HYDE GARY KEVIN (US)
MARTIN BRADLEY G (US)
HAWKS PATRICK E (US)
DIMAIO JEFFREY R (US)
KOKUOZ BARIS (US)
ZDYRKO BOGDAN (US)
OVERMAN III DANA C (US)
CADE DEIDRA SHANELLE (US)
PALOMAKI BRETT RYAN (US)
US20050008763A1 | 2005-01-13 | |||
US20110268899A1 | 2011-11-03 | |||
US20110112221A1 | 2011-05-12 |
THAT WHICH IS CLAIMED IS: 1. An aqueous silane composition comprising: (a) a first silane monomer having a formula of R1-Si(OR2)3, wherein R1 is a C6-C20 alkyl, and each R2 is independently a C1-C4 alkyl (e.g., methyl or ethyl); (b) a second silane monomer having a formula of R3-Si(OR4)3, wherein R3 is a functional group that comprises an epoxide, and each R4 is independently a C1-C4 alkyl (e.g., methyl or ethyl); and wherein the aqueous silane composition comprises the first silane monomer at a concentration in a range of about 90% to about 99% by weight and the second silane monomer at a concentration in a range of about 1% to about 10% by weight, each based on the total weight of silanes in the composition. 2. The aqueous silane composition of claim 1, comprising the first silane monomer at a concentration in a range of about 92.5% to about 96% by weight and the second silane monomer at a concentration in a range of about 4% to about 7.5% by weight, each based on the total weight of the silanes in the composition. 3. The aqueous silane composition of claim 1 or 2, wherein R3 is –X-(Y)i-(Z)j, wherein X is –(CH2)a– or –(CH2)b-O-(CH2)c–, wherein a is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, and b and c are each independently 0, 1, 2, 3, 4, 5, 6, 7 or 8; Y is an epoxycycloalkyl, Z is an epoxide, i is 0 or 1, j is 0 or 1, and i + j = 1. 4. The aqueous silane composition of claim 3, wherein R1 is a C12-C18 alkyl, R2 is methyl or ethyl, R4 is methyl or ethyl, and wherein X is –(CH2)a– and a is 1, 2 or 3, Y is an epoxycycloalkyl (e.g., epoxycyclohexyl), i = 1, and j = 0. 5. The aqueous silane composition of claim 3, wherein R1 is a C12-C18 alkyl, R2 is methyl or ethyl, R4 is methyl or ethyl, and wherein X is –(CH2)b–O–(CH2)c–, b is 1, 2, or 3, c is 1, 2, or 3, Z is an epoxide, j = 1, and i = 0. 6. The aqueous silane composition of any of claims 1-5, further comprising water. 7. The aqueous silane composition of claim 1-6, further comprising a surfactant. 8. The aqueous silane composition of claim 7, wherein the surfactant is an amphoteric surfactant (e.g., an alkyl amine oxide). 9. The aqueous silane composition of any one of claims 1-8, wherein the first silane monomer is present at a concentration of at least about 4.5% to about 28.5% by weight of the composition, the second silane monomer is present at a concentration in a range of about 0.15% to about 1.2% by weight of the composition, water is present about 68% to about 94% by weight of the composition, and surfactant is present at about 0.3% to about 1.8% by weight of the composition. 10. The aqueous silane composition of any of claims 1-9, further comprising a catalyst (e.g., ammonium hydroxide). 11. The aqueous silane composition of any of claims 1-10, wherein the aqueous silane composition is an aqueous emulsion. 12. The aqueous silane composition of any of claims 1-11, wherein at least a portion of the first silane monomer, the second silane monomer, or both, has condensed to form siloxane bonds. 13. The aqueous silane composition of any of claims 1-12, wherein the aqueous silane composition is devoid of fluorine and/or a fluorine-containing compound. 14. A polysiloxane comprising at least a first unit (a): (a) , and a second unit (b) (b) wherein each R1 is a C6-C20 alkyl and each R3 is a functional group comprising an epoxide or a crosslink formed from an epoxide, wherein the first unit (a) is present in the polysiloxane at a concentration in a range of about 90% to about 99% by weight, and the second unit (b) is present in the polysiloxane at a concentration in a range of about 1% to about 10 % by weight, each based on the total weight of the polysiloxane. 15. The polysiloxane of claim 14, wherein the weight percent of first unit (a) in the polysiloxane is in a range of about 92.5% to about 96% by weight and the weight percent of second unit (b) is in a range of about 4% to about 7.5% by weight, based on the total weight of the polysiloxane. 16. The polysiloxane of claim 14 or 15, wherein R3 is -X-(Y)i-(Z)j, wherein X is –(CH2)a– or –(CH2)b-O-(CH2)c–, wherein a is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, and b and c are each independently 0, 1, 2, 3, 4, 5, 6, 7 or 8; Y is a cycloalkyl, Z is an epoxide, i is 0 or 1, j is 0 or 1, and i + j = 1. 17. The polysiloxane of claim 16, wherein R1 is a C12-C18 alkyl, and wherein X is – (CH2)a–, a is 1, 2 or 3, Y is an epoxycycloalkyl (e.g., epoxycyclohexyl), i = 1, and j = 0. 18. The polysiloxane of claim 16, wherein R1 is a C12-C18 alkyl, and X is –(CH2)b– O–(CH2)c–, b is 1, 2, or 3, c is 1, 2, or 3, Z is an epoxide, j = 1, and i = 0. 19. The polysiloxane of claim 16, wherein R1 is a straight chain C12-C18 alkyl (e.g., a straight chain C16 alkyl) and R3 is (epoxycyclohexyl)ethyl. 20. The polysiloxane of any of claims 14-19, wherein the polysiloxane has a weight average molecular weight in a range of about 5,000 daltons to about 50,000 daltons. 