WO2016101185A1 - Perfluoropolyéthersilanes et leur procédé de préparation - Google Patents

Perfluoropolyéthersilanes et leur procédé de préparation Download PDF

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WO2016101185A1
WO2016101185A1 PCT/CN2014/094848 CN2014094848W WO2016101185A1 WO 2016101185 A1 WO2016101185 A1 WO 2016101185A1 CN 2014094848 W CN2014094848 W CN 2014094848W WO 2016101185 A1 WO2016101185 A1 WO 2016101185A1
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formula
coating
perfluoropolyether
independently
coating composition
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Gang ZUO
Jingzhong WANG
Xu Han
Tian TANG
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EIDP Inc
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EI Du Pont de Nemours and Co
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/002—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds
    • C08G65/005—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens
    • C08G65/007—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/321—Polymers modified by chemical after-treatment with inorganic compounds
    • C08G65/328—Polymers modified by chemical after-treatment with inorganic compounds containing other elements
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/338—Polymers modified by chemical after-treatment with inorganic and organic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/10—Block or graft copolymers containing polysiloxane sequences
    • C09D183/12—Block or graft copolymers containing polysiloxane sequences containing polyether sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
    • C08G2650/46—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing halogen
    • C08G2650/48—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing halogen containing fluorine, e.g. perfluropolyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences

Definitions

  • Novel perfluoropolyether silanes, methods for their preparations, and coating compositions made therefrom are provided. Also provided are articles being coated with the coating compositions, and methods of making the same.
  • glass surfaces such as surfaces of handheld electronics, display or optical devices, monitors, eyewear (e.g., glasses and goggles) , windows and mirrors are susceptible to contaminations like fingerprints, soil, cosmetics, etc.
  • eyewear e.g., glasses and goggles
  • windows and mirrors are susceptible to contaminations like fingerprints, soil, cosmetics, etc.
  • surfaces with high surface energy are more liable to be stained and harder to clean than those with low surface energy.
  • perfluoropolyether silanes for rendering substrates such as glass and ceramics oil and water repellent are known.
  • U.S. Pat. No. 3,646,085 discloses fluorinated polyether amidoalkylsilanes having the general formula of R f O (C 3 F 6 O) n CF (CF 3 ) C (O) N (R) R’ Si (OR” ) 3 for rendering the surface of glass oil and water repellent and scratch resistant.
  • WO2009/008380 A1 discloses a surface treating agent containing a compound of formula (a) : R F1 O (CF 2 CF 2 O) a CF 2 -X, wherein R F1 is a perfluoro monovalent saturated hydrocarbon group having 1-20 carbon atoms or the like, a represents an integer of 1-200, X, inter alia, is–C (O) N (CH 2 CH 2 CH 2 SiL p R 3-p ) 2 (X7) , L is a hydrolyzable group, R represents H or monovalent hydrocarbon group, and p represents an integer of 1-3.
  • WO2013/074299 A9 also discloses a curable fluorinated coating composition including both a perfluoropolyether silane of Formula (I) : F (CF (CF 3 ) CFO) n CF (CF 3 ) CH 2 O-CH 2 CH 2 CH 2 -L-Si (R 1 ) 3-x (R 2 ) x and a fluorinated polyether oil.
  • L is a single bond or-S-CH 2 CH 2 CH 2 -
  • R 1 is hydroxy or a hydrolyzable group
  • R 2 is a non-hydrolyzable group
  • n is an integer of 4 to 100
  • x is 0, 1 or 2.
  • the present invention provides novel perfluoropolyether silanes of Formula 1:
  • R f is R 3 O (CF (CF 3 ) CF 2 O) p CF (CF 3 ) –, R 3 O (CF 2 CF 2 CF 2 O) q CF 2 CF 2 –, or R 3 O (CF 2 CF 2 O) r CF 2 –;
  • R 1 is hydroxy or C 1 -C 4 alkoxy
  • R 2 is H or C 1 -C 4 alkyl
  • R 3 is C 1 -C 6 perfluoroalkyl
  • n are each independently an integer ranging from 3 to 20;
  • x is 1, 2, or 3;
  • p, q and r are each independently an integer ranging from 5 to 60.
  • the present invention also provides a method for preparing the perfluoropolyether silane of Formula 1
  • R f is R 3 O (CF (CF 3 ) CF 2 O) p CF (CF 3 ) –, R 3 O (CF 2 CF 2 CF 2 O) q CF 2 CF 2 –, or R 3 O (CF 2 CF 2 O) r CF 2 –;
  • R 1 is hydroxy or C 1 -C 4 alkoxy
  • R 2 is H or C 1 -C 4 alkyl
  • n are each independently an integer ranging from 3 to 20;
  • x is 1, 2, or 3;
  • p, q and r are each independently an integer ranging from 5 to 60.
  • the present invention further provides a method for preparing the carbinol of Formula 2
  • R f is R 3 O (CF (CF 3 ) CF 2 O) p CF (CF 3 ) –, R 3 O (CF 2 CF 2 CF 2 O) q CF 2 CF 2 –, or R 3 O (CF 2 CF 2 O) r CF 2 –;
  • R 3 is C 1 -C 6 perfluoroalkyl
  • R 4 is H, or C 1 -C 3 alkyl
  • M is Mg, Li, or Sn
  • Hal is Cl, Br, or I.
