Aqueous silane systems based on bis(trialkoxysilylalkyl)amines
View Patent ↗The invention relates to an aqueous composition of bis-amino-functional silicon compounds which is essentially free of organic solvents and releases essentially no further alcohol in the course of crosslinking, and to processes for preparing it and to the use thereof, for example for hydrophobization of metal or glass surfaces.
1. A composition containing substantially water-soluble, bis-aminofunctional silicon compounds and water, the silicon compounds being derived from alkoxysilanes and having crosslinking structural elements which form chain-like, cyclic, crosslinked and/or three-dimensionally crosslinked structures, at least one structure in idealized form corresponding to the general formula I,
(R 2 O)[(R 2 O) 1-x (R 3 ) x Si(B)O] b [(Y) 2 Si(A)Si(Y) 2 O] a [Si(C)(R 5 ) y (OR 4 ) 1-y O] c [Si(D)(R 7 ) u (OR 6 ) 1-u O] d [Si(E)(R 8 ) v (OR 9 ) 1-v O] w R 9 .(HX) e (I),
in the structural elements derived from alkoxysilanes, with
A corresponding to a bisaminoalkyl radical,
B corresponding to an aminoalkyl radical,
C corresponding to an alkyl radical,
D corresponding to an epoxy or ether radical and
E corresponding to an organofunctional radical,
Y corresponding to OR 1 or, in crosslinked and/or three-dimensionally crosslinked structures, independently of one another, OR 1 or O 1/2 ,
R 1 , R 2 , R 4 , R 6 and/or R 9 substantially corresponding to hydrogen and R 3 , R 5 , R 7 and/or R 8 corresponding to organofunctional radicals, and
HX being an acid, in which X is an inorganic or organic acid radical,
with 0≦x≦1, 0≦y≦1, 0≦u≦1, a≧1, b≧0, c≧0, d≧0, w≧0, e≧0 and (a+b+c+d+w)≧2, and
the composition being substantially free of organic solvents and releasing substantially no more alcohol on crosslinking.
2. The composition as claimed in claim 1 ,
wherein
A in the structural element corresponds to a bisaminoalkyl radical derived from the general formula II
(OR 1 ) 3 Si-A-Si(OR 1 ) 3 (II)
where A is a bis-aminofunctional group of the formula III
—(CH 2 ) i —[NH(CH 2 ) f ] g NH[(CH 2 ) f* NH] g* —(CH 2 ) i* — (III),
in which i, i*, f, f*, g or g* are identical or different, with i and/or i*=from 0 to 8, f and/or f*=1, 2 or 3, g and/or g*=0, 1 or 2 and R 1 corresponds to a linear, cyclic and/or branched alkyl radical having 1 to 4 C atoms.
3. The composition as claimed in claim 1 ,
wherein
B in the structural element corresponds to an aminofunctional radical derived from the general formula IV
B—Si(R 3 ) x (OR 2 ) 3-x (IV)
with x=0 or 1, R 2 corresponding to a linear, branched and/or cyclic alkyl radical having 1 to 4 C atoms, R 3 corresponding to a linear, branched or cyclic alkyl radical having 1 to 12 C atoms and/or aryl radical and B corresponding to one of the following aminofunctional groups of the general formula Va or Vb
R 10 h* NH (2-h*) [(CH 2 ) h (NH)] j [(CH 2 ) l (NH)] n —(CH 2 ) k — (Va),
in which 0≦h≦6; h*=0, 1 or 2, j=0, 1 or 2; 0≦l≦6; n=0, 1 or 2;
0≦k≦6 and R 10 corresponds to a benzyl, aryl, vinyl or formyl radical and/or to a linear, branched and/or cyclic alkyl radical having 1 to 8 C atoms, and/or
[NH 2 (CH 2 ) m ] 2 N(CH 2 ) p — (Vb),
in which 0≦m≦6 and 0≦p≦6.
