DE102005046704A1 - Hydrophobic treatment of a substrate comprises treating the substrate with siloxane compounds - Google Patents

Abstract

Hydrophobic treatment of a substrate comprises treating the substrate with siloxane compounds. Hydrophobic treatment of substrate comprises treating the substrate with siloxane compounds formed from the units of formula [A1>zR1>pSiO(4-p-z)/2]. A1>H, 1-18C hydrocarbon (containing additional heterocyclic atoms: O, S, Si, Cl, F, Br, P or N), alkoxy, aryloxy or OH; R1>1-18C hydrocarbon (containing additional heterocyclic atoms: O, S, Si, Cl, F, Br, P or N), OH, H or phosphonic acid ester of formula -C(R3>)2-P(=O)(OR4>)(OR5>); R3>-R5>H, Oh or optionally substituted 1-10C hydrocarbon optionally containing heteroatom; and z, p : 0-3. Where at least 10% of the sum of the R1> and A1> are R1> and at least 5% of R1> are -C(R3>)2-P(=O)(OR4>)(OR5>).

Description

The The invention relates to a process for the hydrophobization of substrates with phosphonic ester residues containing siloxanes and preparations containing the Phosphonsäureesterreste containing siloxanes.

DE 199 04 496 A1 describes a process for the hydrophobic primer and impregnation of building materials with aqueous creams of organosilicon compounds.

WHERE 95/25706 describes a process for hydrophobing with solvent-free, Bentonite-thickened silane / siloxane mixtures.

DE 198 44 654 A1 describes a method for strengthening and hydrophobing of clayey and gravelly soil materials with alkali metal siliconates and alkali silicates.

DE 44 33 864 A1 describes a process for water-repellent impregnation of gypsum by treatment with Si-bonded hydrogen atoms containing organosiloxane and alkali silicate, preferably at high drying temperatures.

These Processes either have the disadvantage that the silicon-containing impregnating either not water soluble and are water-dispersible without foreign emulsifiers, or the silicon-based ones impregnating are water soluble though strongly basic, so that appropriate precautions with the impregnating agent order must be taken and base sensitive substrates, such as wood, without damaging the Substrates or unsightly discoloration waterproof can be.

DE 1 076 946 teaches that the reaction products of alkylalkoxysilanes with ethylene glycol give organopolysiloxanes which are suitable for imparting water repellency to porous and solid bodies. The alkylalkoxysilanes used are used here as a mixture of monoalkoxy, dialkoxy, trialkoxy and tetraalkoxysilanes, it also being permissible that only one trialkoxysilane be used. The trialkoxysilane or the Alkoxysilangemisch is reacted with ethylene glycol, wherein each silicon-bonded alkoxy group at least one hydroxyl group of the ethylene glycol is used in excess. This means that one molecule of ethylene glycol is used per alkoxy group. It is expressly pointed out that the special properties of the product such as storage stability in the undiluted state, water solubility and water repellency can only be achieved by maintaining the proportions described. Due to the synthesis process, up to 5% of silicon-bonded alkoxy groups are present in the end product which have not reacted with ethylene glycol. Also present in the product are residues of split off alcohol that can not be completely removed. The synthesis requires accurate temperature control to ensure that the reaction temperature does not exceed 100 ° C. The hydrophobing effect of the products is only obtained if they are added a sufficient amount of water.

US 2,887,467 describes the synthesis of water-soluble silsesquioxanes by reacting non-water-soluble silsesquioxanes with ethylene glycol at temperatures of about 150 ° C, each silicon atom must be present at least 3 equivalents of ethylene glycol. The products thus obtained are basically suitable for use as water repellents.

Out EP 0 068 671 For example, compositions containing organopolysiloxane containing dilute mixtures of water are known. These compositions contain salt of water-soluble organic or inorganic acid and organopolysiloxane containing, in addition to other siloxane units, such siloxane units having SiC-bonded radicals with basic nitrogen, a sol-soluble silicon compound such as methyltrimethoxysilane and water-soluble solvent.

EP 0 186 847 B1 on dilution with water, discloses compositions containing organopolysiloxane containing transparent mixtures. These compositions contain salt of water-soluble organic or inorganic acid and organopolysiloxane containing, in addition to other siloxane units, those siloxane units having SiC-bonded radicals with basic nitrogen and which are free of water-soluble solvents.

