EP2178984A1

EP2178984A1 - Silane-based, aqueous coating system, production and use thereof

Info

Publication number: EP2178984A1
Application number: EP08785901A
Authority: EP
Inventors: Adolf KÜHNLE
Original assignee: Evonik Degussa GmbH
Current assignee: Evonik Operations GmbH
Priority date: 2007-08-17
Filing date: 2008-07-02
Publication date: 2010-04-28
Also published as: US20110039972A1; CN101367943B; JP2010536966A; WO2009024386A1; DE102007060334A1; US8349911B2; CN101367943A

Abstract

Production of a composition based on silanes for the scratch-resistant, hydrophobic, aqueous coating of metals, plastics, chemical products, ceramic materials, concrete and glass.

Description

Silane-based and aqueous coating system, its preparation and use

The invention relates to a water-dispersed coating composition based on silanes with amino groups and a double bond-containing organic acid. Furthermore, the invention relates to a process for their preparation and use.

According to the state of the art, in addition to solutions, aqueous coating systems are generally subdivided into dispersions and emulsions, where the term dispersion denotes the state of aggregation for a finely divided solid in a liquid, while a finely and homogeneously distributed liquid is used under an emulsion Phase in a second fluid understands. So-called polymer dispersions are water-dispersed polymers which, depending on the glass transition temperature or chain length, are viscous liquids to solids. In order to be able to disperse these polymers in water or make them water-compatible, emulsifiers are used. These are oligomeric or polymeric compounds having a hydrophilic and a lipophilic moiety. While the lipophilic end will usually always be a long branched or unbranched alkyl chain, depending on whether the hydrophilic end contains a polyalkyl ether, a carboxylate function or an ammonium salt, one speaks of nonionic, anionogenic or cationogenic emulsifier systems. In principle, an emulsifier is firmly anchored in the polymer via its lipophilic radical, so that the polymer receives hydrophilic groups and can be dispersed in water. These emulsifier systems can be modified such that the polymer itself already carries carboxylate or ammonium functions which can be reacted for dispersion in water with alkali metal, alkaline earth metal hydroxides or amines or with acids such as formic acid or acetic acid. Depending on the structure, these emulsifier systems have various disadvantages. In the case of nonionic emulsifiers, larger amounts are usually required so that the coating becomes sensitive to moisture. Furthermore, nonionic emulsifiers diffuse to the surface, causing them becomes greasy and the intercoat adhesion deteriorates. If alkali metal or alkaline earth metal hydroxides are used, anionogenic emulsifiers also provide moisture-sensitive coatings. When amines are used in anionogenic systems, their volatilization achieves higher water resistance, but amines are released into the environment. Similarly, it is the case of cationogenic systems that usually a volatile acid such as. B. release acetic acid or formic acid.

Further details can be found in "Aqueous polymer dispersions - synthesis, properties, applications (Dieter Distler, Wiley-VCH Weinheim, 1999).

The products offered on the market are very diverse and include, for example, dispersions based on acrylates, styrene-acrylates, butadiene-styrene, vinylidene-styrene, polyurethane, vinyl acetates, vinyl acrylates, butadiene-acrylonitrile and ethene-vinyl acetates. Which dispersion is used for which application is usually a question of the desired property picture and the costs. Areas of application can be found in the paper and graphic arts industry, the paints and coatings industry, the adhesives industry, the textile and carpet industry, the leather industry, the construction industry, the foam manufacturing industry and in medicine and pharmacy.

In addition, under the trade names DYNASYLAN® ^® HS or Hydrosil by Degussa GmbH types, such as 2909, 2775, 2627, 2776 and 2907, offered as an aqueous silane systems, raise the surfaces very well containing hydroxyl groups on the basis of existing silanol and stick there. The resulting films are highly transparent, but unfortunately soft and not scratch-resistant, so that coatings based on these products on surfaces of finished products excrete. Accordingly, these types can only be used as additives, as primers, as adhesion promoters, for glass fiber size or for surface treatment. Treatment of minerals are recommended. In addition, for reasons of stability or occupational safety, they can only be offered either as acidic solutions with a pH of about 4 or as a basic system with a pH of about 11. As mentioned above, the acid solutions contain volatile acids, eg. For example, formic acid, which volatilizes during drying and is released as a hazardous substance. Alkaline or basic systems in turn hydrolyze and condense faster than acidic systems, so that oligomers are formed by this partial condensation. After the application, they can no longer crosslink to the required extent due to already used crosslinking groups and relatively soft films are formed. (EP 0 716 127, EP 0 716 128, EP 0 832 911, EP 1 101 787, WO 06/010666, WO 05/014741)

The object was to develop a polymer dispersion based on silanes, which, on the one hand, is hydrolyzed on the other hand, but prevents oligomer formation by virtue of its low basicity. When the polymer dispersions dry, again no volatile acids should be released into the environment.