4. The composition as claimed in claim 1 ,
wherein
C in the structural element corresponds to an alkyl radical derived from the general formula VI
C—Si(R 5 ) y (OR 4 ) 3-y (VI)
with y=0 or 1, C corresponding to a linear, branched or cyclic alkyl radical having 1 to 20 C atoms, R 5 corresponding to a linear, branched or cyclic alkyl radical having 1 to 12 C atoms and/or aryl radical, and R 4 corresponding to a linear, branched and/or cyclic alkyl radical having 1 to 4 C atoms.
5. The composition as claimed in claim 1 ,
wherein
D in the structural element corresponds to an epoxy or ether radical derived from the general formula VII
D-Si(R 7 ) u (OR 6 ) 3-u (VII)
with u=0 or 1, D corresponding to a 3-glycidyloxyalkyl, 3-glycidyloxypropyl, epoxyalkyl, epoxycycloalkyl or polyalkylglycolalkyl radical or to a polyalkylglycol-3-propyl radical, R 7 corresponding to a linear, branched and/or cyclic alkyl radical having 1 to 4 C atoms and R 6 corresponding to a linear, branched and/or cyclic alkyl radical having 1 to 4 C atoms.
6. The composition as claimed in claim 1 ,
wherein
E in the structural element corresponds to an organofunctional radical derived from the general formula VIII
E-Si(R 8 ) v (OR 9 ) 3-v (VIII)
with v=0 or 1, R 8 corresponding to a linear, branched or cyclic alkyl radical having 1 to 4 C atoms,
E corresponding to a radical R 8 *—Y m —(CH 2 ) s —, R 8 * corresponding to a mono-, oligo- or perfluorinated alkyl radical having 1 to 9 C atoms or to a mono-, oligo- or perfluorinated aryl radical, and Y corresponding to a CH 2 , O, aryl or S radical, and m being 0 or 1 and s being 0 or 2 and/or
E corresponding to a vinyl, allyl or isopropenyl radical, mercaptoalkyl radical, sulfanealkyl radical, ureidoalkyl radical, to an acryloyloxyalkyl radical or to a linear, branched or cyclic alkoxy radical having 1 to 4 C atoms and
R 9 corresponding to a linear, branched and/or cyclic alkyl radical having 1 to 4 C atoms.
7. The composition as claimed in any of claim 1 ,
wherein
it has a flashpoint above 90° C.
8. The composition as claimed in claim 1 ,
wherein
it has a stability at room temperature of at least 3 months in a closed container.
9. The composition as claimed in claim 1 ,
wherein
the acid is formic acid, acetic acid, an acidic silica sol, glacial acetic acid, nitric acid, sulfuric acid and/or phosphoric acid.
10. The composition as claimed in claim 1 ,
wherein
it crosslinks from as low as 0° C.
11. The composition as claimed in claim 10 ,
wherein
it crosslinks at from 15 to 25° C.
12. The composition as claimed in claim 1 ,
wherein
it has a pH of from 1 to 5.4.
13. The composition as claimed in claim 12 ,
wherein
in that
it has a pH of from 3.0 to 5.4.
14. The composition as claimed in claim 13 ,
wherein
it has a pH of from 3.5 to 5.4.
15. The composition as claimed in claim 1 ,
wherein
it has a content of from 7.5 to 40% by weight of silicon compounds, based on the alkoxysilanes used.
16. The composition as claimed in claim 15 ,
wherein
it has a content of from 12.5 to 30% by weight of silicon compounds at a pH of from 3.0 to 4.8.
17. The composition as claimed in claim 1 ,
wherein
for the structural element containing C, an alkyl radical, c is ≧1.
18. The composition as claimed in claim 17 ,
wherein
the pH is less than 12.
19. The composition as claimed in claim 1 ,
wherein
it is dilutable with water or with a water-soluble solvent.
20. The composition as claimed in claim 19 ,
wherein
it can be diluted as desired.
21. A mixture comprising silane-based compositions and a composition as claimed in claim 1 .
22. The mixture as claimed in claim 21 ,
wherein
the mixture contains a composition comprising bis-aminofunctional silicon compounds together with a silane-based composition based on alkyl-, alkenyl-, aryl-, epoxy-, dihydroxyalkyl-, aminoalkyl-, polyalkylglycolalkyl-, haloalkyl-, mercaptoalkyl-, sulfanealkyl-, ureidoalkyl- or acryloyloxyalkyl-functional and/or tetraalkoxy-functional silanes and/or mixtures thereof.
