Silane coating compositions containing silicon-based polyether copolymers, methods for coating metal surfaces and articles made therefrom
View Patent ↗A silane coating composition containing a silicon-based copolymer, a method for treating the surfaces of a metal such as steel, zinc-coated steels, or aluminum, to provide for the formation of a uniform conversion and/or passivation coating which increases the corrosion resistance of bare or painted metal and/or the adhesion properties of the metal, along with a metal having a conversion and/or passivation coating applied thereto are disclosed. Methods of the invention include contacting the requisite metal surface with an aqueous solution of a silane compound and a silicon-based polyether copolymer.
1. A coating composition comprising
(a) at least one silane of the general formula (1):
or hydrolyzates or condensates thereof
wherein
each occurrence of R 1 independently is a hydrogen atom, an acyl, a monovalent hydrocarbyl, or an alkoxy-substituted alkyl group of from 1 to 16 carbon atoms;
each occurrence of R 2 independently is alkyl, alkoxy-substituted alkyl, aryl, or aralkyl group of from 1 to 16 carbon atoms;
each occurrence of R 3 independently is a covalent chemical bond or a linear, branched or cyclic divalent organic group of from 1 to 12 carbon atoms;
each occurrence of Y independently is a mono-, di- or polyvalent organofunctional group of valence m;
each occurrence of subscripts a, b, m and n is independently an integer where a is 0 to 3; b is 0 to 2; and m is 1 to 4;
(b) at least one silicon-based polyether copolymer of the general formula (2):
(R 4 )(R 5 )(R 6 )SiR 7 Si(R 8 )(R 9 )[OSi(R 10 )(R 11 )] x R 12 (C 2 H 4 O) d (C 3 H 6 O) e (C 4 H 8 O) f R 13 (2)
wherein
each occurrence of R 4 , R 5 , R 6 , R 8 , R 9 , R 10 and R 11 independently is a monovalent hydrocarbyl group of from 1 to 10 carbon atoms;
each occurrence of R 7 independently is a divalent hydrocarbylene group of 1 to 3 carbon atoms;
each occurrence of R 12 independently is a divalent organic group having the structure:
—CH 2 —CH(R 14 )(R 15 ) g O—
where each occurrence of R 14 independently is a hydrogen atom or methyl; each occurrence of R 15 independently is a divalent alkylene radical of 1 to 6 carbon atoms; and the subscript g is 0 or 1;
each occurrence of R 13 independently is selected from the group consisting of a hydrogen atom, a monovalent hydrocarbon group, and an acyl group of 1 to 6 carbon atoms; and
each occurrence of the subscripts d, e, f and x is an integer where d is 2 to 20, e is 0 to 18, f is 0 to 18 and x is 0 or 1 with the proviso that 2≦d+e+f≦20; and
(c) water,
with the proviso that, where the composition comprises condensates of silane (1), it may have a degree of polymerization of between 2 and 50.
2. The coating composition of claim 1 wherein Y is a univalent organofunctional group selected from the group consisting of amino (—NR 16 2 ), diamino (—N(R 16 )R 3 NR 16 2 ), mercapto (—SH), acryloxy (CH 2 ═CHCO 2 —), methacryloxy (CH 2 ═C(CH 3 )CO 2 —), acetoxy (CH 3 CO 2 —), glycidoxy (—O—CH 2 —C 2 H 3 O), epoxycyclohexyl (—C 6 H 9 O); epoxy (—CR 16 (—O—)CR 16 2 ), hydroxyl (HO—), dithiocarbonate (—SC(═O)SR 16 ), trithiocarbonate (—SC(═S)SR 16 ), carbamate (—NR 16 (C═O)OR 16 ), thioester (—S(C═O)R 16 , thiocarbamate (—NR 16 (C═O)SR 16 ), dithiocarbamate (—NR 16 (C═S)SR 16 ), urethane (—O(C═O)NR 16 R 16 ), univalent ureido (—NR 16 (C═O)NR 16 2 , silyl (—Si(R 2 ) b (OR 1 ) 3-a-b (—O—) 0.5a ) and isocyanurato , ((—N)(NR 16 )(NR 16 )C 3 O 3 ) where each occurrence of R 16 is independently selected from the group consisting of hydrogen and straight, branched and cyclic alkyl, alkenyl or aryl of from 1 to 6 carbon atoms.
3. The coating composition of claim 1 wherein Y is a divalent organofunctional group selected from the group consisting of sulfide (—S—), disulfide (—SS—), trisulfide (—SSS—), tetrasulfide (—SSSS—), carbamate ((—)) 2 N(C═O)OR 16 or —R 16 N(C═O)O—), ureido ((—) 2 N (C═O)NR 16 2 or (—)NR 16 (C═O)N(—)R 16 ), and isocyanurato ((—N) 2 (NR 16 )C 3 O 3 ) where each occurrence of R 16 is independently selected from the group consisting of hydrogen and straight, branched and cyclic alkyl, alkenyl or aryl of from 1 to 6 carbon atoms.
4. The coating composition of claim 1 wherein Y is a trivalent organofunctional group selected from the group consisting of carbamate ((—) 2 N(C═O)O(—)), ureido ((—)NR 16 C═O)N(—) 2 ), and isocyanurato ((—N) 3 C 3 O 3 )) where each occurrence of R 16 is independently selected from the group consisting of hydrogen and straight, branched and cyclic alkyl, alkenyl, aryl or alkaryl of from 1 to 6 carbon atoms.
5. The coating composition of claim 1 wherein Y is the tetravalent organofunctional group ureido ((—) 2 (C═O)N(—) 2 ).
6. The coating composition of claim 1 wherein silane (a) is selected from the group consisting of vinylmethyldiethoxysilane, vinyltrimethoxysilane, vinyldimethylethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, vinyl-tris(2-methoxyethoxysilane), styrylethyltrimethoxysilane, gamma-acryloxypropyltrimethoxysilane, gamma-(acryloxypropyl)methyldimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, gamma-methacryloxypropyltriethoxysilane, gamma-methacryloxypropylmethyldimethoxysilane, gamma-methacryloxypropylmethyldiethoxysilane, gamma-methacryloxypropyl-tris-(2-methoxyethoxy)silane, beta-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, beta-(3,4-epoxycyclohexyl)ethyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxypropyltriethoxysilane, gamma-glycidoxypropylmethyldiethoxysilane, gamma-glycidoxypropylmethyldimethoxysilane, gamma-mercaptopropyltrimethoxysilane, gamma-mercaptopropyltriethoxysilane, gamma-thiooctanoylpropyltrimethoxysilane, gamma-thiooctanoylpropyltriethoxysilane, bis-(trimethoxysilylpropyl)tetrasulfane, bis-(triethoxysilylpropyl)disulfane, gamma-ureidopropyltrimethoxysilane, gamma-ureidopropyltriethoxysilane, gamma-ureidopropyldimethoxyethoxysilane, gamma-ureidopropylmethoxydiethoxysilane, gamma-ureidopropylmethyldimethoxysilane, gamma-ureidopropylmethyldiethoxysilane, gamma-ureidopropylmethylmethoxyethoxysilane, gamma-carb amatopropyltrim ethoxysilane, gamma-carbamatopropyltriethoxysilane, N,N′-bis-(3-triethoxysilylpropyl)urea, N,N′-bis-(3-trimethoxysilylpropyl)urea, N,N′-bis-(3-diethoxymethylsilylpropyl)urea, N,N′-bis-(3-diisopropoxymethylsilylpropyl)urea, N,N-bis-(3-triethoxysilylpropyl)urea, N,N-bis-(3-trimethoxysilylpropypurea, N,N-bis-(3-diethoxymethylsilylpropyl)urea, N,N-bis-(3-diisopropoxymethylsilylpropyl)urea, N,N,N′-tris-(3-triethoxysilylpropyl)urea, N,N,N′-tris-(3-trimethoxysilylpropyl)urea, N,N,N′-tris-(3-diethoxymethylsilylpropyl)urea, N,N,N′-tris-(3-diisopropoxysilylpropyl)urea, N,N,N,'N′tetrakis-(3-triethoxysilylpropyl)urea, N,N,N,'N′-tetrakis-(3-trimethoxysilylpropyl)urea, N,N,N,'N′-tetrakis-(3-diethoxymethylsilylpropyl)urea, N,N,N,'N′-tetrakis-(3diisopropoxymethylsilylpropyl)urea, N,N′,N″-tris-(3-trimethoxysilylpropyl)isocyanurate, and partial or complete hydrolyzates thereof.
