DE102005012411A1 - Oberflächenhydrophobierung - Google Patents

Abstract

The invention relates to a process for the hydrophobization of substrates with organosilicon compounds O, which can be prepared by reacting DOLLAR A of one molar equivalent of silane S, which is selected from hydrocarbon trihalosilane, Kohlenwasserstofftrikohlenstoffoxy-silane or mixtures thereof with DOLLAR A 2.0-2.99 molar equivalents a glycol G or a mixture of glycols G.

Description

The The invention relates to a process for the hydrophobization of substrates with glycole-functional organosilicon compounds.

WHERE 95/25706 describes a method 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 metal silicate, preferably at high drying temperatures.

These Processes either have the disadvantage that the silicon-containing Impregnating agent either not water soluble and are water-dispersible without foreign emulsifiers, or the silicon-based ones impregnating are water-soluble but strong alkaline, so take appropriate precautions at the impregnant application must be taken and base sensitive substrates, such as wood, without damaging the Substrates or unsightly discoloration waterproof can be.

DE 1 076 946 AS 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 Hydrohpobierende effect of the products is obtained only if they are added a sufficient amount of water.

US 2 887 467 A 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.

The after DE 1 076 946 AS and US 2 887 467 A products described are water-soluble hydrophobic impregnating agents. They are characterized in that an unobtainable at least three-fold excess of polar substituents per silicon atom is required in order to obtain a suitable hydrophobizing agent. Hydrophobic does not affect the polar group, but the silicon-based portion. Due to the high proportion of polar substituents that have to be eliminated for good hydrophobing at least to the extent that a no longer water-soluble hydrophobizing product is formed, high amounts of water repellents must be dosed in order to obtain a good efficiency. The removal of the polar groups requires the adjustment of suitable reaction conditions for the hydrolysis and condensation, which limits the usability of these products. On essentially neutral substrates such as bricks, paper, wood and textiles, these products have no hydrophobic effect.

The object of the present invention was to develop a process for the hydrophobic impregnation and priming of mineral substances, of wood, paper and textiles, in which preparations containing highly efficient water-soluble or readily water-dispersible non-basic silicon-based impregnating agents.

The invention relates to a process for the hydrophobization of substrates with organosilicon compounds O, which can be prepared by reaction
one molar equivalent of silane S selected from hydrocarbyltrihalosilane,
Hydrocarbon tricarboxylic oxy-silane or mixtures thereof with 2.0 to 2.99 molar equivalents of a glycol G or a mixture of glycols G.

opposite DE 1 076 946 AS It was found that the conversion of 1 to silane A with 2.0 to 2.99 molar equivalents of glycol G leads to stable, very hydrophobic products. These glycol-functional organosilicon compounds O are more efficient than ethylene glycol-functional siloxanes according to DE 1 076 946 AS since the amounts of polar glycol groups which have to be removed in order to form the hydrophobicity are lower and, correspondingly, in turn, the amount of siloxane fraction having a hydrophobicizing effect is greater. This also reduces the amount of volatile organic compounds that are eliminated when these products are used.

Preferably, the hydrocarbon radicals of the silane SC are C ₁ -C ₁₅ hydrocarbon radicals. Examples of the C ₁ -C ₁₅ hydrocarbon radicals are alkyl radicals, such as the methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, 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 ₁₅ -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 ₈ -alkyl radicals, in particular the methyl radical and the ethyl radical.

Preferably, the Kohlenwasserstoffoxyreste the silane SC ₁ -C ₁₅ hydrocarbon radicals. Examples of the C ₁ -C ₁₅ -hydrocarbonoxy radicals are the above C ₁ -C ₁₅ -hydrocarbon radicals which are bonded to the silicon atom via a divalent oxygen atom. Particularly preferred are the unsubstituted C ₁ -C ₃ -alkyl radicals, in particular the methyl radical and the ethyl radical.

Preferably are the halogen radicals of the silane S chlorine radicals.

The Silane S can still small proportions, preferably at most 5 mol%, especially at most 2 mol% of silanes selected from dihydrocarbyl dihalosilane, Trihydrocarbylhalosilane, tetrahalosilane, dihydrocarbyldichlorohydrogenoxy-silane, Trihydrocarbyl hydrocarbonoxy silane and tetrahydrocarbonoxy silane.

The glycol G is preferably a linear or branched monomeric or oligomeric C ₂ -C ₆ glycol, and mixed glycols, in particular C ₂ -C ₄ glycol having a total of at most 40 carbon atoms, preferably at most 25, in particular at most 15 carbon atoms.