  • the present invention further provides a coating composition comprising:
  • the at least one solvent is miscible with the perfluoropolyether silane of Formula 1, and the weight % is based on the total weight of the coating composition.
  • the present invention provides an article comprising:
  • the coating composition comprises the perfluoropolyether silane of Formula 1 described herein.
  • the present invention provides a method for making the above mentioned article.
  • the term “produced from” is synonymous to "comprising” .
  • the terms “comprises, ” “comprising, ” “includes, ” “including, ” “has, ” “having, ” “contains” or “containing, ” or any other variation thereof, are intended to cover a non- exclusive inclusion.
  • a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
  • transitional phrase "consisting essentially of” is used to define a composition, method or apparatus that includes materials, steps, features, components, or elements, in addition to those literally discussed, provided that these additional materials, steps features, components, or elements do not materially affect the basic and novel characteristic (s) of the claimed invention.
  • the term “consisting essentially of” occupies a middle ground between “comprising” and “consisting of” .
  • a condition A “or” B is satisfied by any one of the following: A is true (or present) and B is false (or not present) , A is false (or not present) and B is true (or present) , and both A and B are true (or present) .
  • fluorinated refers to a group or compound contains at least one fluorine atom attached to a carbon atom.
  • perfluorinated refers to a group or compound having all C-H bonds replaced with C-F bonds. Examples include perfluoropolyether (PFPE) groups or compounds, or perfluoroether groups or compounds, and perfluoroalkane groups or compounds. Perfluorinated groups of compounds are a subset of fluorinated groups or compounds.
  • ether refers to a group or compound having an oxygen group between two carbon atoms.
  • hydrofluorocarbon means a compound containing hydrogen, carbon, and fluorine, which is a “fluorinated” compound and has been partially fluorinated.
  • a hydrofluorocarbon in this disclosure can be saturated or unsaturated.
  • hydrofluoroolefin or “unsaturated hydrofluorocarbon” as used herein, means a compound containing hydrogen, carbon, fluorine, and at least one carbon-carbon double bond.
  • saturated hydrofluorocarbon ether means a compound containing hydrogen, carbon, fluorine, and at least one ether functional group.
  • unsaturated hydrofluorocarbon ether as used herein, means a compound containing hydrogen, carbon, fluorine, at least one carbon-carbon double bond, and at least one ether functional group.
  • fluorocarbon or “perfluorocarbon” , as used herein interchangeably, means a compound containing carbon and fluorine, which is a “perfluorinated” compound and has all C-H bonds replaced with C-F bonds completely.
  • a (per) fluorocarbon in this disclosure can be saturated or unsaturated.
  • unsaturated fluorocarbon means a compound containing carbon, fluorine, and at least one carbon-carbon double bond.
  • unsaturated fluorocarbon ether as used herein, means a compound containing carbon, fluorine, at least one carbon-carbon double bond, and at least one ether functional group.
  • Embodiments of the present invention as described in the Summary of the Invention include any other embodiments described herein, can be combined in any manner, and the descriptions of variables in the embodiments pertain not only to the perfluoropolyether silanes of the present invention, but also to the coating compositions made therefrom.
  • the present disclosure provides novel perfluoropolyether silanes of Formula 1:
  • R f is R 3 O (CF (CF 3 ) CF 2 O) p CF (CF 3 ) –, R 3 O (CF 2 CF 2 CF 2 O) q CF 2 CF 2 –, or R 3 O (CF 2 CF 2 O) r CF 2 –;
  • R 1 is hydroxy or C 1 -C 4 alkoxy
  • R 2 is H or C 1 -C 4 alkyl
  • R 3 is C 1 -C 6 perfluoroalkyl
  • n are each independently an integer ranging from 3 to 20;
  • x is 1, 2, or 3;
  • p, q and r are each independently an integer ranging from 5 to 60.
  • Embodiments of the present invention include:
  • Embodiment 1A A perfluoropolyether silane of Formula 1, wherein R f is a monovalent perfluoropolyether group, and is R 3 O (CF (CF 3 ) CF 2 O) p CF (CF 3 ) –, R 3 O (CF 2 CF 2 CF 2 O) q CF 2 CF 2 –, or R 3 O (CF 2 CF 2 O) r CF 2 –.
  • Embodiment 1B The compound of Embodiment 1A, wherein R f is R 3 O (CF (CF 3 ) CF 2 O) p CF (CF 3 ) –or R 3 O (CF 2 CF 2 CF 2 O) q CF 2 CF 2 –.
  • Embodiment 1C The compound of Embodiment 1B, wherein R f is R 3 O (CF (CF 3 ) CF 2 O) p CF (CF 3 ) –.
  • Embodiment 2A A perfluoropolyether silane of Formula 1, wherein R 1 is hydroxy or C 1 -C 4 alkoxy.
  • Embodiment 2B A compound of Embodiment 2A, wherein R 1 is C 1 -C 4 alkoxy.
  • Embodiment 2C The compound of Embodiment 2B, wherein R 1 is–OCH 3 or –OC 2 H 5 .
  • Embodiment 3A A perfluoropolyether silane of Formula 1, wherein R 2 is H or C 1 -C 4 alkyl.
  • Embodiment 3B The compound of Embodiment 3A, wherein R 2 is C 1 -C 4 alkyl.
