HK1134510A - Poly(meth)acrylamides and poly(meth)acrylates containing fluorinated amide - Google Patents

Description

Poly (meth) acrylamides and poly (meth) acrylates comprising fluorinated amides

Background

Various compositions are known for use as treating agents to provide surface effects to substrates. Surface effects include moisture resistance, stain resistance, soil resistance, and other effects that are 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 used as treating agents for imparting repellency to substrates contain predominantly eight or more carbon atoms in the perfluoroalkyl chain to provide the desired repellency properties. Honda et al in Macromolecules, 2005, 38, 5699-_fThe orientation of the groups is maintained in a parallel configuration, whereas for chains with less than 6 carbon atoms, reorientation occurs, which reduces surface properties, such as contact angle. Short chain perfluorinated chain hydrocarbons are therefore generally not commercially successful.

Various attempts have been made to enhance specific surface effects and to increase fluorine efficiency; i.e., to increase the efficiency or performance of the treating agent so that less of the high cost fluorinated polymer is needed to achieve equivalent performance or to use an equivalent amount of fluorine with better performance. It is desirable to reduce the chain length of the perfluoroalkyl group and thus the amount of fluorine present, while still achieving the same or better surface effect. U.S. Pat. No. 3,576,018 discloses fluorinated acrylamide monomers comprising perfluoroalkyl groups or fluorinated isoalkoxyalkyl groups having 3 to 17 carbon atoms for use as oil and water repellent agents. No polymers or copolymers are disclosed.

The following polymer compositions are needed: the compositions significantly improve the resistance to and stain resistance of fluorinated polymer treatments for fibrous and hard surface substrates while using less fluorine. The present invention provides such compositions.

Summary of The Invention

The present invention includes compositions comprising copolymers having repeating units of formula I in any order

Formula I

Wherein

R_fIs a linear or branched perfluoroalkyl group having from about 1 to about 20 carbon atoms, optionally interrupted by at least one oxygen atom, or a mixture thereof,

X³is oxygen or X¹，

Each X¹Independently an organic divalent linking group having from about 1 to about 20 carbon atoms optionally containing oxygen, nitrogen or sulfur or combinations thereof,

g is F or CF₃，

A is an amide of a carboxylic acid or a carboxylic acid,

j is zero or a positive integer and,

X²is an organic linking group and is a hydroxyl group,

y is O, N or S, and Y is,

h is zero when Y is N, h is 1 when Y is O or S,

z is H, straight or branched chain alkyl having from about 1 to about 4 carbon atoms, or halogen,

b is H or

Wherein

R_f、X¹、X³G, A and j are as defined above, with the proviso that when B is H, j is a positive integer,

m is a positive integer,

q is zero or a positive integer when Y is O, and is a positive integer when Y is N or S,

when Y is O, p is zero or a positive integer, when Y is N or S, p is a positive integer, and

each W is independently

Or [ R ]¹-X¹-Y-C(O)-C(Z)-CH₂]，

Wherein

X¹Y and Z are as defined above,

rx is C (O) O (R)¹)、C(O)N(R²)₂、OC(O)(R¹)、SO₂(R¹)、C₆(R³)₅、O(R¹) Halogen or R¹；

Each R¹Independently is H, C_nH_2n+1、C_nH_2n-CH(O)CH₂、[CH₂CH₂O]_iR⁴、[C_nC_2n]N(R⁴)₂Or [ C_nH_2n]C_nF_2n+1，

n is 1 to 40, and n is,

R⁴is H or C_sH_2s+1，

s＝0-40，

i＝1-200，

Each R²Independently is H or C_tH_2t+1Wherein t is 1 to 20,

each R³Independently is H, COOR¹Halogen, N (R)¹)₂、OR¹、SO₂NHR¹、CH＝CH₂Or SO₃M, wherein R¹As defined above, and

m is H, an alkali metal salt, an alkaline earth metal salt or ammonium.

The present invention also includes compositions comprising formula 2

Formula 2

Wherein

R_f、X¹、X³、G、j、A、Y、X²H, B and Z are each as defined above for formula 1, provided that when Y is N or S, j is a positive integer.

The invention also includes compositions comprising formula 3.

Formula 3

Wherein

R_f、X¹、X³、G、j、A、B、X²And h are each as defined above for formula 2, E is selected from the group consisting of hydroxy, amine, halogen, and thiol, with the proviso that when E is amine, h is zero, and when E is not amine, h is 1.

The present invention also includes a method of imparting water and oil repellency to a substrate comprising contacting the substrate with a composition of formula 1 as defined above.

The invention also includes a substrate to which has been applied a composition of formula 1 as defined above.

Detailed Description

All trademarks are indicated herein in capitalization. In all examples herein, the term "(meth) acrylate" is used to refer to either acrylate or methacrylate. The term "(meth) acryloyl chloride" is used to refer to both acryloyl chloride and methacryloyl chloride. The term "(meth) acrylamide" is used to refer to either acrylamide or methacrylamide.

The present invention includes copolymers having repeating units of formula I in any order

Formula 1

Wherein

R_fIs a linear or branched perfluoroalkyl group having from about 1 to about 20 carbon atoms, optionally interrupted by at least one oxygen atom, or a mixture thereof,

X³is oxygen or X¹，

Each X¹Independently an organic divalent linking group having from about 1 to about 20 carbon atoms optionally containing oxygen, nitrogen or sulfur or combinations thereof,

g is F or CF₃，

A is an amide of a carboxylic acid or a carboxylic acid,

j is zero or a positive integer, provided that when B is H, j is a positive integer,

X²is an organic linking group and is a hydroxyl group,

y is O, N or S, and Y is,

h is zero when Y is N, h is 1 when Y is O or S,

z is H, straight or branched chain alkyl having from about 1 to about 4 carbon atoms, or halogen,

b is H or

Wherein

R_f、X¹、X³G, j and A are as defined above, with the proviso that when B is H, j is positiveThe number of the whole numbers is an integer,

m is a positive integer,

q is zero or a positive integer when Y is O, and is a positive integer when Y is N or S,

when Y is O, p is zero or a positive integer, when Y is N or S, p is a positive integer,

each W is independently

Or [ R ]¹-X¹-Y-C(O)-CH₂Z]，

Wherein

X¹Y and Z are as defined above,

rx is C (O) O (R)¹)、C(O)N(R²)₂、OC(O)(R¹)、SO₂(R¹)、C₆(R³)₅、O(R¹) Halogen or R¹；

Each R¹Independently is H, C_nH_2n+1、C_nH_2n-CH(O)CH₂、[CH₂CH₂O]_iR⁴、[C_nC_2n]N(R⁴)₂Or [ C_nH_2n]C_nF_2n+1，

n is 1 to 40, and n is,

R⁴is H or C_sH_2s+1，

s＝0-40，

i＝1-200，

Each R²Independently is H or C_tH_2t+1Wherein t is 1 to 20,

each R³Independently is H, COOR¹Halogen, N (R)¹)₂、OR¹、SO₂NHR¹、CH＝CH₂Or SO₃M, and

m is H, an alkali metal salt, an alkaline earth metal salt or ammonium.

Preferably R_fIs a linear or branched perfluoroalkyl group having from about 1 to about 18 carbon atoms or a mixture thereof. More preferably R_fFrom about 1 to about 12 carbon atoms, or mixtures thereof. More preferably R_fFrom about 1 to about 6 carbon atoms or mixtures thereof.

A is an amide. Specifically, A is-CONR⁵-or-MR⁵C (O) -, wherein R⁵Is H or alkyl.