One The disadvantage of the last two inventions is that that meant the so-called silicone microemulsion concentrates after dilution with water within a few hours, but at the latest after a few Days to their effectiveness as a penetrating hydrophobing agent a significant part, if not completely lost. That means once diluted with water, lose such preparations their storage stability.

With phosphonic Modified silicones are of great economic interest for one Variety of areas.

For example, they can act as a lubricant Metals and textiles, flame retardant additives, adhesion promoters, additives for cosmetics or detergents, defoamers, release agents, damping fluids, fluids for heat transfer, antistatic agents or polishes and coatings are used.

With Phosphorus modified siloxanes are generally by reaction of trialkyl phosphites with chloropropyl-modified siloxanes, as for example in Gallagher et al., J. Polym. Sci. Part A, Vol. 41, 48-59 (2003).

Unfortunately In this reaction, long reaction times and high temperatures are needed, which to rearrangements in the product and thus to yield losses as well as undesirable By-products leads.

The reaction of trialkyl phosphites with chloromethyl-modified siloxanes as in US 2,768,193 or by Gallagher et al. described, goes much faster, but has the disadvantage that the siloxanes thus prepared are difficult to clean by distillation because of their high boiling point. However, this reaction also proceeds slowly because the concentration of the reactive groups is greatly reduced by dilution with unreactive dimethylsiloxy units, resulting in reaction times in the range of several hours.

WHERE 2004/089961 describes meets a process for the preparation of with phosphonic acid ester modified organosilicon particles by reaction of at least an alpha-phosphonatosilane having at least one silanol-functional Polyorganosiloxanharzpartikel. Alpha silanes are silanes, at where the phosphorus atom of the phosphonate moiety is linked to the Si atom by an alkylene bridge, which comprises exactly 1 carbon atom.

WHERE 2005/005519 describes a process for the preparation of phosphonic acid esters modified organosilicon compounds by reaction of phosphonic contained alpha silanes with reactive silicon compounds, the Silanes, linear polyorganosiloxanes and silicone resins, wherein as products according to also except linear polyorganosiloxanes Silicone resins are obtained.

The invention relates to a process for the hydrophobicization of substrates, in which the substrates are treated with siloxanes (P) which are composed of units of the general formula 1, [A ¹ _z R ¹ _p SiO _{(4-pz) / 2} ] (1), in the
A ^{1 denotes} a hydrogen or hydrocarbon radical which contains up to 18 C atoms and may additionally contain heteroatoms selected from O, S, Si, Cl, F, Br, P or N atoms, an alkoxy, aryloxy or hydroxyl radical,
R ^{1 is} a hydrocarbonoxy radical having up to 18 C atoms, which may additionally contain heteroatoms selected from O, S, Si, Cl, F, Br, P or N atoms, hydroxy radicals, H or phosphonic acid ester radicals of the general formula (2) -CR ³ ₂ -P (= O) (OR ⁴ ) (OR ⁵ ) (2), means, where
R ³ , R ⁴ and R ^{5 is} hydrogen, hydroxy or optionally substituted hydrocarbon radical having 1-10 carbon atoms, which may optionally contain heteroatoms, and
z and p are each 0, 1, 2 or 3, wherein at least 10% of the sum of the radicals R ¹ and A ^{1 are} radicals R ¹ and wherein at least 5% of the radicals R ^{1 are} radicals of the general formula (2).

The Siloxanes (P) are due to their content of alpha-Phosphonsäureesterresten of the general formula (2) soluble in water or without surfactant in water dispersible. The siloxanes (P) give storage stability with water Products dilutable Mixtures used for the hydrophobization of substrates, in particular the surface impregnation mineral substrates and masonry treatment are well suited. The siloxanes (P) harden according to a mechanism independent of the evaporation of water, and have good penetration depths.

siloxanes (P) can to be condensed irreversibly by alkaline. Thereby, that they are molecularly dispersed or completely dissolved, they penetrate into suitable dilution very far into a substrate, especially mineral substrate or in a masonry. On the substrate, they produce a hydrophobic Movie. In masonry, they have a pore-filling effect and form one after curing hydrophobic barrier against wall moisture. That's why they are special suitable for impregnation and masonry sealing.

