Classifications

• • 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
  • C09D9/00—Chemical paint or ink removers
  • C09D9/04—Chemical paint or ink removers with surface-active agents
• • 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 Table
  • 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
  • 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
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/47—Levelling agents
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09G—POLISHING COMPOSITIONS; SKI WAXES
  • C09G1/00—Polishing compositions
  • C09G1/04—Aqueous dispersions
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
  • C09K23/007—Organic compounds containing halogen
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
  • C09K23/14—Derivatives of phosphoric acid
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/004—Surface-active compounds containing F
  • C11D1/006—Surface-active compounds containing fluorine and phosphorus

Definitions

• the field of invention is fluorochemical surfactants, in particular phosphate surfactants which contain a hydrocarbon diol or polyaikyiene gfycof hydrophiiic taii and a fluorinat ⁇ d hydrophobic tail.
• U.S. Serial Number 11/890,414 (Docket Number CH3195) filed August 8, 2007, discloses fluoroalkyl-alkyl twin tailed phosphate surfactants which have two dissimilar terminal hydrophobic groups attached to a single connecting group.
• U.S. Patent 5,643,864 discloses anionic surfactants having at least two hydrophobic chains and at least two hydrophiiic groups per molecule useful as emulsifiers, detergents, dispersant and solubiiizing agents.
• surfactant performance in particular lowering of surface tension in aqueous systems, and to increase the fluorine efficiency, i.e.. boost the efficiency or performance of the surfactants so a lower proportion of the expensive fluorine component is required to achieve the same level of performance, or to have better performance using the same level of fluorine.
• surfactants having both a hydrophobic and a hydrophiiic group in the same compound which are fluorine efficient. It is also desirable to have surfactants that are stable in brine and aggressive media (acid and base) while stilt maintaining improved performance The present invention provides such surfactants.
• the present invention comprises a compound of Formula 1 Rf-A-OP(O)(O- M + XOROH) Formula 1 wherein
• Rf is a C2 to CQ linear or branched perftuoroalky! optionally interrupted by one, (wo or three ether oxygen atoms;
• A is ⁇ CH 2 CF 2 ) m (CH2)n-.
• (CH 2 ) O SO 2 N(CH 3 )(CH 2 )P-, O(CF 2 ) q (CH 2 ) r ! or OCHFCF 2 OE-;
• m is O to 4;
• n, o, p, and r are each independently 2 to 20;
• q is 2;
• E is a C 2 to C 2 o linear or branched aikyl group optionally interrupted by oxygen, sulfur, or nitrogen atoms; a cyclic alkyf group, or a Ce to Cf o aryl group;
• M is H or a Group I metal or an ammonium cation (NH x R ⁇ y) + wherein R ⁇ IS a C ⁇ to C4 alkyf, x is O to 4, y is O to 4 and x + ⁇ y is 4; and
• R is a C 2 to CgQ linear or branched alkyi group optionally interrupted by hetero atoms selected from the group consisting of an oxygen, sulfur, or nitrogen atom; a cyclic alkyl. or a Cg to C-JQ aryl; provided that when R is greater than 8 carbons, the ratio of hetero atoms to carbon atoms is at least 1 ;2.
• the present invention further comprises a method of lowering the surface tension of an aqueous medium comprising contacting the medium with a composition of Formula 1 as defined above,
• the present invention further comprises a method of providing soil repellency, leveling, and resistance to blocking to a coated substrate comprising adding to a coating base prior to deposition on the substrate a compound of Formula 1 as defined above.
• DETAiLED DESCRIPTION Trademarks are shown herein in upper case.
• aggressive medium means an acidic solution having a maximum pH of about 4, or a basic solution having a pH of at least about 10.
• the present invention comprises a compound of Formula 1 Rf U A-OP(O)(O- M + )(OROH) Formula 1 wherein
• Rf is a C2 to Cg linear or branched perfiuoroalkyl optionally interrupted by one, two or three ether oxygen atoms;
• A is (CH 2 CF 2 ) m (CH 2 ) n -, (CH 2 )OSO 2 N(CH 3 )(CH 2 )P-, O(CF 2 ) q (CH 2 )r. or OCHFCF 2 OE-;
• m is O to 4;
• n, O 1 p, and r are each independently 2 to 20;
• q is 2;
• E is a C 2 to C 2 Q linear or branched alkyi group optionally interrupted by oxygen, sulfur, or nitrogen atoms; a cyclic alkyl group, or a Ce to C-tn aryl group;
• M is H or a Group I metal or an ammonium cation (NH x R 2 y ) + wherein R ⁇ is a C-j to C4 alkyl, x is 0 to 4, y is 0 to 4 and x + y is 4; and
• R is a C 2 to Cgo linear or branched alkyl group optionally interrupted by hetero atoms selected from the group consisting of an oxygen, sulfur, or nitrogen atom; a cyclic alkyl; or a Cg to C ⁇ ⁇ aryi; provided ⁇ hat when R is greater than 8 carbons, the ratio of hetero atoms to carbon atoms is at least 1 :2.
• R ⁇ is a C3 to Cg perfkioroaikyi. Also preferred are those wherein R? is C3. C4 or C ⁇ perfiuoroalkyl. Also preferred are compounds of Formula 1 wherein M is sodium or potassium or an ammonium cation (NH x R ⁇ y) + wherein R2 is a Ct to C4 alkyl. x is 0 to 4, y is 0 to 4 and x + y is 4 More preferred are compounds of Formula 1 wherein M is an ammonium cation (NH x R ⁇ y) + wherein R ⁇ is a Ci to C4 alkyi, x is 0 to 4, y is 0 to 4 and x + y is 4.
• E is a C2 to C20 ⁇ ear or branched alkyi group optionally interrupted by oxygen. More preferred are compounds of Formula 1 wherein E is a C2 to C-JQ linear or branched alkyl group optionally interrupted by oxygen.
