HK1202576B - Fluorophosphate surfactants - Google Patents
Fluorophosphate surfactants Download PDFInfo
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- HK1202576B HK1202576B HK15102893.7A HK15102893A HK1202576B HK 1202576 B HK1202576 B HK 1202576B HK 15102893 A HK15102893 A HK 15102893A HK 1202576 B HK1202576 B HK 1202576B
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Description
Technical Field
The field of the invention relates to fluorophosphates and their use as additives for surfactants, coatings or treatment agents to impart water and oil repellency to substrates coated with such compositions.
Background
Typically, fluoroalkyl phosphate surfactants and surface treatment agents contain multiple fluorochemical chains, contain a higher percentage of fluorine at a given concentration, and are commonly used because they are believed to provide better performance. However, fluorinated starting materials are expensive and in short supply. It is desirable to reduce the amount of fluorinated starting material in these surfactants while maintaining the same or better performance. Reducing the amount of fluorinated starting component required will not only reduce costs, but also shorten cycle times because fewer steps are required in surfactant production and less energy is required. Reducing the fluorine content will reduce costs, but it is essential to maintain the properties of the product.
Brace and Mackenzie are described in U.S. Pat. No. 3,083,224 as having the formula [ C ]mF2m+1CnH2nO]yPO(OM)3-yWherein m is 4 to 12, n is 1 to 16, and y averages 1.0 to 2.5. Brace and Mackenze describe their use as oil repellents, especially when y is 2.
Phosphate ester surfactants with ammonium as the counterion can potentially release ammonia into the environment. Alternative counterions are needed that provide stable surfactants while not adversely affecting surfactant performance.
It is desirable to improve surfactant performance, in particular, to reduce surface tension in coating compositions while using less fluorinated starting materials and counterions that are not simple ammonium compounds. It is also desirable to impart improved surface effects to the coated surface. The present invention provides methods for increasing surfactant performance and imparting improved surface effects to coated surfaces while utilizing less fluorinated starting materials.
Disclosure of Invention
The invention comprises compositions comprising formula I, formula II or formula III
Wherein
RfIs C optionally interrupted by one, two or three ether oxygen atoms1-C6A linear or branched perfluoroalkyl group;
x is 1 to 2;
a is (CH)2)k、(CH2CF2)m(CH2)n、(CH2)oSO2N(CH3)(CH2)p、O(CF2)2(CH2)rOr OCHFCF2OE；
Z is O or S;
m is 1 to 4;
k. n, 0, p and r are each independently 1 to 20;
e is C optionally interrupted by an oxygen, sulfur or nitrogen atom2-C20A linear or branched alkyl group; cycloalkyl radicals or C6-C10An aryl group;
r is C optionally interrupted by a heteroatom2-C60A linear or branched alkyl group, the heteroatom being selected from oxygen, sulphur or nitrogen atoms; a cycloalkyl group; or C6-C10An aryl group; provided that when R is greater than 8 carbons, the ratio of heteroatoms to carbon atoms is at least 1: 2; and is
M is ammonium cation (NH)2R1R2)+Wherein R is1And R2Independently a straight or branched organic group comprising at least one carboxylated moiety (e.g., carboxylic acid moiety) and one amino moiety, and optionally substituted, interrupted, or both substituted and interrupted by oxygen, sulfur or nitrogen containing moieties, or by cycloalkyl or aryl moieties containing up to 10 carbon atoms.
Another aspect of the present invention is a method of providing reduced surface tension, water repellency, oil repellency, and stain resistance to a substrate comprising contacting the substrate with a composition comprising one or more compounds of formula (I), (II), or (III).
Another aspect of the present invention is a method of providing block resistance, extended open time, and oil repellency to a substrate having a coating composition deposited thereon, said method comprising adding to the coating composition a composition comprising one or more compounds of formula (I), (II), or (III) prior to deposition of the coating composition on the substrate.
Another embodiment of the invention is a substrate to which has been applied a composition comprising one or more compounds of formula (I), (II) or (III).
Detailed Description
Hereinafter, trademarks are designated by capital letters. The invention comprises compositions comprising formula I, formula II or formula III
Wherein
RfIs C optionally interrupted by one, two or three ether oxygen atoms1-C6A linear or branched perfluoroalkyl group;
x is 1 to 2;
a is (CH)2)k、(CH2CF2)m(CH2)n、(CH2)oSO2N(CH3)(CH2)p、O(CF2)2(CH2)rOr OCHFCF2OE；
Z is O or S;
m is 1 to 4;
k. n, o, p and r are each independently 1 to 20;
e is C optionally interrupted by an oxygen, sulfur or nitrogen atom2-C20A linear or branched alkyl group; cycloalkyl radicals or C6-C10An aryl group;
r is C optionally interrupted by a heteroatom2-C60A linear or branched alkyl group, the heteroatom being selected from oxygen, sulphur or nitrogen atoms; a cycloalkyl group; or C6-C1oAn aryl group; provided that when R is greater than 8 carbons, the ratio of heteroatoms to carbon atoms is at least 1: 2; and is
M is ammonium cation (NH)2R1R2)+Wherein R is1And R2Independently a straight or branched organic group comprising at least one carboxylated moiety and one amino moiety, and optionally substituted, interrupted or both substituted and interrupted by oxygen, sulfur or nitrogen containing moieties, or by cycloalkyl or aryl moieties containing up to 10 carbon atoms.
The fluorinated compounds of formulae (I), (II) and (III) above that are useful in the various embodiments of the present invention are obtained synthetically.
Fluoroalkyl phosphate esters of formula (I) and (II) were prepared according to the methods described by Longoria et al in U.S. patent 6,271,289, and Brace and Mackenzie in U.S. patent 3,083,224, each incorporated herein by reference. Typically, phosphorus pentoxide (P)2O5) Or phosphorus oxychloride (POCl)3) With a fluoroalkyl alcohol or fluoroalkyl thiol to obtain a mixture of mono (fluoroalkyl) or bis (fluoroalkyl) phosphoric acids. For example, neutralization with amino acids such as L-arginine and L-lysine provides the corresponding phosphate. Reacting excess fluoroalkyl alcohol or fluoroalkyl thiol with P2O5Reaction followed by neutralization provides a mixture of mono (fluoroalkyl) phosphate and bis (fluoroalkyl) phosphate. Higher ratios of bis (fluoroalkyl) phosphate to mono (fluoroalkyl) phosphate are obtained by using the method of Hayashi and Kawakami in U.S. patent No. 4,145,382. Phosphite and phosphinate compositions were prepared in a similar manner.
The resulting composition is then diluted with water, a mixture of water and a solvent, or further dispersed or dissolved in a solvent selected from simple alcohols, glycol ethers and ketones suitable as solvents for final application to a substrate (hereinafter "application solvent"). Alternatively, aqueous dispersions made by conventional methods with surfactants are prepared by removal of the solvent (by evaporation) and use of emulsification or homogenization procedures known to those skilled in the art. Such solventless emulsions may be preferred to minimize flammability and Volatile Organic Compound (VOC) concerns. The final product applied to the substrate may be a dispersion (if water-based) or a solution.
