Aqueous silane systems based on tris(alkoxysilylalkyl)amines and the use thereof

Abstract

The invention relates to an aqueous composition based on tris-silylated amino-functional silicon compounds, which is substantially free of organic solvents and which substantially does not release any alcohol even during the cross-linking process, and to method for the production thereof, and to the use thereof, for example for the hydrophobization of metal, glass or mineral surfaces, such as concrete and bricks, as adhesion promoter or for rock consolidation, among other things.

1 . A composition, comprising a water-soluble, tris-silylated amino-functional silicon-containing compound and water,
 wherein   the silicon-containing compound comprises crosslinking structural elements which form catenated, cyclic, crosslinked and/or three-dimensionally crosslinked structures,   at least one structure consists of formula (Ia),   
       
         
           
           
               
               
           
         
         wherein
 A is a bivalent aminoalkyl radical, 
 Z is independently a bivalent alkenyl radical, 
 Y is OR 1  or, in crosslinked and/or three-dimensionally crosslinked structures, is independently OR 1  or O 1/2 , 
 R 1  is independently hydrogen or a linear, cyclic and/or branched alkyl radical having 1 to 24 carbon atoms, 
 
         R 11  and/or R 12  are each independently organofunctional radicals,
 HX is an acid wherein X is an inorganic or organic acid radical, 
 
         0≦Δ≦2, 
         0≦Ω2, 
         a≧0, Σ≧1, e≧0 and (a+Σ+e)≧1, and
 the composition is essentially free of organic solvents and releases essentially no further alcohol in the course of crosslinking. 
 
       
     
     
         2 . A composition, comprising a water-soluble, tris-silylated amino-functional silicon compound and water,
 wherein   the silicon-containing compound comprises crosslinking structural elements which form catenated, cyclic, crosslinked and/or three-dimensionally crosslinked structures,   at least one structure consists of formula (I),   
       
         
           
           
               
               
           
         
         wherein
 A is a bivalent aminoalkyl radical, 
 B is an aminoalkyl radical, 
 C is an alkyl radical, 
 D is an epoxy or ether radical, 
 E is an organofunctional radical, 
 Z is independently a bivalent alkylene radical, 
 Y is OR 1  or, in crosslinked and/or three-dimensionally crosslinked structures, is independently OR 1  or O 1/2 , 
 R 1  is independently hydrogen or a linear, cyclic and/or branched alkyl radical having 1 to 24 carbon atoms, 
 
         R 3 , R 5 , R 7 , R 8 , R 11  and/or R 12  are each independently organofunctional radicals,
 HX is an acid wherein X is an inorganic or organic acid radical, 
 
         0≦Δ≦2, 
         0≦Ω≦2, 
         0≦x≦1, 
         0≦y≦1, 
         0≦u≦1, 
         0≦v≦1, a≧0, b≧0, c≧0, d≧0, w≧0, Σ≧1, e≧0 and (a+b+c+d+w+Σ+e)≧2, 
         and
 the composition is essentially free of organic solvents and releases essentially no further alcohol in the course of crosslinking. 
 
       
     
     
         3 . The composition of  claim 2 , wherein:
 A is derived from formula (II)
   (OR 1 ) 3-Δ (R 11 ) Δ Si-A-Si(R 11 ) Δ (OR 1 ) 3-Δ   (II)
 
   wherein   A is a bivalent amino-functional group of the formula (III)
   —Z*—[NH(CH 2 ) f ] g NH[(CH 2 ) f* NH] g* —Z*—  (III)
 
   Z* is independently a bivalent alkylene radical, and f, f*, g or g* are the same or different,   f and/or =1, 2 or 3,   g and/or g*=0, 1 or 2, and   R 11  is a linear, branched and/or cyclic alkyl radical having 1 to 24 carbon atoms or an aryl radical;
 Z is derived from formula (IX)
   N[ZSi(R 12 ) Ω (OR 1 ) 3-Ω ] 3   (IX)
 
 
   wherein   Z is independently a bivalent alkylene radical, and   R 12  is a linear, branched and/or cyclic alkyl radical having 1 to 24 carbon atoms or an aryl radical, and,   Ω is, independently, 0 or 1;
 B is derived from formula (IV)
   B—Si(R 3 ) x (OR 1 ) 3-x   (IV)
 
 
   wherein   x=0 or 1,   R 3  is a linear, branched or cyclic alkyl radical having 1 to 24 carbon atoms and/or an aryl radical, and   B is one of the following amino-functional groups of formula (Va) or (Vb)
   R 10   h* NH (2-h*) [(CH 2 ) h (NH)] j [(CH 2 ) l (NH)] n —(CH 2 ) k —  (Va)
 