21. The polysiloxane of any of claims 14-20, wherein the polysiloxane is in the form of latex particles, optionally wherein the latex particles have a particle size in a range of about 100 or about 300 nm to about 500 or about 600 nm. 22. The polysiloxane of claim 21, wherein the latex particles have a surface energy in a range of about 25 dyne/cm to about 45 dyne/cm. 23. A polysiloxane formed by reacting an aqueous silane composition comprising a first silane monomer and a second silane monomer: wherein the first silane monomer has a formula of R1-Si(OR2)3, wherein R1 is a C6- C20 alkyl, and each R2 is independently a C1-C4 alkyl (e.g., methyl or ethyl); wherein the second silane monomer has a formula of R3-Si(OR4)3, wherein R3 is a functional group that comprises an epoxide, and each R4 is independently a C1-C4 alkyl (e.g., methyl or ethyl); and wherein the aqueous silane composition comprises the first silane monomer at a concentration in a range of about 90% to about 99% by weight and the second silane monomer at a concentration in a range of about 1% to about 10% by weight, each based on the total weight of silanes in the composition. 24. The polysiloxane of claim 23, wherein R3 is -X-(Y)i-(Z)j, wherein X is –(CH2)a– or –(CH2)b-O-(CH2)c–, wherein a is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, and b and c are each independently 0, 1, 2, 3, 4, 5, 6, 7 or 8; Y is a cycloalkyl; Z is an epoxide; i is 0 or 1, j is 0 or 1, and wherein i + j = 1. 25. The polysiloxane of claim 23 or 24, wherein the composition further comprises water and a surfactant (e.g., an amphoteric surfactant), and wherein R1 is a C12-C18 alkyl, each R2 is independently methyl or ethyl, X is –(CH2)a–, a is 1, 2, or 3, Y is an epoxycycloalkyl, i = 1, j = 0, and each R4 is independently methyl or ethyl. 26. A composition comprising the polysiloxane of any one of claims 14-25. 27. The composition of claim 26, further comprising water. 28. The composition of claim 27, wherein the composition has a solids content in a range of about 5% to about 30%. 29. The composition of any of claims 26-28, wherein the composition is devoid of fluorine and/or a fluorine-containing compound. 30. The composition of any of claims 26-29, further comprising a surfactant, optionally wherein the surfactant is an amphoteric surfactant. 31. The composition of claim 30, wherein the composition comprises an amphoteric surfactant at a concentration in a range of about 0.3 to about 3 weight percent, based on the total weight of the composition. 32. The composition of any of claims 26-31, wherein the composition has a lower alcohol (e.g., methanol) content of less than 5% by weight of the composition (e.g., substantially devoid of a lower alcohol). 33. The composition of any of claims 26-32, wherein the composition has a pH in a range of about 4.5 to about 8 (e.g., about 6). 34. A coated article comprising a fabric, and a coating on at least one surface of the fabric, the coating comprising the polysiloxane of any one of claims 14-25 or the composition of any one of claims 26-33. 35. The coated article of claim 34, wherein the fabric comprises at least one of acrylic, polyester, nylon, and olefin fibers. 36. The coated article of claim 34 or 35, wherein an add-on percentage for the coating on the coated article is in a range of about 0.3 % to about 5% (e.g., about 0.4% to about 0.65%). 37. The coated article of any one of claims 34-36, wherein the coating has a surface energy of 30 dyne/cm or less, as determined by AATCC TM193 (2017). 38. The coated article of any one of claims 34-37, wherein the coating has a spray test rating of 80 or higher as measured in accordance with ATTCC TM22. 39. The coated article of any one of claims 34-38, wherein a spray test rating of the coated article, as measured in accordance with ATTCC TM22, decreases by less than 5 or 10% or increases by 5, 10, 15, 20, 25, 30%, or more after exposure to at least 100 days of outdoor conditions. 40. The coated article of any of claims 34-39, wherein a spray test rating of the coated article, as measured in accordance with ATTCC TM22, decreases by less than 5 or 10%, or increases by 5, 10, 15, 20, 25, 30%, or more after exposure to accelerated weathering of 500, 1000, or 1500 kJ according to SAE J2527. 41. A method of forming a polysiloxane comprising: emulsifying the composition of any of claims 1-13; heating the composition; adding a catalyst to the composition; and then reacting the composition to form the polysiloxane. 42. The method of claim 41, wherein emulsifying the composition produces an emulsion with a droplet size of less than about 500 nm. 43. The method of claim 42, wherein emulsifying the composition produces an emulsion with a droplet size of less than about 350 nm. 44. The method of any of claims 41-43, wherein the catalyst is ammonium hydroxide. 45. The method of any of claims 41-44, wherein adding the catalyst to the composition comprises adding the catalyst in an amount of about 0.02% to about 1.4% by weight of the composition. 46. The method of any of claims 41-45, wherein heating the composition comprises heating the composition to a temperature in a range of about 70°C to about 100°C and/or wherein reacting the composition comprises reacting the composition at a temperature in a range of about 70°C to about 100°C, optionally for a time period in a range of about 10 minutes to about 10 hours. 47. The method of any of claims 41-46, further comprising removing at least a portion of the lower alcohol (e.g., methanol) formed during the reaction of the composition. 48. The method of claim 47, wherein all or substantially all of the lower alcohol (e.g., methanol) is removed. 49. The method of any of claims 41-48, further comprising coating the polysiloxane onto a surface of an article and, optionally, drying the polysiloxane on the surface of the article. 50. The method of claim 49, further comprising heating the article. 51. The method of claim 50, wherein the silane composition further comprises an amphoteric surfactant (e.g., an alkyl amine oxide), and wherein the coated article is heated for a time and temperature sufficient to decompose at least a portion of the amphoteric surfactant in the coating. |