Suitable linking groups X¹Examples of (a) include a linear, branched or cyclic alkylene group, a phenyl group, an arylene group, an aralkylene group, a sulfonyl group, a sulfoxy group (sulfoxy), a sulfonamido group (sulfonimide), a carbonamide group (carbonamide), a carbonyloxy group, a urethanylene group (urethanylene), a ureylene group (ureylene) (-NR)⁵CONR⁵-, wherein R⁵H or alkyl) and combinations thereof, such as sulfonamidoalkylene (sulfonamidoalkylene).

The copolymer of formula 1 is prepared by polymerizing a fluorinated amide-containing acrylic monomer, an alkyl (meth) acrylate monomer, and optionally other monomers. Preparing a copolymer of formula 1 by reacting a fluorinated (meth) acrylate or a non-fluorinated (meth) acrylate with a fluorinated amide-containing fluorinated acrylic monomer of formula 2:

formula 2

Wherein

R_f、X¹、X³、G、j、A、B、Y、X²H and Z are each as defined above for formula 1, provided that when Y is N or S, j is a positive integer.

The fluorinated amide-containing acrylic monomer of formula 2 used to prepare the copolymer of formula 1 is prepared by contacting acrylic acid, acrylate or acryloyl chloride with a fluorochemical of formula 3:

formula 3

Wherein

R_f、X¹、X³、G、j、A、X²And h are each as defined above for formula 2, E is selected from the group consisting of hydroxy, amine, halogen, and thiol, with the proviso that when E is amine, h is zero, and when E is not amine, h is 1. Preferably E is hydroxy or amine.

Preferred reaction conditions are at a temperature of from about 0 ℃ to about 60 ℃. Suitable solvents include tetrahydrofuran, methyl isobutyl ketone, acetone or ethyl acetate. A tertiary amine is used as a base to scavenge any acid chloride formed during the reaction.

The compounds of formula 3 are prepared by reacting a perfluorinated ester (prepared according to the methods reported in U.S. Pat. No. 6,054,615 and U.S. Pat. No. 6,376,705, which are incorporated herein by reference) with a triamine or diamine alcohol, with or without a solvent. The reaction conditions for this reaction depend on the structure of the ester. The reaction of the α, α -difluoro-substituted ester with the diamine is conducted at a temperature of from about 5 ℃ to about 35 ℃. Suitable solvents for this reaction include tetrahydrofuran, methyl isobutyl ketone, acetone, CHCl3, CH₂Cl₂Or an ether. The reaction of the ester without alpha-fluoro substitution with the diamine is carried out at a temperature of from about 90 ℃ to about 160 ℃, preferably from about 100 ℃ to about 140 ℃. Preferably, no solvent is used for the reaction, but suitable solvents include chlorobenzene, dimethylformamide or 2-methoxyethyl ether.

The compounds of formula 3 are also prepared by reacting a perfluorinated acyl fluoride with a diamine alcohol or an amine alcohol. The reaction is carried out at a temperature of from about-30 ℃ to about 40 ℃, preferably from about 5 ℃ to about 25 ℃. Suitable solvents for this reactionThe agent comprises tetrahydrofuran, methyl isobutyl ketone, acetone, CHCl3, CH₂Cl₂2-methoxyethyl ether or diethyl ether.

The fluorinated amide-containing fluorinated acrylic monomer of formula 2 of the present invention is then polymerized with a fluorinated (meth) acrylate or a non-fluorinated (meth) acrylate to produce the copolymer of formula 1.

Non-fluorinated (meth) acrylate monomers suitable for use in preparing the copolymers of formula 1 of the present invention include alkyl (meth) acrylates wherein the alkyl group is straight or branched chain containing from 1 to about 20 carbon atoms or mixtures thereof, preferably from about 1 to about 18 carbon atoms. (meth) acrylic acid C₁-C₂₀Examples of alkyl esters (linear or branched) include, but are not limited to, alkyl (meth) acrylates wherein the alkyl group is methyl, ethyl, propyl, butyl, isopentyl, hexyl, cyclohexyl, octyl, 2-ethylhexyl, decyl, isodecyl, dodecyl, hexadecyl, or octadecyl. Preferred examples are 2-ethylhexyl acrylate, dodecyl acrylate and octadecyl acrylate.

Other optional monomers may also be used in the polymerization reaction to produce the copolymer of formula 1 comprising other repeating units. These optional monomers include N-methylol (meth) acrylate, hydroxyalkyl (meth) acrylate, alkoxy (meth) acrylate, fluorinated (meth) acrylate, glycidyl (meth) acrylate, octadecyl acrylate, aminoalkyl methacrylate hydrochloride, acrylamide, alkyl acrylamide, vinyl acetate, vinyl stearate, alkyl vinyl sulfone, styrene, vinyl benzoic acid, alkyl vinyl ether, maleic anhydride, vinylidene chloride, vinyl chloride, and olefins.

Examples of optional N-methylol monomers are N-methylolacrylamide and N-methylolmethacrylamide. The optional hydroxyalkyl (meth) acrylates have alkyl chain lengths of from about 2 to about 4 carbon atoms, examples being 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate. The optional alkoxy (meth) acrylate also has an alkyl chain length of from about 2 to about 4 carbon atoms and contains from 1 to about 12 oxyalkylene units per molecule, preferably from about 4 to about 10 oxyalkylene units per molecule, and most preferably from about 6 to about 8 oxyalkylene units per molecule as measured by gas chromatography/mass spectrometry. Specific examples of poly (alkylene oxide) (meth) acrylates include, but are not limited to, the reaction product of 2-hydroxyethyl methacrylate ethylene oxide. Reacted with 9 moles of ethylene oxide to give a 2-hydroxyethyl methacrylate/9-ethylene oxide adduct and reacted with 6 moles of ethylene oxide to give a 2-hydroxyethyl methacrylate/6-ethylene oxide adduct. Other optional non-fluorinated monomers may be styrene, maleic anhydride and vinylidene chloride. When such optional monomers are present, the polymerization method used is conventional as known to those skilled in the art.

The fluorinated copolymers of formula 1 of the present invention are prepared by free radical initiated polymerization of a mixture of fluorinated amide-containing acrylic monomers of formula 2 and (meth) acrylic acid esters in an organic solvent with any of the optional monomers listed above. The fluorinated copolymers of the present invention are prepared by stirring the above monomers in an organic solvent in a suitable reaction vessel equipped with stirring means and external heating and cooling means. Adding a free radical initiator and heating to about 40 ℃ to about 60 ℃. Polymerization regulators or chain transfer agents may be added to control the molecular weight of the resulting polymer. An example of the polymerization initiator is [2, 2' -azobis (2, 4-dimethylvaleronitrile) ]. These initiators are sold under the name "VAZO" by e.i. du Pont de Nemours and company, Wilmington, Delaware. An example of a polymerization regulator or chain transfer agent is dodecyl mercaptan. Suitable organic solvents for preparing the copolymer of formula 1 of the present invention include tetrahydrofuran, acetone, methyl isobutyl ketone, isopropanol, ethyl acetate and mixtures thereof. Tetrahydrofuran is preferred. The reaction is carried out under an inert gas such as nitrogen to exclude oxygen. The solution may be maintained for dilution and application to a substrate. Alternatively, the polymer may be isolated by precipitation with methanol and then dissolved in a suitable solvent, such as tetrahydrofuran, for application to a substrate. The reaction product is a fluorinated amide-containing copolymer of formula 1.

The fluorinated amide-containing copolymer of formula 1 can be prepared using from about 25 to about 80 weight percent of the fluorinated amide-containing acrylate of formula 2, from about 1 to about 40 weight percent of the (meth) acrylate, and from 0 to about 75 weight percent of the optional monomers.

The resulting fluorinated amide-containing copolymer of formula 1 is then poured into water. The collected polymer is dissolved in a solvent selected from simple (simple) alcohols, ketones or tetrahydrofuran, which are suitable for use as solvents for the final application to a substrate (hereinafter referred to as "application solvents"). The final product for application to a substrate is a solution of fluorinated amide-containing copolymer of formula 1.