23. The mixture as claimed in claim 21 ,
wherein
the curing temperature of the mixture is lower than that of the silane-based composition.
24. A composition for hydrophobization, as corrosion protection, for rock consolidation and/or for oleophobization of substrate surfaces comprising the mixture as claimed in claim 21 .
25. A composition for the hydrophobization of metal, glass, plastic, polymers, mineral surfaces, concrete, bricks, mortar, screed, sandstone, natural fibers, paper, wood, for the priming of glass surfaces, metal surfaces, mineral surfaces, concrete, mortar, screed, sandstone or natural fibers, paper, wood, as corrosion protection for metals, concrete, mortar and/or bricks and/or as an additive in aqueous coating or resin formulations or as an anti-fingerprint coating comprising the mixture as claimed in claim 21 .
26. A composition for use as corrosion protection of untreated or pretreated metals or metal surfaces and galvanized metal surfaces comprising the mixture as claimed in claim 21 .
27. A composition for modifying or for treating substrate surfaces and/or for building up a barrier layer on substrate surfaces comprising the composition as claimed in claim 1 .
28. A coated or consolidated product comprising the composition as claimed in claim 27 .
29. The product as claimed in claim 28 ,
wherein
it is a steel reinforcement, a concrete pipe and/or a prefabricated concrete component.
30. A process for the preparation of a composition containing substantially water-soluble, bis-aminofunctional silicon compounds substantially free of alkoxy groups, and water and an acid, wherein water, an acid, optionally an alcohol and optionally a catalyst are initially introduced and
at least one bisaminoalkoxysilane of the formula II
(OR 1 ) 3 Si-A-Si(OR 1 ) 3 (II)
where A is a bis-aminofunctional group of the formula III
—(CH 2 ) i —[NH(CH 2 ) f ] g NH[(CH 2 ) f* NH] g* —(CH 2 ) i* — (III),
in which i, i*, f, f*, g or g* are identical or different, with i and/or i*=from 0 to 8, f and/or f*=1, 2 or 3, g and/or g*=0, 1 or 2 and R 1 corresponds to a linear, cyclic and/or branched alkyl radical having 1 to 4 C atoms, and/or the condensates thereof, and optionally
at least one aminoalkylalkoxysilane of the formula IV
B—Si(R 3 ) x (OR 2 ) 3-x (IV)
where x=0 or 1, R 2 corresponds to a linear, branched and/or cyclic alkyl radical having 1 to 4 C atoms and B corresponds to one of the following aminofunctional groups of the general formula Va or Vb
R 10 h* NH (2-h*) [(CH 2 ) h (NH)] j [(CH 2 ) l (NH)] n —(CH 2 ) k — (Va),
in which 0≦h≦6; h*=0, 1 or 2, j=0, 1 or 2; 0≦l≦6; n=0, 1 or 2; 0≦k≦6 and R 10 corresponds to a benzyl, aryl, vinyl or formyl radical and/or to a linear, branched and/or cyclic alkyl radical having 1 to 8 C atoms, and/or
[NH 2 (CH 2 ) m ] 2 N(CH 2 ) p — (Vb),
in which 0≦m≦6 and 0≦p≦6, and/or the condensates thereof, and optionally
at least one alkylalkoxysilane of the general formula VI
C—Si(R 5 ) y (OR 4 ) 3-y (VI)
where y=0 or 1, corresponds to a linear, branched or cyclic alkyl radical having 1 to 20 C atoms, R 5 corresponds to a linear, branched or cyclic alkyl radical having 1 to 12 C atoms and/or an aryl radical, and R 4 corresponds to a linear, branched and/or cyclic alkyl radical having 1 to 4 C atoms, and/or the condensates thereof, and optionally
at least one epoxy- or ether-alkoxysilane of the general formula VII
D—Si(R 7 ) u (OR 6 ) 3-u (VII)