By reacting phosphorus pentoxide (P)2O5) Or phosphorus oxychloride (POCl)3) With a fluorinated alcohol followed by the addition of a hydrocarbon diol or poly (diol) to produce a fluoroalkyl phosphate of formula (III). Typically, phosphorus pentoxide or phosphorus oxychloride is added to the fluorinated alcohol in approximately equimolar percent amounts. For example, when phosphorus pentoxide is used, it is added relative to P2O5About 0.4 to about 1.6 molar equivalents of a fluorinated alcohol. The mixture is heated to a temperature of from about 70 ℃ to about 120 ℃, preferably to about 100 ℃ to about 110 ℃, and maintained for several hours, preferably from about 3 to about 15 hours. The diol or poly (diol) is then added to the reaction mixture and heating is continued at the above temperature for an additional time period of about 3 to about 15 hours. Diols or poly (diols) with P2O5Is from about 1.4 to about 2.6. Followed by optional addition of surfactant at about 1% to about 3% by weight. Any of a variety of surfactants can be used, such as TERGITOL from SigmaAldrich (St. Louis, Mo.). After about 1 to about 2 hours, ammonia is added and stirred, followed by the addition of water to provide the phosphate ester of formula 1.
Diols useful in the synthesis of compounds of formula (III) include C optionally having one or two double bonds2-C60Straight and branched chain alcohols. Examples include 1, 3-propanediol; propylene glycol (1, 2-propanediol); di (ethylene glycol); tri (ethylene glycol); tetra (ethylene glycol); poly(s) are polymerized(ethylene glycol) [ PEG (OH)2]Preferably from about 4 to about 20 repeating units, and more preferably from about 5 to about 15 repeating units; poly (ethylene glycol) -polypropylene glycol-poly (ethylene glycol) triblock polymer [ PEG-PPG-PEG- (OH)2](ii) a And random copolymers of ethylene oxide and propylene oxide, preferably having a molecular weight M of from about 200 to about 1250w. Poly (1.3-propanediol) was purchased from e.i. du Pont DE Nemours and Company (Wilmington, DE). Polyethylene glycols having a nominal molecular weight of 200 to 2000 are available from Aldrich Chemical Company (st. louis, MO). Triblock copolymers of polyethylene oxide and polypropylene oxide (PEG-PPG-PEG) were purchased from BASF (Mount Olive, NJ).
It will be apparent to those skilled in the art that many variations of any or all of the procedures described above may also be used to optimize reaction conditions to obtain maximum yield, productivity, or product quality.
The fluoroalkyl alcohols used as reactants in the preparation of the compositions comprising formula (I), (II) or (III) are described below for the various examples.
One embodiment of the present invention is a composition comprising formula (I), (II) or (III) wherein A is (CH)2)k. Formula RfThe fluorinated alkyl iodides of formula I may be treated with ethylene by the procedure described in U.S. Pat. No. 3,979,469(Ciba-Geigy, 1976) to provide telomer ethylene iodides wherein k is from 2 to 6 or higher. Telomer ethylene iodides may be treated with oleum and hydrolyzed according to the procedure disclosed in WO95/11877(elf atochem s.a.) to provide the corresponding telomer alcohols. Fluorinated alcohols C6F13CH2CH2OH and C4F9CH2CH2OH was purchased from E.I.du Pont DE Nemours and Company (Wilmington, DE). Higher homologues of telomer ethylene iodides are obtained with excess ethylene at elevated pressure. The telomer ethylene iodides may be treated with various reagents to provide the corresponding thiols according to the procedure described in "J.fluorine chemistry" Vol.104, 2, p.173-183 (2000). One example is the reaction of telomer ethylene iodides with sodium thioacetate, followed by hydrolysis.
One embodiment of the present invention is a composition comprising formula (I), (II) or (III) wherein A is (CH)2CF2)m(CH2)n。
Telomerization of vinylidene fluoride (VDF) with linear or branched perfluoroalkyl iodides is well known and results in the structure Rf(CH2CF2)mCompounds of formula (I) wherein m is 1 to 3 or greater, and RfIs C1-C6A linear or branched perfluoroalkyl group. See, for example, Balague et al, "Synthesis of fluorinated polymers, Part1, Telomerization of vinylidine fluoride with perfluorinated ethylene oxides", J.Flourchem. (1995), 70(2), 215-23. Formula Rf(CH2CF2)pThe particular telomer iodides of I are isolated by fractional distillation and may be treated with ethylene as described above to produce compounds of formula Rf(CH2CF2)m(CH2)nA compound of formula I. Formula Rf(CH2CF2)m(CH2)nThe compounds of I can be treated as described above to produce alcohols and thiols.
One embodiment of the invention is a composition comprising a compound of formula (I), (II) or (III) A is (CH)2)oSO2N(CH3)(CH2)p-. Preferred compositions of formula (I), (II) or (II) include those wherein o and p are each 2. For the preparation of Rf(CH2)oSO2N(CH3)(CH2)pFluoroalkyl alcohols of the-OH compounds were purchased from E.I. du Pont DE Nemours and company (Wilmington, DE). Alternatively, the fluoroalkyl alcohol R is prepared by reaction of fluoroalkyl ethylene iodide with potassium thiocyanate in waterf(CH2)oSO2N(CH3)(CH2)p-OH, wherein o and p are defined above in formula (1). Distillation of the product R as a colorless liquidf(CH2)oSCN, which is then converted to have the formula R by reaction with chlorine and acetic acid in an autoclave at about 45-50 ℃ for several hoursf(CH2)oSO2Fluorinated sulfonyl chloride of Cl. The sulfonyl chloride is then reacted with an amine, such as N-methylethanolamine, to produce a compound of formula Rf(CH2)oSO2N(CH3)(CH2)p-fluorinated alcohols of OH.
One embodiment of the invention is a composition comprising formula (I), (II) or (III), A is O (CF)2)q(CH2)r. Preferred compositions of formula (I) or (II) are those wherein A is O (CF)2)q(CH2)rQ and R are each 2, RfIs C3F7Those of (a). Preferred compositions of formula (III) are those wherein A is O (CF)2)q(CH2)rQ and R are each 2, and RfIs C3F7R is CH2CH2Those of (a).
Used as a starting material to prepare compounds wherein A is O (CF)2)q(CH2)rThe fluoroalcohol of the composition of (1) is obtainable synthetically.
Formula RfOCF2CF2The starting perfluoroalkyl ether iodides of I can be prepared by the procedure described in example 8 of U.S. patent 5,481,028, which discloses the preparation of perfluoroalkyl ether iodides from perfluoro-n-propyl vinyl ether. The perfluoroalkyl ether iodide is then reacted with an excess of ethylene at elevated temperature and pressure. Although the addition of ethylene can be carried out under heating, it is preferred to use a suitable initiator. The initiator is preferably a peroxide, such as benzoyl peroxide, isobutyryl peroxide, propionyl peroxide, or acetyl peroxide. The peroxide is more preferably benzoyl peroxide. The temperature of the reaction is not limited, but is preferably a temperature in the range of 110 ℃ to 130 ℃. The reaction time may vary depending on the initiator and the reaction conditions, but 24 hours is usually sufficient. The product is purified by any method that separates unreacted starting materials from the final product, but distillation is preferred. Using about 2.7 moles of ethylene per mole of perfluoroalkylether iodide, a temperature of 110 ℃ and autogenous pressure, a reaction time of 24 hours, and passingThe product is purified by distillation, satisfactory yields of up to 80% of theory having been obtained.