The object is achieved according to the disclosure in the patent claims.

Thus, this object could surprisingly be achieved in that an aminoalkoxysilane whose amino groups was reacted with a double bond-containing organic acid, wherein a corresponding ammonium salt is generally formed, is dispersed in water. By setting a suitable pH on the one hand hydrolysis can take place, but on the other hand, the condensation to oligomers but are largely prevented.

When a composition is applied to a substrate before or after the drying process or the film formation, the double bonds containing organic acid can be crosslinked easily and thus can remain as a polymer in the formed silane film. As a result, the silane film is surprisingly hard and scratch-resistant.

Due to the fact that silanes in the neutral range are the most stable and have little hydrolysis, at alkaline pH (> 8), however, increasingly hydrolyze better and form by condensation oligomers and polymers, at acidic pH (<4) in turn also hydrolyze and in addition to liberate volatile acid on drying, the process according to the invention offers the advantage that the pH of the reaction solution can be tailor-made to a range from 4 to 7 and no acids are liberated.

For the process according to the invention, one or more aminosilanes or aminoalkylsilanes of the general formula I

A _m SiY _n (I),

used in which

A represents a substituted or unsubstituted aminoalkyl group, a substituted or unsubstituted diaminodialkyl group or substituted or unsubstituted triaminothalkyl group.

Such aminosilanes or aminoalkylsilanes include, but are not limited to, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminoethyl-3-aminopropyltrimethoxysilane, amino-functional propyltrimethoxysilane, bis (3-trimethoxysilylpropyl) amine, bis (3-thethoxysilylpropyl) amine, N-benzyl-N- (2-aminoethyl) -3-aminopropylthmethoxysilane hydrochloride, N-

Benzyl N- (2-aminoethyl) -3-aminopropylthmethoxysilane Hydroacetate, N- (n-

Butyl) -3-aminopropyltrimethoxysilane, 3-aminopropylmethyldiethoxysilane, N- Vinyl benzyl N- (2-aminoethyl) -3-anninopropylpolysiloxane and N- (2-aminoethyl) -3-aminopropylmethyldinnethoxysilane.

Preferred aminosilanes or aminoalkylsilanes are substituted or unsubstituted aminosilane compounds, in particular 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, N- (2-aminoethyl) -3-aminopropyltrinnethoxysilane, 2-aminopropyl-3-aminopropyltrimethoxysilane, 2 -Aminopropyl-3-aminopropylthethoxysilane, 2-aminoethyl-2-aminoethyl-3-aminopropyltrinnethoxysilane, 2-aminoethyl-2-aminoethyl-3-aminopropylthethoxysilane and N- (n-butyl) -3-aminopropyltrimethoxysilane.

Particular preference DYNASYLAN® ^® AMMO, DYNASYLAN® ^® AMEO, DYNASYLAN® ^® 1505 DYNASYLAN® ^® 1189, DYNASYLAN® ^® DAMO and DYNASYLAN® ^® TRIAMO.

The groups Y are identical or different, Y being OH, ONa, OK, OR ',

OCOR ', OSiR's, Cl, Br, I or NR' ₂ , m is 1 or 2 and n is 1, 2 or 3, with the proviso m + n = 4, wherein the group R 'is independently hydrogen, linear or branched alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl groups, each having 1 to 18 carbon atoms and may each be optionally substituted.