[0052] In some embodiments of the invention, a portion of the first silane monomer and/or the second monomer in the silane composition has condensed to form siloxane bonds. Specifically, in some embodiments of the invention, a portion of the alkoxy groups from the first silane monomer and/or second silane monomer (-OR 2 and/or -OR 4 groups, respectively) hydrolyze and condense to form siloxane bonds. As such, compositions of the invention may include, in some embodiments, one or both reactant silane monomers, polysiloxanes formed therefrom, and/or any intermediate therebetween. In particular embodiments, a mixture of silane monomers and polysiloxanes may be included in the composition.
[0053] In some embodiments of the invention, any of the silane monomers described above may be devoid of fluorine and/or fluorine-containing compounds. Further, in some embodiments, the silane composition as a whole may be devoid of fluorine and/or fluorine- containing compounds.
Polysiloxanes
[0054] As described above, the silane monomers in the silane compositions of the invention may hydrolyze and condense to form polysiloxanes. As such, provided according to embodiments of the invention are poly siloxanes formed from a hydrolysis and/or condensation reaction of silane compositions described herein. Thus, in some embodiments of the invention, provided are polysiloxanes having at least a first unit (a): , and a second unit (b): (b) [0055] wherein R 1 is a C 6 -C 20 alkyl, and wherein R 3 is a functional group that includes at least one epoxide and/or a crosslink formed from at least one epoxide. The crosslink is a bond formed by the reaction of the epoxide with another portion of a silane, polysiloxane, composition, and/or article on which the polysiloxane and/or composition is applied. In the structures above, the across a bond indicates that the atom is bonded to another group not shown in the structure, such as, for example, another silane monomer. [0056] In some embodiments of the invention, R 1 is a C 6 -C 20 straight chain alkyl. In some embodiments, R 1 is a C 12 -C 18 straight chain alkyl. In particular embodiments, R 1 is a C 14 - C 18 straight chain alkyl, and, in particular embodiments, R 1 is a C 16 straight chain alkyl. [0057] In some embodiments of the invention, R 3 is –X-(Y) i -(Z) j , [0058] wherein X is –(CH 2 ) a – or –(CH 2 ) b -O-(CH 2 ) c –, wherein a is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, and b and c are each independently 0, 1, 2, 3, 4, 5, 6, 7 or 8; [0059] Y is an epoxycycloalkyl, [0060] Z is an epoxide, [0061] i is 1 or 0, j is 1 or 0, and i + j = 1. [0062] Thus, if i = 0, then j = 1, Y is not present, and X connects to Z via a single bond. Conversely, if i = 1, then j = 0, and Z and the bond between Y and Z are not present. [0063] In some embodiments of the invention, X is –(CH 2 ) a –, a is 1, 2 or 3, Y is an epoxycycloalkyl (e.g., epoxycyclohexyl), i = 1, and j = 0. In particular embodiments, X is – (CH 2 ) a – , a is 2, Y is a epoxycyclohexyl, i = 1, and j = 0. In some embodiments of the invention, X is – (CH 2 ) b –O–(CH 2 ) c –, b is 1, 2, or 3, c is 1, 2, or 3, Z is an epoxide, j = 1, and i = 0. In some embodiments, X is –(CH 2 ) b –O–(CH 2 ) c –, b is 2 or 3, c is 1 or 2, Z is an epoxide, j = 1, and i = 0. [0064] In particular embodiments, R 3 is epoxypropyl, epoxybutyl, epoxypentyl, epoxyhexyl, epoxyheptyl, epoxyoctyl, epoxycyclobutyl, epoxycyclopentyl, epoxycyclohexyl, (epoxycyclohexyl)methyl, (epoxycyclohexyl)ethyl, (epoxycyclohexyl)propyl, glycidoxyethyl, glycidoxymethyl, glycidoxypropyl (e.g., 3-glycidoxypropyl), glycidoxybutyl, glycidoxypentyl, glycidoxyhexyl, glycidoxyheptyl, or glycidoxyoctyl. In some embodiments, R 3 is 2-(3,4-epoxycyclohexyl)ethyl, 3-glycidoxypropyl, or 3-glycidoxyoctyl. [0065] In some embodiments, at least a portion of the epoxy functional groups in the second silane monomer is unreacted in the polysiloxane. However, in some embodiments, at least a portion of the epoxy groups in the second silane monomer react during the polysiloxane formation process, and as such, the epoxy group is no longer present in this portion but instead becomes a crosslink derived from the epoxy functional group. In some embodiments, the epoxide reacts with a portion of the polysiloxane, a portion of a silane monomer, water, or a surface on which the polysiloxane is applied (e.g., an article as described herein). In some embodiments, at least a portion of the epoxide reacts with another epoxide group to form a crosslink. In some embodiments, at least a portion of the epoxide reacts with functional groups (e.g., hydroxyl and/or carboxyl groups) on the surface of an article (e.g., a fabric) on which the coating is applied. [0066] The units (a) and (b) of the polysiloxane may be in any order, and thus, in some embodiments, the (a) and (b) units may form a block copolymer wherein one or more of the silane monomers react in a sequential fashion. However, in some embodiments, the silane monomers react at a similar or substantially similar rate and so units (a) and (b) are randomly dispersed within the polysiloxane polymer. Additionally, the tri-functional silane monomers, once reacted, create a three-dimensional network of siloxane bonds, and the R 1 and R 3 subunits may or may not be randomly distributed in the three-dimensional network. In some embodiments, unit (a) is present in the polysiloxane at a concentration in a