HK1188234B - Fluorinated copolymer coating copolymer - Google Patents

Description

Fluorinated copolymer coating copolymers

Technical Field

The present invention relates to a coating copolymer for stain resistance, oil repellency and water repellency of hard substrates comprising a copolymer of a fluorinated (meth) acrylate and an amine salt of (meth) acrylic acid.

Background

Hard surfaces such as stone, masonry, concrete, unglazed tile, brick, porous clay, and various other substrates are used decoratively and functionally in indoor and outdoor environments. When untreated, these materials are prone to staining from water, oils and food products such as ketchup, mustard, coffee, cooking oil, wine and beverages. There are a variety of products on the market for treating these substrates. Stone and tile treatment products are typically copolymers comprising fluorinated monomers to provide soil and oil repellency and non-fluorinated monomers to provide water repellency.

Linert et al, in WO199700230, describe compositions comprising fluoroaliphatic groups, carboxyl-containing groups, oxyalkylene groups, and optionally silyl groups that provide porous substrates with repellency to oil-based and water-based stains.

Ueda et al in US20070197717 describe a masonry treatment agent comprising a fluorine-containing monomer, a monomer having at least one acidic group, and a non-fluorinated monomer having a hydrophobic group.

What is needed is a self-dispersing coating copolymer that provides excellent stain resistance, oil repellency, and water repellency properties for hard substrates. These coating copolymers should have good adhesion to the substrate, be able to withstand multiple rinse cycles, and also maintain good stain resistance as well as oil and water repellency properties. These coating copolymers should be easy to produce without the need for extensive processing steps. The present invention meets these needs.

Disclosure of Invention

The invention comprises copolymers of formula (I)

Wherein

R_fIs optionally substituted by one or more-O-, -CH₂-, -CFH-or combinations thereof₂To C₁₀A fluoroalkyl group;

n is an integer of 1 to 10;

R¹and R²Each independently is H or CH₃；

R³Is H, CH₃Or CH₂CH₃；

R⁴Is H, CH₃Or CH₂CH₃；

R⁵Is C₆To C₁₈Alkyl or Y;

R⁶is H, CH₃Or CH₂CH₃；

R⁷Is H, CH₃Or CH₂CH₃；

R⁸Is H, CH₃、CH₂CH₃Or Y;

a is 20 to 60 mole%;

b is 0 to 20 mole%; and is

c is 40 to 70 mole%;

provided that (a + b + c) equals 100;

y is

R⁹Each is independentThe vertical place is alkyl, alkyl alcohol or hydrogen; and is

m is 1 to 10.

The invention also includes a process for producing the copolymer of formula I.

The invention also includes a method of treating a substrate comprising contacting the substrate with the copolymer of formula I.

The invention also includes a substrate treated according to the above method.

Detailed Description

Trademarks herein are shown in upper case.

The term "(meth) acrylic" refers to both methacrylic and acrylic compounds, and the term "(meth) acrylate" refers to both methacrylate and acrylate compounds.

The invention comprises copolymers of formula (I)

Wherein

R_fIs optionally substituted by one or more-O-, -CH₂-, -CFH-or combinations thereof₂To C₁₀A fluoroalkyl group;

n is an integer of 1 to 10;

R¹and R²Each independently is H or CH₃；

R³Is H, CH₃Or CH₂CH₃；

R⁴Is H, CH₃Or CH₂CH₃；

R⁵Is C₆To C₁₈Alkyl or Y;

R⁶is H, CH₃Or CH₂CH₃；

R⁷Is H, CH₃Or CH₂CH₃；

R⁸Is H, CH₃、CH₂CH₃Or Y;

a is 20 to 60 mole%;

b is 0 to 20 mole%; and is

c is 40 to 70 mole%;

provided that (a + b + c) equals 100;

y is

R⁹Each independently is an alkyl, alkyl alcohol or hydrogen; and is

m is 1 to 10.

Preferably, R_fIs C₄To C₆More preferably R_fIs C₆. n is preferably 2 to 6, and n is more preferably 2. Preferably, a is 30 to 50 mole%, b is 1 to 10 mole%, and c is 45 to 65 mole%. Preferably, a is 30 to 60 mole%; b is 0 mol%; and c is from 40 to 70 mole%, more preferably a is from 35 to 45 mole%; b is 0 mol%; and c is 55 to 65 mole%. Preferably, R⁵Is C₆To C₁₈Alkyl, more preferably R⁵Is C₁₀To C₁₆Alkyl, more preferably R⁵Is C₁₂. Preferably, R⁵Is Y. Preferably Y is- (CH) - (CH)₂)_m—Si(OR⁹)₃. Preferably Y isPreferably Y isPreferably Y isPreferably, Y is a 3-aminopropyl functionalized silica nanoparticle, wherein the functionalized nanoparticle is about 100 nm. m is preferably 2 to 8, more preferably 2 to 6. Preferably, R⁹Each independently is an alkyl group, an alkyl alcohol, or hydrogen. Preferably, R⁹Is hydrogen. Preferably, R⁹Is alkyl alcohol. Preferably, R⁹Is alkyl, wherein alkyl is CH₃Or C₂H₅。