Optionally, one or more silanes of the general formula (II)

(R) _a (X) _b SiY _n (II)

in which the groups R are independently hydrogen, alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl groups and each have 1 to 18 carbon atoms and may optionally be substituted, the groups X are the same or different and X is an oxy, hydroxy, alkoxy, carboxy, silyl, alkylsilyl, alkoxysilyl, siloxy, alkylsiloxy, alkoxysiloxy, silylalkyl, alkoxysilylalkyl, alkylsilylalkyl, halogen , omega-haloalkyl, epoxy, omega-glycidyloxyalkyl, ester, fluoroalkyl or perfluoroalkyl, blocked isocyanate, cyanatoalkyl, isocyanatoalkyl, omega-methacryloxy-alkyl, acrylate, methacrylate, mercapto , omega-mercaptoalkyl, nitrile or phosphine group, the groups Y are the same or different and Y is OH, ONa, OK, OR ', OCOR', OSiR ' _3j Cl, Br, I or NR' ₂ , wherein the R 'is independently hydrogen, linear or branched alkyl, cycloalkyl, alkenyl, cycloalkenyl,

Are each alkynyl, cycloalkynyl, aryl or heteroaryl groups and each have 1 to 18 carbon atoms and may optionally be substituted, and a is 0 or 1 and b is 0 or 1 and n is 1, 2 or 3, with the proviso a + b + n = 4.

Thalkoxysilanes, in particular alkyltrialkoxysilanes of the RSi (OR ') 3 type are preferably used here, the alkoxy group (OR') having from 1 to 4 carbon atoms, in particular methoxy or ethoxy group, and the alkyl group (R) having from 1 to 5 carbon atoms, in particular from 2 to 4 carbon atoms, but preferably has 3 carbon atoms. Examples of alkyltrialkoxysilanes of the formula RSi (OR ') ₃ are isobutyltrimethoxysilane (DYNASYLAN ^® IBTMO), Isobutyltriethoxy- silane, Propylthmethoxysilan (DYNASYLAN ^® PTMO), Propylthethoxysilan, ethyl trimethoxysilane, ethyltriethoxysilane, methyltrimethoxysilane (DYNASYLAN ^® MTMS) or methyltriethoxysilane. In the inventive method also Thalkoxysilane can with a substituent of the type X according to the formula XSi (OR ') 3, such as 3-chloropropyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane (DYNASYLAN ^® GLYMO), 3-mercaptopropyltrimethoxysilane (DYNASYLAN ^® MTMO), 3-Methacryloxypropylthmethoxysilan (DYNASYLAN ^® MEMO) are used. In a particular embodiment, be (DYNASYLAN ^® VTMO) or vinyltriethoxysilane used such as vinyltrimethoxysilane Alkenylthalkoxysilane. To achieve certain properties, it is additionally possible to use silanes modified with fluorine groups. For the production of systems for hydrophobing, these are preferably fluoroalkyltrialkoxysilanes, preferably fluoroalkylthalkoxysilanes according to the formula CF ₃ ((CF ₂ ) o (CH ₂ ) p) Si (OR ') 3 with o, p = 0-12, such as 3, 3,4,4,5,5,6,6,7,7,8,8,8-Tridecafluorothethoxysilan (DYNASYLAN ^® F 8261) was used.

In a further embodiment, in particular halosilanes, preferably trichlorosilanes, are used together with alkoxysilanes in the process according to the invention. The hydrochloric acid formed during the hydrolysis must be removed.

In the first partial process step of the process according to the invention, the aminosilane or aminoalkylsilane used according to formula I is advantageously partially or completely neutralized with an acid containing carbon double bonds. These may be mono- or poly-protic acids. However, acrylic acid, methacrylic acid, maleic acid, fumaric acid, aconitic acid, oleic acid and the derivatives of the abovementioned acids are preferably used in the process according to the invention. The molar ratio of aminosilanes or aminoalkylsilanes to the acid is preferably to be selected so that per primary, secondary or tertiary amino group of 0.2 to 2.0 molar equivalents of a monoprotic acid are available. There are 0.8 to 1, 2 molar equivalents, preferably 0.95 to 1, 05 molar equivalents of a einpronigen acid added. When using organic acids with multiple acid functions such. As maleic acid or fumaric acid is to choose a corresponding molar ratio.

The preparation can be done for example by dropwise addition of the appropriate amount of acid to the silane mixture with cooling, this variant is particularly suitable when equivalent amounts of acid and amine are used. This can be done both in a solvent and run without the use of a solvent. If a solvent is used, alcohols such as example, ethanol and methanol, advantageous. The concentrations of the solutions are from 0.1 to 99.9% by weight, preferably from 20 to 90% by weight, in particular from 30 to 80% by weight. In principle, however, the reaction can also be carried out in any other organic solvent, provided that the reaction components dissolve here. Such a mixture may be stored as an intermediate for an extended period if necessary.