range of about 90% to about 99% by weight, and unit (b) is present in the polysiloxane at a concentration in a range of about 1% to about 10 % by weight, each based on the total weight of the polysiloxane. In particular embodiments, unit (a) is present in the polysiloxane at a concentration in a range of about 92.5% to about 96% by weight, and unit (b) is present in the polysiloxane at a concentration in a range of about 4% to about 7.5 % by weight, each based on the total weight of the polysiloxane. In some embodiments of the invention, any of the polysiloxanes described above may be devoid of fluorine and/or fluorine-containing compounds. [0067] Also provided according to embodiments of the invention are polysiloxanes formed by reacting a silane composition of the invention. Such reactions may be performed by any suitable method, but in some embodiments, the polysiloxanes are formed by a reaction method described herein. [0068] In some embodiments, a polysiloxane of the invention has a weight average molecular weight in a range of about 5,000 daltons to about 50,000 daltons. In some embodiments, the weight average molecular weight of the polysiloxane is in a range of about 5,000 daltons to about 25,000 daltons, and in some embodiments, in a range of about 5,000 daltons to about 10,000 daltons. Thus, in some embodiments, the polysiloxane has a weight average molecular weight of about 5,000, 10,000, 15,000, 20,000, 25,000, 30,000, 35,000, 40,000, 45,000, or 50,000 daltons, or any molecular weight range defined there between. [0069] In some embodiments of the invention, the silane monomers condense within the emulsion droplets, thus creating polysiloxane particles. In some embodiments, the polysiloxane particles have an average particle diameter in a range of about 100 to about 600 nm; in some embodiments, in a range of about or about 200 nm to about 500 nm; and in some embodiments, in a range of about 300 nm to about 500 nm. Thus, in some embodiments, the average particle diameter of the polysiloxane particles is 100, 200, 300, 400, 500, 600 nm, or any range defined there between. The polysiloxane particles may be present in an aqueous composition as latex particles. Particle size may be determined, for example, by a laser particle analyzer such as NanoPlus HD Nano Particle Analyzer. Polysiloxane Compositions [0070] Also provided according to embodiments of the invention are compositions that include a polysiloxane according to an embodiment of the invention. In some embodiments, the compositions include a polysiloxane according to an embodiment of the invention and water. In some embodiments of the invention, the polysiloxane composition has a solids content in a range of about 3% to about 35% by weight of the composition, and in some embodiments, in a range of about 5% to about 30% by weight of the composition. In some embodiments of the invention, the polysiloxane composition has a solids content of about 4, 5, 6, 7, 8, 9, 10, 12, 14, 16,18, 20, 22, 24, 26, 28, 30, 31, 32, 33, 34, or 35, or any solid content range there between, based on the weight of the composition. [0071] In some embodiments, the polysiloxane compositions may further include a surfactant. In some embodiments, the surfactant in the polysiloxane is surfactant remaining from the emulsion polymerization of a silane composition of the invention. A cationic surfactant, anionic surfactant, and/or an amphoteric surfactant may be included in the polysiloxane compositions in some embodiments. In particular embodiments, the surfactant is an amphoteric surfactant such as an amphoteric alkyl amine oxide surfactant. In some embodiments, the surfactant includes lauramine oxide, lauryl betaine, dodecylbetaine, tetradecylbetaine, alkyl(C 12-14 )betaine, hexyldecylbetaine, betaine citrate, sodium lauroamphoacetate, sodium hydroxymethylglycinate, cocoamphodiacetates, cocoiminodiproprionate, dodecyliminodiproprionate, and/or (carboxymethyl)dimethyl-3-[(1- oxododecyl)amino]propyl ammonium hydroxide. In some embodiments, a degradation product of the surfactant may additionally or alternatively be present in a polysiloxane composition of the invention. [0072] A lower alcohol is a byproduct of the condensation of the silane monomers of a silane composition of the invention. As such, in some embodiments, the polysiloxane composition includes a lower alcohol at a concentration in a range of about 0% to about 15% by weight of the polysiloxane composition. In particular embodiments, the lower alcohol (e.g., methanol) concentration in the polysiloxane composition is less than about 10% by weight, or less than about 5% by weight of the composition. In particular embodiments, the lower alcohol concentration in the polysiloxane composition is less than about 4, 3, 2, 1 or 0.5 percent by weight of the composition. In some embodiments, the polysiloxane composition is substantially or essentially devoid of a lower alcohol such as methanol. The lower alcohol may be removed from the polysiloxane composition by methods known in the art such as, for example, evaporation and/or vacuum stripping. [0073] In some embodiments of the invention, the polysiloxane composition has a pH in a range of about 4.5 to about 8; in some embodiments, in a range of about 5 to about 7; and in some embodiments, at about 6. Thus, the pH of the polysiloxane composition may be about 4.5, 5, 5.5, 6, 6.5, 7, 7.5 or 8, or any pH range defined there between. [0074] The polysiloxane composition may have some unreacted silane monomer (e.g., a silane monomer having the formula of I or II) present in the composition. The unreacted silane monomer may