• R is a Smear or branched C2 to Cg aikyl, and more preferably C3 alkyl.
• R is a CQ to C ⁇ Q more preferably Cg to 040, linear or branched alkyl group optionally interrupted by oxygen atoms.
• R is greater than 8 carbon atoms, the ratio of hetero atoms to carbon atoms is at least 1 :2, preferably from about 1 :2 to about 1 :3.
• R is a linear or branched alkyl group of about 8 to about 50 carbon atoms, and more preferably about 8 to 40 carbon atoms, interrupted by about 2 to about 20 ether oxygen atoms, wherein the ratio of ether oxygen atoms to carbon atoms is from about 1 :2 to about 1.4: more preferably from about 1 :2 to about 1 :3.
• the R group has a molecular weight of between about 200 to about 1250.
• Formula 1 is a surfactant containing both a hydrophobic group and a hydrophilic group.
• the compounds of Formula 1 are prepared by reacting either phosphorus pentoxide (P2O5) or phosphorus oxychloride (POCI3) with fiuonnated alcohol, followed by the addition of hydrocarbon dioi or poly(glycol).
• P2O5 phosphorus pentoxide
• POCI3 phosphorus oxychloride
• the phosphorus pentoxide or phosphorus oxychloride is added to the fluorinated alcohol in an amount that is approximately equivalent mol percent. For example, when phosphorus pentoxide is used from about 0.4 to about 1 .8 mole equivalent of fluorinated alcohol to P2O5 is added.
• the mixture is heated to a temperature of from about 7O°C to about 120° C, preferably to from about IQO°C to about 1 10°C 1 and maintained for several hours, preferably from about 3 to about 15 hours.
• a dio! or poly(glycol) is then added to the reaction mixture with continued heating at the above temperature for an additional time of from about 3 to about 15 hours.
• the mole ratio of diol or poly(gfycol) to P2O5 is from about 1.4 to about 2.6.
• a surfactant tn from about 1% to about 3% by weight. Any of a variety of surfactants can be employed, such as TERGiTOL available from Sigma Aldrich, St. Louis, MO.
• ammonia is added with mixing, followed by water, to provide the phosphate of Formula 1.
• Diols useful in the synthesis of compounds of Formula 1 include C2 to CQO straight and branched chain alcohols optionally having one or two double bonds. Examples include 1 ,3-propanedioi; propylene glycol (1.2- propanediol); di(ethylene glycol); t ⁇ (ethylene glycol); tetra(ethylene glycol); po!y(ethylene glycols [PEG(OHh].
• polyCethylene glycol)-polypropyiene glycol-poly(ethylene glycol) triblock polymers [PEG-PPG-PEG-(OH) 2 ]; and random copolymers of ethylene oxide and propylene oxide, preferably with a molecular weight
• Polyethylene glycols with nominal molecular weights of 200 to 2000 are available from Aldrich Chemical Company, St. Louis, MO. Tri-block copolymers of polyethylene oxide and polypropylene oxide (PEG-PPG-)
• PEG PEG are available from BASF, Mount Olive, NJ.
• One embodiment of the invention is a compound of Formula 1 wherein A is (CH2CF2)m(CH2)rr> herein denoted as Formula 2,
• Preferred compounds of Form ⁇ ia 2 include those wherein Rf is a C4 or Cg perfiuoroaikyi n is 2 R is ChHCh ⁇ 1 and m is 0. 1 , or 2
• Fiuo ⁇ ated aicohois useful tn the preparation of various embodiments of Formula 2 are available commercially or by synthesis
• Fluorinated alcohols CeF-(3CH2CH2 ⁇ H and C4F9GH2CH2QH are available f 1 om E I du Pont de Nemoui s and Company Wilmington. DE Fluorinated alcohols are available by synthesis according to the following Scheme 1
• telome ⁇ zatton of vinyfidene fluoride (VDF) with linear or branched perfiuoroaikyi iodides is well known and produces compounds of the structure R ⁇ (CH ⁇ CF ⁇ ) P I wherein p is 1 to 3 or more and R ⁇ is a C- to Ct perfiuoroaikyi group
• R ⁇ is a C- to Ct perfiuoroaikyi group
• telomer ethylene iodides Vf
• V! tetomer ethylene iodides
• reagents to provide the corresponding thiols according to procedures described in J Fluorine Chemistry, 104, 2 173-183 (2000)
• One example is the reaction of the telomer ethylene iodides (Vi) with sodium thioacetate, followed by hydrolysis.
• a further embodiment of the invention is a compound of Formula 1 wherein A is (CH2)oSO2N(CH3)(CH2>p-. herein denoted as Formula 3,
• Preferred compounds of Formula 3 include those wherein o and p are each 2, Rf is C f cHi3, and R is CH2CH2
• the fluoroalkyl alcohol used to prepare compounds of Formula 3 is available from E. I du Pont de Nemours and Company, Wilmington DE. Alternatively the fluoroalkyl alcohol Rf(CH2)oSO2N(CH3)(CH2)p-OH, wherein 0 and p are defined above in
• Formula (1 is prepared by the reaction of a fluoroalkyl ethylene iodide with potassium thiocyanat ⁇ in water
• the product RKCHJ) 0 SCN IS distilled as a colorless liquid, which then is converted to fluo ⁇ nated sutfonyf chloride having the formula Rr(CH ⁇ ) 0 SOrCi by a reaction with chlorine and acetic acid over several hours at about 45- ⁇ 50 l C in an autoclave.
• the sulfonyl chloride is then reacted with an amine, for example, such as H- methylethanolamine, to produce the fluo ⁇ nated alcohol of the formula Rf(CH 2 ) o S ⁇ 2N(CH3)(CH2)p-OH
• a further embodiment of the invention is a compound of Formula 1 wherein A is O(CF2)q(CH2V. herein denoted as Formula 4,
• Preferred compounds of Formula 4 include those wherein q and r are each 2.