7. The coating composition of claim 6 wherein silane (a) is selected from the group consisting of unhydrolyzed, partially hydrolyzed and hydrolyzed gammaureidopropyltrimethoxysilane and gamma-ureidopropyltriethoxysilane.
8. The coating composition of claim 1 wherein the silicon-based polyether copolymer (b) is selected from the group consisting of (CH 3 ) 3 SiCH 2 Si(CH 3 ) 2 CH 2 CH 2 O(CH 2 CH 2 O) 2 H, (CH 3 ) 3 SiCH 2 CH 2 Si(CH 3 ) 2 CH 2 CH 2 O(CH 2 CH 2 O) 3 CH 3 , (CH 3 ) 3 SiCH 2 CH 2 Si(CH 3 ) 2 CH 2 CH 2 CH 2 O(CH 2 CH 2 O) 7 CH 3 , (CH 3 ) 3 SiCH 2 CH 2 Si(CH 3 ) 2 CH 2 CH 2 CH 2 O(CH 2 CH 2 O) 20 CH 3 , (CH 3 ) 3 SiCH 2 CH 2 Si(CH 3 ) 2 CH 2 CH(CH 3 )CH 2 O(CH 2 CH 2 O) 4 CH 3 , (CH 3 ) 3 SiCH 2 CH 2 Si(CH 3 ) 2 CH 2 CH 2 O(CH 2 CH 2 O) 4 (CH 2 CH(CH 3 )O) 1 CH 3 , (CH 3 CH 2 ) 3 SiCH 2 CH 2 Si(CH 2 CH 3 ) 2 CH 2 CH 2 O(CH 2 CH 2 O) 4 (CH 2 CH(CH 3 )O) 1 CH 3 , (CH 3 CH 2 CH 2 ) 3 SiCH 2 CH 2 Si(CH 2 CH 2 CH 3 ) 2 CH 2 CH 2 O(CH 2 CH 2 O) 4 (CH 2 CH(CH 3 )O) 1 CH 3 , (CH 3 ) 2 (CH 3 CH 2 CH 2 ) SiCH 2 CH 2 Si(CH 3 ) 2 CH 2 CH 2 O(CH 2 CH 2 O) 4 (CH 2 CH(CH 3 )O) 1 CH 3 , (CH 3 ) 2 (C 6 H 5 CH 2 CH 2 )SiCH 2 CH 2 Si(CH 3 ) 2 CH 2 CH 2 O(CH 2 CH 2 O) 7 (CH 2 CH(CH 3 )O) 1 CH 3 , (CH 3 ) 3 SiCH 2 CH 2 Si(CH 3 ) 2 CH 2 CH 2 CH 2 O(CH 2 CH 2 O) 5 (CH 2 CH(CH 3 )O) 2 CH 3 , (CH 3 ) 3 SiCH 2 CH 2 Si(CH 3 ) 2 CH 2 CH 2 CH 2 O(CH 2 CH 2 O) 15 (CH 2 CH(CH 3 )O) 5 H, (CH 3 ) 3 SiCH 2 CH 2 Si(CH 3 ) 2 CH 2 CH 2 CH 2 O(CH 2 CH 2 O) 2 (CH 2 CH(CH 3 )O) 18 CH 3 , (CH 3 ) 3 SiCH 2 CH 2 Si(CH 3 ) 2 CH 2 CH 2 CH 2 O(CH 2 CH 2 O) 8 (CH 2 CH(CH 3 )O) 3 CH 3 , (CH 3 ) 3 SiCH 2 CH 2 Si(CH 3 ) 2 CH 2 CH 2 CH 2 O(CH 2 CH 2 O) 4 (CH 2 CH(CH 2 CH 3 )O) 1 CH 3 , (CH 3 ) 3 SiCH 2 CH 2 Si(CH 3 ) 2 CH 2 CH 2 CH 2 O(CH 2 CH 2 O) 10 (CH 2 CH(CH 2 CH 3 )O) 5 CH 3 , (CH 3 ) 3 SiCH 2 CH 2 Si(CH 3 ) 2 CH 2 CH 2 CH 2 O(CH 2 CH 2 O) 10 (CH 2 CH(CH 2 CH 3 )O) 10 C(═O)CH 3 , (CH 3 ) 3 SiCH 2 CH 2 Si(CH 3 ) 2 CH 2 CH 2 O(CH 2 CH 2 O) 4 (CH 2 CH(CH 3 )O) 1 (CH 2 CH(CH 2 CH 3 )O)H (CH 3 ) 3 SiCH 2 CH 2 Si(CH 3 ) 2 CH 2 CH 2 O(CH 2 CH 2 O) 8 (CH 2 CH(CH 3 )O) 5 (CH 2 CH(CH 2 CH 3 )O)H (CH 3 ) 3 SiCH 2 CH 2 Si(CH 3 ) 2 CH 2 CH 2 CH 2 O(CH 2 CH 2 O) 4 (CH 2 CH(CH 3 )O) 1 CH 3 , (CH 3 ) 3 SiCH 2 CH 2 CH 2 Si(CH 3 ) 2 CH 2 CH 2 O(CH 2 CH 2 O) 4 CH 3 , (CH 3 ) 3 SiCH 2 CH 2 CH 2 Si(CH 3 ) 2 CH 2 CH 2 O(CH 2 CH 2 O) 5 C(═O)CH 3 , (CH 3 ) 3 SiCH 2 CH 2 CH 2 Si(CH 3 ) 2 CH 2 CH 2 O(CH 2 CH 2 O) 4 (CH 2 CH(CH 3 )O) 1 CH 3 , (CH 3 CH 2 ) 3 SiCH 2 CH 2 CH 2 Si(CH 2 CH 3 ) 2 CH 2 CH 2 O(CH 2 CH 2 O) 4 (CH 2 CH(CH 3 )O) 1 CH 3 , (CH 3 ) 3 SiCH 2 CH 2 CH 2 Si(CH 3 ) 2 CH 2 CH 2 CH 2 O(CH 2 CH 2 O) 4 (CH 2 CH(CH 3 )O) 1 CH 3 , (CH 3 ) 3 SiCH 2 Si(CH 3 ) 