HK1161855A - Ethylene-tetrafluoroethylene phosphate composition - Google Patents

Description

Ethylene-tetrafluoroethylene phosphate composition

Technical Field

The present invention relates to the field of polyfluoro compounds, in particular to fluorophosphates comprising ethylene-tetrafluoroethylene moieties, and to their use as surfactants and as coating additives.

Background

The polyfluorinated compositions are useful in the preparation of a variety of surface treatment materials. A variety of materials made from perfluorinated compositions are known to be useful as surfactants or treating agents to provide surface effects to substrates. Surface effects include repellency to moisture, dirt and stains, and other effects that are particularly useful for fibrous substrates and other substrates such as hard surfaces. Many such surfactants and treatments are fluorinated polymers or copolymers.

As disclosed in U.S. patent No. 3,956,000, perfluoroiodoethane or 1, 2-diiodotetrafluoroethylene is telomerized with tetrafluoroethylene and optionally with a small amount of chlorotrifluoroethylene, bromotrifluoroethylene, iodotrifluoroethylene, hexafluoropropylene, 1-difluoroethylene or ethylene to produce fluorocarbon waxes having molecular weights of 10,000 to 200,000 by employing an emulsion process using a pure aqueous phase as the reaction medium while applying a specific stirring energy. The use of up to 15% of a telogen and at least 85% of an olefin is disclosed. This technique does not allow the use of oligomeric iodides having a molecular weight of less than 2,000. This patent does not disclose oligomerization of tetrafluoroethylene with ethylene to produce short chain oligomeric iodides or other useful oligomeric derivatives such as the corresponding alcohols or thiols.

Consumer demand for surfactants and surface protection products is in a continuing state of development and there is a continuing need for cost effective, environmentally friendly new chemical intermediates and products. The industry is constantly searching for compounds that have minimal environmental impact and higher fluorine efficiency. In particular, there is a need for surfactants and surface treatments comprising short chain fluorochemical groups in which certain high cost fluorocarbon moieties are replaced by lower cost and more biodegradable moieties. The present invention provides such surfactants and surface treatment agents.

Brief description of the invention

The present invention encompasses compounds having the structure of formula (I) or (II):

(A)_w-P(O)(O^-M⁺)_3-w(I) or

Wherein

A is R_f-(CH₂)_k-[(CF₂CF)_y-(CH₂CH₂)_z]_mO and contains from about 8 to about 22 carbon atoms;

R_fis C_nF_2n+1；

n and k are each independently 1 to about 6;

y, z and m are each independently 1,2, 3, or mixtures thereof;

w is 1 or 2, or mixtures thereof; and is

M is hydrogen, ammonium ion, alkali metal ion, or alkanolammonium ion.

The invention also comprises a method of modifying the surface behaviour of a liquid, which method comprises adding to the liquid a compound of formula (I) or (II) or a mixture thereof.

The present invention also includes a method of providing block resistance and leveling to a substrate on which a coating composition is deposited, the method comprising adding to the coating composition prior to deposition of the coating composition onto the substrate a composition comprising one or more compounds of formula (I) or (II) or mixtures thereof.

The present invention also includes a substrate having applied thereto a composition comprising one or more compounds of formula (I) or (II) or mixtures thereof.

Detailed Description

Hereinafter trademarks are indicated in upper case.

The present invention includes fluorinated aqueous compounds that can be used as surfactants or as surface treatment agents to impart surface characteristics to substrates treated therewith. The compounds of the present invention may also be used as additives to liquid and coating compositions to impart certain surface characteristics to substrates coated with such compositions. Other embodiments of the invention include methods of treating substrates to impart surface effects and substrates having improved surface characteristics.

The invention includes compounds of formula (I) or (II):

(A)_w-P(O)(O^-M⁺)_3-w(I) or

Wherein

A is R_f-(CH₂)_k-[(CF₂CF)_y-(CH₂CH₂)_z]_mO and contains from about 8 to about 22 carbon atoms;

R_fis C_nF_2n+1；

n and k are each independently 1 to about 6;

y, z and m are each independently 1,2, 3, or mixtures thereof;

w is 1 or 2, or mixtures thereof; and is

M is hydrogen, ammonium ion, alkali metal ion, or alkanolammonium ion.

One embodiment of the present invention is a composition of formula (I) or (II) wherein R_fHaving 2to 6 carbon atoms, preferably 2to 4 carbon atoms, and y, z and m are each 1 or 2, preferably each 1. Other particular embodiments are compositions wherein M is ammonium or alkanolammonium ion. Another embodiment of the present invention comprises a mixture of from about 15 mol% to 80 mol% of a mono (fluoroalkyl) phosphate having the structure of formula (I) wherein x is 1, and from about 20 mol% to about 85 mol% of a bis (fluoroalkyl) phosphate having the structure of formula (I) wherein x is 2. These particular compositions may be used in all other embodiments of the present invention, including the application methods and treated substrates as described herein.

Fluoroalkyl phosphates having the structure of formulas (I) and (II) can be prepared according to the methods described in U.S. patent publication nos. 4,064,067 and 2,597,702 using the phosphorus pentoxide pathway, or according to the methods described in U.S. patent publications nos. 6,271,289 and 3,083,224 using the phosphorus oxychloride pathway, each of which is incorporated herein by reference. 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 such as 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. Corresponding phosphite and phosphinate compositions were prepared in a similar manner.