The invention also includes a composition of formula 2 as defined above, wherein R is_fIs linear. The composition is prepared by reacting acrylic acid, an acrylic ester or acryloyl chloride with a fluorochemical compound of formula 3 (wherein R is as defined above) as described above_fLinear) contact preparation. The composition is used for preparing R_fIs a linear composition of formula 1.

The invention also includes a composition of formula 3 as defined above, wherein R is_fIs linear. The composition is prepared as described above by reacting a triamine or diamine alcohol with a perfluorinated ester in which the perfluoro groups are linear. The composition is used for preparing R_fIs a linear composition of formula 2.

The present invention also includes a method of imparting oil repellency and water repellency to a substrate comprising contacting a fluorinated amide-containing copolymer solution of formula 1 of the present invention with the substrate. Suitable substrates include fibrous or hard surface substrates as defined below. The contacting is performed using conventional methods. The copolymer of formula 1 is usefully applied to the fibrous substrate by a number of methods known to those skilled in the art, for example: rubbing (padding), spraying, foaming with a foaming agent, flexing nip (flex-nip), nip (nip), roller-lick (kiss-roll), exhaustion (exhaustion), winch vat (beck), skein (skein), winch (winch), liquid jet (liquid ejection), overflow (overflow flow), exhaustion in a rope dyeing (beck dying) apparatus (exhaust) or continuous exhaustion during a continuous dyeing operation. It is applied to dyed or undyed substrates by such methods. For hard surface substrates, methods of application include, for example, using brushes, rollers, swabs for rubbing, pads, sponges, combs, hand pump dispensers, compressed air driven spray guns, electric or electrostatic sprayers, backpack spray application equipment, cloths, paper, feathers, styluses, knives, and other conventional application tools. If impregnation is used as the method of applying the copolymer, no special equipment is required.

The fluorinated amide-containing copolymer solution of formula 1 of the present invention is applied directly to a substrate or combined with other optional fabric finishes or surface treatments. Such optional other components include treating agents or finishes intended to achieve other surface effects, or additives commonly used with such agents or finishes. Such other components include compounds or compositions that provide surface effects such as no iron, easy iron, shrink control, wrinkle free, permanent press, moisture control, softness, strength, anti-slip, anti-static, anti-snag, anti-pilling, anti-stain, stain release, water repellency, oil repellency, odor control, anti-microbial, sun protection, and similar effects. One or more such treatments or finishes may be applied to the substrate before, after, or simultaneously with the copolymers of the present invention. For example, for fibrous substrates, when treating mixed fiber or cotton fabrics, it may be desirable to use a wetting agent, such as ALKANOL 6112 from e.i. du Pont DE nemours and Company, Wilmington, DE. When treating cotton or cotton blends, 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 extenders, and other additives known to those skilled in the art. Suitable surfactants include anionic, cationic and nonionic surfactants. Anionic surfactants are preferred, such as sodium dodecyl sulfate sold as DUPONOL WAQE from Witco corporation, Greenwich, CT. Examples of such finishes or agents include processing aids, blowing agents, lubricants, and stain repellents, among others. The composition is applied at the manufacturing plant, retail location, prior to installation and use, or at the consumer location.

The fluorinated amide-containing copolymer solution of formula 1 of the present invention is used in an amount of about 10 to about 1000g/m depending on the porosity of the substrate². The fluorine content of the treated fibrous substrate is typically from about 0.05% to about 1.0% by weight. Generally, the higher the fluorine content, the greater the oil and water repellency provided, but this is not economically feasible. The fluorine carrying amount is optimized according to the kind of the substrate.

The optimum resistance to treatment for a given substrate depends on (1) the identity of the fluorinated copolymer, (2) the identity of the substrate surface, (3) the amount of fluorinated copolymer applied to the surface, (4) the method of applying the fluorinated copolymer to the surface, and many other factors. Certain fluorinated copolymer resists are suitable for many different substrates and are resistant to oils, water, and many other liquids. Other fluorinated copolymer resists exhibit more excellent resistance or require higher loading on certain substrates.

The present invention also includes substrates treated with the fluorinated amide-containing fluorinated copolymer solution of formula 1 of the present invention. Suitable substrates include fibrous or hard surface substrates. Fibrous substrates include woven and non-woven fibers, fabrics, blend fabrics, textiles, nonwovens, paper, leather, and carpets. It is made from natural or synthetic fibers including cotton, cellulose, wool, silk, polyamides, polyesters, polyolefins, polyacrylonitrile, polypropylene, rayon, nylon, aramids, and acetates or mixtures thereof. "blended fabric" refers to a fabric made from two or more fibers. Generally, these blend fabrics are a combination of at least one natural fiber and at least one synthetic fiber, but may also include a blend of two or more natural fibers or two or more synthetic fibers. These substrates are commonly used in many applications including, for example, textiles, clothing, furniture, and carpets. Hard surface substrates include porous and non-porous mineral surfaces such as glass, stone, masonry, cement, unglazed ceramic tiles, bricks, porous clays, and various other substrates that are porous in surface. Specific examples of such substrates include unglazed cement, 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 made with gypsum board). It is used to build buildings, roads, tarmac, driveways, floors, fireplaces, fireplace floors, work tops and other ornaments for interior and exterior applications. The substrates of the present invention have excellent water and oil repellency.

The fluorinated amide-containing copolymer compositions of the present invention having perfluoroalkyl chains of 1 to about 20 carbon atoms are useful for providing one or more of excellent water and oil repellency to treated substrates. The fluorinated amide-containing copolymers of the present invention allow the use of shorter perfluoroalkyl groups containing 6 or less carbon atoms, whereas conventional commercially available acrylates typically exhibit poor oil and water repellency if the perfluoroalkyl groups contain less than 8 carbon atoms.

Materials and test methods

Tetrahydrofuran (THF) and Stearyl Methacrylate (SMA) were obtained from Sigma-Aldrich, St Louis, Mo. THF as used in the examples herein refers to tetrahydrofuran.

Perfluoro-2-methyl-3-oxahexanoyl fluoride and CF₃(OCF₂)_nCO₂CH₃From e.i. dupont DE Nemours and Company, Wilmington, DE.

The cotton fabric was 100% Levi's cotton fabric (medium tan) from INVISTA, Wilmington, DE.

100% Nylon fabric was from Burlington Industries (ITG), Greensboro, NC.

Test methods 1-treatment of fibrous substrates

The fibrous substrate (e.g., fabric) is treated with the copolymer dispersion or solution using the following method. The copolymer solution was prepared in tetrahydrofuran to contain 2000mg/kg of fluorine. The solution was applied to cotton and nylon substrates by pipetting the copolymer solution to the substrate until saturated. After application, the substrate was dried in air and cured at about 150 ℃ for about 2 minutes. The substrate was cooled to room temperature before the oil and water repellency measurements were performed.

Test method 2-Water repellency

The water repellency of the treated substrates was measured according to AATCC Standard test method No.193-2004 and the TEFLON general Specification and Quality Control Tests (TEFLON Global Specifications and Quality Control Tests) as described in the DuPont Technical laboratory method (DuPont Technical laboratory method). The test determines the resistance of the treated substrate to wetting by aqueous liquids. Several drops of water-alcohol mixtures of different surface tensions were placed on the substrate and the degree of surface wetting was visually assessed. The test provides a general indication of the resistance to water staining.

The composition of the water-repellent test liquid is shown in table 1.

TABLE 1 waterproof test liquids

The test method comprises the following steps:

three drops of test liquid 1 were placed on the treated substrate. After 10 seconds, the droplets were removed by vacuum suction. If no liquid penetration or partial absorption (appearance of a darker wet patch on the substrate) is observed, the test is repeated with test liquid 2. The test was repeated with test liquid 3 and progressively larger test liquid numbers until liquid penetration (appearance of darker wet patch on the substrate) was observed. The test results are the maximum test fluid number that did not penetrate into the substrate. Higher scores indicate greater resistance.

