HK1117179B - Fluorocarbon-grafted polysiloxanes - Google Patents

Description

Fluorocarbon grafted polysiloxane

Background

Silicone-based and fluorochemical-based compositions have been disclosed for protecting hard substrate surfaces, such as mineral substrates, and soft substrate surfaces, such as fibrous substrates. Although siloxane-based treatments provide water repellency at a relatively low price per square meter and have good weatherability, they are inadequate in terms of oil and stain repellency (see, e.g., Stempf, a.; Muller, p.; Pabon, m.; Corpart, j.m. int.j. retrieval Buildings & motors 1999, 5, 273-) -288). Treatments based on fluorochemicals can provide both oil and water repellency properties, but are relatively costly due to the high fluorine content required.

Atherton in U.S. Pat. No. 3,859,320 discloses compounds in which the perfluoroalkyl group (R) is_f) Attached to the amine-substituted poly (dialkylsiloxane) via an oxygen and/or alkylene group and through a sulfonamide group as shown in Structure 1 below, wherein- (C)₆H₄) -O-or-CH ═ CH-O-at R_fWith SO₂Between the groups. With those in R_fWith SO₂Compounds of structure 1 are relatively difficult to synthesize compared to compounds that do not contain oxygen and/or alkylene groups between the groups.

--[-Si(CH₃)-O-]-

|

R-NH-SO₂-CH＝CH-O-R-R_fStructure 1

It would be desirable to combine the advantages of silicones and fluorochemicals to provide improved oil, water and stain repellency to hard and soft surfaces with readily synthesized compounds. It is desirable that such compounds have improved fluorine efficiency. The present invention provides such a composition.

Summary of The Invention

The present invention includes a composition comprising a perfluoroalkylsulfonamide-grafted poly (alkylsiloxane) polymer prepared by contacting a polyfluoroalkylsulfonyl halide of formula I with a silane compound of formula II, III or IV,

R_f-R¹-SO₂X I

wherein

R_fIs a linear or branched perfluoroalkyl group having from about 2 to about 20 carbon atoms,

R¹is a divalent linking group C_kH_2kWherein k is 0 to about 20, and

x is a halogen atom or a halogen atom,

formula II:

[0016](E-(O)_q)₃Si-O-(Si(R²)₂-O)_m-[Si(R³-NHR⁴)(R²)O]_n-Si-((O)_q-E)₃

[0017]formula III:

HR⁴N-R³-Si(R²)₂-O-[Si(R²)₂-O]_m-[Si(R³-NHR⁴)(R²)O]_n-Si(R²)₂-R³-NHR⁴

formula IV:

[0020]HR⁴N-R³-Si(R²)₂-O-[Si(R²)₂-O]_m-Si-((O)_q-E)₃

[0021]wherein

Each R²Independently is C₁To C₈An alkyl group, a carboxyl group,

each one of which isR³Independently a divalent group containing carbon, hydrogen, and optionally at least one of nitrogen and sulfur,

each R⁴Independently is H or C₁To C₈An alkyl group, a carboxyl group,

each E is independently C₁To C₈A branched or linear alkyl group, which may be,

each q is independently zero or 1,

m is a positive integer, n is independently zero or a positive integer, such that n/(m + n) is zero or has a positive fraction up to a value of about 0.7, and at a temperature of 20 ℃ at 0.1s^-1Has a viscosity of less than or equal to 10000mpa.s at a shear rate of (a).

The present invention also includes a process for preparing perfluoroalkyl sulfonamide-grafted poly (alkylsiloxanes), which comprises contacting a polyfluoroalkylsulfonyl halide of formula I with a silane compound of formula II, III or IV,

R_f-R¹-SO₂X I

wherein

R_fIs a linear or branched perfluoroalkyl group having from about 2 to about 20 carbon atoms,

R¹is a divalent linking group C_kH_2kWherein k is 0 to about 20, and

x is a halogen atom or a halogen atom,

formula II:

(E-(O)_q)₃Si-O-(Si(R²)₂-O)_m-[Si(R³-NHR⁴)(R²)O]_n-Si-((O)_q-E)₃

formula III:

HR⁴N-R³-Si(R²)₂-O-[Si(R²)₂-O]_m-[Si(R³-NHR⁴)(R²)O]_n-Si(R²)₂-R³-NHR⁴

formula IV:

HR⁴N-R³-Si(R²)₂-O-[Si(R²)₂-O]_m-Si-((O)_q-E)₃

wherein

Each R²Independently is C₁To C₈An alkyl group, a carboxyl group,

each R³Independently a divalent group containing carbon, hydrogen, and optionally at least one of nitrogen and sulfur,

each R⁴Independently is H or C₁To C₈An alkyl group, a carboxyl group,

each E is independently C₁To C₈A branched or linear alkyl group, which may be,

each q is independently zero or 1,

m is a positive integer, n is independently zero or a positive integer, such that n/(m + n) is zero or has a positive fraction up to a value of about 0.7, and at a temperature of 20 ℃ at 0.1s^-1Has a viscosity of less than or equal to 10000mpa.s at a shear rate of (a).

The present invention also includes a method of providing oil repellency, water repellency, and stain resistance to a substrate surface comprising contacting said surface with the above-described polymer composition.

The invention also includes substrates treated according to the above method.

Detailed Description

Trademarks are shown herein in upper case.