The resulting composition is then diluted with water, a mixture of water and solvent, or further dispersed or dissolved in a solvent selected from simple alcohols and ketones suitable for use as a solvent for the final application of the substrate (hereinafter referred to as "application solvent"). Alternatively, the solvent may be removed by evaporation and an emulsification or homogenization process known to those skilled in the art is used to prepare an aqueous dispersion formed with the surfactant via conventional methods. 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.

Specific fluorinated alcohols useful in preparing the phosphate compounds of the present invention are listed in table 1.

TABLE 1

Numbering structure for compounds

1. C₂F₅CH₂CH₂CF₂CF₂CH₂CH₂OH，

2. C₂F₅CH₂CH₂(CF₂CF₂)₂CH₂CH₂OH，

3. C₂F₅(CH₂CH₂)₂CF₂CF₂CH₂CH₂OH，

4. C₂F₅CH₂CH₂CF₂CF₂(CH₂CH₂)₂OH，

5. C₂F₅CH₂CH₂(CF₂CF₂CH₂CH₂)₂OH，

6. C₂F₅(CH₂CH₂)₂(CF₂CF₂CH₂CH₂)₂OH，

7. C₂F₅(CH₂CH₂CF₂CF₂)₂(CH₂CH₂)₂OH，

8. C₂F₅CH₂CH₂(CF₂CF₂)₃CH₂CH₂OH，

9. C₂F₅CH₂CH₂CF₂CF₂(CH₂CH₂)₂CF₂CF₂CH₂CH₂OH，

10. C₂F₅(CH₂CH₂)₂(CF₂CF₂)₂CH₂CH₂OH，

11. C₄F₉CH₂CH₂CF₂CF₂CH₂CH₂OH，

12. C₄F₉CH₂CH₂(CF₂CF₂)₂CH₂CH₂OH，

13. C₄F₉(CH₂CH₂)₂CF₂CF₂CH₂CH₂OH，

14. C₄F₉CH₂CH₂CF₂CF₂(CH₂CH₂)₂OH，

15. C₄F₉CH₂CH₂(CF₂CF₂CH₂CH₂)₂OH，

16. C₄F₉(CH₂CH₂)₂(CF₂CF₂CH₂CH₂)₂OH，

17. C₄F₉(CH₂CH₂CF₂CF₂)₂(CH₂CH₂)₂OH，

18. C₄F₉CH₂CH₂(CF₂CF₂)₃CH₂CH₂OH，

19. C₄F₉CH₂CH₂CF₂CF₂(CH₂CH₂)₂CF₂CF₂CH₂CH₂OH，

20. C₄F₉(CH₂CH₂)₂(CF₂CF₂)₂CH₂CH₂OH，

21. C₆F₁₃CH₂CH₂CF₂CF₂CH₂CH₂OH，

22. C₆F₁₃CH₂CH₂(CF₂CF₂)₂CH₂CH₂OH，

23. C₆F₁₃(CH₂CH₂)₂CF₂CF₂CH₂CH₂OH，

24. C₆F₁₃CH₂CH₂CF₂CF₂(CH₂CH₂)₂OH，

25. C₆F₁₃CH₂CH₂(CF₂CF₂CH₂CH₂)₂OH，

26. C₆F₁₃(CH₂CH₂)₂(CF₂CF₂CH₂CH₂)₂OH，

27. C₆F₁₃(CH₂CH₂CF₂CF₂)₂(CH₂CH₂)₂OH，

28. C₆F₁₃CH₂CH₂(CF₂CF₂)₃CH₂CH₂OH，

29. C₆F₁₃CH₂CH₂CF₂CF₂(CH₂CH₂)₂CF₂CF₂CH₂CH₂OH，

30. C₆F₁₃(CH₂CH₂)₂(CF₂CF₂)₂CH₂CH₂OH。

Specific fluorinated thiols useful in forming the compounds of the invention include those analogous to those listed in table 1A above, but with SH replacing OH.

The alcohols used for the preparation of the compounds of the formulae (I) and (II) according to the invention can be prepared from the corresponding oligomeric iodides by treatment with oleum and hydrolysis. It has been found, for example, that reaction with oleum (15% SO) at about 60 deg.C₃) The reaction was allowed to proceed for about 1.5 hours, then ice-cold dilute K was used₂SO₃Satisfactory results were obtained by hydrolysis of the solution followed by heating at about 100 c for about 30 minutes. However, other reaction conditions may be used. After cooling to ambient room temperature, a solid precipitated out, isolated and purified. For example, the liquid is then decanted off and the solid is dissolved in ether and washed with NaCl-saturated water, over anhydrous Na₂SO₄Dried, concentrated and dried in vacuo. Other conventional purification methods may be employed.

Alternatively, the alcohol used to prepare the compounds of the present invention may be prepared by oligomerizing iodide (C)_nF_2n+1C₂H₄ I、C_nF_2n+1CH₂I. Or C_nF_2n+1I) Heating to about 150 ℃ with N-methylformamide, and holding for about 19 hours. The reaction mixture was washed with water to obtain a residue. This residue was gently refluxed (at about 85 ℃ bath temperature) with a mixture of ethanol and concentrated hydrochloric acid for about 2.5 hours. The reaction mixture was washed with water, diluted with dichloromethane and dried over sodium sulfate. The dichloromethane solution was concentrated and distilled under reduced pressure to obtain the alcohol. Optionally, N-dimethylformamide is used instead of N-methylformamide. Can also be usedOther conventional purification methods.

