HK1143166A - Mixed fluoroalkyl-alkyl surfactants - Google Patents

Description

Mixed fluoroalkyl-alkyl surfactants

Technical Field

The field of the invention relates to the synthesis and use of fluorochemical surfactants.

Background

For surfactants and surface treatments having fluorochemical chains, the longer the perfluoroalkyl chain, the higher the percentage of fluorine contained and the better the performance generally provided at a given concentration. However, fluorinated materials derived from longer perfluoroalkyl chains are relatively expensive. Therefore, it is desirable to reduce the fluorine content while producing the same or higher performance. Reducing the fluorine content will reduce costs, but the product properties must be maintained.

Desimone et al in WO 02/26921 describe a compound having the structure R_fO-PO(OR_H)(O^-M⁺) In which R is_fIs C_nF_(2n+1)(CH₂)_m，R_HIs C_nH_(2n+1)Or C_nF_(2n+1))(CH₂)_mN and M are 1 to 24, and M⁺Is K⁺、Na⁺Or NH₄ ⁺. Desimone et al describe the use of these compounds as surfactants in liquid carbon dioxide, but not in water or other media.

It is desirable to improve surfactant performance, in particular to reduce surface tension in aqueous systems, and to increase fluorine efficiency, i.e., to increase the efficiency or performance of the surfactant, so that lower proportions of the expensive fluorine component are required to achieve the same level of performance, or to have better performance when the same level of fluorine is used. It is particularly desirable for surfactants to have similar or more desirable properties in aqueous systems than current commercial products but with shorter perfluoroalkyl groups. The present invention provides such a surfactant.

Summary of The Invention

The present invention comprises compounds of formula 1

R_f-A-OP(O)(O^-M⁺)(O-R_H) Formula 1

Wherein

R_fIs C optionally interrupted by one, two or three ether oxygen atoms₂-C₆A linear or branched perfluoroalkyl group;

a is (CH)₂CF₂)_m(CH₂)_n-、(CH₂)_oSO₂N(CH₃)(CH₂)_p-、O(CF₂)_q(CH₂)_r-, or OCHFCF₂OE-；

m is 1 to 4; n, o, p and r are each independently 2 to 20; q is 2;

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;

m is a group I metal or an ammonium cation (NH)_xR² _y)⁺Wherein R is²Is C₁-C₄Alkyl, x is 1 to 4, y is 0 to 3, and x + y is 4; and is

R_HIs C₁-C₂₀Linear, branched or cyclic alkyl, or C₆-C₁₀And (4) an aryl group.

The present invention also includes a method of reducing the surface tension of an aqueous medium comprising contacting the medium with a composition of formula 1 as defined above.

The invention also includes a method of providing leveling, open time extension and blocking resistance to a coated substrate, said method comprising adding to the coating base a compound of formula 1 as defined above prior to deposition onto said substrate.

The invention also includes substrates treated by the above method.

Detailed Description

Trademarks are herein shown in upper case.

Herein, the term "two-tailed surfactant" is used to describe a surfactant having two hydrophobic groups attached to a single hydrophilic linking group. The two hydrophobic groups may be the same (referred to as "symmetric double tail surfactants") or different (referred to as "hybrid double tail surfactants").

The invention includes fluoroalkyl alkyl compounds of formula 1

R_f-A-OP(O)(O^-M⁺)(O-R_H) Formula 1

Wherein

A is (CH)₂CF₂)_m(CH₂)_n-、(CH₂)_oSO₂N(CH₃)(CH₂)_p-、O(CF₂)_q(CH₂)_r-, or OCHFCF₂OE-；

R_fIs C optionally interrupted by one, two or three ether oxygen atoms₂-C₆A linear or branched perfluoroalkyl group;

R_His C₁-C₂₀Linear, branched or cyclic alkyl, or C₆-C₁₀Aryl radical, and

m is a group I metal or an ammonium cation (NH)_xR² _y)⁺Wherein R is²Is C₁-C₄Alkyl, x is 1 to 4, y is 0 to 3, andx + y is 4;

m is 1 to 4; n, o, p and r are each independently 2 to 20; and q is 2.

E is C optionally interrupted by an oxygen, sulfur or nitrogen atom₂-C₂₀A linear or branched alkyl group; cycloalkyl or C₆-C₁₀And (4) an aryl group.

Formula 1 is a hybrid two-tailed surfactant. The compounds of formula 1 can be prepared according to the methods described by Longoria et al in U.S. patent publication 6,271,289 and by Brace and Mackenzie in U.S. patent publication 3,083,224. Typically, phosphorus pentoxide (P)₂O₅) Or phosphorus oxychloride (POCl)₃) With fluoroalkyl alcohols or fluoroalkyl thiols to give mixtures of mono-or bis- (fluoroalkyl) phosphoric acids. Neutralization is carried out using a common base such as ammonium hydroxide or sodium hydroxide, or an alkanolamine (e.g., Diethanolamine (DEA)) to provide the corresponding phosphate ester. 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 can be obtained by using the method of Hayashi and Kawakami in U.S. patent publication 4,145,382. Phosphite and phosphinate compositions were prepared in a similar manner. In various embodiments, the fluoroalkyl alcohol or fluoroalkyl thiol used as a reactant in the preparation of the compound of formula 1 is described below. Preference is given to compounds of the formula 1, in which R_fIs C₃-C₆A perfluoroalkyl group. More preferably wherein R_fIs C₄Or C₆Those of perfluoroalkyl groups.

An embodiment of the invention are compounds of formula 1 wherein A is (CH)₂CF₂)_m(CH₂)_n-, represented herein by the formula 2,

R_f-(CH₂CF₂)_m(CH₂)_n-O-P(O)(OR¹)(O^-M⁺) Formula 2

Wherein

R_f、R¹M, n and M are as defined above in formula 1. Preferred compounds of formula 2 include those wherein R_fIs C₄Or C₆Perfluoroalkyl and n is 2.

The fluorinated alcohols used in the preparation of the various embodiments of formula 2 can be obtained synthetically according to the following scheme:

telomerization of vinylidene fluoride (VDF) with linear or branched perfluoroalkyl iodides is well known and can be used to prepare R_f(CH₂CF₂)_pA compound of structure I wherein p is 1 to 3 or greater, and R_fIs a C1-C6 perfluoroalkyl group. See, for example, Balague et al, "Synthesis of fluorinated polymers, Part 1, catalysis of vinylidenefluoride with perfluorinated alkyls", J.Flourchem.1995, 70(2), 215-23. The specific telomer iodides (V) are isolated by fractional distillation. Telomer iodides (V) are treated with ethylene to provide telomer ethylene iodides (VI) according to the method described in U.S. Pat. No. 3,979,469(Ciba-Geigy, 1976) wherein q is from 1 to 3 and higher. Telomer ethylene iodides (VI) can be treated with oleum and hydrolyzed to give the corresponding telomer alcohols (VII) according to the procedure disclosed in WO95/11877(Elf Atochem S.A.). The higher homologues (q ═ 2, 3) of telomer ethylene iodide (VI) were obtained with excess ethylene at high pressure. The telomer ethylene iodides (VI) can be treated with various reagents to provide the corresponding thiols according to the procedure described in "J.fluorine Chemistry", 104, 2, 173-183 (2000). One example is the reaction of telomer ethylene iodide (VI) with sodium thioacetate, followed by hydrolysis.

Another embodiment of the invention are the compounds of formula 1 wherein A is (CH)₂)_oSO₂N(CH₃)(CH₂)_p-, represented herein by the formula 3,

R_f-(CH₂)_oSO₂N(CH₃)(CH₂)_p-OP(O)(O^-M⁺)(O-R_H)

formula 3

Wherein

R_f、R_HO, p and M are as defined above in formula 1. Preferred compounds of formula 3 include those wherein o and p are each 2, R_fIs C₆H₁₃And R is_HIs C₈H₁₇Those of (a). Fluoroalkyl alcohols useful in the preparation of compounds of formula 3 are available from e.i. du Pont DE Nemours and Company (Wilmington, DE).