With basic compounds, the siloxanes (P) react with elimination of phosphonic ester residues the general formula (2) of the silicon atom, wherein the free Valences on the silicon atom with addition of hydroxy groups from the surrounding Water and optionally subsequent condensation under training saturate Si-O-Si bonds.

Examples of the C ₁ -C ₁₈ -hydrocarbon radicals A ¹ are alkyl radicals, such as the methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-Bu tyl, n-pentyl, iso-pentyl, neo-pentyl, tert-pentyl; Hexyl radicals, such as the n-hexyl radical; Heptyl radicals, such as the n-heptyl radical; Octyl radicals, such as the n-octyl radical and iso-octyl radicals, such as the 2,2,4-trimethylpentyl radical; Nonyl radicals, such as the n-nonyl radical; Decyl radicals, such as the n-decyl radical; Dodecyl radicals, such as the n-dodecyl radical; Alkenyl radicals, such as the vinyl and allyl radicals; Cycloalkyl radicals, such as cyclopentyl, cyclohexyl, cycloheptyl radicals and methylcyclohexyl radicals; Aryl radicals, such as the phenyl, naphthyl, anthryl and phenanthryl radicals; Alkaryl radicals, such as o-, m-, p-tolyl radicals; Xylyl radicals and ethylphenyl radicals; Aralkyl radicals, such as the benzyl radical, the alpha- and the 3-phenylethyl radical. Examples of halogen-substituted C ₁ -C ₁₈ -hydrocarbon radicals are alkyl radicals substituted by fluorine, chlorine, bromine and iodine atoms, such as the 3,3,3-trifluoro-n-propyl radical, 2,2,2, -2 ', 2 ', 2'-Hexafluorisopropylrest, Heptafluorisopropylrest, and Halogenarylreste, such as the o-, m- and p-chlorophenyl.

Particularly preferred are the unsubstituted C ₁ -C ₆ -alkyl radicals A ¹ , in particular the methyl radical, the ethyl radical and the isooctyl radical.

Examples of the C ₁ -C ₁₈ -hydrocarbonoxy radicals R ¹ are the above C ₁ -C ₁₈ -hydrocarbon radicals which are bonded to the silicon atom via a divalent oxygen atom. Particular preference is given to the hydroxyalkoxy and aryloxy radicals R ¹ , in particular the unsubstituted C ₁ -C ₆ -alkoxy radicals, such as the methoxy radical and the ethoxy radical.

Typical examples of radicals of the general formula (2) are the radicals CH ₂ P (= O) (OC ₂ H ₅ ) ₂ , CH ₂ P (= O) (OCH ₃ ) ₂ , CH ₂ P (= O) (OH ₂ .

Examples of the C ₁ -C ₁₀ -hydrocarbonoxy radicals R ³ , R ⁴ and R ⁵ are optionally substituted branched and unbranched alkyl, cycloalkyl, alkenyl or aryl radicals having 1-10 carbon atoms listed above for A ¹ .

Particularly preferred as R ⁴ and R ⁵ are the hydroxy and optionally substituted branched alkoxy and Aryloxyreste, in particular the unsubstituted C ₁ -C ₆ alkoxy, such as the methoxy and the ethoxy.

For surface impregnation or masonry treatments become certain application concentrations preferably adjusted, which has a sufficient shelf life have. Preferably, the compounds used are according to the Application too insoluble Compounds irreversibly crosslinkable. The concentrations will be preferably chosen that the preparation is only so highly concentrated that it is easy pourable is and that the penetration into the substrate or the masonry sufficiently deep and that they are only so low concentrated that the desired application goal is reached.

A Another preferred requirement is that no volatile toxic compounds be released or only minimal quantities. The residual alkoxy contents the siloxanes (P), in particular residual methoxy contents, are preferably below 1.0 percent by weight, in particular in the range of the detection limit of conventional analytical Methods or below. This mainly affects methanol.

There depending on ambient conditions such as humidity and temperature Evaporating the water a longer May take time, the curing rate of the preparation should be not or not exclusively depend on the rate of evaporation of the water. The Hydrophobizing preferably penetrates into the surface, or in the masonry sufficiently far to an effective hydrophobing to effect.

Preferably are the siloxanes (P) oils or resins. The siloxanes (P) preferably have molecular weights of Mw = 500 to 600,000 g / mol, in particular 600 to 30,000 g / mol.