Thiol C for the preparation of the Compounds of the invention_nF_2n+1(CH₂)_x[(CF₂CF₂)_y(CH₂CH₂)_z]_mSH, (where m, n, x, y and z are as described above for formula (I)) can be prepared by oligomerizing iodides (C.Org.Chem., 1977, 42, 2680) according to literature methods (Rondestvedt, C.S., Jr., Thayer, G.L., Jr., "J.Org.Chem.", 1977, 42, 2680)_nF_2n+1C₂H₄ I、C_nF_2n+1CH₂I. Or C_nF_2n+1I) Reacting with thiourea, and hydrolyzing the thiourea salt. The oligomeric iodide and thiourea are typically refluxed in ethanol for about 36h and hydrolyzed using sodium hydroxide to obtain the corresponding oligomeric thiol. Alternatively, the conversion can be achieved using NaSH ethanol solution and employing a substitution reaction.

The iodide used for the preparation of the above alcohol and thiol compounds is preferably a mixture of Ethylene (ET) and Tetrafluoroethylene (TFE) from C_nF_2n+1C₂H₄ I、C_nF_2n+1CH₂I or C_nF_2n+1Oligomerization of I. The reaction can be carried out at any temperature from room temperature to about 150 ℃ using a suitable free radical initiator. The reaction is preferably carried out at a temperature of about 40 ° to about 100 ℃ using an initiator having a half-life of about 10 hours in this range. The conversion of the reaction can be controlled by the feed ratio of the starting materials in the gas phase, i.e.Cx_nF_2n+1C₂H₄ I、C_nF_2n+1CH₂I or C_nF_2n+1The ratio of the number of moles of I to the sum of the moles of ethylene and tetrafluoroethylene. This molar ratio is from about 1: 3 to about 20: 1, preferably from about 1: 2to about 5: 1. The molar ratio of ethylene to tetrafluoroethylene is from about 1: 10 to about 10: 1, preferably from about 3: 7 to about 7: 3, and more preferably from about 4: 6 to about 6: 4.

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 achieve maximum yield, productivity or product quality.

The invention comprises fluorinated aqueous mixtures comprising a mixture of anionic aqueous compounds of formula (I) or (II) neutralized with a base, preferably an amine such as a dialkanolamine base. The composition is neutralized to a pH of about 5 to about 10, preferably to a pH of about 6 to about 9, and most preferably to a pH of about 6 to about 8.

Various molar ratios of fluoroalcohol or fluorothiol, acid and base can be represented by the format (a: 1: b): thus, the (2: 1) salt is, for example, the amine salt of a bis (fluoroalkyl) phosphate, the (1: 2) salt is, for example, the fluoroalkyl phosphate bis (amine salt), and the (1: 1) salt is, for example, the fluoroalkyl phosphate amine salt. Preferably, the (2: 1) salt is the bis (fluoroalkyl) phosphate diethanolamine salt, the (1: 2) salt is the fluoroalkyl phosphate bis (diethanolamine salt), and the (1: 1) salt is the fluoroalkyl phosphate diethanolamine salt.

The product of the reaction is a fluorinated sulfonate surfactant, which can reduce surface tension and provide improved surface effects such as blocking resistance, enhanced hiding (leveling), spreading, wetability, permeability, suds suppression, dispersibility, and water and oil repellency. These improved surface effects are advantageous for many industrial applications, including aqueous coatings such as inks, coatings, varnishes, and the like.

The invention also includes a method of reducing the surface tension of a medium (typically a liquid) comprising adding to the medium a compound of formula (I), (II) or a mixture thereof as described above. The surfactant of the present invention can effectively reduce the surface tension of various media. Examples of suitable media include, for example, 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 waxes, or adhesives. Due to the surfactant properties of the composition of the invention, the addition of the composition of the invention to the medium results 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. These surfactants are particularly suitable for reducing the surface tension of water, aqueous solutions and emulsions. Low concentrations of compounds of formula (I) or (II) of less than about 0.01% by weight in the liquid are effective. The amphoteric nature of the surfactant of formula (I) or (II) of the present invention makes it effective over a wide pH range. The pH is preferably greater than about 4.

The invention also comprises a method of modifying the surface behaviour of a liquid, which method comprises adding to the liquid a compound of formula (I) or (II) as defined above. Including various surface behaviors. Examples are wetting, penetration, spreading, leveling, flow emulsification, stabilization and dispersion in wetting liquids. Other examples include blocking resistance, repellency, and release in the dried coating composition on the treated substrate. Thus, the surfactants of formula (I) or (II) can be used in a variety of end uses.

The present invention also includes a method of providing surface characteristics to a substrate on which a coating composition is deposited, the method comprising adding to the coating composition prior to deposition of the coating composition onto the substrate a composition of formula (I) or (II) above, or a mixture thereof. The compounds of the formula (I) or (II) according to the invention are suitable for use in coatings, paints, pigments, varnishes, finishes, floor polishes or finishes, inks and dyes. The surface effects provided include enhanced hiding, leveling, blocking resistance, anti-cratering, regulated soil, water and oil repellency, wetting, dispersion, blocking resistance, color development, and addressing the problem of flooding.