Test method 3-oil repellency

The treated fabric samples were tested for oil repellency using modified AATCC standard test method No 118, performed as follows. The fabric samples were treated with the polymer solution as described above. The series of organic liquids shown in table 2 below was then applied drop-wise to the fabric samples. Starting from the minimum test liquid number (resistance rating scale No. 1), one drop (about 5mm diameter or 0.05mL volume) was placed at each of three positions separated by at least 5 mm. The droplets were observed for 30 seconds. If at the end two of the three drops are still spherical in shape and do not wick around the drop, the three drops of the next higher numbered liquid are placed in adjacent positions and similarly observed for 30 seconds. The method is continued until one test liquid causes two of the three drops to fail to remain spherical to hemispherical or wetting or wicking occurs.

The oil repellency rating of the fabric was the largest numbered test liquid with two of the three drops remaining spherical to hemispherical for 30 seconds and no wicking. In general, treated fabrics rated 5 or higher are considered good to excellent; fabrics rated 1 or greater may be useful for certain applications.

The treated hard surface substrate samples were tested for oil repellency using modified AATCC standard test method No 118, conducted as follows. Three drops of test oil 1 in table 2 were placed on the treated substrate. After 30 seconds, the droplets were removed by vacuum suction. If no liquid penetration or partial absorption (appearance of a darker wet patch on the substrate) was observed, the test was repeated with test oil 2. The test was repeated with test oil 3 and progressively larger test oils until liquid penetration (appearance of darker wet patch on the substrate) was observed. The test result is the maximum test oil number that does not exhibit liquid penetration into the substrate. Higher scores indicate greater resistance.

TABLE 2 oil repellency test liquids

Oil repellency rating number	Test solutions
		1	NUJOL purified mineral oil
2	NUJOL/n-hexadecane in a volume ratio of 65/35, 21 deg.c
		3	N-hexadecane
4	N-tetradecane
		5	N-dodecane
6	N-decane
		7	N-octane
8	N-heptane

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

Examples

Example 1

A50-mL flask was charged with methyl 2, 2, 3, 3-tetrahydroperfluorononanoate (9.0g, prepared according to the method of U.S. Pat. No. 6,054,615) and 1, 3-diamino-2-propanol (1.0 g). 140 deg.CThe resulting mixture was stirred for 8 h. After cooling to room temperature the reaction mixture solidified and was dried under full vacuum for 8h to give a solid (8.95 g). The product is N, N' -bis (2, 2, 3, 3-tetrahydroperfluorononanoyl) -1, 3-diamino-2-propanol as shown by the following analysis. H NMR (CDCl)₃)2.52(m, 9H), 3.36(m, 4H), 3.80 (quintuple, J ═ 5Hz, 1H), 6.36(br.s, 2H) ppm. F NMR-81.2(tt, J ═ 10, 3Hz, 6F), -114.9(m, 4F), -122.3(m, 4F), -123.3(m, 4F), -123.9(m, 4F), -126.5(m, 4F) ppm. For HNMR and FNMR for this example and all examples herein, ppm represents one part per million of frequency shift.

A25-mL flask was charged with N, N' -bis (2, 2, 3, 3-tetrahydroperfluorononanoyl) -1, 3-diamino-2-propanol (6.0g) prepared according to the above procedure, triethylamine (1.42g), and tetrahydrofuran (20 mL). Methacryloyl chloride (1.45g) in tetrahydrofuran (3mL) was added dropwise to the above mixture at about 10 ℃. The mixture was stirred at room temperature for 15 h. The mixture was poured into water (40mL) and extracted with ether (2X 100 mL). The ether solution was washed with water (3X 50mL) and saturated NaCl solution (10mL), Na₂SO₄Drying, concentration and vacuum drying to obtain 6.35g of waxy product. The product is N, N' -bis (2, 2, 3, 3-tetrahydroperfluorononanoyl) -1, 3-diamino-2-propyl methacrylate.

A mixture of N, N '-bis (2, 2, 3, 3-tetrahydroperfluorononanoyl) -1, 3-diamino-2-propyl methacrylate (2.0g), stearyl methacrylate (0.8g), 2' -azobis (2, 4-dimethylvaleronitrile) (VAZO 52) (25mg), and tetrahydrofuran (5mL) was heated to 60 ℃ for 15 h. The mixture was poured into methanol (100 mL). The precipitated polymer was washed with methanol (2X 30mL) and dried in vacuo to give a polymer (1.28 g). It was a copolymer, NMR showed about 38.7% F.

A solution of the copolymer was prepared and applied to cotton and nylon fabrics using the method of test method 1. The treated fabrics were tested for water repellency and oil repellency using test methods 2 and 3, respectively. The results are shown in Table 3.

Example 2

Add two to 100-mL bottleEthylene triamine (6.64g) and 52.6g methyl 2, 2, 3, 3-tetrahydroperfluorononanoate (prepared according to the method of U.S. Pat. No. 6,054,615). The resulting mixture was heated to 120 ℃ for 20 h. The reaction mixture was dried under vacuum at 70 ℃ for 2h to give a solid (54 g). The product is 1, 7-bis (2, 2, 3, 3-tetrahydroperfluorononanoyl) -1, 4, 7-triazaheptane as shown by the following analyses. H NMR (CDCl)₃)1.66(br.s，1H)，2.51(m，8H)，2.78(t，J＝6Hz，4H)，3.35(q，J＝6Hz，4H)，6.20(br.s，2H)ppm。F NMR(CDCl3)-81.3(tt，J＝10，3Hz，6F)，-115.1(m，4F)，-122.4(m，4F)，-123.4(m，4F)，-124.0(m，4F)，-126.6(m，4F)ppm。

A100-mL flask was charged with 1, 7-bis (2, 2, 3, 3-tetrahydroperfluorononanoyl) -1, 4, 7-triazaheptane (15.7g), triethylamine (2.49g), and tetrahydrofuran (22 mL). Methacryloyl chloride (2.58g, dissolved in 7mL of tetrahydrofuran) was added dropwise to the above mixture at about 10 ℃. The mixture was stirred at room temperature for 2 h. The reaction mixture was poured into water (200mL) and extracted with dichloromethane (250 mL). The dichloromethane extract was washed with water (3X 50 mL). The initial aqueous layer was extracted with ether (200mL), and the ether extract was washed with water (3X 50mL) and saturated NaCl solution. Na (Na)₂SO₄The combined dichloromethane and solution was dried, concentrated and dried in vacuo to give a solid (14.8 g). The product is 1, 7-bis (2, 2, 3, 3-tetrahydroperfluorononanoyl) -4-methacryloyl-1, 4, 7-triazaheptane as shown by the following analyses. H NMR (CDCl)₃)1.89(m，3H)，2.51(m，8H)，3.55(m，8H)，4.90(m，1H)，5.16(m，1H)，6.31(br.s，1H)，7.51(br，s，1H)ppm。F NMR(CDCl₃)-81.3(t，J＝10Hz，6F)，-115.1(m，4F)，-122.4(m，4F)，-123.4(m，4F)，-124.0(m，4F)，-126.6(m，4F)ppm。

A mixture of octadecyl methacrylate (1.6g), 1, 7-bis (2, 2, 3, 3-tetrahydroperfluorononanoyl) -4-methacryloyl-1, 4, 7-triazaheptane (4.0g), tetrahydrofuran (10mL), and 2, 2' -azobis (2, 4-dimethylpentanenitrile) (45mg) was heated to 60 ℃ for 36 h. The mixture was poured into methanol (100 mL). The precipitated polymer was washed with methanol (2X 30mL) and dried in vacuo to give a solid (1.85 g). It is a copolymer and contains about 9.4% fluorine.