In the present invention, a, b and c represent the mole percentages of each individual component used to prepare the copolymers of the present invention. The copolymer of formula I is shown as the random order of monomers in the copolymer indicated by the dashed line. The mole percentages of each reactant (a, b, and c) are selected such that they are within the mole ranges specified above and the sum of the combined components equals 100%. The skilled person can easily select the mole percentages of each monomer within the stated range such that the sum equals 100%. For example, a is any one of 20, 21, 22, 23, etc. up to 60; b is 0, 1, 2, 3, 4, etc. up to 20; and c is 40, 41, 42, 43, 44, etc. up to 70. Combinations of 20 to 60 for any individual value of a, 0 to 20 for any individual value of b, and 20 to 60 for any individual value of c are included within the invention, the sum of which is 100.

In one embodiment, the copolymers of the present invention are prepared via free radical polymerization by contacting fluorinated (meth) acrylate monomers with methacrylic monomers together in the presence of a free radical initiator to produce the copolymer. The copolymer is then subsequently subjected to a neutralization step with one or more amines to produce the corresponding ammonium (meth) acrylate salt or salts. In a second embodiment, the copolymers of the present invention are prepared by contacting a fluorinated (meth) acrylate monomer, (meth) acrylic acid, and one or more amines in the presence of a free radical initiator. In a third embodiment, the copolymer of the present invention is prepared by contacting fluorinated (meth) acrylate monomers, (meth) acrylic acid, and one or more amines in the presence of a free radical initiator, wherein the molar amount of amine is less than the molar amount of copolymer prepared with (meth) acrylic acid comprising fluorinated (meth) acrylate, amine salt of (meth) acrylic acid, and (meth) acrylic acid. In this third example, the corresponding copolymer is then neutralized with one or more amines to produce the corresponding second (meth) acrylate salt or salts.

The copolymers of formula I are prepared via polymerization and are carried out in the presence of one or more free radical initiators. The content of free-radical initiator is from 0.1 to 6.0% by weight, relative to the weight of the monomers used. Initiators which may be used are peroxides, such as, for example, benzoyl peroxide, dilauroyl peroxide, succinic acid peroxide and tert-butyl peroxypivalate, or azo compounds, such as 2, 2 '-azobisisobutyronitrile, 4' -azobis (4-cyanovaleric acid) and azodicarbonamide. Such azo initiators are commercially available under the trade names "VAZO" 67, 52 and 64, from e.i. dupont DE nemours and company (Wilmington, DE), and "V-501" from wakopure industries, Ltd. (Osaka, Japan). The process may also be carried out in the presence of ultraviolet radiation and a photoinitiator such as benzophenone, 2-methylanthraquinone or 2-chlorothioxanthone.

The reaction temperature varies within a wide range, i.e. between room temperature and the boiling point of the reaction mixture. The process is preferably carried out at between about 50 ° and about 90 ℃.

The fluorinated methacrylate monomers used to prepare the copolymer of formula I have the formula (II)

Wherein R is_fIs optionally substituted by one or more-O-, -CH₂-, -CFH-or combinations thereof₂To C₁₀Fluoroalkyl, n is an integer from 1 to 10, and R¹Is H or CH₃。R_fExamples of (A) include, but are not limited to, CF₃(CF₂)_x-、CF₃(CF₂)_x(CH₂CF₂)_y-、CF₃(CF₂)_yO(CF₂)_yAnd CF₃(CF₂)_yOCFH(CF₂)_z-, wherein each x is independently 1 to 9, each y is independently 1 to 3, and each z is independently 1 to 4. R_fPreferably C₄To C₈Fluoroalkyl radical, R_fMore preferably C₆A fluoroalkyl group. n is preferably 2 to 6, and n is more preferably 2.

The fluorinated (meth) acrylates of formula (II) are synthesized from the corresponding alcohols. These fluorinated methacrylate compounds are prepared by esterification with acrylic or methacrylic acid with the corresponding alcohol or by transesterification with methyl acrylate or methyl methacrylate. These preparations are well known and described in U.S. Pat. No. 3,282,905, which is incorporated herein by reference.

Fluorinated (meth) acrylates useful in the present invention are prepared from compounds having the formula CF₃(CF₂)_x(CH₂)_nOH, wherein each x is independently 1 to 9, and n is 1 to 10, are commercially available from e.i. dupont DE nemours company, Wilmington, DE. These alcohols can also be prepared by reaction and hydrolysis of the corresponding perfluoroalkyl iodides with oleum according to the method described in WO95/11877, which is incorporated herein by reference. These alcohols are available as a mixture of homologue distributions or fractionated into individual chain lengths.

