WO2018118962A1 - Polymères anioniques fluorés et compositions les comprenant - Google Patents

Polymères anioniques fluorés et compositions les comprenant Download PDF

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WO2018118962A1
WO2018118962A1 PCT/US2017/067374 US2017067374W WO2018118962A1 WO 2018118962 A1 WO2018118962 A1 WO 2018118962A1 US 2017067374 W US2017067374 W US 2017067374W WO 2018118962 A1 WO2018118962 A1 WO 2018118962A1
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group
fluorinated polymer
hydrogen
independently
formula
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PCT/US2017/067374
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Wayne W. Fan
Kevin J. Rink
Frans A. Audenaert
Rudolf J. Dams
Yu Yang
Patricia M. Savu
Sean M. Smith
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3M Innovative Properties Company
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • C09D133/16—Homopolymers or copolymers of esters containing halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/22—Esters containing halogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L43/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium or a metal; Compositions of derivatives of such polymers
    • C08L43/02—Homopolymers or copolymers of monomers containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
    • C09D143/02—Homopolymers or copolymers of monomers containing phosphorus

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, stability (e.g., with respect to phase separation or foam half-life), easy-cleanability, and stain resistance.
  • fluorochemicals have been used to provide properties such as hydrophobicity and oleophobicity to various materials (e.g., ceramics, fibrous substrates and porous stones).
  • the present disclosure provides a fluorinated polymer that includes a first divalent unit represented by formula:
  • Rf represents a fluoroalkyl group having from 1 to 8 carbon atoms
  • R 1 is hydrogen or methyl
  • Q is a bond or -S0 2 -N(R)-, wherein R is alkyl having from 1 to 6 carbon atoms
  • m is an integer from 1 to 20.
  • the present disclosure provides this fluorinated polymer for use in an aqueous composition.
  • the aqueous composition may be a paint or coating composition.
  • the fluorinated polymer may be useful, for example, for making the resulting paint or coating easier to clean or more stain- resistant.
  • the present disclosure provides a composition including the aforementioned fluorinated polymer and a film-forming polymer.
  • the composition can also include at least one of a pigment, a thickener, or an inorganic filler.
  • the composition may be an aqueous composition with a pH of at least 7.
  • the fluorinated polymer described herein has several repeating units and therefore a higher molecular weight than monomeric fluoroalkyl surfactants, e.g., perfluoroalkyl diester and mono-ester phosphate surfactants.
  • monomeric fluoroalkyl surfactants e.g., perfluoroalkyl diester and mono-ester phosphate surfactants.
  • the fluorinated polymer described herein poses less health and safety concerns such as inhalation toxicity in compositions that are applied by spraying. When used in paint and coating compositions, the fluorinated polymers disclosed herein typically provide excellent surface properties and stain and soil resistant performance.
  • phrases “comprises at least one of followed by a list refers to comprising any one of the items in the list and any combination of two or more items in the list.
  • the phrase “at least one of followed by a list refers to any one of the items in the list or any combination of two or more items in the list.
  • solvent refers to a homogeneous liquid material (inclusive of any water with which it may be combined) that is capable of at least partially dissolving the fluorinated polymer disclosed herein at 25 °C.
  • alkyl group and the prefix “alk-” are inclusive of both straight chain and branched chain groups and of cyclic groups. Unless otherwise specified, alkyl groups herein have up to 20 carbon atoms. Cyclic groups can be monocyclic or polycyclic and, in some embodiments, have from 3 to 10 ring carbon atoms.
  • polymer refers to a composition having a structure which essentially includes the multiple repetition of units derived, actually or conceptually, from monomers of low relative molecular mass.
  • polymer encompasses oligomers. Polymers are usually a mixture of molecules having a distribution of molecular weights.
  • fluoroalkyl group includes linear, branched, and/or cyclic alkyl groups in which all C- H bonds are replaced by C-F bonds as well as groups in which hydrogen or chlorine atoms are present instead of fluorine atoms. In some embodiments, up to one atom of either hydrogen or chlorine is present for every two carbon atoms. In some embodiments of fluoroalkyl groups, when at least one hydrogen or chlorine is present, the fluoroalkyl group includes at least one trifluoromethyl group.
  • phosphate group refers to groups having the structure
  • a phosphate group is represented by formula -0-P(0)(OY)2, wherein each Y is independently hydrogen or a counter cation, that is bonded to a pendant group of the polymer.
  • phosphonate group refers to groups having the structure
  • each oxygen is independently bonded to hydrogen, a counter cation, or an alkyl group.
  • a phosphonate group is represented by formula -P(0)(OY)2, wherein each Y is independently hydrogen or a counter cation, that is bonded to a pendant group of the polymer.
  • the fluorinated polymer according to and useful for practicing the present disclosure comprises (e.g., at least 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, or at least 20 up to 30, 35, 40, 45, 50, 100, or up to 200) first divalent units independently represented by formula:
  • Q is a bond or -S02N(R)-, wherein R is alkyl having 1 to 4 carbon atoms (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, or isobutyl).
  • R is alkyl having 1 to 4 carbon atoms (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, or isobutyl).
  • Q is a bond.
  • Q is -S0 2 N(R)-.
  • R is methyl or ethyl
  • m is an integer from 1 to 11 (i.e., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or 11). In some of these embodiments, m is 1; in other of these embodiments, m is 2.
  • m is an integer from 2 to 11, 2 to 6, or 2 to 4. In some embodiments wherein Q is a bond, m is an integer from 1 to 6, 1 to 4, or 1 to 2. In embodiments wherein Q is a bond, it should be understood that the first divalent units may also be represented by formula:
  • fluorinated polymers according to the present disclosure comprise (e.g., at least 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, or at least 20 up to 30, 35, 40, 45, 50, 100, or up to 200) first divalent units independently represented by formula:
  • n is an integer from 2 to 20 (i.e., 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20). In some embodiments, n is an integer from 2 to 6 or 2 to 4.
  • R is alkyl having 1 to 6 carbon atoms (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, or n-hexyl). In some embodiments, R is methyl, ethyl, or n-hexyl.
  • each Rf independently represents a fluorinated alkyl group having from 1 to 8 (in some embodiments, 1 to 6, 2 to 6 or 2 to 4) carbon atoms (e.g., trifluoromethyl, perfluoroethyl, 1,1,2,2-tetrafluoroethyl, 2-chlorotetrafluoroethyl, perfluoro-n-propyl, perfluoroisopropyl, perfluoro-n-butyl, 1,1,2,3,3,3-hexafluoropropyl, perfluoroisobutyl, perfluoro-seobutyl, or perfluoro-/er -butyl, perfluoro-n-pentyl, pefluoroisopentyl, or perfluorohexyl).
  • 1 to 8 in some embodiments, 1 to 6, 2 to 6 or 2 to 4
  • carbon atoms e.g., trifluoromethyl, perfluoroethyl, 1,
  • Rf is perfluorobutyl (e.g., perfluoro-n-butyl, perfluoroisobutyl, or perfluoro-seobutyl).
  • Rf is perfluoropropyl (e.g., perfluoro-n-propyl or perfluoroisopropyl).
  • Rf may contain a mixture of fluoroalkyl groups (e.g., with an average of up to 8, 6, or 4 carbon atoms).