The compounds provided by the present invention combine the advantages of siloxanes and fluorine-containing compounds with improved fluorine efficiency. "fluorine efficiency" refers to the ability to achieve repellency properties equivalent to those obtained using higher levels of fluorine by using a minimum amount of fluorine-containing compound when applied to a hard or soft substrate.

The present invention includes polymers formed by contacting, optionally but preferably in the presence of a suitable acid acceptor in a suitable inert solvent, at least one poly (dialkylsiloxane) having an amine-terminated side with at least one perfluoroalkylethyl sulfonyl halide

A chain, an amine-terminated end group, or both, the perfluoroalkylethyl sulfonyl halide having the structure of formula I. Polyfluoroalkylsulfonyl halides suitable for practicing the present invention have the following structure:

R_f-R¹-SO₂x formula I

Wherein

R_fIs a linear or branched perfluoroalkyl group having from about 2 to about 20 and preferably from about 4 to about 16 carbon atoms,

R¹is a divalent linking group-C_kH_2k-, where k is from 0 to about 20, preferably from 0 to about 10, more preferably from 0 to about 2, and

x is a halogen selected from F, Cl, Br or I, and preferably Cl or Br. Preferably of formula F (CF)₂CF₂)_pCH₂CH₂SO₂Perfluoroalkylethylsulfonyl chloride of Cl and mixtures thereof, wherein p is from 1 to about 10, preferably from about 2 to about 8, more preferably from about 4 to about 6, and mixtures thereof. Such polyfluoroalkylsulfonyl halides may be conveniently prepared by methods well known to those skilled in the art, for example by reacting thionyl chloride with a selected perfluoroalkylethyl sulfonic acid or mixture of perfluoroalkylethyl sulfonic acids available from e.i. du Pont DE nemourand Company, Wilmington DE.

Hereinafter, this product is referred to as "perfluoroalkyl sulfonamide-grafted poly (alkylsiloxane)".

The poly (dialkylsiloxane) s having amine-terminated side chains and/or end groups used in the practice of the present invention have the structure of formula II, III or IV or mixtures thereof:

formula II (side chain amine):

(E-(O)_q)₃Si-O-(Si(R²)₂-O)_m-[Si(R³-NHR⁴)(R²)O]_n-Si-((O)_q-E)₃

formula III (terminal diamine):

HR⁴N-R³-Si(R²)₂-O-[Si(R²)₂-O]_m-[Si(R³-NHR⁴)(R²)O]_n-Si(R²)₂-R³-NHR⁴

formula IV (terminal monoamine):

HR⁴N-R³-Si(R²)₂-O-[Si(R²)₂-O]_m-Si-((O)_q-E)₃

wherein

Each R²Independently selected from C₁To C₈Alkyl, preferably C₁To C₄The alkyl group, more preferably the methyl group,

each R³Independently selected from divalent groups containing carbon, hydrogen, and optionally at least one of nitrogen, oxygen, and sulfur,

each R⁴Independently is H or C₁-C₈An alkyl group, a carboxyl group,

each E group is independently the same or different C₁-C₈Branched or linear alkyl end groups, and is inert under the reaction conditions,

each q is independently 0 or 1,

m is a positive integer, n is independently zero or a positive integer, such that n/(m + n) is zero or has a positive fraction up to about 0.7, and such that at 20 deg.CAt a temperature of 0.1s^-1Has a product viscosity of less than or equal to 10000mpa.s at a shear rate of (a).

It is possible to obtain amine-substituted poly (dimethylsiloxanes) with a range of molecular weights, which have corresponding viscosities. The preparation of such amine-substituted poly (dialkylsiloxanes) is well known to those skilled in the art. Dialkyldihydroxysilanes (HO)₂Si(C_xH_(2x+1))₂With alkylaminohydroxysilanes (HO)₂Si(C_yH_2yNH₂)(C_xH_(2x+1)) Can provide a dihydroxy-terminated amine-substituted poly (dialkylsiloxane). With trialkylhydroxysilane (HO) Si (C)_xH_(2x+1))₃To produce a trialkyl-terminated amine-substituted poly (dialkylsiloxane), or with a trialkoxychlorosilane ClSi (OC)_xH_(2x+1))₃To form a trialkoxy terminated amine-substituted poly (dialkylsiloxane). Many structures of formulae II, III and IV can be prepared using combinations of these reactions, x and y each independently being a positive integer. Poly (dimethylsiloxane bis [ [3- [ (2-aminoethyl) amino group]Propyl radical]Dimethoxysilyl group]Ethers are available from Aldrich Chemicals, Milwaukee WI or Wacker Company, Duncan, SC.

The reaction of formula I with formula II, III or IV will provide fluorocarbon-grafted poly (alkylsiloxanes) of any viscosity. For ease of application, perfluoroalkyl sulfonamide grafted poly (alkylsiloxanes) having a viscosity of from about 10 to about 10000mpa.s are preferred, with those having from about 500 to about 5000mpa.s being most preferred.

The present invention also includes a process for preparing perfluoroalkyl sulfonamide-grafted poly (alkylsiloxanes) comprising contacting (with or without agitation and heating) one or more poly (dialkylsiloxanes) having amine-terminated side chains or terminal groups as described above for formulas II, III or IV, with one or more polyfluoroalkylsulfonyl halides in the presence of a solvent and optionally an acid acceptor at a temperature of about 10 ℃ to about 90 ℃. If an acid acceptor is used, it may then be removed by washing and/or filtration. The solvent is then replaced with a volatile solvent selected from the group consisting of simple alcohols and ketones, or simply with water, to form a solution or dispersion of the reaction product in the selected solvent.