where u=0 or 1, D corresponds to a 3-glycidyloxyalkyl, 3-glycidyloxypropyl, epoxyalkyl, epoxycycloalkyl or polyalkylglycolalkyl radical or to a polyalkylglycol-3-propyl radical, R 7 corresponds to a linear, branched or cyclic alkyl radical having 1 to 4 C atoms and R 6 corresponds to a linear, branched and/or cyclic alkyl radical having 1 to 4 C atoms, and/or the condensates thereof, and optionally
at least one organofunctional alkoxysilane of the formula VIII
E-Si(R 8 ) v (OR 9 ) 3-v (VIII)
where v=0 or 1, R 8 corresponds to a linear, branched or cyclic alkyl radical having 1 to 4 C atoms, E corresponds to a radical R 8 *—Y m —(CH 2 ) s —, with R 8 * corresponding to a mono-, oligo- or perfluorinated alkyl radical having 1 to 9 C atoms or to a mono-, oligo- or perfluorinated aryl radical, and Y corresponding to a CH 2 , O, aryl or S radical, and m being 0 or 1 and s being 0 or 2, or to a vinyl, allyl or isopropenyl radical, mercaptoalkyl radical, sulfanealkyl radical, ureidoalkyl radical, to an acryloyloxyalkyl radical or to a linear, branched or cyclic alkoxy radical having 1 to 4 C atoms and R 9 corresponds to a linear, branched and/or cyclic alkyl radical having 1 to 4 C atoms, and/or the condensates thereof,
are hydrolyzed and the alcohol is substantially removed.
31. The process as claimed in claim 30 ,
wherein
the silanes of the general formulae II, IV, VI, VII and/or VIII, the condensates thereof and/or mixtures of these are added in aqueous and/or alcoholic solution.
32. The process as claimed in claim 30 ,
wherein
the silanes of the general formula II, IV, VI, VII or VIII and/or the condensates thereof are added in succession or as a mixture.
33. The process as claimed in claim 30 ,
wherein
the water content during the hydrolysis is from 50 to 90% by weight.
34. The process as claimed in claim 30 ,
wherein
the pH is adjusted by further addition of an acid.
35. The process as claimed in claim 30 ,
wherein
the silicon compounds are present altogether with a content of from 7.5 to 40% by weight.
36. The process as claimed in claim 30 ,
wherein
the hydrolysis is carried out in an aqueous alcoholic solution at a pH below 12.
37. The process as claimed in claim 30 ,
wherein
substantially unhydrolyzed bisaminoalkylalkoxysilane of the formula II is used.
38. The process as claimed in claim 30 ,
wherein
a bisaminoalkylalkoxysilane of the formula II and an alkylalkoxysilane of the general formula VI are used.
39. The process as claimed in claim 30 ,
wherein
the hydrolysis and optionally condensation are carried out at from 55 to 80° C.
40. The process as claimed in claim 30 ,
wherein
inorganic fillers are added.
41. The process as claimed in claim 30 ,
wherein
water is added and an alcohol/water mixture is removed until the composition is substantially free of alcohols.
42. The process as claimed in claim 30 ,
wherein
the pH of the composition after removal of the alcohol is from 1.0 to 5.4.
43. The process as claimed in claim 42 ,
wherein
the pH of the composition after removal of the alcohol is from 3.0 to 5.4.
44. The composition obtained as claimed in claim 30 .
45. The process as claimed in claim 30 ,
wherein
further water is added after addition of at least one silane.
46. The process as claimed in claim 45 ,
wherein
the water content during the hydrolysis is from 65 to 90% by weight.
47. The process as claimed in claim 30 ,
wherein
the pH during the hydrolysis is from 2.0 to 5.4.
48. The process as claimed in claim 47 ,
wherein
the pH during the hydrolysis is from 3.0 to 5.4.