  • Embodiment 4A A perfluoropolyether silane of Formula 1, wherein R 3 is C 1 -C 6 perfluoroalkyl.
  • Embodiment 4B The compound of Embodiment 4A, wherein R 3 is C 1 -C 3 perfluoroalkyl.
  • Embodiment 5A A perfluoropolyether silane of Formula 1, wherein m and n are each independently an integer ranging from 3 to 20.
  • Embodiment 5B The compound of Embodiment 5A, wherein m and n are each independently an integer ranging from 3 to 10.
  • Embodiment 5C The compound of Embodiment 5B, wherein m and n are each independently an integer ranging from 3 to 7.
  • Embodiment 5D The compound of Embodiment 5A, 5B or 5C, wherein m and n are the same.
  • Embodiment 6A A perfluoropolyether silane of Formula 1, wherein x is 1, 2, or 3.
  • Embodiment 6B The compound of Embodiment 6A, wherein x is 2 or 3.
  • Embodiment 6C The compound of Embodiment 6B, wherein x is 3.
  • Embodiment 7A A perfluoropolyether silane of Formula 1, wherein p, q and r are each independently an integer ranging from 5 to 60.
  • Embodiment 7B The compound of Embodiment 7A, wherein p, q and r are each independently an integer ranging from 6 to 45.
  • Embodiment 7C The compound of Embodiment 7B, wherein p, q and r are each independently an integer ranging from 7 to 30.
  • Embodiment A A perfluoropolyether silane of Formula 1, wherein
  • R f is R 3 O (CF (CF 3 ) CF 2 O) p CF (CF 3 ) –or R 3 O (CF 2 CF 2 CF 2 O) q CF 2 CF 2 –;
  • R 1 is hydroxy or C 1 -C 4 alkoxy
  • R 2 is H or C 1 -C 4 alkyl
  • R 3 is C 1 -C 6 perfluoroalkyl
  • n are each independently an integer ranging from 3 to 20;
  • x is 1, 2, or 3;
  • p, q and r are each independently an integer ranging from 6 to 45.
  • Embodiment B A perfluoropolyether silane of Formula 1, wherein
  • R 1 is–OCH 3 or–OC 2 H 5 ;
  • n are each independently an integer ranging from 3 to 10;
  • p, q and r are each independently an integer ranging from 6 to 45.
  • Embodiment C A perfluoropolyether silane of Formula 1, wherein
  • p, q and r are each independently an integer ranging from 7 to 30.
  • Embodiment D A perfluoropolyether silane of Formula 1, wherein
  • R f is R 3 O (CF (CF 3 ) CF 2 O) p CF (CF 3 ) –;
  • R 1 is C 1 -C 4 alkoxy
  • R 3 is C 1 -C 6 perfluoroalkyl
  • n are each independently an integer ranging from 3 to 10;
  • x 3;
  • p, q and r are each independently an integer ranging from 7 to 30.
  • Specific embodiments include perfluoropolyether silanes of Formula 1 selected from the group consisting of:
  • p, q and r are each independently an integer ranging from 5 to 60.
  • PFPE perfluoropolyether
  • PFPE silanes of Formula 1 suitable for compositions for treating substrates of the present invention have a molecular weight of at least about 1,000, and preferably, at least about 1,500. Preferably, their molecular weights are no greater than about 10,000.
  • the PFPE silane of Formula 1 can be synthesized by contacting a carbinol of Formula 2 with a hydrosilane of Formula 3 in the presence of a catalyst 4 as shown in Scheme 1.
  • R 1 , R 2 , R f , m, n and x are as previously defined for Formula 1.
  • hydrosilane 3 to the carbinol of Formula 2 may be effected using a catalyst 4 suitable for hydrosilylation.
  • Hydrosilylation of olefin was firstly reported by Sommer in 1947 using peroxide as catalyst. It has become an important synthetic route to organosilicon compounds since the discovery of Speier catalyst (hexachloroplatinic acid) in 1957 and Karstedt catalyst in 1973 (See references: Sommer, L.H.; Pietrusza, E.W.; Whitmore, F.C.J. Am. Chem. Soc. 1947, 69, 188; Speier, J.L.; Webster, J.A.; Barnes, G.H.J. Am. Chem. Soc.
  • the catalyst 4 is a late transition metal catalyst based on Pt, Rh, Pd, Ru, Ir and Fe. More preferably, the catalyst 4 is a Pt based catalyst, also known as Karstedt catalyst, i.e. platinum (0) -1, 3-divinyl-1, 1, 3, 3-tetramethyldisiloxane complex.
  • Karstedt catalyst i.e. platinum (0) -1, 3-divinyl-1, 1, 3, 3-tetramethyldisiloxane complex.
  • the above mentioned catalysts may be readily synthesized by known methods or are commercially available.
  • the carbinol of Formula 2 may be prepared by contacting a compound of Formula 5 at a temperature below 10°C with a mixture of a compound of Formula 6 and a compound of Formula 7 as shown in Scheme 2.
  • the compounds of Formula 6 and Formula 7 are the same.
  • R f , m, and n are as previously defined for Formula 1;
  • R 4 is H or C 1 -C 3 alkyl
  • M is Mg, Li, or Sn
  • Hal is Cl, Br, or I.
