HK1135714B

HK1135714B - Polyfluoroether based polymers

Info

Publication number: HK1135714B
Application number: HK10102471.2A
Authority: HK
Inventors: Sheng Peng; Stephen James Getty; Timothy Edward Hopkins; Ying Wang
Original assignee: E. I. Du Pont De Nemours And Company
Priority date: 2006-11-13
Filing date: 2007-09-21
Publication date: 2013-05-03

Description

Polyfluoroether-based polymers

Technical Field

The present invention relates to the field of polyfluorinated compounds comprising ether linkages in the polyfluoro chain, and in particular to such polyurethane fluoropolymers used to provide surface characteristics to substrates treated therewith.

Background

A variety of polymers made from perfluorinated compositions are known to be useful as treating agents to provide surface effects to substrates. Surface effects include repellency to moisture, dirt, and stains and other effects particularly useful for fibrous substrates and other substrates such as hard surfaces. Many such treating agents are fluorinated polymers or copolymers.

Most commercially available fluorinated polymers useful as treating agents to impart surface efficacy to substrates contain predominantly eight or more carbons in the perfluoroalkyl chain to provide the desired properties. Honda et al, 2005, "Macromolecules", Vol 38, pages 5699 to 5705, propose that for perfluoroalkyl chains containing more than 8 carbons, R is_fThe orientation of the perfluoroalkyl groups represented by the groups remains in a parallel configuration, whereas for such chains having less than 6 carbon atoms, reorientation occurs. This reorientation reduces surface properties such as contact angle. Thus, the conventional shorter chain perfluoroalkyl groups have not been successfully commercialized to impart surface characteristics to substrates.

It is desirable to improve specific surface effects and increase fluorine efficiency; i.e., to promote the efficacy or performance of the treatment agent so that a lesser amount of the expensive fluorinated polymer is required to achieve the same level of performance, or to use the same level of fluorine for better performance. It is desirable to reduce the chain length of the perfluoroalkyl group, thereby reducing the fluorine content, while still achieving the same or better surface efficacy.

U.S. patent 3,564,059 discloses perfluorinated ethers and polyethers for use as plasticizers and solvents. No application in providing a repellent surface to a substrate is disclosed.

There is a need for polymer blends that can significantly improve the stain and soil resistance of fluorinated polymer treating agents for fibrous substrates and hard surface substrates while using lower levels of fluorine. The present invention provides such compositions.

Summary of The Invention

The present invention includes compositions comprising a polymer comprising at least one urea linkage, the polymer being prepared by:

(i) reacting (1) at least one organic diisocyanate, polyisocyanate or mixture thereof with (2) at least one fluorochemical compound of formula I

R_f-O(CF₂CF₂)_r(CH₂CH₂)_q(R¹)_sXH formula I

Wherein

R_fIs a straight-chain or branched C optionally interrupted by one to three oxygen atoms₁To C₇A perfluoroalkyl group,

r is 1 to 3, q is 1 to 3, s is 0 or 1,

x is O, S or NR²Wherein R is²Is H, or C₁To C₆Alkyl radical, and

R¹is a divalent radical-S (CH)₂)_n-、

n is 2 to 4, p is 1 to 50, and R³、R⁴And R⁵Each independently is H or C₁To C₆An alkyl group;

(ii) and then with (3) water, a linking agent, or a mixture thereof.

The present invention also includes a method of providing water repellency, oil repellency, stain release, hydrophilic stain release, and cleanability to a substrate comprising contacting said substrate with the above-described polymers.

The present invention also includes a method of providing soil resistance to a substrate comprising contacting the substrate with the above-described polymer, wherein the diisocyanate, polyisocyanate, or mixture thereof comprises one or more cyclic diisocyanates selected from the group consisting of 2, 4-toluene diisocyanate; 2, 6-toluene diisocyanate; diphenylmethane-4, 4' -diisocyanate; diphenylmethane-2, 4' -diisocyanate; 3-isocyanatomethyl-3, 4, 4-trimethylcyclohexyl isocyanate; and bis (4-isocyanatocyclohexyl) methane and diisocyanate trimers of formula (IIa), (IIb):

the invention also includes substrates to which the above polymers have been applied.

Detailed Description

Hereinafter trademarks are shown in upper case.

The present invention provides a polymer as described above, which can be prepared from a fluorinated alcohol, a fluorinated thiol or a fluorinated amine comprising a perfluoroalkyl ether. These compositions are useful for providing soil release, oil repellency, water repellency, hydrophilic stain release, cleanability, and soil resistance to fibers and hard substrates, and for other uses in which the perfluorinated end groups provide unique surface modification characteristics. The perfluoroalkyl groups in the polymers of the present invention contain 1 to 7 carbon atoms and typically exhibit surface characteristics equal to or better than conventional commercial surface treatments, which typically contain perfluoroalkyl groups having 8 to about 20 carbon atoms.

The fluoroalcohol used to prepare the composition of the present invention may be obtained via a series of reactions:

the starting perfluoroalkyl ether iodides were prepared via the method described in U.S. patent 5,481,028, example 8, which discloses the preparation of compounds of formula (V) from perfluoro-n-propyl vinyl ether, which is incorporated herein by reference.

In the above-mentioned second reaction step, the perfluoroalkyl ether iodide (V) is reacted with an excess of ethylene at high temperature and high pressure. Although the addition reaction of ethylene can be carried out under heating, it is preferable 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 catalyst is benzoyl peroxide. The reaction temperature is not limited, but a temperature in the range of 110 ℃ to 130 ℃ is preferred. The reaction time varies depending on the catalyst and the reaction conditions, but usually 24 hours is sufficient. The product may be purified by any method that allows the unreacted starting materials to be separated from the final product, but distillation is preferred. Satisfactory yields of up to 80% of theory were obtained using about 2.7 moles of ethylene per mole of perfluoroalkylether iodide, a temperature and autogenous pressure of 110 ℃, a reaction time of 24 hours, and purifying the product via distillation.

According to the process disclosed in WO 95/11877, the perfluoroalkylether ethylene iodide (VI) is treated with oleum and hydrolyzed to obtain the corresponding alcohol (VII). Alternatively, the perfluoroalkylether ethylene iodide was treated with N-methylformamide, followed by ethanol/acid hydrolysis. Temperatures of about 130 ℃ to 160 ℃ are preferred. The higher homolog of telomer ethylene iodides (VI) (q-2, 3) is obtained with an excess of ethylene at elevated pressure.

Telomer ethylene iodides (VI) may be treated with various reagents to obtain the corresponding thiols according to the procedure described in "fluorine Chemistry" volume 104, pages 2173 to 2183 (2000). One example is the reaction of telomer ethylene iodides (VI) with sodium thiocyanate, followed by hydrolysis.

Telomer ethylene iodides (VI) can be treated with omega-mercapto-1-alkanols according to the following scheme to obtain compounds of formula (VIII):

telomer ethylene iodides (VI) may be treated with omega-mercapto-1-alkylamines according to the following scheme to obtain compounds of formula (IX):

preferred compounds of formulae (VIII) and (IX) for use in the practice of the present invention are those wherein q ═ 1 and n ═ 2 to 3.

Specific fluoroether alcohols useful in forming the polymers of the present invention include those listed in Table 1A. Unless otherwise specifically indicated, the perfluoroalkyl groups in the listed alcohols are all linear.

TABLE 1A

1 F₃COCF₂CF₂CH₂CH₂OH，

3 C₂F₅OCF₂CF₂CH₂CH₂OH，

5 C₃F₇OCF₂CF₂CH₂CH₂OH，

6 C₃F₇O(CF₂CF₂)₂CH₂CH₂OH，

7 C₄F₉OCF₂CF₂CH₂CH₂OH，

8 C₄F₉O(CF₂CF₂)₂CH₂CH₂OH，

9 C₆F₁₃OCF₂CF₂CH₂CH₂OH，

10 C₆F₁₃O(CF₂CF₂)₂CH₂CH₂OH，

11 F₃COCF(CF₃)CF₂OCF₂CF₂CH₂CH₂OH，

12 F₃COCF(CF₃)CF₂O(CF₂CF₂)₂CH₂CH₂OH，

13 C₂F₅OCF(CF₃)CF₂OCF₂CF₂CH₂CH₂OH，

14 C₂F₅OCF(CF₃)CF₂O(CF₂CF₂)₂CH₂CH₂OH，

15 C₃F₇OCF(CF₃)CF₂OCF₂CF₂CH₂CH₂OH，

16 C₃F₇OCF₃CF₂O(CF₂CF₂)₂CH₂CH₂OH。

To prepare the fluoropolymers of the present invention, a perfluoroalkyl ether ethyl alcohol or the corresponding thiol or amine is reacted with a polyisocyanate. The polyisocyanate reactant increases the branching characteristics of the polymer. The term "polyisocyanate" refers to diisocyanates and higher isocyanates, and the term includes oligomers. Any polyisocyanate having predominantly two or more isocyanate groups, or any isocyanate precursor of a polyisocyanate having predominantly two or more isocyanate groups, is suitable for use in the present invention. For example, hexamethylene diisocyanate homopolymer is suitable for use herein and is commercially available. It is recognized that polymers formed from small amounts of diisocyanates may be present in products made from multiple isocyanate groups. An example of this is the biuret containing residual small amounts of hexamethylene diisocyanate.