2 (OSi(CH 3 ) 2 )CH 2 CH 2 O(CH 2 CH 2 O) 2 H, (CH 3 ) 3 SiCH 2 CH 2 Si(CH 3 ) 2 (OSi(CH 3 ) 2 )CH 2 CH 2 O(CH 2 CH 2 O) 3 CH 3 , (CH 3 ) 3 SiCH 2 CH 2 Si(CH 3 ) 2 (OSi(CH 3 ) 2 )CH 2 CH 2 CH 2 O(CH 2 CH 2 O) 7 CH 3 , (CH 3 ) 3 SiCH 2 CH 2 Si(CH 3 ) 2 (OSi(CH 3 ) 2 )CH 2 CH 2 CH 2 O(CH 2 CH 2 O) 20 CH 3 , (CH 3 ) 3 SiCH 2 CH 2 Si(CH 3 ) 2 (OSi(CH 3 ) 2 )CH 2 CH(CH 3 )CH 2 O(CH 2 CH 2 O) 4 CH 3 , (CH 3 ) 3 SiCH 2 CH 2 Si(CH 3 ) 2 (OSi(CH 3 ) 2 )CH 2 CH 2 O(CH 2 CH 2 O) 4 (CH 2 CH(CH 3 )O) 1 CH 3 , (CH 3 CH 2 ) 3 SiCH 2 CH 2 Si(CH 2 CH 3 ) 2 (OSi(CH 3 ) 2 )CH 2 CH 2 O(CH 2 CH 2 O) 4 (CH 2 CH(CH 3 )O) 1 H, (CH 3 CH 2 CH 2 ) 3 SiCH 2 CH 2 Si(CH 2 CH 2 CH 3 ) 2 (OSi(CH 3 ) 2 )CH 2 CH 2 O(CH 2 CH 2 O) 4 —(CH 2 CH(CH 3 )O) 1 CH 3 , (CH 3 ) 2 (CH 3 CH 2 CH 2 )SiCH 2 CH 2 Si(CH 3 ) 2 (OSi(CH 3 ) 2 )CH 2 CH 2 O(CH 2 CH 2 O) 4 —(CH 2 CH(CH 3 )O) 1 CH 3 , (CH 3 ) 2 (C 6 H 5 CH 2 CH 2 )SiCH 2 CH 2 Si(CH 3 ) 2 (OSi(CH 3 ) 2 )CH 2 CH 2 O—(CH 2 CH 2 O) 7 (CH 2 CH(CH 3 )O) 1 CH 3 , (CH 3 ) 3 SiCH 2 CH 2 Si(CH 3 ) 2 (OSi(CH 3 ) 2 )CH 2 CH 2 CH 2 O(CH 2 CH 2 O) 5 (CH 2 CH(CH 3 )O) 2 CH 3 , (CH 3 ) 3 SiCH 2 CH 2 Si(CH 3 ) 2 (OSi(CH 3 ) 2 )CH 2 CH 2 CH 2 O(CH 2 CH 2 O) 15 (CH 2 CH(CH 3 )O) 5 H, (CH 3 ) 3 SiCH 2 CH 2 Si(CH 3 ) 2 (OSi(CH 3 ) 2 )CH 2 CH 2 CH 2 O(CH 2 CH 2 O) 2 (CH 2 CH(CH 3 )O) 18 CH 3 , (CH 3 ) 3 SiCH 2 CH 2 Si(CH 3 ) 2 (OSi(CH 3 ) 2 )CH 2 CH 2 CH 2 O(CH 2 CH 2 O) 8 (CH 2 CH(CH 3 )O) 3 CH 3 , (CH 3 ) 3 SiCH 2 CH 2 Si(CH 3 ) 2 (OSi(CH 3 ) 2 )CH 2 CH 2 CH 2 O(CH 2 CH 2 O) 4 —(CH 2 CH(CH 2 CH 3 )O) 1 CH 3 , (CH 3 ) 3 SiCH 2 CH 2 Si(CH 3 ) 2 (OSi(CH 3 ) 2 )CH 2 CH 2 CH 2 O(CH 2 CH 2 O) 10 —(CH 2 CH(CH 2 CH 3 )O) 5 CH 3 , (CH 3 ) 3 SiCH 2 CH 2 Si(CH 3 ) 2 (OSi(CH 3 ) 2 )CH 2 CH 2 CH 2 O(CH 2 CH 2 O) 10 —(CH 2 CH(CH 2 CH 3 )O) 10 C(═O)CH 3 , (CH 3 ) 3 SiCH 2 CH 2 Si(CH 3 ) 2 (OSi(CH 3 ) 2 )CH 2 CH 2 O(CH 2 CH 2 O) 4 (CH 2 CH(CH 3 )O) 1 —(CH 2 CH(CH 2 CH 3 )O)H,(CH 3 ) 3 SiCH 2 CH 2 Si(CH 3 ) 2 (OSi(CH 3 ) 2 )CH 2 CH 2 O(CH 2 CH 2 O) 8 —(CH 2 CH(CH 3 )O) 5 (CH 2 CH(CH 2 CH 3 )O)H, (CH 3 ) 3 SiCH 2 CH 2 Si(CH 3 ) 2 (OSi(CH 3 ) 2 )CH 2 CH 2 CH 2 O(CH 2 CH 2 O) 4 (CH 2 CH(CH 3 )O) 1 CH 3 , (CH 3 ) 3 SiCH 2 CH 2 CH 2 Si(CH 3 ) 2 (OSi(CH 3 ) 2 )CH 2 CH 2 O(CH 2 CH 2 O) 4 CH 3 , (CH 3 ) 3 SiCH 2 CH 2 CH 2 Si(CH 3 ) 2 (OSi(CH 3 ) 2 )CH 2 CH 2 O(CH 2 CH 2 O) 5 C(═O)CH 3 , (CH 3 ) 3 SiCH 2 CH 2 CH 2 Si(CH 3 ) 2 (OSi(CH 3 ) 2 )CH 2 CH 2 O(CH 2 CH 2 O) 4 (CH 2 CH(CH 3 )O) 1 CH 3 , (CH 3 CH 2 ) 3 SiCH 2 CH 2 CH 2 Si(CH 2 CH 3 ) 2 (OSi(CH 3 ) 2 )CH 2 CH 2 O(CH 2 CH 2 O) 4 —(CH 2 CH(CH 3 )O) 1 CH 3 , (CH 3 ) 3 SiCH 2 CH 2 CH 2 Si(CH 3 ) 2 (OSi(CH 3 ) 2 )CH 2 CH 2 CH 2 O(CH 2 CH 2 O) 4 —(CH 2 CH(CH 3 )O) 1 CH 3 , and mixtures thereof.