  • each Rf 2 independently represents a fluorinated alkyl group having from 1 to 8 (in some embodiments, 1 to 8, 1 to 6, or 2 to 4) carbon atoms (e.g., trifluoromethyl, perfluoroethyl, 1,1,2,2-tetrafluoroethyl, 2-chlorotetrafluoroethyl, perfluoro-n-propyl, perfluoroisopropyl, perfluoro-n-butyl, 1, 1,2,3, 3,3-hexafluoropropyl,
  • 1 to 8 in some embodiments, 1 to 8, 1 to 6, or 2 to 4
  • carbon atoms e.g., trifluoromethyl, perfluoroethyl, 1,1,2,2-tetrafluoroethyl, 2-chlorotetrafluoroethyl, perfluoro-n-propyl, perfluoroisopropyl, perfluoro-n-butyl, 1, 1,2,3, 3,
  • Rf 2 is perfluorobutyl (e.g., perfluoro-n-butyl, perfluoroisobutyl, or perfluoro-seobutyl). In some embodiments, Rf 2 is
  • Rf 2 may contain a mixture of fluoroalkyl groups (e.g., with an average of up to 8, 6, or 4 carbon atoms).
  • the first divalent units have up to 6 fluorinated carbon atoms.
  • R 1 is hydrogen or methyl. In some embodiments, R 1 is hydrogen. In some embodiments, R 1 is methyl.
  • each R 1 , Rf, Q, and m and Rf 2 , R, and n can be independently selected.
  • the second divalent unit in the fluoropolymer according to the present disclosure comprises a poly(alkyleneoxy) group.
  • the poly (alky leneoxy) group in fluorinated polymers according to and useful for practicing the present disclosure can comprise a plurality (i.e., multiple) of repeating alkyleneoxy groups having from 2 to 4 or 2 to 3 carbon atoms (e.g., -CH 2 CH 2 0- -CH(CH 3 )CH 2 0-,
  • the poly(alkyleneoxy) group comprises a plurality of ethoxy groups, propoxy groups, butoxy groups, or combinations thereof. In some embodiments, the poly(alkyleneoxy) group comprises a plurality of ethoxy groups, propoxy groups, or combinations thereof.
  • the poly(alkyleneoxy) group may have a number average molecular weight of at least 200, 300, 500, 700, or even at least 1000 grams per mole up to 2000, 4000, 5000, 8000, 10000, 15,000, or even up to 20000 grams per mole. Two or more differing alkyleneoxy groups may be distributed randomly in the series or may be present in alternating blocks.
  • the poly(alkyleneoxy) group may be pendant from the polymer chain, or it may be a segment incorporated into the polymer backbone.
  • the fluoropolymer according to the present disclosure may also have both a poly(alkyleneoxy) group pendant from the polymer chain and a poly (alkyleneoxy) segment incorporated into the polymer backbone.
  • the fluorinated polymer comprises at least one (e.g., at least 1, 2, 5, 10, 15, 20, or at least 25) second divalent unit represented by formula:
  • each R 2 is independently hydrogen or methyl (in some embodiments, hydrogen and in some embodiments, methyl).
  • Each R 3 is independently alkyl having up to 4 carbon atoms (e.g., methyl, ethyl, n-propyl, isopropyl, butyl, isobutyl, or t-butyl), -P(0)(OY)2, wherein each Y is independently as described below in connection with formula XVIII, or hydrogen.
  • R 3 is R 3a , and each R 3a is independently alkyl having up to 4 carbon atoms (e.g., methyl, ethyl, n-propyl, isopropyl, butyl, isobutyl, or t-butyl) or hydrogen.
  • EO represents -CH 2 CH 2 0-.
  • Each R 4 0 is
  • each R 4 0 independently represents -CH(CH 3 )CH 2 0- or -CH 2 CH(CH 3 )0-).
  • Each p is independently a value from 0 to 150 (in some embodiments, from 7 to about 130, or from 14 to about 130, or from 10 to 20); and each q is independently a value from 0 to 150 (in some embodiments, from about 20 to about 100, 1 to 55, or from about 9 to about 25, or from 15 to 25).
  • the sum p + q is at least 5 (in some embodiments, at least 10 or at least 20.) In some embodiments, the ratio p/q has a value from at least 0.5, 0.75, 1 or 1.5 to 2.5, 2.7, 3, 4, 5, or more.
  • At least one of the second divalent units is represented by formula XVI:
  • R 2 is hydrogen or methyl (in some embodiments, hydrogen, and in some embodiments, methyl).
  • R 4 is independently alkyl having from 1 to 4 carbon atoms (e.g., methyl, ethyl, n-propyl, isopropyl, n- butyl, or isobutyl). In some embodiments, R 4 is methyl or ethyl.
  • r is in a range from 1 to 50 (in some embodiments, 1 to 25, 5 to 25, or 5 to 20).
  • the fluorinated polymer may include at least one (e.g., at least 1, 2, 5, 10, 15, 20, or at least 25) and up to 200, 100, or 50 of these second divalent units.
  • the second divalent unit is represented by formula:
  • the second divalent unit may be a sulfur-terminated segment (e.g., -S(0)o-2-C 3 H 2s -C(0)-0-(EO)p-C(0)-CsH 2s -S(0)o-2-,
  • the second divalent unit comprising the poly(alkyleneoxy) group also comprises a phosphate group.
  • at least one of the second divalent units is represented by formula:
  • p, q, R 2 , EO, and R 4 0 are as defined above for formulas XII and XIII in any of their embodiments, and Y is independently hydrogen or a counter cation.
  • the counter cation may be any of those described below in connection with formula XVIII.
  • each p, q, r, Y, R 2 , R 3 , R 3a , R 4 , and R 4 0 can be independently selected.
  • fluorinated polymers according to and useful for practicing the present disclosure further comprise at least one (e.g., at least 1, 2, 5, 10, 15, 20, or at least 25) third divalent unit represented by formula:
  • the third divalent units are optional in the fluorinated polymer of the present disclosure.
  • the second divalent unit includes a phosphate or phosphonate group
  • the third divalent unit need not be present.
  • the fluorinated polymer includes a third divalent unit.
  • Q 1 is -0-, -S-, or -N(R 7 )- (in some embodiments, -0-).
  • Each R 7 is independently hydrogen or alkyl having from 1 to 4 carbon atoms (e.g., methyl, ethyl, n-propyl, isopropyl, butyl, isobutyl, or t-butyl).
  • V is alkylene that is optionally interrupted by at least one ether linkage (i.e., -0-) or amine linkage (i.e., -N(R 7 )-). In some embodiments, V is not a poly(alkyleneoxy) group.
  • V is alkylene that is optionally interrupted by one ether linkage (i.e., -0-), thioether (i.e., -S-) linkage, or amine linkage (i.e., -N(R 7 )-).
  • V is alkylene having from 2 to 4 (in some embodiments, 2) carbon atoms.
  • each Z is independently selected from the group consisting of -P(0)(OY)2 and -0-P(0)(OY)2.
  • each R' is independently hydrogen or methyl (in some embodiments, hydrogen, and in some embodiments, methyl), and each Y is independently selected from the group consisting of hydrogen, a counter cation, and an alkyl group. In some embodiments, each Y is independently selected from hydrogen and a counter cation. In some embodiments, each Y is hydrogen. In some embodiments, each Y is a counter cation.
  • Y counter cations include alkali metal (e.g., sodium, potassium, and lithium), ammonium, mono-, di-, tri- or tetraalkyl 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 atom,
  • Y is alkyl having from 1 to 4 carbon atoms (e.g., methyl, ethyl, n-propyl, isopropyl, butyl, isobutyl, or t-butyl).
  • a combination of different third divalent units may be useful. When there is more than one third divalent unit, each R', Z, Y, Q 1 , and V can be independently selected.