The compound of formula R is prepared according to the procedure disclosed in WO95/11877(Elf Atochem S.A.)fO(CF2)2(CH2)rPerfluoroalkyl ether ethylene iodides of formula I (wherein R isfAnd r is as defined above) is treated with oleum and hydrolyzed to provide the corresponding alcohol. Alternatively, the perfluoroalkylether ethyl iodide may be treated with N-methylformamide, followed by hydrolysis with ethanol/acid. Temperatures of about 130 ° to 160 ℃ are preferred. Higher homologues (r) can be obtained with an excess of ethylene at elevated pressure>2). Treatment of formula R with various reagents according to the procedure described in J.fluorine Chemistry (104, 2, 173-183(2000))fO(CF2)2(CH2)rl fluorinated alkyl ether vinyl iodide to provide the corresponding thiol. The fluorinated alkyl ether ethylene iodides may also be treated by conventional methods to provide the corresponding thioalcohols or thioethylamines.
One embodiment of the invention is a composition comprising formula (I), (II) or (III), A is OCHFCF2And (6) OE. The fluoroalcohol used as starting material to prepare the composition of formula 5 is prepared by reacting dioxane with a diol in the presence of an alkali metal compound. For example, dioxane and formula R are typically reacted in the presence of an alkali metal such as KOH in a sealed stainless steel reaction vesselfOCF＝CF2With glycols such as HO (CH)2)2The OH is reacted at about 70 ℃ for about 8 hours. The glycol is used in about 1 to about 15 moles per mole of ether, preferably about 1 to about 5 moles per mole of ether. Suitable alkali metal compounds include alkali metals, alkaline earth metals, alkali metal hydroxides, alkali metal hydrides, or alkali metal amides. Preference is given to alkali metals such as Na, K or Cs, or alkali metal hydrides such as NaH or KH. The reaction is carried out at a temperature of about 40 ℃ to about 120 ℃. The reaction may be carried out in an optional solvent such as ether or nitrile.
The present invention comprises a fluorinated aqueous mixture comprising a mixture of an anionic aqueous fluoroalkyl phosphate, phosphite or phosphonite acid solution neutralized with an amino acid, preferably L-arginine and L-lysine. The composition is neutralized to a pH of about 5 to about 10, preferably about 6 to about 9, and most preferably about 6 to about 8.
One embodiment of the invention is a method of reducing the surface tension of a liquid, the method comprising contacting the liquid with a composition comprising formula I, formula II, or formula III
Wherein R isfX, A, Z, M, k, n, o, p, R, E, R and M are as defined above.
Liquids that may be used to reduce surface tension using the present invention include, but are not limited to, water, brine solutions, KCl solutions, drilling fluids, well fluids, liquid or gas treatment streams for subterranean formations and well bore areas, hydrocarbons, halocarbon systems, coating compositions, latexes, polymers, floor finishes, floor polishes, fire extinguishants, inks, emulsifiers, foaming agents, release agents, repellents, flow modifiers, film evaporation inhibitors, wetting agents, penetrants, cleaning agents, abrasives, plating agents, corrosion inhibitors, etchant solutions, welding agents, dispersion aids, biocides, pulping aids, rinse aids, polishes, personal care compositions, desiccants, antistatic agents, or adhesives.
The coating composition is an alkyd coating, a type I urethane coating, an unsaturated polyester coating, or a water-dispersible coating.
The present invention also includes a method of providing water repellency, oil repellency, and soil resistance to a substrate comprising contacting the substrate with a composition of formula (I) or (II) as defined above, or a mixture thereof. The compositions of the present invention are typically applied by contacting the substrate with the composition using conventional methods including, but not limited to, brushes, sprayers, rollers, doctor blades, swabbing, dipping techniques, foaming, liquid injection, and casting. Optionally, more than one coating may be used, especially on porous surfaces.
The compositions of the present invention may be used as additives in the preparation of substrates. It may be added at any suitable point in the preparation process. For example, in the case of paper, it may be added to the pulp at the time of sizing. Preferably, from about 0.3% to about 0.5% by weight of the composition of the present invention is added to the pulp stock, based on the dry solids and dry paper fibers of the composition.
When used as a surface treatment for paper, the compositions of the present invention are typically diluted with water to give a use solution containing from about 0.01% to about 20%, preferably from about 0.1% to about 10%, and most preferably from about 0.5% to about 5% by weight of the solids-based composition. When applied to paper, the coverage was about 10g/m2To about 200g/m2And preferably about 10g/m2To about 100g/m2The use solution of (1). Preferably, the application results in about 0.1g/m2To about 5.0g/m2Is applied to the paper.
When used on stone, tile and other hard surfaces, the compositions of the present invention are typically diluted with water to give a use solution containing from about 0.1% to about 20%, preferably from about 1.0% to about 10%, and most preferably from about 2.0% to about 5.0% by weight of the solids-based composition. When applied to a substrate, for a semi-porous substrate (e.g., limestone), the coverage is about 100 grams of application solution per square meter (g/m)2) And for a porous substrate (e.g., Saldui. RTM.), the coverage is about 200g/m2. Preferably, the application results in about 0.1g/m2To about 2.0g/m2Is applied to the surface.
The composition of the present invention is applied to or contacted with a substrate either by itself or in combination with one or more other polishing materials or surface treatment agents. The compositions of the present invention optionally further comprise additional components such as treating agents or polishing materials to achieve additional surface effects, or additives commonly used with such agents or finishes. Such additional components include compounds or compositions that provide surface effects such as stain resistance, stain release, soil repellency, soil release, water repellency, oil repellency, antimicrobial protection, and the like. One or more such treatments or finishes may be blended with the compositions of the present invention and applied to a substrate.
Other additives commonly used with such treatments or finishes may also be present, such as surfactants, pH adjusters, leveling agents, wetting agents, and other additives known to those skilled in the art. Examples of such finishing agents or agents include processing aids, foaming agents, lubricants, anti-soiling agents, and the like. The composition is applied at the manufacturing site, at the retailer site, or prior to installation and use, or at the consumer site.
The present invention also includes a method of providing block resistance, extended open time, and oil repellency to a substrate having a coating composition deposited thereon, said method comprising adding to the coating composition a composition of formula (I) or (II) above, or a mixture thereof, prior to deposition of the coating composition onto the substrate. Suitable coating compositions, termed "coating binders" herein, include compositions (typically liquid formulations) of: alkyd, type I polyurethane, unsaturated polyester or water dispersible coatings and are applied to a substrate for creating a durable film on the substrate surface. These are conventional paints, stains, and similar coating compositions.
The term "alkyd coating" as used herein refers to a conventional liquid coating, typically a paint, clear coat or stain, based on an alkyd resin. The alkyd resins are complex branched and crosslinked polyesters containing unsaturated aliphatic acid residues. Conventional alkyd coatings use cured or dried alkyd resins as binders or film-forming components. Alkyd resin coatings comprise unsaturated aliphatic acid residues derived from drying oils. These resins spontaneously polymerize in the presence of oxygen or air to produce a solid protective film. The polymerization reaction is referred to as "drying" or "curing" and occurs as a result of autoxidation of unsaturated carbon-carbon bonds in the aliphatic acid component of the oil by atmospheric oxygen. When applied to a surface as a thin liquid layer of a formulated alkyd coating, the resulting cured film is relatively strong, non-melting, and substantially insoluble in many organic solvents that serve as solvents or diluents for the unoxidized alkyd resin or drying oil. Such drying oils have been used as raw materials for oil-based coatings and are described in the literature.
The term "polyurethane coating" used hereinafter refers to a conventional liquid coating based on a polyurethane resin of type I, typically a lacquer, a clear paint or a stain. Polyurethane coatings typically comprise the reaction product of a polyisocyanate, typically toluene diisocyanate, and a polyol ester of a drying oleic acid. The polyurethane coatings were classified into five categories by ASTM D-1. The polyurethane I Coatings comprise a pre-reacted autoxidisable binder as described in "Surface Coatings" volume 1, previously cited. These are also known as polyurethane-modified alkyds (uralkyds), polyurethane-modified alkyds, oil-modified polyurethanes, polyurethane oils or polyurethane alkyds, which are the largest class of polyurethane coatings and include lacquers, clear coats or stains. The cured coating is formed by air oxidation and polymerization of unsaturated drying oil residues in the binder.