49. A process for the preparation of a composition containing substantially water-soluble, bis-aminofunctional silicon compounds substantially free of alkoxy groups, and water and an acid, wherein an aqueous solution of at least one water-soluble silane of the general formulae II, IV and/or VII or the water-soluble condensates thereof or the water-soluble hydrolysis products of a silane of the general formula VI is initially introduced,
the silane of the formula II corresponding to a bisaminoalkoxysilane
(OR 1 ) 3 Si-A-Si(OR 1 ) 3 (II)
where A is a bis-aminofunctional group of the formula III
—(CH 2 ) i —[NH(CH 2 ) f ] g NH[(CH 2 ) f* NH] g* —(CH 2 ) i* — (III),
in which i, i*, f, f*, g or g* are identical or different, with i and/or i*=from 0 to 8, f and/or f*=1, 2 or 3, g and/or g*=0, 1 or 2 and R 1 corresponds to a linear, cyclic and/or branched alkyl radical having 1 to 4 C atoms, and/or the condensates thereof,
the silane of the formula IV corresponding to an aminoalkylalkoxysilane
B—Si(R 3 ) x (OR 2 ) 3-x (IV)
where x=0 or 1, R 2 corresponds to a linear, branched and/or cyclic alkyl radical having 1 to 4 C atoms and B corresponds to one of the following aminofunctional groups of the general formula Va or Vb
R 10 h* NH (2-h*) [(CH 2 ) h (NH)] j [(CH 2 ) l (NH)] n —(CH 2 ) k — (Va),
in which 0≦h≦6; h*=0, 1 or 2, j=0, 1 or 2; 0≦l≦6; n=0, 1 or 2; 0≦k≦6 and R 10 corresponds to a benzyl, aryl, vinyl or formyl radical and/or to a linear, branched and/or cyclic alkyl radical having 1 to 8 C atoms, and/or
[NH 2 (CH 2 ) m ] 2 N(CH 2 ) p — (Vb),
in which 0≦m≦6 and 0≦p≦6, and/or the condensates thereof,
the silane of the formula VII corresponding to an epoxy- or ether-alkoxysilane
D-Si(R 7 ) u (OR 6 ) 3-u (VII)
where u=0 or 1, D corresponds to a 3-glycidyloxyalkyl, 3-glycidyloxypropyl, epoxyalkyl, epoxycycloalkyl or polyalkylglycolalkyl radical or to a polyalkylglycol-3-propyl radical, R 7 corresponds to a linear, branched or cyclic alkyl radical having 1 to 4 C atoms and R 6 corresponds to a linear, branched and/or cyclic alkyl radical having 1 to 4 C atoms, and/or the condensates thereof,
the silane of the formula VI corresponding to an alkylalkoxysilane
C—Si(R 5 ) y (OR 4 ) 3-y (VI)
where y=0 or 1, C corresponds to a linear, branched or cyclic alkyl radical having 1 to 4 C atoms, R 5 corresponds to a linear, branched or cyclic alkyl radical having 1 to 4 C atoms and/or an aryl radical, and R 4 corresponds to a linear, branched and/or cyclic alkyl radical having 1 to 4 C atoms,
and optionally acid, optionally alcohol and optionally a catalyst and optionally one or more further silanes of the general formulae II, IV, VI, VII and/or VIII or the condensates thereof are added
the added silane of the formula VI corresponding to an alkylalkoxysilane
C—Si(R 5 ) y (OR 4 ) 3-y (VI)
where y=0 or 1, C corresponds to a linear, branched or cyclic alkyl radical having 1 to 20 C atoms, R 5 corresponds to a linear, branched or cyclic alkyl radical having 1 to 12 C atoms and/or an aryl radical, and R 4 corresponds to a linear, branched and/or cyclic alkyl radical having 1 to 4 C atoms,
the silane of the formula VIII corresponding to an organofunctional alkoxysilane
E-Si(R 8 ) v (OR 9 ) 3-v (VIII)
where v=0 or 1, R 8 corresponds to a linear, branched or cyclic alkyl radical having 1 to 4 C atoms, E corresponds to a radical R 8 —Y m —(CH 2 ) s —, with R 8 * corresponding to a mono-, oligo- or perfluorinated alkyl radical having 1 to 9 C atoms or to a mono-, oligo- or perfluorinated aryl radical, and Y corresponding to a CH 2 , O, aryl or S radical and m being 0 or 1 and s being 0 or 2, or to a vinyl, allyl or isopropenyl radical, mercaptoalkyl radical, sulfanealkyl radical, ureidoalkyl radical, to an acryloyloxyalkyl radical or to a linear, branched or cyclic alkoxy radical having 1 to 4 C atoms and R 9 corresponds to a linear, branched and/or cyclic alkyl radical having 1 to 4 C atoms, and/or the condensates thereof,
and are hydrolyzed and the alcohol is substantially removed.