  • the first divalent units independently represented by Formula X, XIa, or Xlb are present in a range from 10 to 60 (in some embodiments, from 10 to 55, from 15 to 50, from 20 to 50, from 20 to 45, or from 25 to 45) weight percent, based on the total weight of the fluorinated polymer.
  • the second divalent unit is present in an amount of at least 30 percent by weight, based on the total weight of the fluorinated polymer. In some embodiments, the second divalent units are present in a range from 30 to 90 (in some embodiments, from 30 to 75, from 30 to 65, or from 35 to 65) weight percent, based on the total weight of the fluorinated polymer. This is advantageous because lower amounts of fluorinated monomers may be used; therefore, the fluorinated polymer may be lower in cost. Even with a relatively low amount of fluorinated carbons in the fluorinated polymer, useful soil resistance can be achieved, as shown in the Examples, below.
  • the fluorinated polymer comprises the optional third divalent unit, and the third divalent unit is present in an amount up to 20 percent by weight, based on the total weight of the fluorinated polymer.
  • the third divalent units are present in a range from 1 to 20 (in some embodiments, from 1 to 15, from 1 to 10, or from 1 to 5) weight percent, based on the total weight of the fluorinated polymer.
  • the combination of the poly(alkyleneoxy) group and the phosphate group aids in the solubility of the fluorinated polymer in aqueous compositions.
  • the presence of the poly(alkyleneoxy) groups in the second divalent unit allows for fewer phosphate groups to be present in the fluorinated polymer to achieve good solubility in aqueous compositions. While the phosphate groups are beneficial for promoting solubility in the aqueous compositions and imparting soil and stain resistance to the composition, phosphate groups can be sensitive to certain cations (e.g., magnesium and calcium) found in the aqueous compositions. For compositions that contain magnesium and calcium ions, for example, the presence of too many phosphate groups can cause precipitation in the aqueous composition.
  • certain cations e.g., magnesium and calcium
  • the first and second divalent groups and optionally third divalent units or any other divalent units present are randomly connected.
  • the fluorinated polymer according to the present disclosure and/or useful in the compositions according to the present disclosure is represented by formula:
  • Rf, Q, m, EO, R 4 0, p, q, Q 1 , V, Y, R', R 1 , R 2 , and R 3 are as defined above in any of their embodiments, x is in a range from 1 to 100 or more, y is in a range from 1 to 150 or more, and z is in a range from 1 to 50 or more, or x, y, and z are any of the ranges described above for the number of divalent units. It should be understood that the representation of the order of the divalent units in this formula is for convenience only and not meant to specify that the copolymers are block copolymers. Random copolymers having first, second, and third divalent units are also included in the representation.
  • divalent units of formula XIII, XIV, XV, and XVI may also be used instead of the divalent unit of formula XII.
  • divalent units of formula XVII and XVIII may be used instead of the divalent unit of formula XVIIIb.
  • the fluorinated polymer according to the present disclosure and/or useful in the compositions according to the present disclosure is represented by formula:
  • Rf, Q, m, EO, R 4 0, p, q, Y, R 1 and R 2 are as defined above in any of their embodiments, x is in a range from 1 to 100 or more and y is in a range from 1 to 150 or more, or x and y are any of the ranges described above for the number of divalent units. It should be understood that the representation of the order of the divalent units in this formula is for convenience only and not meant to specify that the copolymers are block copolymers. Random copolymers having first and second divalent units are also included in the representation. Also, in this formula divalent units of formula XX may also be used instead of the divalent unit of formula XIX.
  • fluorinated polymers useful for practicing the present disclosure further comprise at least one (e.g., at least 1, 2, 5, 10, 15, 20, 25, or at least 50) divalent unit represented by Formula XXI:
  • each R 6 is independently hydrogen or methyl (in some embodiments, hydrogen, in some embodiments, methyl), and wherein each R 5 is independently alkyl having from 1 to 30 (in some embodiments, 1 to 25, 1 to 20, 1 to 10, 4 to 25, 8 to 25, or 12 to 25) carbon atoms. In some embodiments, each R 5 is independently alkyl having up to 8 carbon atoms (e.g., methyl, ethyl, n-propyl, isopropyl, n- butyl, iso-butyl, n-pentyl, neopentyl, hexyl, heptyl, or octyl).
  • R 5 is hexadecyl or octadecyl.
  • fluorinated polymers useful for practicing the present disclosure are substantially free divalent units represented by formula XXI.
  • Substantially free of units of formula XXI can mean free of these divalent unit or having up to 5, 4, 3, 2, 1, or less than 1 percent by weight of these divalent units, based on the total weight of the fluorinated polymer. Units of formula XXI are typically hydrophobic and may compromise the solubility of the fluorinated polymer in water. Fluorinated polymers according to the present disclosure are generally considered to be anionic polymers. In some embodiments, including any of the aforementioned embodiments, fluorinated polymers according to and useful for practicing the present disclosure can be essentially free of cationic and amphoteric divalent units such as those described in U.S. Pat. Appl. Pub. No.
  • Essentially free of cationic and amphoteric divalent units can mean free of these divalent unit or having up to 1, 0.5, 0.1, 0.05, 0.01, or less than 0.01 percent by weight of these divalent units, based on the total weight of the fluorinated polymer.
  • Fluorinated polymers disclosed herein can be prepared, for example, by polymerizing a mixture of components typically in the presence of an initiator.
  • polymerizing it is meant forming a polymer or oligomer that includes at least one identifiable structural element due to each of the components.
  • the polymer that is formed has a distribution of molecular weights and compositions.
  • the polymer may have one of many structures (e.g., a random or graft copolymer or a block copolymer).
  • the components that are useful for preparing the polymers disclosed herein include a fluorinated free-radically polymerizable monomer independently represented by formula
  • the components that are useful for preparing the polymers disclosed herein include a poly(alkyleneoxy) acrylate (e.g., monoacrylate, diacrylate, or a mixture thereof).
  • a poly(alkyleneoxy) acrylate e.g., monoacrylate, diacrylate, or a mixture thereof.
  • Some alky leneoxy -containing polymerizable compounds are commercially available (e.g., polyoxyalkylene glycol acrylates and diacrylates (e.g., diethylene glycol diacrylate, tri(ethylene glycol) dimethacrylate, tri(ethylene glycol) divinyl ether, and available, for example, from Nippon Oil & Fats Company, Tokyo, Japan under the trade designation "BLEMMER").
  • alky leneoxy -containing polymerizable compounds can be prepared by known methods, for example, combining one or two equivalents of acryloyl chloride or acrylic acid with a polyethylene glycol or a monoalkyl ether thereof having a molecular weight of about 200 to 10,000 grams per mole (e.g., those available from Dow Chemical Company, Midland, MI, under the trade designation "CARBOWAX”) or a block copolymer of ethylene oxide and propylene oxide having a molecular weight of about 500 to 15000 grams per mole (e.g., those available from BASF Corporation, Ludwigshafen, Germany, under the trade designation "PLURONIC”).
  • the reaction of acrylic acid with a poly(alkylene oxide) is typically carried out in the presence of an acid catalyst and a polymerization inhibitor at an elevated temperature in a suitable solvent; (see, e.g., Example 1 of U. S. Pat. No. 3,787,351 (Olson), the disclosure of which is incorporated herein by reference).
  • Sulfur-terminated polyalkyleneoxy segments can be incorporated into the fluorinated polymers by copolymerization of a difimctional mercaptan, which can react with fluorinated acrylates (e.g.,
  • Examples of difimctional mercaptans include HS-C 3 H 2s -C(0)-0-(EO) p -C(0)-C 3 H 2s -SH, HS- C s H 2s -C(0)-0-(EO) p -(R 4 0) q -(EO) p -C(0)-C 3 H 2s -SH, or HS-C 3 H 2s -C(0)-0-(PO) q -(EO) p -(PO) q -C(0)-C 3 H 2s -SH, wherein p, q, EO, and R 4 0 are as defined above for formulas XII and XIII in any of their embodiments and s is an integer from 1 to 5, or in some embodiments, 2 to 3.