   wherein   0≦h≦6,   h*=0, 1 or 2,   j=0, 1 or 2,   0≦1≦6;   n=0, 1 or 2,   0≦k≦6, and   R 10  is a benzyl, aryl, vinyl, formyl radical and/or a linear, branched and/or cyclic alkyl radical having 1 to 8 carbon atoms,
   [NH 2 (CH 2 ) m ] 2 N(CH 2 ) p —  (Vb)
 
   wherein   0≦m≦6 and 0≦p≦6;
 C is derived from formula (VI)
   C—S(R 5 ) y (OR 1 ) 3-y   (VI)
 
 
   wherein   y=0 or 1,   C is a linear, branched or cyclic alkyl radical having 1 to 20 carbon atoms, and   R 5  is a linear, branched or cyclic alkyl radical having 1 to 24 carbon atoms and/or an aryl radical;
 D is ether radical derived from formula (VII)
   D-Si(R 7 ) u (OR 1 ) 3-u   (VII)
 
 
   wherein   u=0 or 1,   D is a 3-glycidoxyalkyl, 3-glycidoxypropyl, epoxyalkyl, epoxycycloalkyl, polyalkylglycolalkyl radical or a polyalkylglycol-3-propyl radical,   R 7  is a linear, branched and/or cyclic alkyl radical, having 1 to 24 carbon atoms, or an aryl radical;
 E is derived from formula (VIII)
   E-Si(R 8 ) v (OR 1 ) 3-v   (VIII)
 
 
   wherein   v=0 or 1,   R 8  is a linear, branched or cyclic alkyl radical having 1 to 4 carbon atoms,
 E is at least one selected from the group consisting of 
   an R 8* —Y m —(CH 2 ) s — radical where wherein R 8*  is a mono-, oligo- or perfluorinated alkyl radical having 1 to 9 carbon atoms or a mono-, oligo- or perfluorinated aryl radical, Y is a CH 2 , O, aryl or S radical, m=0 or 1, and s=0 or 2, and
 a vinyl, allyl, isopropenyl radical, mercaptoalkyl radical, sulphanealkyl radical, ureidoalkyl radical, an acryloyloxyalkyl radical or a linear, branched or cyclic alkoxy radical having 1 to 24 carbon atoms; and 
 R 1  in the Formulae II, IX, IV, VI, VII and/or VIII is in each case independently a linear, cyclic and/or branched alkyl radical having 1 to 24 carbon atoms. 
   
     
     
         4 . The composition of  claim 1 , wherein
 the molar ratio of silicon atoms in the silicon compound to HOR 1  or —OR 1  in the general formula Ia is greater than 1:0.1, and   R 1  is independently a linear, cyclic and/or branched alkyl radical having 1 to 24 carbon atoms.   
     
     
         5 . The composition of  claim 1 , wherein the composition
 has a pH in the range from 1 to 12.   
     
     
         6 - 7 . (canceled) 
     
     
         8 . The composition of  claim 1 , wherein
 the acid is at least one selected from the group consisting of formic acid, acetic acid, citric acid, an acidic silica sol, glacial acetic acid, nitric acid, sulphuric acid and phosphoric acid.   
     
     
         9 . A process for preparing a composition, comprising hydrolysing in the presence of water at least one selected from the group consisting of:
 at least one tris-silylated aminoalkoxysilane of formula (IX)
   N[ZSi(R 12 ) Ω (OR 1 ) 3-Ω ] 3   (IX)
 
   wherein   Z is independently a bivalent alkylene radical,   R 12  is a linear, branched or cyclic alkyl radical having 1 to 24 carbon atoms, and   Ω is independently 0 or 1;
 at least one bisaminoalkoxysilane of formula (II)
   (OR 1 ) 3-Δ (R 11 ) Δ Si-A-Si(R 11 ) Δ (OR 1 ) 3-Δ   (II)
 
 
   wherein   A is a bisamino-functional group of formula (III)
   —(CH 2 ) i —[NH(CH 2 ) f ] g NH[(CH 2 ) f* NH] g* —(CH 2 ) i* —  (III)
 
   i*, f, f*, g and g* are the same or different,   i and/or i*=0 to 8,   f and/or f*=1, 2 or 3,   g and/or g*=0, 1 or 2,   R 11  is a linear, branched or cyclic alkyl radical having 1 to 24 carbon atoms or an aryl radical,   Δ=0 or 1;
 at least one aminoalkylalkoxysilane of formula (IV)
   B—Si(R 3 ) x (OR 1 ) 3-x   (IV)
 