Suitable solvents for practicing the present invention are toluene, xylene, 1-propanol, 2-propanol, 1-methoxy-2-propanol (available as DOWANOL PM) or 1-methoxy-2-acetoxypropane (DOWANOL dpm) available from Dow Chemical co. Toluene is preferred. The solvent may be removed by evaporation, or the solution may be retained for dilution and application on a substrate. The perfluoroalkyl sulfonamide grafted poly (alkylsiloxane) is then dispersed or dissolved in a volatile "application solvent" selected from simple alcohols and ketones, suitable for use as a solvent (application solvent) for final application to a substrate. The preferred application solvent is isopropanol.

Alternatively, aqueous dispersions prepared in a conventional manner with surfactants may also be prepared by removing the solvent by evaporation and employing emulsification or homogenization procedures well known to those skilled in the art. Such solvent-free emulsions may be preferred to minimize flammability and Volatile Organic Compounds (VOCs).

The final product for application to the substrate is a dispersion (if water-based) or solution (if a solvent other than water is used) of the perfluoroalkyl sulfonamide-grafted poly (alkylsiloxane).

Suitable acid acceptors for practicing the present invention are trialkylamines and basic ion exchange resins. Examples are trimethylamine and AMBERLYST a21 (a tertiary amine divinylbenzene/styrene ion exchange copolymer available from Rohm & Haas, Philadelphia, PA). The hydrohalide form of the acid acceptor is removed from the reaction product by washing with water and/or by filtration.

The dispersion of the perfluoroalkyl sulfonamide-grafted poly (alkylsiloxane) in the application solvent is further diluted with the application solvent as necessary to provide a solution or dispersion of the perfluoroalkyl sulfonamide-grafted poly (alkylsiloxane) having a concentration of about 1% to about 10% by weight for application to a substrate. Typically, a solution or aqueous dispersion of the perfluoroalkyl sulfonamide grafted poly (alkylsiloxane) in isopropanol at a concentration of about 2% by weight is used for application to the substrate.

The dispersion or solution applied to the substrate may optionally further comprise an adhesion promoter such as an epoxy silane (e.g. 3-glycidoxypropyl-trimethoxysilane) or a cross-linking agent such as a diepoxy compound (diepoxy). Examples of suitable diepoxy compounds are: poly [ oxy (dimethylsilylene) ], - [ dimethyl [3- (oxiranylmethoxy) propyl ] silyl ], - [ [ dimethyl ] [3- (oxiranylmethoxy) propyl ] silyl ] oxy ]; dipropylene glycol diglycidyl ether; and poly [ oxy (methyl-1, 2-ethanediyl) ], - (oxiranylmethyl), - (oxiranylmethoxy). Further examples of suitable diepoxy compounds that react at room temperature are EPIKOTE828 and 10% solutions of EPIKOTE828 in xylene (EPIKOTE-X-90), both available from Resolution Performance Products, Houston TX. EPIKOTE828 is the reaction product of 4, 4' -isopropylidenediphenol (bisphenol a) and epichlorohydrin.

The present invention also includes a method of providing water, oil and stain repellency to a substrate comprising contacting a perfluoroalkyl sulfonamide grafted poly (alkylsiloxane) solution or dispersion of the present invention with the surface of a substrate. Suitable substrates include hard surfaces and soft fibrous surfaces. Hard surfaces include porous and non-porous inorganic surfaces such as glass, stone, masonry, concrete, unglazed brick, porous clay and various other substrates having surface porosity. Specific examples of such substrates include unglazed concrete, bricks, ceramic tiles, stone (including granite and limestone), cement mortar, marble, limestone, statues, monuments, wood, composite materials such as terrazzo, and walls and ceilings including those made of gypsum board. These are used in interior and exterior applications for building buildings, roads, tarmac, driveways, floors, fireplaces, fireplace floors, countertops, and other decorative uses. Wood can also be treated. Fibrous surfaces include textile, fiber, nonwoven, paper, fabric, carpet, and leather substrates. Specific examples of fibrous substrates include fabrics and carpets made from: 1) natural fibers such as wool, cotton, jute, sisal, seaweed, coir and blends thereof, and 2) synthetic fibers such as polyamides, polyaramides, polyesters, polyolefins, acrylic polymers and blends thereof.

The invention also includes hard and fibrous surfaces treated with the perfluoroalkyl sulfonamide grafted poly (alkylsiloxane) solutions or dispersions described above.

The diluted solution is applied to the substrate surface by any suitable method. Such methods are well known to those skilled in the art and include, but are not limited to, application by brush, roller, spray, dipping, immersion, and the like. The application rate of the perfluoroalkylsulfonamide-grafted poly (alkylsiloxane) solution or dispersion is from about 10 to about 1000g/m depending on the porosity of the substrate². The substrate surface is dried. The substrate is dried for about 16 to about 48 hours prior to being subjected to the oil, water, and stain repellency tests in order to bring the fluorinated telomer to its equilibrium conformation on the substrate surface.