Also suitable as polyisocyanate reactants are isocyanurate trimers derived from hydrocarbon diisocyanates. Preferred is DESMODUR N-3300 (an isocyanurate based on hexamethylene diisocyanate, also available from Bayer Corporation, Pittsburgh, Pa.). Other polyisocyanates which can be used for the purposes of the present invention are those triisocyanates which are obtained by reacting three moles of toluene diisocyanate with 1, 1, 1-tris (hydroxymethyl) ethane or 1, 1, 1-tris (hydroxymethyl) propane. The isocyanurate trimer of toluene diisocyanate and the isocyanurate trimer of 3-isocyanatomethyl-3, 4, 4-trimethylcyclohexyl isocyanate are other examples of triisocyanates useful for the purposes of this invention, such as methine-tris (phenyl isocyanate). Precursors of polyisocyanates, such as diisocyanates, are also suitable for use as the matrix for the polyisocyanates in the present invention. DESMODUR N-3600, DESMODUR Z-4470 and DESMODURXP 2410 from Bayer Corporation (Pittsburgh, Pa.), and bis (4-isocyanatocyclohexyl) methane are also suitable for use in the present invention.

Preferred polyisocyanate reactants are aliphatic and aromatic polyisocyanates containing biuret structures, or polydimethylsiloxanes containing isocyanates. Such polyisocyanates also contain aliphatic and aromatic substituents. Particularly preferred as the polyisocyanate reactant is hexamethylene diisocyanate homopolymer, commercially available under the trade names, e.g., DESMODUR N-100, DESMODUR N-75 and DESMODUR N-3200, from Bayer Corporation (Pittsburgh, Pa.); 3-isocyanatomethyl-3, 4, 4-trimethylcyclohexyl isocyanate, which is available under the trade name, for example, DESMODUR I (Bayer Corporation); bis (4-isocyanatocyclohexyl) methane, which is available under the trade name, for example, DESMODUR W (Bayer Corp), and diisocyanate trimers of the formulae (IIa), (IIb), which are available from Bayer corporation under the trade names DESMODUR Z2447 and DESMODUR N-3300, respectively.

To prepare the fluoropolymers of the present invention, a perfluoroalkyl ether ethyl alcohol or the corresponding thiol or amine is reacted with a polyisocyanate. The polyisocyanate is generally added to the reaction vessel; a fluorinated alcohol, a fluorinated thiol, a fluorinated amine, or mixtures thereof; and optionally a non-fluorinated organic compound. The order of addition of the reagents is not critical. The specific weights of polyisocyanate and other reactants added are based on their equivalent weight and working capacity of the reaction vessel and can be adjusted so that the alcohol, thiol or amine can be consumed in the first step. The addition was stirred and the temperature was adjusted to about 40 ℃ to 70 ℃. A solution of a catalyst such as a titanium chelate in an organic solvent is then typically added and the temperature is raised to about 80 to 100 ℃. After a holding time of several hours, additional solvent and water, linking agent or combination thereof is added and the mixture is allowed to react for an additional several hours or until all of the isocyanate has reacted. Water and surfactant (if necessary) are then added and stirred until well mixed. After homogenization, the organic solvent may be removed by distillation under reduced pressure, and the remaining aqueous fluoropolymer solution may be used as it is or subjected to further treatment.

A preferred embodiment of the present invention is where R is_fIs straight chain C₁To C₃Perfluoroalkyl, and more preferably wherein r is 1, q is 1, and s is 0. Other preferred embodiments are polymers in which the fluorinated compound is reacted with from about 5 mole% to about 90 mole%, and more preferably from about 10 mole% to about 70 mole%, of the isocyanate groups. Other preferred embodiments are polymers wherein the linking group is a diamine or polyamine.

In another preferred embodiment, the reacting step (i) further comprises (d) a non-fluorinated organic compound comprising a single functional group selected from the group having the formula

R¹⁰-(R¹¹)_k-YH

Wherein

R¹⁰Is C₁-C₁₈Alkyl radical, C₁-C₁₈Omega-alkenyl, or C₁-C₁₈Omega-alkenoyl;

R¹¹is composed of

Wherein R is²、R³And R⁴Independently is H or C₁To C₆Alkyl, and s is 1 to 50;

k is 0 or 1; and is

Y is-O-, -S-or-N (R)⁵) -, wherein R⁵Is H or an alkyl group containing 1 to 6 carbon atoms. Preferably, of the formula R¹⁰-(R¹¹)_k-YH with about 0.1 to about 60 mole% of said isocyanate groups.

In another preferred embodiment, of formula R¹⁰-(R¹¹)_k-YH comprises a hydrophilic, water-soluble species comprising at least one hydroxyl-terminated polyether of formula (III):

wherein R is a monovalent hydrocarbon radical containing from about 1 to about 6 aliphatic or cycloaliphatic carbon atoms; m and m2 are each independently an average number of oxyethylene (EO) repeating groups and m1 is an average number of oxypropylene (PO) repeating groups; provided that m is always a positive integer and that m1 and m2 are positive integers or zero. When m1 and m2 are zero, formula (III) represents an oxyethylene homopolymer. When m1 is a positive integer and m2 is zero, formula (III) represents a block or random copolymer of oxyethylene and oxypropylene. When m1 and m2 are positive integers, formula (III) represents a triblock copolymer represented by PEG-PPG-PEG (polyethylene glycol-polypropylene glycol-polyethylene glycol). More preferably, the hydrophilic, water-soluble component (3) is a commercially available methoxypolyethylene glycol (MPEG) or mixtures thereof having an average molecular weight equal to or greater than about 200, and most preferably between 350 and 2000. Also commercially available and suitable for use in preparing the polyfluoro organic compounds of the present invention are butoxypolyoxyalkylenes containing equal amounts by weight of oxyethylene and oxypropylene groups (Union Carbide Corp.50-HB series UCON fluids and lubricants) and having an average molecular weight of greater than about 1000.

This non-fluorinated compound is reacted in step (I) with a polyisocyanate and a fluorinated compound having formula (I) as described above, prior to reaction with water, a linking agent or a mixture thereof. This initial reaction is carried out such that less than 100% of the polyisocyanate groups are reacted. After this reaction, water, a linking agent or a mixture thereof is added. The reaction of water or linking agent with the remaining NCO groups allows all isocyanate groups to be fully reacted and eliminates further purification steps that may be required if other reactants are used in a ratio sufficient to react with 100% of the isocyanate groups. Furthermore, this addition greatly increases the molecular weight of the polymer and ensures proper mixing when more than one reactant is used in the first step of polyurethane preparation, i.e., if a water-soluble component is added, at least one unit may be present in each polymer.

Linkers useful in forming the polymers of the invention are Organic Compounds having two or more Zerewitinov Hydrogen atoms (Zerichov, Th., "quantitative determination of the Active Hydrogen in Organic Compounds", Berichte der Deutschen Chemischen Gesellschaft, 1908, 41, pages 2233 to 2243). Examples include compounds having at least two functional groups capable of reacting with isocyanate groups. Such functional groups include hydroxyl, amino, and thiol groups. Examples of polyfunctional alcohols useful as linking agents include: a polyoxyalkylene having 2, 3 or 4 carbon atoms in the oxyalkylene group and having two or more hydroxyl groups. Examples include polyether diols such as polyethylene glycol, polyethylene-polypropylene glycol copolymers, and polytetramethylene glycol, polyester diols such as those derived from the polymerization of adipic acid or other aliphatic dibasic acids with organic aliphatic diols having 2 to 30 carbon atoms; non-polymeric polyols, including alkylene glycols and polyhydroxyalkanes, including 1, 2-ethanediol, 1, 2-propanediol, 3-chloro-1, 2-propanediol, 1, 3-butanediol, 1, 4-butanediol, 2-dimethyl-1, 3-propanediol, 1, 2-hexanediol, 1, 5-hexanediol and 1, 6-hexanediol, 2-ethyl-1, 6-hexanediol, 1, 8-octanediol, 1, 10-decanediol, glycerol, trimethylolethane, trimethylolpropane, 2-ethyl-2- (hydroxymethyl) -1, 3-propanediol, 1, 2, 6-hexanetriol and pentaerythritol.