Another embodiment of the invention are compounds of formula 1 wherein A is O (CF)₂)_q(CH₂)_r-, represented herein by formula 4,

R_f-O(CF₂)_q(CH₂)_r-OP(O)(O^-M⁺)(O-R_H)

formula 4

Wherein

R_f、R_HQ, r and M are as defined above in formula 1. Preferred compounds of formula 4 include those wherein q and R are each 2, R_fIs C₃F₇And R is_HIs C₈H₁₇Those of (a).

The fluoroalcohol used as the starting material to prepare the composition of formula 4 may be obtained by a series of reactions:

the starting perfluoroalkyl ether iodide of formula (V) is prepared via the method described in U.S. patent publication 5,481,028, example 8, which discloses a method for preparing a compound of formula (V) from perfluoro-n-propyl vinyl ether.

In the above second reaction, the perfluoroalkyl ether iodide (V) is reacted with an excess of ethylene at high temperature and high pressure. Although the addition of ethylene can be carried out by heating, it is preferred to use a suitable catalyst. The catalyst is preferably a peroxide catalyst such as benzoyl peroxide, isobutyryl peroxide, propionyl peroxide or acetyl peroxide. More preferably, the peroxide catalyst is benzoyl peroxide. The temperature of the reaction is not limited, but a temperature in the range of 110 ℃ to 130 ℃ is preferred. The reaction time may vary depending on the catalyst 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, using a temperature of 110 ℃ and autogenous pressure, a reaction time of 24 hours, and purifying the product by distillation, satisfactory yields up to 80% were obtained.

Perfluoroalkyl ether ethylene iodide (VI) was treated with oleum and hydrolyzed to provide the corresponding alcohol (VII) according to the procedure disclosed in WO95/11877(Elf Atochem s.a.). 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. The higher homologues (q ═ 2, 3) of telomer ethylene iodide (VI) were obtained with excess ethylene at high pressure.

Telomer ethylene iodides (VI) are treated with various reagents to provide the corresponding thiols following the procedures described in J.fluorine Chemistry, 104, 2, 173-183 (2000). One example is the reaction of telomer ethylene iodide (VI) with sodium thioacetate, followed by hydrolysis. Telomer ethylene iodides (VI) can also be treated by conventional methods to provide the corresponding thioethanol or thioethylamine.

Another embodiment of the invention are compounds of formula 1 wherein A is OCHFCF₂OE-, represented herein by formula 5,

R_f-OCHFCF₂OE-OP(O)(O^-M⁺)(O-R_H)

formula 5

Wherein

R_f、R_HE and M are as defined above in formula 1. Preferred compounds of formula 5 include those wherein R_fIs C₃F₇And R is_HIs C₈H₁₇Those of (a).

The fluoroalcohol used as the starting material to prepare the composition of formula 5 may be prepared by reacting dioxane with a diol in the presence of an alkali metal compound. For example, dioxane having the formula RfOCF ═ CF2 is reacted with a diol such as HO (CH2) OH at about 70 ℃ for about 8 hours, typically in a closed stainless steel reaction vessel, in the presence of an alkali metal such as KOH. Other details are provided in U.S. patent application 2005/0107645.

The compositions of the present invention are surfactants that can be used in aqueous formulations where very low surface tension is required (about 18dyne/cm to 18 mN/m). The surfactants of the present invention provide "fluorine efficiency". The term "fluorine efficiency" refers to increasing the efficiency or performance of a surfactant or treatment agent such that a lower proportion of expensive fluorine component is required to achieve the same level of performance, or better performance can be achieved when the same level of fluorine is used. The fluorine content in the surfactants of the present invention is from about 25% to about 36% lower than the fluorine content in conventional fluorinated surfactants, as compared to conventional fluorinated surfactants.

Without being bound by theory, mixtures of fluoroalkyl surfactants and alkyl surfactants alone are generally less effective than fluoroalkyl surfactants in reducing surface tension. It is believed that the more hydrophobic fluoroalkyl group preferentially replaces the less hydrophobic alkyl group at the interface. However, when both fluoroalkyl and alkyl hydrophobic groups are present in the same molecule, the alkyl hydrophilic group cannot be replaced, thereby improving surfactant performance. Furthermore, in the surfactant of the present invention, both the fluoroalkyl group and the alkyl group have a high degree of rotational freedom, allowing unrestricted orientation at the interface. In the prior art, when the fluoroalkyl, alkyl, and hydrophilic groups of the fluoroalkyl/alkyl surfactant are all bonded to a single carbon atom, the tetrahedral structure of the carbon atom forces the orientation of the fluoroalkyl and alkyl groups to separate (the H-C-H bond angle in the symmetric tetrahedral methane molecule is 109.5 °). Typically, such fluoroalkyl/alkyl surfactants, in which the fluoroalkyl, alkyl and hydrophilic groups are all bonded to a single carbon atom, do not exhibit a surface tension effect as low as 18 mN/m. It is believed that the forced separation of about 110 ° in such prior art examples can diminish the effectiveness of the fluoroalkyl/alkyl combination compared to the structure of formula 2 above, where the fluoroalkyl and alkyl orientations are not limited and can be oriented substantially parallel to each other.

The present invention also includes a method of reducing the surface tension of an aqueous medium comprising contacting the medium with a composition of formula 1 as described above. Any of a variety of media are suitable for use in the methods of the invention. The medium is typically a liquid. Aqueous hydrocarbon and halocarbon systems are preferred. Examples of suitable media include coating compositions, latexes, polymers, floor finishes, inks, emulsifiers, foaming agents, release agents, repellents, flow modifiers, film evaporation inhibitors, wetting agents, penetrants, cleaning agents, abrasives, plating agents, corrosion inhibitors, etchant solutions, soldering agents, dispersion aids, microbial agents, pulping aids, rinse aids, polishes, personal care compositions, desiccants, antistatic agents, floor polishes, or adhesives. Due to the surfactant properties of the composition of the invention, addition of the composition of the invention to the medium will result in a reduction of the apparent tension of the medium. The compositions of the present invention are typically simply blended with or added to the medium. A low surfactant concentration of about 0.1 wt.% is sufficient to reduce the surface tension to less than about 24mN/m, preferably less than about 22 nM/m. For many surfactants of the present invention, a surfactant concentration of 0.01 wt.% is effective to achieve a surface tension of less than about 22 mN/m.

The invention also includes a method of providing leveling, open time extension, and blocking resistance to a coated substrate comprising adding a compound of formula 1 to a coating primer prior to deposition onto the substrate. As used herein, "leveling" refers to the uniformity of coverage of the coating when applied to a substrate. Undesirably, there is unevenness in quality, surface defects, or recession of the coating along the substrate surface at the edges or elsewhere. A uniform coating will provide an excellent dry coating on the substrate surface. 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 marks of application. It is also known as wet edge time. Latex paints containing low boiling point Volatile Organic Chemicals (VOCs) have shorter open times than desired due to the lack of high boiling point VOC solvents. The lack of extended open time will result in surface defects such as overlapping scratches or other marks. Longer open times are beneficial when the appearance of the coated surface is important, as they allow the application of the coating without leaving overlapping marks, scratches, or other application marks in the overlapping areas between the coating layers. "blocking" is the undesirable sticking together of two coated sides when pressed together or placed in contact with each other for an extended period of time after the coating has dried. When adhesion occurs, separation of the surfaces can result in cracking of the coating on one or both surfaces. Therefore, blocking resistance is beneficial in many cases (where two coated surfaces need to be in contact, e.g. on a window frame).