A solution of the copolymer was prepared and applied to cotton and nylon fabrics using the method of test method 1. The treated fabrics were tested for water repellency and oil repellency using test methods 2 and 3, respectively. The results are shown in Table 3.

Example 3

A25-mL bottle was charged with 1, 3-diamino-2-propanol (0.61g) and tetrahydrofuran (4 mL). Ethyl 3, 3, 4, 4-tetrahydroperfluorooctanoate (5.0g) (prepared according to the method of U.S. Pat. No. 6,376,705) in tetrahydrofuran (2mL) was added dropwise at about 10 ℃. The resulting mixture was stirred at room temperature for 15 h. The reaction mixture was concentrated and dried in vacuo to give 5.0g of a solid. The product is N, N' -bis (3, 3, 4, 4-tetrahydroperfluorooctanoyl) -1, 3-diamino-2-propanol as shown by the following analysis. H NMR (CDCl)₃)1.53(br.s, 1H), 2.41(m, 8H), 3.45(m, 4H), 3.97 (quintuple, J ═ 5Hz, 1H), 6.99(br.s, 2H) ppm. F NMR-81.5(tt, J ═ 10, 3Hz, 6F), -107.1(m, 4F), -115.1(m, 4F), -124.7(m, 4F), -126.4(m, 4F) ppm.

A50-mL flask was charged with N, N' -bis (3, 3, 4, 4-tetrahydroperfluorooctanoyl) -1, 3-diamino-2-propanol (4.8g) prepared according to the above procedure, triethylamine (0.80g), and tetrahydrofuran (20 mL). Methacryloyl chloride (0.82g) in tetrahydrofuran (3mL) was added dropwise to the above mixture at room temperature. The mixture was stirred at room temperature for 15 h. GC analysis of the reaction mixture indicated the formation of the product and about 4% of the starting alcohol. Methacryloyl chloride (0.1g) and triethylamine (0.10g) were added to the reaction mixture. The resulting mixture was stirred for a further 15h at 35 ℃. The reaction mixture was concentrated and dried in vacuo to give 5.0g of a solid. The following analysis shows that the product is N, N' -bis (3, 3, 4, 4-tetrahydroperfluorooctanoyl) -1, 3-diamino-2-propyl methacrylate. H NMR (tetrahydrofuran-d 8)2.00(m, 3H), 2.54(m, 8H), 3.60(m, 4H), 5.26(m, 1H), 5.69(m, 1H), 6.19(m, 1H), 8.45(br.s, 2H) ppm. F NMR-81.5(tt, J ═ 10, 3Hz, 6F), -106.9(ABq t, J ═ 258, 15Hz, 4F), -114.7(m, 4F), -124.2(m, 4F), -126.1(m, 4F) ppm.

A mixture of N, N '-bis (3, 3, 4, 4-tetrahydroperfluorooctanoyl) -1, 3-diamino-2-propyl methacrylate (2.0g), stearyl methacrylate (0.80g), 2' -azobis (2, 4-dimethylvaleronitrile) (25mg) and tetrahydrofuran (5mL) was heated to 60 ℃ for 15 h. The mixture was poured into methanol (100 mL). The precipitated polymer was washed with methanol (2X 30mL) and dried in vacuo to give a white solid (2.44 g). It was a copolymer, and NMR showed about 44.6% F.

A solution of the copolymer was prepared and applied to cotton and nylon fabrics using the method of test method 1. The treated fabrics were tested for water repellency and oil repellency using test methods 2 and 3, respectively. The results are shown in Table 3.

Example 4

A25-mL bottle was charged with diethylenetriamine (0.85g) and tetrahydrofuran (4 mL). Ethyl 3, 3, 4, 4-tetrahydroperfluorooctanoate (6.25g, prepared according to the method of U.S. Pat. No. 6,376,705) in tetrahydrofuran (2mL) was added dropwise at about 10 ℃. The resulting mixture was stirred at room temperature for 15 h. The reaction mixture was concentrated and dried in vacuo to give 6.27g of a solid. The product is 1, 7-bis (2, 2, 3, 3-tetrahydroperfluorooctanoyl) -1, 4, 7-triazaheptane as shown by the following analyses. H NMR (CDCl)₃)1.55(br.s，1H)，2.39(m，8H)，2.85(t，J＝6Hz，4H)，3.42(q，J＝6Hz，4H)，6.80(br.s，2H)ppm。F NMR-81.5(tt，J＝10，3Hz，6F)，-107.3(t，J＝16Hz，4F)，-115.2(m，4F)，-124.8(m，4F)，-126.5(m，4F)ppm。

A25-mL flask was charged with 1, 7-bis (2, 2, 3, 3-tetrahydroperfluorooctanoyl) -1, 4, 7-triazaheptane (3g), triethylamine (0.49g), and tetrahydrofuran (5 mL). Methacryloyl chloride (0.50g) in tetrahydrofuran (2mL) was added dropwise to the above mixture at about 10 ℃. The mixture was stirred at room temperature for 3 h. The reaction mixture was poured into water (40mL) and extracted with dichloromethane (50 mL). The organic layer was washed with water (2X 30mL), Na₂SO₄Drying, concentration and vacuum drying gave a waxy product (3.3 g). The product is 1, 7-bis (2, 2, 3, 3-tetrahydroperfluorooctanoyl) -4-methacryloyl-1, 4, 7-triazaheptane as shown by the following analyses. H NMR (CDCl)₃)1.93(s，3H)，2.38(m，8H)，3.57(m，4H)，3.62(m，4H)，5.01(m，1H)，5.22(m，1H)，6.23(br.s，2H)ppm。F NMR-81.5(tt，J＝10，3Hz，6F)，-107.3(m，4F)，-115.2(m，4F)，-124.7(m，4F)，-126.5(m，4F)ppm。

A mixture of 1, 7-bis (2, 2, 3, 3-tetrahydroperfluorooctanoyl) -4-methacryloyl-1, 4, 7-triazaheptane (2.0g), stearyl methacrylate (0.8g), 2' -azobis (2, 4-dimethylpentanenitrile) (25mg), and tetrahydrofuran (3mL) was heated to 60 ℃ for 15 h. The mixture was poured into methanol (100 mL). The precipitated polymer was washed with methanol (2X 30mL) and dried in vacuo to give a white solid (0.85 g). It is a copolymer, and NMR showed about 5.1% F.

A solution of the copolymer was prepared and applied to cotton and nylon fabrics using the method of test method 1. The treated fabrics were tested for water repellency and oil repellency using test methods 2 and 3, respectively. The results are shown in Table 3.

Example 5

A25-mL bottle was charged with 1, 3-diamino-2-propanol (0.5g) and tetrahydrofuran (2 mL). Ethyl 3, 3, 4, 4-tetrahydroperfluorodecanoate (5.45g) (prepared according to the method of U.S. Pat. No. 6,376,705) in tetrahydrofuran (2mL) was added dropwise at about 15 ℃. The resulting mixture was stirred at room temperature for 3 hours, then at 50 ℃ for 2 hours. The reaction mixture was concentrated and dried in vacuo to give 5.08g of a white solid with a yield of about 96%. The product is N, N' -bis (3, 3, 4, 4-tetrahydroperfluorodecanoyl) -1, 3-diamino-2-propanol as shown by the following analysis. H NMR 2.49(m, 8H), 2.78(br.s, 1H), 3.37(m, 4H), 3.95 (quintuple, J ═ 6Hz, 1H), 8.07(br.s, 2H) ppm. F NMR-82.2(tt, J ═ 10, 3Hz, 6F), -107.9(m, 4F), -115.3(m, 4F), -122.9(m, 4F), -123.8(m, 4F), -124.2(m, 4F), -127.2(m, 4F) ppm.