• Rf is C?.F 7 , and R is CH2CH2
• the fiuoroaicohols used as starting materials to make the compositions of Formula 4 are available by the following series of reactions of Scheme 2:
• (V) is reacted with an excess of ethylene at an elevated temperature and pressure. While the addition of ethylene can be carried out thermally, the use of a suitable initiator is preferred.
• the initiator is a peroxide such as benzoyl peroxide, isobutyryl peroxide, propiony! peroxide, or acetyl peroxide. More preferably the peroxide is benzoyl peroxide.
• the temperature of the reaction is not limited, but a temperature in the range of 110 * 0 to 130 s C is preferred.
• the reaction time can vary with the initiator and reaction conditions, but 24 hours is usually adequate.
• the product is purified by any means that separates unreacted starting material from the final product., but distillation is preferred.
• the perfluoroalkylether ethyl iodides can be treated with N-r ⁇ ethyl formarnide followed by ethyl alcohol/a ⁇ d hydrolysis.
• a temperature of about 130° to 160*C is preferred.
• the teiomer ethylene iodides (Vl) in Scheme 2 are treated with a variety of reagents to provide the corresponding thiols according to procedures described in J. Fluorine Chemistry, 104, 2 173-183 (2000).
• One example is the reaction of the teiomer ethylene iodides (Vl) of Scheme 2 with sodium thioacetate, followed by hydrolysis.
• the teiomer ethylene iodide (Vl) of Scheme 2 can also be treated to provide the corresponding thioethanols or thioethylamines by conventional methods.
• a further embodiment of the invention is a compound of Formula 1 wherein A is QCHFCF2OE-, herein denoted as Formula 5.
• Preferred compounds of Formula 5 include those wherein Rf is C 3 F7 and R is CH2CH2.
• the fluoroalcohols used as starting materials to make the compositions of Formula 5 are prepared by reacting a dioxane with a diol in the presence of an alkali metal compound.
• alkali metal compounds include an alkali metal, alkali earth metal, alkali hydroxide, alkali hyd ⁇ de, or an alkali amide.
• alkali metals such as Na, K or Cs 1 or alkali hydrides such as NaH or KH.
• the reaction is conducted at a temperature of from about 4O°C to about 12O 0 C
• the reaction can be conducted in an optional solvent, such as ether or nttrile.
• the compounds of the present invention of Formula 1 are surfactants for use in aqueous formulations, where extremely low surface tensions of about 18 dynes/cm or 18 mN/m (miili-newtons per meter) are required.
• the surfactants of the present invention provide "fluonne efficiency".
• fluorine efficiency '1 means to increase the efficiency or improve the performance of the surfactants or treating agents so a lower proportion of the expensive fluorine component is required to achieve the same level of performance, or to have better performance using the same level of fluorine.
• the fluorine content in the surfactants of the present invention is from about 50% to about 70% lower than in conventional fluorinated surfactants.
• the above compound of Formula (1 ) is a fluorinated phosphate surfactant which lowers surface tension at very low concentration.
• Such surface tension values in a medium, typically a liquid are fess than about 25 milii-newtons per meter, preferably less than about 20 mtltt-newtons per meter, at a concentration of the surfactant in the medium of less than about 0.2 % by weight, and preferably less than 0.1 % by weight,
• the surfactant is characterized by its efficiency in lowering the surface tension at low concentrations by selective adsorption on the interface, which is determined by the amphiphilic nature of the surfactants.
• amphiphilic means attraction to two different kinds of media.
• the surfactants comprise a water-soluble hydrophilic part and a water- insoluble hydrophobic part.
• the present invention further comprises a method of lowering surface tension of an aqueous medium comprising contacting the medium with a composition of Formula 1 as described above.
• a composition of Formula 1 as described above.
• the medium is a liquid.
• suitable medium include a coating composition, latex, polymer, floor finish, ink.
• composition of the present invention emulsifying agent, foaming agent, release agent, repe ⁇ ency agent, flow modifier, film evaporation inhibitor, wetting agent, penetrating agent, cieaner, grinding agent, electroplating agent, corrosion inhibitor, etchant solution, soldering agent, dispersion aid, microbial agent, pulping aid, rinsing aid, polishing agent, personal care composition, drying agent, antistatic agent, floor polish, or bonding agent.
• Adding a composition of the present invention to the medium results in lowering the surface tension of the medium due to the surfactant properties of the composition of the present invention.
• the composition of the present invention is typically simply blended with or added to the medium.
• a low concentration of about 0.1% by weight of surfactant is sufficient to lower surface tension to less than about 22 mN/m, preferably less than about 20 nM/m, more preferably less than about 18 mN/m.
• the present invention further comprises a method of providing soil repellency, leveling, and resistance to blocking to a coated substrate comprising adding to a coating base prior to deposition on the substrate a compound of Formula 1 "Leveling" as used herein refers to the uniformity of coverage of the coating when applied to a substrate. It is undesirable to have streaking, surface defects, or withdrawal of the coating from the substrate surface at the edges or otherwise. An even coating will provide a superior dried coating on the substrate surface.
• Blocking 11 is the undesirable sticking together of two coated surfaces when pressed together, or placed in contact with each other for an extended period of time, after the coating has dried. When blocking occurs separation of the surfaces can result in disruption of the coating on one or both surfaces Thus resistance to blocking is beneficial in many situations where two coated surfaces need to be in contact, for example on window frames.
• Suitable coating compositions include a composition, typically a liquid formulation, of an alkyd coating, Type I uretnane coating, unsaturated polyester coating, or water-dispersed coating, and is applied to a substrate for the purpose of creating a lasting film on the substrate surface.