50. A process for the preparation of a composition containing substantially water-soluble, bis-aminofunctional silicon compounds substantially free of alkoxy groups, and water and an acid, wherein an organic solvent, optionally water, optionally an acid and/or optionally a catalyst are initially introduced and
at least one bisaminoalkoxysilane of the formula H
(OR 1 ) 3 Si-A-Si(OR 1 ) 3 (H)
where A is a bis-aminofunctional group of the formula III
—(CH 2 ) i —[NH(CH 2 ) f ] g NH[(CH 2 ) f* NH] g* —(CH 2 ) i* — (III),
in which i, i*, f, f*, g or g* are identical or different, with i and/or i*=from 0 to 8, f and/or f*=1, 2 or 3, g and/or g*=0, 1 or 2 and R 1 corresponds to a linear, cyclic and/or branched alkyl radical having 1 to 4 C atoms, and/or the condensates thereof, and optionally
at least one aminoalkylalkoxysilane of the formula IV
B—Si(R 3 ) x (OR 2 ) 3-x (IV)
where x=0 or 1, R 2 corresponds to a linear, branched and/or cyclic alkyl radical having 1 to 4 C atoms and B corresponds to one of the following aminofunctional groups of the general formula Va or Vb
R 10 h* NH (2-h*) [(CH 2 ) h (NH)] j [(CH 2 ) l (NH)] n —(CH 2 ) k — (Va),
in which 0≦h≦6; h*=0, 1 or 2, j=0, 1 or 2; 0≦l≦6; n=0, 1 or 2; 0≦k≦6 and R 10 corresponds to a benzyl, aryl, vinyl or formyl radical and/or to a linear, branched and/or cyclic alkyl radical having 1 to 8 C atoms, and/or
[NH 2 (CH 2 ) m ] 2 N(CH 2 ) p — (Vb),
in which 0≦m≦6 and 0≦p≦6, and/or the condensates thereof, and optionally
at least one alkylalkoxysilane of the general formula VI
C—Si(R 5 ) y (OR 4 ) 3-y (VI)
where y=0 or 1, C corresponds to a linear, branched or cyclic alkyl radical having 1 to 20 C atoms, R 5 corresponds to a linear, branched or cyclic alkyl radical having 1 to 12 C atoms and/or an aryl radical, and R 4 corresponds to a linear, branched and/or cyclic alkyl radical having 1 to 4 C atoms, and/or the condensates thereof, and optionally
at least one epoxy- or ether-alkoxysilane of the general formula VII
D-Si(R 7 ) u (OR 6 ) 3-u (VII)
where u=0 or 1, D corresponds to a 3-glycidyloxyalkyl, 3-glycidyloxypropyl, epoxyalkyl, epoxycycloalkyl or polyalkylglycolalkyl radical or to a polyalkylglycol-3-propyl radical, R 7 corresponds to a linear, branched or cyclic alkyl radical having 1 to 4 C atoms and R 6 corresponds to a linear, branched and/or cyclic alkyl radical having 1 to 4 C atoms, and/or the condensates thereof, and optionally
at least one organofunctional alkoxysilane of the formula VIII
E-Si(R 8 ) v (OR 9 ) 3-v (VIII)
where v=0 or 1, R 8 corresponds to a linear, branched or cyclic alkyl radical having 1 to 4 C atoms, E corresponds to a radical R 8 *—Y m —(CH 2 ) s —, with R 8 * corresponding to a mono-, oligo- or perfluorinated alkyl radical having 1 to 9 C atoms or to a mono-, oligo- or perfluorinated aryl radical, and Y corresponding to a CH 2 , O, aryl or S radical and m being 0 or 1 and s being 0 or 2, or to a vinyl, allyl or isopropenyl radical, mercaptoalkyl radical, sulfanealkyl radical, ureidoalkyl radical, to an acryloyloxyalkyl radical or to a linear, branched or cyclic alkoxy radical having 1 to 4 C atoms and R 9 corresponds to a linear, branched and/or cyclic alkyl radical having 1 to 4 C atoms, and/or the condensates thereof,
are hydrolyzed and the hydrolysis alcohol and the solvent are substantially removed.