Preferably, at least 20%, in particular at least 30%, of the sum of the radicals R ¹ and A ^{1 are} radicals R ¹ .

Preferably, at least 10%, in particular at least 20% of the radicals R ^{1 are} radicals of the general formula (2).

Preferably become the siloxanes (P) by cocondensation of alkylalkoxysilanes or arylalkoxysilanes with alkoxyphosphonatosilanes or alkylalkoxyphosphonatosilanes produced. Depending on the selection of the respective silane you get at a molar fraction of typically 50% or more of the corresponding Alphaphosphonatosilane to easily water-soluble products. Because the chemical nature, polarity and the solubility behavior all raw materials involved in the formation reaction have an influence on the solubility behavior of the final product, this information is only approximate to understand. Where the solubility limit for the product composition is accurate, must, if necessary, in test series be determined. As a rule of thumb, however, the water solubility is improves, the more of the polar Phophonatogruppen on the formation of the product are involved.

Preferably use is made of siloxanes (P) which are at least 3 percent by weight, in particular at least 10 percent by weight are soluble in water at 20 ° C.

Preferably, the siloxanes (P) in the Hy hydrophobing of substrates in the form of preparations used, in particular together with water. The preparations preferably contain at least 3 percent by weight, in particular at least 10 percent by weight, of water.

preparations the siloxanes (P) and at least 3, in particular at least 10 percent by weight Contain water are also the subject of the invention.

Preferably Water is the only solvent in these preparations, so that in particular no further organic solvent more is available.

Farther can in the watery Preparations additional Components are used for which will be given in the following examples.

aqueous, non-aqueous or solvent-based Preparations are obtained by mixing the siloxanes (P) with others Components combined, these combinations are not necessarily homogeneous Give mixtures.

• – Emulgatoren
• – H-Siloxan,
• – Alkoxy- und Aryloxysilane, die zusätzlich organofunktionelle Reste wie Epoxyreste, Aminoreste, Diaminoreste, Triaminoreste, Phosphonsäurereste und/oder Phosphonsäureesterreste, bei denen der Phoshponsäurerest, bzw. der Phosphonsäureesterrest nicht zwangsläufig über genau ein C-Atom an das Si-Atom gebunden sein muß, sondern beispielsweise auch über drei C-Atome (Propylspacer) an das Si-Atom gebunden sein kann, Mercaptoreste, Acrylatreste, Methacrylatreste, Carbonsäurereste, Carbonsäureanhydridreste, Morpholinoreste, Piperazinoreste, oder Alkyl- oder Arylreste aufweisen können, sowie die daraus erhältlichen Hydrolysate und Kondensate sowie Gemische derselben,
• – Alkyl- oder Arylsiliconate,
• – Wasserglas
• – Polydimethlysiloxanöle, die gegebenenfalls anstelle einer oder mehrerer Methylgruppen andere organische Gruppen tragen können, wie anderen Kohlenwasserstoffresten als Methylresten, wobei in diesen Kohlenwasserstoffreste durch den Einbau von Heteroatomen wie S, N, O, P, die Kohlenstoffkette unterbrochen sein kann, oder auch organische Funktionalitäten beinhaltet sein können,
• – Siliconharze,
• – einem oder mehreren organischen Lösemitteln, wie aromatischen Lösemitteln, Ketonen, Estern, Alkoholen, aliphatischen und cycloaliphatischen Lösemitteln, ionischen Flüssigkeiten, Glykolen.
• – Wasser,
• – organischen Tenside,
• – organischen Polymere in gelöster, fester oder in Wasser dispergierter Form, wie Polyvinylalkohol, Polyvinylacetat, Polyacrylate, Styrolacrylatcopolymere, Polyvinylbutyrale, Polyurethane, Polyepoxide.
• – linearen und verzweigten gegebenenfalls organisch funktionalisierten polyhydroxylierten Kohlenwasserstoffe, wie Ethylenglykol, Diethylenglykol, Propylenglykol, Dipropylenglykol, und höheren Glykolen, Zuckern wie Glykolen, Mannosen, Hexosen,
• – Zement
• – Kalk
• – Gips
• – pulversierte anorganische gegebenenfalls höchstens teilweise mit Wasser benetzbare Metalloxid, wie z.B. feste Oxide der Haupt- und Nebengruppenelemente, wie der 3. Hauptgruppe, wie Bor-, Aluminium-, Gallium- und Indiumoxid, der 4. Hauptgruppe wie Siliciumdioxid, Germaniumdioxid, und Zinnoxid sowie -dioxid, Bleioxid und -dioxid, und ein Oxid der 4. Nebengruppe, wie Titandioxid, Zirkonoxid und Hafniumoxid,

oder Kombinationen aus den aufgezählten Komponenten, wobei außer den hier aufgezählten Komponenten auch weitere, wie sie zur Herstellung von Zubereitungen zur hydrophobierenden Grundierungen und Imprägnierungen üblich sind eingesetzt werden können.Possible such constituents which can be used to prepare preparations are, for example