• coating base typically a liquid formulation, of an alkyd coating, Type I uretnane coating, unsaturated polyester coating, or water-dispersed coating, and is applied to a substrate for the purpose of creating a lasting film on the substrate surface.
• coating base include a composition, typically a liquid formulation, of an alkyd coating, Type I uretnane coating, unsaturated polyester coating, or water-dispersed coating, and is applied to a substrate for the purpose of creating a lasting film on the substrate surface.
• coating base typically a liquid formulation, of an alkyd coating, Type I uretnane coating, unsaturated polyester coating, or water-dispersed coating, and is applied to a substrate for the purpose of creating a lasting film
• alkyd coating as used herein is meant a conventional liquid coating based on alkyd resins, typically a paint, clear coating, or stain.
• the alkyd resins are complex branched and cross-linked polyesters containing unsaturated aliphatic acid residues.
• Conventional alkyd coatings utilize, as the binder or film-forming component, a curing or drying alkyd resin.
• Alkyd resin coatings contain unsaturated aliphatic acid residues derived from drying oils. These resins spontaneously polymerize in the presence of oxygen or air to yield a solid protective film.
• drying or "curing” and occurs as a result of autoxidation of the unsaturated carbon-carbon bonds in the aliphatic acid component of the oil by atmospheric oxygen.
• drying oils have been used as raw materials for oil-based coatings and are described in the literature.
• urethane coating as used hereinafter is meant a conventional liquid coating based on Type I urethane resins, typically a paint, clear coating, or stain.
• Urethane coatings typically contain the reaction product of a polytsocyanate. usually toluene diisocyanate, and a polyhydric alcohol ester of drying oil acids. Urethane coatings are classified by ASTM D- 1 into five categories. Type I urethane coatings contain a pr ⁇ -reacted autoxidizable binder as described in Surface Coatings Vol. I, previously cited.
• uralkyds urethane-modified alkyds, oil-modified urethanes, urethane oils, or urethane aikyds
• urethane aikyds are the largest volume category of poiyurethane coatings and include paints, clear coatings, or stains.
• the cured coating is formed by air oxidation and polymerization of the unsaturated drying oil residue in the binder.
• unsaturated polyester coating as used hereinafter is meant a conventional liquid coating based on unsaturated polyester resins dissolved in monomers and containing initiators and catalysts as needed, typically as a paint, clear coating or gel coat formulation
• Unsaturated polyester tesins contain as the unsaturated prepolymer the product obtained from the condensation polymerization of a glycol such as 1 ,2- propylene glycol or 1.3-butylene glycol with an unsaturated acid such as maleic t,or of maleic and a saturated acid, e g , phthalic) in the anhydride form
• the unsaturated prepoiymer is a linear polymer containing unsaturation in the chain This is dissolved in a suitable monomer, for instance styr ⁇ ne.
• the film is produced by copolyme ⁇ zation of the linear polymer and monomer by means of a free radical mechanism
• the free radicals can be generated by heat, or more usually by addition of a peroxide, such as benzoyl peroxide, separately packaged and added before use
• a peroxide such as benzoyl peroxide
• Such coating compositions are frequently termed "gel coat" finishes
• the decomposition of peroxides into free radicals is catalyzed by certain metal tons, usually cobalt.
• water-dispersed coatings as used herein is meant coatings intended for ⁇ he decoration or protection of a substrate composed of water as an essential dispersing component such as an emulsion, latex, or suspension of a film-forming material dispersed in an aqueous phase
• Water-dispersed coating is a general classification that describes a number of formulations and includes members of the above described classifications as well as members of other classifications Water- dispersed coatings in general contain other common coating ingredients Water-dispersed coatings are exemplified by, but not limited to.
• pigmented coatings such as latex paints, unpigmented coatings such as wood sealers, stains, and finishes, coatings for masonry and cement, and water- based asphalt emulsions.
• a water dispersed coating optionally contains surfactants, protective colloids and thickeners, pigments and extender pigments, preservatives, fungicides, freeze-thaw stabilizers, antifoam agents, agents to control pH.. coalescing aids, and other ingredients.
• the film forming material is a iatex polymer of acryiate acrylic, vinyl-acrylic, vinyl, or a mixture thereof
• Such water-dispersed coating compositions are described by C. R. Martens in "Emulsion and Water- Soluble Paints and Coatings" (Reinhold Publishing Corporation, New York, NY, 1965).
• dried coating as used herein is meant the final decorative and/or protective film obtained after the coating composition has dried, set or cured.
• a final film can be achieved by, for non- limiting example, curing, coalescing, polymerizing, interpenetrating, radiation curing, UV curing or evaporation.
• Final films can also be applied in a dry and final state as in dry coating.
• the compounds of the present invention of Formula 1 as defined above are effectively introduced to the coating base or other composition by thoroughly stirring it in at room or ambient temperature. More elaborate mixing can be employed such as using a mechanical shaker or providing heat or other methods. Such methods are not necessary and do not substantially improve the final composition.
• the compositions of the invention When used as an additive to latex paints, the compositions of the invention generally are added at about 0.001 weight % to about 5 weight % by dry weight of the composition of the invention in the wet paint. Preferably about from about 0.01 weight % to about 1 weight %, and more preferably from about 0.1 weight % to about 0.5 weight % is used.
• Floor waxes, polishes, or finishes are generally water based or solvent based polymer emulsions.
• the surfactants of Formula 1 of the present invention are suitable for use in such floor finishes.
• Commercially available floor finish compositions typically are aqueous emulsion-based polymer compositions comprising one or more organic solvents, plasticizers, coating aides, anti-foaming agents, surfactants, polymer emulsions, metal complexing agents, and waxes.
• the particle size range and solids content of the polymer are usually controlled to control the product viscosity, film hardness and resistance to deterioration.
• Polymers containing poiar groups function to enhance solubility and may also act as wetting or leveling agents providing good optical properties such a high gioss and distinctness of reflected image.