The term "unsaturated polyester coating" as used hereinafter refers to a conventional liquid coating based on an unsaturated polyester resin, which is dissolved in monomers and contains the required initiators and catalysts, typically a lacquer, a clear coat or a gel coat formulation. Unsaturated polyester resins comprise as unsaturated prepolymer a product obtained from the polycondensation of a diol such as 1, 2-propanediol or 1, 3-butanediol with an unsaturated acid in the form of an anhydride such as maleic acid (or maleic acid and a saturated acid such as phthalic acid). The unsaturated prepolymer is a linear polymer containing unsaturation in the chain. Which is dissolved in a suitable monomer (e.g., styrene) to produce the final resin. The film is produced by copolymerization of a linear polymer and a monomer by a free radical mechanism. The free radicals are generated by heat or more commonly by the addition of peroxides such as benzoyl peroxide, which are packaged separately and added prior to use. Such coating compositions are often referred to as "gel coat" finishes. In order for curing to occur at room temperature, decomposition of the peroxide to free radicals is catalyzed by certain metal ions (usually cobalt). Before application, the solution of peroxide and cobalt compound was added separately to the mixture and stirred well. Unsaturated polyester resins that cure by a free radical mechanism are also suitable for curing using, for example, ultraviolet radiation. This form of curing, in which no heat is generated, is particularly suitable for films of wood or wood boards. Other radiation sources, such as electron beam curing, may also be used.
As used herein, the term "water-dispersible coating" refers to a decorative or protective coating for a substrate, such as an emulsion, latex or suspension of a film-forming material dispersed in an aqueous phase, with water as the primary dispersing component. "Water-dispersible coatings" is a general class that describes many formulations and includes members of the above classes as well as members of other classes. Water-dispersible coatings typically comprise other common coating ingredients. Water-dispersible coatings are exemplified by, but not limited to, pigmented coatings such as latex paints, unpigmented coatings such as wood sealants, stains, and finishes, coatings for masonry and cement, and water-based asphalt emulsions. The water-dispersible coating optionally comprises surfactants, protective colloids and thickeners, pigments and filler pigments, preservatives, fungicides, freeze-thaw stabilizers, defoamers, pH control agents, coalescing aids, and other ingredients. For latex paints, the film-forming material is a latex polymer of acrylate acrylic, vinyl-acrylic, vinyl or mixtures thereof. Martens is described in "Emulsion and Water-solvent Paints and coatings" (Reinhold Publishing Corporation, New York, NY, 1965).
As used herein, the term "dried coating" refers to the final decorative and/or protective film obtained after the coating composition has dried, shaped, or cured. By way of non-limiting example, such a final film may be obtained by curing, coalescing, polymerizing, interpenetrating, radiation curing, uv curing, or evaporation. The final film may also be applied in a dry and final state in a dry coating.
Blocking is undesirable when two coated surfaces are pressed together or placed in contact with each other for an extended period of time. When adhesion occurs, separation of the surfaces can result in cracking of the coating on one or both surfaces. Thus, improved blocking resistance is beneficial in many cases where two coated surfaces need to be in contact, for example on a window frame.
As used herein, the term "extended open time" refers to a period of time during which one layer of a liquid coating composition can be blended into an adjacent layer of the liquid coating composition without exhibiting wrinkles, scratches, or other application marks. It is also known as wet edge time. Latex paints containing low boiling Volatile Organic Compounds (VOC) have shorter open times than desired due to the lack of VOC solvents at high boiling temperatures. The lack of extended open time will result in surface defects such as overlapping scratches or other marks. A longer open time extension is beneficial when the appearance of the coated surface is important, as it allows the application of the coating without leaving overlapping marks, scratches or other application marks in the overlapping area between one layer of the coating and an adjacent layer of the coating.
When used as an additive, the composition of the present invention is effectively incorporated into a coating base or other composition by thoroughly stirring it at room or ambient temperature. More complex mixing may be employed, such as using a mechanical shaker or providing heat or other methods. Such methods are not necessary and do not significantly improve the final composition. When used as an additive to latex paints, the compositions of the present invention are typically added to wet paints in an amount of from about 0.001% to about 5% by weight based on the dry weight of the composition. Preferably, about 0.01 wt.% to about 1 wt.%, and more preferably 0.1 wt.% to about 0.5 wt.% is used.
The invention also includes substrates treated with the compositions of the invention. Suitable substrates include fibers and hard surface substrates. Fibrous substrates include wood, paper, and leather. Hard surface substrates include porous and non-porous mineral surfaces such as glass, stone, tiles, concrete, unglazed tiles, bricks, porous clays, and various other substrates having surface porosity. Specific examples of such substrates include: glazed concrete, bricks, tiles, stone (including granite, limestone and marble), grout, stucco, statues, monuments, wood, composite materials (such as terrazzo), and wall and ceiling panels (including those made with gypsum board). These are used in the construction of buildings, roads, parking ramps, driveways, floor materials, fireplaces, fireplace hearths, countertops for kitchens and other decorative uses in interior and exterior applications.
The compositions of the present invention are useful for providing one or more of excellent water repellency, oil repellency, and soil resistance to treated substrates. They may also be used to provide blocking resistance, extended open time and oil repellency to substrates coated with a coating composition to which the compositions of the present invention are added. These properties are achieved using lower fluorine concentrations than conventional perfluorocarbon surface treating agents, thereby providing improved "fluorine efficiency" in the protection of the treated surface. The compositions of the present invention are effective at fluorine concentrations of about one-half to one-third of the fluorine concentration of conventional fluorochemical surface protectors. The compositions of the present invention also allow the use of lower fluoroalkyl groups containing 6 or less fluorinated carbon atoms, which typically show poor oil and water repellency properties for conventional commercially available surface treatment products if the fluoroalkyl group contains less than 8 carbon atoms.
Materials and test methods
The following materials and test methods were used in the examples herein.
C6F13CH2CH2OH and C4F9CH2CH2OH may beCommercially available from Sigma Aldrich (st. louis, MO).
i-C3F7CF2CF2CH2CH2OH is commercially available from SynQuest Labs, inc.
By adding ethylene (25g, 0.53 mol) to the charged C4F9CH2CF2Preparation of C in an autoclave of I (217g, 0.87mol) and D-limonene (1g) and then heating the reactor at 240 ℃ for 12 hours4F9CH2CF2CH2CH2And (5) OH. The product is obtained in 62% yield by vacuum distillation at 81-91 ℃ and 19-24 mmHg. Fuming sulfuric acid (70mL) was added slowly to 50gC4F9CH2CF2CH2CH2I and the mixture was stirred at 60 ℃ for 1.5 hours. Using ice-cold 1.5 wt% Na2SO3The aqueous solution quenched the reaction and was heated at 95 ℃ for 0.5 h. The bottom layer was separated and washed with 10 wt% aqueous sodium acetate solution and distilled to provide formula C4F9CH2CF2CH2CH2Compound of OH: bp54-57 ℃ at 2mmHg (267 pascals).