• - emulsifiers
• - H-siloxane,
• - Alkoxy- and aryloxysilanes, which additionally organofunctional radicals such as epoxy radicals, amino radicals, Diaminoreste, Triaminoreste, Phosphonsäurereste and / or Phosphonsäureesterreste in which the Phoshponsäurerest, or the Phosphonsäureesterrest must not necessarily be bound via exactly one carbon atom to the Si atom but may also be bonded to the Si atom via three C atoms (propyl spacer), mercapto radicals, acrylate radicals, methacrylate radicals, carboxylic acid radicals, carboxylic anhydride radicals, morpholino radicals, piperazino radicals, or alkyl or aryl radicals, and also the hydrolyzates and condensates obtainable therefrom and mixtures thereof,
• - alkyl or aryl silicates,
• - water glass
• - Polydimethlysiloxanöle, which may optionally carry instead of one or more methyl groups other organic groups, such as other hydrocarbon radicals as methyl radicals, which may be interrupted in these hydrocarbon radicals by the incorporation of heteroatoms such as S, N, O, P, the carbon chain, or organic functionalities can be included
• - silicone resins,
• - One or more organic solvents, such as aromatic solvents, ketones, esters, alcohols, aliphatic and cycloaliphatic solvents, ionic liquids, glycols.
• - Water,
• - organic surfactants,
• Organic polymers in dissolved, solid or water-dispersed form, such as polyvinyl alcohol, polyvinyl acetate, polyacrylates, styrene acrylate copolymers, polyvinyl butyrals, polyurethanes, polyepoxides.
• Linear and branched optionally organically functionalized polyhydroxylated hydrocarbons, such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, and higher glycols, sugars, such as glycols, mannoses, hexoses,
• - Cement
• - Lime
• - plaster
• - Powdered inorganic optionally at most partially wettable with water metal oxide, such as solid oxides of the main and subgroup elements, such as the 3rd main group, such as boron, aluminum, gallium and indium, the 4th main group such as silica, germanium, and tin oxide and dioxide, lead oxide and dioxide, and a fourth subgroup oxide, such as titanium dioxide, zirconium oxide and hafnium oxide,

or combinations of the enumerated components, wherein besides the components listed here also other, as are customary for the preparation of preparations for hydrophobizing primers and impregnations can be used.

It is not absolutely necessary that the components to be mixed can be processed to a homogeneous uniform active substance mixture. Optionally, multiphase mixtures of several liquid phases or of solid and liquid phases may be formed, wherein the consistency of the products received NEN low-viscosity liquid as pasty or creamy or powdered may be firm. Preferably, the preparations are liquid or pasty. For impregnation applications, they are distributed by conventional methods of distribution on the surface of the substrate, such as by brushing, spraying, squeegeeing, rolling, pouring, filling, dipping, spincoating, rolling. For the masonry treatment, it is necessary that the preparations penetrate far into the masonry, or moisten it. Therefore, for the masonry treatment low-viscosity preparations are preferred. The property to penetrate the masonry may be a material property or the penetration is artificially promoted by the preparations are transported with increased pressure in the masonry. Conventional methods for building pressure are based on the use of gravity, which are generated by liquid columns of such preparations or it who the devices that promote the preparations with pressure.

to Acceleration of the curing reaction It may prove advantageous to prepare a component added, which produces an acidic or basic pH value. The Setting basic pH values leads to faster curing than the setting of acid pH values. The production of basic pH values is therefore preferred. If the substrate to be impregnated or the masonry to be treated is itself basic, catalyzes the substrate or the masonry itself, the curing. On surfaces or Masonry made of building materials such as limestone, fiber cement, concrete etc. is, for example, basic catalysis by the substrate, or given the masonry.