Preferred polyfunctional amines useful as linkers include: amine terminated polyethers such as JEFFAMINE D400, JEFFAMINE ED and JEFFAMINE EDR-148, all available from Huntsman Chemical Co., Salt Lake City, Utah; aliphatic and cycloaliphatic amines including aminoethylpiperazine, 2-methylpiperazine, 4 '-diamino-3, 3' -dimethyldicyclohexylmethane, 1, 4-diaminocyclohexane, 1, 5-diamino-3-methylpentane, isophoronediamine, ethylenediamine, diethylenetriamine, triethylenetetramine, ethanolamine, lysine in any of its stereoisomeric forms and salt forms, hexamethylenediamine and hydrazinopiperazine; and arylaliphatic amines such as xylylenediamine and α, α, o ', α' -tetramethylxylylenediamine. Mono-and dialkanolamines useful as linking agents include: monoethanolamine, monopropanolamine, diethanolamine, dipropanolamine, and the like.

The fluorinated polymers of the present invention can be prepared in a suitable dry organic solvent which is free of groups reactive with isocyanate groups. Ketones are preferred solvents, and methyl isobutyl ketone (MIBK) is particularly preferred for convenience and availability. The reaction of the alcohol with the polyisocyanate is optionally carried out in the presence of a catalyst such as dibutyltin dilaurate or tetraisopropyl titanate, typically in an amount of about 0.01 to about 1.0 wt%. A preferred catalyst is tetraisopropyl titanate.

The resulting composition is then diluted with water or further dispersed or dissolved in a solvent selected from the group comprising: simple alcohols and ketones suitable for use as solvents for final application to a substrate (hereinafter "application solvent").

Alternatively, the solvent may be removed by evaporation and an aqueous dispersion formed with the surfactant via conventional methods is prepared using emulsification or homogenization methods known to those skilled in the art. Such solvent-free emulsions are preferred to minimize flammability and Volatile Organic Compound (VOC) related problems.

The final product applied to the substrate is a dispersion (if water based) or solution (if a solvent is used instead of water) of the fluorinated polymer.

It will be apparent to those skilled in the art that many modifications may also be made to any or all of the steps in the above-described processes to optimize the reaction conditions for maximum yield, productivity or product quality.

The present invention also includes a method of providing water repellency, oil repellency, stain release, hydrophilic stain release, and cleanability to a substrate comprising contacting a fluorinated polymer of the present invention as described above with the substrate. Suitable substrates include fibrous or hard surface substrates as defined below.

The present invention also includes a method of providing soil resistance comprising contacting the polymer of the present invention with a substrate in the form of a solution or dispersion, with the proviso that the at least one organic diisocyanate, polyisocyanate, or mixture thereof comprises one or more cyclic diisocyanates selected from the group consisting of 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, diphenylmethane-4, 4 '-diisocyanate, diphenylmethane-2, 4' -diisocyanate, 3-isocyanatomethyl-3, 4, 4-trimethylcyclohexyl isocyanate, bis (4-isocyanatocyclohexyl) methane, and diisocyanate trimers of formulae (IIa) and (IIb):

in this embodiment, a preferred process is one in which in the polymer of the invention said fluorinated compound of formula (I) has p and q equal to 1, R equal to 0, X equal to-O-and R respectively_fA method having 6 carbon atoms. From about 25% to about 100%, more preferably from about 50% to about 100%, and more preferably from about 75% to about 100%, by weight of the cyclic diisocyanate is used.

The polymers of the present invention are contacted with the substrate surface in the form of a solution or dispersion by any suitable method. Such methods are well known to those skilled in the art and include, for example, application by: exhaust, foam, elastic nip, pad, wet roll, roll forging, skein, capstan, liquid injection, overflow, roller, brush, roller, spray, dip, immersion, and the like. The contacting can also be carried out by using a conventional vat dyeing process, a continuous dyeing process or a spin line application process.

For application, the dispersion or solution is diluted until the percentage of all fluorine in the dispersion or solution is from about 0.001% to about 20%, preferably from about.01% to about 15%, and most preferably from about.1% to about 10% by weight, based on the weight of the dispersion or solution. The application rate of the solution or dispersion of the invention is from about 0.5 to about 1000g/m²Within the range of (1).

The compositions of the present invention are contacted with the substrate alone or in combination with other finishes or surface treatments. The compositions of the present invention optionally further comprise additional components such as treatments or finishes to achieve additional surface efficacy, or additives commonly used with such agents or finishes. Such additional components include compounds or compositions that provide surface effects such as no iron, ease of ironing, shrink control, wrinkle free, permanent set, moisture control, softness, strength, slip resistance, antistatic properties, snag resistance, pilling resistance, stain release, soil resistance, soil release, water repellency, oil repellency, odor control, antimicrobial properties, sun protection, and the like. One or more such treatments or finishes may be combined with the blended composition and applied to the fibrous substrate.

Particularly with respect to fibrous substrates, when treating textile fabrics such as synthetic or cotton fabrics, wetting agents such as ALKANOL 6112 from e.i. du Pont DE Nemours and Company (Wilmington, DE) may be used. When treating cotton or cotton blend fabrics, wrinkle resistant resins such as PERMAFRESH EFC from Omnova Solutions (Chester, SC) may be used.

Other additives commonly used with such treatments or finishes may also be present, such as surfactants, pH adjusters, cross linkers, wetting agents, wax fillers, and other additives known to those skilled in the art. Suitable surfactants include anionic surfactants, cationic surfactants and nonionic surfactants. Anionic surfactants are preferred, such as sodium lauryl sulfate available under the trade name DUPONOL WAQE from Witco Corporation (Greenwich, CT). Examples of such finishes or agents include processing aids, blowing agents, lubricants, soil repellents, and the like. The composition is applied within a manufacturing facility, at a retail point of sale, or prior to installation and use, or at a user location.

Optionally, blocked isocyanates to further enhance durability can be added to the fluorinated polymers of the present invention (i.e., as blended isocyanates). An example of a suitable blocked isocyanate is hydrophobarhyo XAN available from Ciba Specialty Chemicals (High Point, NJ). Other commercially available blocked isocyanates are also suitable for use herein. The desirability of adding the blocked isocyanate depends on the particular application of the treating agent. For most of the presently envisioned applications, their presence is not required to achieve satisfactory cross-linking between warp yarns or attachment to the substrate. When added as a blended isocyanate, the amount may be added in an amount up to about 20% by weight.

Optionally, non-fluorinated filler compositions may also be included in the compositions of the present application to obtain a combination of certain benefits. Examples of such optional additional filler polymer compositions are those disclosed in co-pending U.S. provisional application 60/607,612(CH-2996), filed on 7/9/2004, and U.S. Ser. No. 11/175680(CH-3048), filed on 6/7/2005.

The polymers of the present invention can be applied to a suitable substrate by a variety of conventional methods. For application to washably coated fabrics, the compounds of the invention can be applied, for example, from aqueous dispersions or organic solvent solutions by brushing, dipping, spraying, padding, roller coating, foaming, etc. They can be applied to dyed and undyed textile substrates. For textiles, the polymers are preferably applied in an amount of from about 5g/L to about 100g/L, more preferably from about 10g/L to about 50 g/L.

For carpet substrates, "wet pick-up" is the amount of the dispersion or solution of the present invention applied to a pre-moistened carpet based on the dry weight of the carpet. The low moisture absorption bath system may be interchanged with low moisture absorption spray or foam systems, while the high moisture absorption bath system may be interchanged with other high moisture absorption systems such as ballistic bite systems, foams, pads, or flood systems. The method used will determine the appropriate amount of wet pick-up and whether the application is to one side of the carpet (spray and foam application) or to both sides (bite and pad). Table 2 below provides typical process specifications for application on carpet substrates.

TABLE 2

Mode of application	Wet absorption Range (%)
		Bite with others	150-350
Overflow	100-500
		Foam	5-300
Pad	100-500

Spray mist

5-300

For carpets, the percentage of total fluorine in the dispersion or solution is preferably from about 0.01% to about 20%, more preferably from about 0.01% to about 5%, and more preferably from about 0.01% to about 2% by weight.

Many variations of spray, foam, bite, overflow and pad application conditions are known to those skilled in the art, and the foregoing conditions may be provided as examples and are not intended to be exclusive. The dispersions or solutions of the present invention are typically applied to pre-moistened carpets at a wet pick-up of from about 5% to about 500% and preferably cured at from about 200 ° F to about 260 ° F (104 ℃ to 127 ℃). Alternatively, the treated carpet may be air dried. To pre-wet the carpet, the carpet is soaked in water and excess water is sucked off. The "wet pick-up" is the weight of the dispersion or solution of the present invention applied to the carpet based on the dry weight of the carpet face fiber.