• Preferred polymers for use in floor finishes include acrylic polymers, polymers derived from cyclic ethers, and polymers derived from vinyl substituted aromatics.
• Acrylic polymers include various poly(alkyl acrylates), poly(alkyl methacrylates), hydroxy! substituted poly(alkyt acrylates) and poly(alkyl methacryiates).
• acrylic copolymers used in floor finishes include, for example, methyl methacryiate/butyl acrylate/methacrylic acid (MMA/BA/MAA) copolymers; methyl methacryiate/butyl acrylate/acrylic acid (MMA/BA/AA) copolymers, and the like
• styrene-acrylic copolymers include styrene/methyl methacryiate/butyl acrylate/methacrylic acid (S/MMA/BA/MMA) copolymers; styrene/methy! methacrylate/buty!
• acryiate/acryfic acid (S/MMA/BA/AA) copolymers and the like.
• Polymers derived from cyclic ethers usually contain 2 to 5 carbon atoms in the ring with optional alkyl groups substituted thereon. Examples include various oxiranes, oxetanes. tetrahydrofurans. tetrahydropyrans, dtoxanes, trioxanes, and caprolactone.
• Polymers derived from vinyl substituted aromatics include for example those made from styrenes, pyridines, conjugated dienes, and copolymers thereof. Polyesters, poiyamides, poly ⁇ rethanes and polysiloxanes are also used in floor finishes.
• the waxes or mixtures of waxes that are used in floor finishes include waxes of a vegetable, animal., synthetic, and/or mineral origin.
• Representative waxes include, for example, carnufoa, candelilia, lanolin, stearin, beeswax, oxidized polyethylene wax, polyethylene emulsions, polypropylene, copolymers of ethylene and acrylic esters, hydrogenerated coconut oil or soybean oil, and the mineral waxes such as paraffin or ceresin.
• the waxes typically range from 0 to about 15 weight percent and preferably from about 2 to about 10 weight percent based on the weight of the finish composition.
• compositions of the present invention of Formula 1 as defined above are effectively introduced to the composition by thoroughly stirring it in at room or ambient temperature. More elaborate mixing can be employed such as using a mechanical shaker or providing heat or other methods.
• the compositions of the invention When used as an additive to floor finishes, the compositions of the invention generally are added at about 0 001 weight % to about 5 weight % by dry weight of the composition of the invention in the wet composition. Preferably about from about 0.01 weight % to about 1 weight %, and more preferably from about 0.1 weight % to about 0.5 weight % is used.
• Floor waxes or polishes are water based, solvent based and polymer.
• the surfactants of the present invention me suitable for use with any of these.
• Water-based and polymer waxes dry to a high gloss without buffing; solvent-based wax requires vigorous buffing.
• Water-based wax is recommended for asphalt, vinyl, vinyl asbestos and rubber-tiled floors; solvent-based waxes produce a hard, shiny finish and are best for wood, cork and terrazzo floors.
• Self-polishing waxes, such as polymer or resin will yellow or discolor and wear off in heavy traffic areas; they should be stripped off and reapplied after three or four coats.
• the present invention further comprises a method of providing foaming in a medium comprising contacting the medium with a compound of Formula 1 as defined above.
• the compound of Formula 1 of the present invention is typically stmply blended with or added to the medium.
• the surfactants of the present invention are stable in aqueous, brine, acidic and basic medium.
• the compounds of the present invention of Formula 1 are effectively introduced to the medium by thoroughly stirring it in at room or ambient temperature More elaborate mixing can be employed such as using a mechanical shaker mechanical mixer, or providing heat or other methods More vigorous stirring will typically produce a larger amount of foam
• a low concentration of surfactant tn the medium of a minimum of about 0 01 O 'O by weight, preferably 0 02% by weight, more preferably 0.1% is sufficient to provide foaming
• the surfactants used in the method of the present invention can both create foam and maintain a stable foam in aqueous solution over a period of time
• the degree of foaming and the time a stable foam is maintained useful in various applications
• Foaming is an important property of fiuoros ⁇ rfactants that are used as additives for cleaners, drilling fluid additives for foaming, and fluid additives for oilfield stimulation activities
• foam is often used to promote adhesion of the active cleaning ingredient on the surface
• the aqueous or solvent based drilling fluids foam during drilling and thus aid in the removal of fines from the well around the drill-bit
• the addition of the fluoros ⁇ rfactant boosts the drilling fluid foaming properties.
• the fluorosurfactants also boost properties of the stimulation fluids during well treatments such as hydraulic fracture treatments or matrix treatments, performed to restore or enhance well productivity of oil and gas wells
• the surfactants of Formula 1 and the method of providing foaming of the present invention are useful in these applications
• the surfactants of Formula 1 and the method ot providing foaming of the present invention are also useful in applications requiring an aggressive (acidic or basic) medium Examples of such applications include etching processes in the manufacture of electronic or photovoltaic components, or in aggressive cleaning solutions For aggressive cleaners and etching applications, it is undesirable to have additives that create foams sustainable over a long time period Such sustained foams require the use of defoamers dunng disposal and can create complications during manufacturing processes Thus, providing foaming that is not maintained over a long time period, but instead disintegrates quickly in highly acidic and basic conditions, are desirable.
• the surfactants of Formula 1 and the method of providing foaming of the present invention provide foams that quickly disintegrate in aggressive medium.
• the foams provided by the method of the present invention disintegrate in about 15 minutes in acidic or basic medium, preferably in about 10 minutes, and more preferably in about 5 minutes.
• the surfactants of Formula 1 and the method of providing foaming of the present invention are useful in these applications
• the surfactants of Formula 1 and the methods of the present invention are useful in a wide variety of end-use applications.
• the surfactants of the present invention provide compounds having surfactant effects at low concentrations, such as below 0.5% by weight in water.