Suitable coating compositions, termed "coating primers" herein, include compositions (typically liquid formulations) of: alkyd paints, type I polyurethane paints, unsaturated polyester paints or water-dispersed paints, and are applied to a substrate for the purpose of producing a durable film on the substrate surface. These are conventional coatings, colorants, and similar coating compositions.

As used herein, the term "alkyd coating" refers to a conventional liquid coating based on alkyd resins, typically a paint, clear coat or stain. 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 as a thin liquid layer of a formulated alkyd coating to a surface, the resulting cured film is relatively strong, non-melting, and substantially insoluble in many organic solvents that can be used 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.

As used hereinafter, the term "polyurethane coating" refers to conventional liquid coatings based on type I polyurethane resins, which are typically coatings, clear coatings or stains. Polyurethane coatings typically comprise the reaction product of a polyisocyanate (typically toluene diisocyanate) and a polyol ester of a drying oleic acid. Polyurethane coatings were classified into five categories by ASTM D-1. The polyurethane I coating comprises a pre-reacted autoxidisable binder as described in "Surface Coatings" volume I, cited previously. These are also known as polyurethane-modified alkyds, oil-modified polyurethanes, polyurethane oils or polyurethane alkyds, which are the largest class of polyurethane coatings and include paints, clear paints or stains. The cured coating is formed by air oxidation and polymerization of unsaturated drying oil residues in the binder.

As used hereinafter, the term "unsaturated polyester coating" refers to conventional liquid coatings based on unsaturated polyester resins, which are soluble in the monomers and may contain initiators and catalysts as needed, typically as coating, clear coating or gel coat formulations. 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. It 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 may be 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. For curing at room temperature, peroxides are decomposed into free radicals catalyzed by certain metal ions (usually cobalt). Before application, the solutions of peroxide and cobalt compound were 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 on wood or wood boards. Other radiation sources, such as electron beam curing, may also be used.

As used herein, the term "water-dispersed coating" refers to a coating intended to decorate or protect a substrate, the coating consisting of water as the substantially dispersed component, such as an emulsion, latex, or suspension of a film-forming material dispersed in an aqueous phase. "Water-dispersed coating" is a general class that describes many formulations and includes members of the above classes as well as members of other classes. Water-dispersed coatings typically contain other common coating ingredients. Examples of water-dispersed coatings include, but are not limited to, pigmented coatings such as latex paints; pigment-free coatings such as wood sealants, stains and finishes; coatings for masonry and cement; and water-based asphalt emulsions. The water-dispersed coating optionally contains surfactants, protective colloids and thickeners, pigments and filler pigments, preservatives, fungicides, freeze-thaw stabilizers, defoamers, pH adjusters, 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 describes such water-dispersed coating compositions in "Emulsion and water-solvent Paints and Coatings" (Reinhold publishing corporation, New York, NY, 1965).

As used herein, the term "dry coating" refers to the final decorative and/or protective film obtained after the coating composition has dried, set, or cured. By way of non-limiting example, such a final film may be obtained by curing, coalescence, polymerization, interpenetration, radiation curing, uv curing or evaporation. The final film can also be applied in a dry and final state in a dry coating.

When used as an additive to a coating base, the composition of formula 1 of the present invention as defined above is effectively incorporated into a coating base or other composition by thorough stirring 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 coatings, the compositions of the present invention are typically added to wet coatings in amounts of from about 0.001% to about 5% by weight based on the dry weight of the composition of the present invention. Preferably, about 0.01 wt.% to about 1 wt.%, and more preferably about 0.1 wt.% to about 0.5 wt.% is used.

Floor waxes, polishes or finishes (hereinafter "floor finishes") are typically 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 are typically aqueous emulsion based polymer compositions comprising one or more organic solvents, plasticizers, coating aids, defoamers, surfactants, polymer emulsions, metal complexing agents and waxes. The particle size range and solids content of the polymer are typically adjusted to control product viscosity, film hardness, and resistance to deterioration. Polymers containing polar groups can be used to enhance solubility and can also be used as wetting or leveling agents to provide good optical properties, such as high gloss and clarity of the reflected image.

Preferred polymers useful in floor finishes include acrylic polymers, polymers derived from cyclic ethers, and polymers derived from vinyl-substituted aromatic compounds. Acrylic polymers include various poly (alkyl acrylates), poly (alkyl methacrylates), hydroxy-substituted poly (alkyl acrylates), and poly (alkyl methacrylates). Commercially available acrylic copolymers for use in floor finishes include, for example, methyl methacrylate/butyl acrylate/methacrylic acid (MMA/BA/MAA) copolymers; methyl methacrylate/butyl acrylate/acrylic acid (MMA/BA/AA) copolymers, and the like. Commercially available styrene-acrylic acid copolymers include styrene/methyl methacrylate/butyl acrylate/methacrylic acid (S/MMA/BA/MMA) copolymers; styrene/methyl methacrylate/butyl acrylate/acrylic acid (S/MMA/BA/AA) copolymer; and so on. Polymers derived from cyclic ethers typically contain 2 to 5 carbon atoms in the ring, which is optionally substituted with alkyl groups. Examples include various oxiranes, epoxypropanes, tetrahydrofurans, tetrahydropyrans, dioxanes, trioxanes, and caprolactones. Polymers derived from vinyl-substituted aromatic compounds include, for example, those made from styrene, pyridine, conjugated dienes, and copolymers thereof. Polyesters, polyamides, polyurethanes, and polysiloxanes may also be used in floor finishes.

Waxes or wax mixtures used in floor finishes include waxes of vegetable, animal, synthetic and/or mineral origin. Representative waxes include, for example, carnauba wax, candelilla wax, lanolin, stearin, beeswax, oxidized polyethylene wax, polyethylene emulsions, polypropylene, copolymers of ethylene and acrylic acid esters, hydrogenated coconut oil or soybean oil, and mineral waxes such as paraffin or ceresin. The wax is typically present in an amount ranging from 0% to about 15% by weight, and preferably from about 2% to about 10% by weight, based on the weight of the final composition.

When used as an additive for a floor finish, the composition of formula 1 of the present invention as defined above is effectively incorporated into the composition by thorough stirring at room or ambient temperature. More complex mixing may be employed, such as using a mechanical shaker or providing heat or other methods. When used as an additive for floor finishes, the compositions of the present invention are generally added to the wet composition 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 about 0.1 wt.% to about 0.5 wt.% is used.

Floor waxes or polishes are water-based, solvent-based, and polymeric. The surfactants of the present invention are suitable for use with any of these materials. The water-based wax and the polymer wax do not need polishing and are dried to achieve high glossiness; solvent-based waxes require extensive polishing. Water-based waxes have been suggested for use in asphalt, polyethylene, vinyl asbestos and rubber tile flooring; solvent-based waxes produce hard, brilliant finishes and are best used for wood, cork and terrazzo floors. Self-polishing waxes such as polymers or resins will yellow or discolor and wear in high load areas; they will peel off and reapply after three or four coats.

The compounds of formula 1 may be used in a variety of additional applications. Some examples of applications include use in fire-fighting compositions, for example as wetting agents, emulsifiers and/or dispersions. They are also useful as components in aqueous film-forming fire extinguishing agents, and as dry powder fire extinguishing agent additives in aerosol type fire extinguishers, and as wetting agents for water-jet fire extinguishing systems.

The compounds of formula 1 of the present invention are suitable for use in agricultural compositions. Examples include use as wetting, emulsifying and/or dispersing agents in herbicides, fungicides, herbicides, insect repellents, insecticides, bactericides (germicides), bactericides (bactericides), nematicides, microbicides, defoliants, fertilizers and hormone growth regulators. The compounds of formula I are also suitable for use as wetting agents for leaves, as livestock dips and for wetting livestock skin; as an ingredient in disinfecting, depigmenting and cleaning compositions; and in insect repellent compositions. The compounds of formula 1 can also be used as wetting agents, emulsifiers and/or dispersants in the production of paper and glued plaques. The compounds of formula 1 are also suitable as grease/oil repellents for paper, wood, leather, skin, metal, textiles, stone and brick, and as penetrants for anti-corrosive impregnation.