Typically, for fibrous substrates, the polymer is applied in an amount sufficient to provide at least 100 micrograms fluorine per gram to about 5000 micrograms fluorine per gram by weight based on the weight of the dry substrate. For the dried carpet, the treated carpet preferably contains from about 100 micrograms fluorine per gram to about 1000 micrograms fluorine per gram, based on the weight of the dried carpet.

Another embodiment of the invention is a method wherein the polymer of the invention is applied to a substrate as an additive in a coating. Suitable coating compositions, referred to herein as coated substrates, are typically liquid formulations, including alkyd coating compositions, type I urethane coating compositions, unsaturated polyester coating compositions, or water-dispersed coating compositions, and are applied to a substrate to produce a durable film on the surface of the substrate. These are conventional coatings, colorants and similar coating compositions. The polymers of the invention improve the cleanability of the dried coating.

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 fatty acid residues. Conventional alkyd coatings employ cured or dried alkyd resins as binders or film-forming components. Alkyd resin coatings comprise unsaturated fatty 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 the natural oxidation of unsaturated carbon-carbon bonds in the fatty acid component of the oil by atmospheric oxygen. When a liquid film, which is a formulated alkyd coating, is applied to a surface, the resulting cured film is relatively hard, non-melting, and substantially insoluble in many organic solvents used as solvents or diluents for unoxidized alkyd resins or drying oils. Such drying oils have been used as raw materials for oil-based coatings and are described in the literature.

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

As used hereinafter, the term "unsaturated polyester coating" refers to a conventional liquid coating based on an unsaturated polyester resin, which is soluble in the monomers and may contain initiators and catalysts as needed, typically as a coating, clear coat or gel coat formulation. Unsaturated polyester resins comprise as unsaturated prepolymer a product obtained from the polycondensation reaction of a diol such as 1, 2-propanediol or 1, 3-butanediol with an unsaturated acid such as maleic acid (or maleic acid and a saturated acid such as phthalic acid) in the form of an anhydride. The unsaturated prepolymer is a linear polymer containing unsaturation in the chain. This can be dissolved in a suitable monomer, such as styrene, to obtain the final resin. The films may be formed from the copolymerization of linear polymers and monomers via a free radical mechanism. The free radicals may be generated by heating, or more commonly by adding a peroxide such as benzoyl peroxide, which is packaged separately and added prior to use. Such coating compositions are often referred to as "gel coat" finishes. In order that curing can occur at room temperature, decomposition of the peroxide to free radicals can be catalyzed by certain metal ions (typically cobalt). Solutions of the peroxide and cobalt compound were added separately to the mixture and stirred well before application. Unsaturated polyester resins that cure via a free radical mechanism are also suitable for radiation curing using, for example, ultraviolet light. This form of curing, in which no heat is generated, is particularly suitable for film formation 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 water-dispersed coating consisting of water as the primary dispersed component, such as an emulsion, latex, or suspension of a film-forming material dispersed in an aqueous phase. "Water-dispersible coatings" are a general class that describes a wide variety of formulations and includes members of the above categories as well as members of other categories. Water-dispersed coatings generally comprise other common coating ingredients. Water-dispersed coatings may be exemplified by, but are not limited to, colored coatings such as latex paints, colorless coatings such as wood pore fillers, colorants and finishes, tile and cement coatings, 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 coatings, the film-forming material is a latex polymer of acrylate-acrylic, vinyl acrylate, or mixtures thereof. Such water-dispersed coating compositions are described in "Emulsion and water-solvent Paints and Coatings" (Reinhold publishing corporation, New York, NY, 1965, by C.R.

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. Such final films may be obtained by curing, bonding, polymerization, infiltration, radiation curing, ultraviolet curing, or evaporation, as non-limiting examples. The final film can also be applied in the final dry state as a dry coating.

When used as an additive, the compositions of the present invention can be effectively added to a coated substrate or other composition by thoroughly stirring at room or ambient temperature. More complex mixing methods may be used, such as using mechanical shakers, or heating or other methods. Such methods are not necessary and do not significantly improve the final composition. When used as a coating additive, the compositions of the present invention are typically added to the wet coating or paint in an amount 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 0.1 wt.% to about 0.5 wt.% is employed. Coating compositions comprising the additives of the present invention can be applied to a variety of fibers or rigid substrates.

The invention also includes substrates treated with the compositions of the invention. Suitable substrates include fibrous substrates and rigid substrates. The fibrous substrates include woven and non-woven fibers, yarns, fabrics, fabric blends, paper, leather, and carpet. These may be made from natural or synthetic fibers including cotton, cellulose, wool, silk, polyamide, polyester, polyolefin, polyacrylonitrile, polypropylene, rayon, nylon, aramid, and acetate. By "fabric blend" is meant a fabric made from two or more types of fibers. Typically, these blends are a combination of at least one natural fiber and at least one synthetic fiber, but may also include blends of two or more natural fibers, or blends of two or more synthetic fibers. The carpet substrate may be dyed, pigmented, printed or undyed. The carpet substrate may be degummed or unglued. Substrates to which the polymers of the present invention may be particularly advantageously applied to impart soil resistant properties include those made from polyamide fibers (such as nylon), cotton, and polyester and cotton blends, particularly such substrates used in tablecloths, clothing, washable uniforms, and the like.

Hard surface substrates include porous and non-porous mineral surfaces such as glass, stone, tiles, concrete, unglazed bricks, porous clays, and various other substrates having surface porosity. Specific examples of such substrates include unglazed concrete, bricks, tiles, stone (including granite and limestone), grout, mortar, marble, limestone, statues, monuments, wood, composite materials such as terrazzo, and wall and ceiling panels including those machined with gypsum board. Such substrates have enhanced cleanability when coated with a coating composition comprising the composition of the present invention.

The compositions of the present invention are useful for providing one or more of excellent water repellency, oil repellency, soil resistance, stain release, hydrophilic stain release, and cleanability to treated substrates. These properties can be achieved by using lower fluorine concentrations than conventional perfluorocarbon surface treatments, providing improved "fluorine efficiency" in protecting the treated surface.

The compositions of the present invention also allow for the use of fluoroalkyl short chains containing 6 or less carbon atoms, whereas if the fluoroalkyl contains less than 8 carbon atoms, commercially available conventional surface treatment products typically exhibit poor oil and water repellency.

The following examples are intended only to illustrate the invention and should not be construed as limiting the invention in any way.

Materials and test methods

The following materials and test methods may be used in the examples herein.

Material

Household carpet

Carpet used in the tests of examples 2 to 6 consisted of a household loop floorBlanket construction composition (30oz/sqyd) (1112.4 g/m)²) Having nylon-6, 6 surface fibers that have been dyed beige and have been subjected to a stain resistance treatment of 1.2% SR-500 (100% solids basis). Carpet is available from Invista, inc., Wilmington, DE. SR-500 is available from E.I. duPont DE Nemours and Company, Wilmington, DE.

The carpet was subjected to a water pre-spray treatment at 25% wet pick-up. The dispersed fluoropolymer of examples 2 to 6 was then spray applied at 25% wet pick-up to treat the carpet. The dispersion was diluted with water to the dilution required to obtain a fluorine content of 400ppm fluorine, which could be delivered to carpet by using 25% wet pick-up. The wet pick-up is the weight of the polymer dispersion or solution of the present invention applied to the carpet based on the dry weight of the carpet face fiber. The treated carpet was then dried until the carpet fiber surface temperature reached 250 ° F (121 ℃). The amount of composition applied is that amount which provides the fluorine levels as listed in tables 6 and 7.

Commercial carpet

The carpets tested for examples 1 and 3 to 6 were constructed from commercial loop carpet construction (28oz/sqyd) (1038.2 g/m)²) Composition having nylon-6, 6 surface fibers that have been dyed yellow. Carpet was obtained from Invista, Inc (Wilmington, DE). SR-500 was obtained from E.I. DuPontde Nemours and Company (Wilmington, DE).

The carpet was subjected to a water pre-spray treatment at 25% wet pick-up. The dispersed fluoropolymer of examples 1 and 3 to 6 was then spray applied at 25% wet pick-up to treat the carpet. The dispersion was diluted with water to the dilution required to obtain a fluorine content of 600ppm fluorine, which could be delivered to carpet by using 25% wet pick-up. The wet pick-up is the weight of the polymer dispersion or solution of the present invention applied to the carpet based on the dry weight of the carpet face fiber. The treated carpet was then dried until the carpet fiber surface temperature reached 250 ° F (121 ℃). The amount of composition applied is that amount which provides the fluorine levels as listed in tables 6 and 7.