• the compounds of the invention contain less fluorine (improved fluorine efficiency), have a lower surface tension or are generally comparable to conventional fiuoroalky! surfactants,
• the inventive compounds provide the advantage of altering surface properties, such as repellency, leveling, and resistance to blocking, using less fluorine to achieve the same level of performance, or provide better performance using the same level of fluorine, as prior art compositions.
• the improvements in the surfactant characteristics reduce overall manufacturing cost while improving the performance of the surfactant products.
• the surfactants of the present invention also provide the advantage of stability in brine and aggressive media, such as acids and bases. This stability is unexpected for a phosphate functional surfactant. This stability means the surfactants are useful to provide surface activity and foaming properties in a variety of applications.
• OjFrOCF 2 CFrI 100 g, 0.24 mo! and benzoyl peroxide (3 g) were charged under nitrogen into a vessel A senes of three vacuum/nitrogen gas sequences was then executed at -50 C 'C and ethylene (18 g, 0 64 mof ) was introduced The vessel was heated for 24 hour at 110 °C The autoclave was cooled to 0 'C and opened after degassing Then the product was collected in a bottle The product was distilled giving 80 g of CjFyOCFjCFjCH ⁇ CH ⁇ l in 80% yield The boiling point was 56-60 f C at 25 mm Hg pressure (3325 Pa)
• MAB paints are paints having an acrylic semi-gloss resin with 84% gloss at 85 degrees available from M. A. Br ⁇ der and Sons, inc., Broomall. PA.
• TERGITOL 15-S-9 is available from Sigma Aldrich. St. Louis, MO.
• 1 ,3-Propanediol and poly(1 ,3-1 ,3-propanedio! are available from
• Tetra(ethylene) glycol and poly(ethylene glycol) are available from Sigma Aidrich, St. Louts, MO.
• Test Method 1 Wetting and Leveling Test
• a floor polish RHOPLEX 3829, Formulation N-29-1 , available from Rohm & Haas, Philadelphia, PA]
• the tiles initially had a uniform shiny finish; a uniform dull finish indicated coating removal.
• the tiles were then air-dried overnight
• a 1% by weight solution of the surfactant to be tested was prepared by dilution in deionized water. Following the resin manufacturer protocols, a 100 g portion of the RHOPLEX 3829 N-29-1 formulation was prepared, followed by addition of 0.75 g of the 1% by weight surfactant solution, to provide a test floor polish.
• test floor polish was applied to the tile by placing 3 mL portion of the test polish in the center of the tile, and spreading from top to bottom using a cheesecloth applicator, and finally placing a large 'X ' across the tile, using the applicator.
• the " 1 X- subsequently provides visual evidence of leveling at the rating step.
• the applicator was prepared from a two- layer 18 x 36 inch (46 x 91 cm) sheet of cheesecloth (from VWR 1 West Chester PA) folded twice into an eight-layer pad One corner of the pad was then used as the applicator
• the tile was allowed to dry for 30 mm and a total of 5 coats (Coating #s 1 - 5) were applied and dried, with the X test performed after each coating had be&n dried
• the tiie was rated on a 1 to 5 scale (1 being the worst 5 the best) on the surfactant's ability to promote wetting and leveling of the polish on the tiie surface The rating is determined using the Tile Rating Scale below, based on companson of a tile treated with the floor polish that contains no added surfactant
• Results were in mN/m (dynes/cm) with a Standard Deviation of less than 1 dyne/cm.
• the tensiometer was used according to the manufacturer's recommendations
• test method described herein is a modification of ASTM D4946 - 89. Standard Test Method for Blocking Resistance of Architectural Paints, which is hereby specifically incorporated by reference.
• the face- to-face blocking resistance of paints to be tested was evaluated m this test. Blocking, for the purpose of this test, was defined as the undesirable sticking together of two painted surfaces when pressed together or placed in contact with each other for an extended period of time.
• Each example to be tested was added to paint at 0.018% by weight based on solids of the additive in the paint.
• the paint used was MAB paint available from M. A. Bruder and Sons, Inc., Broomall, PA.
• the paint to be tested was cast on a polyester test pane! using an applicator blade.
• AIi painted panels were protected from surface contamination, such as grease, oil, fingerprints, dust, and the like. Typically, results were sought at 24 hours after casting the paint. After the panels had been conditioned in a conditioned room with controlled temperature and humidity as specified in the ASTM Test Method referenced above for the desired period of time, six squares (3.8 cm x 3 8 cm) were cut out from the painted test panel.
• the cut sections (three pairs) were placed with the paint surfaces face-to-face for each of the paints to be tested.
• the face-to-face specimens were placed in a 50 *C oven on a marble tray.
• a no. 8 stopper was placed on top, with the smaller diameter in contact with the specimens, and then a 1000g weight was placed on top of the stopper. This resulted in a pressure of 1.8 psi (12,400 Pascal) on the specimens.
• One weight and stopper was used for each specimen tested. After exactly 30 minutes, the stoppers and weights were taken off the test specimens which were removed from the oven and allowed to cool in the conditioned room for 30 minutes before determining the resistance to blocking
• the blocking resistance was rated from 0 to 10, corresponding to a subjective tack assessment (sound made upon separation of the painted specimens) or sea! (complete adhesion of the two patnted surfaces) as determined by the operator of the method.
• the specimen was put near the ear to actually hear the degree of tack
• the rating system is described in the Table 2 entitled Blocking Resistance Numerical Ratings below.
• the degree of seal was estimated from the appearance of the specimens and the fraction of the paint surfaces that adhere Patnt tearing away from the test panel backing was an indication of seaf. A higher number indicated better resistance to blocking.
• the test procedure used to evaluate the foaming of fluorosurfactants for oilfield applications is a modified version of the blender foaming test ASTM D3519-88 - Standard Test Method for Foam in Aqueous Media (Blender Test).