react over time, for example, after application (e.g., coating or finishing) of the polysiloxane composition on an article. However, in some embodiments, all or substantially all of the silane monomer present in the composition and/or coating has reacted to form a three-dimensional polysiloxane network. Additionally, in some embodiments, the polysiloxane in the polysiloxane composition may have at least some unreacted epoxy groups from the second silane monomer, and such epoxy groups may be able to react with a surface on which the polysiloxane composition is applied. However, in some embodiments, all or substantially all of the epoxy groups in the polysiloxane have reacted and/or crosslinked during the formation of the polysiloxane. In some embodiments, a polysiloxane composition includes a three-dimensional polysiloxane network. [0075] In some embodiments of the invention, the polysiloxane compositions are devoid of fluorine and/or a fluorine-containing compound. Polysiloxane Coatings and Coated Articles [0076] In some embodiments of the invention, provided are coatings that include a polysiloxane and/or a polysiloxane composition according to an embodiment of the invention. In some embodiments, the coating may be a finish. In some embodiments, coatings include additional components, such as a surfactant, a lower alcohol (e.g., methanol), degraded surfactant, and/or water. In some embodiments, however, the lower alcohol concentration in the coating is less than 4, 3, 2, 1 or 0.5 percent by weight of the coating. Further, in some embodiments, the coatings are devoid of, substantially devoid of, or essentially devoid of the lower alcohol. Additionally, in some embodiments, the coatings are devoid of fluorine and/or fluorine-containing compounds. [0077] Also provided herein are articles that include a coating according to an embodiment of the invention on at least one surface of the article. Any suitable article may be used, and in some embodiments, the article is one in which water-repellent properties may be desirable. In particular embodiments of the invention, the article is a fabric, and as such, the coated article may be a fabric having a coating according to an embodiment of the invention on at least one surface of the fabric. [0078] The add-on percentage of a coated article provides a measure of the amount of coating on the surface of an article such as a fabric. For example, if the article is a fabric, the add-on percentage is measured by weighing the fabric of given area before and after coating. The difference in weight is expressed in percentage with respect to the weight of base fabric. In some embodiments of the invention, the add-on percentage for the coated article of the invention is in a range of about 0.3% to about 5%. In some embodiments, the add-on percentage is in a range of about 0.4% to about 0.65%. [0079] The polysiloxane coatings of the invention may be used with a variety of fabrics, including, but not limited to, acrylic, polyester, nylon, and/or olefin fabrics or other textiles. In particular embodiments, the fabric is an acrylic fabric. In some embodiments, one or more (e.g., 1, 2, 3, 4, 5, 6, or more) pigment(s) may be present in the fabric. A pigment may provide the fabric with a color that is a light, medium, or a dark shade. In some embodiments, the fabric is solution-dyed. In some embodiments, the fabric is unpigmented (also referred to herein as ecru or natural). In some embodiments of the invention, the polysiloxane coating of the invention does not significantly change the color or shade of the article. In some embodiments of the invention, the coated article has a rating of 4 or higher on the American Association of Textile Chemists and Colorists (ATTCC) Evaluation Procedure 1-2007, “Gray Scale for Color Change.” [0080] The surface energy, and thus the water repellency, of the coated articles may be evaluated by a number of different methods. In some embodiments, the water repellency of the coated articles is evaluated by using a water-repellency rating determined using AATCC Test Method 193 (2017). In this method, the resistance of coated fabric to wetting by a series of water/alcohol solutions having different surface tensions (1 being 98:2 water-isopropyl alcohol ratio and 12 being 100% isopropanol) is measured. Drops of standard test liquids are placed on the fabric surface and are observed for wetting and wicking. Such wetting and wicking properties are used to correlate the water repellency to the surface tension as shown in Table 1 below. Table 1 [0081] In some embodiments, polysiloxane coatings of the invention have a surface energy in a range of about 24 dyne/cm to about 45 dyne/cm, and in some embodiments, in a range of about 27 dyne/cm to about 33 dyne/cm as measured by AATCC Test Method 193 (2017). In some embodiments, the surface energy is 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 27, 38, 39, 40, 41, 42, 43, 44, or 45 dyne/cm, or any surface energy range defined there between, as measured by AATCC Test Method 193 (2017). [0082] The coated articles of the invention may provide improved water repellency and/or improved weatherability relative to comparative coated articles or control articles, such as comparative coated fabrics or control fabrics. A "comparative article," as used herein, refers to an article of the same form having a water repellent coating thereon (e.g., a current commercial acrylic outdoor fabric). In some embodiments, a comparative article comprises a coating having an acrylic, paraffin wax and/or polyurethane thereon. In some embodiments, the comparative article is an