A25-mL flask was charged with N, N' -bis (3, 3, 4, 4-tetrahydroperfluorodecanoyl) -1, 3-diamino-2-propanol (2.0g), triethylamine (0.33g), and tetrahydrofuran (3 mL). Methacryloyl chloride (0.33g) in tetrahydrofuran (3mL) was added dropwise at about 10 ℃. The resulting mixture was stirred at room temperature for 15 h. Filtering to remove the solid, and using about 50mL of dichloromethane. The combined filtrate and wash were then poured into about 25mL of water. The organic layer was separated, washed again with water (2X 30mL), Na₂SO₄Dried, concentrated and dried under vacuum overnight to give a solid (2.03 g). The following analysis shows that the product is N, N' -bis (3, 3, 4, 4-tetrahydroperfluorodecanoyl) -1, 3-diamino-2-propyl methacrylate. FNMR (acetone-d 6) -82.2(tt, J ═ 10, 3Hz, 6F), -107.8(ABq m, J ═ 255Hz, 4F), -122.9(m, 4F), -123.8(m, 4F), -124.2(m, 4F), -127.2(m, 4F) ppm. H NMR (acetone-d 6)1.89(m, 3H), 2.47(m, 8H), 3.36(m, 4H), 5.22(m, 1H), 5.62(m, 1H), 6.08(m, 1H), 8.39(br.s, 2H) ppm.

A mixture of N, N '-bis (3, 3, 4, 4-tetrahydroperfluorodecanoyl) -1, 3-diamino-2-propyl methacrylate (2.0g), stearyl methacrylate (1.2g), 2' -azobis (2, 4-dimethylpentanenitrile) (25mg), and tetrahydrofuran (10mL) was heated at 60 ℃ for 15 h. The reaction mixture was poured into methanol (80 mL). The polymer was precipitated, washed with methanol (20mL), and dried in vacuo to give a white solid (2.36 g). It is a copolymer, and NMR showed about 34% F.

A solution of the copolymer was prepared and applied to cotton and nylon fabrics using the method of test method 1. The treated fabrics were tested for water repellency and oil repellency using test methods 2 and 3, respectively. The results are shown in Table 3.

Example 6

A25-mL bottle was charged with diethylenetriamine (1.1g) and tetrahydrofuran (5 mL). Ethyl 3, 3, 4, 4-tetrahydroperfluorodecanoate (10g, prepared according to the method of U.S. Pat. No. 6,376,705) in tetrahydrofuran (4mL) was added dropwise at about 15 ℃. The resulting mixture was stirred at room temperature for 15 h. The reaction mixture was concentrated and dried in vacuo to give 10g of a solid. The product is 1, 7-bis (2, 2, 3, 3-tetrahydroperfluorodecanoyl) -1, 4, 7-triazaheptane as shown by the following analyses. H NMR (CDCl)₃)1.28(br.s，1H)，2.39(m，8H)，2.85(t，J＝5Hz，4H)，3.42(q，J＝5Hz，4H)，6.79(br.s，2H)ppm。F NMR-81.3(tt，J＝10，3Hz，6F)，-107.4(t，J＝16Hz，4F)，-115.0(m，4F)，-122.4(m，4F)，-123.3(m，4F)，-123.8(m，4F)，-126.6(m，4F)ppm。

A25-mL flask was charged with 1, 7-bis (2, 2, 3, 3-tetrahydroperfluorodecanoyl) -1, 4, 7-triazaheptane (5g), triethylamine (0.64g), and tetrahydrofuran (15 mL). Methacryloyl chloride (0.67g) in tetrahydrofuran (3mL) was added dropwise to the above mixture at about 10 ℃. The mixture was stirred at room temperature for 15 h. The reaction mixture was poured into water (50mL) and extracted with dichloromethane (100 mL). The organic layer was washed with water (2X 50 mL). During the second wash, the organic layer became a gel. The gel was separated and air dried to give 4.9g of a solid. The product is 1, 7-bis (2, 2, 3, 3-tetrahydroperfluorodecanoyl) -4-methacryloyl-1, 4, 7-triazaheptane as shown by the following analyses. H NMR (THF-d8)2.00(m, 3H), 2.52(m, 8H), 3.55(m, 4H), 3.67(m, 4H), 5.12(m, 1H), 5.23(m, 1H), 8.41(br.s, 2H) ppm. F NMR (THF-d8) -81.5(tt, J ═ 10Hz, 6F), -107.2(m, 4F), -114.8(m, 4F), -122.2(m, 4F), -123.1(m, 4F), -123.6(m, 4F), -126.5(m, 4F) ppm.

A mixture of 1, 7-bis (2, 2, 3, 3-tetrahydroperfluorodecanoyl) -4-methacryloyl-1, 4, 7-triazaheptane (2.0g), stearyl methacrylate (0.8g), 2' -azobis (2, 4-dimethylpentanenitrile) (25mg), and tetrahydrofuran (3mL) was heated to 60 ℃ for 24 h. The reaction mixture was poured into methanol (100 mL). The precipitated polymer was washed with methanol (2X 30mL) and dried in vacuo to give a white solid (0.81 g). It was a copolymer, and NMR showed about 5.6% F.

A solution of the copolymer was prepared and applied to cotton and nylon fabrics using the method of test method 1. The treated fabrics were tested for water repellency and oil repellency using test methods 2 and 3, respectively. The results are shown in Table 3.

Example 7

A mixture of N, N '-bis (2, 2, 3, 3-tetrahydroperfluorononanoyl) -1, 3-diamino-2-propyl acrylate (2.0g), stearyl methacrylate (0.8g), 2' -azobis (2, 4-dimethylvaleronitrile) (35mg), and tetrahydrofuran (5mL) was heated to 60 ℃ for 15 h. The mixture was poured into methanol (100 mL). The precipitated polymer was washed with methanol (2X 20mL) and dried in vacuo to give a solid (2.48 g). It was a copolymer, and NMR showed about 32.7% F.

A solution of the copolymer was prepared and applied to cotton and nylon fabrics using the method of test method 1. The treated fabrics were tested for water repellency and oil repellency using test methods 2 and 3, respectively. The results are shown in Table 3.

Example 8

A mixture of N, N '-bis (2, 2, 3, 3-tetrahydroperfluorononanoyl) -1, 3-diamino-2-propyl methacrylate (1.8g), styrene (0.88g), 2' -azobis (2, 4-dimethylvaleronitrile) (25mg), and tetrahydrofuran (5mL) was heated to 60 ℃ for 15 h. The mixture was poured into methanol (100 mL). The precipitated polymer was washed with methanol (2X 30mL) and dried in vacuo to give a solid (1.56 g). It is a copolymer, and NMR showed about 38% F.

A solution of the copolymer was prepared and applied to cotton and nylon fabrics using the method of test method 1. The treated fabrics were tested for water repellency and oil repellency using test methods 2 and 3, respectively. The results are shown in Table 3.

Example 9

A25-mL flask was charged with 1, 3-diamino-2-propanol (1.5g) and THF (5 mL). CF was added dropwise at about 10 deg.C₃(OCF₂)_nCO₂Me (n: 2-5, 14.5g)/THF (5 mL). The resulting mixture was stirred at room temperature for 15 h. The reaction mixture was concentrated and dried in vacuo to give 13.5g of a viscous oil, HNMR (CDCl)₃)1.55(br.s, 1H), 3.41(m, 4H), 4.02 (quintuple, J ═ 5Hz, 1H), 6.95(br.s, 2H) ppm. The product is N, N' -di (polyoxaperfluoroacyl) -1, 3-diamino-2-propanol.