In a second process substep, the adduct of the silanes A _n SiY _n according to formula I and (R) _a (X) bSiY _n according to formula II and the acid used according to the invention is dissolved either in 100% concentration or in an organic solvent at temperatures above 20 ⁰ C and below 80 ⁰ C, preferably stirred at temperatures between 30 ⁰ C and 70 ⁰ C, in particular at temperatures between 35 ⁰ C and 45 ⁰ C in water, wherein the ratio of silanes used according to the invention and acid is to be selected in that, after stirring in, the reaction solution has a pH of from 2 to 9, preferably a pH of from 3 to 8, particularly preferably a pH of from 4 to 7.5. The resulting in the hydrolysis alcohols such as methanol or ethanol and optionally with solvent used are then at temperatures above 20 ⁰ C and below 80 ⁰ C, preferably at temperatures between 30 ⁰ C and 70 ⁰ C, in particular at temperatures between 35 ⁰ C and Distilled off 45 ⁰ C, wherein in the latter cases with a vacuum pump, the pressure is to be lowered. If during this distillation of the alcohol and the optionally used solvent water is discharged with, the amount of water can be replaced later.

After dilution with water, the aqueous solutions then have a content of acid-neutralized silane of <50% by weight, preferably from 5 to 40% by weight, in particular from 10 to 30% by weight.

In a particular embodiment, the present method may be practiced be that a pH of the reaction solution of about 3 to 4.5 results. In this case, the silanol groups formed during the hydrolysis are partially retained, since the further condensation is hindered at this pH. This means that a condensation or crosslinking, especially at a pH change, z. After application, when the system is applied to a basic surface such as concrete or metals. The condensation or cross-linking also occurs when the water has volatilized.

In a further embodiment of this two-stage process, the second method step is advantageously carried out on site and immediately before the application itself. This means that in this second process step, the adduct of the silanes A _n SiY _n according to formula I and (R) _a (X) b SiY _n according to formula II and the acid used in the invention either in 100% concentration or in solution Place at a temperature above 0 ⁰ C, preferably at a temperature above 10 ⁰ C, in particular at a temperature between 20 ⁰ C and 40 ⁰ C is stirred into water. One then has, for example, the advantage of a transport cost savings.

A particularly preferred method is based on a one-step process. In this case, the organic acid is placed in water and the silane or silane mixture is stirred in the course of 0.1 to 10 hours. Conveniently, then just enough acid is initially charged that the silanol groups are partially retained or, after addition of the silane or silane mixture, a pH of from 3 to 8, preferably from 7 to 7.5 results. In order to prevent an excessive lowering of the pH in the acidic range, the addition of the acid - distributed over the entire reaction time - can be done in up to 100 individual portions. On the one hand, this method offers the advantage of a particularly simple method of assembly, on the other hand can between already during the addition of the silane mixture produced by hydrolysis of alcohols such as methanol or ethanol at temperatures above 20 ⁰ C and below 80 ⁰ C, preferably at temperatures 30 ⁰ C and 70 ⁰ C, in particular at temperatures between 35 ⁰ C and 45 ⁰ C are distilled off, in the latter cases with a vacuum pump, the pressure is to be lowered. During the azeotropic distillation of the alcohol, the amount of water entrained must be replaced.

Finally, the aqueous solutions have a content of acid-neutralized silane of <50% by weight, preferably from 5 to 40% by weight, in particular from 10 to 30% by weight.

The reaction of the silanes and modified amino silanes and aminoalkyl silanes in accordance with this one-step process in water is preferably at a temperature from 0 to 200 ⁰ C, preferably at a temperature of 10 to 100 ⁰ C, particularly preferably at a temperature of 20 to 90 ⁰ C. carried out. Most preferably, this reaction of the silanes is carried out at a temperature of 60 ± 15 ⁰ C. In a particular embodiment of the process according to the invention, the temperature is not kept constant over the entire reaction time. Thus, for example, it is advantageous to raise the reaction temperature slightly towards the end of the reaction time in order to distill off the solvent which may be present and the alcohols formed during the hydrolysis, such as methanol, ethanol or a mixture of these alcohols, as mentioned.