9. The coating composition of claim 7 wherein the silicon-based polyether copolymer (b) is selected from the group consisting of (CH 3 ) 3 SiCH 2 Si(CH 3 ) 2 CH 2 CH 2 (CH 2 CH 2 O) 2 H, (CH 3 ) 3 SiCH 2 CH 2 Si(CH 3 ) 2 CH 2 CH 2 O(CH 2 CH 2 O) 3 CH 3 , (CH 3 ) 3 SiCH 2 CH 2 Si(CH 3 ) 2 CH 2 CH 2 CH 2 O(CH 2 CH 2 O) 7 CH 3 , (CH 3 ) 3 SiCH 2 CH 2 Si(CH 3 ) 2 CH 2 CH 2 CH 2 O(CH 2 CH 2 O) 20 CH 3 , (CH 3 ) 3 SiCH 2 CH 2 Si(CH 3 ) 2 CH 2 CH(CH 3 )CH 2 O(CH 2 CH 2 O) 4 CH 3 , (CH 3 ) 3 SiCH 2 CH 2 Si(CH 3 ) 2 CH 2 CH 2 O(CH 2 CH 2 O) 4 (CH 2 CH(CH 3 )O) 1 CH 3 , (CH 3 CH 2 ) 3 SiCH 2 CH 2 Si(CH 2 CH 3 ) 2 CH 2 CH 2 O(CH 2 CH 2 O) 4 (CH 2 CH(CH 3 )O) 1 CH 3 , (CH 3 CH 2 CH 2 ) 3 SiCH 2 CH 2 Si(CH 2 CH 2 CH 3 ) 2 CH 2 CH 2 O(CH 2 CH 2 O) 4 (CH 2 CH(CH 3 )O) 1 CH 3 , (CH 3 ) 2 (CH 3 CH 2 CH 2 )SiCH 2 CH 2 Si(CH 3 ) 2 CH 2 CH 2 O(CH 2 CH 2 O) 4 (CH 2 CH(CH 3 )O) 1 CH 3 , (CH 3 ) 2 (C 6 H 5 CH 2 CH 2 )SiCH 2 CH 2 Si(CH 3 ) 2 CH 2 CH 2 O(CH 2 CH 2 O) 7 (CH 2 CH(CH 3 )O) 1 CH 3 , (CH 3 ) 3 SiCH 2 CH 2 Si(CH 3 ) 2 CH 2 CH 2 CH 2 O (CH 2 CH 2 O) 5 (CH 2 CH(CH 3 )O) 2 CH 3 , (CH 3 ) 3 SiCH 2 CH 2 Si(CH 3 ) 2 CH 2 CH 2 CH 2 O(CH 2 CH 2 O) 15 (CH 2 CH(CH 3 )O) 5 H, (CH 3 ) 3 SiCH 2 CH 2 Si(CH 3 ) 2 CH 2 CH 2 CH 2 O(CH 2 CH 2 O) 2 (CH 2 CH(CH 3 )O) 18 CH 3 , (CH 3 ) 3 SiCH 2 CH 2 Si(CH 3 ) 2 CH 2 CH 2 CH 2 O (CH 2 CH 2 O) 8 (CH 2 CH(CH 3 )O) 3 CH 3 , (CH 3 ) 3 SiCH 2 CH 2 Si(CH 3 ) 2 CH 2 CH 2 CH 2 O(CH 2 CH 2 O) 4 (CH 2 CH(CH 2 CH 3 )O) 1 CH 3 , (CH 3 ) 3 SiCH 2 CH 2 Si(CH 3 ) 2 CH 2 CH 2 CH 2 O(CH 2 CH 20 ) 10 (CH 2 CH(CH 2 CH 3 )O) 5 CH 3 , (CH 3 ) 3 SiCH 2 CH 2 Si(CH 3 ) 2 CH 2 CH 2 CH 2 O (CH 2 CH 2 O) 10 (CH 2 CH(CH 2 CH 3 )O) 10 C(═O)CH 3 , (CH 3 ) 3 SiCH 2 CH 2 Si(CH 3 ) 2 CH 2 CH 2 O(CH 2 CH 2 O) 4 (CH 2 CH(CH 3 )O) 1 (CH 2 CH(CH 2 CH 3 )O)H(CH 3 ) 3 SiC H 2 CH 2 Si(CH 3 ) 2 CH 2 CH 2 O(CH 2 CH 2 O) 8 (CH 2 CH(CH 3 )O) 5 (CH 2 CH(CH 2 CH 3 )O)H (CH 3 ) 3 SiCH 2 CH 2 Si(CH 3 ) 2 CH 2 CH 2 CH 2 O(CH 2 CH 2 O) 4 (CH 2 CH(CH 3 )O) 1 CH 3 , (CH 3 ) 3 SiCH 2 CH 2 CH 2 Si(CH 3 ) 2 CH 2 CH 2 O (CH 2 CH 2 O) 4 CH 3 (CH 3 ) 3 SiCH 2 CH 2 CH 2 Si(CH 3 ) 2 CH 2 CH 2 O(CH 2 CH 2 O) 5 C(═O) CH 3 , (CH 3 ) 3 SiCH 2 CH 2 CH 2 Si(CH 3 ) 2 CH 2 CH 2 O(CH 2 CH 2 O) 4 (CH 2 CH(CH 3 )O) 1 CH 3 , (CH 3 CH 2 ) 3 SiCH 2 CH 2 CH 2 Si(CH 2 CH 3 ) 2 CH 2 CH 2 O(CH 2 CH 2 O) 4 (CH 2 CH(CH 3 )O) 1 CH 3 , (CH 3 ) 3 SiCH 2 CH 2 CH 2 Si(CH 3 ) 2 CH 2 CH 2 CH 2 O(CH 2 CH 2 O) 4 (CH 2 CH(CH 3 )O) 1 CH 3 , (CH 3 ) 3 SiCH 2 Si(CH 3 ) 2 (OSi(CH 3 ) 2 )CH 2 CH 2 O(CH 2 CH 2 O) 2 H, (CH 3 ) 3 SiCH 2 CH 2 Si(CH 3 ) 2 (OSi(CH 3 ) 2 )CH 2 CH 2 O(CH 2 CH 2 O) 3 CH 3 , (CH 3 ) 3 SiCH 2 CH 2 Si(CH 3 ) 2 (OSi(CH 3 ) 2 )CH 2 CH 2 CH 2 O(CH 2 CH 2 O) 7 CH 3 , (CH 3 ) 3 SiCH 2 CH 2 Si(CH 3 ) 2 (OSi(CH 3 ) 2 )CH 2 CH 2 CH 2 O(CH 2 CH 2 O) 20 CH 3 , (CH 3 ) 3 SiCH 2 CH 2 Si(CH 3 ) 2 (OSi(CH 3 ) 2 )CH 2 CH(CH 3 )CH 2 O(CH 2 CH 2 O) 4 CH 3 , (CH 3 ) 3 SiCH 2 CH 2 Si(CH 3 ) 2 (OSi(CH 3 ) 2 )CH 2 CH 2 O(CH 2 CH 2 O) 4 (CH 2 CH(CH 3 )O) 1 CH 3 , (CH 3 CH 2 ) 3 SiCH 2 CH 2 Si(CH 2 CH 3 ) 2 (OSi(CH 3 ) 2 )CH 2 CH 2 O(CH 2 CH 2 O) 4 (CH 2 CH(CH 3 )O) 1 H, (CH 3 CH 2 CH 2 ) 3 SiCH 2 CH 2 Si(CH 2 CH 2 CH 3 ) 2 (OSi(CH 3 ) 2 )CH 2 CH 2 O(CH 2 CH 2 O) 4 —(CH 2 CH(CH 3 )O) 1 CH 3 , (CH 3 ) 2 (CH 3 CH 2 CH 2 )SiCH 2 CH 2 Si(CH 3 ) 2 (OSi(CH 3 ) 2 )CH 2 CH 2 O(CH 2 CH 2 O) 4 —(CH 2 CH(CH 3 )O) 1 CH 3 , (CH 3 ) 2 (C 6 H 5 CH 2 CH 2 )SiCH 2 CH 2 Si(CH 3 ) 2 (OSi(CH 3 ) 2 )CH 2 CH 2 O—(CH 2 CH 2 O) 7 (CH 2 CH(CH 3 )O) 1 CH 3 , (CH 3 ) 3 SiCH 2 CH 2 Si(CH 3 ) 2 (OSi(CH 3 ) 2 )CH 2 CH 2 CH 2 O(CH 2 CH 2 O) 5 (CH 2 CH(CH 3 )O) 2 CH 3 , (CH 3 ) 3 SiCH 2 CH 2 Si(CH 3 ) 2 (OSi(CH 3 ) 2 )CH 2 CH 2 CH 2 O(CH 2 CH 2 O) 15 (CH 2 CH(CH 3 )O) 5 H, (CH 3 ) 3 SiCH 2 CH 2 Si(CH 3 ) 2 (OSi(CH 3 ) 2 )CH 2 CH 2 CH 2 O(CH 2 CH 2 O) 2 (CH 2 CH(CH 3 )O) 18 CH 3 , (CH 3 ) 3 SiCH 2 CH 2 Si(CH 3 ) 2 (OSi(CH 3 ) 2 )CH 2 CH 2 CH 2 O(CH 2 CH 2 O) 8 (CH 2 CH(CH 3 )O) 3 CH 3 , (CH 3 ) 3 SiCH 2 CH 2 Si(CH 3 ) 2 (OSi(CH 3 ) 2 )CH 2 CH 2 CH 2 O(CH 2 CH 2 O) 4 —(CH 2 CH(CH 2 CH 3 )O) 1 CH 3 , (CH 3 ) 3 SiCH 2 CH 2 Si(CH 3 ) 2 (OSi(CH 3 ) 2 )CH 2 CH 2 CH 2 O(CH 2 CH 2 O) 10 —(CH 2 CH(CH 2 CH 3 )O) 5 CH 3 , (CH 3 ) 3 SiCH 2 CH 2 Si(CH 3 ) 2 (OSi(CH 3 ) 2 )CH 2 CH 2 CH 2 O(CH 2 CH 2 O) 10 —(CH 2 CH(CH 2 CH 3 )O) 10 C(═O)CH 3 , (CH 3 ) 3 SiCH 2 CH 2 Si(CH 3 ) 2 (OSi(CH 3 ) 2 )CH 2 CH 2 O(CH 2 CH 2 O) 4 (CH 2 CH(CH 3 )O) 1 —(CH 2 CH(CH 2 CH 3 )O)H, (CH 3 ) 3 SiCH 2 CH 2 Si(CH 3 ) 2 (OSi(CH 3 ) 2 )CH 2 CH 2 O(CH 2 CH 2 O) 8 —(CH 2 CH(CH 3 )O) 5 (CH 2 CH(CH 2 CH 3 )O)H, (CH 3 ) 3 SiCH 2 CH 2 Si(CH 3 ) 2 (OSi(CH 3 ) 2 )CH 2 CH 2 CH 2 O(CH 2 CH 2 O) 4 (CH 2 CH(CH 3 )O) 1 CH 3 , (CH 3 ) 3 SiCH 2 CH 2 CH 2 Si(CH 3 ) 2 (OSi(CH 3 ) 2 )CH 2 CH 2 O(CH 2 CH 2 O) 4 CH 3 , (CH 3 ) 3 SiCH 2 CH 2 CH 2 Si(CH 3 ) 2 (OSi(CH 3 ) 2 )CH 2 CH 2 O(CH 2 CH 2 O) 5 C(═O)CH 3 , (CH 3 ) 3 SiCH 2 CH 2 CH 2 Si(CH 3 ) 2 (OSi(CH 3 ) 2 )CH 2 CH 2 O(CH 2 CH 2 O) 4 (CH 2 CH(CH 3 )O) 1 CH 3 , (CH 3 CH 2 ) 3 SiCH 2 CH 2 CH 2 Si(CH 2 CH 3 ) 2 (OSi(CH 3 ) 2 )CH 2 CH 2 O(CH 2 CH 2 O) 4 —(CH 2 CH(CH 3 )O) 1 CH 3 , (CH 3 ) 3 SiCH 2 CH 2 CH 2 Si(CH 3 ) 2 (OSi(CH 3 ) 2 )CH 2 CH 2 CH 2 O(CH 2 CH 2 O) 4 —(CH 2 CH(CH 3 )O) 1 CH 3 , and mixtures thereof.
10. The coating composition of claim 1 further comprising a colloidal oxide selected from the group consisting of silica (SiO 2 ), cerium oxide, cerium oxide nitrate, cerium oxide acetate, zinc oxide (ZnO), zirconium dioxide (ZrO 2 ), titanium dioxide (TiO 2 ), aluminum oxide (Al 2 O 3 ) and combinations thereof.
11. The coating composition of claim 9 further comprising a colloidal oxide selected from the group consisting of silica (SiO 2 ), cerium oxide, cerium oxide nitrate, cerium oxide acetate, zinc oxide (ZnO), zirconium dioxide (ZrO 2 ), titanium dioxide (TiO 2 ), aluminum oxide (Al 2 O 3 ) and combinations thereof.
12. The coating composition of claim 1 further comprising a stabilizing agent selected from the group consisting of ethanol, 1-propanol, 2-propanol, 2-methyl-1-propanol, 2-methyl-2-propanol, 1-butanol, 2-butanol, 2-methyl-1-butanol, 2-methyl-2-butanol, 2,2-dimethyl-1-propanol, 1-pentanol, 2-pentanol, 4-methyl-2-pentanol; glycols including propylene glycol, 1,3-butanediol, 1,4-butane diol, 2-methyl-1,3-propanediol, 2-methyl-2,4-pentanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, poly(ethylene glycol), dipropylene glycol, tripropylene glycol, poly(propylene glycol), 1,5-pentanediol, esterdiol 204, 2,2,4-trimethylpentanediol, 2-ethyl-1,3-hexanediol, glycerol, glycerol ethoxylate, glycerol ethoxylate- co-propoxylate triol, glycerol propoxylate, pentaerythritol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-propoxy-2-propanol, 1-butoxy-2-propanol, 2-methoxyethanol, 2-ethoxyethanol, 2-propoxyethanol, 2-butoxyethanol, 2-(2-methoxyethoxy)ethanol, 2-(2-ethoxyethoxy)ethanol, 2-(2-propoxyethoxy)ethanol, 2-(2-butoxyethoxy)ethanol, di(propylene glycol) butyl ether, methoxytriglycol, ethoxytriglycol, butoxytriglycol methoxypolyethylene glycol, poly(ethylene glycol) butyl ether, poly(ethylene glycol) dimethylether, poly(ethylene glycol-co-propylene glycol), poly(ethylene glycol-co-propylene glycol) monobutyl ether, poly(propylene glycol) monobutyl ether, di(propylene glycol) dimethylether methyl acetate, ethyl acetate, ethyl lactate, 2-methoxyethyl acetate, 2-ethoxyethyl acetate, 2-butoxyethyl acetate, 2-(2-methoxyethoxy)ethyl acetate, 2-(2-ethoxyethoxy)ethyl acetate, 2-(2-butoxyethoxy)ethyl acetate, glycol diacetate, triethylene glycol diacetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, acetone, methyl ethyl ketone, 2,4-pentane dione, diacetone alcohol and polyether silanes of the general formula R 17 O—(CH 2 CH 2 O—) u (CH 2 ) v —Si—(OR 18 ) 3 wherein R 17 is a hydrogen atom, or a linear, branched or cyclic alkyl, aryl, aralkyl or acyl group of from 1 to 6 carbon atoms; R 18 is a linear, branched or cyclic alkyl group of from 1 to 6 carbon atoms; u is 1 to about 20; and v is 1 to 12.