Fluorinated (meth) acrylates useful in the present invention are prepared from compounds having the formula CF₃(CF₂)_y(CH₂CF₂)_p(CH₂)_nAlcohol preparation of OH, wherein each y is independently 1 to 9, each p is independently 1 to 2, and n is 1 to 10. These alcohols are prepared by reacting perfluoroalkyl iodides with vinylidene fluorideTelomerization of ethylene followed by incorporation of ethylene. A detailed discussion of the vinylidene fluoride reaction is described in "Synthesis of fluorinated polymers" section 1 of Balague et al, "thermoplastic of vinylidenefluoride with fluorinated alkyldioxides" (J.Fluor.chem. (1995), 70(2), 215-23. the reaction details of the ethylene incorporation reaction are described in U.S. Pat. No. 3,979,469. the alcohol is prepared using oleum and hydrolysis as described above.

Fluorinated (meth) acrylates useful in the present invention are prepared from compounds having the formula CF₃(CF₂)_yO(CF₂)_y-(CH₂)_nOH, wherein each y is independently 1 to 3, and n is 1 to 10. These alcohols are of the formula CF₃(CF₂)_yO(CF₂)_yI, wherein each y is independently 1 to 3. These iodides were prepared by reacting perfluorovinyl ethers with ICl/HF and BF according to the method described in U.S. Pat. No. 5,481,028₃Reaction, whereby said document is incorporated by reference. Ethylene incorporation and alcohol conversion are as described above.

The (meth) acrylic acid salts useful in the present invention are prepared by contacting (meth) acrylic acid with one or more amines in a solvent. The contacting of the one or more amines with the (meth) acrylic acid can be carried out before, during, or after polymerization has occurred. The (meth) acrylate salt may also be prepared in one or more steps. For example, the polymer may contain monomeric repeat units of (meth) acrylic acid and a (meth) acrylate salt formed from one or more amines. These (meth) acrylic acid repeat unit monomers can then be neutralized with one or more amines to prepare the corresponding salts.

The amines useful in the present invention are those capable of forming salts with (meth) acrylic acid easily. The amines useful in the present invention have the general formula NR₃Wherein each R is independently R as defined above³、R⁴、R⁵、R⁶、R⁷And R⁸. Amines useful in the present invention include, but are not limited to, ammonium hydroxide, alkylamines, alkanolamines, and the like,Alkoxyamines, aminoalkyl sulfates, aminoalkyl sulfonates, aminoalkyl phosphonates, and aminoalkyl silanes. Specific examples of linear amines useful in the present invention include, but are not limited to, ammonium hydroxide, monomethylamine, dimethylamine and trimethylamine, monoethylamine, diethylamine, triethylamine, monoethanolamine, diethanolamine and triethanolamine, 2-aminoethanesulfonic acid, 2-aminoethanol hydrogen sulfate, dodecylamine and N-N-dimethyldodecylamine, butylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, hexadecylamine, dibutylamine, dioctylamine, tripentylamine, tripropylamine, tributylamine, trilaurylamine, 3-methoxypropylamine, N-dimethylethylamine, N-dimethylbutylamine, N-diethylbutylamine, N-methyldibutylamine, N-dimethyloctylamine, N-dimethyldodecylamine. Specific examples of branched amines include, but are not limited to, isopropylamine, isobutylamine, tert-butylamine, pentylamine, diisopropylamine, diisobutylamine, 3-isopropoxypropylamine, 2-ethylhexylamine. Specific examples of cyclic amines include, but are not limited to, cyclopentylamine, cyclohexylamine, cyclodecamine, 1-adamantylamine, dicyclohexylamine, N-dimethylcyclohexylamine. Specific examples of arylamines include, but are not limited to, N-diethylaniline, N-dimethylbenzylamine, 4-N, N-trimethylaniline, 3-phenyl-1-propylamine. Specific examples of siloxane-containing amines include, but are not limited to, (3-aminopropyl) trimethoxysilane, (3-aminopropyl) triethoxysilane, N-dimethylaminopropyl trimethoxysilane, N-dimethylaminopropyl triethoxysilane, 3-aminopropyl-functionalized silica nanoparticles, (trimethylsilyl) methylamine, N-diethyltrimethylsilylamine, 3- (2-aminoethylamino) propyldimethoxymethylsilane, (3-aminopropyl) tris (trimethylsiloxy) silane.

The copolymers of the invention are preferably in the form of dispersions. Preferably as an aqueous dispersion.