there the basic component can be incorporated into the preparation itself optionally masked in the preparation it will not be until later Application is set free or it is readily used in the preparation, if this does not limit the usability of the preparation. Optionally, the basic component may also be used in a separate manner First apply to the substrate or masonry or introduced and then only the preparation, the contains phosphonato siloxane. The order can also be reversed, that is, first The preparation containing the phosphonato siloxane (P) is added to the Substrate applied and then the basic component. It can in each of these variants the basic component as pure substance or be applied as a preparation. The basic component must be themselves have no hydrophobing effect. She will only be in needed catalytic amounts. Usual quantities the basic activation component is in the range of 0.01-5.0 weight percent based on the mass of the siloxane (P) used and is selected as appropriate how quickly the formation of hydrophobicity is desired, respectively How strongly the catalytic effect of the respective component is pronounced.

Preferably Are the preparations as aqueous solution or formulated with other ingredients, as an emulsion or as aqueous Foam used. Surfactants can be used to prepare aqueous preparations can be used or you can without Addition of surfactants are produced. As the phosphonato-functional Siloxanes (P) water-soluble are, will be for their distribution in water requires no surfactant.

In The following application examples refer to all data from Divide and percentages on the weight. The examples were at a pressure of the surrounding The atmosphere, So at about 0.1 MPa, and at room temperature, ie at about 21 ° C, carried out. The viscosities were at 25 ° C measured.

Production of preparations, the siloxanes (P) contain:

Examples 1: Preparation and hydrolysis of diethylphosphonatomethyltrimethoxysilane and aqueous solution of resulting siloxane:

In a 2 1 three-necked flask, a mixture of 682.7 g (4.0 mol) of chloromethyltrimethoxysilane and 664.6 g (4.0 mol) of triethyl phosphite at a pressure of 300 mbar for 4 h at 100 ° C and the resulting ethyl chloride in caught a cold trap. Then, by means of a riser, a constant volume of about 450 ml / h of the reaction mixture is applied to a thin-film evaporator (p = 5 mbar, T = 100 ° C.). The diethylphosphonatomethyltrimethoxysilane is collected in the high boiler fraction while the distillate is returned by a pump to the reaction vessel. The volume of the reaction mixture is kept constant by the addition of educt mixture. The yield of diethylphosphonatotrimethoxysilane is 125 ml / h. The product is obtained in a purity of 96% (according to GC). In the ¹ H-NMR spectrum no methoxy signals are present. (Ethoxy signals are present and are derived from the phosphonic ester residue.)

550.5 g (2.0 mol) diethylphosphonatotrimethoxysilane and 109.2 g (6.0 mol) Water are stirred in a rotary evaporator at 80 ° C for 4 h at 2 mbar and the resulting methanol is condensed off immediately. You get one colorless, viscous water-soluble Polymer (viscosity 24.54 Pas at 25 ° C; Mn = 2603 g / mol according to GPC).

From This polymer is a 50% aqueous solution by Added the appropriate amount of water. You get one colorless, clear, easily mobile liquid.

To the thus prepared aqueous Solution becomes 0.5 weight percent based on the amount of phosphonosiloxane one 30% aqueous solution a methyl (dimethoxy) (aminopropyl amioethyl) silane. The solution heated Exothermic and after a few minutes, a white, insoluble mass forms in the reaction vessel, the polymerized Siloxane is.

Example 2: Cohydrolysis of diethylphosphonatomethyltrimethoxysilane with methyltrimethoxysilane and watery solution of the resulting siloxane:

17.9 g (0.065 mol) of diethylphosphonatomethyltrimethoxysilane and 4.4 g (0.033 mol) of trimethoxysilane are placed in a 100 ml Schlenk flask with reflux condenser. Then 2.4 ml of NaOH (0.1 mol / l) and 20 ml of toluene are slowly added. It is then heated to 110 ° C. The enthaled methanol is distilled off, at the end of the reaction, the mixture is neutralized with HCl. Then all volatiles are removed in vacuo. This gives 16.6 g of a colorless in water clear and colorless soluble silicone resin. In the ¹ H-NMR spectrum no methoxy signals are present. (Ethoxy signals are present and are from the phosphonic acid ester radical.) From this siloxane, a 50% aqueous solution is prepared by adding the appropriate amount of water. This gives a colorless, clear, easily mobile liquid.