  • the resulting polymer or oligomer can then optionally be oxidized using conventional techniques.
  • Difimctional mercaptans can be prepared, for example, by reaction of a diol-functional polyethylene glycol or a block copolymer of ethylene oxide and propylene oxide with, for example, mercaptoacetic acid or mercaptopropionic acid.
  • polyalkyleneoxy -containing diacrylates can be treated with H 2 S or other sulfhydryl-containing compounds according to the methods of U.S. Pat. No. 3,278,352 (Erickson), incorporated herein by reference, to provide mercaptan-terminated polyalkyleneoxy compounds.
  • Third divalent units of Formula XVIII and XVIIIb can be incorporated into the fluorinated polymers disclosed herein by copolymerization of a compound of formula
  • Useful compounds of these formulas include ethylene glycol methacrylate phosphate and polyethylene glycol methacrylate phosphate.
  • Mono (or di) acryloxyethyl acid phosphate, dimethacryloxyethyl acid phosphate, mono (or di) aery loxy propyl acid phosphate, mono (or di) methacryloxypropyl acid phosphate, and 2-methacryloxyethyl acid phosphate monoethanolamine mono salt may also be useful for incorporating a pendant phosphate group into a polymer.
  • the thiol-terminated monomer can be reacted with allyl phosphonic acid or a salt thereof under free-radical conditions.
  • a polymer made by copolymerization of a compound of formula Rf 2 -Q-(C m H 2m )-0-C(0)-C(R 1 ) CH 2 or
  • a poly(alkyleneoxy) acrylate e.g., monoacrylate, diacrylate, or a mixture thereof
  • P 2 03 ⁇ 4, POCI3, or pyrophosphoric acid at elevated temperature using conventional techniques.
  • any of the hydroxyl-terminated monomers useful for making the second divalent units described above in any of their embodiments can be treated with P 2 03 ⁇ 4, POCI3, or pyrophosphoric acid at elevated temperature using conventional techniques to make acrylates and methacrylates including phosphate groups.
  • a terminal hydroxyl group can be converted to a thiol using conventional functional group transformation.
  • the thiol terminated polymer can be reacted with allyl phosphonic acid or a salt thereof under free-radical conditions.
  • any of the hydroxyl-terminated monomers useful for making the second divalent units described above in any of their embodiments can be converted to thiol-terminated monomers using conventional functional group transformation.
  • the thiol-terminated monomer can be reacted with allyl phosphonic acid or a salt thereof under free-radical conditions.
  • Fluorinated polymers useful for practicing the present disclosure may also be preparable by adding additional monomers to the polymerization reaction.
  • a compound formula for example, a compound formula
  • HO-V-0-C(0)-C(R') CH 2 , wherein R' and V are as defined above may be used.
  • these monomers include hydroxyethyl methacrylate.
  • Other examples include vinylidene chloride, vinyl chloride, silicone acrylates available, for example, from Shin-Etsu Silicones of America, Inc., Akron, OH, under the trade designation "X22-2426", and urethane acrylates available, for example, from Sartomer Company, Exton, PA under the trade designation "CN966J75.
  • allyl esters e.g., allyl acetate and allyl heptanoate
  • vinyl ethers or allyl ethers e.g., cetyl vinyl ether, dodecylvinyl ether, 2- chloroethylvinyl ether, or ethylvinyl ether
  • alpha-beta unsaturated nitriles e.g., acrylonitrile, methacrylonitrile, 2-chloroacrylonitrile, 2-cyanoethyl acrylate, or alkyl cyanoacrylates
  • alpha-beta- unsaturated carboxylic acid derivatives e.g., allyl alcohol, allyl glycolate, acrylamide, methacrylamide, n- diisopropyl acrylamide, or diacetoneacrylamide
  • styrene and its derivatives e.g., vinyltolu
  • fluorinated polymers useful for practicing the present disclosure are free of divalent units comprising a pendant silane group and free of silane terminal groups.
  • the polymerization reaction can be carried out in the presence of an added free-radical initiator.
  • Free radical initiators such as those widely known and used in the art may be used to initiate
  • the polymer or oligomer that is formed is a random graft copolymer. In some embodiments, the polymer or oligomer that is formed is a block copolymer.
  • the polymerization reaction is carried out in solvent.
  • the components may be present in the reaction medium at any suitable concentration, (e.g., from about 5 percent to about 80 percent by weight based on the total weight of the reaction mixture).
  • suitable solvents include aliphatic and alicyclic hydrocarbons (e.g., hexane, heptane, cyclohexane), aromatic solvents (e.g., benzene, toluene, xylene), ethers (e.g., diethyl ether, glyme, diglyme, and diisopropyl ether), esters (e.g., ethyl acetate and butyl acetate), alcohols (e.g., ethanol and isopropyl alcohol), ketones (e.g., acetone, methyl ethyl ketone and methyl isobutyl ketone), halogenated solvents (e.g.,
  • hydrofluoroethers available, for example, from 3M Company, St. Paul, MN under the trade designations "HFE-7100” and "HFE-7200"), and mixtures thereof.
  • Polymerization can be carried out at any temperature suitable for conducting an organic free- radical reaction. Temperature and solvent for a particular use can be selected by those skilled in the art based on considerations such as the solubility of reagents, temperature required for the use of a particular initiator, and desired molecular weight. While it is not practical to enumerate a particular temperature suitable for all initiators and all solvents, generally suitable temperatures are in a range from about 30 °C to about 200 °C (in some embodiments, from about 40 °C to about 100 °C, or from about 50 °C to about 80 °C). Free-radical polymerizations may be carried out in the presence of chain transfer agents.
  • Typical chain transfer agents that may be used in the preparation compositions according to the present invention include hydroxyl-substituted mercaptans (e.g., 2-mercaptoethanol, 3-mercapto-2-butanol, 3-mercapto-2- propanol, 3-mercapto-l-propanol, and 3-mercapto-l,2-propanediol (i.e., thioglycerol)); poly(ethylene glycol)-substituted mercaptans; carboxy-substituted mercaptans (e.g., mercaptopropionic acid or mercaptoacetic acid): amino-substituted mercaptans (e.g., 2-mercaptoethylamine); difunctional mercaptans (e.g., di(2-mercaptoethyl)sulfide); and aliphatic mercaptans (e.g., octylmercaptan, dodecy
  • Adjusting, for example, the concentration and activity of the initiator, the concentration of each of the reactive monomers, the temperature, the concentration of the chain transfer agent, and the solvent using techniques known in the art can control the molecular weight of a polyacrylate polymer or copolymer.
  • fluorinated polymers disclosed herein have weight average molecular weights in a range from 1000 grams per mole to 100,000 grams per mole. In some embodiments, the weight average molecular weight is at least 2000, 3000, 4000, 5000, 6000, 7000, 8000, 9000, or 10000 grams per mole up to 30,000, 40,000, 50,000, 60,000, 70,000, 80,000, or up to 90,000 grams per mole. Fluorinated polymers disclosed herein typically have a distribution of molecular weights and compositions. Weight average molecular weights can be measured, for example, by gel permeation chromatography (i.e., size exclusion chromatography) using techniques known to one of skill in the art.