The present invention also includes a method of treating a substrate to provide stain resistance, oil repellency, and water repellency comprising contacting the substrate surface with the copolymer of formula I. The copolymers of the invention are in the form of aqueous dispersions. The dispersion is added separately or may optionally contain additives or treatments. The copolymers of the present invention are applied to a substrate by known methods including, but not limited to, brushing, spraying, rolling, dipping, padding, doctor blading, wiping, dipping techniques, and wet on wet (web) printing processes. Those skilled in the art understand that the type of substrate, i.e., hard surface or textile, will determine the appropriate manner of application. For example, in the case of hard surfaces such as brick, application of the copolymer is carried out by brushing or spraying. In the case of fibrous substrates such as cotton or nylon, padding or impregnation is selected to apply the copolymer to the substrate.

The present invention also includes one or more substrates treated according to the methods of the present invention. These substrates include hard surface substrates or fibrous substrates. Examples of hard surface substrates include, but are not limited to, unglazed concrete, brick, tile, stone such as limestone and Salitz tile, mortar, stucco, composite materials such as terrazzo, wall and ceiling panels (including those formed from gypsum board, marble, sculpture, monument, and wood). Suitable fibrous substrates include, but are not limited to, woven and non-woven fibers, yarns, fabrics, fabric blends, textiles, nonwovens, paper, leather, mats, and carpets. These are made from natural or synthetic fibers including cotton, cellulose, wool, silk, polyamide, polyester, polyolefin, polyacrylonitrile, polypropylene, rayon, nylon, aramid, and acetate. The treated substrates have improved repellency to water, oil and grease and provide protection against staining.

The copolymers, methods, and treated substrates of the present invention are useful for providing stain resistance as well as water and oil repellency to a variety of substrates. The copolymers are readily adaptable to a variety of applications.

Examples of the invention

Materials and test methods

Application and testing of polymers on surfaces of natural stone

The copolymers of the invention were applied in dispersion form and tested on limestone and Salti tile natural stone. Natural stone is wiped with a moist SONTARA wipe (commercially available from e.i. dupont DE nemours and company (Wilmington, DE)). The stone was allowed to dry overnight at room temperature and was divided into 9 equal parts with adhesive tape. Two polymer wt% solutions of the copolymer of the invention were applied as a dispersion to each portion using a brush. The amount of polymer applied was determined by recording the difference in weight of the polymer dope before and after application. Each section was brushed with the dispersion to form a uniform coating. Four main brushes are typically used to cover the surface. After 15 minutes, any excess polymer on the surface was removed by wiping the surface with a wipe. The coating was allowed to dry overnight and then the performance was assessed by the test method described below.

Test method 1: beading and beading test

Individual water and vegetable oil droplets (about 4 to 5mm diameter, or 0.04 to 0.05mL volume) were placed on the coating surface using a glass pipette. The droplets were allowed to stand on the surface for five minutes and the degree of beading (i.e., contact angle) was determined visually. The beading degree was scored from 0 to 5 as shown in table 1 below. A higher score is an indication of excellent repellency performance.

Table 1: water and oil contact angle measurement

Scoring	Contact angle (°)	Significance of
			0	＜10	Penetration of liquids
1	10 to 25	Difference of pearl formation
			2	25 to 45	Beading general
3	45 to 75	Good pearl effect
			4	75 to 90	Beading very well
5	90 to 120	Excellent beading property

The test method 2: 24 hour stain test：

A drop of various common indoor stains (mustard, ketchup, vegetable oil, salad dressing, coffee) was placed individually on the treated tile surface and allowed to stand for 24 hours. The stains were removed by brushing with water and nylon bristles. The treated stone was allowed to dry at room temperature (72 to 78 ° f) until the stone was completely dry (about 12 to 24 hours). The stain residue remaining on the tile surface was visually rated as follows from 0 to 4. The lower the score, the better the performance. Liquid stains that do not leave visible surface stains but penetrate deeply into the substrate are scored 4 points. The staining procedure was repeated 4 times and averaged.

Table 2: 24 hour staining score。

The total stain score was calculated by summing all stain scores of the test samples, and the performance was compared to the total maximum possible score (i.e. the highest score of 20 for 5 stains).

Test method 3: water repellency test

The water repellency of the Salti tile substrates was tested according to AATCC (American society for textile dyeing workers) Standard test method No. 193-2004. The test determines the resistance of the treated substrates to wetting by aqueous test solutions (see table 3 for test solution copolymers). Drops of water-alcohol mixture test solutions (about 5mm diameter or 0.05mL volume) with different surface tensions were placed on the treated substrates and the degree of surface wetting was determined visually. Three drops of test solution #1 were placed on the substrate. After 10 seconds, the droplets were removed by using vacuum suction. If no liquid penetration or partial absorption is observed (deeper wet-spot appearance on the substrate), the test is repeated with test liquid 2 and the test liquid number is progressively increased until liquid penetration (deeper wet-spot appearance on the substrate) is observed. The score was the highest test liquid number that did not penetrate into the substrate. Higher scores indicate better water repellency and excellent performance

The composition of the water repellency test liquid is shown in table 3 below.