51. The process as claimed in claim 50 ,
wherein
the solvent comprises at least one alcohol selected from the group consisting of methanol, ethanol, propanol and/or mixtures thereof.
52. The process as claimed in claim 50 ,
wherein
the silanes of the general formulae II, IV, VI, VII and/or VIII, the condensates thereof and/or mixtures of these are added in aqueous and/or alcoholic solution.
53. The process as claimed in claim 50 ,
wherein
the silanes of the general formula II, IV, VI, VII or VIII and/or the condensates thereof are added in succession or as a mixture.
54. The process as claimed in claim 50 ,
wherein
substantially unhydrolyzed bisaminoalkylalkoxysilane of the formula II is used.
55. The process as claimed in claim 50 ,
wherein
a bisaminoalkylalkoxysilane of the formula II and an alkylalkoxysilane of the general formula VI are used.
56. The process as claimed in claim 50 ,
wherein
the pH during the hydrolysis is below 12.
57. The process as claimed in claim 50 ,
wherein
inorganic fillers are added.
58. The process as claimed in claim 50 ,
wherein
the hydrolysis and optionally condensation are carried out at from 55 to 80° C.
59. The process as claimed in claim 50 ,
wherein
the pH after the hydrolysis and optionally condensation is adjusted to a value of from 1.0 to 7.0.
60. The process as claimed in claim 50 ,
wherein
the pH is adjusted by addition of an acid.
61. The process as claimed in claim 50 ,
wherein
water is added and a solvent/water mixture is removed until the composition is substantially free of solvent.
62. The process as claimed in claim 50 ,
wherein
an alcohol is initially introduced and at least one bisaminoalkoxysilane of the general formula II and/or the condensate thereof are added and are hydrolyzed by addition of water and optionally an acid and are optionally condensed.
63. The process as claimed in claim 62 ,
wherein
at least one alkylalkoxysilane of the formula VI and optionally at least one aminoalkylalkoxysilane of the formula IV, optionally at least one epoxy- or ether-alkoxysilane of the general formula VII and optionally at least one organofunctional alkoxysilane of the formula VIII and/or the condensates thereof are then added in succession or as a mixture.
64. The process as claimed in claim 50 ,
wherein
the pH of the composition after removal of the hydrolysis alcohol and solvent is from 1.0 to 5.4.
65. The process as claimed in claim 64 ,
wherein
the pH of the composition after removal of the hydrolysis alcohol and solvent is from 3.0 to 5.4.
66. The composition obtained as claimed in claim 50 .
67. A process for the preparation of a composition containing substantially water-soluble, bis-aminofunctional silicon compounds substantially free of alkoxy groups, and water and an acid, wherein
at least one epoxy- or ether-alkoxysilane of the general formula VII
D-Si(R 7 ) u (OR 6 ) 3-u (VII)
where u=0 or 1, D corresponds to a 3-glycidyloxyalkyl, 3-glycidyloxypropyl, epoxyalkyl, epoxycycloalkyl or polyalkylglycolalkyl radical or to a polyalkylglycol-3-propyl radical, R 7 corresponds to a linear, branched or cyclic alkyl radical having 1 to 4 C atoms and R 6 corresponds to a linear, branched and/or cyclic alkyl radical having 1 to 4 C atoms, and/or the condensates thereof, and/or
at least one alkylalkoxysilane of the general formula VI
C—Si(R 5 ) y (OR 4 ) 3-y (VI)
where y=0 or 1, C corresponds to a linear, branched or cyclic alkyl radical having 1 to 20 C atoms, R 5 corresponds to a linear, branched or cyclic alkyl radical having 1 to 12 C atoms and/or an aryl radical, and R 4 corresponds to a linear, branched and/or cyclic alkyl radical having 1 to 4 C atoms, and/or the condensates thereof, and/or