The compounds of the present invention represented by formula 1 are also suitable for use as wetting agents, emulsifying agents and/or dispersing agents for polymerization reactions, especially for polymerization of fluoromonomers. These compounds are also suitable for use as latex stabilizers; suitable for use as an additive for foam applications to control diffusion, surface coating irregularities, and edge build-up; suitable for use as a blowing agent; suitable as release agent or suitable as mold release agent; internal antistatic agents suitable for use as polyolefins as well as antiblocking agents; suitable for use as a flow modifier to extrude hot melts, spread, homogenize, prevent shrinkage cavities; and as a retarder of plasticizer migration or evaporation in the plastics and rubber industry.

The compounds of formula 1 of the present invention are also suitable for use as wetting agents for oil well treatments, drilling muds in the petroleum industry; film evaporation inhibitors suitable for use as gasoline, jet fuel, solvents and hydrocarbons; suitable for use as a lubricant or cutting oil improver to improve penetration times; suitable for use as an oil spill collector; and as an additive to improve tertiary oil well recovery.

The compounds of formula 1 according to the invention are also suitable as wetting, defoaming, penetrating or emulsifying agents in the textile and leather industry; or as lubricants for textile, nonwoven and leather treatment; suitable for use in a fiber finish to provide spreading and uniformity; suitable for use as a dye wetting agent; suitable for use as a binder in nonwoven fabrics; and as a penetrant additive suitable for use as a bleaching agent.

The compounds of formula 1 of the present invention are also suitable for use in the mining and metal working industries, in the pharmaceutical industry, in automotive vehicles, in building maintenance and cleaning, in homes, in cosmetic and personal products, and in photography and graphic arts to provide improved surface effects.

The hybrid fluoroalkyl/alkyl surfactants of the present invention provide surfactant-effective compounds at low concentrations, such as less than 0.5 wt% aqueous solutions. The compounds of the present invention contain lower fluorine (improved fluorine efficiency), have lower surface tension, or are generally comparable to conventional fluoroalkyl surfactants. Thus, the compositions of the present invention provide the advantage of modifying the surface characteristics using less fluorine to achieve the same level of performance as prior art compositions or using the same amount of fluorine as prior art compositions to provide better performance. Thus, the improved surfactant properties reduce the overall production cost while improving the performance of the surfactant product.

Materials and test methods

The following raw materials were used in the examples herein.

1)C₄F₉CH₂CF₂CH₂CH₂OH

Ethylene (25g) was added to the charge C₄F₉CH₂CF₂I (217g) and d- (+) -limonene (1g) in an autoclave and the reactor was heated at 240 ℃ for 12 hours. The product is separated by vacuum distillation to give C₄F₉CH₂CF₂CH₂CH₂I。

To 50g C₄F₉CH₂CF₂CH₂CH₂Fuming sulfuric acid (70mL) was added slowly to I, 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 off and used in an amount of 10% by weightWashing with aqueous sodium acetate solution, followed by distillation to give C₄F₉CH₂CF₂CH₂CH₂OH: bp at 2mmHg (267 pascals) is 54 ℃ to 57 ℃.

2)C₄F₉(CH₂CF₂)₂CH₂CH₂OH

Ethylene (18g) was added to the charge C₄F₉(CH₂CF₂)₂I (181g) and d- (+) -limonene (1g) in an autoclave and the reactor was heated at 240 ℃ for 12 hours. Distilling the product to obtain C₄F₉(CH₂CF₂)₂CH₂CH₂I。

Then C is mixed₄F₉(CH₂CF₂)₂CH₂CH₂I (10g) was heated with N-methylformamide (8.9mL) at 150 ℃ for 26 h. The reaction was then cooled to 100 ℃ followed by addition of water to isolate the crude ester. To the crude ester were added ethanol (3mL) and p-toluenesulfonic acid (0.09g), 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 alcohol was dissolved in ether, washed with aqueous sodium sulfite, water and brine in that order, and then dried over magnesium sulfate. Distilling the product to obtain C₄F₉(CH₂CF₂)₂CH₂CH₂OH: bp at 2mmHg (257 pascals) is from 90 ℃ to 94 ℃.

3)C₆F₁₃CH₂CF₂CH₂CH₂OH

Ethylene (15g) was added to the flask containing C₆F₁₃CH₂CF₂I (170g) and d- (+) -limonene (1g) in an autoclave and the reactor was heated at 240 ℃ for 12 hours. The product is separated by vacuum distillation to give C₆F₁₃CH₂CF₂CH₂CH₂I. To C₆F₁₃CH₂CF₂CH₂CH₂To I (112g) was added oleum (129mL) slowly. The mixture was stirred at 60 ℃ for 1.5 hours. Then cooled with ice-cooled 1.5 wt.% Na₂SO₃The reaction was quenched with aqueous solution and heated at 95 ℃ for 0.5 h. The bottom layer was separated and washed with 10% aqueous sodium acetate solution, then distilled to obtain C₆F₁₃CH₂CF₂CH₂CH₂OH: mp was 38 ℃.

4)C₆F₁₃(CH₂CF₂)₂CH₂CH₂OH

Ethylene (56g) was added to the charge C₆F₁₃(CH₂CF₂)₂I (714g) and d- (+) -limonene (3.2g) in an autoclave and the reactor was heated at 240 ℃ for 12 hours. The product is separated off by vacuum distillation to give C₆F₁₃(CH₂CF₂)₂CH₂CH₂I. Then C is mixed₆F₁₃(CH₂CF₂)₂CH₂CH₂I (111g) and N-methylformamide (81mL) were heated at 150 ℃ for 26 h. The reaction was then cooled to 100 ℃ followed by addition of water to isolate the crude ester. To the crude ester were added ethanol (21mL) and p-toluenesulfonic acid (0.7g), and the reaction was stirred at 70 ℃ for 15 minutes. Ethyl formate and ethanol were then distilled off to give the crude alcohol. The crude alcohol was dissolved in ether, washed with aqueous sodium sulfite, water and brine in that order, and then dried over magnesium sulfate. The product was distilled under vacuum to afford compound 12: mp 42 ℃.

5)C₃F₇OCF₂CF₂CH₂CH₂OH

Under nitrogen atmosphere, C is₃F₇OCF₂CF₂I (100g, 0.24mol) and benzoyl peroxide (3g) were charged to a vessel. A series of three vacuum/nitrogen sequences was then carried out at-50 ℃ and ethylene (18g, 0.64mol) was introduced. The vessel was heated at 110 ℃ for 24 hours. The autoclave was cooled to 0 ℃ and opened after venting. However, the device is not suitable for use in a kitchenThe product was then collected in a bottle. The product was distilled to give 80g of C in 80% yield₃F₇OCF₂CF₂CH₂CH₂I. At a pressure of 25mmHg (3325Pa), the boiling point is 56 to 60 ℃.

C is to be₃F₇OCF₂CF₂CH₂CH₂A mixture of I (300g, 0.68mol) and N-methyl-formamide (300mL) was heated to 150 ℃ and held for 26 hours. The reaction was then 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 successively with 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% yield₃F₇OCF₂CF₂CH₂CH₂I. A boiling point of 71 ℃ to 73 ℃ at 40mmHg (5320 Pa).