Example 3: Mixture of a aqueous solution according to example 2 with polyacrylate dispersion:

To 100 g of a 50% aqueous Solution of the Cohydrolyzates of diethylphosphonatomethyltrimethoxysilane and trimethoxysilane according to example 2, 100 g of a 50% polystyrene acrylate dispersion with a average particle diameter of 150 nm. The polystyrene acrylate dispersion was according to the prior art by free-radical emulsion polymerization produced. You get a milky cloudy Mixture.

Application examples:

Example 1: Hydrophobic impregnation a fiber cement board:

The aqueous solutions according to Examples 1 and 2 are each spread on a commercial fiber cement slab with a brush in an application amount of 200 g / m ² . After 1 day of drying time at room temperature, water is added dropwise to the fiber cement boards treated in this way and the wetting behavior is qualitatively evaluated. In both cases a very good beading effect is observed.

Example 2: Hydrophobic impregnation a limestone tile:

The aqueous solutions according to Examples 1 and 2 are each spread on a commercial sand-lime brick with a brush in an application amount of 200 g / m ² . After 1 day of drying time at room temperature, water is dripped onto the treated sand-lime bricks and the wetting behavior is qualitatively assessed. In both cases a very good beading effect is observed.

Example 3: Hydrophobic impregnation of concrete cylinders:

In the watery solutions according to the examples 1 and 2, each small concrete cylinders are immersed produced from a commercial concrete (w / c value 0.35 - 0.6) according to manufacturer's instructions. After 1 day of drying at room temperature is dripped onto the treated concrete body water and the wetting behavior is qualitatively evaluated.

Example 4: Hydrophobic impregnation of spruce boards:

The aqueous solutions according to Examples 1 and 2 are each treated with aminoethylaminopropyltrimethoxysilane (0.5 percent by weight based on the solids content of the aqueous solutions according to Examples 1 and 2) and in each case immediately on a spruce wood panel (10 × 15 cm, annual rings about 45 ° to the Cut surface inclined) with a brush in an application amount of 250 g / m ² struck. After 1 day of drying time at room temperature, water is added dropwise to the spruce boards treated in this way and the wetting behavior is assessed qualitatively. One observes a very good beading effect.

Example 5:

10.0 g of a 1% aqueous solution of a methyl (dimethoxy) (aminopropylamioethyl) silane are spread evenly on a spruce board (10 × 15 cm) with a brush. Thereafter, the aqueous preparations according to Example 1 and 2 in an amount of 200 g / m ^{2 are} uniformly painted over. After 1 day of drying time at room temperature, water is added dropwise to the spruce boards treated in this way and the wetting behavior is assessed qualitatively. One observes a very good beading effect.

Example 6:

On spruce boards (10 × 15 cm) 200 g / m ^{2 of} the aqueous solutions according to Example 1 and 2 are evenly spread with a brush. Thereafter, 10.0 g of a 1% aqueous solution of a methyl (dimethoxy) (aminopropylamioethyl) silane are evenly painted over with a brush. After 1 day of drying time at room temperature, water is added dropwise to the spruce boards treated in this way and the wetting behavior is assessed qualitatively. One observes a very good beading effect.

Example 7:

An aqueous solution according to Example 1 is added to the following mortar formulation as an additive:
1350 g of standard sand
450 g of cement
250 g water - x g additive
xg additive

The Amounts are between 0.1 and 1% by mass based on the Solid content (x = 1.8 g - 18.0 G). The water absorption of the specimens prepared in this way is lower than that of untreated test specimens.

Example 8: masonry treatment:

to fight The rising wall moisture will be pore clogging or pore hydrophobing or combination systems from both since at least 40 years old. The new product is in this application classify as pore clogging and pore hydrophobing system.

in the Laboratory test were in brick test specimen with the basic size 5 × 11 cm and a height of 11 cm over a hole with a diameter of 8 mm by means of dowel packer the watery solutions according to the examples 1 and 2 injected, with the original 50% solutions optionally diluted to lower use levels.

to Application came 10 - 50 % solutions according to example 1 and 2, the injection time is 3 minutes, the pressure in Injection vessel was on 2 bar set.