article of the same form coated with a melamine reacted with long chain alkyl, such as Freepel® 1225 (Dystar®). A “control article” refers to an article of the same form as the coated article but without the coating thereon. [0083] In some embodiments, the water repellency of coatings may be measured by a spray testing method such as ATTCC Test Method 22 (2017), Test Method for Water Repellency: Spray. Such water repellency may be measured, both initially and after exposure to certain conditions, including, but not limited to, real world outdoor conditions, heat exposure, and the like. In ATTCC TM22, the water repellency of the fabric is given a rating from 0 to 100 based on the level of wetting of a specimen after a controlled spray of distilled water on the specimen’s surface, wherein a rating of 100 refers to no sticking or wetting of water on the specimen face after the spray procedure, and 0 refers to complete wetting of the entire face of the specimen. In some embodiments of the invention, a coated article of the invention achieves a spray test rating of 80 to 100, based on ATTCC TM22. Furthermore, in some embodiments of the invention, a coated article of the invention may retain its water repellency after weathering. In some embodiments, a coated article may have a spray test rating of 70 or higher after the specimen has been exposed to 100 days or more of outdoor conditions, such as, for example, in South Carolina or Florida. In some embodiments, the temperature of the outdoor conditions falls within a range of about 32 °F to about 94 °F during the 100 days or more and the humidity of the outdoor conditions falls within in a range of about 13% to about 100% during the 100 days or more. In some embodiments, the spray test rating of a coated article decreases 10 points or less between the initial spray test rating and the spray test rating after 100 days or more of outdoor exposure, based on ATTCC TM22. 2. [0084] SAE J2527, "Performance Based Standard for Accelerated Exposure of Automotive Exterior Materials Using a Controlled Irradiance Xenon-Arc Apparatus," is a standard for accelerated weathering that uses a Xenon Arc as a light source to simulate outdoor exposure to sunlight. In some embodiments of the invention, a coated article of the invention may have a spray test rating of at least 70, in some embodiments, at least 80, in some embodiments, at least 90, and in some embodiments, 100, after accelerated weathering in accordance with SAE J2527. In some embodiments, the water repellency of a coated article of the invention is determined and/or measured (e.g., in accordance with ATTCC TM22) after the coated article is exposed to 500, 1000, or 1500 kJ in accordance with SAE J2537. In some embodiments, a coated article of the invention may have a spray test rating in accordance with ATTCC TM22 of at least 70, in some embodiments, at least 80, in some embodiments, at least 90, and in some embodiments, 100, after exposure to 500 kJ in accordance with SAE J2527. In some embodiments, a coated article may have a spray test rating in accordance with ATTCC TM22 of at least 70, in some embodiments, at least 80, in some embodiments, at least 90, and in some embodiments, 100, after exposure to 1000 kJ in accordance SAE J2527. In some embodiments, a coated article may have a spray test rating in accordance with ATTCC TM22 of at least 70, in some embodiments, at least 80, in some embodiments, at least 90, and in some embodiments, 100, after exposure to 1500 kJ in accordance SAE J2527. In some embodiments, a coated article of the invention may decrease less than 10 points between the initial spray test rating in accordance with ATTCC TM22 and the spray test rating after exposure to 500, 1000, or 1500 kJ in accordance with SAE J2527. In some embodiments of the invention, the spray test rating in accordance with ATTCC TM22 of a coated article of the invention is increased 10, 20, 25 points or more after exposure to 500, 1000, or 1500 kJ in accordance SAE J2527. In some embodiments, a spray test rating of the coated article, as measured in accordance with ATTCC TM22, decreases by less than 5 or 10%, or increases by 5, 10, 15, 20%, or more after exposure to accelerated weathering of 500, 1000, or 1500 kJ according to SAE J2527. [0085] In some embodiments, coated articles of the invention may thus have improved weatherability relative to comparative articles. The weatherability may be measured and/or determined based on the change in the water repellency of the article between that measured upon initial formation of the coated article and that measured at about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24 month(s) or more after initial formation of the coated article and/or after exposure to outdoor conditions and/or real or simulated sunlight (e.g., based on SAE2527). In some embodiments, a coated article of the invention has water repellency (e.g., based on ATTCC TM22) that decreases less than by about at 5%, 10%, 15%, or 20% or less after about 3, 6, 9, 12 months, or more of outdoor conditions, and/or after exposure to 500, 1000, or 1500 kJ in accordance with SAE J2527. In some embodiments, a coated article of the invention has water repellency (e.g., based on ATTCC TM22) that increases by about at 5%, 10%, 15%, 20%, 25%, 30% or more after about 3, 6, 9, 12 months, or more of outdoor conditions, and/or after exposure to 500, 1000, or 1500 kJ in accordance with SAE J2527. Methods of Forming Polysiloxanes [0086] Also provided according to embodiments of the invention are methods of forming polysiloxanes. In some embodiments, such methods generally include