The process according to the invention for the conversion of aminosilanes and silanes advantageously leads to silanols and siloxanes and / or to siloxanes with ammonium groups which have as counterion an acrylate, methacrylate, maleate, fumarate, oleate, itacon, aconitic acid anion or a derivative of the abovementioned Contain acids.

Overall, aqueous solutions are prepared in concentrations of less than 50 wt .-%, preferably from 5 to 40 wt .-%, in particular from 10 to 30 wt .-%. The process according to the invention can be carried out continuously or in batch mode.

To crosslink the double bonds containing acid after application of the dispersion (. Eg by brushing, dipping, spraying or knife coating), an electron beam crosslinking can (for example, at a temperature of 100 ⁰ C; radiation dose of 3 Mrad; electron gun.: Elektrocurtain, Fa. Energy Sciences Int.) Or regulators and initiators can be used.

Regulators are added to the dispersion for adjusting the molecular weights, wherein, based on the amount of acid, preferably from 0.05 to 5 wt .-%, preferably from 0.1 to 2 wt .-% and particularly preferably from 0.2 to 1 wt. -% be used. In particular, the coating composition according to the invention has a molecular weight regulator selected from mercaptans, such as, for example, n-butyl mercaptan, n-dodecyl mercaptan, 2-mercaptoethanol, or 2-ethylhexyl thioglycolate. The coating composition according to the invention preferably has n-dodecylmercaptan.

For a radical polymerization or crosslinking of the coating composition according to the invention, this may contain what are known as polymerization initiators. In particular, the coating composition according to the invention from 0.01 to 2 wt .-% based on the amount of acid. As polymerization initiators, the dispersion of the invention preferably azo compounds such as 2,2'-azobis (isobutyronitrile), 2,2 ^'azobis- (isobuttersäureamidin) - dihydrochloride or 2,2'-azobis (2,4-dimethylvaleronitrile), redox Systems, such as the combination of tertiary amines with peroxides on. The dispersion according to the invention preferably comprises peroxides, more preferably peroxodisulfate, dilauroyl peroxide, tert-butyl peroctoate, tert-butyl phesononanoate, dicyclohexyl peroxydicarbonate, dibenzoyl peroxide or 2,2-bis (tert-butylperoxy) butane. The dispersion according to the invention can also be a mixture of different polymers. tion initiators with different half-life, such as dilauroyl peroxide and 2,2-bis (tert-butylperoxy) butane, to keep constant the radical during the polymerization and at different polymerization temperatures. In a particular embodiment of invention, the dispersion according to photoinitiators, such as DAROCUR ^® - or IRGACURE ^® grades include, in particular, these are α-hydroxy ketones, phenylglyoxylates, benzyl dimethyl or α-aminoketones.

As far as they are soluble in water or are dispersed with the system according to the invention as dispersing aids or with additional commercially available dispersing aids in water, a wide range of acrylate and methacrylate compounds can be admixed to the system according to the invention, such as, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, hexyl (meth) acrylate, Heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, decyl (meth) acrylate, benzyl (meth) acrylate, tetrahydrofurfuryl ( meth) acrylate, octadecyl (meth) acrylate, dodecyl (meth) acrylate, tetradecyl (meth) acrylate, oleyl (meth) acrylate, 4-methylphenyl (meth) acrylate, benzyl (meth) acrylate, furfuryl (meth) acrylate, Cetyl (meth) acrylate, 2-phenylethyl (meth) acrylate, isobornyl (meth) acrylate, neopentyl (meth) acrylate.

If desired, so-called molecular weight regulators, for example from the class of known mercaptans, can be added to adjust the molecular weights, such as n-butylmercaptan, n-dodecylmercaptan, 2-mercaptoethanol or 2-ethylhexylthioglycolate, the molecular weight regulators generally being used in amounts of 0 , 05 to 5 wt .-%, based on the monomer mixture, preferably in amounts of 0.1 to 2 wt .-% and particularly preferably in amounts of 0.2 to 1 wt .-% are used on the monomer mixture. Preference is given to using n-dodecylmercaptan as molecular weight regulator. The mixing ratio of the inventive silane-based system to optionally added acrylate or methacrylate compounds is 0.1 to 99.1 wt .-% to 99.9 to 0.1 wt .-%. It is preferably 30 to 70% by weight to 70 to 30% by weight. In particular, at most 15% by weight of the acrylate or methacrylate compounds are added to the aqueous system.