TABLE 3

Test method 4: oil repellency test

The basic oil repellency of the treatments was determined using the revision of AATCC standard test method No.118 and was corrected as follows. A series of drops of organic liquid, identified in table 4 below, were applied to the substrate. Starting with the lowest numbered test liquid (repellency grade number 1), a drop (about 5mm diameter or 0.05mL volume) of liquid is placed at each of 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, three drops of the highest numbered liquid are placed in close proximity and again observed for 30 seconds. The process is continued until a test liquid appears in which 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. Higher values indicate greater oil repellency.

TABLE 4

^*NUJOL (commercially available from Plough, Inc. (Memphis, Tennesse)) is a mineral oil having a Saybolt viscosity of 360/390 at 38 ℃ and a specific gravity of 0.880/0.900 at 15 ℃.

Examples of the invention

Example 1

The copolymer of formula I is prepared in an organic solvent. Will have the formula CF₃(CF₂)₅CH₂CH₂OC(O)C(CH₃)＝CH₂Perfluoroalkyl methacrylate (10g, 23.1m moles), methacrylic acid (3.3g, 38.4 mmol), (3-aminopropyl) trimethoxysilane (0.14g, 0.77 mmol), triethylamine (3.8g, 37.6 mmol) and tetrahydrofuran (THF, 62g) were added to a nitrogen purged reaction vessel equipped with a magnetic stir bar and condenser. The reaction vessel was then purged with nitrogen at room temperature (about 23 ℃) for one hour. The reaction vessel was then heated to 60 ℃ and initiator (0.27g in 2g isopropanol, VAZO67, commercially available from e.i. dupont DE nemours company, Wilmington, DE) was added to the reaction flask using a syringe. The temperature of the reaction vessel was raised to 6 deg.C8 ℃ and held at 68 ℃ for 20 minutes. The temperature was then reduced to 65 ℃ and stirred for 18 hours. The reaction mixture was then cooled to room temperature (23 ℃) and the solid settled to the bottom of the flask. The liquid supernatant was decanted. The solid was pulverized and dissolved in water (90mL) and mixed with the liquid supernatant. The mixture was then concentrated in vacuo to 13.5 wt.% solids in water. It was then further diluted with water and tested according to the test method described above.

Example 2

Will have the formula CF₃(CF₂)₅CH₂CH₂OC(O)C(CH₃)＝CH₂Perfluoroalkyl methacrylate (50g, 115.5 mmol), methacrylic acid (16.5g, 192 mmol) and tetrahydrofuran (THF, 155g) were charged to a nitrogen purged reaction vessel equipped with a magnetic stir bar and condenser. The reaction vessel was then purged with nitrogen at room temperature (about 23 ℃) for one hour. The reaction was then heated to 60 ℃ and stirred for five minutes. Initiator (1.35g in 10g THF, VAZO67) was added to the reaction flask using a syringe. The temperature of the reaction mixture was raised to 68 ℃ and maintained at 68 ℃ for 16 hours. The reaction mixture was then cooled to room temperature (23 ℃) and analyzed as a fluorinated methacrylate/methacrylic acid copolymer as 33 wt.% solids in THF.

Fluorinated methacrylate/methacrylic acid copolymer in THF (23.2g), (N, N-dimethylaminopropyl) trimethoxysilane (0.1g, 0.44 mmol), triethylamine (2.2g, 21.6 mmol) and THF (25g) were added to a nitrogen purged reaction vessel equipped with a magnetic stir bar and condenser. The reaction mixture was heated to 68 ℃ and stirred under a nitrogen blanket for two hours. Water (50mL) was then added and the mixture was stirred at 68 ℃ for an additional 30 minutes. The reaction mixture was then cooled to room temperature. The mixture was concentrated under vacuum to remove residual THF and a 16.5 wt% solid dispersion in water was obtained and tested according to the test method described above.

Example 3

Fluorinated methacrylate/methacrylic acid copolymer in THF (25.5g) prepared in example 2, 3-aminopropyl functionalized silica nanoparticles (1g, 3 wt% in ethanol) and THF (25g) were added to a nitrogen purged reaction vessel equipped with a magnetic stir bar and condenser. The reaction mixture was heated to 68 ℃ and stirred under a nitrogen blanket for 1 hour. To the reaction mixture was added additional 3-aminopropyl functionalized silica nanoparticles (1g, 3 wt% in ethanol), followed by addition of triethylamine (0.9g, 8.9 mmol). Water (50mL) was then added and the mixture was stirred at 68 ℃ for an additional 30 minutes. The reaction mixture was then cooled to room temperature. The mixture was concentrated in vacuo to remove residual THF and a 12.4 wt% solid dispersion in water was obtained. It was then further diluted with water and tested according to the test method described above.