at least one organofunctional alkoxysilane of the formula VIII
E-Si(R 8 ) v (OR 9 ) 3-v (VIII)
where v=0 or 1, R 8 corresponds to a linear, branched or cyclic alkyl radical having 1 to 4 C atoms, E corresponds to a radical R 8 *—Y m —(CH 2 ) s —, with R 8 * corresponding to a mono-, oligo- or perfluorinated alkyl radical having 1 to 9 C atoms or to a mono-, oligo- or perfluorinated aryl radical, and Y corresponding to a CH 2 , O, aryl or S radical, and m being 0 or 1 and s being 0 or 2, or to a vinyl, allyl or isopropenyl radical, mercaptoalkyl radical, sulfanealkyl radical, ureidoalkyl radical, to an acryloyloxyalkyl radical or to a linear, branched or cyclic alkoxy radical having 1 to 4 C atoms and R 9 corresponds to a linear, branched and/or cyclic alkyl radical having 1 to 4 C atoms, and/or the condensates thereof, are initially introduced
and are at least partly hydrolyzed in the presence of water and in the presence of an acid and/or of a catalyst and water and optionally of a solvent and
then, in a second hydrolysis step,
in the presence of further water and optionally of further acid,
at least one bisaminoalkoxysilane of the formula II
(OR 1 ) 3 Si-A-Si(OR 1 ) 3 (II)
where A is a bis-aminofunctional group of the formula III
—(CH 2 ) i —[NH[(CH 2 ) f ] g NH[(CH 2 ) f* NH] g* —(CH 2 ) i* — (III),
in which i, i*, f, f*, g or g* are identical or different, with i and/or i*=from 0 to 8, f and/or f*=1, 2 or 3, g and/or g*=0, 1 or 2 and R 1 corresponds to a linear, cyclic and/or branched alkyl radical having 1 to 4 C atoms, and/or the condensates thereof, and optionally
at least one aminoalkylalkoxysilane of the formula IV
B—Si(R 3 ) x (OR 2 ) 3-x (IV)
where x=0 or 1, R 2 corresponds to a linear, branched and/or cyclic alkyl radical having 1 to 4 C atoms and B corresponds to one of the following aminofunctional groups of the general formula Va or Vb
R 10 h* NH (2-h*) [(CH 2 ) h (NH)] j [(CH 2 ) l (NH)] n —(CH 2 ) k — (Va),
in which 0≦h≦6; h*=0, 1 or 2, j=0, 1 or 2; 0≦l≦6; n=0, 1 or 2; 0≦k≦6 and R 10 corresponds to a benzyl, aryl, vinyl or formyl radical and/or to a linear, branched and/or cyclic alkyl radical having 1 to 8 C atoms, and/or
[NH 2 (CH 2 ) m ] 2 N(CH 2 ) p — (Vb),
in which 0≦m≦6 and 0≦p≦6, and/or the condensates thereof, are added
and are hydrolyzed and the alcohol is substantially removed.
68. The process as claimed in claim 67 ,
wherein
the silanes of the general formulae VI, VII, VIII and/or the condensates thereof are added in succession or as a mixture.
69. The process as claimed in claim 67 ,
wherein
further water is added for the second hydrolysis step.
70. The process as claimed in claim 67 ,
wherein
the pH during the hydrolysis is from 2.0 to 5.4.
71. The process as claimed in claim 67 ,
wherein
the pH is adjusted by further addition of an acid.
72. The process as claimed in claim 67 ,
wherein
substantially unhydrolyzed bisaminoalkylalkoxysilane of the formula II is used.
73. The process as claimed in claim 67 ,
wherein
a bisaminoalkylalkoxysilane of the formula II and an alkylalkoxysilane of the general formula VI are used.
74. The process as claimed in claim 67 ,
wherein
inorganic fillers are added.
75. The process as claimed in claim 67 ,
wherein
water is added and an alcohol/water mixture is removed until the composition is substantially free of alcohols.
76. The composition obtained as claimed in claim 67 .
77. The process as claimed in claim 67 ,
wherein
the pH of the composition after removal of the alcohol is from 1.0 to 5.4.
78. The process as claimed in claim 77 ,
wherein
the pH of the composition after removal of the alcohol is from 3.0 to 5.4.