Specific coating compositions suitable for use with the surfactants of the present invention (herein referred to by the term "coating primer") include compositions (typically liquid formulations) of: alkyd coatings, type I polyurethane coatings, unsaturated polyester coatings, or water dispersible coatings, and are applied to a substrate for creating 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 coating, a clear coating, or a 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, 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 Coatings comprise a pre-reacted autoxidisable binder as described in "Surface Coatings" volume 1, previously cited. 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 that comprises water as the primary dispersing component, such as an emulsion, latex, or a suspension of a film-forming material dispersed in an aqueous phase. "Water-dispersed coating" is a general category that describes many formulations and includes members of the above categories as well as members of other categories. 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 is described 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.

Blocking is the undesirable sticking together of two coated surfaces when pressed together or left 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.

When used as an additive to a coating base, the composition of formula (I) or (II) 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.%, 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 2to 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, preferably from about 2% to about 10% by weight, based on the weight of the final composition.

When used as an additive for floor finishes, the compositions of formulae (I), (II) or mixtures thereof of the present invention as defined above are 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.

The compounds of formula (I), (II) or mixtures thereof may be used in a number of additional applications. Examples of some applications include the following.

The compounds of the present invention are suitable for use in fire-fighting compositions, for example as wetting agents, emulsifiers and/or dispersants. They are also useful as components in aqueous film-forming fire extinguishing agents, 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 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) or (II) 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 the invention can also be used as wetting agents, emulsifiers and/or dispersants in the production of paper and veneer. The compounds of the invention 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 are also useful as wetting, emulsifying and/or dispersing agents in polymerization reactions, especially in the 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; and are suitable as blowing agents, release agents or mold release agents; internal antistatic agents suitable for use as polyolefins as well as antiblocking agents; suitable for use as a flow modifier for extruded hot melts to help adjust spreadability, leveling, anti-cratering; and as a retarder of plasticizer migration or evaporation in the plastics and rubber industry.

The compounds of the invention are also useful in the petroleum industry as wetting agents for oil well treatments and drilling muds; suitable for use as thin film evaporation inhibitors for gasoline, jet fuel, solvents, 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 the invention are also suitable as wetting, defoaming, penetrating or emulsifying agents in the textile and leather industries; 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 the invention are also useful in the mining and metal working industries, in the pharmaceutical industry, automotive, building maintenance and cleaning, in household, cosmetic and personal products, and in photography and graphic arts to provide improved surface effects.

The compositions of the present invention can be used as surfactants to adjust the surface tension of a liquid, which results in various surface properties of the liquid being changed. These properties can be obtained using lower concentrations of fluorine compared to conventional surfactants, providing improved "fluorine efficiency" in terms of protection of the treated surface, or they can be obtained using more environmentally friendly compositions.

Test method

The following test methods are used in the examples herein.

Test method 1Blocking resistance of the architectural latex coating

The test method described herein is a variation of ASTM D4946-89-Standard test method for blocking resistance of architectural coatings and is hereby specifically incorporated 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 cast onto a polyester test panel using a paint scraper. All paint templates should be free of grease, oil, fingerprints, dust, etc.; surface contamination can affect the blocking resistance results. Typically, the test results began 24 hours after casting the dope. The panel was conditioned for the duration of time required for treatment in the air conditioned room specified by the test method, and six squares (3.8cm by 3.8cm) were cut from the paint test panel. For each paint to be tested, the cut-out (three pairs) were placed with the paint surfaces in face-to-face relationship. The cut pieces (three pairs) were placed with the paint surfaces of each paint to be tested facing each other. The samples facing each other were placed on marble trays in an oven at 50 ℃. A No. 8 plug with a smaller diameter that contacted the sample was placed on top, 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. One weight and stopper was used for each sample to be tested. After exactly 30 minutes, the test specimen was removed from the oven and the stopper and weight removed and the block resistance determined after 30 minutes of cooling in an air conditioned room.

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 table 2B. 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-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 excellent in
7	Light 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% to 25% sealing	Is poor
			2	25% to 50% sealing	Is poor
1	50% to 75% sealing	Extreme difference
			0	75% to 100% ofSealing device	Extreme difference

Test method 2Surface tension measurement

Surface tension was measured using a Kruess tensiometer according to the equipment instructions K11 version 2.501. The Wilhelmy plate method was used. A vertical plate of known perimeter was attached to a balance and the force due to wetting was determined. 10 replicates were performed for each dilution and the following instrument settings were used:

the method comprises the following steps: surface tension test by plate method

Spacing: 1.0s

Wet growth: 40.2mm

Reading limit value: 10:

minimum standard deviation: 2 dyne/cm

Acceleration of gravity (gr.acc): 9.80665m/s 2

Test method 3 wetting and leveling test

To determine the performance of the samples in terms of their wetting and leveling capabilities, the samples were added to floor wax (RHOPLEX 3829, supplied by Rohm & Haas (Spring House, Pa.), used to prepare the final test formulation) and applied to half of a stripped 12 inch by 12 inch (30.36cm by 30.36cm) vinyl tile. 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 manufacturer's protocol followed by the addition of 0.75g1 wt% 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 an applicator, and finally a large "X" was placed across the tile using the applicator. The tiles were allowed to dry for 25 to 30 minutes and a total of 5 coats were applied. 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 rating is determined according to a comparison with floor tiles treated with floor wax without added surfactant and according to the following criteria:

floor tile grade scale

1 film surface coating unevenness, marked streaks and surface defects

Visible streaks and surface defects, film recession along the edges of the tiles

3 many surface defects and streaks were evident, but generally, the film covered the entire tile surface