  • PFPE esters or acids of Formula 5 are commercially available or may be readily synthesized by known methods.
  • anionic polymerization of hexafluoropropylene epoxide (C 3 F 6 O, HFPO) as described by Moore in U.S. Pat. No. 3,322,826 can result in a PFPE carbonyl fluoride R f C (O) F, wherein R f is C 3 F 7 O (CF (CF 3 ) CF 2 O) p CF (CF 3 ) -.
  • the methyl ester can also be prepared by the method described in WO2013/074299 A9, preparative example 2.
  • PFPE esters of Formula 5 where R f is C 3 F 7 O (CF 2 CF 2 CF 2 O) q CF 2 CF 2 - can be produced by sequential oligomerization and fluorination of 2, 2, 3, 3-tetrafluorooxetane.
  • R f is C 2 F 5 O (CF 2 CF 2 O) r CF 2 -
  • C 2 F 4 O tetrafluoroethylene oxide
  • the carbonyl fluoride produced initially from polymerization may be converted into a corresponding acid or ester of Formula 5 by reactions well known to those skilled in the art.
  • Suitable fluorinated carboxylic acid are commercially available, for example, C 3 F 7 O (CF (CF 3 ) CF 2 O) p CF (CF 3 ) COOH under the trade name 157FS with different number average molecular weight (M n ) are available from E.I. DuPont de Nemours Co., Wilmington, DE, USA, hereunder is referred as “DuPont. ”
  • a mixture of perfluoropolyether acid or ester of Formula 5 may be used to yield a mixture of the fluorinated polyether silanes of Formula 1, and coating composition made therefrom.
  • the perfluoropolyether silanes of Formula 1 having a PFPE moiety with a number average molecular weight of at least more than about 1,000 and less than about 10,000; or from about 1,500 to about 8,000.
  • the present invention further provides a coating composition comprising:
  • the at least one solvent is miscible with the PFPE silane of Formula 1 described herein and the weight % is based on the total weight of the coating composition.
  • the coating composition comprises at least one solvent.
  • a coating composition of the present invention for many siliceous substrates may include one or more solvents.
  • the at least one solvent is a fluorinated solvent, a non-fluorinated solvent, or a mixture thereof.
  • the solvent or mixture of solvents used must be capable of dissolving at least 0.01% by weight of the PFPE silane of Formula 1. If the solvent or mixture of solvents do not meet the criteria, it may not be possible to obtain a homogeneous composition having the PFPE silane of Formula 1, solvent (s) , and optional additives. Although such non-homogeneous compositions could be used to treat a substrate, the coating obtained therefrom will generally not have the desired oil/water repellency and will not have sufficient durability properties.
  • Suitable solvents have normal boiling points of from about 50°C to about 150°C; and preferably, from about 60°C to about 120°C and can be a fluorinated solvent, a non-fluorinated solvent, or a mixture thereof.
  • the at least one solvent has normal boiling points of from about 50°C to about 150°C; or from about 60°C to about 120°C. In some embodiments of the present coating composition, the at least one solvent is a fluorinated solvent, a non-fluorinated solvent, or a mixture thereof.
  • Suitable fluorinated solvents include hydrofluorocarbons, hydrofluorocarbon ether, fluorocarbons, fluorocarbon ether, and mixtures thereof. These fluorinated solvents can be saturated or unsaturated. In some embodiments of this invention, the fluorinated solvent is selected from the group consisting of hydrofluorocarbons, hydrofluorocarbon ethers, fluorocarbons, fluorocarbon ethers, and mixtures thereof.
  • fluorinated solvents examples include hydrofluorocarbons such as pentafluorobutane, available from Solvay Solexis, or 2, 3-dihydrodecafluoropentane (CF 3 CFHCFHCF 2 CF 3 ) available from DuPont as VERTREL TM ; hydrofluorocarbon ethers including alkyl perfluoroalkyl ether such as methyl perfluorobutyl ether or ethyl perfluorobutyl ether, available from 3M as NOVEC TM HFE 7100 and NOVEC TM HFE 7200, respectively; fluorocarbons such as perfluorohexane, perfluoroheptane, or perfluorooctane, available from 3M.
  • hydrofluorocarbons such as pentafluorobutane, available from Solvay Solexis, or 2, 3-dihydrodecafluoropentane (CF 3 CFHCFHCF 2 CF 3
  • the at least one solvent comprises, consists essentially of, or consists of a saturated hydrofluorocarbon. In some embodiments of this invention, the at least one solvent comprises, consists essentially of, or consists of CF 3 CHFCHFCF 2 CF 3 .
  • unsaturated fluorocarbons have lower global warming potentials (GWPs) than their saturated counterparts.
  • the unsaturated fluorocarbon include hydrofluoroolefins, alkyl perfluoroalkene ethers, and mixtures thereof.
  • the alkyl perfluoroalkene ether is methyl perfluoroalkene ether, ethyl perfluoroalkene ether, or mixtures thereof. More preferably, the methyl perfluoroalkene ether is methyl perfluoroheptene ether, methyl perfluoropentene ether, or mixtures thereof.
  • methyl perfluoroheptene ether or methyl perfluoropentene ether is a mixture of its isomers respectively.