By adding C under nitrogen3F7OCF2CF2I (100g, 0.24mol) and benzoyl peroxide (3g) were charged to a pressure vessel to give C3F7OCF2CF2CH2CH2And (5) OH. Three successive series of evacuation/nitrogen charges were then carried out at-50 ℃ and ethylene (18g, 0.64mol) was then added. The vessel was heated at 110 ℃ for 24 hours. The autoclave was cooled to 0 ℃ and opened after venting. The product was then collected in a bottle. The product was distilled to give 80g of C in 80% yield3F7OCF2CF2CH2CH2I. A boiling point of 56-60 ℃ at 25mmHg (3333 Pa). C is to be3F7OCF2CF2CH2CH2A mixture of I (300g, 0.68mol) and N-methylformamide (300mL) was heated to 150 ℃ for 26 h. Then theThe reaction was cooled to 100 ℃ and water was then added to isolate the crude ester. Ethanol (77mL) and p-toluenesulfonic acid (2.59g) were added to the crude ester, and the reaction was stirred at 70 ℃ for 15 minutes. Ethyl formate and ethanol were then distilled off to give the crude product. The crude product was dissolved in ether, washed with an aqueous sodium sulfite solution, water and brine, and then dried over magnesium sulfate. The product was then distilled to give 199g of C in 85% yield3F7OCF2CF2CH2CH2And (5) OH. A boiling point of 71 to 73 ℃ at 40mmHg (5333 Pa).
L-lysine and L-arginine are commercially available from Sigma Aldrich (St. Louis, Mo.).
RHOPLEX3829, formulation N-29-1, is commercially available from The Dow Chemical Company (Philadelphia, Pa.).
MAB paints have an acrylic semi-gloss resin with 84% gloss at 85 degrees and are commercially available from m.a. bruder and sons, Inc (Broomall, PA).
Method of producing a composite material
Test method 1-measurement of surface tension
Surface tension was measured on a KRUSS K11 tensiometer model 2.501 (KRUSS USA, 5Matthews NC) according to the American society for testing and materials ASTM # D1331-56 using the Wilhelmy plate method in accordance with the instructions for the operation of the apparatus. A vertical plate of known perimeter was attached to the balance and the force due to wetting was measured. Each sample to be tested was added to the coating composition by weight of additive solids in deionized water. Several different concentrations were formulated. Ten replicates were performed for each dilution and were set up using the following instrument: the method comprises the following steps: plate method SFT, space: 1.0s, wet length: 40.2mm, 15 reading limit: 10, minimum standard deviation: 2 dynes/cm, and acceleration of gravity: 9.80665m/s2。
The results are in dynes/cm (mN/m) with a standard deviation of less than 1 dyne/cm. A tensiometer was used according to manufacturing recommendations. A stock solution is prepared corresponding to the highest concentration of surfactant in the coating composition to be analyzed. The solution concentrations are in terms of mole percent surfactant in a commercially available floor polish (RHOPLEX3829, formulation N-29-1), in deionized water, and in 2% aqueous KCl. The solution was stirred overnight (about 12 hours) to ensure complete mixing. A lower concentration stock solution was prepared for each sample by diluting the original stock solution. Floor polishes are used in applications in the consumer, institutional and industrial cleaning sectors to demonstrate the surface effect imparted to a substrate. The lower surface tension results show excellent performance.
Test method 2 blocking resistance of building latex paint
The test method described herein is a variation of the standard test method for blocking resistance of architectural paints ASTM D4946-89.
In this test, the face-to-face blocking resistance of the paints to be tested was evaluated. For the purposes of this test, blocking is defined as two painted surfaces undesirably sticking together when pressed together or placed in contact with each other for an extended period of time.
The paints to be tested were spread on polyester test panels using a doctor blade, all painted panels were protected from grease, oil, fingerprints, dust, etc. to avoid surface contamination, which may affect the anti-blocking results, the results were typically evaluated 24 hours after painting, as described in the ASTM method cited above, six squares (3.8cm ×.8cm) were cut from painted test panels after conditioning the panels in a conditioning chamber for the time required3Pa) of the pressure. For each sample tested, a weight and plug were used. Precisely after a time of 30 minutes, the time of the reaction,the plug and weight were removed from the test specimen. The samples were removed from the oven and allowed to cool in the conditioning chamber for 30 minutes before testing for blocking resistance.
After cooling, the sample was peeled off with a slow and steady force. The blocking resistance was rated from 0 to 10, as determined by the operator of the process, corresponding to a subjective tack assessment (sound produced when painted samples were separated) or sealing (complete adhesion of two painted surfaces). The sample was placed near the ear to actually hear the tack. The classification system is described in table 1. The extent of the seal was evaluated from the appearance of the sample and the adhered paint surface portion. The tearing of the lacquer from the test panel backing is an indication of the seal. Higher numbers show higher blocking resistance.
Table 1: evaluation of blocking resistance value
| Evaluation of blocking resistance value | Description of the isolation | Description of Performance |
| 10 | Non-sticking | Perfection |
| 9 | Trace amount of adhesion | Is excellent in |
| 8 | Very slight tack | Is very good |
| 7 | Slight tack | Good/very good |
| 6 | Moderate to light tack | Good effect |
| 5 | Moderate tack | In general |
| 4 | Very sticky-without sealing | Poor to moderate |
| 3 | 5% to 25% sealing | Too poor |
| 2 | 25% to 50% sealing | Too poor |
| 1 | 50% to 75% sealing | Very poor |
| 0 | 75％To 100% sealing | Very poor |
Test method 3-contact Angle
The contact angle was determined by sessile drop method described by A.W. Adamson in "The physical chemistry of Surfaces" fifth edition (Wiley & Sons, New York, NY, 1990). Additional information on the equipment and procedures for measuring contact angles is provided by r.h. dettre et al in "wettabilitity" (edited by j.c. berg, marcel dekker, New York, NY, 1993). In the sessile drop method, Ramde-Hart optical bench (available from Ramde-HartInc., 43Bloomfield Ave., Mountain Lakes, NJ) is used to hold the substrate in a horizontal position. The contact angle was measured at the specified temperature using a telescopic goniometer from the same manufacturer. Each example to be tested was added to the MAB paint at 0.018 wt% based on the weight of additive solids in the paint. A drop of test liquid was placed on a polyester frosted test panel (Leneta P-121 dark black type or equivalent, Leneta Company, Mahwah, NJ) and the tangent line was precisely determined at the point of contact between the drop and the surface. By increasing the droplet size, the advance angle is determined. Data are expressed as advancing contact angles.
The relationship between organic liquid contact angle and surface cleanability and dirt retention is described by a.w. adamson above. Generally, a higher hexadecane contact angle indicates that the surface has better dust and scale repellency, and easier surface dusting.
Test methods 4-wetting/leveling test
To test the wetting and leveling ability of the samples, the samples were added to a floor polish (RHOPLEX3829, formulation N-29-l, available from Dow Chemical Company (Philadelphia, Pa.), and applied to one half of a 12 inch by 12 inch (30.36cm by 30.36cm) Vinyl tile (available from intersue Vinyl Tiles, Estrie, Sherbrooke, QC, Canada) that was thoroughly cleaned. The tile was thoroughly cleaned by wetting the tile, adding powdered oxygen bleach cleaner, and scrubbing using a green SCOTCH-BRITE scrubbing pad (available from 3M Company, st. paul MN). This scrubbing procedure is used to remove the pre-existing coating on the tile. The tile initially has a uniform bright finish; a uniform dull finish indicates coating removal. The tile was then allowed to air dry overnight. A 1 wt% solution of the surfactant to be tested was prepared by dilution in deionized water. Following the resin manufacturer's protocol, 100g parts of RHOPLEX3829(N-29-1 formulation) were prepared, followed by the addition of 0.75g of a 1 wt% surfactant solution to provide a test floor polish.