  • gel permeation chromatography i.e., size exclusion chromatography
  • the fluorinated polymer according to the present disclosure is substantially free of volatile organic solvent.
  • “Substantially free of volatile organic solvent” can mean that volatile organic solvent may be present (e.g., from synthesis of the fluorinated polymer, a previous synthetic step, or in a commercially available monomer) in an amount of up to 2.5 (in some embodiments, up to 2, 1, 0.5, 0.1, 0.05, or 0.01) percent by weight, based on the total weight of the composition.
  • “Substantially free of volatile organic solvent can also mean free of volatile organic solvent. Volatile organic solvents are typically those have a boiling point of up to 150 °C at atmospheric pressure.
  • a volatile organic solvent can be a volatile organic compound (VOC) as defined in the California Consumer Products Regulations, Subchapter 8.5, Article 2, 94508, last amended September 17, 2014 (Register 2014, No. 38).
  • VOC volatile organic compound
  • a person skilled in the art may understand a volatile organic solvent as a solvent not listed as "exempt” or otherwise excluded in the California Consumer Products Regulations, Subchapter 8.5, Article 2, 94508, last amended September 17, 2014 (Register 2014, No. 38).
  • VOCs include hydrocarbon solvents (e.g., benzene, toluene, xylenes, and d-limonene); acyclic and cyclic ketones (e.g., pentanone, hexanone, cyclopentanone, and cyclohexanone); acyclic or cyclic acetals, ketals or ortho esters (e.g., diethoxy methane, dimethoxy methane, dipropoxy methane, dimethoxy ethane, diethoxy ethane, dipropoxy ethane, 2,2-dimethoxy propane, 2,2-diethoxy propane, 2,2- dipropoxy propane, 2,2-dimethyl-l,3-dioxalane, trimethyl orthoformate, triethyl orthoformate, trimethyl orthoacetate, triethyl orthoacetate, trimethyl orthobenzoate, and triethyl ortho
  • compositions according to the present disclosure that include the fluorinated polymer disclosed herein according to any of the above embodiments can also include at least one polymeric material, typically a film-forming polymer.
  • suitable polymers include acrylic polymers, (e.g., poly(methyl methacry late-co-ethyl acrylate) or poly(methyl aery late-co-acrylic acid)); polyurethane s, (e.g., reaction products of aliphatic, cycloaliphatic or aromatic diisocyanates with polyester glycols or polyether glycols); polyolefins, (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.
  • the film-forming polymer comprises at least one of an acrylate, methacrylate, vinyl, styrene, methyl styrene, or acrylonitrile.
  • the film-forming polymer comprises at least one of an acrylate, methacrylate, or acrylonitrile.
  • compositions including such film-forming polymers may be useful, for example, as paints and coatings.
  • compositions according to the present disclosure that include a film- forming polymer further include water.
  • Methods and materials for preparing aqueous emulsions or latexes of any of the film-forming polymers described above are known, and many of such waterborne formulations are available from commercial sources.
  • the film- forming polymer is selected from the group consisting of an acrylic polymer, a polyurethane, polystyrene, and a copolymer of styrene and at least one acrylate.
  • Waterborne compositions according to the present disclosure may also contain one or more cosolvents (e.g., coalescing solvents) including ethers of polyhydric alcohols (e.g., ethylene glycol monomethyl (or monoethyl) ether, diethylene glycol methyl (or ethyl or butyl) 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,
  • cosolvents e.g., coalescing solvents
  • ethers of polyhydric alcohols e.g., ethylene glycol monomethyl (or monoethyl) ether, diethylene glycol
  • polypropylene glycol polypropylene glycol
  • 2-phenoxyethanol dibutylphthalate
  • 2,2,4-trimethyl-l,3-pentanediol monoisobutyrate an ester alcohol available from Eastman Chemical Company, Kingsport, TN, under the trade designation "TEXANOL").
  • Other water-miscible organic solvents that may be added to the composition include alcohols having 1 to 4 carbon atoms (e.g., methanol, ethanol, isopropanol, or isobutanol); amides and lactams, (e.g., ⁇ , ⁇ -dimethylformamide, N,N-dimethylacetamide, or N- methylpyrrolidone); ketones and ketoalcohols (e.g., acetone, cyclohexanone, methyl isobutyl ketone, diacetone alcohol); ethers (e.g., tetrahydrofuran, dimethoxyethane, and dioxane); esters (e.g., methyl acetate); propylene carbonate; dimethylsulfoxide; sulfolane; l,3-dimethyl-2-imidazolidinone; and combinations thereof.
  • alcohols having 1 to 4 carbon atoms e.g., m
  • Coalescing solvent is preferably utilized at a level between about 12 to 60 grams (e.g., about 40 grams) of coalescing solvent per liter of the aqueous composition or at about 20 to 30 weight percent based on the weight of the polymer solids in the aqueous composition.
  • the composition is substantially free of VOCs as described above, and/or no coalescing solvent is used in the formulation.
  • the composition according to the present disclosure further comprises at least one pigment, including either natural or synthetic pigments.
  • useful pigments include various clays (e.g., natural or calcined clays), calcium carbonate (e.g., natural or precipitated calcium carbonate), mica, silicas (e.g., natural or synthetic pyrogenic silicas), talcs, engineered molecules, blanc fixe, lithopone, zinc sulfide, lead titanate, antimony oxide, zirconium oxide, leaded zinc oxide, titanium dioxide (e.g., rutile or anatase), carbon black, phthalo blue, hansa yellow, red iron oxide, brown oxide, ochres, umbers, and combinations of any of these.
  • clays e.g., natural or calcined clays
  • calcium carbonate e.g., natural or precipitated calcium carbonate
  • mica e.g., silicas (e.g., natural or synthetic pyrogenic silicas), talcs, engineered molecules
  • the composition according to the present disclosure further comprises at least one inorganic filler.
  • useful inorganic fillers include diatomaceous earth, talc, lime, barytes, clay, sand, nepheline syenite, and ceramic microspheres (e.g., solid beads or glass bubbles).
  • the inorganic filler includes titanium dioxide, carbon black, calcium carbonate, nepheline syenite, ceramic microspheres, and combinations thereof. Examples of commercially available ceramic microspheres include glass bubbles marketed by 3M Company, Saint Paul, Minnesota, as "3M
  • GLASS BUBBLES in grades Kl, K15, K20, K25, K37, K46, S15, S22, S32, S35, S38, S38HS, S60, and S60HS; ceramic microspheres marketed by 3M Company under the trade designation "3M CERAMIC MICROSPHERES” (e.g., grades W-610 and W-410); silica-alumina ceramic hollow spheres with thick walls marketed by Valentine Chemicals of Lockport, Louisiana, as "ZEEOSPHERES CERAMIC MICROSPHERES” in grades G-200, G200-PC, G-400, G600, G-800, G-850,N-200, N-200PC, N-400, N-600, N-800, N1000, and N1200; solid glass spheres available from Cospheric LLC, Santa Barbara, California as "SODA LIME SOLID GLASS MICROSPHERES", “BOROSILICATE SOLID GLASS MICROSPHERES”, "BARIUM
  • inorganic fillers and pigment particles may be present in a variety of useful amounts.
  • the filler and pigment particles combined may provide in a range from 20 percent to 80 percent by weight of the paint or coating composition, based on the total weight of the composition. In some embodiments, the filler and pigment particles combined may provide in a range from 25 percent to 55 percent or 30 percent to 50 percent by weight of the paint or coating composition.