4 fewer surface irregularities or striations

5 No visible surface defects or streaks

Examples

Example 1

Perfluoroethylaodoethane (PFEEI) (45g) and VAZO 64(1g) (polymerization initiator from E.I. du Pont DE Nemours and Company, Wilmington, DE) were added to a 400mL vibrating tube. After cold evacuation, ethylene (6g) and tetrafluoroethylene (25g) were added. The resulting mixture was heated at 80 ℃ for 20 hours. The unreacted perfluoroethyl iodoethane was recovered by vacuum distillation at room temperature. By CH₃CN (3X 100mL) extracted the remaining solid. Will CH₃And concentrating the CN extracting solution and distilling under reduced pressure to obtain pure iodide 1, 1,2, 2,5, 5, 6, 6-octahydroperfluoro-1-iodooctane. Extraction of CH with hot tetrahydrofuran₃The solid remaining after extraction of CN. Concentrating and drying the tetrahydrofuran extract to obtainObtaining pure 1, 1,2, 2,5, 5, 6, 6, 9, 9, 10, 10-dodecahydroperfluoro-1-iodododecane. The solids remaining after the extraction of tetrahydrofuran are predominantly of the formula C₂F₅(CH₂CH₂CF₂CF₂)_nCH₂CH₂Iodides of the structure I (where n ═ 3, and higher oligomers) have very low solubility in common solvents.

The products 1, 1,2, 2,5, 5, 6, 6-octahydroperfluoro-1-iodooctane and 1, 1,2, 2,5, 5, 6, 6, 9, 9, 10, 10-dodecahydroperfluoro-1-iodododecane were characterized by H NMR and F NMR as follows:

1, 1,2, 2,5, 5, 6, 6-octahydroperfluoro-1-iodooctane: mp 75-77 ℃:

H NMR(CDCl3)2.33(m，4H)，2.68(m，2H)，3.24(m，2H)ppm。

F NMR(CDCl3)-85.9(s，3F)，-115.8(m，4F)，-119.2(m，2F)ppm。

1, 1,2, 2,5, 5, 6, 6, 9, 9, 10, 10-dodecahydroperfluoro-1-iodododecane: mp 125-8 ℃:

h NMR (acetone-d 6)2.46(m, 8H), 2.77(m, 2H), 3.37(m, 2H) ppm.

F NMR (acetone-d 6) -86.7(s, 3F), -117.1(m, 6F), -117.3(m, 2F), -119.5(m, 2F) ppm.

A mixture of 1, 1,2, 2,5, 5, 6, 6-octahydroperfluoro-1-iodooctane (136.91g, 248.88mmol) and N-methylformamide (NMF) (273mL), prepared as above, was heated at 150 ℃ for 19 hours. The reaction mixture was washed with water (4X 500mL) to obtain a residue. A mixture of the residue, ethanol (200mL) and concentrated hydrochloric acid (1mL) was gently refluxed (85C bath temperature) for 2.5 hours. The reaction mixture was washed with water (200 mL. times.2), diluted with dichloromethane (200mL) and dried over sodium sulfate overnight. The methylene chloride solution was concentrated and distilled under reduced pressure to obtain 50.8g of 1, 1,2, 2,5, 5, 6, 6-octahydroperfluoro-1-octanol.

To 500mL of 4-NRBF equipped with an overhead stirrer, condenser, nitrogen inlet and solid addition funnel was added 1, 1,2, 2,5, 5, 6, 6-octahydroperfluoro-1-octanol (36.8g) prepared as described above. The flask was heated to 85 ℃ (bath temperature) while stirring (125 rpm). Phosphorus pentoxide (8g) was slowly added to the flask via the solid addition funnel. The reaction mixture was stirred (125rpm) at 100 ℃ for 16 hours. The reaction mixture was then cooled to 86 ℃ and DI water (144g, 80 ℃) was added while increasing the stirring rate to 250 rpm. The reaction mixture was stirred for 20 minutes, then ammonium hydroxide (28% ammonia, 8.1g) was added. The reaction mixture was stirred for an additional 4 hours and cooled to room temperature. A gel-like product is obtained. The calculated weight of solids was 47.1g and the total amount of water technically reported was 150 g. This gave a product with 23.9 w/w% solids. Surface tension was measured using test method 2. The results are shown in Table 3.

TABLE 3

Surface tension in water:

example 2

Oligomerizing iodide mixture F (CF)₂CF₂CH₂CH₂)_nI (where N-2, 3 is the major component, in a ratio of about 2: 1) (46.5g) was mixed with N-methylformamide (NMF) (273mL) and heated at 150 ℃ for 19 hours. The reaction mixture was washed with water (4X 500mL) to obtain a residue. A mixture of this residue, ethanol (200mL) and concentrated hydrochloric acid (1mL) was gently refluxed (85C bath temperature) for 24 hours. The reaction mixture was poured into water (300 mL). The solid was washed with water (2X 75mL) and dried in vacuo (2torr, 267Pa) to give 24.5g of solid. Sublimation was about 2g of product. The total yield of the oligomeric alcohol was 26.5 g.