In order to simulate the practical case, the tile test specimens were injected "dry" (corresponds to the sorption moisture at room temperature) and "wet" (adjusted to a moisture penetration level of about 90). After 3 minutes the Ziegelprüfkörper was saturated, which was clearly observed at the exit of the product on the long sides. In non-pressurized applications, ie gravitational loading via attached and sealed funnels, the soak time was increased by about a factor of 4 for the "dry" specimens and about a factor of 8 for the "wet" specimens. The material consumption for the "dry" specimens was about 110 g / specimen, for the "wet" specimens at 10 g / specimen. The average maximum moisture content of this test brick can be stated as approx. 16% by mass, the bulk density as 1.83 [g / cm ³ ].

To 6 weeks were the specimens with a Hydraulic press split centrally in the hole level and the penetration by the so-called staining test by spraying with a methylene blue solution as well the hydrophobicity determined by attached water droplets. In all make the product was sufficient in the test piece and demonstrated the effectiveness in terms of pore densification and hydrophobicity. additionally became an effectiveness test based on the WTA leaflet 4-4-04 (Scientific and Technical Association for Building Conservation and preservation of monuments e. V.). The measuring method is based on the water passage test (WDL test) and evaluates the water passage based on the horizontal wall cross-sectional area as a function of time. The Effectiveness is given when the water passage at least 50% over reduced the reference specimen becomes. All samples were over this set value.

Farther was the product on a real existing object on practicality and effectiveness checked. The Object is about 100 years old, the masonry is made of solid brick in the monastery format and is built in block association. The joints are from lime mortar produced. The masonry injection took place via drill holes at a distance of 10 cm and a diameter of 18 mm by means of screw packer made of metal. When Borehole depth was set to 4/5 of the masonry depth. Over a Diaphragm pump was about 3 - 5 injected for about 10 minutes per well. The masonry thickness averaged 34-36 cm.

Of the Material consumption was determined at about 8 1 per meter. For use, 10 to 50% dilutions were used in the laboratory experiment.

The review of Efficacy was over Removal of cores by dry drilling below and above injection level and determination of moisture by the Darr method. The review was after a service life of about 12 weeks.

As an example, the moisture contents of a measuring point are selected.
Moisture content below injection level: 13.2 M-%
Moisture content above injection level: 2.7 M-%

By the introduction of a moisture barrier in the borehole method is it leads to a serious reduction of moisture in the brickwork came. The activation of the product used by the residual alkalinity has a much faster onset compared to others Products.

Claims (8)

Process for the hydrophobization of substrates, in which the substrates are treated with siloxanes (P) which are composed of units of the general formula 1, [A ¹ _z R ¹ _p SiO _{(4-pz) / 2} ] (1) in the A ^{1 is} a hydrogen or hydrocarbon radical containing up to 18 carbon atoms and may additionally contain heteroatoms selected from O, S, Si, Cl, F, Br, P or N atoms, an alkoxy, aryloxy or hydroxy R ¹ denotes a hydrocarbonoxy radical having up to 18 C atoms, which may additionally contain heteroatoms selected from O, S, Si, Cl, F, Br, P or N atoms, hydroxy radicals, H or phosphonic acid ester radicals of the general formula (2 ) -CR ³ ₂ -P (= O) (OR ⁴ ) (OR ⁵ ) (2) where R ³ , R ⁴ and R ⁵ denote hydrogen, hydroxyl or optionally substituted hydrocarbon radical having 1-10 carbon atoms, which may optionally contain heteroatoms and z and p are each 0, 1, 2 or 3, with at least 10% the sum of the radicals R ¹ and A ¹ radicals R ¹ and wherein at least 5% of the radicals R ^{1 are} radicals of the general formula (2). The method of claim 1, wherein at least 10% of the radicals R ^{1 are} radicals of the general formula (2). Process according to claims 1 and 2, wherein the residual alkoxy contents the siloxanes (P) are below 1.0 percent by weight. The method of claim 1 to 3, wherein A ^{1 is} selected from methyl, ethyl and Isooctylrest. The process of claims 1 to 4, wherein R ^{1 is} selected from hydroxy and unsubstituted C ₁ -C ₆ alkoxy. The process of claims 1 to 5, wherein R ⁴ and R ^{5 are} selected from hydroxy and unsubstituted C ₁ -C ₆ alkoxy. The method of claim 1 to 6, wherein the mineral substrates be treated. Preparations containing siloxanes (P) and at least 3 Weight percent water.