emulsifying a silane composition according to an embodiment of the invention; heating the emulsified composition; and then reacting the emulsified composition to form the polysiloxane polymer. Such silane compositions may include the first silane monomer, the second monomer, the surfactant and/or water, as described herein. In some embodiments, a catalyst is added to the emulsified composition. The catalyst includes those catalysts described herein. [0087] In some embodiments, emulsifying the composition produces an emulsion having an average particle size of less than about 500 nm, and in particular embodiments, an average particle size of less than 350 nm. In some embodiments, the average particle size is in a range of 100 nm to about 600 nm, such as in a range of about 200 nm to about 400 nm. [0088] In some embodiments, heating the composition includes heating the composition to a temperature in a range of about 70°C to about 100°C for a time sufficient for polysiloxane formation. In some cases, the emulsified composition is reacted at a temperature in a range of about 70°C to about 100°C for a time period in a range of 10 minutes to about 10 hours, about 2 hours to about 8 hours, or about 5 hours to about 7 hours, including about 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 hours or more. [0089] The polysiloxane formation process may produce a lower alcohol such as methanol or ethanol. As such, in some embodiments of the invention, after reaction, the methanol is removed from the polysiloxane composition. Such methods of removal of the lower alcohol are known in the art but, in some embodiments, methods include evaporation and vacuum stripping of the lower alcohol. [0090] In some embodiments, methods further include applying a polysiloxane polymer or polysiloxane composition of the invention onto a surface of an article to form a coating. In some embodiments, the polysiloxane coating is dried on the surface of the article. Further, in some embodiments, the coated article is heated. Such heating may increase removal of methanol and/or water, may further react the polysiloxane composition, may cause reaction of one or more epoxy groups, and/or may cause degradation of the surfactant. In some embodiments, the coated article is heated at a temperature and for a time sufficient to degrade the surfactant (e.g., an amphoteric surfactant). In some embodiments, the degradation of an amphoteric surfactant, such as an amphoteric alkyl amine oxide surfactant, may increase the water repellency and/or weatherability of a coated article of an embodiment of the invention. [0091] Having described the present invention, the same will be explained in greater detail in the following examples, which are included herein for illustration purposes only, and which are not intended to be limiting to the invention. EXAMPLES Example 1: Preparation of a Polysiloxane Latex [0092] The following raw materials were combined at the following concentrations to form a mixture: [0093] The mixture was then emulsified with a high shear mixer at 20,000 RPM for 15 minutes (IKA Ultra Turrax homogenizer). The emulsion particle size was then sampled and measured. If the emulsion particle size was determined to be greater than about 500 nm, the high shear emulsification was continued until the particle size was less than about 500 nm, and in some cases, less than about 350 nm. [0094] The emulsion was then transferred to a reaction vessel. The emulsion was agitated at a moderate rate (with a magnetic stir bar at about 200 RPM for the smaller reactions and an overhead stirrer for batches that are 1 kg or larger) to facilitate heat transfer. The emulsion was then heated using an oil bath heated on a hot plate. While the emulsion is being heated, ammonium hydroxide (28% aqueous) was added as a catalyst to facilitate the reaction. The emulsion was heated to 80°C while continuing agitation. The reaction vessel was then vented or sparged with nitrogen at a moderate level to facilitate methanol removal. The emulsion was heated for 6 hours at 80°C. Then, the reaction was cooled and sampled to determine final latex particle size. [0095] The resulting latices were milky white and were determined to have a molecular weight (Mw) of approximately 6500 daltons. The solids content was determined to be approximately 25-26%. The pH was determined to be approximately 6. The particle sizes were determined to be in a range of 300-500 nm. The methanol content was determined to be approximately 10 weight %. The surface energy provided by a polysiloxane latex on acrylic fabric was in the range of 36-40 dyne/cm using AATCC 193 (2017), as described above. . Example 2: Weatherability of Polysiloxane Coatings [0096] The water repellency of coated articles of the invention was measured using ATTCC TM22 (also referred to herein, as the “spray test”) and compared with the spray test ratings of comparative articles, both initially, after exposure to outdoor conditions (outdoors in Anderson, South Carolina, between August 13, 2020 and November 15, 2020, wherein the temperature ranged rom 32 °F to 94 °F and the humidity ranged from was 13% to 100%), and after accelerated weathering in accordance with SAE J2527. Referring to Table 2, an acrylic awning was coated with a polysiloxane composition (Sample #1) formed from the general reaction described in Example 1, using 10 weight percent of the epoxysilane based on the total silane concentration. This coated acrylic awning article was compared with two fluorinated comparative articles. As can be seen in Table 2, the initial spray test rating of Sample #1 was 80, but