Test method 1: water repellency

The water repellency of the treated substrates was determined according to AATCC Standard test Method No.193-2004 and the DuPont Technical Laboratory Method (DuPont Technical Laboratory Method) as described in the TEFLON Global Specifications and Quality Control Tests (Global Specifications and Quality Control Tests) package. The test determines the resistance of the treated substrate to wetting by aqueous liquids. Droplets of hydroalcoholic mixtures of different surface tensions were placed on the substrate and the degree of surface wetting was determined visually. The higher the water repellency rating, the better the repellency of the final substrate to staining by water-based materials.

The water repellency test liquids are shown in table 3.

TABLE 3

Water repellency test liquid

The testing steps are as follows: three drops of test liquid 1 were placed on the treated substrate. After 10 seconds, the droplets were removed by vacuum aspiration. If no liquid penetration or partial absorption (deeper wet spots on the substrate) is observed, the test is repeated with test liquid 2. The test was repeated with test liquid 3 and progressively higher test liquid numbers were used until liquid penetration (deeper wet spots on the substrate) was observed. The test result is the highest number of test liquids that do not penetrate into the substrate. Higher values indicate greater water repellency.

The test method 2: oil repellency

The treated samples were tested for oil repellency using a variation of AATCC standard test method 118 as follows. The substrates treated with the aforementioned aqueous polymer dispersions were conditioned at 23 ℃ and 20% relative humidity and at 65 ℃ and 10% relative humidity for at least 2 hours. Then, a series of organic liquids shown in table 4 were applied dropwise to the sample. First, a minimum number of test liquids (oil repellency grade number 1) was dropped one drop (approximately 5mm in diameter or 0.05mL in volume) at three locations spaced at least 5mm apart. The droplets were observed for 30 seconds. If at the end of this period, two of the three drops of liquid are still spherical with no wicking around the drop, the next highest numbered three drops of liquid are placed in close proximity, again for 30 seconds. This process is continued until one test liquid appears that two of the three drops fail to remain spherical to hemispherical, or wetting or wicking occurs.

The oil repellency rating is the highest numbered test liquid for which two of the three drops of test liquid still remained spherical to hemispherical with no wicking for 30 seconds. In general, treated samples with a rating of 5 or higher are considered to be excellent; samples with a rating of 1 or higher may be used in some applications.

TABLE 4

Oil repellency test liquid

Oil repellency rating number	Test solution
		1	NUJOL purified mineral oil
2	65/35 NUJOL/n-hexadecane by volume at 21 DEG C
		3	N-hexadecane
4	N-tetradecane
		5	N-dodecane
6	N-decane
		7	N-octane
8	N-heptane

Note: NUJOL is a trademark of Plough, inc. mineral oil having a saybolt viscosity of 360/390 at 38 ℃ and a specific gravity of 0.880/0.900 at 15 ℃.

Test method 3: accelerated dirty roller test

A drum mill (on a roller) is used to shake the synthetic soil onto the carpet sample. The synthetic fouls were prepared as described in AATCC test method 123-. Soil-coated beads were prepared as follows. Synthetic soil (3g) and 1 liter of clean nylon resin beads (SURLYN ionomer resin beads, 1/8 to 3/16 inches (0.32 to 0.48cm) in diameter) were placed into a clean empty tank. SURLYN is an ethylene/methacrylic acid copolymer available from e.i. du Pont DE Nemoursand co., Wilmington, DE. The can lid was closed and sealed with duct tape and the can was rotated on a roller for 5 minutes. Removing the soil-coated beads from the jar.

Carpet samples inserted into the drum were prepared as follows. The total size of the carpet samples used for these tests was 8X 25 inches (20.3X 63.5 cm). One test sample and one control sample are measured simultaneously. The carpet pile of all samples was laid in the same direction. The shorter side (with pile courses) of each carpet sample was cut longitudinally. A strong adhesive tape is placed on the back of the carpet tile to secure them together. The carpet samples were placed in a clean, empty drum mill with the pile facing toward the center of the drum. The carpet is secured in the drum mill with rigid wires. Soil coated resin beads (250cc) and 250cc ball bearings (diameter 5/16 inches, 0.79cm) were placed into a drum mill. The drum mill lid was closed and sealed with duct tape. The roller was rotated on a roller at 105rpm for 21/2 minutes. The roll is stopped and the direction of the drum mill is reversed. The roller was rotated on the roller at 105rpm for an additional 21/2 minutes. The carpet samples were removed and the excess soil was removed uniformly with vacuum. The soil-coated beads were discarded.

The delta E color difference of the soiled carpet was measured for the test and control compared to the original unsoiled carpet. After the accelerated soiling test, color measurements were performed on each carpet. For each control and test sample, the color of the carpet was determined, the carpet was soiled, and the color of the soiled carpet was determined. Δ E is the color difference between soiled and unsoiled carpets, expressed as a positive number. The color difference was measured for each item using a Minolta colorimeter CR-310. Color readings were taken on five different areas of the carpet sample and the average Δ Ε was recorded. The control carpet for each test article had the same color and construction as the test article. The control carpet was not treated with any fluorochemical. Lower Δ E indicates lower staining and excellent soil resistance.

Test method 4: wicking test

For the wicking test, 5 drops of DI water were placed on cotton samples on different areas of the material. The time (in seconds) it took to fully absorb into the cotton was recorded. 180 seconds (3 minutes) is the point where the water drop is not absorbed and the test is rated as failing. Wicking is an indication of hydrophilicity, and the test results are referred to herein as wicking or hydrophilic stain removal.

Test method 5: detergency property

The stain release test was performed according to AATCC test method 130-. Five drops of mineral or corn oil were placed in the center of the treated cotton sample on a piece of blotter paper. A piece of cellophane (weighing paper) was placed over the spot and a five pound weight was placed over the paper. After 60 seconds, the weight and cellophane were removed. Four red dots are marked along the oil spot. The cotton material was placed in a Kenmore brand washing machine with the following settings: heavy duty, warm (100F)/cold, one rinse, ultra clean (setting 12) and normal speed (fast/slow). 100g of AATCC WOB detergent and 41b material including ballast were then added to the washing machine. After washing, the samples were placed in a Kenmore brand dryer and dried for 45 minutes at a high temperature setting. From the decontaminated replica, the sample was assessed.

TABLE 5

Stain removal rating

Grade 5	The stain was equivalent to standard stain 5
		Class 4	Equivalent stainOn standard stains 4
Class 3	The stain was equivalent to standard stain 3
		Class 2	The stain is equivalent to standard stain 2
Class 1	The stain was equivalent to standard stain 1

Grade 5 represents the best stain removal, while grade 1 is the worst stain removal.

Test method 6: durability in washing

The fabric samples were washed according to the international standard washing procedure used for textile testing. The fabric samples were loaded into a horizontal drum front loading type (type a, wascatofom 71MP-Lab) automatic washing machine with ballast to provide a total of 41b dry load. Commercial detergent was added (AATCC 1993 standard refer to detergent WOB) and the washing machine was programmed to: high water level, using warm water (105 ° F, 41 ℃), normal wash cycle 15 minutes, then rinse twice, each for 13 minutes, followed by spin drying for 2 minutes. The samples and ballast were washed a specified number of times (5HW washes 5 times, 20HW washes 20 times, etc.). After washing, the samples were placed in a Kenmore dryer and dried for 45 minutes at a high temperature setting. The samples were again tested for stain release using test methods 4 and 5. Hydrophilic stain removal (wicking) tests were performed on a 100% Avondale Cotton on the same weight loading basis (bath concentration 30 g/L).

Test method 7: leneta oil cleanability test

The test methods described herein are variations of ASTM 3450-00-Standard test method for washability of interior architectural coatings, which is expressly incorporated herein by reference.

The coatings were prepared by applying a coating of The coating composition on a Leneta Black MYLAR card (The Leneta Company, Mahwah, NJ) using a BYK-Gardner Autofilm coater (BYK-Gardner, Silver Spring, MD) and a 5 mil (0.127mm) Bird coating blade application apparatus (BYK-Gardner, Silver Spring, MD). The coating speed is set to be slow enough to prevent pinholes or voids in the resulting coating. Several coatings were prepared for each coating and additive combination. The coated cards were dried for several days to determine cleanability.

Soiled media was prepared using VASELINE NURSERY JELLY (Marietta Corporation, Cortland, NY) and a dispersion of Leneta carbon black in mineral oil (ST-1) (The Leneta Company, Mahwah, NJ). The petroleum gel in a clean glass container was melted for 30 minutes in an oven set at 70 ℃. The petroleum gel was then mixed with 5% by weight of Leneta carbon black. For example, 95g of petroleum jelly was mixed with 5g of Leneta carbon black to prepare 100g of the staining medium. The mixed staining medium was allowed to cool for several hours in a refrigerator set at 4 ℃.