• ASTM D3519-88 - Standard Test Method for Foam in Aqueous Media Blender Test.
• the ability of the samples to create foam and maintain stable foam in aqueous solution over a penod of time was evaluated in this test.
• a blender, graduated cylinder, glass sample bottles and a stop watch were the only materials required
• stock solutions of the testing base solutions were made. These solutions were hard water, tap water, deiomzed water, or artificial sea water. Samples of 100 ml of the fi ⁇ orosurfactant to be tested at 0.1 % active ingredient in the desired base testing solution were prepared and stirred overnight to ensure complete mixing.
• the blender was cleaned with copious amounts of deionized water. Once clean, the blender was assembled for use
• the test fluid sample of 100 mL was poured into the blender jar.
• the temperature of the test fluid was measured with a thermometer and recorded.
• the blender was then run for 20 seconds at 50-60% power.
• the liquid and foam were immediately poured into a 500 mL graduated cylinder.
• the initial liquid and foam height were measured in mL and a timer was started. This was designated the maximum total foam height at time zero.
• the graduated cylinder was allowed to stand undisturbed. Additional liquid and foam height (in mL) measurements were taken 5, 10 and 15 minutes after the stop watch was started. In addition, the half-life of the foam was also recorded.
• the half-life was the time when half of the liquid had drained to the bottom of the graduated cylinder. During this time, any observations of the foam were recorded such as dense or thin foam and foam persistency. A larger height (in mL) of the foam indicated that the sample foamed more. A consistently high height (in mL) of foam demonstrated persistent foam.
• the blender foaming test was used as an indicator of the amount of foam that a sample produced and also displayed the persistence of that foam.
• Test Method 6 Nitrogen Bubbling Foam Test The nitrogen bubbling foam test procedure was used to evaluate the foaming of fiuorosurfactants in acidic and basic solutions for cleaning and etching application. First, stock solutions of the testing base solutions were made. These solutions were 15% HCi and 15% KOH Samples of 20 mL of the ff ⁇ orosurfactant to be tested at 0.1 % active ingredient tn the desired base testing solution were prepared and stirred overnight to ensure complete mixing. The sample solution was then added to a 10O mL graduated cylinder (glass). Nitrogen was then bubbled through the solution to produce foam at a rate that filled the cylinder in 20-30 seconds.
• a fritted glass tube was used to bubble the nitrogen through the solution When the foam reached the top of the cylinder, the nitrogen was turned off and a timer was started. The heights of the foam and liquid in mL were measured after 30 seconds. 5 minutes, 10 minutes, and 15 minutes. Observations of the quality and persistency of the foam were aiso recorded. The nitrogen bubbling foam test was used as an indicator of the amount of foam that a sample produced and the persistency of that foam.
• Phosphorus pentoxide (1 51 g 0.011 mol) was added to CeFuCH ⁇ CH 2 OH (2 g, 0 0055 mol) at 80 °C and the reaction was heated to 105 °C for 6 hours Propanediol (2 09 g, 0 0275 mol) was added to the reaction mixture at 95 ⁇ C. stirred for 3 5 hours, followed by the addition of TERGITOL 15-S-9 surfactant available from Sigma Aldrich. St. Louis, MO, ⁇ 1 26 g) at 86 "C After 10 mm, ammonia (1 49 mL.
• Phosphorus pentoxide (1 51 g. 0 011 mol) was added to C ⁇ FuCH-CH-OH (4 g. 0 011 mol) at 80 °C and the reaction was heated to 105 ⁇ C for 12 hours
• Polyethylene glycol (MW 200 4 4 g, 0 022 mol) was added to the reaction mixture at 100 ⁇ C and stirred for 12 hours, followed by the addition of TERGITOL 15-S-9 surfactant, available from Sigma Aldrich. St. Lotus. MO, (1.37 g) at 86 °C After 10 mm.
• Phosphorus pentoxide (1.33 g, 0.0096 mol) was added to CeFi 3 CH 2 CH 2 OH (3.5 g, 0.0096 mot) at 80 °C and the reaction was heated to 105 °C for 12 hours.
• Polyethylene glycol (MW 300: 5.77 g. 0.019 mol) was added to the reaction mixture at 95 °C and stirred for 12 hours, followed by the addition of TERGITOL 15-S-9 surfactant, available from Sigma Aidrich, St. Louis, MO 1 (1 .24 g) at 86 °C. After 10 min, ammonia (1.31 ml, 0.021 mot, 30 %) was added and the reaction was stirred for 10 min at 70 °C.
• Phosphorus pentoxide (1.01 g, 0.0073 mol) was added to CeFi 3 CH 2 CH 2 OH (4 g, 0.011 mol) at 80 °C and the reaction was heated to 105 °C for 12 hours.
• Polyethylene glycol (MW 600. 6.59 g, 0.011 mo!) was added to the reaction mixture at 100 °C and stirred for 12 hours, followed by the addition of TERGiTOL 15-S-9 surfactant, available from Sigma Aldrich, St. touts, MO, (1.03 g) at 86 °C. After 10 min, ammonia (1 .0 ml, 0.016 mo!, 30 %) was added and the reaction was stirred for 10 min at 7O°C.
• Phosphorus pentoxide (1 18 g, 0 0086 mot) was added to CpF 13 CH 2 CH-OH (5 g. 0.014 mo! at 80 °C and the reaction was heated to 105 °C for 12 hours
• Polypropylene dioi (MVV 650: 7 82 g, 0 0086 mo!) was added to the reaction mixture at 100 '3 C and stirred for 12 hours followed by the addition of TERGITOL 15-S-9 surfactant, available from Sigma Ald ⁇ ch, St Louis, MO. (1.21 g) at 86 °C. After 10 mm. ammonia (1 17 mL.
• Phosphorus pentoxide ( 1 08 g. 0.0076 mo!) was added to C 4 FeCH 2 CFrCH 2 CH 2 OH (2.5 g. 0 0076 mot) at 80 °C and the reaction was heated to 105 1 C for 6 hours.