To a 250mL 3-neck round bottom flask equipped with an overhead stirrer (stainless steel stir bar), solid addition funnel, condenser, and nitrogen blanket was added the alcohol mixture (34.9g) prepared as described above. The oligomeric alcohol was heated to 120 ℃ to melt the alcohol and then cooled to 100 ℃. Phosphorus pentoxide (7.7g) was added to the flask. The resulting mixture was stirred at 100 ℃ for 17 hours. Warm water (80 ℃, 176g) was added and the resulting mixture was stirred for 10 minutes, then ammonium hydroxide (28% ammonia, 7.3g) was added slowly. The resulting mixture was stirred for an additional 1.5 hours. While the reaction mixture was still hot, it was transferred to a jar. The reaction flask was washed with hot water and the wash water was combined with the product. The product was determined to contain 11.9 wt/wt% solids. Surface tension was measured using test method 2. Surface tension measurements a portion of E111879-135(11.9 wt/wt% solids) was used to formulate test solutions. The results are shown in Table 4.

TABLE 4

Sample description	Concentration of	Surface tension	Standard deviation of
					By weight%	mN/M	mN/M
Deionized water	0	73.1	0.1
				Example 2	0.0001	72.8	0.1
Example 2	0.001	71.4	0.1
				Example 2	0.01	32.6	0.1
Example 2	0.1	22.6	0.1

Example 3

To a 400mL shaking tube was added Perfluorobutyliodoethane (PFBEI) (75g) and VAZO 64 as described in example 1 (1.5 g). After cold evacuation, ethylene (6g) and tetrafluoroethylene (25g) were added. The resulting mixture was heated at 80 ℃ for 20 hours. The reaction mixtures from 10 identical reactions were combined and the unreacted perfluorobutyliodoethane was recovered by vacuum distillation at room temperature. By CH₃CN (10X 300mL) extracted the remaining solid (648 g). To merge CH₃The CN extracting solution is concentrated and distilled under reduced pressure to obtain iodide 1, 1,2, 2,5, 5, 6, 6-octahydroperfluoro-1-iododecane. CH (CH)₃The solid remained after extraction of CN is mainly1, 1,2, 2,5, 5, 6, 6, 9, 9, 10, 10-dodecahydroperfluoro-1-iodotetradecane and higher oligomers. The product 1, 1,2, 2,5, 5, 6, 6-octahydroperfluoro-1-iododecane from H

NMR and F NMR characterization, as follows.

1, 1,2, 2,5, 5, 6, 6-octahydroperfluoro-1-iododecane: mp 72-74 ℃:

H NMR(CDCl3)2.36(m，4H)，2.69(m，2H)，3.25(m，2H)ppm。

F NMR(CDCl3)-81.5(tt，J＝10，3Hz，3F)，-115.3(m，2F)，-115.7(m，4F)，-124.7(m，2F)，-126.4(m，2F)ppm。

1, 1,2, 2,5, 5, 6, 6-octahydroperfluoro-1-iododecane (12g) prepared as described above was mixed with oleum (15% SO)₃215mL) was heated at 60 ℃ for 2 h. At 60 deg.C, adding Na₂SO₃The solution (4g in 100mL of water) was slowly added to the reaction mixture with an internal temperature between 65 ℃ and 90 ℃. The resulting mixture was heated at 90 ℃ for 30 minutes. After cooling to room temperature, a solid precipitated out. The liquid was decanted off and the solid was dissolved in ether (150mL) and taken up with Na₂SO₃(1M, 20mL), water (2X 20mL), NaCl (saturated, 20mL) and washed with anhydrous Na₂SO₄Dried above, concentrated and dried in vacuo to give a residue which is further purified by distillation to give 6.2g of an off-white solid, 1,2, 2,5, 5, 6, 6-octahydroperfluoro-1-decanol at 65-79 ℃ bp at 2torr (267 Pa). The product was characterized by MS, H NMR and F NMR as shown below.

MS(m/e)392(M+，0.16％)，372(3.3％)，342(60％)，323(53％)，223(29％)，95(100％)。H NMR(CDCl3)1.58(s，1H)，2.36(m，6H)，3.97(t，J＝7Hz，2H)ppm。F NMR(CDCl3)-81.5(tt，J＝9.5，3Hz，3F)，-114.1(m，2F)，-115.4(m，2F)，-116.0(m，2F)，-124.8(m，2F)，-126.4(m，2F)ppm。

In a 100mL flask equipped with a stir bar, condenser and nitrogen blanket, 1,2, 2,5, 5, 6, 6-octahydroperfluoro-1-decanol (3g) prepared as described above and phosphorus pentoxide (0.56g) were added under nitrogen. The mixture was heated at 100 ℃ for 18 hours. The reaction mixture was cooled to 86 ℃ and warm water (80 ℃, 16.5g) was added. The resulting mixture was stirred for 1 hour, and ammonium hydroxide (28% ammonia, 2.19g) was added. The mixture was stirred for an additional hour and transferred to a jar while it was still hot. The product was calculated to contain 19.2 w/w% solids. Surface tension was measured using test method 2. The results are shown in Table 5.