  • compositions according to the present disclosure may also include biocides (e.g., fungicides or mildewcides), surfactants (e.g., for improved wetting or leveling), emulsifiers, defoamers, pH adjuster, anticorrosive agents, dispersants, rust inhibitors, thickeners (i.e., that may be polymeric or inorganic), UV absorbers, fireproofing agents, or any combination of these. Other additives may also be useful. Such typical ingredients are listed, for example, in TECHNOLOGY OF PAINTS, VARNISHES AND LACQUERS, edited by C. R. Martens, R. E. Kreiger Publishing Co., p. 515 (1974).
  • compositions according to the present disclosure are neutral to alkaline.
  • a pH adjuster is added to provide the composition with a pH of at least 7, in some embodiments, a pH of 7 to 9.
  • the thickener may be an associative thickener.
  • useful associative thickeners include hydrophobically modified alkali swellable acrylic copolymers and hydrophobically modified urethane copolymers.
  • associative thickeners include polyacrylic acids (available, for example, from Rohm & Haas Co., Philadelphia, Pa., under the trade designations "ACRYSOL RM-825" and “QR-708 Rheology Modifier”) and activated attapulgite (available from Engelhard, Iselin, N.J., under the trade designation "ATTAGEL 40").
  • a thickener such as magnesium aluminum silicate, sold by R.T. Vanderbilt Co., Norwalk, CT, under the trade designation "VEEGUM T” is another suitable thickening agent that may be used at 0.3 to about 0.6 % by weight, based on the total weight of the composition.
  • xanthan gums e.g., available from CP Kelco, Houston, TX, under the trade designation "KELZAN” and from R. T. Vanderbilt Co. under the trade designation “VANZAN”
  • diutan gums e.g., available from CP Kelco under the trade designation "GEOVIS XT”
  • gellan gums e.g., available from CP Kelco under the trade designation "KELCOGEL”
  • carrageenan gums e.g., available from CP Kelco under the trade designation "GENUVISCO X-906-02
  • hydrocolloids e.g., available from Noveon, Inc. under the trade designation "NOVEGUM C865"
  • the fluorinated polymer is present in the composition at 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, based on the total weight of the treatment composition.
  • the amount of the fluorinated polymer in the compositions may be in a range of from 0.01 to 10, 0.1 to 10, 0.1 to 5, 1 to 10, 0.5 to 2, 1 to 5, 0.001 to 1, 0.001 to 0.5, or 0.01 to 0.3 percent by weight, based on the total weight of the composition. Lower and higher amounts of the fluorinated polymer in the compositions may also be used, and may be desirable for some applications.
  • compositions described herein including fluorinated polymers can be combined using techniques known in the art for combining these types of materials, including using conventional magnetic stir bars or mechanical mixer (e.g., in-line static mixer and recirculating pump).
  • Latex paint compositions can be prepared using conventional techniques. For example, some of the paint ingredients are generally blended together under high shear to form a mixture commonly referred to as "the grind" by paint formulators. The consistency of this mixture is comparable to that of mud, which is desirable in order to efficiently disperse the ingredients with a high shear stirrer. During the preparation of the grind, high shear energy is used to break apart agglomerated pigment particles.
  • the ingredients not included in the grind are commonly referred to as "the letdown".
  • the letdown is usually much less viscous than the grind, and is usually used to dilute the grind to obtain a final paint with the proper consistency.
  • the final mixing of the grind with the letdown is typically carried out with low shear mixing. Paints are generally prepared by adding the latex polymer in the letdown.
  • Waterborne compositions according to the present disclosure are typically applied, dried, and optionally heated, leaving the finished product with a solid coating. They may be applied by a variety of useful methods (e.g., brushing, mopping, bar coating, spraying, dip coating, gravure coating, or roll coating).
  • the composition is allowed to dry on the substrate surface at a temperature in a range from about 10 °C (50 °F) to about 40 °C (100 °F) and a humidity in a range from about 20% to about 90% relative humidity. Drying conditions may be selected such that at least some of the fluorinated polymer can migrate to the surface of the coating as it dries so that the resulting dried coating has a fluorine-enriched surface.
  • the composition according to the present disclosure is an architectural paint composition.
  • the fluorinated polymers according to the present disclosure provide excellent soil and stain resistance.
  • cleanability of a paint composition including the fluorinated polymer of the present disclosure is better than the cleanability of a paint composition including a fluorinated polymer having the first and second divalent units but having no pendant phosphate group.
  • fluorinated polymers including first and third divalent units but having no second divalent units did not mix well into the paint composition.
  • the present disclosure provides a fluorinated polymer comprising:
  • Rf represents a fluoroalkyl group having from 1 to 8 carbon atoms
  • R 1 is hydrogen or methyl
  • Q is a bond or -S02-N(R)-, wherein R is alkyl having from 1 to 4 carbon atoms; and m is an integer from 1 to 11,
  • a second divalent unit comprising a poly (alky leneoxy) group
  • the present disclosure provides the fluorinated polymer of the first embodiment, wherein the phosphate group is represented by formula -0-P(0)(OY)2, wherein the phosphonate group is represented by formula -P(0)(OY)2, and wherein each Y is independently hydrogen or a counter cation.
  • the present disclosure provides the fluorinated polymer of the first or second embodiment, wherein the second divalent unit is present in an amount of at least 30 by weight, based on the total weight of the fluorinated polymer.
  • the present disclosure provides the fluorinated polymer of any one of the first to third embodiments, wherein at least one of the second divalent units is represented by formula:
  • R 2 is hydrogen or methyl
  • R 3 is alkyl having up to 4 carbon atoms, -0-P(0)(OY)2, or hydrogen;
  • each Y is independently selected from the group consisting of hydrogen and a counter cation
  • EO represents -CH 2 CH 2 0-
  • each R 4 0 is independently selected from the group consisting of -CH(CH 3 )CH 2 0-, -CH2CH2CH2O-, -CH 2 CH(CH 3 )0-, -CH2CH2CH2CH2O-, -CH(CH2CH 3 )CH 2 0-, -CH2CH(CH 2 CH 3 )0-, and -CH 2 C(CH 3 ) 2 0-;
  • each p is independently a value from 0 to 150;
  • each q is independently a value from 0 to 150 , wherein p+q is at least 5;
  • fluorinated polymer may further comprise at least one third divalent unit represented by formula:
  • Q 1 is selected from the group consisting of -0-, -S-, and -N(R 7 )-;
  • each R 7 is independently selected from the group consisting of hydrogen and alkyl having from 1 to 4 carbon atoms;
  • each R' is independently hydrogen or methyl
  • V is alkylene that is optionally interrupted by at least one ether linkage, thioether linkage, or amine linkage;
  • Z is -P(0)(OY) 2 or -0-P(0)(OY) 2 ;
  • each Y is independently selected from the group consisting of hydrogen and a counter cation
  • the present disclosure provides the fluorinated polymer according to the fourth embodiment, wherein the fluorinated polymer comprises the third divalent unit, and wherein the third divalent unit is present in an amount up to 20 percent by weight, based on the total weight of the fluorinated polymer.
  • the present disclosure provides the fluorinated polymer of any one of the first to fifth embodiments, wherein the first divalent unit is present in an amount up to 60 percent by weight, based on the total weight of the fluorinated polymer.
  • the present disclosure provides the fluorinated polymer of any one of the first to sixth embodiments, further comprising a third divalent unit represented by formula:
  • Q 1 is selected from the group consisting of -0-, -S-, and -N(R 7 )-;
  • R 7 is selected from the group consisting of hydrogen and alkyl having from 1 to 4 carbon atoms
  • R' is hydrogen or methyl
  • V is alkylene that is optionally interrupted by at least one ether linkage, thioether linkage, or amine linkage;
  • Z is -P(0)(OY) 2 or -0-P(0)(OY) 2 ;
  • each Y is independently hydrogen or a counter cation.