6)C₃F₇OCFHCF₂CH₂CH₂OH

In an initial step, CF is prepared as follows₃CF₂CF₂OCHFCF₂OCH₂CH₂OCH₂Ph. In a glove box, a 500mL Pyrex bottle was charged with 2- (benzyloxy) ethanol (98%, Aldrich chemical company) (40.0g, 0.263 mole) and 130mL anhydrous dimethylformamide (Aldrich SURE/SEAL). NaH (0.632g, 0.026 mole) was added slowly with magnetic stirring until hydrogen evolution was complete. The capped vial was removed from the glove box and the solution was transferred to a 400mL metal shaker tube inside a nitrogen-filled glove bag. The shaker tube was cooled to an internal temperature of-18 ℃, shaking was started, and perfluoropropyl vinyl ether (PPVE, 77g, 0.289 mole) was added from a metal cylinder. The mixture was allowed to warm to room temperature and shaken for 20 hours. All reaction mixtures were added to 600mL of water saturated with sodium chloride and the mixture was extracted with 800mL of dichloromethane in a separatory funnel. With MgSO₄Dry dichloroThe methane layer, and was concentrated in vacuo on a rotary evaporator to give a liquid (52.0g), which was vacuum distilled on a Kugelrohr apparatus: the first fraction at 75 ℃ and 0.175mm (11.0g), the second fraction at 110 ℃ and 0.175mm (35.7 g). Of the first fraction¹HNMR showed a large amount of dimethylformamide, so it was remixed with the material remaining in the still, and redistilled to obtain 14.0g of a material having a purity equivalent to fraction 2. This redistilled fraction is mixed with fraction 2, and¹H NMR(CDCl₃TMS low field ppm) indicated traces of DMF and 2- (benzyloxy) ethanol starting material, and the desired product: 3.689, 4.125(t, t, OCH)₂CH₂O，4.0H)，4.563(s，OCH₂Ph，2.0H)，5.879(d，²J_H-F＝55Hz，OCF₂CFHOC₃F₇，1.0H)，7.333(m，Ph)。

2.0g of 10% palladium on carbon, 49.6g of CF prepared as described above, was added to a 400mL metal shaker tube₃CF₂CF₂OCHFCF₂OCH₂CH₂OCH₂Ph, and 150mL ethanol. The tube was purged with nitrogen, sealed, cooled to an internal temperature of 15 ℃, evacuated, and pressurized to 100 psig (689.5 x 103Pa) with hydrogen. The tube was heated and shaken, and when it reached 60 ℃, the hydrogen pressure was increased to 400 psig (2758 x 10)³Pa) is added. The temperature and hydrogen pressure were maintained for 24 hours. The tube was cooled to room temperature, evacuated, and the reaction mixture was filtered through a pad of celite to remove the palladium on carbon catalyst. The filtered solution was poured into 300mL of water and the mixture was extracted three times with 100mL of diethyl ether. With MgSO₄The combined ether extracts were dried and then concentrated in vacuo on a rotary evaporator to yield 33.2g of a colorless liquid.¹H NMR showed this material to be the desired product C₃F₇OCFHCF₂CH₂CH₂A mixture of OH and ethanol. It was washed twice with 100mL of water to remove ethanol. The yield of the product after washing was 26.4 g.¹H NMR(CDCl₃TMS low field ppm): 2.296(bs, -OH, 1.0H), 3.840, 4.095(t, t, OCH)₂CH₂O，4.0H)，5.945(d，²J_H-F＝51Hz，OCF₂CFHOC₃F₇，1.0H)。

7) The 2- [ methyl [ (3, 3, 4, 4, 5, 5, 6, 6, 7, 7, 8, 8, 8-tridecafluorooctyl) -sulfonyl ] amino ] ethyl ester of 2-propanoic acid is available from e.i. du Pont DE Nemours and Company (Wilmington, DE).

8) Hydrocarbon alcohols (hexanol, heptanol, octanol, nonanol, decanol, and decanol) are available from Aldrich (st.

9) RHOPLEX3829 (formulation N-29-1) is available from Rohm & Haas (Philadelphia, Pa.).

10) VISTA 6400 is a coating containing an acrylic semi-gloss resin with 84% gloss at 85 degrees, available from VISTA Paints (Fullerton, Calif.).

11)C₆H₁₃CH₂CH₂SO₂N(CH₃)CH₂CH₂OH was obtained from e.i. du Pont DE Nemours and company (Wilmington, DE).

Test method 1 wetting and leveling test

To test the wetting and leveling properties of the samples, the samples were added to floor wax (rhoflex 3829, formulation N-29-1, available from Rohm & Haas, philiadelphia, PA) and applied to half of a thoroughly cleaned 12 inch x 12 inch (30.36cm x 30.36cm) Vinyl floor tile (available from intersue Vinyl Tiles, estree, shelbroke, QC, Canada). The tiles were thoroughly cleaned by wetting the tiles, adding powdered oxygen bleach cleaner, and scrubbing with a green SCOTCH-BRITE scrubbing pad (available from 3M Company, st. paul, MN). This scrubbing step is used to remove the pre-existing coating on the tiles. The floor tile initially has a uniform, shiny finish; a uniform dull finish indicates that the coating has been removed. The tiles were then allowed to air dry overnight. A 1 wt% solution of the surfactant to be tested was prepared by dilution with deionized water. A 100g portion quantity of the rhopelex 3829 formulation was prepared following the resin manufacturer's protocol, followed by the addition of 0.75g of a 1% by weight surfactant solution to provide the test floor wax.

The test floor wax was applied to the floor tile by the following method: a 3mL portion of the test floor wax was placed in the center of the tile, then spread from top to bottom using a cheesecloth applicator, and finally a large "X" was placed across the tile using the applicator. Subsequently in the assessment step, said "X" provides the basis for leveling. 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 tiles were allowed to dry for 30 minutes and a total of 5 coats (coat numbers 1 to 5) were applied and dried, and the X test was performed after each coat had dried. After each application, the tiles are rated on a 1 to 5 scale (1 for worst and 5 for best) according to the ability of the surfactant to promote wetting and leveling of the floor wax on the tile surface. The following floor tile evaluation criteria were used to determine the rating based on comparison to floor tiles treated with floor wax without added surfactant.

TABLE 1 visual evaluation criteria for leveling floor tiles

Score the points	Description of the invention
		1	Uneven film surface coverage, significant streaks and surface defects
2	Many surface defects and streaks are evident, but generally, the film covers the entire tile surface
		3	Visible streaks and surface defects, film recession along the edges of the tiles
4	Less surface irregularities or striations
		5	No visible surface defect or streak

Test method 2 surface tension measurement

Surface tension was measured on a KRUSS K11 tensiometer (KRUSS USA, Matthews, NC) using the Wilhelmy plate method according to American society for testing and materials ASTM # D1331-56. The results were expressed in mN/m (dyne/cm). A tensiometer was used according to manufacturing recommendations.

Test method 3-open time extension

Open time refers to the period of time during which one layer of the applied liquid coating composition can be blended into an adjacent layer of the liquid coating composition without exhibiting wrinkles, scratches, or other marks of application. It is also known as wet edge time. Low VOC latex paints have shorter open times than desired due to the lack of high boiling VOC solvents. Lack of sufficient open time will result in scratches or other marks overlapping. Open time testing is performed by accepted industry practice, referred to as finger pressure as described herein. Double-band tensile panels of the control sample and the sample containing 0.1% of the active ingredient of the sample to be tested were used. The coating composition to be tested and the control are the same coating composition, wherein the control does not contain the additive to be tested, while the sample to be tested comprises the composition of the invention as an additive. The plates were prepared with a 7cm doctor blade at a temperature of 20-25 ℃ and a relative humidity of 40% -60%. A double thumb press with equal pressure was then applied to each sample juxtaposed at intervals of 1 to 2 minutes. The endpoint was when no paint residue was observed on the thumb. The time from coating formation to endpoint was recorded as open time. The percent difference between the control and the sample containing the additive was recorded as percent open time extension. The compositions of the present invention were tested in semi-gloss latex paints.