Example 4

Will have the formula CF₃(CF₂)₅CH₂CH₂OC(O)C(CH₃)＝CH₂Perfluoroalkyl methacrylate (10g, 23.1 mmol), methacrylic acid (16.5g, 192 mmol), triethylamine (1.9g, 18.9 mmol) and tetrahydrofuran (28.7g) were charged to a nitrogen purged reaction vessel equipped with a magnetic stir bar and a condenser. The reaction vessel was then purged with nitrogen at room temperature (about 23 ℃) for one hour. The reaction was then heated to 60 ℃. Initiator (0.27g, 1g in THF, VAZO67) was added to the reaction flask using a syringe. The temperature of the reaction mixture was raised to 68 ℃ and maintained at 68 ℃ for 16 hours. The reaction mixture was then cooled to room temperature (23 ℃) and analyzed as a fluorinated methacrylate/methacrylic acid/triethylammonium methacrylate copolymer as a 30 wt.% solid in THF.

To a fluorinated methacrylate/methacrylic acid/triethylammonium methacrylate copolymer (28g) in THF in a nitrogen purged reaction vessel equipped with a magnetic stir bar and condenser was added 2-aminoethanesulfonic acid (1.0g, 8.1 mmol in 23.2g water). The reaction mixture was heated to 45 ℃ and stirred under a nitrogen blanket for one hour. The mixture was concentrated in vacuo to remove residual THF and a 24.0 wt% solid dispersion in water was obtained. It was then further diluted with water and tested according to the test method described above.

Example 5

To a methacrylate/methacrylic acid/triethylammonium methacrylate copolymer (26g) fluorinated in THF as prepared in example 4 above, was added 2-aminoethanol hydrogen sulfate (1.1g, 8.1 mmol) in 23.2g of water. The reaction mixture was heated to 68 ℃ and stirred under a nitrogen blanket for 1 hour. The reaction mixture was then cooled to room temperature. The mixture was concentrated in vacuo to remove residual THF and a 22.0 wt% solid dispersion in water was obtained. It was then further diluted with water and tested according to the test method described above.

Example 6

Will have the formula CF₃(CF₂)₅CH₂CH₂OC(O)C(CH₃)＝CH₂Perfluoroalkyl methacrylate (10g, 23.1 mmol), methacrylic acid (2.3g, 26.9 mmol), 2-aminoethanesulfonic acid (1.0g, 8.1 mmol) and tetrahydrofuran (28.7g) were charged to a nitrogen purged reaction vessel equipped with a magnetic stir bar and condenser. The reaction vessel was then purged with nitrogen at room temperature (about 23 ℃) for one hour. The reaction was then heated to 60 ℃. Initiator (0.27g, 1g in THF, VAZO67) was added to the reaction flask using a syringe. The temperature of the reaction mixture was raised to 68 ℃ and maintained at 68 ℃ for 16 hours. The reaction mixture was then cooled to room temperature (23 ℃) and analyzed as a fluorinated methacrylate/methacrylic acid/methacrylate salt of 2-aminoethanesulfonic acid copolymer as 30% by weight solids in THF.

Ammonium hydroxide (14.6M, 3.9g, 23.1 mmol in water) was then added to the reaction mixture, and the reaction mixture was heated to 45 ℃ and stirred under a nitrogen blanket for one hour. The mixture was cooled to room temperature and concentrated in vacuo to remove residual THF and obtain a solid dispersion of 23.9 wt% in water. It was also diluted with water and tested according to the test method described above.

Example 7

Will have the formula CF₃(CF₂)₅CH₂CH₂OC(O)C(CH₃)＝CH₂Perfluoroalkyl methacrylate (10g, 23.1 mmol), methacrylic acid (2.3g, 26.9 mmol), N-dimethyldecylamine (0.86, 4.65 mmol), and tetrahydrofuran (30.7g) were charged to a nitrogen purged reaction vessel equipped with a magnetic stir bar and condenser. The reaction vessel was then purged with nitrogen at room temperature (about 23 ℃) for one hour. The reaction was then heated to 60 ℃. Initiator (0.27g, 1g in THF, VAZO67) was added to the reaction flask using a syringe. The temperature of the reaction mixture was raised to 68 ℃ and maintained at 68 ℃ for 16 hours. The reaction mixture was then cooled to room temperature (23 ℃) and analyzed as a fluorinated methacrylate/methacrylic acid/N, N-dimethyldecylammonium methacrylate copolymer as a 17.4 wt.% solid in THF.

Fluorinated methacrylate/methacrylic acid/N, N-dimethyldecylammonium methacrylate copolymer (6.6g in THF) was heated to 45 deg.C and ammonium hydroxide (14.6M, 0.81g in 24.8g water) was added. The reaction mixture was stirred at 45 ℃ for one hour under a nitrogen blanket. The mixture was concentrated in vacuo to remove residual THF and a 17.4 wt% solid dispersion in water was obtained. It was then further diluted with water and tested according to the test method described above.