A test floor polish was applied to the tile by the following method: a 3mL portion of the test floor polish was placed in the center of the tile, then spread from top to bottom using a cheesecloth applicator, and finally a large "X" was applied across the tile using the applicator. Subsequently in the assessment step, the "X" provides a leveling basis. The applicator was prepared by folding two 18X 36 inch (46X 91cm) pieces of cheesecloth (available from VWR, West Chester, Pa.) twice into eight-ply fabric pads. One corner of the cloth pad was then used as an applicator. The tile was allowed to dry for 30 minutes and a total of 5 coats (coat numbers 1 to 5) were applied and dried, with the X test being performed after each coat had dried. After each application, the tile is rated 1 to 5 (1 being the worst, 5 being the best) according to the ability of the surfactant to promote wetting and leveling of the polish on the tile surface. The following tile rating criteria were used to determine the rating based on comparison to a tile treated with a floor polish without added surfactant.
Table 2: visual rating scale for leveling of brick
Test method 5-foaming test of blender
The test procedure used to assess the foamability of fluorosurfactants used in oilfield applications (e.g., drilling and stimulation) and cleaning applications is a modified form of the blender foam test ASTM D3519-88 — standard test method for foam in aqueous media (blender test). In this test, the ability of a sample to generate foam in an aqueous solution and maintain a stable foam for a period of time is assessed. Blenders, graduated cylinders, glass sample bottles and stopwatches are the only materials required. First, a stock solution of the test base solution was prepared. These solutions were deionized water and 100mL of a 2% KCl sample of the fluorosurfactant to be tested with 0.1% active ingredient was prepared in the desired test base and stirred overnight to ensure complete mixing. The blender was cleaned with copious amounts of deionized water. After cleaning, the blender was assembled for use. A 100mL sample of the test fluid was poured into a stirred cup. The temperature of the test fluid was measured with a thermometer and recorded. The blender was then run at 50-60% power for 20 seconds. After 20 seconds, the liquid and foam were immediately poured into a 500mL graduated cylinder. The initial liquid and foam height was measured in mL and a timer was started. It was designated as the maximum total foam height at time zero. The graduated cylinder was allowed to stand. Liquid and foam height (in mL) were measured again 5 minutes, 10 minutes and 15 minutes after the start of the stopwatch. In addition, the half-life of the foam was also recorded. Half-life is the time for half of the liquid to flow to the bottom of the graduated cylinder. During this time, any foam observations were recorded, such as dense or sparse foam and foam persistence. A greater foam height (in mL) indicates that the sample is more foaming. Consistent high foam height (in mL) indicates sustained foaming. The blender foaming test was used as an indication of the amount of foam generated by the sample and also demonstrates the permanence of the foam.
Examples of the invention
Example 1
Phosphorus pentoxide (5.24g, 0.03692mol) was added to C at 80 deg.C6F13CH2CH2OH (30g, 0.08242mol) and the reaction was heated at 105 deg.COvernight. The reaction mixture was cooled to 60 ℃ and added to an aqueous solution of lysine (12.77g lysine in 181mL water). The mixture was stirred at 70 ℃ for 1 hour. The resulting products were tested for surface tension, contact angle, blocking resistance, and leveling as described below, and the results are shown in tables 3 to 7.
Example 2
Phosphorus pentoxide (1.23g, 0.008682mol) was added to C at 80 deg.C4F9CH2CH2OH (5.12g, 0.01938mol) and the reaction was heated at 105 ℃ overnight. The reaction mixture was cooled to 60 ℃ and an aqueous solution of lysine (3g lysine in 37g water) was added. The phospholysine salt solution was stirred at 70 ℃ for 1 hour. The resulting products were tested for surface tension, contact angle, blocking resistance, and leveling as described below, and the results are shown in tables 3 to 7.
Example 3
Phosphorus pentoxide (0.97g, 0.00683mol) was added to C at 80 deg.C4F9CH2CF2CH2CH2OH (5g, 0.01524mol) and the reaction was heated at 105 ℃ overnight. The reaction mixture was cooled to 60 ℃ and an aqueous solution of lysine (2.36g lysine in 33g water) was added. The phospholysine salt solution was stirred at 70 ℃ for 1 hour. The resulting products were tested for surface tension, contact angle, blocking resistance, and leveling as described below, and the results are shown in tables 3 to 7.
Example 4
Phosphorus pentoxide (0.96g, 0.00679mol) was added to C at 80 deg.C3F7OCF2CF2CH2CH2OH (5g, 0.01515mol) and the reaction was heated at 105 ℃ overnight. The reaction mixture was cooled to 60 ℃ and then an aqueous solution of lysine (2.34g lysine in 47g water) was added. The phospholysine salt solution was stirred at 70 ℃ for 1 hour. The resulting products were tested for surface tension, contact angle, blocking resistance, and leveling as described below, and the results are shown in Table 3To 7.
Example 5
Phosphorus pentoxide (1.01g, 0.00713mol) was added to i-C at 80 deg.C3F7CF2CF2CH2CH2OH (5g, 0.01592mol) and the reaction was heated at 105 ℃ overnight. The reaction mixture was cooled to 60 ℃ and an aqueous solution of lysine (2.94g lysine in 34g water) was added. The phospholysine salt solution was stirred at 70 ℃ for 1 hour. The resulting products were tested for surface tension, contact angle, blocking resistance, and leveling as described below, and the results are shown in tables 3 to 7.
Example 6
Phosphorus pentoxide (0.87g, 0.006154mol) was added to C at 80 deg.C6F13CH2CH2OH (5g, 0.01374mol) and the reaction was heated at 105 ℃ overnight. The reaction mixture was cooled to 60 ℃ and an aqueous arginine solution (2.54g arginine in 34g water) was then added. The phospholysine salt solution was stirred at 70 ℃ for 1 hour. The resulting products were tested for surface tension, contact angle, blocking resistance, and leveling as described below, and the results are shown in tables 3 to 7.
Example 7
Phosphorus pentoxide (1.20g, 0.008485mol) was added to C at 80 deg.C4F9CH2CH2OH (5g, 0.01894mol) and the reaction was heated at 105 ℃ overnight. The reaction mixture was cooled to 60 ℃ and an aqueous arginine solution (3.5g arginine in 39g water) was then added. The phospholysine salt solution was stirred at 70 ℃ for 1 hour. The resulting products were tested for surface tension, contact angle, blocking resistance, and leveling as described below, and the results are shown in tables 3 to 7.
Example 8
Phosphorus pentoxide (0.97g, 0.00683mol) was added to C at 80 deg.C4F9CH2CF2CH2CH2OH(5g，0.01524mol) and the reaction was heated at 105 ℃ overnight. The reaction mixture was cooled to 60 ℃ and an aqueous arginine solution (2.81g arginine in 35g water) was then added. The phospholysine salt solution was stirred at 70 ℃ for 1 hour. The resulting products were tested for surface tension, contact angle, blocking resistance, and leveling as described below, and the results are shown in tables 3 to 7.
Example 9
Phosphorus pentoxide (0.96g, 0.00679mol) was added to C at 80 deg.C3F7OCF2CF2CH2CH2OH (5g, 0.01515mol) and the reaction was heated at 105 ℃ overnight. The reaction mixture was cooled to 60 ℃ and an aqueous arginine solution (2.8g arginine in 35g water) was then added. The phospholysine salt solution was stirred at 70 ℃ for 1 hour. The resulting products were tested for surface tension, contact angle, blocking resistance, and leveling as described below, and the results are shown in tables 3 to 7.