Of course, other additives such as heat and light stabilizers, in particular UV absorbers, optical brighteners, antistatic agents, lubricants, antiblocking agents, nucleating agents, fillers and dyes, pigments and flame retardants may be included in the inventive system. Based on the solids content of the dispersion, these additives have a total of preferably from 0.01 wt .-% to 5.0 wt .-%. Also, the use of wetting and leveling agents in amounts of 0.01 wt .-% to 5.0 wt .-% may be advisable for certain surfaces.

The composition of the invention can be used in many ways such. As for metal surfaces, the coating of fillers, for the water-repellent coating of salts, in particular the coating of perborates, for coating tacky plastic granules, for the coating of concrete and glass, for the synthesis of catalysts and their starting compounds, for stabilizers and for the synthesis or modification of ceramic compositions and polymers and for the coating of polymer granules, polymer plates, polymer fibers and polymer semifinished products.

The examples which follow are intended to explain the coating composition according to the invention, its preparation and use as well as the moldings coated according to the invention without restricting the invention.

Example 1 Synthesis of a composition with (aminopropyl) _x Si _x Oi, ₅ χ portions and methacrylic acid

In 100 ml of ethanol, 176.8 g (0.8 mol) of 3- aminopropyltriethoxysilane (DYNASYLAN ^® AMEO) are added under stirring at room temperature. These are rapidly mixed with 68.87 g (0.8 mol) of methacrylic acid. Then, at room temperature, 400 g of water are added. The temperature is then raised to 60 ⁰ C and allowed to stir for 6 hours at this temperature. After distilling off the ethanol in vacuo and replacing the azeotropically distilled off with water, a pale yellow solution is obtained as the final product.

Example 2

Synthesis of a composition with (aminopropyl) _x . ₅ , 6 (methyl) _x-2 , ₄ Si _x 0i, _5x -

Proportions and methacrylic acid

In 100 ml of ethanol 53.04 g (0.24 mol) of 3- aminopropyltriethoxysilane (DYNASYLAN ^® AMEO) are added under stirring at room temperature. These are quickly mixed with 20.66 g (0.24 mol) of methacrylic acid. Are then added to 76.25 g (0.56 mol) of methyltrimethoxysilane (DYNASYLAN ^® MTMS) and then 300 g of water at room temperature. The temperature is then raised to 50 ⁰ C and allowed to stir for 6 hours at this temperature. After distilling off the ethanol and methanol in vacuo and replacing the azeotropically distilled off with water, a pale yellow solution is obtained as the final product.

Example 3 Synthesis of a composition with (aminopropyl) _x . ₅ (methyl) _x .3Siχ0i _j5 χ- shares and acrylic acid

In 300 ml of water, into which 21, 62 g (0.30003 mol) of acrylic acid were previously stirred at room temperature, 66.3 g (0.30 mol) are then added with further stirring at room temperature over the course of 10 minutes. aminopropyltriethoxysilane (DYNASYLAN AMEO). Are then added at room temperature 68.08 g (0.50 mol) Methylthmethoxysilan (DYNASYLAN ^® MTMS) were added and the temperature is raised to 50 ⁰ C increased. Then allowed to stir for 6 hours at this temperature. After distilling off the ethanol and methanol in vacuo and replacing the azeotropically distilled off with water, a pale yellow solution is obtained as the final product.

Example 4

Preparation of an activated solution from Example 2

In 100 ml of product from Example 2 are stirred with a laboratory dissolver at room temperature, 1.0 g peroxodisulfate and stirred for 30 minutes further. After that, the activated solution is ready.

Example 5

Preparation of an activated dispersion of the product from Examples 1 and 2

50 ml of product from Example 1 and 50 ml of product from Example 2 are stirred with a laboratory dissolver and heated to 40 ⁰ C. Thereafter, 0.5 g of 2,2 ^'azobis (isobuttersäureamidin) dihydrochloride are added and stirred further at this temperature for 30 minutes. After cooling to room temperature, the activated dispersion is ready.