Example 8

The fluorinated methacrylate/methacrylic acid/N, N-dimethyldecylammonium methacrylate copolymer prepared in example 7 (6.6g) was heated to 45 ℃ in a reaction vessel equipped with a magnetic stir bar and condenser. To the reaction mixture was added triethylamine (1.13g, 11.1 mmol) dropwise. The mixture was stirred at 45 ℃ for one hour. To the reaction mixture was added water (24.8 g). The mixture was concentrated in vacuo to remove residual THF and a 19.7 wt% solid dispersion in water was obtained. It was then further diluted with water and tested according to the test method described above.

Example 9

Will have the formula CF₃(CF₂)₅CH₂CH₂OC(O)C(CH₃)＝CH₂Perfluoroalkyl methacrylate (10g, 23.1 mmol), methacrylic acid (2.3g, 26.9 mmol), dodecylamine (0.86g, 4.65 mmol) and tetrahydrofuran (30.7g) were charged to a nitrogen purged reaction vessel equipped with a magnetic stir bar and condenser. The reaction vessel was then purged with nitrogen at room temperature (about 23 ℃) for one hour. The reaction was then heated to 60 ℃. Initiator (0.27g, 1g in THF, VAZO67) was added to the reaction flask using a syringe. The temperature of the reaction mixture was raised to 68 ℃ and maintained at 68 ℃ for 16 hours. The reaction mixture was then cooled to room temperature (23 ℃) and analyzed as a fluorinated methacrylate/methacrylic acid/dodecylammonium methacrylate copolymer as a 30 wt.% solid in THF.

Fluorinated methacrylate/methacrylic acid/dodecylammonium methacrylate copolymer (6.6g in THF) and ammonium hydroxide (14.6M, 0.81g, 13.4 mmol in 24.8g water) were charged to a nitrogen purged reaction vessel equipped with a magnetic stir bar and condenser. The reaction mixture was heated to 45 ℃ and stirred under a nitrogen blanket for one hour. The mixture was concentrated in vacuo to remove residual THF and a 20.1 wt% solid dispersion in water was obtained. It was then further diluted with water and tested according to the test method described above.

Example 10

The fluorinated methacrylate/methacrylic acid/dodecylammonium methacrylate copolymer prepared in example 9 (6.6g) was heated to 45 ℃ in a reaction vessel equipped with a magnetic stir bar and a condenser. To the reaction mixture was added triethylamine (1.13g, 11.1 mmol) dropwise. The mixture was stirred at 45 ℃ for one hour. To the reaction mixture was added water (24.8 g). The mixture was concentrated in vacuo to remove residual THF and a 22.3 wt% solid dispersion in water was obtained. It was then further diluted with water and tested according to the test method described above.

Example 11

Will have the formula CF₃(CF₂)₅CH₂CH₂OC(O)C(CH₃)＝CH₂Perfluoroalkyl methacrylate (2.5g, 5.75 mmol), methacrylic acid (0.82g, 9.6 mmol), diethylaminomethyl phosphonate (0.8g, 4.8 mmol) and tetrahydrofuran (11.2g) were charged to a nitrogen purged reaction vessel equipped with a magnetic stir bar and condenser. The reaction vessel was then purged with nitrogen at room temperature (about 23 ℃) for one hour. The reaction was then heated to 60 ℃. The initiator (0.35g of VAZO67 in 0.5g of thf) was added to the reaction flask using a syringe. The temperature of the reaction mixture was raised to 68 ℃ and maintained at 68 ℃ for 16 hours. The reaction mixture was then cooled to room temperature (23 ℃) and analyzed as a fluorinated methacrylate/methacrylic acid salt of diethylaminomethylphosphonic acid copolymer (28% by weight solids in THF). The copolymer (14.8g in THF) was heated to 45 deg.C and ammonium hydroxide (0.290g (28 wt% NH) was added₃) 4.8 mmol) in 24g of water). The reaction mixture was stirred at 55 ℃ for one hour under a nitrogen blanket. The mixture was concentrated in vacuo to remove residual THF and a 19.4 wt% solid dispersion in water was obtained. It was then further diluted with water and tested according to the test method described above.

Examples 1 to 11 were applied to a surface of a sali tile and tested for oil repellency according to test method 1, oil and water beading, test method 2, 24 hour stain test, test method 3, water repellency and test method 4, according to the methods described above. Untreated salti tiles were also tested for comparison. The results are listed below in table 5 for water and oil beading, table 6 below for stain test results, and table 7 below for test methods 3 and 4 for oil and water repellency.

Table 5: oil and water beading scores for stone and tile (best on a scale of 0 to 5), Sal Tislight tiles

Examples of the invention	Oil beading	Beading of water
			Control substance	0	0
Example 1	4	4
			Example 2	5	5
Example 3	2	3
			Example 4	4	4
Example 5	5	5
			Example 6	3	3
Example 7	3	3
			Example 8	3	3
Example 9	3	3
			Example 10	4	4
Example 11	3	3

Examples 1 to 11 performed well when applied to the surface of a sali tile compared to untreated sali tiles.