Especially preferred are ethylene glycol or its oligomers but also Propylene glycol or its oligomers and mixed glycols with propylene glycol and ethylene glycol units. Preferably, the oligomers at the most 6, in particular at most 3 monomer units on.

preferably be 2.3 - 2.9 molar equivalents, in particular 2.5 to 2.9 of the glycol G per molar equivalent of silane S used.

Out Organosilicon compounds 0 are in use on the substrate Silicon resin networks formed, leading to the pronounced hydrophobicity to lead.

in der
R einen einwertigen, gegebenenfalls halogensubstituierten C₁-C₁₅-Kohlenwasserstoffrest oder einwertige Kohlenwasserstoffoxyreste oder Hydroxylgruppen,
a den Wert 1,
b 0, 1, 2 oder 3 bedeutet und im Mittel über das gesamte Molekül einen Mindestwert von 0,1 besitzt,
G einen Hydroxyrest oder einen einwertigen- oder zweiwertigen verzweigten oder linearen C₂-C₂₅-Glykolrest bedeutet.The resulting glycol-functional organosilicon compounds used in the process according to the invention are silanes, oils or resins or a mixture of both, wherein they are synthesized are from units of general formula 1,

in the
R is a monovalent, optionally halogen-substituted C ₁ -C ₁₅ -hydrocarbon radical or monovalent hydrocarbonoxy radicals or hydroxyl groups,
a is 1,
b is 0, 1, 2 or 3 and has an average value of 0.1 over the entire molecule,
G represents a hydroxy radical or a monovalent or bivalent branched or linear C ₂ -C ₂₅ glycol radical.

Preferably are at most 5% of the radicals R Kohlenwasserstoffoxyreste.

Examples of branched or linear C ₂ -C ₂₅ glycol radicals are alpha-omega hydroxy-functional glycols such as ethylene glycol, propylene glycol, di-, tri- and tetraethylene glycol, di-, tri- and tetrapropylene glycol, alpha-omega hydroxy-functional mixed glycols from 1 to 5 ethylene glycol units and 1 - 5 propylene glycol units and mixtures thereof.

Examples of C ₁ -C ₁₅ -hydrocarbon radical and Kohlenwasserstoffoxyreste R are the radicals described above for the silane S.

The Organosilicon compounds O can either used as a pure substance for hydrophobing, or they are in preparations together with other components used. In the simplest case, these are the preparations around watery Solutions, which comprise at least one organosilicon compound O and water. Such preparations can also the usual used hydrophobing agents, such as in the above cited documents reproduced silanes, siloxanes and silicates, also possibly additional Emulsifiers.

aqueous, non-aqueous or solvent-based Preparations are obtained by adding the organosilicon compounds O combined with other ingredients, these combinations not necessarily give homogeneous mixtures.

• – H-Siloxan,
• – Alkoxy- und Aryloxysilane, die zusätzlich organofunktionelle Reste oder Alkyl- oder Arylreste aufweisen können, sowie die daraus erhältlichen Hydrolysate und Kondensate sowie Gemische derselben,
• – Alkyl oder Arylsiliconate,
• – Wasserglas
• – Polydimethlysiloxanöle, die 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, etc. 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 und Glykolen,
• – Wasser,
• – organischen Tenside,
• – organischen Polymere, wie Polyvinylalkohol, Polyvinylacetat, Polyacrylate, Styrolacrylatcopolymere, Polyvinylbutyrale, Polyurethane und Polyepoxide,
• – linearen und verzweigten ggf. organisch funktionalisierten polyhydroxylierten Kohlenwasserstoffe, wie Ethylenglykol, Diethylenglykol, Propylenglykol, Dipropylenglykol, und höheren Glykolen, Zuckern wie Glykolen, Mannosen und Hexosen,
• – Zement
• – Gips
• – Kalk 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 components which can be used to prepare preparations for carrying out the method according to the invention are, for example

• - H-siloxane,
• Alkoxy and aryloxysilanes, which may additionally have organofunctional radicals or alkyl or aryl radicals, and also the hydrolysates and condensates obtainable therefrom, and also mixtures thereof,
• Alkyl or aryl silicates,
• - water glass
• - Polydimethlysiloxanöle which can carry other organic groups in place of one or more methyl groups, such as other hydrocarbon radicals than methyl radicals, in these hydrocarbon radicals by the incorporation of heteroatoms such as S, N, O, P, etc., the carbon chain may be interrupted, 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 and glycols,
• - Water,
• - organic surfactants,
• Organic polymers, such as polyvinyl alcohol, polyvinyl acetate, polyacrylates, styrene acrylate copolymers, polyvinyl butyrals, polyurethanes and polyepoxides,
• Linear and branched optionally organofunctionalized polyhydroxylated hydrocarbons, such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, and higher glycols, sugars, such as glycols, mannoses and hexoses,
• - Cement
• - plaster
• Lime or combinations of the listed components, wherein besides the components listed here, it is also possible to use further ones which are customary for the preparation of preparations for hydrophobizing primers and impregnations.