Cleaning media were prepared using JOY ULTRA CONCENTRATED COUNTRY LEMON dish washing liquid (the Procter & Gamble Company, Cincinnati, OH). The dishwashing liquid was mixed with deionized water at a rate of 1g dishwashing liquid per 99g water.

Each coating was stained in the same manner. A staining panel was prepared from MYLAR Leneta card by cutting a 3 "by 1" (7.6cm by 2.5cm) strip from the interior of the card. The template is placed on the coated card to be stained. The soiled medium was spread over the coated card and the template using a spatula so that none of the coated card was visible. Excess stain was removed with a spatula. The stained card was allowed to stand and dry for 60 minutes.

In preparation for cleaning, MYLAR chips were used to gently scrape excess dry stain from the stained portion of the card (washed and unwashed portions). Similarly, unsolidified stains were removed from the entire card (washed and unwashed portions) using c-folded cleaning wipes. The cards were then secured to a BYK-Gardner abrasion tester (BYK-Gardner, Silver Spring, MD) or other method. A piece of cheesecloth (VWR International, San Diego, Calif.) was placed on the cleaning wipe of the abrasion tester. The cheesecloth was folded and placed so that the contact surface was 8 layers thick. 10mL of the cleaning solution prepared as described above was applied to the contact surface of the cheesecloth. The abrasion tester was run for 5 cycles (10 rubs) over the stained area of the drawdown card, which area is hereinafter referred to as the stained and cleaned area. Excess cleaning solution was washed away with deionized water within a few seconds and then allowed to dry for 2 hours, or until completely dry by visual inspection. One area of each stained coated card is cleaned in this manner.

Cleanability can be determined by evaluating the soiled, washed coated portion of the coated card in comparison to the unsoiled coated portion of the card and the soiled unwashed coated portion of the card. Three different measurements were made for each designated coated portion of the coated card using a Hunter Laboratory Pro colorimeter (Hunter Associates Laboratory, inc., Reston, VA): a soiled washed portion, an unsoiled portion and a soiled unwashed portion. The measurements were averaged to obtain an average value for the portion, which was used to evaluate the cleanability rating of the card as described below. The colorimeter is set up to read L^*And the aperture is no greater than 3/4 inches (1.9 cm).

The cleanability score was calculated in the range of 0 to 10, where 0 is not cleanable and 10 is completely cleanable. The values 1 to 9 are determined numerically in order with linear slopes equidistant from 0, 10 and from each other. The above description conforms to the following formula: [ (average L of the stained laundry coating area)^*Value) - (average L of stained unwashed coating area^*Value)]/[ (mean L of the unstained coating areas)^*Value) - (average L of stained unwashed coating area^*Value)]Cleanability rating of 10 ═。

Examples

Example 1

Under nitrogen atmosphere, C is₃F₇OCF₂CF₂I (100g, 0.24mol) and benzoyl peroxide (3g) were charged to a pressure vessel. A series of three vacuum/nitrogen sequences was carried out at-50 ℃ and ethylene (18g, 0.64mol) was added. The vessel was heated at 110 ℃ for 24 hours. The autoclave was cooled to 0 ℃ and opened after venting. The product was then collected in a bottle. The product was distilled to give 80g C in 80% yield₃F₇OCF₂CF₂CH₂CH₂I. The boiling point of the water is 56-60 ℃ under 25mm Hg (3333 Pa).

C is to be₃F₇OCF₂CF₂CH₂CH₂A mixture of I (300g, 0.68mol) and N-methylformamide (300mL) was heated at 150 ℃ 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. The ethyl formate and ethanol are then distilled off to give the crude product. The crude product was dissolved in ether, washed with aqueous sodium sulfite solution, water and brine in this order, and then dried over magnesium sulfate. The product was then distilled to yield 199gC in 85% yield₃F₇OCF₂CF₂CH₂CH₂And (5) OH. A boiling point of 71 to 73 ℃ at 40mm Hg (5333 Pa).

To a 250mL 3-necked round bottom flask equipped with a reflux condenser with nitrogen inlet, magnetic stirrer, and temperature probe, was added C dried over sodium sulfate₃F₇OCF₂CF₂CH₂CH₂OH alcohol (20.30g, 61.50mmol), and DESMODUR N100 (63% solution in methyl isobutyl ketone (MIBK), 23.43g, 78.11mmol NCO). The mixture was heated to 55 ℃. To the aboveDibutyltin dilaurate (2.0g of a 0.4 wt% solution of catalyst MIBK) was added dropwise to the solution to form an exotherm of 30 ℃. The reaction was held at 84 ℃ for 2 hours. MIBK (28.75g) and water (0.23g) were added dropwise to the reaction, followed by heating at 84 ℃ for 24 hours until isocyanate was no longer detected using an isocyanate test strip from Colormetric technologies, Inc. The hot product (20.0g) was added to a hot surfactant solution (70 ℃, 20g deionized water and 1.63g WitcoC6094 surfactant). The solution was homogenized using a digital sonicator for 5 minutes and MIBK was removed via vacuum distillation to give a stable dispersion of urethane polymer (15.5% solids, 6.11% F).

The dispersion was applied to a carpet as described in "materials" above. The water repellency of the carpet was determined via test method 1 and the oil repellency was determined via test method 2. The results are shown in Table 6.

Example 2

Samples were prepared using the method described in example 1, except that the hot product (20.0g) was added to a hot surfactant solution (70 ℃, 20g deionized water, 0.32g MERPOL SE, and 1.46g ARQUAD 16-50 surfactant). The solution was homogenized using a digital sonicator for 5 minutes and MIBK was removed via vacuum distillation to give a stable dispersion of urethane polymer (15.5% solids, 5.51% F).

Example 3

To a 250mL 3-necked round bottom flask equipped with a reflux condenser with nitrogen inlet, a magnetic stirrer, and a temperature probe, was added C prepared according to example 1 and dried over sodium sulfate₃F₇OCF₂CF₂CH₂CH₂OH alcohol (24.65g, 74.67 mmol)) And a solution of DESMODUR N3300(17.98g, 93.34mmol (NCO)) in 11g of MIBK. The mixture was heated to 65 ℃. To the solution, dibutyltin dilaurate (2.4g of a 0.4 wt% solution of catalyst MIBK) was added dropwise, resulting in an exotherm of 30 ℃. The reaction was held at 84 ℃ for 3 hours. MIBK (34.40g) and water (0.27g) were added dropwise to the reaction, followed by heating at 84 ℃ for 24 hours. Water 0.27g was added again and the reaction was heated until isocyanate was no longer detected. The hot product (40.0g) was added to a hot surfactant solution (70 ℃, 65g deionized water and 3.09g WitcoC6094 surfactant). The solution was homogenized using a digital sonicator for 5 minutes and MIBK was removed via vacuum distillation to give a stable dispersion (24% solids, 8.9% F).

The dispersion was applied to a carpet as described in "materials" above. The water and oil repellency of the carpet was determined via test methods 1 and 2, respectively. The data obtained are shown in Table 6.

Example 4

A sample was prepared using the method described in example 3, except that the hot product (12.5.0g) was added to a hot surfactant solution (70 ℃, 12.5g deionized water, 0.70g SADPO, and 0.05g TERGITOL surfactant). The solution was homogenized using a digital sonicator for 5 minutes and MIBK was removed via vacuum distillation to give a stable dispersion (24% solids, 8.9% F).

Example 5

To a 500mL 4-necked round bottom flask equipped with a reflux condenser with nitrogen inlet, overhead stirrer, and temperature probe was added sodium sulfate-dried C prepared according to example 1₃F₇OCF₂CF₂CH₂CH₂OH alcohol (19.00g, 57.58mmol), butyl acetate (3g), and DESMODUR Z4470 (70% solution in butyl acetate, 27.10g, 76.77mmol NCO). The mixture was heated to 65 ℃. To the solution, dibutyltin dilaurate (1.4g of a 0.4 wt% solution of catalyst MIBK) was added dropwise, resulting in an exotherm of 17 ℃. The reaction was held at 84 ℃ for 4 hours. Butyl acetate (32g) and water (0.35g) were added dropwise to the reaction, followed by heating at 84 ℃ for 8 hours. Butyl acetate (20g) and water (0.35g) were added and heating was continued for 5 hours until isocyanate was no longer detected. The hot product (15.0g) was added to a hot surfactant solution (70 ℃, 28g deionized water, 0.24g Merpol SE and 1.107g Arquad 16-50 surfactant). The solution was homogenized using a digital sonicator for 5 minutes and the butyl acetate was removed via vacuum distillation to obtain a stable dispersion of urethane polymer (20.0% solids, 4.6% F).