• Propanediol (1 16 g. 0 015 mo!) was added to the reaction mixture at 95 °C, stirred overnight, followed by the addition of TERGITOL 15-S-9 surfactant, available from Sigma Ald ⁇ ch. St. Louis, MO, (0 90 g) at 86 °C After 10 mm, ammonia (1.04 mL. 0 017 mol, 30 %) was added and the reaction was stirred for 10 mm at 70 °C.
• Phosphorus pentoxide (1 08 g, 0.0076 moi) was added to C 3 FTOCIF 4 CH 2 CH 2 OH (2.5 g, 0.0076 mot) at 80 °C and the reaction was heated to 105 'C for 6 hours Propanediol (1 15 g, 0 015 mol) was added to the reaction mixture at 95 °C, stirred for overnight, followed by the addition of TERGITOL 15-S-9 surfactant, available from Sigma Ald ⁇ ch. St Louis, MO, (0 89 g) at 86 °C. After 10 mm, ammonia (0 94 mL, 0 017 rnol, 30 %) was added and the reaction was stirred for 10 min at 70 °C.
• Phosphorus pentoxide ⁇ 0.77 g. 0.0054 mo! was added to 0 4 FSCH 2 CF 2 CH 2 CH 2 OH (2.5 g, 0.0076 moi) at 80 °C and the reaction was heated to 105 °C for 12 hours.
• Polypropylene diol (MW 25Q: 2.16 g, 0.0086 moi) was added to the reaction mixture at 100 C C and stirred for 12 hours, followed by the addition of TERGITOL 15-S-9 surfactant, available from Sigma Aldrich. St. Louis, MO, (0.69 g) at 86 °C. After 10 min.. ammonia (0.73 mL, 0.012 moi, 30 %) was added and the reaction was stirred for 10 min at 70 °C.
• Phosphorus pentoxide (0.72 g, 0.005 mol) was added to C-JFrOC 2 F 4 CH 2 CH 2 OH (2.5 g, 0.0076 mol) at 80 °C and the reaction was heated to 105 °C for 12 hours.
• Polyethylene glycol (MVV 600: 4.57 g, 0.0076 mol) was added to the reaction mixture at 95 °C, stirred for overnight, followed by the addition of TERGITOL 15-S-9 surfactant, available from Sigma Aldrich, St. Louis, MO, (0.70 g) at 86 °C. After 10 min, ammonia (0.69 mL, 0.011 mol, 30 %) was added and the reaction was stirred for 10 min at 70 °C.
• Phosphorus pentoxide (1.26 g, 0.0092 mol) was added to C 6 F 1 V 1 CH 2 CH 2 OH (2.5 g, 0.0067 mol) at 80 °C and the reaction was heated to 105 °C for 12 hours.
• Tetra(ethylene) glycol (3.67 g, 0.019 mol) was added to the reaction mixture at 100 °C and stirred for 12 hours, followed by the addition of TERGiTOL 15-S-9 surfactant, available from Sigma Aidrich, St. Louis, MO, (1.06 g) at. 86 °C. After 10 min. ammonia (1 .17 ml. 0.019 mof, 30 %) was added and the reaction was stirred for 10 min at 70 °C.
• Phosphorus pentoxide (1.26 g, 0.0092 mol) was added to CgFi 3 CH 2 CH 2 OH ⁇ 2.5 g, 0.0067 mol) at 80 °C and the reaction was heated to 105 '3 C for 12 hours.
• Tetra(ethylene) glycol (4.27 g, 0.022 mol) was added to the reaction mixture at 100 °C and stirred for 12 hours, followed by the addition of TERGITOL 15-S-9 surfactant, available from Sigma Aldrtch, St. Louis. MO, (1.12 g) at 86 °C. After 10 min. ammonia (1 24 ml, 0.2 mol, 30 %) was added and the reaction was stirred for 10 min at 70 °C.
• Phosphorus pentoxide (1.34 g, 0.0092 mol) was added to C 3 F 7 OC ⁇ F 4 CH 3 CH 2 OH (2.5 g, 0.0077 mol) at 80 °C and the reaction was heated to 105 C C for 12 hours Tetra( ⁇ thylene) glycol (4.05 g, 0.021 mol) was added to the reaction mixture at 100 '3 C and stirred for 12 hours, followed by the addition of TERGITOL 15-S-9 surfactant, available from Sigma Ald ⁇ ch, St. Louis, MO, (1.16 g) at 86 °C. After 10 min. ammonia (1.29 ml..
• Phosphorus pentoxide (1 equivalent) was added to a perfluoroalkylethyl alcohol mixture of the formula F(CFa) 8 CH 2 CH 2 OH (2.3 equivalents).at 80 °C.
• the reaction was heated to 105 °C for 24 hours. Ammonia (30% solution in water, 2.6 equivalents) was added and the reaction was stirred for 10 min. at 70 °C. Water was added and the reaction was stirred at 70 "C for 1 hour to provide a phosphate product.
• the resulting product was tested for leveling, surface tension, contact angle, and resistance to blocking using Test Methods 1 to 4. The results are listed in Tables 3 to 6.
• the phosphates of Examples 1 to 18 exhibited excellent wetting ability in a fioor finish (RHOPLEX) formulation. They performed equally to or better than Comparative Example A comprising fluorinated phosphate having a higher fluorine content when tested on vinyl tile. Table 6 - Advancing Contact Angie in Paint
• the Comparative Example A was not stable in 10% NaCI and thus the blender foaming test could not be conducted.
• Foaming properties are desirable for cleaning solutions where the foam is used to promote adhesion of the active cleaning ingredient on the surface, in oiffiefd stimulation and drilling applications surfactant additives that help boost the foaming properties of the fluids are desirable

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