  • the at least one solvent comprises, consists essentially of, or consists of an unsaturated fluorocarbon. In some embodiments of this invention, the at least one solvent comprises, consists essentially of, or consists of a hydrofluoroolefin. In some embodiments of this invention, the at least one solvent comprises, consists essentially of, or consists of an alkyl perfluoroalkene ether. In some embodiments of this invention, the alkyl perfluoroalkene ether is methyl perfluoroalkene ether, ethyl perfluoroalkene ether, or mixtures thereof. In some embodiments of this invention, the methyl perfluoroalkene ether is methyl perfluoroheptene ether, methyl perfluoropentene ether, or mixtures thereof.
  • Suitable non-fluorinated solvents include alcohols, ketones, nitriles, cyclic ethers, noncyclic ethers, and mixtures thereof.
  • the non-fluorinated solvent is selected from the group consisting of alcohols, ketones, nitriles, cyclic ethers, noncyclic ethers, and mixtures thereof.
  • non-fluorinated solvents examples include alcohols such as methanol, ethanol, 1-propyl alcohol, 2-propanol; ketones such as acetone or methyl ethyl ketone; nitriles such as acetonitrile, cyclic ethers such as tetrahydrofuran, noncyclic ethers such as diethyl ether, diisopropyl ether, methyl t-butyl ether, and dipropylene glycol monomethyl ether, and mixtures thereof.
  • alcohols such as methanol, ethanol, 1-propyl alcohol, 2-propanol
  • ketones such as acetone or methyl ethyl ketone
  • nitriles such as acetonitrile
  • cyclic ethers such as tetrahydrofuran
  • noncyclic ethers such as diethyl ether, diisopropyl ether, methyl t-butyl ether, and dipropylene
  • the non-fluorinated solvent is selected from the group consisting of methanol, ethanol, 1-proponol, 2-proponol, acetone, methyl ethyl ketone, acetonitrile, tetrahydrofuran, and mixtures thereof. In some embodiments of this invention, the non-fluorinated solvent is selected from the group consisting of methanol, ethanol, 1-proponol, 2-proponol, tetrahydrofuran, and mixtures thereof.
  • the amount of the at least one solvent used in the coating composition can be selected to provide the desired viscosity for application of the coating composition to a siliceous substrate.
  • the coating compositions based on the total weight of the coating compositions, may contain at least 70 weight %, up to 80 weight %, up to 90 weight %, up to 95 weight %, up to 99.9 weight %, or up to 99.99 weight % of at least one solvent.
  • the coating compositions can comprise 70 to 99.99 weight %, 80 to 99.9 weight %, or 90 to 95 weight % of at least one solvent.
  • a coating composition of the present invention may further comprise additives such as curing catalysts, provided they do not react with the perfluoropolyether silane of Formula 1.
  • the curing catalysts can be any of the catalysts typically used to cure reactive organosilanes by hydrolysis and condensation. Suitable curing catalysts are those that are soluble in the coating composition (e.g., in the fluorinated solvent, non-fluorinated solvent, or mixtures thereof) .
  • the at least one curing catalyst comprises, consists essentially of, or consists of acids, bases, or water.
  • acids include inorganic acids, alkyl sulfonic acids, halogenated alkyl sulfonic acids, carboxylic acids, halogenated carboxylic acids, and mixtures thereof.
  • inorganic acids include HCl, H 2 SO 4 , HNO 3 , and mixtures thereof.
  • carboxylic acids include formic acid, acetic acid, trifluoroacetic acid, and mixtures thereof.
  • bases include inorganic bases, substituted and unsubstituted trialkylamines, pyridine and its derivatives, and mixtures thereof.
  • inorganic bases include NaOH, KOH, and mixtures thereof.
  • the curing catalysts are used in amounts that are soluble in the coating compositions.
  • the moisture curing agents are present in an amount ranging from about 0.001-5 weight %, about 0.01-3 weight %, or in a range of about 0.1-2 weight %, based on a total weight of the coating composition.
  • Coated articles and Method of manufacturing the coated article are Coated articles and Method of manufacturing the coated article.
  • the present invention provides a coated article comprising: a siliceous substrate, and a layer of a coating composition cured on at least one surface of the siliceous substrate, wherein the coating composition comprises a perfluoropolyether silane of Formula 1 described herein.
  • Siliceous substrates include those formed of various materials that contain silicon distributed throughout the substrate. Examples of siliceous substrates include, but are not limited to, glass, ceramic materials, glazed ceramic materials, concrete, mortar, grout, and natural or man-made stone.
  • the siliceous substrate can be, for example, part of an electronic display (e.g., an outer surface of an electronic display such as a touch screen) , mirror, window, windshield, ceramic tile, shower stall, toilet, sink, or the like.
  • the siliceous substrate is transparent, which means that it is possible to see through the siliceous substrate with an unaided human eye.
  • the transparent substrate can be clear or colored.
  • the coating composition of the invention can be applied onto the siliceous substrate by either wet coating methods or dry coating methods.
  • dry coating methods include chemical vapor deposition (CVD) and physical vapor deposition (PVD) .
  • PVD physical vapor deposition
  • wet coating methods include spray coating, knife coating, dip coating, spin coating, meniscus coating, flow coating, roll coating, gravure coating, or the like.
  • the coating composition is applied using a method selected from spray coating, knife coating, dip coating, spin coating, meniscus coating, flow coating, roll coating, and gravure coating.