  • the present disclosure provides the fluorinated polymer according to any one of the first to seventh embodiments, wherein at least one of the second divalent units or third divalent units is represented by formula:
  • R 2 is independently hydrogen or methyl
  • EO represents -CH 2 CH 2 0-
  • each R 4 0 is independently selected from the group consisting of -CH(CH 3 )CH 2 0- -CH2CH2CH2O- -CH 2 CH(CH 3 )0-, -CH2CH2CH2CH2O-, -CH(CH 2 CH3)CH 2 0- -CH 2 CH(CH 2 CH3)0- and -CH 2 C(CH 3 )20-;
  • each p is independently a value from 0 to 150;
  • each q is independently a value from 0 to 150, wherein p+q is at least 5; and each Y is independently hydrogen or a counter cation.
  • the present disclosure provides the fluorinated polymer according to any one of the first to eighth embodiments, wherein Q is -S0 2 N(R)- and R is methyl or ethyl.
  • the present disclosure provides the fluorinated polymer according to any one of the first to ninth embodiments, wherein Rf represents a fluoroalkyl group having up to 4 carbon atoms.
  • the present disclosure provides the method according to any one of the first to tenth embodiments, wherein at least one of the second divalent units is represented by formula:
  • EO represents -CH 2 CH 2 0-
  • each R 4 0 is independently selected from the group consisting of -CH(CH 3 )CH 2 0- -CH2CH2CH2O- -CH 2 CH(CH 3 )0- -CH2CH2CH2O-, -CH(CH 2 CH3)CH 2 0- -CH 2 CH(CH 2 CH3)0- and -CH 2 C(CH 3 )20-;
  • each p is independently a value from 0 to 150;
  • each q is independently a value from 0 to 150 , wherein p+q is at least 5.
  • the present disclosure provides the fluorinated polymer according to any one of the first to eleventh embodiments, wherein at least one of the second divalent unit is represented by formula:
  • each R 2 is independently hydrogen or methyl
  • EO represents -CH 2 CH 2 0-
  • each R 4 0 is independently selected from the group consisting of -CH(CH 3 )CH 2 0-, -CH2CH2CH2O-, -CH 2 CH(CH 3 )0- -CH2CH2CH2CH20-,-CH(CH2CH 3 )CH 2 0-, -CH 2 CH(CH 2 CH 3 )0-, and
  • each r is independently a value from 0 to 150;
  • each q is independently a value from 0 tol50 , wherein p+q is at least 150.
  • the present disclosure provides the fluorinated polymer according to any one of the first to eleventh embodiments, wherein the second divalent unit comprises a pendant poly(alkyleneoxy) group.
  • the present disclosure provides the fluorinated polymer according to any one of the first to thirteenth embodiments, wherein the fluorinated polymer further comprises at least one divalent unit represented by formula:
  • each R 5 is independently alkyl having from 1 to 30 carbon atoms
  • each R 6 is independently hydrogen or methyl.
  • the present disclosure provides the fluorinated polymer according to any one of the first to thirteenth embodiments, wherein the fluorinated polymer is substantially free of divalent units represented by formula:
  • each R 5 is independently alkyl having from 1 to 30 carbon atoms
  • each R 6 is independently hydrogen or methyl.
  • the present disclosure provides the fluorinated polymer according to any one of the first to fifteenth embodiments, wherein the fluorinated polymer is substantially free of divalent units represented by formula:
  • Q 1 is selected from the group consisting of -0-, -S-, and -N(R 7 )-;
  • each R 7 is independently selected from the group consisting of hydrogen and alkyl having from 1 to 4 carbon atoms;
  • each R' is independently hydrogen or methyl
  • V is alkylene that is optionally interrupted by at least one ether linkage or amine linkage
  • Z 1 is selected from the group consisting of -[N(R 8 ) 3 ] + M ⁇ , -N + (R 8 )2-(CH 2 )g-S0 3 Y 1 , and -N + (R 8 )2-(CH 2 )g-C0 2 Y 1 ,wherein each R 8 is independently selected from the group consisting of hydrogen and alkyl having from 1 to 6 carbon atoms;
  • each g is independently an integer from 2 to 6;
  • M " is a counter anion
  • Y 1 is selected from the group consisting of hydrogen and a free anion.
  • the present disclosure provides the fluorinated polymer according to any one of the first to sixteenth embodiments, wherein the fluorinated polymer is free of divalent units comprising a pendant silane group and free of silane terminal groups.
  • the present disclosure provides the fluorinated polymer according to any one of the first to seventeenth embodiments, wherein the fluorinated polymer is free of pendent amino groups.
  • the present disclosure provides the fluorinated polymer according to any one of the first to eighteenth embodiments, wherein the fluorinated polymer is substantially free of volatile organic solvent.
  • the present disclosure provides the fluorinated polymer according to any one of the first to nineteenth embodiments, wherein the fluorinated polymer is a polymer having a weight average molecular weight in a range from 1,000 grams per mole to 100,000 grams per mole.
  • the present disclosure provides the fluorinated polymer according to any one of the first to twentieth embodiments, used in a paint composition.
  • the present disclosure provides a composition comprising a film- forming polymer and the fluorinated polymer according to any one of the first to twenty -first embodiments.
  • the present disclosure provides the composition according to the twenty -second embodiment, further comprising a pigment.
  • the present disclosure provides the composition according to the twenty -second or twenty -third embodiment, further comprising an inorganic filler.
  • the present disclosure provides the composition according to any one of the twenty-second to twenty -fourth embodiments, further comprising a thickener.
  • the present disclosure provides the composition according to any one of the twenty-second to twenty -fifth embodiments, further comprising water.
  • the present disclosure provides the composition according to any one of the twenty-second to twenty-sixth embodiments, having a pH of at least 7.
  • the present disclosure provides the composition according to the twenty -seventh embodiment, having a pH of 7 to 9.
  • MeFBSEA was prepared according to the method of U.S. Pat. No. 6,664,354 (Savu), Example 2, Parts A and B, incorporated herein by reference, except using 4270 kilograms (kg) of N-methylperfluorobutanesulfonamidoethanol, 1.6 kg of phenothiazine, 2.7 kg of methoxyhydroquinone, 1590 kg of heptane, 1030 kg of acrylic acid, 89 kg of methanesulfonic acid (instead of triflic acid), and 7590 kg of water in Part B.
  • 4270 kilograms (kg) of N-methylperfluorobutanesulfonamidoethanol 1.6 kg of phenothiazine, 2.7 kg of methoxyhydroquinone, 1590 kg of heptane, 1030 kg of acrylic acid, 89 kg of methanesulfonic acid (instead of triflic acid), and 7590 kg of water in Part B.
  • NATROSOL PLUS 330 Hydroxyethylcellulose available under the trade designation NATROSOL from Ashland, Lexington, KY, USA
  • VANTEX - T A tertiary amine additive available under the trade designation "VANTEX-T” from Eastman Chemical Company, Kingsport, TN, USA.