 
   wherein   x=0 or 1,   R 3  is a linear, branched and/or cyclic alkyl radical having 1 to 24 carbon atoms,   B is one of the amino-functional groups of formula Va or Vb
   R 10   h* NH (2-h*) [(CH 2 ) h (NH)] j [(CH 2 ) l (NH)] n —(CH 2 ) k —  (Va)
 
   wherein   0≦h<6,   h*=0, 1 or 2,   j=0, 1 or 2,   0≦1≦6,   n=0, 1 or 2;   0≦k≦6, and   R 10  is a benzyl, aryl, vinyl, formyl radical and/or a linear, branched and/or cyclic alkyl radical having 1 to 8 carbon atoms, or
   [NH 2 (CH 2 ) m ] 2 N(CH 2 ) p —  (Vb)
 
   wherein   0≦m≦6, and   0≦p≦6;
 at least one alkylalkoxysilane of formula (VI)
   C—Si(R 5 ) y (OR 1 ) 3-y   (VI)
 
 
   wherein   y=0 or 1,   C is a linear, branched or cyclic alkyl radical having 1 to 20 carbon atoms,   R 5  is independently a linear, branched or cyclic alkyl radical having 1 to 24 carbon atoms or an aryl radical;
 at least one epoxy or ether alkoxysilane of the formula (VII)
   D-Si(R 7 ) u (OR 1 ) 3-u   (VII)
 
 
   wherein   u=0 or 1,   D is a 3-glycidoxyalkyl, 3-glycidoxypropyl, epoxyalkyl, epoxycycloalkyl, polyalkylglycolalkyl or a polyalkylglycol-3-propyl radical,   R 7  is a linear, branched or cyclic alkyl radical having 1 to 24 carbon atoms or an aryl radical;
 at least one organofunctional alkoxysilane of formula (VIII)
   E-Si(R 8 ) v (OR 1 ) 3-v   (VIII)
 
 
   wherein   v=0 or 1,   R 8  is a linear, branched or cyclic alkyl radical having 1 to 4 carbon atoms,   E is an R 8* —Y, —(CH 2 ) s — radical,   R 8*  is a mono-, oligo- or perfluorinated alkyl radical having 1 to 9 carbon atoms or a mono-, oligo- or perfluorinated aryl radical,   Y is a CH 2 —, O—, aryl or S radical and m=0 or 1 and s=0 or 2, or a vinyl, allyl, isopropenyl radical, mercaptoalkyl radical, sulphanealkyl radical, ureidoalkyl radical, an acryloyloxyalkyl radical or a linear, branched or cyclic alkoxy radical having 1 to 24 carbon atoms; and
 a mixture of at least two of the abovementioned alkoxysilanes or hydrolysis and/or condensation products thereof, 
   wherein   R 1 , in each case independently, in the Formulae IX, II, IV, VI, VII and/or VIII is a linear, cyclic and/or branched alkyl radical having 1 to 24 carbon atoms, and
 the hydrolysis optionally occurs in the presence of an acid, and optionally with initial charging and/or addition of alcohol and/or of a catalyst, and essentially removing the alcohol. 
   
     
     
         10 . The process of  claim 9 , wherein hydrolysis is essentially complete. 
     
     
         11 . The process of  claim 9 , wherein the pH during the hydrolysis is below 12. 
     
     
         12 . (canceled) 
     
     
         13 . The process of  claim 9 , further comprising adding water and removing an alcohol/water mixture until the composition is essentially free of alcohols. 
     
     
         14 . A composition obtained by the process of  claim 9 . 
     
     
         15 . A coating obtained by curing the composition of  claim 1  with a substrate or on a substrate surface. 
     
     
         16 . A coated or consolidated product obtained by curing the composition of  claim 1  with a substrate or on a substrate surface. 
     
     
         17 . (canceled) 
     
     
         18 . A process for modification and/or treatment of a substrate or a substrate surface, comprising applying the composition of  claim 1  to the substrate or surface. 
     
     
         19 . A process for protecting a substrate or material from corrosion and/or UV radiation, comprising forming a partial layer with the composition of  claim 1 . 
     
     
         20 . The composition of  claim 3 , wherein Z* is —CH 2 —, —(CH 2 ) 2 —, —(CH 2 ) 3 —, or —[CH 2 CH(CH 3 )CH 2 ]—. 
     
     
         21 . The composition of  claim 3 , wherein Z is independently —CH 2 —, —(CH 2 ) 2 —, —(CH 2 ) 3 —, or —[CH 2 CH(CH 3 )CH 2 ]—.