EP3221282A1 - Procédé d'hydrophobisation par imprégnation d'éléments en argile moulés cuits - Google Patents

Procédé d'hydrophobisation par imprégnation d'éléments en argile moulés cuits

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Publication number
EP3221282A1
EP3221282A1 EP15795139.3A EP15795139A EP3221282A1 EP 3221282 A1 EP3221282 A1 EP 3221282A1 EP 15795139 A EP15795139 A EP 15795139A EP 3221282 A1 EP3221282 A1 EP 3221282A1
Authority
EP
European Patent Office
Prior art keywords
optionally
formula
radicals
units
siloxanes
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP15795139.3A
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German (de)
English (en)
Inventor
Hartmut Ackermann
Rudolf Hager
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Wacker Chemie AG
Original Assignee
Wacker Chemie AG
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Filing date
Publication date
Application filed by Wacker Chemie AG filed Critical Wacker Chemie AG
Publication of EP3221282A1 publication Critical patent/EP3221282A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • 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
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81—Coating or impregnation
    • C04B41/82—Coating or impregnation with organic materials
    • C04B41/84—Compounds having one or more carbon-to-metal of carbon-to-silicon linkages
    • 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
    • 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
    • C04B41/4505—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements characterised by the method of application
    • C04B41/4535—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements characterised by the method of application applied as a solution, emulsion, dispersion or suspension
    • C04B41/4539—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements characterised by the method of application applied as a solution, emulsion, dispersion or suspension as a emulsion, dispersion or suspension
    • 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
    • C04B41/4922—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 monomers, i.e. as organosilanes RnSiX4-n, e.g. alkyltrialkoxysilane, dialkyldialkoxysilane
    • 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
    • C08G77/38—Polysiloxanes modified by chemical after-treatment
    • C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
    • C08G77/385—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing halogens
    • 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
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00586—Roofing materials