after exposure to 104 days of outdoor conditions, the spray test rating only decreased 10 points. Furthermore, after performing accelerated weather test methods on Sample #1 according to SAE J2527 at 1000 and 1500 kJ, the spray rating of the coated article remained the same. In contrast, while the fluorinated comparative articles (Samples #2 and #3) had a high spray rating initially (100), after exposure to 104 days of outdoor conditions, the spray rating decreased to 70-80. After performing accelerated weathering according to SAE J2527 at 1000 and 1500 kJ on Sample #2, the spray test ratings decreased to 70 and 70, respectively. After performing accelerated weathering according to SAE J2527 at 1000 and 1500 kJ on Sample #3, the spray test ratings decreased to 80 and 70, respectively. Thus, the coated article according to an embodiment of the invention showed improved weatherability relative to the fluorinated comparative articles. The inventive coated article did not substantially decease its spray test rating (10 points or less) after the application of weathering conditions, while the fluorinated comparative articles decreased 20-30 points after application of the weathering conditions. TABLE 2 a – initial AATCC TM22 water repellency spray test score b – AATCC TM22 water repellency spray test score after 104 days outside exposure c – AATCC TM22 water repellency spray test score after 1000 kJ SAE J2527 Accelerated Weathering d – AATCC TM22 water repellency spray test score after 1500 kJ SAE J2527 Accelerated Weathering [0097] Table 3 provides additional comparative data. Acrylic furniture coated with a polysiloxane composition (Sample #1) formed from the general reaction described in Example 1, using 10 weight percent of the epoxysilane based on the total silane concentration, was compared with two fluorinated comparative articles. As can be seen in Table 3, the initial spray test rating for Sample #1 was 80, and after exposure to 120 days of outdoor conditions, the spray test rating decreased to 50 – 70, similar to the fluorinated counterparts in Samples #2 and #3 after the same exposure. Furthermore, after performing accelerated weathering according to SAE J2527 at 500 and 1000 kJ on Sample #1, the spray test rating actually increased to 90, while after performing accelerated weathering according to SAE J2527 at 1500 kJ, the spray rating decreased to 70. In contrast, while the fluorinated comparative articles (Samples #2 and #3) had higher initial repellency grade numbers and lower surface energies than Sample #1, their weatherability was worse than Sample #1. For example, Sample #2 had an initial spray test rating of 100 but after exposure to outdoor conditions for 120 days, the spray test rating decreased to 60. Furthermore, after performing accelerated weathering according to SAE J2527 at 500 kJ, the spray rating decreased to 50. Likewise, in Sample #3, the initial spray test rating was 80, but the spray test rating decreased to 50-60 after exposure to outdoor conditions for 120 days. Furthermore, after performing accelerated weathering according to SAE J2527 at 500 kJ, the spray rating decreased to 50. Thus, the non-fluorinated coating of the invention showed superior water repellency upon weathering relative to the comparative fluorinated coatings.
TABLE 3 a - initial AATCC TM22 water repellency spray test score b - AATCC TM22. water repellency spray test score after 119 days outside exposure c -- AATCC TM22 water repellency spray test score after 500 kJ SAE J2527 Accelerated Weathering d - AATCC TM22 water repellency spray test score after 1000 kJ SAE J2527 Accelerated Weathering e - AATCC TM22 water repellency spray test score after 1500 kJ SAE J2527 Accelerated Weathering f- as determined by AATCC TM193 g - as determined by AATCC TM193
[0098] Table 4 compares initial water repellency results for fabrics coated with a polysiloxane composition, formed as generally described in Example 1 with 4 weight percent of the epoxysilane based on the weight of the silane monomers, with a non-fluorinated comparative articles (coated with Freepel® 1225 and Starsil 2980). As seen in Table 4, the water repellency of Samples #1-3 was superior to the water repellency of the non-fluorinated comparative articles. TABLE 4 [0099] Table 5 provides additional comparative data regarding weatherability. Acrylic furniture coated with a polysiloxane composition (Sample #1) formed from the general reaction described in Example 1, using 4 weight percent of the epoxysilane based on the total silane concentration, was compared with 100% acrylic furniture with various non-fluorinated commercial coatings, Curb® (Sciessent, LLC), Hipel EF-50, Freepel® 1225 (Dystar), Phobotex® JVA (Huntsman International LLC), Ruco®-Dri Bio CGR (Rudolf GmbH), and Ruco®-Dri Bio NPE (Rudolf GmbH). While other non-fluorinated coatings had higher initial spray test scores, Sample #1 showed superior weatherability with the spray tests scores increasing after performing accelerated weathering according to SAE J2527 at 500 kJ, 1000 kJ, and 1500 kJ. TABLE 5 a – initial AATCC TM22 water repellency spray test score b - AATCC TM22 water repellency spray test score after 500 kJ SAE J2527 Accelerated Weathering c – AATCC TM22 water repellency spray test score after 1000 kJ SAE J2527 Accelerated Weathering d – AATCC TM22 water repellency spray test score after 1500 kJ SAE J2527 Accelerated Weathering The foregoing is illustrative of the present invention and is not to be construed as limiting thereof. The invention is defined by the following claims, with equivalents of the 30 claims to be included therein.