The present invention relates to a composition comprising at least two fluorosilanes and at least one aminosilane, a condensation product of said fluorosilanes and said aminosilane, and a surface protective agent made thereof.
1. A reactive composition comprising
(a) at least two different fluorosilanes each of the same general formula I
R tf —SiX 3 (formula I),
wherein
X is selected from the group of alkoxy, halide, oxime, carboxyl, phenoxide and polyether, and
R tf is a straight, branched or cyclic residue of the general formula II or III
—Y—R f (formula II) or
—Y—(SiR 1 R 2 O) x SiR 1 R 2 —Y—R f (formula III),
wherein
Y is a moiety selected from the group of —(CH 2 ) n —, —CO 2 —, —O—, —CONH—, —Ph—, —SO 2 —, and —SO 2 NH—, —(CH 2 ) o —O—(CH 2 ) m , —(CH 2 ) o —CONH—(CH 2 ) m , —(CH 2 ) o —Ph—(CH 2 ) m , —(CH 2 ) o SO 2 —(CH 2 ) m , —(CH 2 ) o—SO 2 NH—(CH 2 ) m , —SO 2 —O— and —SO 2 NH—, wherein o is an integer from 1 to 30, m is a number in the range from 0 to 30 and, wherein n is an integer from 1 to 30,
R f is a C2 to C7 linear or branched perfluoralkylene group, wherein the fluorosilanes differ in their number of carbon atoms in R f at least by 2,
R 1 and R 2 are independently selected from monovalent organic residues,
x is an integer from 0 to 5, and
(b) and at least one aminosilane of the general formula IV
R a —SiR 3 R 4 R 5 (formula IV),
where
R a is a straight, branched or cyclic alkyl residue comprising 1 to 7 carbon atoms and at least one primary, secondary, ternary or quaternary amino-group,
R 3 and R 4 are independently selected from —R a , —OR 6 and/or —R 6 , and
R 5 is —OR 6 , and
R 6 is a straight, branched or cyclic alkyl residue comprising 1 to 3 carbon atoms.
2. A composition according to claim 1 , characterized in that the two different fluorosilanes are present in a weight ratio of the fluorosilane with an R f group with less carbon atoms to the fluorosilane with an R f group with more carbon atoms between 0.7 to 1.3.
3. A composition according to claim 1 , characterized in that R f is a C4 and a C6 group for the at least two different silanes, respectively.
4. A composition according to claim 1 , characterized in that X is
a halide selected from the group of F, Br, Cl and I,
an alkoxide OR 7 wherein R 7 is a C1 to C22 linear or branched alkylene group,
an oxime R 8 R 9 C═N—O, wherein R 8 and R 9 are independently selected from C1 to C30 linear or branched alkylene groups, wherein R 8 and R 9 may be same or different,
a carboxyl residue R 10 CO 2 wherein R 10 is a C1 to C30 linear or branched alkylene group,
a phenoxide M-Ph-O—, where M is hydrogen or a monovalent organic group, or
a polyether selected from the group of polyalkylene oxides containing one or more of the following repeating structural units (CH 2 CH 2 O) q , or (CH 3 CHCH 2 O) q wherein q is a value in the range from 1 to 100, terminated by a C1 to C30 linear or branched alklylene group.
5. A composition according to claim 1 , characterized in that Y is a moiety selected from the group of —(CH 2 ) o —, —CO 2 —, —(CH 2 ) o —O—(CH 2 ) m , —(CH 2 ) o —CONH—(CH 2 ) m , —(CH 2 ) o -Ph-(CH 2 ) m , —(CH 2 ) o —SO 2 —(CH 2 ) m , —(CH 2 ) o —SO 2 NH—(CH 2 ) m , —SO 2 —O—, —SO 2 NH—, and wherein o is a number in the range from 1 to 30 and m is a number in the range from 0 to 30.
6. A composition according to claim 1 , characterized in that R f is
(a) selected from the group of CF 3 CF 2 —, CF 3 (CF 2 ) 3 —, C 3 F 7 —, (CF 3 ) 2 CF—, C 4 F 9 —, C 5 F 11 — or C 6 F 13 — or
(b) a perflourinated polyether of the general formula V
F—(CF 2 ) r —(OC 3 F 6 ) s —(OC 2 F 4 ) t —(OCF 2 ) n (formula (V),
wherein r is an integer in the range from 1 to 3, and
s, t, and u are independently integers in the range from 0 to 200.
7. A composition according to claim 1 , characterized in that R 1 or R 2 are independently selected from the group of C1 to C30 linear or branched alkylene groups, aromatic containing groups, aminoalkyl containing groups, and fluoroalkyl containing groups.
8. A composition according to claim 1 , characterized in that X, R 3 , R 4 , and/or R 5 independently are selected from the group of alkoxy groups.
9. A composition according to claim 1 , characterized in that the molar ratio of R f -groups of formula I to amino-groups present in formula IV is in a range from 2:1 to 6:1.
10. A composition according to claim 1 , further comprising a hydrophilic silane conforming with the general formula
R 11 R 12 MeSi—Y—Z (formula VI),
where R 11 and R 12 are independently selected from the group of R 3 or Me, and
Z is a polar monovalent organic group.
11. A composition according to claim 1 , further comprising an acid in a range between 20 and 50 wt. %.
12. A non-aqueous composition according to claim 1 .
13. A process for preparing a reactive composition by combining a fluorosilane and an aminosilane each according to claim 1 followed by an acid treatment.
14. A process according to claim 13 characterized in that the fluorosilane and/or the aminosilane are reacted in protonated form.
15. A process according to claim 13 in a non-aqueous reaction system.
16. A condensation product of a fluorosilane and an aminosilane each according to claim 1 , wherein the fluorosilane is of the general formula I with residues as defined in general formulas II and/or III and the aminosilane is of the general formula IV, and wherein the condensation product is obtainable by a catalytic promoted treatment of a mixture of the fluorosilane and the aminosilane.
17. A condensation product according to claim 16 , characterized in that the promoted treatment comprises treatment with an acid that exhibits a pK a value in a range from 3 to 7.
18. A surface protective agent comprising the composition according to claim 1 and/or a condensation product of the composition, the surface protective agent further comprising additives for surface protective agents.
19. A surface protective agent according to claim 18 , characterized in that it comprises 0.5 to 5 weight % of a compound or mixture of compounds selected from the group of silicones/siloxanes, acrylic compounds, melamine compounds, and waxes.