there it is not absolutely necessary that the ones to be mixed Process components to a homogeneous uniform mixture of active ingredients to let. Optionally, multiphase Mixtures of several liquid Phases or solid and liquid Phases emerge, with the consistency of the products obtained both low viscosity liquid as well as pasty or creamy or also pulverfömig can be firm. Preferably, the preparations are liquid or pasty and become commonplace Distributed distribution methods on the surface of the substrate, such as painting, spraying, squeezing, rolling, pouring, filling, Diving, spincoating and rolling.

The Hydrophobization of the substrates includes priming and impregnation.

to Hydrophobization of basic surfaces such as limestone, fiber cement, concrete, etc., it is not necessary that the preparations themselves contain a basic activator. On neutral substrates such as wood, paper or brick is for quick Training the hydrophobicity of a basic activator recommended. 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 she will readily in the preparation used, if thereby the usability of the preparation is not limited becomes. The basic component may optionally also in a separate step to be applied first to the substrate and then the preparation containing the organosilicon compounds O contains. The sequence can also be reversed, that is, first The preparation is the organosilicon compound O on the substrate applied and then the basic component. It can with each of these Variants the basic component as a pure substance or as a preparation be applied. The basic component itself does not have to be hydrophobic Own effect. It is needed only in 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 organosilicon compound used O and will be chosen depending on how quickly the formation of the hydrophobicity is desired, or how strong the catalytic effect of each Component pronounced is.

Preferably Are the preparations as aqueous Preparation, used as an emulsion or as an aqueous foam. to Preparation of aqueous Preparations can Surfactants can be used or they can be added without the addition of surfactants be prepared by the organosilicon compounds O directly be introduced in water. The production of aqueous Preparations without the use of surfactants is particular then possible when the organosilicon compounds self-emulsify O in water or water-soluble are.

In The following application examples refer to all data from Divide and percentages 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.

Preparation of preparations for the inventive method:

Examples 1: Preparations to exercise of the method according to the invention:

Example 1a:

Condensation product Methyltrichlorosilane and ethylene glycol, preparation of organosilicon compounds O:

Apparatus:

2 l three-necked flask with intensive cooler, Dropping funnel and paddle stirrer. The Gas discharge and the application of vacuum via the intensive cooler.

methyltrichlorosilane is with toluene in the ratio 1: 1 mixed and to a template from the 2.8-fold molar excess added to ethylene glycol by means of dropping funnel. To the apparatus is constantly a slight water jet vacuum applied (about 200 mbar).

Template: 550.00 g of ethylene glycol

In In a closed three-necked flask stirring apparatus, ethylene glycol is used presented in the flask.

dosing: Mixture of 473.10 g of methyltrichlorosilane and 473.10 g of toluene filled in the dropping funnel.

The Mixture of methyltrichlorosilane and toluene is removed from the dropping funnel under the surface added to the ethylene glycol template. The temperature is over the Dosage speed between 50 ° C and 55 ° C maintained. The duration of the Dosage is about 70 minutes.

To complete Metering of the methyltrichlorosilane / toluene mixture becomes the system for 2 hours under reflux held. After refluxing, the batch is brought to room temperature cooled. This forms two phases, one phase being toluene and the second phase is the product phase, which is the polyether-modified Contains polysiloxane. The HCl content of the crude product is <50 ppm.

The Phases are separated and the product phase becomes toluene distilled off using a rotary evaporator under vacuum (about 10 mbar, 110 ° C).

The resulting product is used without further components the inventive method exercise.

Example 1b:

From the glycol-functional siloxane from Example 1a is by addition of water a 10% aqueous solution produced. The solution is clear.

Example 1c:

To the aqueous solution of the glycol-functional siloxane according to Example 1b becomes 0.5% by weight based on the amount of glycol siloxane of a 30% aqueous solution a methyl (dimethoxy) (aminopropylaminoethyl) silane.

Example 1d:

Identical the procedure of Example 1a is isooctyltrichlorosilane instead of methyltrichlorosilane reacted with ethylene glycol. The stoichiometry is set exactly the same as described for example 1a. The Implementation and product isolation also takes place in the same way as in Example 1a indicated.