Example 6

To be coated molded body made of sheet steel

Sheet metal test specimen (Chemetall No. 129611 with bonder rust protection 26 / NL 60). At room temperature, the solution / dispersion from Example 4 is applied to this test specimen - the uncoated specimen representing the blank specimen (Test specimen 6.1) or from Example 5 (test specimen 6.2) in a layer thickness of 200 microns aufgerakelt (laboratory blade). After this application, the film is allowed to dry at room temperature. This is followed by storage for 24 hours at 50 ⁰ C in a vacuum oven. Thereafter, an annealing of 1 hour in a drying oven at 100 ⁰ C and then cooling in the course of 24 hours to room temperature.

Example 7

To be coated form of transparent polyamide body

Self-made transparent Polyamidprüfkörper (trogamid ^® CX 7323, Degussa

GmbH).

Format (length / width / depth): 15 cm x 10 cm x 0.5 cm.

The coating and treatment are carried out analogously with the same solution / dispersion

Example 6. However, only half of the area is coated, the uncoated area serves as a blank. The two test specimens carry the

Designation 7.1 and 7.2.

Example 8 Tests

The samples of Example 6 are stored in vertical position 6 months (March to August period) under outdoor weather (Central European climate) and then assessed visually, the grade 1 is a very good and grade 5 is a very poor rating.

Coated specimens no. 2 and no. 3 have a water-resistant, transparent and hard film which does not change in outdoor weathering. The drying of the solution / dispersion proceeds without any solvent, amine or acid emission.

The scratch resistance of the samples of Example 7 is checked so that after removal of the test specimens from the oven and cooling in the course of 24 hours commercially available steel wool (amount about 1 cm ³ ) by hand under low load (about 100 pond) each 10 times in forward and backward on the entire substrate was moved. This means that scrubbing is done with equal intensity over both the coated and uncoated surfaces. It is then visually assessed which of the two polyamide surfaces (ie, uncoated-coated) has more scratch marks, with grade 1 being a very good rating and grade 5 being a very poor rating.

Coated specimens no. 5 and no. 6 are significantly more scratch resistant than the blank specimen.

Claims

claims:

1. A process for preparing a composition containing functionalized silanes and / or functionalized siloxanes, characterized in that

- One or more aminosilanes of general formula I.

A _m SiY _n (I),

wherein

A represents a substituted or unsubstituted aminoalkyl group, a substituted or unsubstituted diaminodialkyl group or substituted or unsubstituted triaminothalkyl group, the Y groups are the same or different and Y is OH, ONa, OK, OR ',

OCOR ', OSiR's, Cl, Br, I or NR' ₂ , m is 1 or 2 and n is 1, 2 or 3, with the proviso m + n = 4, wherein the group R 'is independently hydrogen, linear or branched alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl groups are each having 1 to 18 carbon atoms and may each be optionally substituted,

and optional

one or more silanes of the general formula (II)

(R) _a (X) _b SiY _n (II)

wherein the groups R are independently hydrogen, alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl groups and each having 1 to 18 carbon atoms and may optionally be substituted, the groups X are the same or different and X is an oxy, hydroxy,

Alkoxy, carboxy, silyl, alkylsilyl, alkoxysilyl, siloxy, alkylsiloxy, alkoxysiloxy, silylalkyl, alkoxysilylalkyl, alkylsilylalkyl, halogen, omega

Haloalkyl, epoxy, omega-glycidyloxyalkyl, ester, fluoroalkyl or

Perfluoroalkyl, blocked isocyanate, cyanatoalkyl, isocyanatoalkyl, omega

Methacryloxyalkyl, acrylate, methacrylate, mercapto, omega-mercaptoalkyl,

Nitrile or phosphine group, the groups Y are the same or different and Y is OH, ONa, OK, OR ',

OCOR ', OSiR's, Cl, Br, I or NR' ₂ , a is O or 1 and b is O or 1 and n is 1, 2 or 3, with the

Assume a + b + n = 4, wherein the groups R 'are independently hydrogen, linear or branched alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or

Are heteroaryl groups and in each case have 1 to 18 C atoms and may optionally be substituted,

with the addition of at least one carbon double bonds containing acid and water.

2. The method according to claim 1, characterized in that in the formula (R) _a (X) bSiY _n, the group X is connected via at least one carbon atom to the silicon atom.