  • the surface of the siliceous substrate should be extremely clean prior to applying the coating composition for optimum coating characteristics, particularly durability, to be obtained. That is, the surface of the siliceous substrate to be coated should be substantially free of organic contamination prior to coating.
  • Cleaning techniques depend on the type of siliceous substrate and include, for example, ultrasound cleaning in a solvent bath (e.g., ethanol/chloroform) , gas-phase discharge techniques such as air corona treatment, plasma treatment, UV ozone treatment, washing with detergent and/or hot water, or combinations of these techniques. Specific examples of support surface preparation are described in the Example section.
  • article of the present invention comprises a siliceous substrate and a layer of a coating composition cured on at least one surface of the siliceous substrate.
  • the cured coating includes a reaction product of the PFPE silane of Formula 1 present in the coating composition with the siliceous substrate surface. Any coating composition comprising the PFPE silane of Formula 1 described herein can be used to form the cured coating composition.
  • the term “curing” refers to the reaction of the silyl group of the PFPE silane of Formula 1 with the siliceous substrate.
  • the term “cured coating” refers to a layer of coating formed by a coating composition that has undergone curing. The curing reaction results in the formation of a-Si-O-Si-group (i.e. a siloxane group) and the covalent attachment of the PFPE silane to at least one surface of the siliceous substrate.
  • a-Si-O-Si-group i.e. a siloxane group
  • the cured coating shall comprise a reaction product of the present coating composition with at least one surface of the siliceous substrate, said reaction product is covalently attached to the siliceous substrate surface.
  • a cured coating prepared from the coating composition containing the PFPE silane of Formula 1 may also include unreacted or uncondensed silyl groups. It is believed that the curing reaction is formed as a result of hydrolysis of the silyl groups of the PFPE silane with residual water, which is either in the coating composition or adsorbed to the substrate surface, for example, and then condensation of the hydrolyzed silyl groups on and to the siliceous substrate surface.
  • sufficient water is present for the preparation of a durable coating if the coating method is carried out at room temperature in the atmosphere, preferably, with a relative humidity (RH) of at least about 30% and up to 90% at an elevated temperature, such as at least about 30°C or higher.
  • RH relative humidity
  • the coating composition is dried to remove solvent and then cured at a temperature in a range of about 30°C to about 160°C for a time sufficient for curing to take place.
  • the coated substrate is often held at the curing temperature for at least 5 minutes and up to 24 hours. The drying and curing steps can occur concurrently or separately by adjustment of the temperature.
  • the article of the present invention is prepared by the method comprising:
  • step i comprising:
  • the at least one solvent is miscible with the perfluoropolyether silane, and the weight % is based on the total weight of the coating composition.
  • the layer of the cured coating of the present article can have any desired thickness.
  • the layer thickness of the cured coating is generally greater than a monolayer, which is typically greater than about 10 Angstroms thick. Generally, it is less than about 500 Angstroms thick, and preferably, less than about 400 Angstroms thick.
  • the layer thickness of the cured coating corresponds to at least one monolayer. This thickness is often in a range of about 10 to 400 Angstroms. In some embodiments, the overall coating thickness of the cured coating composition can be in a range of about 10 to 400, about 50-300, about 100 to 250, or about 150 to 200 Angstroms.
  • the articles having a cured coating often have improved abrasion resistance compared to the uncoated siliceous substrate.
  • the coated siliceous substrate can be abraded with steel wool (e.g., steel wool No. 0000 that is capable of scratching a glass surface) while retaining water repellant and/or oil repellant properties of the cured coating.
  • the articles having a cured coating provide a good tactile response. That is, a finger can slide over the surface of the articles easily. This is particularly desirable when the article is used in electronic displays such in touch screens.
  • the articles also have an easy to clean surface.
  • This easy to clean surface is provided by the PFPE silane of Formula 1 present in the coating composition.
  • the surfaces of the articles with cured coatings tend to be hydrophobic.
  • the initial water contact angle is often equal to at least 100°, at least 105°, or at least 110°.
  • PE Preparative Example
  • E stands for “Example”
  • CE stands for “Comparative Example” is followed by a number indicating in which example the PFPE silanes and their precursors is synthesized, or prepared. The examples and comparative examples were all prepared and tested in a similar manner. Percentages are based by mole unless otherwise indicated.
  • NOVEC TM 7100 methyl perfluorobutyl ether, CAS number: 163702-07-6, purchased from 3M Company (Saint Pual, MN, USA) , b.p. is 64.5°C.
  • VERTREL TM XF 2, 3-dihydrodecafluoropentane, CAS number: 138495-42-8, obtained from DuPont DC&F, b.p. is 55°C.
  • Perfluoropolyether methyl ester-A C 3 F 7 O (CF (CF 3 ) CF 2 O) p CF (CF 3 ) C (O) OCH 3 , p is about 9, M n is approximately 1600, derived from 157FSL, which available from DuPont.
  • Perfluoropolyether methyl ester-B C 3 F 7 O (CF (CF 3 ) CF 2 O) p CF (CF 3 ) C (O) OCH 3 , p is about 20, M n is approximately 3860, derived from 157FSM, which is available from DuPont.