  • TAMOL 1124 A hydrophilic copolymer pigment dispersant available from Dow Chemical Company, Midland, MI, USA
  • 3M W-410 Alkali alumino silicate ceramic microspheres, available under the trade designation, "3MTM Ceramic Microspheres White Grade W-410,” from 3M Company, St Paul, MN, USA
  • ⁇ 4 A micronized functional filler and/or extender produced from nepheline syenite with a median particle size of 6.8 ⁇ , available under the trade designation, " ⁇ 4," from Unimin Corporation, New Canaan, CT, USA
  • DURAMITE A coarse, medium particle size marble, available under the trade designation, "DURAMITE,” from Imerys Carbonates, Roswell, GA, USA
  • ACRONAL PLUS 4130 All acrylic latex, available under the trade designation, "ACRONAL PLUS 4130,” from BASF Corporation, Florham Park, NJ, USA
  • ACRYSOL TT-935 A hydrophobically modified anionic thickener, available under the trade designation, "ACRYSOL TT-935,” from Dow Chemical Company
  • CAPSTONE FS-61 Anionic fluoro surfactant, available in a water- based dispersion under the trade designation, "CAPSTONE FLUOROSURFACTANT FS- 61,” From Chemours
  • SPS-2001 A standard carpet dry soil, formerly available under the trade designation, "SPS-2001,” from 3M Company Method for determining Surface Tension
  • the paint formulation used to evaluate dirt pick up resistance and washability performance was prepared by first mixing the components listed in Table 2, below, in the order shown, through
  • DURAMITE in a vessel, and mixing them under high speed agitation using a Dispermat D-51580 and a 1.5" (38.1 mm) cowles blade for 20 min at 4000 rpm. The grind was checked using a Hegman gauge, and the considered complete when a minimum 4 rating was obtained. The paste was then added to the pre- mixed letdown (Acronal Plus 4130 and water). After thorough mixing, the last ingredient was added slowly, with agitation of the mixture.
  • Examples were dissolved in the paint formulation described above at a concentration of 0.2% active material based on total paint weight, with the Exception of Comparative Example 3 (CE-3), for which no additive was added to the paint formulation.
  • Paint samples were deposited on one side of Leneta 10 mil (0.25 mm) PVC Black plastic cards, available under the trade designation, "P121-10N Leneta Scrub Test Panels," available from Leneta Company, Inc., Mahwah, NJ, USA were coated on one side using a 7 mil (0.18 mm) U-shaped applicator. Paint was allowed to age under ambient temperature and humidity for 7 d. After aging, 3 in (7.62 cm) x 6 in (15.24 cm) samples were cut from the coated card. The temperature and humidity in the test room was recorded. The initial reflectance of the painted side of the test cards was measured using a ColorFlex EZ spectrophotometer, operated in
  • Illuminant/Observer C/2 Read Y value mode (available under the trade designation ColorFlex EZ 45/0 LAV from Hunter Associates Laboratory, Inc., Reston, VA, USA) and recorded as Rimt-
  • the painted sides of the samples were covered with SPS-2001 for 24 h. After 24 h, the samples were tapped to displace SPS-2001 and reflectance of the painted sides was again recorded as Rfmai-
  • the ratio Rfmai / Rimt was calculated for each sample.
  • the nonabrasive medium used on each test panel was prepared as 5 g of a 10% Dawn dish soap solution in water and applied with a foam brush
  • CE-1 38 g of N-MeFBSEA and 124 g of PLURONIC L-44 acrylate (50% in toluene) were copolymerized with 5.0 g 3-mercapto-l,2-propanediol, with 4.0 g "VAZO 67" in a three-necked flask. The mixture was degassed three times using vacuum and nitrogen pressure and then heated to 65 °C for 6 h. After polymerization, toluene was removed using an aspirator vacuum at 65-70 °C at approximately 20 mmHg (2.7 kPa).
  • CE-2 19 g of N-MeFBSEA and 62 g of PLURONIC L-44 acrylate (50% in toluene) were copolymerized with 2.5 g 3-mercapto-l,2-propanediol and 2.0 g "VAZO 67" in a three necked flask. The mixture was degassed three times using vacuum and nitrogen pressure and then heated to 65 °C for 6 h. After polymerization, toluene was removed using an aspirator vacuum at 60 - 70 °C at approximately 40 mmHg (5.3 kPa) . The polymer was then neutralized with NH 4 OH, however, the neutralized polymer was barely soluble in water. The un-neutralized polymer was not soluble in water.
  • EX-1 through EX-12 were prepared according to the process described for CE-1, except that in place of 3-mercapto-l,2-propanediol, PAM-200, Ethylene glycol phosphate methacrylate, or a combination of PAM-200 and Ethylene glycol phosphate methacrylate was used.
  • the amounts of N- MeFBSEA, PLURONIC L-44 acrylate, PAM-200 and Ethylene glycol phosphate methacrylate used for each Example 1 - 12 are provided in Table 3.
  • Example 13 - 15 For EX-13 through EX-15, the procedure described for CE-1 was followed, except that Poly (ethylene glycol) methyl ether MA, PAM-200 and IPA were used in place of PLURONIC L-44 acrylate.
  • the amounts of N-MeFBSEA, Poly (ethylene glycol) methyl ether MA, PAM-200, 3-mercapto- 1,2-propanediol, and IPA used for each Example 13 - 15 are provided in Table 4.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Paints Or Removers (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

Le polymère fluoré comprend une première unité divalente représentée par la formule : (formule (I)), une seconde unité divalente comprenant un groupe poly(alkylèneoxy), et un groupe phosphate pendant et/ou un groupe phosphonate pendant. Dans la formule, Rf représente un groupe fluoroalkyle possédant de 1 à 8 atomes de carbone, R1 représente hydrogène ou méthyle, Q représente une liaison ou -SO2-N(R)-, R étant un alkyle possédant de 1 à 6 atomes de carbone, et m est un nombre entier de 1 à 20. Le polymère fluoré peut être utile, par exemple, pour améliorer la résistance à la salissure et aux taches dans une composition de peinture ou de revêtement. Les compositions qui comprennent le polymère fluoré peuvent être des compositions aqueuses qui comprennent en outre un polymère filmogène.
PCT/US2017/067374 2016-12-20 2017-12-19 Polymères anioniques fluorés et compositions les comprenant WO2018118962A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020100113A1 (fr) * 2018-11-16 2020-05-22 3M Innovative Properties Company Composition comprenant un solvant et un polymère fluoré et procédé de traitement d'une formation contenant des hydrocarbures

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130012615A1 (en) * 2010-03-30 2013-01-10 Kuraray Noritake Dental, Inc. One-part dental adhesive composition
US20140228450A1 (en) * 2011-08-29 2014-08-14 Agc Seimi Chemical Co., Ltd. Copolymer for cosmetics, surface treatment agent for cosmetic powder, powder for cosmetics, and cosmetic preparation
WO2016028499A1 (fr) * 2014-08-19 2016-02-25 3M Innovative Properties Company Polymères amphiphiles, compositions de revêtement, et procédés
WO2016099952A1 (fr) * 2014-12-18 2016-06-23 3M Innovative Properties Company Polymères fluorés comprenant des fractions phosphoniques

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130012615A1 (en) * 2010-03-30 2013-01-10 Kuraray Noritake Dental, Inc. One-part dental adhesive composition
US20140228450A1 (en) * 2011-08-29 2014-08-14 Agc Seimi Chemical Co., Ltd. Copolymer for cosmetics, surface treatment agent for cosmetic powder, powder for cosmetics, and cosmetic preparation
WO2016028499A1 (fr) * 2014-08-19 2016-02-25 3M Innovative Properties Company Polymères amphiphiles, compositions de revêtement, et procédés
WO2016099952A1 (fr) * 2014-12-18 2016-06-23 3M Innovative Properties Company Polymères fluorés comprenant des fractions phosphoniques

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020100113A1 (fr) * 2018-11-16 2020-05-22 3M Innovative Properties Company Composition comprenant un solvant et un polymère fluoré et procédé de traitement d'une formation contenant des hydrocarbures

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