TABLE 5

Sample description	Concentration of	Surface tension	Standard deviation of
					By weight%	mN/M	mN/M
Deionized water	0	73.1	0.1
				Example 3	0.0001	72.9	0.1
Example 3	0.001	49	0.1
				Example 3	0.01	22.6	0.1
Example 3	0.1	20.4	0.1

Example 4

The products of examples 1,2 and 3 were added to floor wax RHOPLEX 3829 (formulation N-29-1, available from Rohm and Haas Company (Philadelphia, Pa.)) in an amount of 0.015 wt.% of the fluorophosphate salt. Blocking resistance was determined according to test method 1. Floor finishes without the addition of the compounds of the invention were also tested in the same manner. The results are shown in Table 6.

The products of examples 1,2 and 3 were added to the above floor polish at 75 micrograms per gram of active ingredient. The wetting and leveling of the floor finish was determined according to test method 3. Floor finishes without the addition of the compounds of the invention were also tested in the same manner. The results are shown in Table 7.

Comparative example A

A surfactant commercially available from e.i. du Pont DE nerves and Company (Wilmington, DE) was used as comparative example a, which was prepared as described in U.S. patent publication 3,083,224 as an aqueous solution of the ammonium fluoroalkyl phosphate salt. It was added to floor wax RHOPLEX 3829 (formulation N-29-1, available from Rohm and Haas Company (Philadelphia, Pa.)) in an amount of 0.015 wt.% active ingredient. Blocking resistance was determined according to test method 1. The results are shown in Table 6.

TABLE 6Blocking resistance

Examples	Grade
		Blank space	0
Comparative example A	6.7
		1	8

2	8
		3	9

The data in table 6 show that the compounds of the present invention provide superior blocking resistance compared to commercially available surfactants containing higher levels of fluorine.

Comparative example B

A surfactant commercially available from e.i. du Pont DE Nemours and Company (Wilmington, DE), which is a fluoroalkyl ethoxylate made from a fluorinated alcohol and alkylene epoxide in water and glycol solvents, was added to the floor wax rhopelex 3829 (formulation N-29-1, available from Rohm and Haas Company (Philadelphia, PA)) at 75 micrograms per gram of active ingredient. The wetting and leveling of the floor finish was determined according to test method 3. The results are shown in Table 7.

TABLE 7

The data in table 7 show that the compounds of the present invention provide comparable wetting and leveling in floor treatments compared to commercially available surfactants containing higher levels of fluorine.

Example 5

Perfluoroethylaodoethane (PFEEI) (1997.5g) and lauroyl peroxide (7.9g) were charged to a 1 gallon reactor. After cold evacuation, ethylene and tetrafluoroethylene were added in a ratio of 25: 75 until the pressure reached 60psig (413.7X 10)³Pa) is added. The reaction was then heated to 75 ℃. More ethylene and tetrafluoroethylene were added in a 25: 75 ratio until a total of 299g tetrafluoroethylene [ maximum pressure 160psig (1103.2X 10)³Pa)]. The ethylene and tetrafluoroethylene feeds were stopped. The reaction was heated at 75 ℃ for an additional 4 hours. Volatiles were removed by vacuum distillation at room temperature. An oligo ethylene-tetrafluoroethylene iodide solid (537g) was obtained.

To a 1L reactor were charged the above oligo ethylene-tetrafluoroethylene iodide (469g) and N-methylformamide (NMF) (490 g). The mixture was heated at 150 ℃ for 10 hours. The resulting product was washed twice with water (213g) to obtain a residue. A mixture of the residue, ethanol (179g) and methanesulfonic acid (8mL) was heated to reactively distill off the volatiles until the reaction tended to completion to give the crude product. The crude product was washed with sodium sulfite (10 wt% aqueous solution, 95g) and water (940g) to give a wet product. The wet product was dried by removing water by vacuum distillation. A solid (290) consisting of ethylene-tetrafluoroethylene oligool is obtained.

Adding POCl₃(15.4g, 0.1mol) was charged to a three-necked round bottom flask equipped with a thermometer and a magnetic stirrer. 6.0g (0.1mol) of isopropanol was slowly added to the flask at room temperature. The reaction mixture was heated to 70 ℃ and stirred for 2 hours. 13.43g of pale yellow liquid (A) was obtained. The above ethylene-tetrafluoroethylene oligool (18.6g) was heated to 80 ℃ and a portion (5.31g) of the reaction mixture (A) was slowly added. After addition, the reaction mixture was heated to 95 ℃ and stirred for 3 hours. Deionized water (0.21g) was added to the flask and stirred for an additional 2 hours. The reaction mixture was cooled to room temperature, and 20.0g of viscous brown phosphate (B) was obtained. The phosphate (B) (7.0g) was added to another flask and heated to 95 ℃. Diethanolamine (2.3g) was added and stirred for 3 hours to obtain brown phosphate (8.3 g). The product was dissolved in deionized water and the surface tension was determined according to test method 2. The results are shown in Table 8.