Test method 4 blocking resistance of emulsion paints for construction

The test method described herein is a variation of the ASTM D4946-89 standard test method for block resistance testing of architectural coatings, which is incorporated herein by reference. In this test, the face-to-face blocking resistance of the coating to be tested was evaluated. For the purposes of this test, blocking is defined as the two coated sides being pressed together or placed in contact with each other for an extended period of time and undesirably sticking together.

The paint to be tested was applied to a polyester test board using a doctor blade. All coated panels are protected from surface contamination such as grease, oil, fingerprints, dust, etc. Typically, test results began 24 hours after casting the dope. Six squares (3.8cm x 3.8cm) were cut from the coated test panels after conditioning the panels in a conditioning chamber for a desired period of time with controlled temperature and humidity as specified by the test method. For each paint to be tested, the cut-out (three pairs) were placed with the paint surfaces in face-to-face relationship. The face-to-face samples were placed on marble trays in a 50 ℃ oven. A No. 8 plug was placed on top with the smaller diameter end in contact with the sample, and then a 1000g weight was placed on top of the plug. This will generate a pressure of 1.8psi (12,400 pascals) on the sample. For each sample tested, a weight and plug were used. Exactly after 30 minutes, the plug and weight were removed from the test specimen. Before testing for blocking resistance, the samples were removed from the oven and allowed to cool in a conditioning chamber for 30 minutes.

After cooling, the individual samples were peeled apart using a slow and steady force. The blocking resistance is rated from 0 to 10, as determined by the operator of the process, corresponding to a subjective tack assessment (sound produced when the coated samples separate) or a seal (complete adhesion of the two coated surfaces). The sample was placed near the ear to actually hear the degree of tackiness. The rating system is described in the following table entitled "blocking resistance numerical rating". The extent of sealing was evaluated from the appearance of the sample and the adhered paint surface portion. The coating torn off the test panel backing indicated the extent of sealing. Higher numbers indicate better blocking resistance.

TABLE 2 blocking resistance numerical rating

Blocking resistance numerical rating	Description of the isolation	Description of Performance
			10	Non-sticking	Perfection
9	Trace amount of adhesion	Is excellent in
			8	Very slight tack	Is excellent in
7	Slight tack	Good/excellent
			6	Moderate to light tack	Good effect
5	Moderate tack	In general
			4	Very sticky, without sealing	Poor to moderate
3	5-25% sealing	Is poor
			2	25-50% sealing	Is poor

Blocking resistance numerical rating	Description of the isolation	Description of Performance
			1	50-75% sealing	Extreme difference
0	75-100% sealing	Extreme difference

Test method 5-Wickbold spray Lamp method (for fluorine analysis)

An effective method for quantifying the mineralization of fluorinated compounds is the Wickbold burner method. The method (detailed in Angew chem.66(1954) 173) was confirmed to be compound independent for fluorine-containing compounds. In this method, the analytical sample is placed in a ceramic container and the sample is completely burned, typically by external heating in a sufficient flow of oxygen. The gaseous reaction products are passed through an auxiliary hydrogen/oxygen flame containing excess oxygen so that combustion becomes complete. The gaseous effluent is then condensed and the fluoride is dissolved in a water stream, which is collected for analysis. Aqueous fluoride is then conveniently measured, typically using a fluoride ion selective electrode.

Examples

Examples 1 to 5

In a 100mL round-bottom flask equipped with a thermocouple and a magnetic stirrer, POCl was added₃(0.58g, 3.8mmol) was dissolved in anhydrous tetrahydrofuran (25 mL). Using an ice bathThe solution was cooled to 0 ℃. Will comprise a fluorinated alcohol C₃F₇OCFHCF₂CH₂CH₂Separate solutions of OH (1.25g, 3.8mmol) (prepared as disclosed under the materials) and triethylamine (0.96g, 9.5mmol) in dry tetrahydrofuran (15mL) were slowly added to the reactor. The reaction was allowed to proceed at 0 ℃ for 1 to 2 hours. The hydrocarbon alcohol anhydrous tetrahydrofuran (15mL) solution was added slowly to the reaction mass in the amounts listed in table 3. The reaction mass was stirred at ambient temperature overnight. The solid was then filtered and the solvent was evaporated using a rotary evaporator (Heidolph LABOROTA 4000 efficiency, Schwabach, Germany). The resulting oil was diluted in tetrahydrofuran (10mL) and a solution of NaOH (0.34g, 8.6mmol) dissolved in water (1mL) was added to the reaction mass. The mixture was stirred at room temperature overnight. The solvent was then evaporated using a rotary evaporator, the resulting solid was washed with chloroform (50mL), and filtered. The final product was dried at 120 ℃ and 150mmHg (20kPa) overnight in a vacuum oven. The resulting product is a compound of formula 1, wherein R_fIs C₃F₇A is OCFHCF₂OE, E is CH₂CH₂OH, M is Na, and R_HAs C for example 1₆H₁₃C for example 2₇H₁₅C for example 3₈H₁₇C for example 4₉H₁₉And C for example 5₁₀H₂₁. The surface tension of each product was determined using test method 2. The results are shown in Table 5.

Comparative example A

The methods of examples 1 to 5 were performed using two molar equivalents of fluorinated alcohol and no hydrocarbon alcohol. Comparative example A is a compound similar to formula 1 but with an alternative R_HSecond R of_fWherein R is_fIs C₃F₇A is OCFHCF₂OE, E is CH₂CH₂OH, M is Na, and the second R_fIs C₃F₇. Using test method 2, measurementSurface tension of this comparative example. The results are shown in Table 5.

The fluorinated alcohol compositions used in the examples and referenced in table 4 are shown in table 3 below.

TABLE 3 fluorinated alcohols

Table 3 nomenclature	Alcohol(s)
		I	C4H9CH2CF2CH2CH2OH
II	C4F9(CH2CF2)2CH2CH2OH
		III	C6F13CH2CF2CH2CH2OH
IV	C6F13(CH2CF2)2CH2CH2OH
		V	C3F7OCF2CF2CH2CH2OH
VI	C3F7OCFHCF2CH2CH2OH
		VII	C6H13CH2CH2SO2N(CH3)CH2-CH2OH

TABLE 4 Synthesis of hybrid phosphate ester surfactants

TABLE 5-Surface tension results of hybrid surfactants

^*Calculated from the reaction stoichiometry.

Table 5 shows the surface tension of examples 1 to 5. Their performance was determined relative to non-hybrid comparative example a, which contained a higher level of fluorine. At low aqueous concentrations of less than 0.5 wt%, examples 1 to 5 show surface tensions of less than about 25mN/m, typically less than 20mN/m, and thus show excellent surfactant performance. Examples 4, 5 and comparative example a all reduced the surface tension to less than 20mN/m at a concentration of 0.05 wt.% in water. At this concentration of 0.05 wt% aqueous surfactant solution, the fluorine content was diluted to 0.024 for comparative example a and to 0.014% and 0.013% for examples 4 and 5, respectively. Thus, even at this very low concentration, the fluorine efficiencies of examples 4 and 5 are still greater.

Examples 6 to 10

C is used in the amounts listed in Table 3₄F₉CH₂CF₂CH₂CH₂OH as the fluorinated alcohol and the hydrocarbon alcohol was used in the amounts listed in table 3 to perform the methods in examples 1 to 5. The resulting product is a compound of formula 1, wherein R_fIs C₄F₉A is CH₂CF₂CH₂CH₂M is Na, and R_HAs C for example 6₆H₁₃C for example 7₇H₁₅C for example 8₈H₁₇C for example 9₉H₁₉And C for example 10₁₀H₂₁. The surface tension of each product was determined using test method 2. The results are shown in Table 6.