  • Perfluoropolyether trimethoxysilylpropyl ether (Silyl ether-I) : CAS number: 211931-77-0, C 3 F 7 O (CF (CF 3 ) CF 2 O) b CF (CF 3 ) CH 2 O (CH 2 ) 3 Si (OCH 3 ) 3 , b is about 9, M n is approximately 1800, obtained from DuPont, and was used in Comparative Example 1.
  • Karstedt catalyst platinum (0) -1, 3-divinyl-1, 1, 3, 3-tetramethyldisiloxane complex, CAS number 68478-92-2, 2 % Pt solution in xylene, purchased from Sigma-Aldrich.
  • Allymagnesium chloride CAS Number: 2622-05-1, 2 M solution in THF, purchased from Sigma-Aldrich.
  • Triethoxysilane CAS Number: 998-30-1, purchased from TCI.
  • Trimethoxysilane CAS Number: 2487-90-3, purchased from TCI.
  • Mighty ZS-118 a detergent for optical glass, obtained from Zhongsheng Rongtian (Beijing) International Technology and Trading Co., Ltd.
  • R f is C 3 F 7 O (CF (CF 3 ) CF 2 O) p CF (CF 3 ) –, and p is an estimated number based on the M n .
  • the glass slides VWR Micro Slides White, were placed in a glass vertical staining jar containing 100 mL of a detergent solution (5 weight% of Mighty ZS-118) and were sonicated in an ultrasonic bath (Shanghai Kudos Ultrasonic Instrument Co., Ltd. model: Kudos SK5210LHC) for 10 minutes, followed by deionized water rinsing for 4 times. Each rinsing step was consisted of placing the slides in 100 mL of fresh deionized water and sonicated for 3 minutes. The cleaned slides were dried in an oven at 80°C for 10 minutes, then treated with UV ozone in a UVO cleaner machine (Jelight Company Inc., Model No. 42-220) for 20 minutes. The slides were then contacted with a coating composition having 0.5 weight % of a perfluoropolyether silane prepared in PE1-PE5 as specified in Table 2 in VERTREL TM XF within approximately 30 minutes.
  • a detergent solution 5 weight%
  • the coating compositions were applied to the glass slides with a spray gun (Anest Iwata, part number of RG-3L-3S (Yokohama, Japan) ) .
  • Each coating composition (5 mL) was applied to 8 slides, which were placed flat on bench top under a pressure of 0.1 MPa.
  • the wet glass slides were then dried and cured in an oven set at 100°C with 50-60% relative humidity for 1 hour.
  • Contact angle measurements can be used to determine the surface energy of a substrate. Generally, a larger contact angle indicates a smaller surface energy.
  • contact angle means the angle formed between the liquid/substrate surface interface and the liquid/air interface.
  • static contact angle means the contact angle measured on a static sessile drop of liquid on a substrate surface.
  • WCA Static water contact angles
  • a linear abrader (Taber Industries of North Tonawanda, TABER 5900 (NY, USA) ) was fitted with a square tool having a flat surface area of 1 cm 2 .
  • One piece of steel wool (No. 0000) was fixed on the square tool to be used for the abrasion test of the coated glass substrates.
  • the samples were abraded in increments of 100 cycles (or as specified otherwise) at a rate of 60 cycles/minute with a 1 Kg load and a stroke length of 50 millimeters.
  • One cycle consisted of a forwarded scrub followed by a backward scrub.
  • a composition containing silyl ether-I i.e. C 3 F 7 O (CF (CF 3 ) CF 2 O) b CF (CF 3 ) CH 2 O (CH 2 ) 3 Si (OCH 3 ) 3
  • a siliceous substrate i.e. glass slides
  • inventive coating compositions comprising the perfluoropolyether silanes of Formula 1 results in a layer of a cured coating on the siliceous substrate surface.
  • Said cured coatings render the treated surfaces of the articles less retentive of soil and more readily cleanable due to the water and/or oil repellent nature. These desirable properties are maintained despite repeated abrasions because of the high durability of the cured coatings as can be obtained through the coating compositions of this invention.

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Abstract

La présente invention concerne des perfluoropolyéthersilanes de formule 1, leur procédé de préparation et des compositions de revêtement fabriquées à partir de ceux-ci. Dans la formule 1, Rf représente R3O(CF(CF3)CF2O) p-CF(CF3)-, R3O(CF2CF2CF2O)qCF2CF2-, ou R3O(CF2CF2O)rCF2-; et R1, R2, R3, m, n, x, p, q et r sont tels que définis dans la description. L'invention concerne également des articles dont la surface est recouverte d'une couche des compositions de revêtement durcie, et leurs procédés de fabrication. Lesdits revêtements améliorent la résistance à l'abrasion des articles.