The dispersion was applied to a carpet as described in "materials" above. The water repellency of the carpet was determined via test method 1 and the oil repellency was determined via test method 2. Carpet soiling performance was assessed according to test method 3-accelerated soiling test, and was assessed according to color measurements in soiling performance. The results are shown in tables 6 and 7.

Example 6

Samples were prepared using the method described in example 5, except that the hot product (15.0g) was added to a hot surfactant solution (70 ℃, 28g deionized water, 0.07g BRIG 58, and 0.30g ARQUAD 2HT-75 surfactant). The solution was homogenized using a digital sonicator for 5 minutes and the butyl acetate was removed via vacuum distillation to obtain a stable dispersion (20.0% solids, 5.0% F).

TABLE 6: repellency of carpet

The data in table 6 shows that oil and water repellency can be achieved using a variety of commercial isocyanate reactants and surfactants.

TABLE 7

Scale resistance

Examples	Carpet type	Final F, ppm	ΔE
				Untreated	Household appliance	0	21.54
5	Household appliance	400	16.87
				6	Household appliance	400	16.81
Untreated	For commercial use	0	34.88
				5	For commercial use	600	27.18
6	For commercial use	600	28.75

The data in table 7 shows that examples 5 and 6 have effective stain resistance for both commercial and household carpets.

Example 7

To a flask, under nitrogen, DESMODUR N100 (63% MIBK solution, 22.1g, 0.0736mol NCO), poly (methoxy) glycol (MPEG 750, molecular weight about 750, 11.95g, 0.0147mol), and C prepared according to example 1 were added₃F₇OCF₂CF₂CH₂CH₂OH (10g, 0.03 mol). The reaction mixture was heated to 65 ℃ and then a solution of 5 wt% titanium (IV) isopropoxide in methyl isobutyl ketone (MIBK) (1.2g) was added. After 3 hours of reaction at 95 deg.C, MIBK (13.6mL) and water (4.6mL) were added at 85 deg.C. After addition of water, the temperature was reduced to 75 ℃ and allowed to stir overnight. More water (80)46mL) was added to the reaction and stirred for 0.5 h. After evaporation of MIBK under reduced pressure, the resulting polymer (26.04% solids) was obtained.

Fabric samples (100% Avondale cotton) were treated with a water-based fluorinated polymer formulation using a conventional filler bath (immersion) method. A bath containing 30 to 50g/L of the fluorinated polymer treatment agent is used. After application, the fabric samples were cured at about 165 ℃ for 2 minutes and allowed to "rest" after treatment and curing. The samples were tested for wicking, stain release, and wash durability using test methods 4, 5, and 6, respectively. The results are shown in Table 8.

Example 8

Under nitrogen atmosphere, C is₂F₅OCF₂CF₂I (116g, 0.32mol) and benzoyl peroxide (4g) were added to the vessel. A series of three vacuum/nitrogen sequences was carried out at-50 ℃ and ethylene (24g, 0.86mol) was added. The vessel was heated at 110 ℃ for 24 hours. The autoclave was cooled to 0 ℃ and opened after venting. The product was collected in a bottle. The products of the six reactions were combined and the product was distilled to yield C₂F₅OCF₂CF₂CH₂CH₂I (470g, 64% yield, bp 135-137 ℃ under 760mm Hg (1013X 102 Pa)).

130g C was added to the flask₂F₅OCF₂CF₂CH₂CH₂I. 643mL of N-methylpyrrolidone and 48mL of deionized water. The mixture was heated at 132 ℃ for 20 hours. Deionized water was added and the lower layer was separated. The lower layer was dissolved in ether, washed with saturated sodium sulfite solution, and dried over anhydrous sodium sulfate. After rotary evaporation, 48g C was obtained in 52% yield₂F₅OCF₂CF₂CH₂CH₂OH, bp under 60mmHg (7999Pa) is 70-72 ℃.

To a flask, DESMODUR N-100 (63% MIBK solution, 21.02g, 0.07mol NCO), poly (methoxy) ethylene glycol (MPEG) was added under nitrogen atmosphere750, 10.5g, 0.014mol) and C₂F₅OCF₂CF₂CH₂CH₂OH (8.0g, 0.028 mol). The mixture was heated to 65 ℃ and then a 5% solution of titanium (IV) isopropoxide in MIBK (1.15g) was added. After 3 hours of reaction at 95 deg.C, MIBK (13mL) and water (4.16mL) were added at 85 deg.C. After addition of water, the temperature was reduced to 75 ℃ and the liquid was stirred overnight. More water (76.71mL) was added to the reaction and stirred for 0.5 h. After evaporation of MIBK under reduced pressure, the resulting polymer (29.05% solids) was obtained.

Example 9

Reacting CF under nitrogen₃OCF₂CF₂I (285g, 0.91mol) and benzoyl peroxide (12g) were added to the vessel. A series of three vacuum/nitrogen sequences was carried out at-50 ℃ followed by the addition of ethylene (69g, 2.46 mol). The vessel was heated at 110 ℃ for 24 hours. The autoclave was cooled to 0 ℃ and opened after venting. The product was then collected in a bottle. The products of the two reactions were combined and the product was distilled to give 292g CF in 50% yield₃OCF₂CF₂CH₂CH₂I. The product was at 60mm Hg pressure [7999Pa ]]The boiling point of the catalyst is 56-60 ℃.

CF is prepared by₃OCF₂CF₂CH₂CH₂A mixture of I (92g, 0.27mol) and N-methylformamide (119mL) was heated at 150 ℃ for 26 h. The reaction was then cooled to 100 ℃ and water was then added to isolate the crude ester. Ethanol (30mL) and p-toluenesulfonic acid (1.03g) were added to the crude ester, and the reaction was stirred at 70 ℃ for 15 minutes. The ethyl formate and ethanol are then distilled off to give the crude product. The crude product was dissolved in ether, washed with aqueous sodium sulfite solution, water and brine in this order, and then dried over magnesium sulfate. Then the product CF₃OCF₂CF₂CH₂CH₂OH was distilled to yield 44g of product in 71% yield.

The flask was charged with DESMODUR N-100 (63% MIBK solution, 19.11g, 0.0647mol NCO), poly (methoxy) glycol (MPEG 750, 9.59g, 0.013mol), and CF under nitrogen₃OCF₂CF₂CH₂CH₂OH (6g, 0.026 mol). The reaction mixture was heated to 65 ℃ and then a 5% solution of titanium (IV) isopropoxide in MIBK (1.04g) was added. After 3 hours of reaction at 95 deg.C, MIBK (11.82mL) and water (3.78mL) were added at 85 deg.C. After addition of water, the temperature was reduced to 75 ℃ and the liquid was stirred overnight. More water (69.73mL) was added to the reaction and stirred for 0.5 h. After evaporation of MIBK under reduced pressure, the resulting polymer (27.05% solids) was obtained.

Comparative example A

The procedure as in example 7 was followed, but using the formula F (CF)₂)_aCH₂CH₂Perfluoroalkyl ethyl alcohol mixtures of OH where a ranges from 6 to 14, and is predominantly 6, 8, and 10, as the fluorochemical. A typical mixture is as follows: a is 6, 27% to 37%; a is 8, 28% to 32%; a is 10, 14% to 20%; a is 12, 8% to 13%; and a is 14, 3% to 6%.

TABLE 8

	Comparative example A	Example 7	Example 8	Example 9
					Fluorine%	0.3	0.19	0.18	0.14
Wicking property (Horz/sec)
					Initially, the process is started	＞180	7	10	6
5HW	23	3	2	1
					Detergency-initial
Mineral oil	4	4	3+	4
					Corn oil	4	4	3+	3
Detergency-5 HW
					Mineral oil	4	4	3	3
Corn oil	4	3+	3+	3

The data in table 8 show that the compositions of the present invention (examples 7 to 9) generally have excellent stain release properties compared to the control (comparative example a). They impart better hydrophilicity than controls rated for greater than 180 seconds using the same mixture, with initial wicking times rated from 1 to 10 seconds. Thus, the polymer of the present invention is a better hydrophilic stain removal product than comparative example a.

Example 10

To a flask, under nitrogen, DESMODUR N-100D (63% MIBK solution, 8.79g, 0.03mol NCO), poly (methoxy ethylene glycol) (MPEG 350, molecular weight about 350) (4.4g, 0.0125mol), and C prepared according to example 1 were added₃F₇OCF₂CF₂CH₂CH₂OH (4.13g, 0.0125 mol). The reaction mixture was heated to 55 deg.C, then 0.4% dibutyltin dilaurate in methyl isobutyl ketone (MIBK) was added (0.35 g). After 16 hours of reaction at 90 ℃, water (0.225g) was added at 60 ℃ and the reaction was stirred for 3 hours. MIBK (4mL) and water (31.5mL) were added, and the reaction was stirred for 1 hour. After evaporation of MIBK under reduced pressure, the resulting product was poured into a bottle for coating testing.