Example 10
Phosphorus pentoxide (1.01g, 0.00713mol) was added to i-C at 80 deg.C3F7CF2CF2CH2CH2OH (5g, 0.01592mol) and the reaction was heated at 105 ℃ overnight. The reaction mixture was cooled to 60 ℃ and an aqueous arginine solution (2.94g arginine in 36g water) was then added. The phospholysine salt solution was stirred at 70 ℃ for 1 hour. The resulting products were tested for surface tension, contact angle, blocking resistance, and leveling as described below, and the results are shown in tables 3 to 7.
Comparative example A
Phosphorus pentoxide (1 eq.) is added to formula F (CF) at 80 deg.C2)zCH2CH2OH in a perfluoroalkylethyl alcohol mixture (2.3 equivalents). A typical mixture is as follows: 1.6% z 4, 48.3% z 6, 28.7% z 8, 13.9% z 10, 5.3% z 12, 1.7% z 14, 0.4% z 16, and 0.1% z 18. The reaction was heated at 105 ℃ for 24 hours. Ammonia (30% water) was addedSolution, 2.6 equivalents), and the reaction was allowed to stir at 70 ℃ for 10 minutes. Water was added and the reaction was allowed to stir at 70 ℃ for 1 hour to afford the phosphate ester product. The resulting products were tested for leveling, surface tension, contact angle and blocking resistance using test methods 1 to 4. The results are shown in tables 3 to 7.
Table 3: surface tension in DI water at 23 deg.C (dyne/cm)
| Examples | 0.000％ | 0.001％ | 0.010％ | 0.100％ | 0.500％ |
| 1 | 72.2 | 64.1 | 25.7 | 23.8 | 26.9 |
| 2 | 72.1 | 58.4 | 44.7 | 27.4 | 16.4 |
| 3 | 72.3 | 46.9 | 33.4 | 18.2 | 16.5 |
| 4 | 72.3 | 38.7 | 26.6 | 18.2 | 17.1 |
| 5 | 72.0 | 47.4 | 36.5 | 21.6 | 19.0 |
| 6 | 72.4 | 66.4 | 24.6 | 21.6 | 22.0 |
| 7 | 72.6 | 57.0 | 42.0 | 25.1 | 17.0 |
| 8 | 72.6 | 46.9 | 32.2 | 16.8 | 17.0 |
| 9 | 72.2 | 40.7 | 26.0 | 20.1 | 18.0 |
| 10 | 72.3 | 40.2 | 33.0 | 19.4 | 17.7 |
| Comparative example | 72.2 | 61.8 | 39.2 | 34.3 | 26.3 |
Examples were added to deionized water based on the weight of additive solids in DI water.
Standard deviation <1 dyne/cm
The nominal surface tension of the deionized water was 72 dynes/cm (shown as 0.000% in table 3). The surface tension of each aqueous solution was significantly reduced when the compound of the present invention was added at the indicated rate. Better performance is obtained at higher levels.
Table 4: surface tension (dynes/cm) of Rhoplex3829(N-29-1 formulation) floor finish at 23 ℃。
| Examples | 0.000％ | 0.001％ | 0.010％ | 0100％ | 0.500％ |
| 1 | 32.2 | 31.5 | 27.8 | 17.3 | 16.1 |
| 2 | 32.3 | 31.6 | 30.1 | 24.4 | 19.5 |
| 3 | 32.3 | 31.2 | 30.3 | 253 | 199 |
| 4 | 32.1 | 31.8 | 27.4 | 19.1 | 16.8 |
| 5 | 32.2 | 29.2 | 29.0 | 22.7 | 18.1 |
| 6 | 32.3 | 31.7 | 27.8 | 17.9 | 16.4 |
| 7 | 32.2 | 32.1 | 30.6 | 24.8 | 19.5 |
| 8 | 32.0 | 31.8 | 29.7 | 25.8 | 20.1 |
| 9 | 32.4 | 31.9 | 28.2 | 19.9 | 16.5 |
| 10 | 32.5 | 31.9 | 29.7 | 23.6 | 17.9 |
| Comparative example | 32.5 | 31.3 | 28.2 | 21.0 | 20.3 |
Concentration of examples in floor finish, wt%
Standard deviation <1 dyne/cm
RHOPLEX3829 (formulation N-29-1) the coating composition had a nominal surface tension of 32 dynes/cm. When the above examples of the present invention were added at the specified rates, the surface tension of each aqueous coating composition solution was significantly reduced. Better performance (lower surface tension values) is obtained at higher levels, which indicates improved wetting and leveling properties. Examples 1-10 reduced surface tension as well or better than comparative examples containing fluorinated phosphate esters with longer perfluorinated alkyl groups and higher fluorine loading.
Table 5: blocking resistance of semi-gloss latex paint
| Examples | Adhesion rating | Fluorine (ppm) |
| Control | 2.7 | 0 |
| 1 | 8.7 | 85 |
| 2 | 7.3 | 71 |
| 3 | 8.3 | 76 |
| 4 | 8.0 | 76 |
| 5 | 8.0 | 78 |
| 6 | 8.3 | 81 |
| 7 | 7.3 | 67 |
| 8 | 7.0 | 73 |
| 9 | 7.3 | 72 |
| 10 | 7.3 | 74 |
| Comparative example | 8.2 | 114 |
Examples were added to the coating at 002% by weight of the additive solids in the paint.
Mean of 3 replicates
The data in table 5 show that the present invention achieves superior blocking resistance at much lower fluorine content compared to the comparative examples.
Table 6: advancing contact angle of semi-gloss latex paint
| Examples | Hexadecane (Hexadecane) | F(ppm) |
| Control | 0 | 0 |
| 1 | 81.3 | 85 |
| 2 | 84.5 | 71 |
| 3 | 82.2 | 76 |
| 4 | 98.8 | 76 |
| 5 | 95.8 | 78 |
| 6 | 81.9 | 81 |
| 7 | 87.5 | 67 |
| 8 | 73.6 | 73 |
| 9 | 92.5 | 72 |
| 10 | 83.6 | 74 |
| Comparative example | 81.4 | 114 |
Example was added to the paint at 002 wt% based on additive solids in the paint.
The data in table 6 shows a significant increase in hexadecane contact angle for all examples of the invention compared to the comparative examples. An increase in advancing hexadecane contact angle correlates with improved oil repellency. The present invention performs equally or better than the comparative examples at significantly lower F loads.
The product was added to a floor polish in an amount of 0.75 wt% in a 1 wt% surfactant dilution and tested for leveling using test method 3. The results are shown in Table 7.
Table 7: leveling of RHOPLEX3829(N-29-1 formulation) floor finish
| Examples of the invention | Reading (c) | F(ppm) |
| Blank space | 1.2 | 0 |
| 1 | 3.3 | 32 |
| 2 | 3.3 | 27 |
| 3 | 3.3 | 29 |
| 4 | 3.1 | 29 |
| 5 | 3.1 | 30 |
| 6 | 3.3 | 30 |
| 7 | 3.2 | 25 |
| 8 | 3.1 | 27 |
| 9 | 3.3 | 27 |
| 10 | 3.1 | 28 |
| Comparative example | 3.6 | 43 |
Average of 5 coatings
The phosphate esters exhibited excellent wetting ability in a commercially available floor finish (RHOPLEX3829N-29-1 formulation). When tested on vinyl tile, they performed equally to the comparative examples, which contained fluorinated phosphate esters with longer perfluorinated alkyl groups and much higher fluorine loading.
