# US 8,772,432 B2 · Aqueous silane systems based on tris(alkoxysilylalkyl)amines and the use thereof

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- Number: US 8,772,432 B2
- Document ID: US8772432B2
- Status: Granted
- Kind: B2
- Application number: 13/258,724
- Filed: 2010-03-19
- Published: 2012-02-09
- Granted: 2014-07-08
- Earliest claimed: 2009-04-20
- Assignees: Evonik Degussa GmbH
- Applicants: Philipp Albert; Eckhard Just
- Inventors: Philipp Albert; Eckhard Just
- Web page: https://patentgrep.com/patent/US8772432B2

## 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.

## Claims

### Claim 1

A composition, comprising a water-soluble, tris-silylated amino-functional silicon-containing compound and water,
wherein
the a 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),
(R1O)[(R1O)1-x(R3)xSi(B)O]b[Si(C)(R5)y(OR1)1-yO]c[(Y)2-Δ(R11)ΔSi(A)Si(R11)Δ(Y)2-ΔO]a
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 OR1 or, in crosslinked and/or three-dimensionally crosslinked structures, is independently OR1 or O1/2,
R1 is independently hydrogen or a linear, cyclic and/or branched alkyl radical having 1 to 24 carbon atoms,
R3, R5, R7, R8, R11 and/or R12 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≧1, d≧0, w≧0, Σ≧1, e≧0 and (a+b+c+d+w+Σ+e)≧2, and
the composition contains at most 5% by weight of organic solvents.

### Claim 2 (depends on 1)

The composition of claim 1, wherein:
A is derived from formula (II)
(OR1)3-Δ(R11)ΔSi-A-Si(R11)Δ(OR1)3-Δ (II)
wherein
A is a bivalent amino-functional group of the formula (III)
—Z*—[NH(CH2)f]gNH[(CH2)f*NH]g*—Z*— (III)
Z* is independently a bivalent alkylene radical, f, f*, g or g* are the same or different,
f and/or f*=1, 2 or 3,
g and/or g*=0, 1 or 2, and
R11 is a linear, branched and/or cyclic alkyl radical having 1 to 24 carbon atoms or an aryl radical;
Z derived from formula (IX)
N[ZSi(R12)Ω(OR1)3-Ω]3 (IX)
wherein
Z is independently a bivalent alkylene radical, and
R12 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 derived from formula (IV)
B—Si(R3)x(OR1)3-x (IV)
wherein
x=0 or 1,
R3 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)
R10h*NH(2-h*)[(CH2)h(NH)]j[(CH2)l(NH)]n—(CH2)k— (Va)
wherein
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
R10 is a benzyl, aryl, vinyl, formyl radical and/or a linear, branched and/or cyclic alkyl radical having 1 to 8 carbon atoms,
[NH2(CH2)m]2N(CH2)p— (Vb)
wherein
0≦m≦6 and 0≦p≦6;
C derived from formula (VI)
C—Si(R5)y(OR1)3-y (VI)
wherein
y=0 or 1,
C is a linear, branched or cyclic alkyl radical having 1 to 20 carbon atoms, and
R5 is a linear, branched or cyclic alkyl radical having 1 to 24 carbon atoms and/or an aryl radical;
D is derived from formula (VII)
D-Si(R7)u(OR1)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,
R7 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(R8)v(OR1)3-v (VIII)
wherein
v=0 or 1,
R8 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 R8*—Ym—(CH2)s— radical, wherein R8* 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 CH2, 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
R1 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.

### Claim 3 (depends on 2)

The composition of claim 2, wherein Z* is —CH2—, —(CH2)2—, —(CH2)3—, or —[CH2CH(CH3)CH2]—.

### Claim 4 (depends on 2)

The composition of claim 2, wherein Z is independently —CH2—, —(CH2)2—, —(CH2)3—, or —[CH2CH(CH3)CH2]—.

### Claim 5 (depends on 1)

The composition of claim 1, which has a pH in the range from 1 to 12.

### Claim 6 (depends on 1)

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, sulfuric acid and phosphoric acid.

### Claim 7 (depends on 1)

A coating obtained by curing the composition of claim 1 with a substrate or on a substrate surface.

### Claim 8 (depends on 1)

A coated or consolidated product obtained by curing the composition of claim 1 with a substrate or on a substrate surface.

### Claim 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(R12)Ω(OR1)3-Ω]3 (IX)
wherein
Z is independently a bivalent alkylene radical, R12 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)
(OR1)3-Δ(R11)ΔSi-A—Si(R11)Δ(OR1)3-Δ (II)
wherein
A is a bisamino-functional group of formula (III)
—(CH2)i—[NH(CH2)f]gNH[(CH2)f*NH]g*—(CH2)i*— (III)
i, i*, 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,
R11 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(R3)x(OR1)3-x (IV)
wherein
x=0 or 1,
R3 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
R10h*NH(2-h*)[(CH2)h(NH)]j[(CH2)l(NH)]n—(CH2)k— (Va)
wherein
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
R10 is a benzyl, aryl, vinyl, formyl radical and/or a linear, branched and/or cyclic alkyl radical having 1 to 8 carbon atoms, or
[NH2(CH2)m]2N(CH2)p— (Vb)
wherein
0m≦6, and
0≦p≦6;
at least one alkylalkoxysilane of formula (VI)
C—Si(R5)y(OR1)3-y (VI)
wherein
y=0 or 1,
C is a linear, branched or cyclic alkyl radical having 1 to 20 carbon atoms,
R5 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(R7)u(OR1)3-u (VII)
wherein
u=0 or 1,
D is a 3-glycidoxyalkyl, 3-glycidoxypropyl, epoxyalkyl, epoxycycloalkyl, polyalkylglycolalkyl or a polyalkylglycol-3-propyl radical,
R7 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(R8)v(OR1)3-v (VIII)
wherein
v=0 or 1, R8 is a linear, branched or cyclic alkyl radical having 1 to 4 carbon atoms,
E is an R8*—Ym—(CH2)s— radical, R8* 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 CH2—, 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
R1, 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,
wherein the process includes hydrolyzing at least one tris-silylated amino alkylalkoxysilane of formula IX and an alkylalkoxysilane of the general formula VI.

### Claim 10 (depends on 9)

The process of claim 9, wherein hydrolysis is essentially complete.

### Claim 11 (depends on 9)

The process of claim 9, wherein the pH during the hydrolysis is below 12.

### Claim 12 (depends on 9)

The process of claim 9, further comprising adding water and removing an alcohol/water mixture until the composition is essentially free of alcohols.

### Claim 13 (depends on 9)

A composition obtained by the process of claim 9.