The product was added to the acrylic latex paint in the amounts shown in table 9 based on dry weight of the polymer. The cleanability of the samples was determined using test method 7. The results are shown in Table 9.

Example 11

A flask was charged with DESMODUR N-100 (63% MIBK solution, 8.79g, 0.03mol NCO), poly (methoxy) glycol (MPEG 350, molecular weight about 350) (4.4g, 0.0125mol), and C prepared according to example 8 under nitrogen atmosphere₂F₅OCF₂CF₂CH₂CH₂OH (3.5g, 0.0125 mol). The reaction mixture was heated to 55 deg.C, then 0.4% dibutyltin dilaurate in methyl isobutyl ketone (MIBK) was added (0.35 g). After 16 hours of reaction at 90 ℃, water (0.225g) was added at 60 ℃ and the reaction was stirred for 3 hours. MIBK (4mL) and water (31.5mL) were added, and the reaction was stirred for 1 hour. After evaporation of MIBK under reduced pressure, the material was poured into a bottle for coating testing.

Example 12

A flask was charged with DESMODUR N-100 (63% MIBK solution, 8.79g, 0.03mol NCO), poly (methoxy) glycol (MPEG 350, molecular weight about 350) (4.4g, 0.0125mol), and CF prepared according to example 9 under nitrogen atmosphere₃OCF₂CF₂CH₂CH₂OH (2.9g, 0.0125 mol). The reaction mixture was heated to 55 deg.C, then 0.4% dibutyltin dilaurate in methyl isobutyl ketone (MIBK) was added (0.35 g). After 16 hours of reaction at 90 ℃, water (0.225g) was added at 60 ℃ and the reaction was stirred for 3 hours. MIBK (4mL) and water (31.5mL) were added, and the reaction was stirred for 1 hour. After evaporation of MIBK under reduced pressure, the material was poured into a bottle for coating testing.

The product was added to an acrylic matte latex paint having a gloss of 3% at 85 degrees in the amounts shown in table 9 based on the dry weight of the polymer. The examples were added to the primer in amounts to achieve a fluorine content of 675 micrograms per gram F by weight of wet coating. The cleanability of the samples was determined using test method 7. The results are shown in Table 9.

TABLE 9: cleanability of

Examples	By weight%	Cleanability grade
			Control substance^a		3.8
10	2.34	5.3
			11	1.69	6.1
12	2.27	5.2

Examples 10, 11 and 12 have the same fluorine content.

^aWithout fluorinated groupsLatex coating of compound additives

The data in table 9 show that examples 10 to 12 have improved cleanability compared to the control. The control consisted of the same acrylic coating, but no composition of the present invention was added.

Example 13

To a 3-neck round-bottom flask equipped with a reflux condenser with nitrogen inlet, magnetic stirrer and temperature probe, was added compound C₃F₇OCF₂CF₂CH₂CH₂OH (10.10g, 30.6mmol, predried over sodium sulfate) and DESMODUR W (63% solution in MIBK, 5.54g, 41.9mmol NCO). The mixture was heated to 55 deg.C and then dibutyltin dilaurate (1.07g of a 0.4 wt% MIBK solution) was added dropwise, resulting in an exotherm. The reaction was held at 84 ℃ for 2 hours, then MIBK (15.42g) and water (0.10g) were added dropwise and heating was continued at 84 ℃ overnight. A second portion of water (0.10g) was added and the reaction stirred until isocyanate was no longer detected using an isocyanate test strip. The hot product (5g) was added to a hot surfactant solution (70 ℃, 5g deionized water, 0.41g Witco C6094 surfactant). The solution was homogenized using a digital sonicator for 5 minutes and MIBK was removed via vacuum distillation to give an aqueous dispersion of urethane polymer (13) for carpet application (12% solids, 3.47% F).

The dispersion was applied to a carpet as described in "materials" above. The water repellency of the carpet was determined via test method 1 and the oil repellency was determined via test method 2. Carpet soiling performance was assessed according to test method 3-accelerated soiling test, and was assessed according to color measurements in soiling performance. The results are shown in tables 10 and 11.

Example 14

Another sample was prepared using the method described in example 13, except that the hot product (5g) was added to a hot surfactant solution (70 ℃, 5g deionized water, 0.08g MERPOL SE surfactant (available from E.I. DuPont DE Nemours, Wilmington, DE) and 0.37g ARQUAD 16-50 surfactant (Akzo Nobel, Chicago)). The solution was homogenized using a digital sonicator for 5 minutes and MIBK was removed via vacuum distillation to give an aqueous dispersion of urethane polymer (14) for carpet application (12% solids, 4.5% F).

Table 10: commercial carpet

Examples	Final ppm F	Water repellency	Oil repellency	ΔE
					Untreated	0	0	0	50.29
1A	600	4	3	48.51

Table 11: household carpet

Examples	Final ppm F	Water repellency	Oil repellency	ΔE
					Untreated	0	0	0	29.13
1B	400	6	5	26.85

ppm F is microgram per gram of fluorine

The data in tables 10 and 11 show that the polymers of the present invention made using cyclic isocyanates provide excellent water repellency, oil repellency, and soil resistance to carpets.

Claims

1. A polymer comprising at least one urea linkage, the polymer prepared by:

(i) reacting (1) at least one organic diisocyanate or isocyanate of the formula II (a)

(2) Reaction of at least one fluorine-containing compound of the formula I

Formula (IIa)

R_f-O(CF₂CF₂)_r(CH₂CH₂)_q(R¹)_sXH formula (I)

Wherein

R_fIs a straight-chain or branched C optionally interrupted by an oxygen atom₁To C₃A perfluoroalkyl group,

r is 1 to 3, q is 1 to 3, s is 0 or 1,

x is O, S or NR²Wherein R is²Is H, or C₁To C₆Alkyl radical, and

R¹is a divalent group selected from the group consisting of-S (CH)₂)_n-，

n is 2 to 4, p is 1 to 50, and R³、R⁴And R⁵Each independently is H or

C₁To C₆An alkyl group;

(ii) followed by reaction with (3) water, a linking agent which is an organic compound having two or more zerewitinoff hydrogen atoms, or a mixture thereof.

2. The polymer of claim 1, wherein R_fIs straight chain and has one to three carbon atoms, and wherein r is 1, q is 1, and s is 0.

3. The polymer of claim 1 wherein step (i) further comprises reacting with a non-fluorinated organic compound of the formula

R¹⁰-(R¹¹)_k-YH

Wherein

R¹¹is composed of

Wherein R is³、R⁴And R⁵Each independently is H or C₁To C₆Alkyl, and p is 1 to 50;

k is 0 or 1; and is

Y is-O-, -S-or-N (R)²) -, wherein R²Is H or C₁To C₆An alkyl group.

4. The polymer of claim 3 wherein R is¹⁰-(R¹¹)_k-YH is a water-soluble material comprising at least one hydroxyl terminated polyether of formula III:

formula III

Wherein

R is a monovalent hydrocarbon radical comprising 1 to 6 aliphatic or alicyclic carbon atoms;

m is a positive integer, and m1 and m2 are each independently a positive integer or zero,

the polyether has a weight average molecular weight of at most 2000.

5. The polymer of claim 3 wherein said non-fluorinated compound is reacted with from 0.1 mole% to 60 mole% of said isocyanate groups.

6. A composition comprising the polymer of claim 1 and the following components:

A) one or more agents that provide at least one surface effect selected from the group consisting of no ironing, easy ironing, shrink control, wrinkle free, permanent set, moisture control, softness, strength, slip resistance, static resistance, snag resistance, pilling resistance, stain release, soil resistance, soil release, water repellency, oil repellency, odor control, antimicrobial, and sun protection, or

B) Surfactants, pH regulators, crosslinking agents, wetting agents, blocked isocyanates, wax fillers or hydrocarbon fillers,

C) coating a substrate, or

D) Mixtures thereof.

7. A method of providing water repellency, oil repellency, stain release, hydrophilic stain release, and cleanability to a substrate comprising contacting said substrate with the polymer of claim 1.

8. A method of providing soil resistance to a substrate comprising contacting the substrate with the polymer of claim 1, with the proviso that the diisocyanate comprises one or more cyclic diisocyanates selected from the group consisting of 2, 4-toluene diisocyanate; 2, 6-toluene diisocyanate; diphenylmethane-4, 4' -diisocyanate; diphenylmethane-2, 4' -diisocyanate; 3-isocyanatomethyl-3, 4, 4-trimethylcyclohexyl isocyanate; and bis (4-isocyanatocyclohexyl) methane.

9. A substrate having applied thereto the polymer of claim 1.