13. The coating composition of claim 2 further comprising at least one additive selected from the group consisting of colloidal oxides, stabilizing agents, organosilicon compounds, organic surfactants, buffers, colorants, dyes, and organic solvents.
14. The coating composition of claim 13 wherein said organic surfactants are selected from the group consisting of alkyl acetylenic diols, pyrrolidone-based surfactants, 2-ethyl hexyl sulfate, isodecyl alcohol ethoxylates, oxo-tridecyl alcohol ethoxylates, ethylene diamine alkoxylates, ethylene oxide/propylene oxide copolymers, and diphenyl ether Gemini-type surfactants.
15. The coating composition of claim 14 wherein said organic surfactant is present in an amount of from 0.01 to 5 weight percent based on total weight of said coating composition.
16. The coating composition of claim 15 where said organic surfactant is present in an amount of from 0.05 to about 2 weight percent based on total weight percent of said coating composition.
17. The coating composition of claim 1 wherein said coating composition is substantially free of phosphate and substantially free of chromium.
18. The coating composition of claim 1 wherein said coating composition contains less than 2 weight percent volatile organic compound, said weight percent being based on the total weight of the composition.
19. The coating composition of claim 1 wherein said coating composition contains less than 1 weight percent of a hazardous air pollutant, said weight percent being based on the total weight of the composition.
20. The coating composition of claim 1 wherein the composition comprises
(a) 0.01 to 80 weight percent silane (a);
(b) 0.001 to 10 weight percent of silicon-based polyether copolymer (b); and
(c) 1 to 99.99 weight percent water,
said weight percents being based upon the total weight of the composition.
21. The coating composition of claim 20 wherein the coating composition comprises
(a) 1 to 40 weight percent silane (a);
(b) 0.1 to 0.5 weight percent of silicon-based polyether copolymer (b); and
(c) 1 to 99.99 weight percent water,
said weight percents being based upon the total weight of the composition.
22. The coating composition of claim 1 wherein the coating composition comprises
(a) 0.1 to 60 weight percent silane (a);
(b) 0.01 to 3 weight percent of silicon-based polyether copolymer (b);
(c) 2 to 99.9 weight percent water;
(d) 0.01 to 30 weight percent colloidal oxide; and
(e) 2 to 40 weight percent stabilizer agent;
wherein the weight percents are based upon the total weight of the composition.
23. A method of treating a metal surface to form a coating thereon, comprising contacting the metal surface with a coating composition comprising
(a) at least one silane of the general formula (1):
or hydrolyzates or condensates thereof
wherein
each occurrence of R 1 independently is a hydrogen atom, an acyl, a monovalent hydrocarbyl, or an alkoxy-substituted alkyl group of from 1 to 16 carbon atoms;
each occurrence of R 2 independently is alkyl, alkoxy-substituted alkyl, aryl, or aralkyl group of from 1 to 16 carbon atoms;
each occurrence of R 3 independently is a covalent chemical bond or a linear, branched or cyclic divalent organic group of from 1 to 12 carbon atoms;
each occurrence of Y independently is a mono-, di- or polyvalent organofunctional group of valence m;
each occurrence of subscripts a, b, m and n is independently an integer where a is 0 to 3; b is 0 to 2; and m is 1 to 4;
(b) at least one silicon-based polyether copolymer of the general formula (2):
(R 4 )(R 5 )(R 6 )SiR 7 Si(R 8 )(R 9 )[OSi(R 10 )(R l1 )] x R 12 (C 2 H 4 O) d (C 3 H 4 O) e (C 4 H 8 O) f R 13 (2)
wherein
each occurrence of R 4 , R 5 , R 6 , R 8 , R 9 , R 1 ° and R 11 independently is a monovalent
hydrocarbyl group of from 1 to 10 carbon atoms;
each occurrence of R 7 independently is a divalent hydrocarbylene group of 1 to 3 carbon atoms;
each occurrence of R 12 independently is a divalent organic group having the structure:
—CH 2 —CH(R 14 )(R 15 ) g O—
where each occurrence of R 14 independently is a hydrogen atom or methyl; each occurrence of R 15 independently is a divalent alkylene radical of 1 to 6 carbon atoms; and the subscript g is 0 or 1;
each occurrence of R 13 independently is selected from the group consisting of a hydrogen atom, a monovalent hydrocarbon group, and an acyl group of 1 to 6 carbon atoms; and
each occurrence of the subscripts d, e, f and x is an integer where d is 2 to 20, e is 0 to 18, f is 0 to 18 and x is 0 or 1 with the proviso that 2≦d+e+f≦20; and
(c) water,
with the proviso that, where the composition comprises condensates of silane (1), it may have a degree of polymerization of between 2 and 50.
24. The method of claim 23 , wherein said contacting of said metal surface comprises brushing, spray coating, immersion, electrostatic coating, roll coating, reverse roll coating, dip coating, flood coating, drawdown coating, or rinse coating.
25. The method of claim 23 , wherein said metal is selected from the group consisting of cold-rolled steel, zinc-coated steel, aluminum, zinc-aluminum coated steels, tin-plated steels, stainless steels, and magnesium.
26. A metal having a coating composition applied thereto, wherein said coating composition comprises
(a) at least one silane of the general formula (1):
or hydrolyzates or condensates thereof
wherein
each occurrence of R 1 independently is a hydrogen atom, an acyl, a monovalent hydrocarbyl, or an alkoxy-substituted alkyl group of from 1 to 16 carbon atoms;
each occurrence of R 2 independently is alkyl, alkoxy-substituted alkyl, aryl, or aralkyl group of from 1 to 16 carbon atoms;
each occurrence of R 3 independently is a covalent chemical bond or a linear, branched or cyclic divalent organic group of from 1 to 12 carbon atoms;
each occurrence of Y independently is a mono-, di- or polyvalent organofunctional group of valence m;
each occurrence of subscripts a, b, m and n is independently an integer where a is 0 to 3; b is 0 to 2; and m is 1 to 4;
(b) at least one silicon-based polyether copolymer of the general formula (2):
(R 4 )(R 5 )(R 6 )SiR 7 Si(R 8 )(R 9 )[OSi(R 10 ) (R 11 )] x R 12 (C 2 H 4 O) d (C 3 H 6 O) e (C 4 H 8 O) f R 13 (2)
wherein
each occurrence of R 4 , R 5 , R 6 , R 8 , R 9 , R 10 and R 11 independently is a monovalent
hydrocarbyl group of from 1 to 10 carbon atoms;
each occurrence of R 7 independently is a divalent hydrocarbylene group of 1 to 3 carbon atoms;
each occurrence of R 12 independently is a divalent organic group having the structure:
—CH 2 —CH(R 14 )(R 15 ) g O—
where each occurrence of R 14 independently is a hydrogen atom or methyl; each occurrence of R 15 independently is a divalent alkylene radical of 1 to 6 carbon atoms; and the subscript g is 0 or 1;
each occurrence of R 13 independently is selected from the group consisting of a hydrogen atom, a monovalent hydrocarbon group, and an acyl group of 1 to 6 carbon atoms; and
each occurrence of the subscripts d, e, f and x is an integer where d is 2 to 20, e is 0 to 18, f is 0 to 18 and x is 0 or 1 with the proviso that 2≦d+e +f≦20; and
(c) water,
with the proviso that, where the composition comprises condensates of silane (1), it may have a degree of polymerization of between 2 and 50.