Table 6: stain scores (0-4 score, 0 best, 4 worst or representing deep stain penetration), saerthio ceramic tile

Examples of the invention	Mustard	Tomato sauce	Vegetable oil	Seasoning	Coffee	Total of
							Control substance	3	3	4	4	4*	18
Example 1	2	0	2	1	0	5

Example 2	2	3	3	3	1	12
							Example 3	3	2	1	3	2	11
Example 4	1	1	0	0	3	5
							Example 5	2	2	0	1	3	8
Example 6	2	1	0	2	3	8
							Example 7	0	0	0	0	0	0
Example 8	1	1	1	1	1	5
							Example 9	0	0	0	0	0	0
Example 10	0	0	0	0	0	0
							Example 11	1	1	0	1	0	3

^*Representing deep penetration of the stain into the substrate

Examples 1 to 11 performed well when applied to the surface of a sali tile for stain resistance. In examples 7, 8 and 9, no significant stain remained after the test.

Table 7: stone and tile Teflon kit test scores (water: 0-12 score, 12 is the most Preferably; oil: 0-8, 8 being the most preferred), Salti tile

Examples of the invention	Water kit testing	Oil kit testing
			Control substance	0	0
Example 1	10	4
			Example 2	5	4
Example 3	6	6
			Example 4	9	6
Example 5	8	5
			Example 6	9	6
Example 7	10	6
			Example 8	11	6
Example 9	10	6
			Example 10	10	6
Example 11	6	3

Examples 1 to 11 performed well when applied to the surface of a sali tile, when oil and water repellency was compared to untreated.

Claims (10)

1. A copolymer comprising formula (I)

Wherein

R_fIs optionally substituted by one or more-O-, -CH₂-, -CFH-or combinations thereof₄To C₆A fluoroalkyl group;

n is an integer of 1 to 10;

R¹and R²Each independently is H or CH₃；

R³Is H, CH₃Or CH₂CH₃；

R⁴Is H, CH₃Or CH₂CH₃；

R⁵Is C₆To C₁₈Alkyl or Y;

R⁶is H, CH₃Or CH₂CH₃；

R⁷Is H, CH₃Or CH₂CH₃；

R⁸Is H, CH₃、CH₂CH₃Or Y;

a is 30 to 50 mole%;

b is 1 to 10 mole%; and is

c is 45 to 65 mole%;

with the proviso that (a + b + c) equals 100 mol%;

y is

R⁹Each independently is an alkyl, alkyl alcohol or hydrogen; and is

m is 1 to 10.

2. The copolymer of claim 1, wherein R⁵Is C₆To C₁₈An alkyl group.

3. The copolymer of claim 1, wherein R⁵Is Y, wherein Y is

R⁹Each independently is an alkyl, alkyl alcohol or hydrogen; and is

m is 1 to 10.

4. The copolymer of claim 1, wherein R⁵Is C₆To C₁₈An alkyl group; r⁸The molecular weight of the compound is Y,

wherein Y is

R⁹Each independently is an alkyl, alkyl alcohol or hydrogen; and is

m is 1 to 10.

5. The copolymer of claim 1, wherein the copolymer is in the form of a dispersion.

6. A method of providing water repellency, oil repellency, and stain resistance to a substrate surface comprising contacting said substrate surface with a copolymer of formula (I)

Wherein

R_fIs optionally substituted by one or more-O-, -CH₂-, -CFH-or combinations thereof₄To C₆A fluoroalkyl group;

n is an integer of 1 to 10;

R¹and R²Independently is H or CH₃；

R³Is H, CH₃Or CH₂CH₃；

R⁴Is H, CH₃Or CH₂CH₃；

R⁵Is C₆To C₁₈Alkyl or Y;

R⁶is H, CH₃Or CH₂CH₃；

R⁷Is H, CH₃Or CH₂CH₃；

R⁸Is H, CH₃Or CH₂CH₃Or Y;

a is 30 to 50 mole%;

b is 1 to 10 mole%; and is

c is 45 to 65 mole%;

with the proviso that (a + b + c) equals 100 mol%;

y is

R⁹Each independently is an alkyl, alkyl alcohol or hydrogen; and is

m is 1 to 10.

7. The process of claim 6, wherein the copolymer of formula I is in the form of an aqueous dispersion.

8. The method of claim 6, wherein the contacting is by brushing, spraying, rolling, dipping, padding, doctor blade, wiping, dipping technique, or wet-on-wet printing.

9. The method of claim 6, wherein the substrate is unglazed concrete, brick, tile, stone, mortar, stucco, composite, gypsum board, marble, statuary, monuments, or wood.

10. A substrate treated by the method of claim 6, which is unglazed concrete, brick, tile, stone, mortar, plaster, composite, gypsum board, marble, statuary, monuments, or wood.