The perfluoroalkyl sulfonamide grafted poly (alkylsiloxane) compositions of the present invention are useful for providing excellent oil, water and stain repellency to treated substrates, providing "good hand" to soft surfaces such as textiles and leather. The term "good hand" is used to describe the attractive soft or silky feel that textiles and leather have. This superior oil, water and stain repellency, as well as good hand feel, is achieved by using lower fluorine concentrations than conventional perfluorocarbon surface treatments, providing improved "fluorine efficiency" in protecting the treated surface. The perfluoroalkyl sulfonamide grafted poly (alkylsiloxanes) of the present invention are effective at fluorine concentrations of about one-third to one-fourth of the fluorine concentration of conventional fluorochemical surface protectants. As an example of such improved fluorine efficiency, a composition of the present invention having a fluorine concentration of 0.21% provides a test substrate with oil, water and stain repellency equivalent to substrates treated with conventional surfactant dispersions (perfluoroalkylethyl acrylate/dimethylaminoethyl methacrylate/vinyl acetate copolymer having a fluorine content of 0.96%).

Materials and test methods

The following materials were used in the following examples.

Polysiloxane AF16 was purchased from Wacker, Duncan, SC or Aldrich Chemicals, Milwaukee WI.

Perfluoroalkyl ethyl acrylate/dimethylaminoethyl methacrylate/vinyl acetate dispersions were purchased from e.i. du Pont DE Nemours and Company, Wilmington DE.

TEEPOL was purchased from Johnson university, Fortenay-sous-Bois, France.

Perfluoroalkyl ethanesulfonic acid and the mixed perfluoroalkyl ethanesulfonic acids used to prepare perfluorohexylethanesulfonyl chloride, as well as perfluorobutylethylsulfonyl chloride, perfluorohexylethanesulfonyl chloride, perfluorooctylethanesulfonyl chloride, perfluorodecylethylsulfonyl chloride, perfluorododecylethanesulfonyl chloride, and perfluorotetradecylethanesulfonyl chloride, were purchased from e.i. du Pont DE neurological and Company, Wilmington DE.

The stain sources are shown in table 3 below.

Test method 1 Water repellency test

The test liquid is applied to a horizontal substrate at room temperature and ambient humidity and allowed to dry for at least 24 hours. A minimum of three droplets were evaluated. The test liquid was a mixture of deionized water and 99% isopropyl alcohol as shown in table 1.

TABLE 1 Water repellency test liquids

Test liquid #	Deionized water (% by weight)	Isopropanol (% by weight)
			1	90	10
2	80	20

Test liquid #	Deionized water (% by weight)	Isopropanol (% by weight)
			3	70	30
4	60	40
			5	50	50
6	40	60
			7	30	70
8	20	80
			9	10	90
10	0	100

Three drops of test liquid 1 were placed on the treated substrate. After 30 seconds, the droplets were removed by vacuum suction. If no penetration or local absorption of liquid (appearance of a darkened wet spot on the substrate) is observed, the test is repeated with test liquid 2. The test was repeated with test liquid 3 and test liquids with increasing numbers until liquid penetration (appearance of a darkened wet spot on the substrate) was observed. The test result is the highest test liquid number that did not penetrate into the substrate. A higher score indicates a stronger repulsion force.

Test method 2 oil repellency test

The test is based on AATCC 118 of the American Association of Textile Chemists and dyes printers. The test liquid is applied to a horizontal substrate at room temperature and ambient humidity and allowed to dry for at least 24 hours. A minimum of three droplets were evaluated. The liquids used in the tests were eight oily liquids listed in table 2, having different surface energies. Higher numbers have lower surface energy and higher scores indicate greater oil repellency.

Table 2 testing oil composition

Test oil #	Oil composition
		1	Vaseline oil
2	Vaseline oil/n-hexadecane (65/35)
		3	N-hexadecane
4	N-tetradecane (minimum purity 95%)
		5	N-dodecane (minimum purity 99%)
6	N-decane (minimum purity 95%)
		7	N-octane (minimum purity 99%)
8	N-heptane (minimum purity 99%)

Three drops of test oil 1 were placed on the treated substrate. After 30 seconds, the oil droplets were removed by vacuum suction. If no penetration or local absorption of liquid (appearance of a darkened wet spot on the substrate) is observed, the test is repeated with test liquid 2. The test was repeated with test oil 3 and progressively higher number test oils until liquid penetration (appearance of a darkened wet spot on the substrate) was observed. The test result is the highest test liquid number that does not exhibit liquid penetration into the substrate.

Test method 3 measurement of contact Angle

A 76x26mm glass sample ISO-Norm8037 (super front microscope slide from micro International, Walldorf, Germany) with trimmings and ready for use was immersed twice in the application solution or dispersion to be tested for 30 seconds with a drying time of 2 minutes between the two immersions. When using epoxy silane, the glass sample is heated at 150 ℃ for 30 minutes (hereinafter referred to as heat treatment). The sample was then allowed to dry at ambient conditions for 48 hours. Three drops of 40 microliter deionized water were applied at 23 ℃ and the contact angle was measured. Advancing contact angles are used. A larger contact angle indicates a more repellent surface.

Test method 4 contact Angle measurement after coating and boiling Water treatment

Glass samples were prepared as in test method 3 with a2 minute drying time between dips, then 10 minutes at room temperature, 30 minutes at 150 ℃ and finally 48 hours at room temperature. The treated glass samples were immersed in boiling water for 1 hour, followed by flowing tap water at a flow rate of 112L/h over the treated glass for 1 hour, and finally dried at room temperature for 24 hours. Three drops of 40 microliter deionized water were applied to the boiled and dried sample at 23 ℃ and the contact angle was measured. Advancing contact angles are used. A larger contact angle indicates a more repellent surface.

Test method 5 stain test

Treated and untreated (control) substrate samples were prepared and dried at room temperature for 16 to 48 hours. The selected spot was applied to the treated surface and allowed to remain in contact with the substrate for 16 hours at room temperature. The stains and sources are shown in table 3. Petri dishes were used during those 16 hours to reduce the evaporation rate from the stain.

