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

• US 8,889,812 B2
• Filed: 03/19/2010
• Issued: 11/18/2014
• Est. Priority Date: 04/20/2009
• Status: Expired due to Fees

• Current Assignee: Evonik Degussa GmbH
• Original Assignee: Evonik Degussa GmbH
• Inventors: Albert, Philipp, Just, Eckhard
• Primary Examiner(s): PENG, KUO LIANG
• Application Number:
  US13/258,724
• Publication Number:
  US 20120031302A1
• Time in Patent Office: 1,705 Days
• Field of Search: 528/38
• US Class Current: 528/38
• CPC Class Codes: C08G 77/26 nitrogen-containing groups
• CPC Class Codes: C08G 77/452 containing nitrogen-containing sequences
• CPC Class Codes: C09D 183/08 containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
• CPC Class Codes: C09D 183/10 Block or graft copolymers containing polysiloxane sequences obtained by polymerising a compound having a carbon-to-carbon double bond on to a polysiloxane C09D151/08, C09D153/00
• CPC Class Codes: C09D 5/002 Priming paints C09D5/08 takes precedence
• CPC Class Codes: C09D 5/08 Anti-corrosive paints
• CPC Class Codes: C09D 5/14 Paints containing biocides, e.g. fungicides, insecticides or pesticides C09D5/16 takes precedence
• CPC Class Codes: C09D 7/63 organic
• CPC Class Codes: C23C 18/1208 Oxides, e.g. ceramics
• CPC Class Codes: C23C 18/122 Inorganic polymers, e.g. silanes, polysilazanes, polysiloxanes
• CPC Class Codes: C23C 18/1245 Inorganic substrates other than metallic
• CPC Class Codes: C23C 18/1254 Sol or sol-gel processing
• CPC Class Codes: C23C 22/74 for obtaining burned-in conversion coatings
• CPC Class Codes: C23C 22/83 Chemical after-treatment
• CPC Class Codes: C23C 2222/20 Use of solutions containing silanes

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

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)_Δ

Si(A)Si(R¹¹)_Δ

(Y)_2-Δ

O]_a

2. The composition of claim 1, wherein:

A is derived from formula (II)

(OR¹)_3-Δ

(R¹¹)_Δ

Si-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)

R¹⁰_h*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 R^8*—

Y_m—

(CH₂)_s—

radical, 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 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.

3. The composition of claim 2, wherein Z* is —

CH₂—

, —

(CH₂)₂—

, —

(CH₂)₃—

, or —

[CH₂CH(CH₃)CH₂]—

.

4. The composition of claim 2, wherein Z is independently —

CH₂—

, —

(CH₂)₂—

, —

(CH₂)₃—

, or —

[CH₂CH(CH₃)CH₂]—

.

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

6. 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.

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

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

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)_Δ

Si-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

R¹⁰_h*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 R^8*—

Y_m—

(CH₂)_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 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.

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

13. A composition obtained by the process of claim 9.