27. The metal of claim 26 wherein said metal is selected from the group consisting of cold-rolled steel, zinc-coated steel, aluminum, zinc-aluminum coated steels, tin- plated steels, stainless steels, magnesium, and metal alloys.
28. The metal of claim 26 wherein said silane (a) of said coating composition is selected from the group consisting of unhydrolyzed, partially hydrolyzed and hydrolyzed gamma-ureidopropyltrimethoxysilane and gamma-ureidopropyltriethoxysilane.
29. The metal of claim 26 wherein said silicon-based polyether copolymer (b) of said coating composition is selected from the group consisting of (CH 3 ) 3 SiCH 2 Si(CH 3 ) 2 CH 2 CH 2 O(CH 2 CH 2 O) 2 H, (CH 3 ) 3 SiCH 2 CH 2 Si(CH 3 ) 2 CH 2 CH 2 O(CH 2 CH 2 O) 3 CH 3 , (CH 3 ) 3 SiCH 2 CH 2 Si(CH 3 ) 2 CH 2 CH 2 CH 2 O(CH 2 CH 2 O) 7 CH 3 , (CH 3 ) 3 SiCH 2 CH 2 Si(CH 3 ) 2 CH 2 CH 2 CH 2 O(CH 2 CH 2 O) 20 CH 3 , (CH 3 ) 3 SiCH 2 CH 2 Si(CH 3 ) 2 CH 2 CH(CH 3 )CH 2 O(CH 2 CH 2 O) 4 CH 3 , (CH 3 ) 3 SiCH 2 CH 2 Si(CH 3 ) 2 CH 2 CH 2 O(CH 2 CH 2 O) 4 (CH 2 CH(CH 3 )O) 1 CH 3 , (CH 3 CH 2 ) 3 SiCH 2 CH 2 Si(CH 2 CH 3 ) 2 CH 2 CH 2 O(CH 2 CH 2 O) 4 (CH 2 CH(CH 3 )O) 1 CH 3 , (CH 3 CH 2 CH 2 ) 3 SiCH 2 CH 2 Si(CH 2 CH 2 CH 3 ) 2 CH 2 CH 2 O(CH 2 CH 2 O) 4 .(CH 2 CH(CH 3 )O) 1 CH 3 , (CH 3 ) 2 (CH 3 CH 2 CH 2 )SiCH 2 CH 2 Si(CH 3 ) 2 CH 2 CH 2 O(CH 2 CH 2 O) 4 (CH 2 CH(CH 3 )O) 1 CH 3 , (CH 3 ) 2 (C 6 H 5 CH 2 CH 2 )SiCH 2 CH 2 Si(CH 3 ) 2 CH 2 CH 2 O(CH 2 CH 2 O) 7 (CH 2 CH(CH 3 )O) 1 CH 3 , (CH 3 ) 3 SiCH 2 CH 2 Si(CH 3 ) 2 CH 2 CH 2 CH 2 O(CH 2 CH 2 O) 5 (CH 2 CH(CH 3 )O) 2 CH 3 , (CH 3 ) 3 SiCH 2 CH 2 Si(CH 3 ) 2 CH 2 CH 2 CH 2 O(CH 2 CH 2 O) 15 (CH 2 CH(CH 3 )O) 5 H, (CH 3 ) 3 SiCH 2 CH 2 Si(CH 3 ) 2 CH 2 CH 2 CH 2 O(CH 2 CH 2 O) 2 (CH 2 CH(CH 3 )O) 18 CH 3 , (CH 3 ) 3 SiCH 2 CH 2 Si(CH 3 ) 2 CH 2 CH 2 CH 2 O(CH 2 CH 2 O) 8 (CH 2 CH(CH 3 )O) 3 CH 3 , (CH 3 ) 3 SiCH 2 CH 2 Si(CH 3 ) 2 CH 2 CH 2 CH 2 O(CH 2 CH 2 O) 4 (CH 2 CH(CH 2 CH 3 )O) 1 CH 3 , (CH 3 ) 3 SiCH 2 CH 2 Si(CH 3 ) 2 CH 2 CH 2 CH 2 O(CH 2 CH 2 O) 10 (CH 2 CH(CH 2 CH 3 )O) 5 CH 3 , (CH 3 ) 3 SiCH 2 CH 2 Si(CH 3 ) 2 CH 2 CH 2 CH 2 O(CH 2 CH 2 O) 10 (CH 2 CH(CH 2 CH 3 )O) 10 C(═O)CH 3 , (CH 3 ) 3 SiCH 2 CH 2 Si(CH 3 ) 2 CH 2 CH 2 O(CH 2 CH 2 O) 4 (CH 2 CH(CH 3 )O) 1 (CH 2 CH(CH 2 CH 3 )O)H (CH 3 ) 3 SiCH 2 CH 2 Si(CH 3 ) 2 CH 2 CH 2 O(CH 2 CH 2 O) 8 (CH 2 CH(CH 3 )O) 5 (CH 2 CH(CH 2 CH 3 )O)H (CH 3 ) 3 SiCH 2 CH 2 Si(CH 3 ) 2 CH 2 CH 2 CH 2 O(CH 2 CH 2 O) 4 (CH 2 CH(CH 3 )O) 1 CH 3 , (CH 3 ) 3 SiCH 2 CH 2 CH 2 Si(CH 3 ) 2 CH 2 CH 2 O(CH 2 CH 2 O) 4 CH 3 , (CH 3 ) 3 SiCH 2 CH 2 CH 2 Si(CH 3 ) 2 CH 2 CH 2 O(CH 2 CH 2 O) 5 C(═O)CH 3 , (CH 3 ) 3 SiCH 2 CH 2 CH 2 Si(CH 3 ) 2 CH 2 CH 2 O(CH 2 CH 2 O) 4 (CH 2 CH(CH 3 )O) 1 CH 3 , (CH 3 CH 2 ) 3 SiCH 2 CH 2 CH 2 Si(CH 2 CH 3 ) 2 CH 2 CH 2 O(CH 2 CH 2 O) 4 (CH 2 CH(CH 3 )O) 1 CH 3 , (CH 3 ) 3 SiCH 2 CH 2 CH 2 Si(CH 3 ) 2 CH 2 CH 2 CH 2 O(CH 2 CH 2 O) 4 (CH 2 CH(CH 3 )O) 1 CH 3 , (CH 3 ) 3 SiCH 2 Si(CH 3 ) 2 (OSi(CH 3 ) 2 )CH 2 CH 2 O(CH 2 CH 2 O) 2 H, (CH 3 ) 3 SiCH 2 CH 2 Si(CH 3 ) 2 (OSi(CH 3 ) 2 )CH 2 CH 2 O(CH 2 CH 2 O) 3 CH 3 , (CH 