WO2006097206A1 - Hydrophobisation de surface - Google Patents

Hydrophobisation de surface Download PDF

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Publication number
WO2006097206A1
WO2006097206A1 PCT/EP2006/001970 EP2006001970W WO2006097206A1 WO 2006097206 A1 WO2006097206 A1 WO 2006097206A1 EP 2006001970 W EP2006001970 W EP 2006001970W WO 2006097206 A1 WO2006097206 A1 WO 2006097206A1
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WO
WIPO (PCT)
Prior art keywords
silane
radicals
glycol
water
hydrocarbon
Prior art date
Application number
PCT/EP2006/001970
Other languages
German (de)
English (en)
Inventor
Frank Sandmeyer
Heinz Geich
Original Assignee
Wacker Chemie Ag
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Wacker Chemie Ag filed Critical Wacker Chemie Ag
Publication of WO2006097206A1 publication Critical patent/WO2006097206A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/46—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with organic materials
    • C04B41/49—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes
    • C04B41/4905—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes containing silicon
    • C04B41/495—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes containing silicon applied to the substrate as oligomers or polymers
    • C04B41/4961—Polyorganosiloxanes, i.e. polymers with a Si-O-Si-O-chain; "silicones"
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C08G77/18—Polysiloxanes containing silicon bound to oxygen-containing groups to alkoxy or aryloxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
    • C08G77/50—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms by carbon linkages
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
    • D06M15/647—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing polyether sequences
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
    • D06M23/04—Processes in which the treating agent is applied in the form of a foam
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10—Repellency against liquids
    • D06M2200/12—Hydrophobic properties