Example 6

Adding POCl₃(1.53g, 0.01mol) and 20mL of anhydrous tetrahydrofuran were charged to a three-necked round bottom flask equipped with a thermocouple, nitrogen inlet, and a magnetic stir bar. The solution was cooled to 0 ℃ and would contain 6.6A solution of 7g (0.02mol) of ethylene-tetrafluoroethylene oligool (prepared as in example 5) and 2.53g (0.025mol) of triethylamine in 20mL of anhydrous tetrahydrofuran was slowly added to the flask. After the addition, the reaction was allowed to proceed at 0-1 ℃ for 2 hours. The reaction mixture was allowed to warm to ambient temperature and stirred overnight. The solid was removed by filtration and the solvent and excess triethylamine were removed with a rotary evaporator. The resulting oil was diluted in 15mL tetrahydrofuran. NaOH (0.8g, 0.02mol) was dissolved in 1.2mL of water and added to the reaction mixture. The solution was stirred at room temperature overnight. The solvent was evaporated using a rotary evaporator. The resulting solid was dried at 120 ℃ under a vacuum system, and 5.3g of a phosphate solid was obtained. The product was dissolved in deionized water and the surface tension was determined according to test method 2. The results are shown in Table 8.

Example 7

Adding POCl₃(7.7g, 0.1mol) was charged to a three-necked round bottom flask equipped with a thermometer and a magnetic stirrer. Isopropanol (2.9g, 0.048mol) was slowly added to the flask at room temperature. The reaction mixture was heated to 70 ℃ and stirred for 2 hours. The ethylene-tetrafluoroethylene oligomer (15.7g, 0.047mol) as prepared in example 5 was slowly added to the reaction mixture at 50 ℃ and stirred for an additional three hours. The reaction mixture was heated to 80 ℃ and 6.5g (0.05mol) 1-octanol was slowly added to the flask. After the addition, the reaction mixture was heated to 95 ℃ and stirred for 2 hours. Deionized water (0.37g) was added to the flask and the contents stirred for an additional 2 hours. The reaction mixture was cooled to room temperature, and 23.5g of a brown waxy solid was obtained. This compound (7.0g) was added to the flask and heated to 95 ℃. Diethanolamine (2.3g) was added and stirred for 3 hours. 8.0g of a viscous brown liquid phosphate are obtained. The product was dissolved in deionized water and the surface tension was determined according to test method 2. The results are shown in Table 8.

Example 8

Adding POCl₃(1.53g, 0.01mol) and 20mL of anhydrous tetrahydrofuranInto a three-necked round bottom flask equipped with a thermocouple, nitrogen inlet, and a magnetic stir bar. The solution was cooled to 0 ℃ and a solution of 3.34g (0.01mol) of ethylene-tetrafluoroethylene oligool (prepared as in example 5) and 2.53g (0.025mol) of triethylamine in 20mL of anhydrous tetrahydrofuran was slowly added. The reaction was allowed to proceed at 0-1 ℃ for 2 hours. Then 10mL of anhydrous tetrahydrofuran solution containing 1.3g (0.01mol) of octanol was slowly added to the reaction mixture. The reaction mixture was allowed to warm to ambient temperature and stirred overnight. The solid was filtered off and the solvent and excess triethylamine were evaporated off using a rotary evaporator. The resulting oil was diluted in 15mL tetrahydrofuran. NaOH (0.8g, 0.02mol) was dissolved in 1.2mL of water and added to the reaction mixture. The solution was stirred at room temperature overnight. The solvent was evaporated using a rotary evaporator. The resulting solid was dried at 120 ℃ under a vacuum system, and 4.0g of a yellow phosphate solid was obtained. The product was dissolved in deionized water and the surface tension was determined according to test method 2. The results are shown in Table 8.

TABLE 8

Claims (10)

1. A composition comprising a compound of formula (I) or (II):

(A)_w-P(O)(O^-M⁺)_3-w(I) or

Wherein

A is R_f-(CH₂)_k-[(CF₂CF)_y-(CH₂CH₂)_z]_mO and contains from about 8 to about 22 carbon atoms;

R_fis C_nF_2n+1；

n and k are each independently 1 to about 6;

y, z and m are each independently 1,2, 3, or mixtures thereof;

w is 1 or 2, or mixtures thereof; and is

M is hydrogen, ammonium ion, alkali metal ion, or alkanolammonium ion.

2. The composition of claim 1, wherein R_fHaving 4 to 6 carbon atoms; y, z and M are each 1, and M is ammonium or alkanolammonium ion.

3. The composition of claim 1 comprising from about 15 mol% to about 80 mol% of the mono (fluoroalkyl) phosphate of formula (I) wherein x is 1, and from about 20 mol% to about 85 mol% of the bis (fluoroalkyl) phosphate of formula (I) wherein x is 2.

4. A method of modifying the surface behavior of a liquid, said method comprising adding to said liquid a compound of claim 1 or a mixture thereof.

5. The method of claim 4, wherein the modifying the surface behavior is reducing surface tension.

6. The method of claim 4, wherein the surface behavior is selected from the group consisting of wetting, penetrating, spreading, leveling, flowing, emulsifying, dispersing, repelling, releasing, lubricating, etching, bonding, and stabilizing.

7. The method of claim 4, wherein the liquid 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, floor finish, or adhesive.

8. A method of providing block resistance to a substrate on which a coating composition is deposited, the method comprising adding to the coating composition a composition comprising one or more compounds of claim 1 prior to deposition of the coating composition onto the substrate.

9. The method of claim 8, wherein the coating composition is a water-dispersed coating, an alkyd coating, a type I polyurethane coating, or an unsaturated polyester coating.

10. A substrate treated according to the method of claim 4 or 8.