3. The method according to claim 1 or 2, characterized in that one modifies the aminosilane according to formula I by addition of 0.2 to 2.0 molar equivalents of acid.

4. The method according to at least one of claims 1 to 3, characterized in that the aminosilane according to formula I is modified with 0.5 to 1, 5 molar equivalents of acid.

5. The method according to at least one of claims 1 to 4, characterized in that the aminosilane according to formula I with 0.8 to 1, 2 molar equivalent of acid is modified.

6. The method according to at least one of claims 1 to 5, characterized in that the acid is composed of 3 to 20 carbon atoms and contains at least one double bond.

7. The method according to at least one of claims 1 to 6, characterized in that the acid used is an organic acid selected from acrylic acid, methacrylic acid, maleic acid, fumaric acid, aconitic acid, oleic acid, itaconic acid, derivatives of these acids or a mixture of these acids.

8. The method according to at least one of claims 1 to 7, characterized in that after the implementation of the aminosilanes used according to formula I or a Aminosilane- / silanes mixture used (according to formula I and

Formula II) with the organic acid, the reaction solution has a pH of 2 to 9.

9. The method according to at least one of claims 1 to 8, characterized that after the reaction, the reaction solution has a pH of 3 to 8.

10. The method according to claim 9, characterized in that after the reaction, the reaction solution has a pH of 4 to 7.5.

11. The method according to at least one of claims 1 to 10, characterized in that silanes are used according to the formula II, the substituents of the type Y selected from OH, OR ', OCOR' or Cl have.

12. The method according to at least one of claims 1 to 11, characterized in that silanes according to the formula (R) _a (X) b Si (OR ') _n are used, wherein R, R', X, a and b are the same as above Meaning of formula II.

13. The method according to at least one of claims 1 to 12, characterized in that the reaction of the aminosilanes used according to formula I or an aminosilane / silane mixture (according to formulas I and II) is carried out in a water-containing solution.

14. The method according to at least one of claims 1 to 13, characterized in that in the reaction solution present for the reaction, water, acetone, methyl ethyl ketone, propanol, isopropanol, methanol or ethanol or a mixture of two or more of these solvents are present, wherein pro mol of the aminosilanes or silanes used 0.001 to 100 mol of water starts.

15. The method according to at least one of claims 1 to 14, characterized in that after the reaction, the organic present in the reaction solution

Solvent be distilled off.

16. The method according to claim 15, characterized in that in the reaction solution existing alcohol is distilled off.

17. The method according to at least one of claims 1 to 16, characterized in that the reaction is carried out exclusively in the presence of water and the resulting alcohols during the hydrolysis.

18. The method according to at least one of claims 1 to 17, characterized in that the molar ratio of the sum of the aminosilanes used according to formula I and silanes according to formula II to the water at the beginning of

Reaction to a weight ratio of 1: 100 to 100: 1 sets.

19. The method according to at least one of claims 1 to 18, characterized in that the reaction is carried out at a temperature of 0 ⁰ C to 200 ⁰ C.

20. The method according to at least one of claims 1 to 19, characterized in that the reaction is carried out at a temperature below the boiling point of the solvent or solvent mixture.

21. The method according to at least one of claims 1 to 20, characterized in that the carbon double bonds containing acid is crosslinked.

22. The method according to at least one of claims 1 to 21, characterized in that the system contains up to a maximum of 5 wt .-% of photoinitiators.

23. The method according to claim 21 or 22, characterized in that the dispersion film is crosslinked by irradiation, preferably external irradiation.

24. The method according to at least one of claims 1 to 23, characterized in that the product of the reaction before and / or after working up with a solvent, preferably water, diluted, wherein the active ingredient content in the composition to 0.1 to 50 Wt .-%, preferably 5 to 20 wt .-% adjusts.

25. A composition obtainable according to at least one of claims 1 to 24.

26. Use of a composition according to at least one of claims 1 to 25 for the production of coatings for metal surfaces, the coating of fillers, for the water-repellent coating of

Salts, for the coating of sticky plastic granules, for the coating of concrete and glass, for the synthesis of catalysts and their starting compounds, for stabilizers and for the synthesis or modification of ceramic masses and polymers, for the coating of polymer granulates, polymer plates, polymer fibers and polymer semifinished and for the Generation of scratch-resistant and hydrophobic coatings on substrate surfaces.