Definitions

  • the invention relates to a process for the hydrophobization of substrates with glycole-functional organosilicon compounds.
  • WO 95/25706 describes a process for hydrophobing with solvent-free, bentonite-thickened silane / siloxane mixtures.
  • Hydrogen-containing organosiloxane and alkali metal silicate preferably at high drying temperatures.
  • 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 0 C, wherein each silicon atom at least 3 equivalents of ethylene glycol must be present.
  • the products thus obtained are basically suitable for use as water repellents.
  • Products are water-soluble hydrophobic impregnating agents. They are characterized by the fact that they are at least three times more polar Substituents per silicon atom is required 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 invention relates to a process for the hydrophobization of substrates with organosilicon compounds O, which can be prepared by reacting a molar equivalent of silane S, which is selected from
  • the hydrocarbon radicals of the silane S are preferably C 1 -C 2 -5-hydrocarbon radicals.
  • Examples of the C 1 -C 4 -carbon 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.
  • Hexylres- te 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
  • - 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 the allyl radical / cycloalkyl radicals, such as cyclopentyl, cyclohexyl, cycloheptyl radicals and methylcyclohexyl radicals
  • Aryl radicals such as the phenyl
  • alkaryl radicals such as o-, m-, p-tolyl radicals
  • Xylyl radicals and ethylphenyl radicals Aralkylres- te, such as the benzyl radical, the alpha- and the 3-phenylethyl radical.
  • halogen-substituted C 1 -C 4 -hydrocarbon radicals are substituted by fluorine, chlorine, bromine and iodine atoms.
  • ⁇ J te alkyl radicals such as 3, 3, 3-trifluoro-n-propyl, 2,2,2,2 ', 2', 2 '-Hexafluorisopropylrest, the Heptafluoriso- propyl radical, and haloaryl radicals such as the o-, m- and p-chlorophenyl.
  • Particularly preferred are the non-substituted C 1 -C 8 -alkyl radicals, in particular the methyl radical and the ethyl radical.
  • the Kohlenwasserstoffoxyreste the silane S 5 C] _ Ci5 hydrocarbon radicals.
  • 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,
  • the halo radicals of the silane S are chlorine radicals.
  • the silane S may still contain small amounts, preferably at most 5 15 mol%, in particular at most 2 mol% of silanes selected from dihydrocarbyl dihalosilane, trihydrocarbylsilane, tetrahalosilane, dihydrocarbyldikohlenwasserstoffox- silane, Trikohlenwasserstoff-kohlenwassersto ' ffoxy-silane and 20 Tetrakohlenwasserstoffoxy-silam
  • the glycol G is preferably a linear or branched monomeric or oligomeric C2 -Cg glycol, and mixed glycols, in particular C2-C4 glycol having a total of at most 40 25 carbon atoms, preferably at most 25, in particular at most 15 carbon atoms.
  • ethylene glycol or its oligomers but also propylene glycol or its oligomers and i () mixed glycols with propylene glycol and ethylene glycol units.
  • the oligomers have at most 6, in particular at most 3 monomer units.
  • silicone resin networks are formed in the application on the substrate, which lead to the pronounced hydrophobicity.
  • glycol-functional organosilicon compounds O which are used for the process according to the invention are silanes, oils or resins or a mixture of both, wherein they are composed of units of the general formula 1,
  • R is a monovalent, optionally halogen-substituted C 1 -
  • Hydrocarbonoxy or hydroxyl groups a is 1, b is 0, 1, 2 or 3 and on average over the entire
  • Molecule has a minimum value of 0.1
  • G is a hydroxy radical or a monovalent or bivalent branched or linear C2-C25 glycol residue.
  • radicals R are Kohlenwasserstoffoxyreste.
  • branched or linear C 2 -C 25 -glycol radicals are alpha-omega hydroxy-functional glycols, such as ethylene glycol,
  • C] _-Ci_5-hydrocarbon radical and hydrocarbonoxy radicals R are the radicals described above for the silane S.
  • the organosilicon compounds O can be used either as a pure substance for hydrophobization, or they are used in preparations together with other components.
  • the preparations are aqueous solutions comprising at least one organosilicon compound O and water.
  • Such preparations may also contain the commonly used water repellents, such as the silanes, siloxanes and silicates reproduced in the publications cited above, and also, if appropriate, additional emulsifiers.
  • Aqueous, non-aqueous or solvent-based preparations are obtained by adding the
  • Organosilicon compounds O combined with other ingredients, which combinations do not necessarily give homogeneous mixtures.
  • Possible components which can be used to prepare preparations for carrying out the method according to the invention are, for example
  • 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,
  • Silicone resins one or more organic solvents, such as aromatic solvents, ketones, esters, alcohols, aliphatic and cycloaliphatic solvents, ionic liquids and glycols,
  • organic polymers such as polyvinyl alcohol, polyvinyl acetate, polyacrylates, styrene acrylate copolymers, polyvinyl butyrals, polyurethanes and polyepoxides,
  • the components to be mixed can be processed into a homogeneous, uniform active substance mixture. If necessary, you can multiphase mixtures of several liquid phases or of solid and liquid phases are formed, wherein the consistency of the products obtained may be both low viscosity liquid and pasty or creamy or also powdery solid.
  • the formulations are liquid or pasty and are distributed by conventional methods of distribution on the surface of the substrate, such as by brushing, spraying, lolling, rolling, pouring, filling, dipping, spincoating and rolling.
  • the hydrophobing of the substrates comprises the priming and impregnation.
  • the preparations themselves contain a basic activator.
  • a basic activator is recommended for the rapid formation of hydrophobicity.
  • the basic component can be incorporated into the preparation itself, wherein it is optionally masked in the preparation in such a way that it is released only in the later application, or it is readily used in the preparation, if thereby the usability of the preparation is not restricted. If appropriate, the basic component can also first be applied to the substrate in a separate step, followed by the preparation containing the organosilicon compounds O first.
  • the order can also be reversed, that is, first the preparation is applied to the organosilicon compound O on the substrate and then the basic component.
  • the basic component can be applied as a pure substance or as a preparation.
  • the basic component itself does not have a hydrophobing effect have. It is needed only in catalytic amounts. Typical amounts of basic activation activator are in the range of 0.01-5.0 weight percent, based on the weight of organosilicon compound O used, and are selected depending on how quickly the hydrophobicity is desired or how strong the catalytic effect of each component is is.
  • the preparations are preferably used as aqueous preparation, as emulsion or as aqueous foam.
  • Surfactants can be used to prepare aqueous preparations or they can be prepared without the addition of surfactants by introducing the organosilicon compounds O directly into water.
  • the preparation of aqueous preparations without the use of surfactants is possible in particular when the organosilicon compounds O are self-emulsifying or water-soluble in water.
  • Example Ia Condensation product of methyltrichlorosilane and ethylene glycol, preparation of organosilicon compounds 0:
  • 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 mixed with toluene in a ratio of 1: 1 and metered into a receiver of 2.8 times the molar excess of ethylene glycol by means of a dropping funnel.
  • a gentle water-jet vacuum is constantly applied to the apparatus (about 200 mbar).
  • a mixture of 473.10 g of methyltrichlorosilane and 473.10 g of toluene is introduced into the dropping funnel.
  • the mixture of methyltrichlorosilane and toluene is metered from the dropping funnel below the surface of the ethylene glycol reservoir.
  • the temperature is maintained over the dosing between 50 0 C and 55 0 C.
  • the duration of the dosage is about 70 minutes.
  • the system is refluxed for 2 hours. After this. Refluxing the batch is cooled to room temperature.
  • phase is toluene and the second phase being the product phase containing the polyether-modified polysiloxane.
  • the HCl content of the crude product is ⁇ 50 ppm.
  • the phases are separated and from the product phase, the toluene is removed by rotary evaporation under vacuum (about 10 mbar, 110 0 C distilled off.
  • a 10% strength aqueous solution is prepared by adding water. The solution is clear.
  • aqueous solution of the glycol-functional siloxane according to Example Ib is 0.5 percent by weight based on the amount of glycol siloxane of a 30% aqueous solution of
  • Methyl (dimethoxy) (aminopropylaminoethyl) silane is Methyl (dimethoxy) (aminopropylaminoethyl) silane.
  • Example Ia isooctyltrichlorosilane is reacted with ethylene glycol instead of methyltrichlorosilane.
  • the stoichiometry is set exactly the same as described for Example Ia.
  • the reaction and product isolation likewise take place exactly as indicated in Example Ia.
  • Example 2 Hydrophobic impregnation of a fiber cement board:
  • Example 3 Hydrophobic impregnation of a
  • Example 3 Hydrophobic Impregnation of Concrete Cylinders: In the preparations according to Examples Ia, Ib and Id, small concrete cylinders produced from a commercial concrete (w / c value 0.35-0.6) are immersed in accordance with the manufacturer's instructions. After 1 day of drying at room temperature, water is added dropwise to the concrete body treated in this way and the wetting behavior is qualitatively assessed: Ia: very good beading effect Ib: very good beading effect Id: very good beading effect
  • EXAMPLE 5 10.0 g of a 1% aqueous solution of a methyl (dimethoxy) (aminopropylamioethyl) silane are brushed evenly on spruce boards (10 ⁇ 15 cm) with a brush. Thereafter, the preparations Ia and Ib 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 treated in this way and the wetting behavior is assessed qualitatively: Ia: very good beading effect Ib: very good beading effect
  • Example 6 500 g / m 2 of the preparations Ia and Ib 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