Application examples:

Example 2: Hydrophobic impregnation a fiber cement board:

• 1a: sehr guter Abperleffekt
• 1b: sehr guter Abperleffekt
• 1d: sehr guter Abperleffekt

The preparations according to Examples 1a, 1b and 1d are each spread on a commercially available fiber cement board with a brush in an application amount of 500 g / m ² . After drying for 1 day at room temperature, water is dripped onto the fiber cement boards treated in this way and the wetting behavior is qualitatively assessed:

• 1a: very good beading effect
• 1b: very good beading effect
• 1d: very good beading effect

Example 3: Hydrophobic impregnation a limestone tile:

• 1a: sehr guter Abperleffekt
• 1b: sehr guter Abperleffekt
• 1d: sehr guter Abperleffekt

The preparations according to Examples 1a, 1b and 1d are each spread on a commercial sand-lime brick plate with a brush in an application amount of 500 g / m ² . After drying for 1 day at room temperature, water is added dropwise to the calcium silicate blocks treated in this way and the wetting behavior is qualitatively assessed.

• 1a: very good beading effect
• 1b: very good beading effect
• 1d: very good beading effect

Example 3: Hydrophobic impregnation of concrete cylinders:

• 1a: sehr guter Abperleffekt
• 1b: sehr guter Abperleffekt
• 1d: sehr guter Abperleffekt

In the preparations according to Examples 1a, 1b and 1d respectively small concrete cylinders are made of a commercial concrete (w / c value 0.35 - 0.6) immersed according to the manufacturer's instructions. After 1 day of drying time at room temperature, water is added dropwise to the concrete body treated in this way and the wetting behavior is qualitatively assessed:

• 1a: very good beading effect
• 1b: very good beading effect
• 1d: very good beading effect

Example 4: Hydrophobic impregnation of spruce boards:

• 1c: sehr guter Abperleffekt

The preparations according to Examples 1c are each freshly prepared and in each case immediately spread on a spruce wood board (10 × 15 cm, annual rings inclined at about 45 ° to the cut surface) with a brush in an application amount of 250 g / m ² . After drying for 1 day at room temperature, water is added dropwise to the spruce boards thus treated and the wetting behavior is qualitatively assessed:

• 1c: very good beading effect

Example 5: on spruce boards (10 × 15 cm) are each 10.0 g of a 1% aqueous solution of

• 1a: sehr guter Abperleffekt
• 1b: sehr guter Abperleffekt

Apply methyl (dimethoxy) (aminopropylamioethyl) silane evenly with a brush. Thereafter, the preparations 1a and 1b in an amount of 500 g / m ^{2 are} uniformly painted over. After drying for 1 day at room temperature, water is added dropwise to the spruce boards thus treated and the wetting behavior is qualitatively assessed:

• 1a: very good beading effect
• 1b: very good beading effect

Example 6: 500 g / m ² of preparations 1a and 1b are evenly spread on spruce boards (10 × 15 cm) with a brush. Thereafter, in each case 10.0 g of a 1% aqueous solution of

• 1a: sehr guter Abperleffekt
• 1b: sehr guter Abperleffekt

Paint methyl (dimethoxy) (aminopropylamioethyl) silane evenly with a brush. After drying for 1 day at room temperature, water is added dropwise to the spruce boards thus treated and the wetting behavior is qualitatively assessed:

• 1a: very good beading effect
• 1b: very good beading effect

Claims (8)

Process for the hydrophobization of substrates with organosilicon compounds 0 which can be prepared by reaction one molar equivalent at Silan S, that selected is derived from hydrocarbyltrihalosilane, Kohlenwasserstofftrikohlenwasserstoffoxy-silane or mixtures thereof with 2.0 - 2.99 molar equivalents a glycol G or a mixture of glycols G. The process of claim 1 wherein the hydrocarbyloxy radicals of the hydrocarbon trichlorohydrocarboxy silane are SC ₁ -C ₃ hydrocarbyloxy radicals. The method of claim 1 or 2, wherein the silane S is hydrocarbyl trichlorosilane. The process of claims 1 to 3, wherein the hydrocarbyl radicals of the silane SC are C ₁ -C ₁₅ hydrocarbyl radicals. A process as claimed in any of claims 1 to 4, wherein the glycol G is selected from linear or branched monomeric or oligomeric C ₂ -C ₆ glycols, as well as mixed glycols having a total of at most 40 carbon atoms. The method of claims 1 to 5, wherein 2.3 to 2.9 molar equivalents Glycol G per mole equivalent of silane S are used. Process according to Claims 1 to 6, in which organosilicon compounds 0 are used as aqueous preparation, as Emulsion or used as an aqueous foam. The method of claim 1 to 7, wherein the substrates selected are made of mineral materials, wood, paper and textiles.