The substrate sample was then rinsed and 2mL of a 6% by weight solution of TEEPOL (see materials section above) in deionized water was sprayed onto the surface. The scrubber was passed over the substrate 50 times (50 strokes) using a pressure of 0.6N/cm². The substrate was rinsed with tap water and then with deionized water prior to stain evaluation. The surface where the spot was applied was evaluated according to the following criteria shown in table 4.

TABLE 3 stains

Stain or soil	Details, source
		1 percent of red colorant	DEC-A-CAKE from Durke French foods, Paramus NJ in deionized water
Coffee (Cold)	O′CAFFE EXPRESSO，Italvi，Latina，Italy
		Red wine	Villaray rouge，Groupe Uccoar，Montréal，France
Tomato sauce (Heinz)	H J Heinz France，Paris，France
		Coca cola	CocaCola Entreprise，Issy-Les-Moulineaux，France
Dijon Mustard (Dijon Mustard)	Amora，Rueil Malmaison，France
		Waterman blue ink	Waterman，Saint Herblain，France
Used engine oil	Total Fina Elf，Paris La Défense，France
		Olive oil	Groupe Auchan，Villeneuve d′Ascq，France
Geranium slurry	Flowers from SA Leroy Merlin, Lezennes, France, Geranium flower 50%, water 50%, ground together

TABLE 4 stain scores

Scoring	Description of the invention
		5	No detectable stain
4	Slightly detectable stain
		3	Visible stains, but indeterminate profile
2	Clearly defined stains, but not very deep
		1	Clearly defined stains and very deep

Examples

Example 1

Toluene (136g) and triethylamine (6.22g, 6.16X 10) were added to a double jacketed 1L reactor^-2Moles) and polysiloxane AFl6(100 g). The temperature is raised to 45 ℃ and maintainedHeld at this temperature. Preparation of Perfluorohexylethylsulfonyl chloride (C)₆F₁₃C₂H₄SO₂Cl，22.9g，5.13x10^-2Moles) in toluene (34.35g) and injected into the reactor over a two hour period. When the injection was complete, the temperature was raised to 70 ℃ and maintained at this temperature for 2.5 hours. Triethylammonium chloride and excess triethylamine were removed by washing sequentially with equal volumes of aqueous hydrochloric acid (pH about 3), aqueous sodium hydroxide (pH about 10) and then three times with water. The toluene phase containing the perfluoroalkyl sulfonamide grafted poly (alkylsiloxane) was diluted in isopropanol to give a 2% solution on a dry weight basis.

Example 2

The procedure of the example was repeated except that triethylamine was replaced with AMBERLYST a21 resin (22.19g) in the form of a base (hydroxide). After a period of 2.5 hours at 70 ℃, the reaction product was filtered to remove AMBERLYST a 21. After filtration the toluene phase was diluted with isopropanol as in example 1.

Example 3

Using 100g/m²A ceramic tile (terra cotta tile) (30x30cm) from guiroud freses, F-31250, Revel, France, was treated with a solution containing 2% by weight of a perfluoroalkylsulfonamide grafted poly (alkylsiloxane) prepared according to the procedure of example 1 and an appropriate amount of isopropanol to give 100g of solution. The fluorine content of the solution was 0.208%. The solution was applied with a brush. After 24 hours, the water and oil repellency properties were measured (test methods 1 and 2, respectively). Five drops of test solution were applied to the single treated tile in each test method and the results were averaged. The results are shown in Table 5.

Comparative example A

Using 100g/m²A ceramic brick as in example 3 was treated with a solution comprising 2% by weight of perfluoroalkylethyl acrylate/dimethylaminoethyl methacrylate/vinyl acetate copolymer and an appropriate amount of water to give 100g of the solution. The fluorine content of the solution was 0.96%. The solution was applied with a brush. After 24 hours, the water and oil repellency properties were measured using test methods 1 and 2, respectively. Five drops of test solution were applied to the single treated tile in each test method and the results were averaged. The results are shown in Table 5.

TABLE 5 Water and oil repellency

Examples	% F of the application solution	Water repellency (test method 1)	Oil repellency (test method 2)
				3	0.208	10	8
Comparative example A	0.96	10	8

Table 5 shows the equivalent protection provided by the compositions of the present invention at lower% F concentrations.

Comparative example B

Microscope slides were used without any treatment of the perfluoroalkylsulfonamide grafted poly (alkylsiloxane) with dimensions 56X 26X 0.5 mm. The advancing contact angle measurement was carried out with deionized water at 23 ℃ in a temperature-controlled chamber according to test method 3 (no heat treatment was required in this control). The low internal advancing contact angle measured 3 times on the untreated glass control indicates a high wettability of the surface. The results are shown in table 6 below.

Comparative example C

A solution was prepared containing 2% by weight of perfluoroalkylethyl acrylate/dimethylaminoethyl methacrylate/vinyl acetate copolymer and an appropriate amount of water. The fluorine content of the solution was 0.96%. Glass microscope slides of dimensions 56X 26X 0.5mm were immersed in the solution for 30 seconds and allowed to stand at room temperature for 48 hours. The advancing contact angle measurement was carried out with deionized water at 23 ℃ in a temperature-controlled chamber according to test method 3 (no heat treatment was required in this control). The internal advancing contact angle obtained 3 times measurements on the treated glass showed high water repellency of the surface. The results are given in table 6 below.