A25-mL flask was charged with N, N' -bis (polyoxaperfluoroacyl) -1, 3-diamino-2-propanol (5.5g, E110448-72), Et₃N (0.82g) and THF (15 mL). Methacryloyl chloride (0.84g/3mL THF) was added dropwise to the above mixture at about 10 deg.C. The mixture was stirred at room temperature for 15 h. GC analysis of reaction mixThis indicated the formation of the product. The mixture was poured into water (40mL) and extracted with ether (100 mL). The ether solution was washed with water (3X 30mL) and NaCl (saturated, 10mL), Na₂SO₄Drying, concentration and vacuum drying gave 5.7g of a very viscous oil. The product is N, N' -di (polyoxaperfluoroacyl) -1, 3-diamino-2-propyl methacrylate.

A mixture of N, N' -bis (polyoxaperfluoroacyl) -1, 3-diamino-2-propyl methacrylate (2.0g), stearyl methacrylate (0.80g), VAZO 52(25mg), and THF (5mL) was heated to 60 ℃ for 15 h. The mixture was poured into methanol (100 mL). The precipitated polymer was washed with methanol (2X 30mL) and dried in vacuo to give a white solid (1.01 g). It was a copolymer, and NMR showed about 23.7% F.

A solution of the copolymer was prepared and applied to cotton and nylon fabrics using the method of test method 1. The treated fabrics were tested for water repellency and oil repellency using test methods 2 and 3, respectively. The results are shown in Table 3.

Example 10

To a 100-mL flask were added ethanolamine (2.0g) and THF (20 mL). CF was added dropwise to the above mixture at room temperature₃(OCF₂)_nCO₂Me (n: 2-5, 10 g). A slightly exothermic reaction was observed. The mixture was stirred at room temperature for 1 h. GC analysis of the mixture indicated formation of the desired amide. The reaction mixture was stirred at room temperature overnight. The reaction mixture was poured into water (150mL) and CH was used₂Cl₂(100mL) extraction. The extract was washed with water (3X 50mL), concentrated, and dried in vacuo to give an oil (9.5g), H NMR (CDCl)₃)1.77(br.s, 1H), 3.54(q, J ═ 5Hz, 2H), 3.92(t, J ═ 5Hz, 2H), 6.74(br.s, 1H) ppm. The product is N- (polyoxaperfluoroacyl) -2-aminoethanol.

A100-mL flask was charged with triethylamine (3.0g), THF (60mL), and N- (polyoxaperfluoroacyl) -2-aminoethanol (9.1 g). Methacryloyl chloride (3.1g in THF 20mL) was added dropwise to the above mixture at 10 ℃. The mixture was stirred at room temperature for 3 h. The solid was removed by filtration, the filtrate was poured into water (150mL),by CH₂Cl₂(2X 100 mL). The extract was washed with water (3X 50mL), concentrated, and dried in vacuo to give an oil (10.3 g). It is N- (polyoxaperfluoroacyl) -2-aminoethyl methacrylate.

In a dry box, a 25-mL flask was charged with VAZO 52(25mg), THF (5mL), stearyl methacrylate (1.0g), and N- (polyoxaperfluoroacyl) -2-aminoethyl methacrylate (2.0 g). The mixture was heated to 60 ℃ for 15 h. The reaction mixture became very viscous and was poured into MeOH (50 mL). The precipitated polymer was washed with MeOH (2X 20mL) and dried in vacuo to give a solid (2.5 g). It was a copolymer, and NMR showed about 23.5% F.

A solution of the copolymer was prepared and applied to cotton and nylon fabrics using the method of test method 1. The treated fabrics were tested for water repellency and oil repellency using test methods 2 and 3, respectively. The results are shown in Table 3.

Example 11

A mixture of ethanolamine (13g, 28mmole) and ether (30mL) was cooled to 15 ℃. Perfluoro-2-methyl-3-oxahexanoyl fluoride (33g in ether 50mL) was added dropwise to keep the reaction temperature below 25 ℃. After the addition was complete, the reaction mixture was stirred at room temperature for a further 1 hour. The solid was removed by filtration and the filtrate was washed with hydrochloric acid (0.5N, 30mL), water (2 times, 30mL), sodium bicarbonate solution (0.5N, 20mL), water (30mL) and sodium chloride solution (saturated, 20 mL). Then concentrated and dried overnight under vacuum at room temperature to give 35g of a white solid with 95% yield. H NMR (CDCl)₃)1.67(br.s，1H)，3.57(m，2H)，3.80(t，J＝5Hz，2H)，6.91(br.s，1H)ppm。F NMR(CDCl₃) -81.2(dm, J ═ 148Hz, 1F), -81.7(t, J ═ 7Hz, 3F), -82.7(d, J ═ 3Hz, 3F), -85.2(dm, J ═ 148Hz, 1F), -130.1(s, 2F), -133.2(m, 1F) ppm. The product is N- (perfluoro-2-methyl-3-oxahexanoyl) -2-aminoethanol.

A250-mL flask was charged with triethylamine (8.2g), THF (80mL), and N- (perfluoro-2-methyl-3-oxo-hexanoyl) -2-aminoethanol (25 g). Methacryloyl chloride (8.44g in tetrahydrofuran, 20mL) was added dropwise to the above mixture at 5 ℃. At room temperatureThe mixture was stirred overnight. The reaction mixture was poured into water (200mL) to form two layers. The aqueous layer (upper layer) was extracted with dichloromethane (5 times 50 mL). The combined dichloromethane extract and initial organic layer were washed with water (6 times, 60mL), neutralized with dilute hydrochloric acid (0.5N), dried over anhydrous sodium sulfate, concentrated, and dried in vacuo to give N- (perfluoro-2-methyl-3-oxahexanoyl) -2-aminoethyl methacrylate (27.06g) as an oil in 92% yield. H NMR (CDCl)₃)1.94(m，3H)，3.72(m，2H)，4.33(m，2H)，5.63(m，1H)，6.12(m，1H)，6.88(br.s，1H)ppm。F NMR(CDCl₃)-81.2(dm，J＝148Hz，1F)，-81.7(t，J＝7Hz，3F)，-82.7(d，J＝3Hz，3F)，-85.2(dm，J＝148Hz，1F)，-130.1(s，2F)，-133.4(m，1F)ppm。

In a dry box, a mixture of VAZO 52(47mg), THF (5mL), stearyl methacrylate (1.91g), and N- (perfluoro-2-methyl-3-oxahexanoyl) -2-aminoethyl methacrylate (2.48g) was heated to 60 ℃ for 17 hours. The reaction mixture was poured into methanol (60mL), and the precipitated polymer was washed with methanol and dried in vacuo to give a solid (3.72 g). It is a copolymer of N- (perfluoro-2-methyl-3-oxahexanoyl) -2-aminoethyl methacrylate and octadecyl methacrylate and contains 22% F. A solution of the copolymer was prepared and applied to cotton and nylon fabrics using the method of test method 1. The treated fabrics were tested for water repellency and oil repellency using test methods 2 and 3, respectively. The results are shown in Table 3.

Comparative example A

1H, 1H, 2H, 2H-perfluorooctyl acrylate (2.0g) obtained from SynQuest Fluorochemicals (Alachua, FL), stearyl methacrylate (1.2g), tetrahydrofuran (8mL) and 2, 2' -azobis (2, 4-dimethylvaleronitrile) (23mg) were added to a 20mL vial under a nitrogen atmosphere. The reaction was heated at 60 ℃ for 21 h. After cooling to room temperature, the reaction mixture was poured into methanol (100 mL). The precipitated polymer was washed with methanol (20mL) and dried in vacuo to give a polymer (2.56 g).

A solution of the copolymer was prepared and applied to cotton and nylon fabrics using the method of test method 1. The treated fabrics were tested for water repellency and oil repellency using test methods 2 and 3, respectively. The results are shown in Table 3.