PCT/CN2014/094848 2014-12-24 2014-12-24 Perfluoropolyéthersilanes et leur procédé de préparation Ceased WO2016101185A1 (fr)

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WO2017077834A1 (fr) * 2015-11-06 2017-05-11 信越化学工業株式会社 Composé organosilicié modifié par un polymère, contenant un groupe fluoropolyéther, agent de traitement de surface et produit
WO2017104249A1 (fr) * 2015-12-14 2017-06-22 信越化学工業株式会社 Silane modifié par un polymère contenant un groupe fluoropolyéther, agent de traitement de surface et objet
WO2018180561A1 (fr) * 2017-03-27 2018-10-04 Ａｇｃ株式会社 Composition d'éther fluoré et procédé de production associé
WO2018200468A1 (fr) * 2017-04-25 2018-11-01 Corning Incorporated Articles en verre, en vitrocéramique et en céramique dotés de revêtements lubrifiants anti-traces de doigt et leurs procédés de fabrication
WO2018216406A1 (fr) * 2017-05-25 2018-11-29 信越化学工業株式会社 Composé silicium organique modifié par un polymère à teneur en groupe fluoropolyéther, agent de traitement de surface, et article
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CN116144106A (zh) * 2022-12-28 2023-05-23 上海日之升科技有限公司 一种高透明快速成型低生物溶剂残留的聚丙烯材料

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US10093773B2 (en) * 2014-03-31 2018-10-09 Shin-Etsu Chemical Co., Ltd. Fluoropolyether-containing polymer-modified silane, surface treating agent, and article
KR20150113881A (ko) * 2014-03-31 2015-10-08 신에쓰 가가꾸 고교 가부시끼가이샤 플루오로폴리에테르기 함유 중합체 변성 실란, 표면 처리제 및 물품
KR102243225B1 (ko) 2014-03-31 2021-04-22 신에쓰 가가꾸 고교 가부시끼가이샤 플루오로폴리에테르기 함유 중합체 변성 실란, 표면 처리제 및 물품
JP2016204656A (ja) * 2015-04-20 2016-12-08 信越化学工業株式会社 フルオロポリエーテル基含有ポリマー変性シラン、表面処理剤及び物品
US20160319071A1 (en) * 2015-05-01 2016-11-03 Shin-Etsu Chemical Co., Ltd. Fluoropolyether-containing polymer-modified silane, surface treating agent, and article
JP2016210854A (ja) * 2015-05-01 2016-12-15 信越化学工業株式会社 フルオロポリエーテル基含有ポリマー変性シラン、表面処理剤及び物品
US10196483B2 (en) * 2015-05-01 2019-02-05 Shin-Etsu Chemical Co., Ltd. Fluoropolyether-containing polymer-modified silane, surface treating agent, and article
WO2017077834A1 (fr) * 2015-11-06 2017-05-11 信越化学工業株式会社 Composé organosilicié modifié par un polymère, contenant un groupe fluoropolyéther, agent de traitement de surface et produit
JPWO2017104249A1 (ja) * 2015-12-14 2018-09-13 信越化学工業株式会社 フルオロポリエーテル基含有ポリマー変性シラン、表面処理剤及び物品
WO2017104249A1 (fr) * 2015-12-14 2017-06-22 信越化学工業株式会社 Silane modifié par un polymère contenant un groupe fluoropolyéther, agent de traitement de surface et objet
CN110392711B (zh) * 2017-03-27 2022-04-12 Ａｇｃ株式会社 含氟醚组合物及其制造方法
WO2018180561A1 (fr) * 2017-03-27 2018-10-04 Ａｇｃ株式会社 Composition d'éther fluoré et procédé de production associé
CN110392711A (zh) * 2017-03-27 2019-10-29 Ａｇｃ株式会社 含氟醚组合物及其制造方法
US10413948B2 (en) 2017-04-25 2019-09-17 Corning Incorporated Glass, glass-ceramic and ceramic articles with lubricious anti-fingerprint coatings and methods of making the same
CN110582471A (zh) * 2017-04-25 2019-12-17 康宁股份有限公司 具有润滑性防指纹涂层的玻璃、玻璃陶瓷和陶瓷制品及其制造方法
WO2018200468A1 (fr) * 2017-04-25 2018-11-01 Corning Incorporated Articles en verre, en vitrocéramique et en céramique dotés de revêtements lubrifiants anti-traces de doigt et leurs procédés de fabrication
CN110582471B (zh) * 2017-04-25 2022-06-03 康宁股份有限公司 具有润滑性防指纹涂层的玻璃、玻璃陶瓷和陶瓷制品及其制造方法
KR20200013687A (ko) * 2017-05-25 2020-02-07 신에쓰 가가꾸 고교 가부시끼가이샤 플루오로폴리에테르기 함유 폴리머 변성 유기 규소 화합물, 표면처리제 및 물품
WO2018216406A1 (fr) * 2017-05-25 2018-11-29 信越化学工業株式会社 Composé silicium organique modifié par un polymère à teneur en groupe fluoropolyéther, agent de traitement de surface, et article
KR102565511B1 (ko) 2017-05-25 2023-08-10 신에쓰 가가꾸 고교 가부시끼가이샤 플루오로폴리에테르기 함유 폴리머 변성 유기 규소 화합물, 표면처리제 및 물품
US11820912B2 (en) 2017-05-25 2023-11-21 Shin-Etsu Chemical Co., Ltd. Fluoropolyether group-containing polymer-modified organic silicon compound, surface treatment agent, and article
US11365285B2 (en) * 2017-08-31 2022-06-21 AGC Inc. Fluorinated ether compound, fluorinated ether composition, coating liquid, article and its production method
CN116144106A (zh) * 2022-12-28 2023-05-23 上海日之升科技有限公司 一种高透明快速成型低生物溶剂残留的聚丙烯材料
CN116144106B (zh) * 2022-12-28 2024-06-04 上海日之升科技有限公司 一种高透明快速成型低生物溶剂残留的聚丙烯材料

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