Comparative example B

The methods of examples 6 to 10 were performed using two molar equivalents of fluorinated alcohol and no hydrocarbon alcohol. Comparative example B is a compound similar to formula 1 but with an alternative R_HSecond R of_fWherein R is_fIs C₄F₉A is CH₂CF₂CH₂CH₂M is Na, and a second R_fIs C₄F₉The surface tension of the product was determined using test method 2. The results are shown in Table 6.

TABLE 6-Surface tension of hybrid surfactant (Dyne/cm)

^*By reaction stoichiometryThe calculated value is obtained.

Table 6 shows the surface tension results for examples 6 to 10. Their performance was determined relative to non-hybrid comparative example B, which contained a higher level of fluorine. Generally, examples 6 to 10 show excellent surfactant performance in low concentration aqueous solutions, with surface tensions less than about 30mN/m obtained at 0.05 wt% concentration and less than 20mN/m obtained at 0.5 wt% concentration. Example 7 the best performance was obtained using 1-heptanol as the hydrocarbon alcohol. Both example 7 and comparative example B reduced the surface tension of water to 20mN/m or less at a surfactant concentration of 0.05 wt%. However, at this concentration, example 7 contained only 0.018 wt.% fluorine, while comparative example B contained 0.026 wt.% fluorine, which gave similar surface effects, indicating that the fluorine efficiency of example 7 was greater.

Examples 11 to 15

C is used in the amounts listed in Table 3₃F₇OCF₂CF₂CH₂CH₂OH as the fluorinated alcohol and the hydrocarbon alcohol was used in the amounts listed in table 3 to perform the methods in examples 1 to 5. The resulting product is a compound of formula 1, wherein R_fIs C₃F₇A is OCF₂CF₂CH₂CH₂M is Na and RH is C for example 11₆H₁₃C for example 12₇H₁₅C for example 13₈H₁₇C for example 14₉H₁₉And C for example 15₁₀H₂₁. The surface tension of each product was determined using test method 2. The results are shown in Table 7.

Comparative example C

The methods of examples 11 to 15 were performed using two molar equivalents of fluorinated alcohol and no hydrocarbon alcohol. Comparative example A is a compound similar to formula 1 but with an alternative R_HSecond R of_fWherein R is_fIs C₃F₇A is OCF₂CF₂CH₂CH₂M is Na, and the second R_fIs C₃F₇. The surface tension of the product was determined using test method 2. The results are shown in Table 7.

TABLE 7-Surface tension results of hybrid surfactants

^*Measured according to test method 5, torch method.

Table 7 shows the surface tension results for examples 11 to 15. Their performance was compared against non-hybrid comparative example C, which contained a higher amount of fluorine. All of the hybrid surfactants in examples 11 to 15 showed excellent surfactant performance by lowering the surface tension of water to about 20mN/m or less at 0.05 wt% active ingredient. Despite the lower fluorine content in examples 11 to 15, the performance was comparable to comparative example C. All of the hybrid surfactants in examples 11 to 15 as shown in table 7 exhibited higher fluorine efficiencies than comparative example C. At a concentration of 0.05 wt.% in water, examples 11 to 15 and comparative example C each reached a surface tension of about 20mN/m or less, but at this diluted concentration, comparative example C contained 0.025% fluorine, while examples 11 to 15 contained 0.017% to 0.019% fluorine.

Examples 16 to 20

C is used in the amounts listed in Table 3₄F₉(CH₂CF₂)₂CH₂CH₂OH as the fluorinated alcohol and the hydrocarbon alcohol was used in the amounts listed in table 3 to perform the methods in examples 1 to 5. The resulting product is a compound of formula 1, wherein R_fIs C₄F₉A is (CH)₂CF₂)₂CH₂CH₂M is Na, and R_HIs C for example 16₆H₁₃C for example 17₇H₁₅C for example 18₈H₁₇C for example 19₉H₁₉And C for example 20₁₀H₂₁. The surface tension of each product was determined using test method 2. The results are shown in Table 8.

Comparative example D

The methods of examples 16 to 20 were performed using two molar equivalents of fluorinated alcohol and no hydrocarbon alcohol. Comparative example D is a similar compound to formula 1, but with an alternative R_HSecond R of_fWherein R is_fIs C₄F₉A is (CH)₂CF₂)₂CH₂CH₂M is Na, and the second R_fIs C₄F₉The surface tension of the product was determined using test method 2. The results are shown in Table 8.

TABLE 8-Surface tension results of hybrid surfactants

^*Calculated from the reaction stoichiometry.

Table 8 compares the surface tension data from examples 16 to 20 and non-hybrid comparative example D containing a higher level of fluorine. Examples 16 to 20 have similar surface tension characteristics to comparative example D, but achieve these results at lower fluorine levels in the compound. Examples 16 to 20 all exhibited excellent reduction in water surface tension at low concentrations, reaching a surface tension of less than about 20mN/m at a 0.05 wt% aqueous solution concentration.

Example 21

C is used in the amounts listed in Table 3₆F₁₃CH₂CF₂CH₂CH₂OH as the fluorinated alcohol and octanol as the hydrocarbon alcohol in the amounts listed in table 3 were used to perform the methods in examples 1 to 5. The resulting product is a compound of formula 1, wherein R_fIs C₆F₁₃A is CH₂CF₂CH₂CH₂M is Na, and R_HIs C₈H₁₇. The surface tension of the product was determined using test method 2. The results are shown in Table 9.

Comparative example E

The method of example 21 was performed using two molar equivalents of fluorinated alcohol and no hydrocarbon alcohol. Comparative example E is a similar compound to formula 1 but with an alternative R_HSecond R of_fWherein R is_fIs C₆F₁₃A is CH₂CF₂CH₂CH₂M is Na, and the second R_fIs C₆F₁₃The surface tension of the product was determined using test method 2. The results are shown in Table 9.

TABLE 9-Surface tension results of hybrid surfactants

^*Calculated from the reaction stoichiometry.

Table 9 compares the surface tension results for the hybrid surfactant of example 21 with comparative example E. Example 21 reduced the surface tension of water to less than 20mN/m with 0.05 wt% surfactant while containing less fluorine than comparative example E. The integration of the hydrocarbon and fluorocarbon moieties into the phosphate ester surfactant significantly improves its surface effect and increases the fluorine efficiency.

Example 22

C is used in the amounts listed in Table 3₆F₁₃(CH₂CF₂)₂CH₂CH₂OH as the fluorinated alcohol and octanol as the hydrocarbon alcohol in the amounts listed in table 3 were used to perform the methods in examples 1 to 5. The resulting product is a compound of formula 1, wherein R_fIs C₆F₁₃A is (CH)₂CF₂)₂CH₂CH₂M is Na, and R_HIs C₈H₁₇. The surface tension of the product was determined using test method 2. The results are shown in Table 10.

Comparative example F

The method of example 22 was performed using two molar equivalents of fluorinated alcohol and no hydrocarbon alcohol. Comparative example F is a similar compound to formula 1 but with an alternative R_HSecond R of_fWherein R is_fIs C₆F₁₃A is (CH)₂CF₂)₂CH₂CH₂M is Na, and the second R_fIs C₆F₁₃. The surface tension of the product was determined using test method 2. The results are shown in Table 10.

TABLE 10-Surface tension results of hybrid surfactants

^*Calculated from the reaction stoichiometry.

Table 10 presents the surface tension data for the hybrid surfactant of example 22 and comparative example F. Comparative example F is a non-hybrid surfactant containing a higher level of fluorine than example 22. Example 22 achieved excellent performance. The hybrid material is capable of lowering the surface tension of water to less than 25mN/m at a surfactant concentration of 0.005 wt%, and is capable of lowering the surface tension of water to less than 20mN/m at a surfactant concentration of 0.01 wt%. Incorporation of 1-octanol based hydrocarbyl groups into fluorinated phosphate esters provides significant enhancements in surface and fluorine efficiency.