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Textile Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Silicon Polymers (AREA)

Abstract

La présente invention concerne un procédé pour hydrophobiser des substrats comprenant des composés d'organosilicium O qui peuvent être produits en mettant en réaction un équivalent molaire de silane S choisi parmi du trihalogénosilane d'hydrocarbure, du trihydrocarbure-oxysilane d'hydrocarbure ou des mélanges de ceux-ci avec de 2,0 à 2,99 équivalents molaires d'un glycol G ou d'un mélange de glycols G.
PCT/EP2006/001970 2005-03-17 2006-03-03 Hydrophobisation de surface WO2006097206A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE200510012411 DE102005012411A1 (de) 2005-03-17 2005-03-17 Oberflächenhydrophobierung
DE102005012411.9 2005-03-17

Publications (1)

Publication Number Publication Date
WO2006097206A1 true WO2006097206A1 (fr) 2006-09-21

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PCT/EP2006/001970 WO2006097206A1 (fr) 2005-03-17 2006-03-03 Hydrophobisation de surface

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WO (1) WO2006097206A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101100821B (zh) * 2007-07-04 2010-05-26 中国科学院长春应用化学研究所 超疏水棉纤维材料或超疏水纸纤维材料的制备方法及用途
DE102011084301A1 (de) 2011-10-11 2013-04-11 Wacker Chemie Ag Verfahren zur Massehydrophobierung von Baustoffen mit festen Organosiliciumverbindungen
WO2022128994A1 (fr) 2020-12-18 2022-06-23 Evonik Operations Gmbh Compositions aqueuses stables à la dilution pour l'hydrophobisation en masse de matériaux de construction minéraux

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102015102382A1 (de) * 2015-02-19 2016-08-25 Bundesrepublik Deutschland, Vertreten Durch Den Bundesminister Für Wirtschaft Und Energie, Dieser Vertreten Durch Den Präsidenten Der Bundesanstalt Für Materialforschung Und -Prüfung (Bam) Verfahren zur dauerhaften Hydrophobierung und/oder Superhydrophobierung von Betonoberflächen

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2906768A (en) * 1957-12-05 1959-09-29 Dow Corning Method of reacting halosilanes with diols
DE1076946B (de) * 1956-04-30 1960-03-03 Gen Electric Verfahren zur Herstellung von zur Hydrophobierung und Appretierung geeigneten Organopolysiloxane

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1076946B (de) * 1956-04-30 1960-03-03 Gen Electric Verfahren zur Herstellung von zur Hydrophobierung und Appretierung geeigneten Organopolysiloxane
US2906768A (en) * 1957-12-05 1959-09-29 Dow Corning Method of reacting halosilanes with diols

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101100821B (zh) * 2007-07-04 2010-05-26 中国科学院长春应用化学研究所 超疏水棉纤维材料或超疏水纸纤维材料的制备方法及用途
DE102011084301A1 (de) 2011-10-11 2013-04-11 Wacker Chemie Ag Verfahren zur Massehydrophobierung von Baustoffen mit festen Organosiliciumverbindungen
WO2013053609A1 (fr) 2011-10-11 2013-04-18 Wacker Chemie Ag Procédé d'hydrofugation dans la masse de matériaux de construction au moyen de composés d'organosilicium solides
WO2022128994A1 (fr) 2020-12-18 2022-06-23 Evonik Operations Gmbh Compositions aqueuses stables à la dilution pour l'hydrophobisation en masse de matériaux de construction minéraux

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