Example 4

A solution was prepared containing 2g of the perfluoroalkylsulfonamide-grafted poly (alkylsiloxane) prepared according to the procedure of example 1 and the required amount of isopropanol to give 100g of the total mass of the solution. The fluorine content of the solution was 0.208%.

Three glass microscope slides of dimensions 56X 26X 0.5mm were immersed in the solution for 30 seconds and allowed to stand at room temperature for 48 hours. The advancing contact angle measurement was performed with deionized water at 23 ℃ in a temperature controlled chamber according to test method 3 (no heat treatment was required in this example). The internal advancing contact angle measured 3 times on each treated glass showed high water repellency of the surface. The results are given in table 6 below. Example 4 shows the same order of magnitude as the perfluoroalkylethyl acrylate/dimethylaminoethyl methacrylate/vinyl acetate copolymer (comparative example C), but with a much lower fluorine content.

TABLE 6 contact Angle measurement

Examples	% F of the application solution	Advancing contact Angle (three measurements)
			Comparative example B, glass 7	0	5 DEG, 2 DEG, 7 DEG [ average 4.7 DEG ]]
Comparative example C, glass 5	0.96	104 DEG, 105 DEG [ average 104.3 DEG ]]
			Example 4, glass 1	0.208	111 °, 111 °, 116 ° [ average 112.7 ° ]]
Example 4, glass 2	0.208	110 DEG, 111 DEG, 116 DEG [ average 112.3 DEG ]]
			Example 4, glass 3	0.208	112 °, 119 °, 116 ° [ mean 115.7 ° ]]

Table 6 shows the equivalent protection provided by the compositions of the present invention at lower fluorine concentrations. A larger advancing contact angle indicates increased water repellency.

Example 5

A solution was prepared containing 2g of the perfluoroalkylsulfonamide-grafted poly (alkylsiloxane) prepared according to the procedure of example 2 and the required amount of isopropanol to give 100g of the total mass of the solution. The fluorine content of the solution was 0.184%.

Two glass microscope slides with dimensions 56X 26X 0.5mm were immersed in the solution for 30 seconds. The advancing contact angle measurement (heat treatment) was carried out with deionized water at 23 ℃ in a temperature-controlled chamber according to test method 3. The internal advancing contact angle obtained 3 times measurements on the treated glass showed high water repellency of the surface. The results are given in table 7 below.

Example 6

A solution was prepared containing 2g of the perfluoroalkylsulfonamide-grafted poly (alkylsiloxane) prepared according to the procedure of example 2 and the required amount of isopropanol to give 100g of the total mass of the solution. The fluorine content of the solution was 0.184%.

Two glass microscope slides with dimensions 56X 26X 0.5mm were immersed in the solution for 30 seconds. The advancing contact angle measurement was performed with deionized water at 23 ℃ in a temperature controlled chamber according to test method 4. The internal advancing contact angle obtained 3 times measurements on the treated glass showed high water repellency of the surface. The results are given in table 7 below.

Example 7

A solution was prepared containing 1.6g of the perfluoroalkylsulfonamide grafted poly (alkylsiloxane) prepared according to the procedure of example 2, 0.4g of 3-glycidoxypropyl-trimethoxysilane and the required amount of isopropanol to give 100g of the total mass of the solution. The fluorine content of the solution was 0.147%.

Two glass microscope slides with dimensions 56X 26X 0.5mm were immersed in the solution for 30 seconds. The advancing contact angle measurement (heat treatment) was carried out with deionized water at 23 ℃ in a temperature-controlled chamber according to test method 3. The internal advancing contact angle obtained 3 times measurements on the treated glass showed high water repellency of the surface. The results are given in table 7 below.

Example 8

A solution was prepared containing 1.6g of the perfluoroalkylsulfonamide grafted poly (alkylsiloxane) prepared according to the procedure of example 2, 0.4g of 3-glycidoxypropyl-trimethoxysilane and the required amount of isopropanol to give 100g of the total mass of the solution. The fluorine content of the solution was 0.147%.

Two glass microscope slides with dimensions 56X 26X 0.5mm were immersed in the solution for 30 seconds. The advancing contact angle measurement was performed with deionized water at 23 ℃ in a temperature controlled chamber according to test method 4. The internal advancing contact angle obtained 3 times measurements on the treated glass showed high water repellency of the surface. The results are given in table 7 below.

Each of examples 5, 6, 7 and 8 was repeated on 2 different microscope slides and the contact angle was measured on 3 different areas of the treated glass to check the reproducibility of the contact angle measurements. The data given in table 7 show good reproducibility. A larger contact angle indicates a stronger water repellency.

TABLE 7 contact Angle measurement

Examples	% F of the application solution	Advancing contact Angle (three measurements)	Average contact angle
				Example 5 glass A	0.208	112°；115°；119°	115.8°
Example 5 glass B	0.208	119°；115°；115°
				Example 6, glass A	0.208	98°；96°；99°	99.0°
Example 6 glass B	0.208	99°；100°；102°
				Example 7, glass A	0.147	113°；108°；105°	108.5°

Examples	% F of the application solution	Advancing contact Angle (three measurements)	Average contact angle
				Example 7 glass B	0.147	106°；109°；110°
Example 8, glass A	0.147	96°；110°；110°	108.5°
				Example 8, glass B	0.147	112°；110°；113°

Examples 5 and 6 correspond to glasses treated with perfluoroalkyl sulfonamide grafted poly (alkylsiloxane) without any epoxy silane as adhesion promoter. Example 6 shows the contact angle measured after a treated microscope glass slide has been submerged in boiling water for 1 hour. Immersion in boiling water was not carried out for example 5. Thus, the difference in contact angle between examples 5 and 6 demonstrates the effect of immersion of the treated glass in boiling water on the contact angle. Table 7 shows that this immersion in boiling water reduces the contact angle by 17 ° (difference between the mean values obtained from examples 5 and 6).