3 ) 3 SiCH 2 CH 2 Si(CH 3 ) 2 (OSi(CH 3 ) 2 )CH 2 CH 2 CH 2 O(CH 2 CH 2 O) 7 CH 3 , (CH 3 ) 3 SiCH 2 CH 2 Si(CH 3 ) 2 (OSi(CH 3 ) 2 )CH 2 CH 2 CH 2 O(CH 2 CH 2 O) 20 CH 3 , (CH 3 ) 3 SiCH 2 CH 2 Si(CH 3 ) 2 (OSi(CH 3 ) 2 )CH 2 CH(CH 3 )CH 2 O(CH 2 CH 2 O) 4 CH 3 , (CH 3 ) 3 SiCH 2 CH 2 Si(CH 3 ) 2 (OSi(CH 3 ) 2 )CH 2 CH 2 O(CH 2 CH 2 O) 4 (CH 2 CH(CH 3 )O) 1 CH 3 , (CH 3 CH 2 ) 3 SiCH 2 CH 2 Si(CH 2 CH 3 ) 2 (OSi(CH 3 ) 2 )CH 2 CH 2 O(CH 2 CH 2 O) 4 (CH 2 CH(CH 3 )O) 1 H, (CH 3 CH 2 CH 2 ) 3 SiCH 2 CH 2 Si(CH 2 CH 2 CH 3 ) 2 (OSi(CH 3 ) 2 )CH 2 CH 2 O(CH 2 CH 2 O) 4 —(CH 2 CH(CH 3 )O) 1 CH 3 , (CH 3 ) 2 (CH 3 CH 2 CH 2 )SiCH 2 CH 2 Si(CH 3 ) 2 (OSi(CH 3 ) 2 )CH 2 CH 2 O(CH 2 CH 2 O) 4 —(CH 2 CH(CH 3 )O) 1 CH 3 , (CH 3 ) 2 (C 6 H 5 CH 2 CH 2 ) SiCH 2 CH 2 Si(CH 3 ) 2 (OSi(CH 3 ) 2 )CH 2 CH 2 O —(CH 2 CH 2 O) 7 (CH 2 CH(CH 3 )O) 1 CH 3 , (CH 3 ) 3 SiCH 2 CH 2 Si(CH 3 ) 2 (OSi(CH 3 ) 2 )CH 2 CH 2 CH 2 O(CH 2 CH 2 O) 5 (CH 2 CH(CH 3 )O) 2 CH 3 , (CH 3 ) 3 SiCH 2 CH 2 Si(CH 3 ) 2 (OSi(CH 3 ) 2 )CH 2 CH 2 CH 2 O(CH 2 CH 2 O) 15 (CH 2 CH(CH 3 )O) 5 H, (CH 3 ) 3 SiCH 2 CH 2 Si(CH 3 ) 2 (OSi(CH 3 ) 2 )CH 2 CH 2 CH 2 O(CH 2 CH 2 O) 2 (CH 2 CH(CH 3 )O) 18 CH 3 , (CH 3 ) 3 SiCH 2 CH 2 Si(CH 3 ) 2 (OSi(CH 3 ) 2 )CH 2 CH 2 CH 2 O(CH 2 CH 2 O) 8 (CH 2 CH(CH 3 )O) 3 CH 3 , (CH 3 ) 3 SiCH 2 CH 2 Si(CH 3 ) 2 (OSi(CH 3 ) 2 ) CH 2 CH 2 CH 2 O(CH 2 CH 2 O) 4 —(CH 2 CH(CH 2 CH 3 )O) 1 CH 3 , (CH 3 ) 3 SiCH 2 CH 2 Si(CH 3 ) 2 (OSi(CH 3 ) 2 )CH 2 CH 2 CH 2 O(CH 2 CH 2 O) 10 —(CH 2 CH(CH 2 CH 3 )O) 5 CH 3 , (CH 3 ) 3 SiCH 2 CH 2 Si(CH 3 ) 2 (OSi(CH 3 ) 2 )CH 2 CH 2 CH 2 O(CH 2 CH 2 O) 10 —(CH 2 CH(CH 2 CH 3 )O) 10 C(═O)CH 3 , (CH 3 ) 3 SiCH 2 CH 2 Si(CH 3 ) 2 (OSi(CH 3 ) 2 )CH 2 CH 2 O(CH 2 CH 2 O) 4 (CH 2 CH(CH 3 )O) 1 —(CH 2 CH(CH 2 CH 3 )O)H, (CH 3 ) 3 SiCH 2 CH 2 Si(CH 3 ) 2 (OSi(CH 3 ) 2 )CH 2 CH 2 O(CH 2 CH 2 O) 8 —(CH 2 CH(CH 3 )O) 5 (CH 2 CH(CH 2 CH 3 )O)H, (CH 3 ) 3 SiCH 2 CH 2 Si(CH 3 ) 2 (OSi(CH 3 ) 2 )CH 2 CH 2 CH 2 O(CH 2 CH 2 O) 4 (CH 2 CH(CH 3 )O) 1 CH 3 , (CH 3 ) 3 SiCH 2 CH 2 CH 2 Si(CH 3 ) 2 (OSi(CH 3 ) 2 )CH 2 CH 2 O(CH 2 CH 2 O) 4 CH 3 , (CH 3 ) 3 SiCH 2 CH 2 CH 2 Si(CH 3 ) 2 (OSi(CH 3 ) 2 )CH 2 CH 2 O(CH 2 CH 2 O) 5 C(═O)CH 3 , (CH 3 ) 3 SiCH 2 CH 2 CH 2 Si(CH 3 ) 2 (OSi(CH 3 ) 2 )CH 2 CH 2 O(CH 2 CH 2 O) 4 (CH 2 CH(CH 3 )O) 1 CH 3 , (CH 3 CH 2 ) 3 SiCH 2 CH 2 CH 2 Si(CH 2 CH 3 ) 2 (OSi(CH 3 ) 2 )CH 2 CH 2 O(CH 2 CH 2 O) 4 —(CH 2 CH(CH 3 )O) 1 CH 3 , (CH 3 ) 3 SiCH 2 CH 2 CH 2 Si(CH 3 ) 2 (OSi(CH 3 ) 2 )CH 2 CH 2 CH 2 O(CH 2 CH 2 O) 4 —(CH 2 CH(CH 3 )O) 1 CH 3 , and mixtures thereof.
30. The metal of claim 26 , wherein the coating composition further comprises a colloidal oxide selected from the group consisting of silica (SiO 2 ), cerium oxide, cerium oxide nitrate, cerium oxide acetate, zinc oxide (ZnO), zirconium dioxide (ZrO 2 ), titanium dioxide (TiO 2 ), aluminum oxide (Al 2 O 3 ) and combinations thereof.
31. The metal of claim 26 further comprising a paint applied thereto.
32. The metal of claim 30 further comprising a paint applied thereto.
33. An article containing the coated metal of claim 26 .