Example 23

C is used in the amounts listed in Table 3₆F₁₃CH₂CH₂SO₂-N(CH₃)CH₂CH₂OH as the fluorinated alcohol and octanol as the hydrocarbon alcohol in the amounts listed in table 3 were used to perform the methods in examples 1 to 5. The resulting product is a compound of formula 1, wherein R_fIs C₆F₁₃A is CH₂CH₂N(CH₃)SO₂CH₂CH₂M is Na, and R_HIs C₈H₁₇. The surface tension of the product was determined using test method 2. The results are shown in Table 11.

Comparative example G

The method of example 23 was performed using two molar equivalents of fluorinated alcohol and no hydrocarbon alcohol. Comparative example F is a similar compound to formula 1 but with an alternative R_HSecond R of_fWherein R is_fIs C₆F₁₃A is CH₂CH₂N(CH₃)SO₂CH₂CH₂M is Na, and R_HIs C₆H₁₃. The surface tension of the product was determined using test method 2. The results are shown in Table 11.

TABLE 11-Surface tension results of hybrid surfactants

^*Calculated from the reaction stoichiometry.

Table 11 shows the surface tension data for the hybrid surfactant of example 23 and comparative example G containing a higher level of fluorine. Example 23, which contained lower levels of fluorine than comparative example G, gave superior performance. This hybrid of example 23 was able to reduce the surface tension of water to less than 20dyne/cm (mN/m) at 0.05 wt% surfactant. Example 23 shows improved fluorine efficiency, as well as better surface effect than comparative example G.

Testing in coatings

Examples 8 and 18, and comparative examples B and D, respectively, prepared as described above, were added to Vista 6400 paint in amounts to provide 70ppm (micrograms per gram) of fluorine in 100 grams of paint. The coating without additive was used as a control (blank). The coatings were applied to a polyester test panel and the blocking resistance was determined according to test method 4 and the open time extension was determined using test method 3. The data obtained are shown in tables 12 and 13.

TABLE 12 blocking resistance results

Coating material	Examples as additives	Fluorine, ppm	Average adhesion score*
				Vista 6400	Nothing (blank)	0	0
Vista 6400	Comparative example B	70	6.3
				Vista 6400	8	70	6.7
Vista 6400	Comparative example D	70	6.0
				Vista 6400	18	70	3.7

^*As measured by test method 4.

The results of the blocking resistance tests for examples 8 and 18 are shown in Table 12. Their performance was compared to blanks and to comparative examples B and D. Example 8 performed better than the blank and comparative example B, showing excellent antiblocking properties. Example 18 shows better antiblocking performance than the blank, but not as good as comparative example D. Overall, example 8 achieves the best anti-blocking efficacy with an anti-blocking score of 6.7.

TABLE 13 open time extension

Coating material	Additive agent	Fluorine, ppm	% open time extension*
				Vista 6200	Comparative example B	500	4.4
Vista 6200	8	500	4.4
				Vista 6200	Comparative example D	500	2.2
Vista 6200	18	500	7.0

^*As measured by test method 3.

Table 13 shows the open time extension test results using examples 8 and 18. The performance of these examples was evaluated relative to comparative examples B and D. Example 8 achieved equivalent open time extension to comparative example B at the same fluorine dose. On the other hand, example 18 exhibited an extended open time over comparative example D. These results show that the hybrid surfactants of examples 8 and 18 can provide performance equivalent to or better than the non-hybrid comparative examples B and D.

Claims (10)

1. A compound of formula 1

R_f-A-OP(O)(O^-M⁺)(O-R_H) Formula 1

Wherein

R_fIs C optionally interrupted by one, two or three ether oxygen atoms₂-C₆A linear or branched perfluoroalkyl group;

a is (CH)₂CF₂)_m(CH₂)_n-、(CH₂)_oSO₂N(CH₃)(CH₂)_p-、O(CF₂)_q(CH₂)_r-, or OCHFCF₂OE-；

m is 1 to 4; n, o, p and r are each independently 2 to 20; q is 2;

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;

m is a group I metal or an ammonium cation (NH)_xR² _y)⁺Wherein R is²Is C₁-C₄Alkyl, x is 1 to 4, y is 0 to 3, and x + y is 4; and is

R_HIs C₁-C₂₀Linear, branched or cyclic alkyl, or C₆-C₁₀And (4) an aryl group.

2. The compound of claim 1, wherein R_fIs C₃-C₆Linear or branched perfluoroalkyl.

3. The compound of claim 1, wherein R_HIs C₈-C₂₀Alkyl, A is (CH)₂CF₂)_m(CH₂)_nN is 2 and R_fIs C₄H₉Or C₆H₁₃。

4. The compound of claim 1, wherein A is (CH)₂)_oSO₂N(CH₃)(CH₂)_p-, o and p are each 2, R_fIs C₆H₁₃And R is_HIs C₈H₁₇Or wherein A is O (CF)₂)_q(CH₂)_r-, q and R are each 2, R_fIs C₃F₇And R is_HIs C₈H₁₇Or wherein A is OCHFCF₂OE-，R_fIs C₃F₇And R is_HIs C₈H₁₇。

5. The compound of claim 1, having a surface tension of about 25mN/m or less at a concentration of 0.1 wt.% in water.

6. A method of reducing the surface tension of an aqueous medium, the method comprising contacting the medium with a composition of claim 1

R_f-A-OP(O)(O^-M⁺)(O-R_H) Formula 1

Wherein

R_fIs C optionally interrupted by one, two or three ether oxygen atoms₂-C₆A linear or branched perfluoroalkyl group;

a is (CH)₂CF₂)_m(CH₂)_n-、(CH₂)_oSO₂N(CH₃)(CH₂)_p-、O(CF₂)_q(CH₂)_r-, or OCHFCF₂OE-；

m is 1 to 4; n, o, p and r are each independently 2 to 20; q is 2;

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;

m is a group I metal or an ammonium cation (NH)_xR² _y)⁺Wherein R is²Is C₁-C₄Alkyl, x is 1 to 4, y is 0 to 3, and x + y is 4; and is

R_HIs C₁-C₂₀Linear, branched or cyclic alkyl, or C₆-C₁₀And (4) an aryl group.

7. The method of claim 6, wherein the medium is a coating composition, latex, polymer, floor finish, ink, emulsifier, foaming agent, release agent, repellent agent, flow modifier, film evaporation inhibitor, wetting agent, penetrating agent, cleaner, abrasive, plating agent, corrosion inhibitor, etchant solution, soldering agent, dispersion aid, microbial agent, pulping aid, rinse aid, polishing agent, personal care composition, drying agent, antistatic agent, floor polish, or adhesive.

8. A method of providing leveling, open time extension and blocking resistance to a coated substrate, said method comprising adding to a coating primer a compound of formula 1 prior to deposition onto said substrate

R_f-A-OP(O)(O^-M⁺)(O-R_H) Formula 1

Wherein

R_fIs C optionally interrupted by one, two or three ether oxygen atoms₂-C₆A linear or branched perfluoroalkyl group;

a is (CH)₂CF₂)_m(CH₂)_n-、(CH₂)_oSO₂N(CH₃)(CH₂)_p-、O(CF₂)_q(CH₂)_r-, or OCHFCF₂OE-；

m is 1 to 4; n, o, p and r are each independently 2 to 20; q is 2;

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;

m is a group I metal or an ammonium cation (NH)_xR² _y)⁺Wherein R is²Is C₁-C₄Alkyl, x is 1 to 4, y is 0 to 3, and x + y is 4; and is

R_HIs C₁-C₂₀Linear, branched or cyclic alkyl, or C₆-C₁₀And (4) an aryl group.

9. The method of claim 8, wherein the coating primer is a water-dispersed coating, an alkyd coating, a type I urethane coating, an unsaturated polyester coating, or a floor finish.

10. A substrate treated according to the method of claim 6.