Examples 7 and 8 correspond to glass treated with perfluoroalkyl sulfonamide grafted poly (alkylsiloxane) and epoxy silane (3-glycidoxypropyl-trimethoxysilane). Example 8 shows the contact angle measured after a treated microscope glass slide has been submerged in boiling water for 1 hour. Immersion in boiling water was not carried out in example 7. Thus, the difference in contact angle between examples 8 and 7 demonstrates the effect of immersion of the treated glass in boiling water on the contact angle. Table 7 shows that this immersion does not reduce the contact angle (difference between the mean values obtained from examples 7 and 8).

In summary, the results presented in Table 7 show that the use of epoxy silanes reduces the negative effects of immersion of the treated glass in boiling water as employed in examples 6 and 8. In addition, even though epoxysilane reduced the initial value of the contact angle (115.8 ° on average for example 5 and 108.5 ° on average for example 7), when epoxysilane was used, the treated glass maintained a large contact angle after immersion in boiling water. Example 6 (no epoxy silane) averages 99 °, example 8 (epoxy silane) averages 108.5 °.

Example 9

Using 100g/m²A ceramic tile as in example 3 was treated with a solution comprising 2% by weight of a perfluoroalkylsulfonamide grafted poly (alkylsiloxane) prepared according to the procedure of example 1 and an appropriate amount of isopropanol to give 100g of the solution.The fluorine content of the solution was 0.208%. The solution was applied with a brush. After 24 hours, the water repellency, oil repellency, and stain resistance were measured using test methods 1, 2, and 5, respectively. Multiple stain resistance tests were performed on individual tiles. The results are shown in Table 8. The tiles were also treated and tested in the same manner using the composition of comparative example C above. The results are shown in Table 8.

TABLE 8

Testing	Example 9 treated brick	Comparative example C
			Water repellency (method 1)	10	10
Oil repellency (method 2)	8	6
			Stain resistance (method 5)
Red colorant	5	2
			Coffee	4.5	2
Red wine	2.5	3
			Tomato sauce Heinz	5	5
Coca cola	4	4
			Dirong mustard	5	5
Watermann blue ink	2	2.5
			Engine oil (used)	2.5	5
Olive oil	4	5
			Geranium slurry	2	3.5
Total score	54.5	53

^*The stain sources are shown in table 3 above.

Table 8 compares two different bricks treated with the same weight of polymer solution per square meter. However, although the two solutions used in example 9 and comparative example C had the same polymer content, the fluorine content of the example 9 solution was 0.208% and the fluorine content of the comparative example C solution was 0.91%. The overall evaluation of example 9 was slightly higher than that of comparative example C. The fluorine required for the polymer used in example 9 was only 23% of that of comparative example C.

Example 10

Example 10 was prepared as in example 1, except 26.3g (5.1310) of perfluorohexylethylsulfonyl chloride was used^-2Moles) of a mixture comprising perfluorobutylethylsulfonyl chloride (4%, all percentages are by weight), perfluorohexylethylsulfonyl chloride (50%), perfluorooctylethylsulfonyl chloride (29%), perfluorodecylethylsulfonyl chloride (11%), perfluorododecylethylsulfonyl chloride (4%) and perfluorotetradecylethylsulfonyl chloride (2%). After the final wash, the toluene phase was diluted with isopropanol as in example 1.

Claims (22)

1. A composition comprising a polymer prepared by contacting a polyfluoroalkylsulfonyl halide of formula I with a silane compound of formula II, III or IV

R_f-R¹-SO₂X I

Wherein

R_fIs a linear or branched perfluoroalkyl group having 2 to 20 carbon atoms,

R¹is a divalent linking group C_kH_2kWherein k is 2 to 20, and

x is a halogen, and X is a halogen,

formula II:

(E-(O)_q)₃Si-O-(Si(R²)₂-O)_m-[Si(R³-NHR⁴)(R²)O]_n-Si-((O)_q-E)₃

formula III:

HR⁴N-R³-Si(R²)₂-O-[Si(R²)₂-O]_m-[Si(R³-NHR⁴)(R²)O]_n-Si(R²)₂-R³-NHR⁴

formula IV:

HR⁴N-R³-Si(R²)₂-O-[Si(R²)₂-O]_m-Si-((O)_q-E)₃

wherein

Each R²Independently is C₁To C₈An alkyl group, a carboxyl group,

each R³Independently a divalent group containing carbon, hydrogen, and optionally at least one of nitrogen and sulfur,

each R⁴Independently is H or C₁To C₈An alkyl group, a carboxyl group,

each E is independently C₁To C₈A branched or linear alkyl group, which may be,

each q is independently zero or 1,

m is a positive integer, n is independently a positive integer, such that n/(m + n) is a positive fraction having a value up to 0.7 and is at a temperature of 20 ℃ in 0.1s^-1Has a viscosity of less than or equal to 10000mpa.s at a shear rate of (a).