Table 8: surface tension in 2% KCl at 23 deg.C (dyne/cm)
| Examples | 0000％ | 0001％ | 0010％ | 0100％ | 0500％ |
| 1 | 73.5 | - | - | - | - |
| 2 | 73.3 | 46.0 | 24.0 | 15.8 | 16.0 |
| 3 | 73.5 | 48.6 | 19.9 | 17.3 | 17.3 |
| 4 | 72.9 | 28.3 | 19.4 | 18.8 | 15.1 |
| 5 | 73.4 | 29.8 | 17.9 | 17.6 | 16.9 |
| 6 | 73.5 | - | - | - | - |
| 7 | 73.5 | 43.2 | 23.0 | 16.1 | 14.5 |
| 8 | 74.2 | 38.5 | 19.0 | 18.2 | 16.1 |
| 9 | 73.5 | 46.8 | 20.3 | 19.5 | 17.3 |
| 10 | 73.4 | 34.2 | 18.5 | 17.1 | 17.5 |
| Comparative example | 73.6 | 68.4 | 50.2 | 32.9 | 29.0 |
- (Y-O-Si-O) -untested
The nominal surface tension of 2% KCl water was 73.5 dynes/cm (shown as 0.000% in Table X). Examples 1 and 6 were unstable in 2% KCl. When the above phosphate ester is added at a specific ratio, the surface tension of each aqueous solution is significantly reduced. Better performance is obtained at higher levels. From the results obtained from the tests, it is seen that the present invention is superior in surface tension reduction over the comparative examples. Improved surface tension reduction in brine is desirable for oilfield stimulation and drilling fluid applications.
TABLE 9-foaming of Mixer in deionized Water
TABLE 10-2% KCl Mixer foaming
Examples 1 and 6 were unstable in 2% KCl and therefore the blender foaming test could not be performed.
- (Y-O-Si-O) -untested
The blender foaming results in deionized water and 2% KCl are shown in tables 9 and 10, respectively, showing improved foamability and more sustained foam over time over the comparative examples. Foaming characteristics are desirable for cleaning solutions in which foam is used to promote adhesion of the active cleaning ingredient to the surface. In oilfield stimulation and drilling applications, surfactant additives that help promote fluid foaming characteristics are desired.
Claims (13)
1. A composition comprising a compound of formula I or formula II,
wherein
RfIs C optionally interrupted by one, two or three ether oxygen atoms1-C6A linear or branched perfluoroalkyl group;
x is 1 to 2;
a is (CH)2)k、(CH2CF2)m(CH2)n、(CH2)oSO2N(CH3)(CH2)p、O(CF2)2(CH2)rOr OCHFCF2OE；
Z is O or S;
m is 1 to 4;
k. n, o, p and r are each independently 1 to 20;
e is C optionally interrupted by an oxygen, sulfur or nitrogen atom2-C20A linear or branched alkyl group; cycloalkyl radicals or C6-C10An aryl group; and is
M+Is an ammonium cation (NH)3R′)+Wherein R' is a linear or branched organic group comprising at least one carboxylic acid moiety and one amino moiety, and optionally substituted, intercalated, or both substituted and intercalated with a nitrogen containing moiety.
2. The composition of claim 1, wherein RfIs C4-C6Linear perfluoroalkyl radical, A is (CH)2)kAnd k is 2.
3. The composition of claim 1, wherein RfIs C4-C6Linear perfluoroalkyl radical, A is (CH)2CF2)m(CH2)nM is 1, and n is 2.
4. The composition of claim 1, wherein RfIs C3Linear perfluoroalkyl radical, A is O (CF)2)2(CH2)rAnd r is 2.
5. The composition of claim 1, wherein M+Is composed of
6. The composition of claim 1, wherein M+Is composed of
7. A method of reducing the surface tension of a liquid comprising contacting the liquid with a composition comprising formula I or formula II
Wherein
RfIs C optionally interrupted by one, two or three ether oxygen atoms1-C6A linear or branched perfluoroalkyl group;
x is 1 to 2;
a is (CH)2)k、(CH2CF2)m(CH2)n、(CH2)oSO2N(CH3)(CH2)p、O(CF2)2(CH2)rOr OCHFCF2OE；
Z is O or S;
m is 1 to 4;
k. n, o, p and r are each independently 1 to 20;
e is C optionally interrupted by an oxygen, sulfur or nitrogen atom2-C20A linear or branched alkyl group; cycloalkyl radicals or C6-C10An aryl group; and is
M+Is an ammonium cation (NH)3R′)+Wherein R' is a linear or branched organic group comprising at least one carboxylic acid moiety and one amino moiety, and optionally substituted, intercalated, or both substituted and intercalated with a nitrogen containing moiety.
8. The method of claim 7, wherein the liquid is selected from the group consisting of water, brine solutions, KCl solutions, drilling fluids, well fluids, liquid or gas treatment streams for subterranean formations and well bore areas, hydrocarbons, halocarbon systems, coating compositions, latexes, polymers, floor finishes, floor polishes, fire extinguishants, inks, emulsifiers, foaming agents, release agents, repellents, flow modifiers, film evaporation inhibitors, wetting agents, penetrants, cleaners, abrasives, plating agents, corrosion inhibitors, etchant solutions, welding agents, dispersion aids, biocides, pulping aids, rinse aids, polishes, personal care compositions, desiccants, antistatic agents, or adhesives.
9. The method of claim 8, wherein the coating composition is an alkyd coating, a type I polyurethane coating, an unsaturated polyester coating, or a water-dispersible coating.
10. A composition comprising a liquid treated according to claim 7.
11. A method of imparting a surface effect to a substrate comprising contacting at least a portion of the surface of the substrate with a coating composition comprising a composition comprising formula I or formula II
Wherein
RfIs C optionally interrupted by one, two or three ether oxygen atoms1-C6A linear or branched perfluoroalkyl group;
x is 1 to 2;
a is (CH)2)k、(CH2CF2)m(CH2)n、(CH2)oSO2N(CH3)(CH2)p、O(CF2)2(CH2)rOr OCHFCF2OE；
Z is O or S;
m is 1 to 4;
k. n, o, p and r are each independently 1 to 20;
e is C optionally interrupted by an oxygen, sulfur or nitrogen atom2-C20A linear or branched alkyl group; cycloalkyl radicals or C6-C10An aryl group; and is
M + is an ammonium cation (NH)3R′)+Wherein R' is a linear or branched organic group comprising at least one carboxylic acid moiety and one amino moiety, and optionally substituted, intercalated, or both substituted and intercalated with a nitrogen containing moiety.
12. The method of claim 11, wherein the coating composition is an alkyd coating, a type I polyurethane coating, an unsaturated polyester coating, or a water-dispersible coating.
13. The method of claim 11, wherein the surface effect is a reduction in surface tension, water repellency, oil repellency, soil resistance, and blocking resistance, increased contact angle, wetting, and leveling.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US201161556418P | 2011-11-04 | 2011-11-04 | |
| US61/556,418 | 2011-11-07 | ||
| US13/400,176 | 2012-02-20 | ||
| US13/400,176 US9328317B2 (en) | 2011-11-04 | 2012-02-20 | Fluorophosphate surfactants |
| PCT/US2012/036916 WO2013066400A1 (en) | 2011-11-04 | 2012-05-08 | Fluorophosphate surfactants |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| HK1202576A1 HK1202576A1 (en) | 2015-10-02 |
| HK1202576B true HK1202576B (en) | 2018-11-16 |
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