Comparative example B

A250-mL flask was charged with 1H, 1H, 2H, 2H-perfluorodecyl acrylate (20.4g) obtained from SynQuest Fluorochemicals (Alachua, FL), stearyl methacrylate (13.5g), 1-dodecylmercaptan (0.2g), 2' -azobis (2-methylbutyronitrile (VAZO 67, 0.4g), and tetrahydrofuran (100mL), the flask was cooled to 18 ℃ and purged with nitrogen for 30 minutes, the reaction mixture was heated at 66 ℃ for 14.5 hours using a 75 ℃ oil bath to obtain a reaction mixture (115.4g), and the solid content thereof was determined by vacuum-drying a sample (1.82g) of the reaction solution at 80 ℃ to obtain 0.56g of a solid.

A solution of the copolymer was prepared and applied to cotton and nylon fabrics using the method of test method 1. The treated fabrics were tested for water repellency and oil repellency using test methods 2 and 3, respectively. The results are shown in Table 3.

TABLE 3

The data in table 3 show that the examples are comparable or better than the prior art. For cotton fabrics, the perfluoroalkyl chain length of examples 3 and 4 is 4 carbon atoms, thus representing the lower limit for water repellency, but providing superior oil repellency. For nylon, comparative example B has 8 carbon atoms in the perfluoroalkyl chain, and examples of the present invention having 4 or 6 carbon atoms are comparable in terms of water repellency. For nylon, the examples of the present invention have excellent oil repellency.

Claims (13)

1. A composition comprising a copolymer having repeating units of formula I in any order

Formula 1

Wherein

R_fIs a linear or branched perfluoroalkyl group having from about 1 to about 20 carbon atoms, optionally interrupted by at least one oxygen atom, or a mixture thereof,

X³is oxygen or X¹，

Each X¹Independently an organic divalent linking group having from about 1 to about 20 carbon atoms optionally containing oxygen, nitrogen or sulfur or combinations thereof,

g is F or CF₃，

A is an amide of a carboxylic acid or a carboxylic acid,

j is zero or a positive integer and,

X²is an organic linking group and is a hydroxyl group,

y is O, N or S, and Y is,

h is zero when Y is N, h is 1 when Y is O or S,

z is H, straight or branched chain alkyl having from about 1 to about 4 carbon atoms, or halogen,

b is H or

Wherein

R_f、X¹、X³G, A and j are as defined above, with the proviso that when B is H, j is a positive integer,

m is a positive integer,

q is zero or a positive integer when Y is O, and is a positive integer when Y is N or S,

when Y is O, p is zero or a positive integer, when Y is N or S, p is a positive integer, each W is independently

Or [ R ]¹-X¹-Y-C(O)-C(Z)-CH₂]，

Wherein

X¹Y and Z are as defined above,

rx is C (O) O (R)¹)、C(O)N(R²)₂、OC(O)(R¹)、SO₂(R¹)、C₆(R³)₅、O(R¹) Halogen or R¹；

Each R¹Independently is H, C_nH_2n+1、C_nH_2n-CH(O)CH₂、[CH₂CH₂O]_iR⁴、[C_nC_2n]N(R⁴)₂Or [ C_nH_2n]C_nF_2n+1，

n is 1 to 40, and n is,

R⁴is H or C_sH_2s+1，

s＝0-40，

i＝1-200，

Each R²Independently is H or C_tH_2t+1Wherein t is 1 to 20,

each R³Independently is H, COOR¹Halogen, N (R)¹)₂、OR¹、SO₂NHR¹、CH＝CH₂Or SO₃M, wherein R¹As defined above, and

m is H, an alkali metal salt, an alkaline earth metal salt or ammonium.

2. A composition comprising formula 2

Formula 2

Wherein

R_fIs a linear perfluoroalkyl group having from about 1 to about 20 carbon atoms optionally interrupted by at least one oxygen atom or a mixture thereof,

X³is oxygen or X¹，

Each X¹Independently an organic divalent linking group having from about 1 to about 20 carbon atoms optionally containing oxygen, nitrogen or sulfur or combinations thereof,

g is F or CF₃，

A is an amide of a carboxylic acid or a carboxylic acid,

j is zero or a positive integer, provided that when Y is N, j is a positive integer,

X²is an organic linking group and is a hydroxyl group,

y is O, N or S, and Y is,

h is zero when Y is N, h is 1 when Y is O or S,

z is H, straight or branched chain alkyl having from about 1 to about 4 carbon atoms or halogen, and

b is H or

Wherein

R_f、X¹、X³G, A and j are as defined above.

3. A composition comprising formula 3

Formula 3

Wherein

R_fIs a linear perfluoroalkyl group having from about 1 to about 20 carbon atoms optionally interrupted by at least one oxygen atom or a mixture thereof,

X³is oxygen or X¹，

Each X¹Independently an organic divalent linking group having from about 1 to about 20 carbon atoms optionally containing oxygen, nitrogen or sulfur or combinations thereof,

g is F or CF₃，

A is an amide of a carboxylic acid or a carboxylic acid,

j is zero or a positive integer, provided that when Y is N, j is a positive integer,

X²is an organic linking group and is a hydroxyl group,

y is O, N or S, and Y is,

h is zero when Y is N, h is 1 when Y is O or S,

z is H, straight or branched chain alkyl having from about 1 to about 4 carbon atoms or halogen, and

b is H or

Wherein

R_f、X¹、X³G, A and j are as defined above, E is selected from the group consisting of hydroxy, amine, halogen and sulfurAlcohol, provided that when E is an amine, h is zero, and when E is not an amine, h is 1.

4. The composition of claim 1, 2 or 3, wherein R_fIs of the formula F (CF)₂CF₂)_nOr mixtures thereof, wherein n is 2 to about 20.

5. The composition of claim 4, wherein n is 3 or 6.

6. The composition of claim 1, 2 or 3, wherein X¹Selected from the group consisting of linear, branched, or cyclic alkylene, phenyl, arylene, aralkylene, sulfonyl, sulfoxy, sulfonamido, carbonamide, carbonyloxy, urethanylene, ureylene, and combinations thereof.

7. The composition of claim 1, 2 or 3, wherein X²Is R⁵C, wherein R⁵Is H or C₁-C₄An alkyl group.

8. The composition of claim 1 wherein W is

And R_XIs C (O) O (R)¹)、C(O)N(R²)₂、C₆(R³)₅Or a halogen.

9. The composition of claim 1 in the form of an aqueous dispersion or solution.

10. The composition of claim 1, further comprising at least one of

a) Providing an agent that is ironless, easy to iron, shrink-controlled, wrinkle-free, permanent press, moisture-controlled, soft, strong, slip-resistant, static-resistant, snag-resistant, pilling-resistant, stain-removing, water-resistant, oil-resistant, odor-controlling, antimicrobial, or sun-blocking,

b) surfactants, antioxidants, light stabilizers, tints, water, pH adjusters, cross-linking agents, wetting agents, extenders, blowing agents, processing aids, lubricants, blocked isocyanates, non-fluorinated extenders, or

c) Combinations thereof.

11. The composition of claim 1 further comprising repeat units from optional monomers selected from the group consisting of N-methylol (meth) acrylate, hydroxyalkyl (meth) acrylate, alkoxy (meth) acrylate, fluorinated (meth) acrylate, glycidyl (meth) acrylate, octadecyl acrylate, aminoalkyl methacrylate hydrochloride, acrylamide, alkyl acrylamide, vinyl acetate, vinyl stearate, alkyl vinyl sulfone, styrene, vinyl benzoic acid, alkyl vinyl ether, maleic anhydride, vinylidene chloride, vinyl chloride, and olefins.

12. A method of imparting water and oil repellency to a substrate comprising contacting said substrate with the composition of claim 1, 10 or 11.

13. A substrate to which has been applied a composition according to claim 1, 10 or 11.