2. The composition of claim 1 wherein the sulfonyl halide is of the formula F (CF)₂)_nCH₂CH₂SO₂Sulfonyl halides of Cl and mixtures thereof, wherein n is 2 to 20.

3. The composition of claim 1, wherein R_fIs a perfluoroalkyl group having 4 to 16 carbon atoms.

4. The composition of claim 1, wherein the silane compound is a compound of formula II

(E-(O)_q)₃Si-O-(Si(R²)₂-O)_m-[Si(R³-NHR⁴)(R²)O]_n-Si-((O)_q-E)₃

Wherein R is²、R³、R⁴E, q, m and n are as defined in claim 1.

5. The composition of claim 1, which is at a temperature of 20 ℃ in 0.1s^-1Has a viscosity of 500 to 5000mpa.s at a shear rate of (a).

6. The composition of claim 1 in the form of a dispersion or solution.

7. A process for preparing perfluoroalkyl sulfonamide-grafted poly (alkylsiloxane), said process comprising contacting a polyfluoroalkylsulfonyl halide of formula I with a silane compound of formula II, III or IV

R_f-R¹-SO₂X I

Wherein

R_fIs a linear or branched perfluoroalkyl group having 2 to 20 carbon atoms,

R¹is a divalent linking group C_kH_2kWherein k is 2 to 20, and

x is a halogen, and X is a halogen,

formula II:

(E-(O)_q)₃Si-O-(Si(R²)₂-O)_m-[Si(R³-NHR⁴)(R²)O]_n-Si-((O)_q-E)₃

formula III:

HR⁴N-R³-Si(R²)₂-O-[Si(R²)₂-O]_m-[Si(R³-NHR⁴)(R²)O]_n-Si(R²)₂-R³-NHR⁴

formula IV:

HR⁴N-R³-Si(R²)₂-O-[Si(R²)₂-O]_m-Si-((O)_q-E)₃

wherein

Each R²Independently is C₁To C₈An alkyl group, a carboxyl group,

each R³Independently a divalent group containing carbon, hydrogen, and optionally at least one of nitrogen and sulfur,

each R⁴Independently is H or C₁To C₈An alkyl group, a carboxyl group,

each E is independently C₁To C₈A branched or linear alkyl group, which may be,

each q is independently zero or 1,

m is a positive integer, n is independently a positive integer, such that n/(m + n) is a positive fraction having a value up to 0.7 and is at a temperature of 20 ℃ in 0.1s^-1Has a viscosity of less than or equal to 10000mpa.s at a shear rate of (a).

8. The process of claim 7, further comprising contacting in the presence of a tertiary amine or a basic ion exchange resin.

9. A method for providing oil repellency, water repellency, and stain resistance to a substrate surface comprising contacting said surface with a polymer prepared by contacting a polyfluoroalkylsulfonyl halide of formula I with a silane compound of formula II, III, or IV

R_f-R¹-SO₂X I

Wherein

R_fIs a linear or branched perfluoroalkyl group having 2 to 20 carbon atoms,

R¹is a divalent linking group C_kH_2kWherein k is 2 to 20, and

x is a halogen, and X is a halogen,

formula II:

(E-(O)_q)₃Si-O-(Si(R²)₂-O)_m-[Si(R³-NHR⁴)(R²)O]_n-Si-((O)_q-E)₃

formula III:

HR⁴N-R³-Si(R²)₂-O-[Si(R²)₂-O]_m-[Si(R³-NHR⁴)(R²)O]_n-Si(R²)₂-R³-NHR⁴

formula IV:

HR⁴N-R³-Si(R²)₂-O-[Si(R²)₂-O]_m-Si-((O)_q-E)₃

wherein

Each R²Independently is C₁To C₈An alkyl group, a carboxyl group,

each R³Independently a divalent group containing carbon, hydrogen, and optionally at least one of nitrogen and sulfur,

each R⁴Independently is H or C₁To C₈An alkyl group, a carboxyl group,

each E is independently C₁To C₈A branched or linear alkyl group, which may be,

each q is independently zero or 1,

m is a positive integer, n is independently a positive integer, such that n/(m + n) is a positive fraction having a value up to 0.7 and is at a temperature of 20 ℃ in 0.1s^-1Has a viscosity of less than or equal to 10000mpa.s at a shear rate of (a).

10. The method of claim 9, wherein the polymer is an aqueous dispersion or solution.

11. The method of claim 10, wherein the dispersion or solution further comprises an epoxy silane or a crosslinking agent.

12. The method of claim 9, wherein the polymer is applied at a concentration of 1% to 10% by weight.

13. The method of claim 9, wherein the amount of polymer deposited on the surface of the substrate is from 10 to 1000g/m²。

14. The method of claim 9, wherein said contacting provides softness to textiles and leather substrates.

15. A substrate treated according to the method of claim 9.

16. A substrate having a surface in contact with the composition of claim 1.

17. The substrate of claim 15, which is a hard surface selected from the group consisting of minerals, stone, concrete, bricks, clay, granite, limestone, mortar, statuary, monuments, wood, composites, and gypsum board.

18. The substrate of claim 15, which is a fibrous substrate selected from the group consisting of textiles, fibers, nonwovens, paper, and leather.

19. The substrate of claim 17, said hard surface being selected from the group consisting of glass, masonry, unglazed brick, unglazed concrete, cement mortar, marble, and terrazzo.

20. The substrate of claim 18, said fibrous substrate being a fabric.

21. The substrate of claim 20, said fibrous substrate being a carpet.

22. The substrate of claim 17, said hard surface being selected from limestone.