2)5-.
10. The compound according to claim 1, wherein Rf is CF3-(O-CF2)Z-, and wherein z is 3 or 4.
11. The compound according to claim 1, wherein Rf is CF3-O-(CF2)3-O-CF2-.
12. The compound according to any preceding claim, wherein Q is -C(O)-N(R')-, and wherein X is alkylene having up to 5 carbon atoms.
13. The compound according to any one of claims 1 to 11, wherein Q is -C(O)O- 4NH(R^2-, and wherein X is selected from the group consisting of alkylene having up to 5 carbon atoms, -[EOMR2O]8-[EO]^, and -[R2O]8-[EO]^[R2O]8-, wherein EO represents -CH2CH2O-; each R2O independently represents -CH(CH3)CH2O-, -CH2CH(CH3)O-, -CH(CH2CH3)CH2O-, -CH2CH(CH2CH3)O-, or -CH2C(CH3)2O-; each f is independently a number from 1 to 150; and each g is independently a number from 0 to 55.
14. The compound according to claim 13, wherein the compound is represented by a formula selected from the group consisting of
[Rf-C(O)O 4NH(R)2-X]2-NH(R)+RfC(O)O" and Rf-C(O)O 4NH(R)2-X-NH(R)2 +RfC(O)O", and wherein each R is independently selected from the group consisting of hydrogen and alkyl having from 1 to 6 carbon atoms.
15. The compound according to any one of claims 1 to 12, wherein Z is selected from the group consisting of -[N(R)3]+M", -N(O)(R^2, -N+(R)2-X^SO3A, and -N+(R)2-X^CO2A, wherein each R is independently selected from the group consisting of hydrogen and alkyl having from 1 to 6 carbon atoms; each R1 is independently selected from the group consisting of hydrogen and alkyl having from 1 to 6 carbon atoms, wherein alkyl is optionally substituted by at least one halogen, alkoxy, nitro, or nitrile group, or two R1 groups may join to form a 5 to 7-membered ring optionally containing at least one O, N, or S and optionally substituted by alkyl having 1 to 6 carbon atoms; each X1 is selected from the group consisting of alkylene and arylalkylene, wherein alkylene and arylalkylene are each optionally interrupted by at least one ether linkage;
M" is a counter anion; and
A is selected from the group consisting of hydrogen and a free anion.
16. The compound according to claim 15, wherein Z is -[N(R)3J+M", wherein each R and is independently hydrogen or methyl, and wherein M- is selected from the group consisting of chloride, acetate, iodide, bromide, methylsulfate, ethylsulfate, and formate.
17. The compound according to claim 15, wherein Z is -N(O)(R^2, -N+(R)2-X^SO3A, or -N+(R)2-X^CO2A, wherein each R and R1 are independently hydrogen or methyl, and wherein X1 is alkylene having up to 5 carbon atoms.
18. The compound according to any one of claims 1 to 12, wherein Z is selected from the group consisting of -P(O)(OY)2, -0-P(O)(OY)2, -SO3Y, -0-SO3Y, and -CO2Y, and wherein Y is selected from the group consisting of hydrogen and a counter cation.
19. The compound according to any one of claims 1 to 11, wherein X-Z is selected from the group consisting of:
-[EOMR2O]8-[EO]^R3; and
-[R2O]8-[EOMR2O]8-R3, wherein EO represents -CH2CH2O-; each R2O independently represents -CH(CH3)CH2O-, -CH2CH(CH3)O-, -CH(CH2CH3)CH2O-, -CH2CH(CH2CH3)O-, or -CH2C(CH3)2O-;
R3 is hydrogen or alkyl having up to 4 carbon atoms; each f is independently a number from 1 to 150; and each g is independently a number from 0 to 55.
20. A composition comprising the compound according to any preceding claim and at least one of organic solvent or water.
21. The composition according to claim 20, further comprising a non-fluorinated polymer.
22. The composition according to claim 21, wherein the non-fluorinated polymer is at least one of an acrylic polymer, a polyurethane, a polyolefm, a styrene-acrylate copolymer, a polyester, a polyamide, a vinyl polymer, a polydiene, or a cellulosic polymer.
23. A method comprising treating a surface with the composition according to any one of claims 20 to 22.
24. An article comprising a surface, wherein at least a portion of the surface is in contact with the compound according to any one of claims 1 to 19.
25. A method of making a foam, the method comprising combining at least a liquid, a gas, and the compound according to any one of claims 1 to 19 to make the foam.
26. A method of reducing the surface tension of a liquid, the method comprising combining at least the liquid with an amount of the compound according to any of claims 1 to 19 sufficient to reduce the surface tension of the liquid.
27. The method according to claim 26, wherein the surface tension of the liquid is reduced to an extent not less than when an equivalent liquid is combined with an amount of a surfactant, wherein the surfactant is the same as the compound except Rf is replaced with a group represented by formula CsF7-O-CF(CFs)-, and wherein the amount by weight of the surfactant is the same as the amount by weight of the compound.
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