Definitions

  • the invention relates to a process for the hydrophobic impregnation of fired clay moldings, in particular roofing tiles, using aqueous dispersions of organosilicon compounds.
  • the invention relates to a process for the hydrophobic impregnation of fired clay moldings by treatment of the fired clay moldings containing aqueous compositions comprising
  • R denotes monovalent, SiC-bonded hydrocarbon radicals having 1 to 5 carbon atoms
  • R 1 denotes monovalent, SiC-bonded hydrocarbon radicals having 6 to 22 carbon atoms, R may be the same or different and is hydrogen or monovalent hydrocarbon radicals and
  • a 0 or 1
  • R 3 may be the same or different and represents a monovalent, SiC-bonded, nitrogen-containing hydrocarbon radical
  • R 4 may be identical or different and is a monovalent, SiC-bonded, unsubstituted or optionally halogen-substituted hydrocarbon radical,
  • R 5 may be the same or different and is hydrogen or monovalent hydrocarbon radicals
  • b 0, 1, 2 or 3
  • c 0, 1, 2 or 3
  • d 0, 1, 2 or 3
  • radicals R are alkyl radicals, such as the methyl, ethyl, n-propyl, iso-propyl, 1-n-butyl, 2-n-butyl, iso-butyl, tert. Butyl radicals and alkenyl radicals, such as the vinyl, 1-propenyl and the 2-Propenylrest. Radicals R are preferably alkyl radicals having 1 to 5 carbon atoms, more preferably the methyl radical.
  • radicals R are alkyl radicals, such as 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-trimethylphenyl 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; Tetradecyl radicals, such as the n-tetradecyl radical; Hexadecyl radicals, such as the n-hexadecyl radical; Octadecyl radicals, such as the n-octadecyl radical; Cycloalkyl radicals, such as cyclohexyl, cycloheptyl and methylcycl
  • Radicals R 1 are preferably alkyl radicals having 6 to 16 carbon atoms, more preferably alkyl radicals having 8 to 12 carbon atoms, in particular the iso-octyl radical.
  • Radical R 2 is preferably an alkyl radical having 1 to 4 carbon atoms, more preferably the methyl or ethyl radical.
  • silane (A) in the composition used according to the invention are hexyltriethoxysilane, hexylmethyldiethoxysilane, n-octyltrimethoxysilane, n-octyltriethoxysilane, n-octyltrigoxysilane, isooctyltrimethoxysilane, isooctyltriethoxysilane, n-decyltriethoxysilane, dodecylmethyldimethoxysilane, tetradecyltrimethoxysilane, hexadecyltrimethoxysilane, Octadecylmethyldimethoxysilane, octadecylmethyldiethoxysilane and octadecyltriethoxysilane.
  • Silane (A) is preferably n-hexyltriethoxysilane, n-octyltriethoxysilane or isooctyltriethoxysilane and / or their partial hydrolysates having a maximum of 5 Si atoms, particularly preferably isooctyltriethoxysilane and / or their partial hydrolysates, where a particularly preferred isomer of Isooctyltriethoxysilane which is 2, 2, 4-trimethylpentyltriethoxysilane.
  • Partial hydrolysates are usually formed by part of the OR 2 residue in the silanes of the formula (I) being split off by reaction with water or steam, and OH groups bonded to silicon are formed. These in turn can condense with elimination of water to form siloxane bonds, resulting in oligomers which, in addition to groups OR 2, can also contain OH groups. Partial hydrolysates of silanes of the formula (I) may also be present as an impurity in the silane of the formula (I).
  • radicals R 3 are radicals of the formulas H 2 N (CH 2 ) 3 - ,
  • H 2 N (CH 2 ) 2 NH (CH 2 ) 3 H 2 N (CH 2 ) 2 NH (CH 2 ) 2 NH (CH 2 ) 3 -, H 3 CNH (CH 2 ) 3,
  • R 3 is H 2 N (CH 2 ) 3 - , H 2 N (CH 2 ) 2 NH (CH 2 ) 3- or cyclo-C 6 HnNH (CH 2 ) 3 radical, in particular around the H 2 N (CH 2 ) 2 NH (CH 2 ) 3 radical.
  • radicals R 4 are alkyl radicals, such as the methyl,
  • -Pentyl radical 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; Tetradecl radicals, such as the n-tetradecyl radical, hexadecyl radicals, such as the n-hexadecyl radical, octadecyl radicals, such as the n-octadecyl radical; Cycloalkyl radicals such as the cyclopentyl, cyclohexyl, cycloheptyl
  • radical R 4 to unsubstituted alkyl ⁇ radicals having 1 to 18 carbon atoms particularly preferably methyl, n-hexyl, n-octyl or Isooctylreste, in particular ⁇ sondere the methyl radical.
  • the radicals R 5 are preferably alkyl radicals having 1 to 4 carbon atoms, more preferably the methyl or ethyl radical.
  • the inventively used siloxanes (B) may be any, previously known linear, cyclic or verzweig ⁇ te siloxanes.
  • the siloxanes (B) are preferably those which consist of units of the formula (II).
  • Siloxanes (B) are particularly preferably those selected from the group consisting of
  • (B2) siloxanes comprising units of the formula (II), wherein in Minim ⁇ least one unit b is not 0 in at least 50% of all units of formula (II), the sum b + c is equal to 2 in the organopolysiloxane.
  • the silicone resins (Bl) is, preferably Si ⁇ liconharze of units of formula (II), where in 0 to 30%, particularly preferably 0 to 5%, of the units in the resin is equal to c.
  • R 4 , R 5 , c and d have the meanings given above,
  • c has the value 1 in at least 30% of all repeat units of the formula ( ⁇ ⁇ ) and can also have the value 1 in 100% of all repeat units of the formula ( ⁇ ⁇ ),
  • the organopolysiloxane resins (B1) may be solid or liquid.
  • the organopolysiloxane (Bl) are liquid and have at 25 ° C and the pressure of the surrounding atmosphere, ie at 900 to 1100 hPa, a viscosity of 1000 to 400 000 mPas.
  • the determined by gel permeation chromatography weight average molecular weight ⁇ (based on a standard of Polystyrolstan-) of these resins is preferably from 200 to 200,000 g / mol, especially 1000-20000 g / mol.
  • the siloxanes (B2) are preferably siloxanes of units of the formula (II) in which the sum of the units b + c is 2 in 60 to 100%, preferably in 80 to 100%, of the units in the molecule.
  • siloxanes (B2) are products which are prepared in a known manner, for example by equilibration or condensation of organopolysiloxanes, the alkoxy groups and / or
  • Hydroxyl groups and which are free of nitrogen be ⁇ particularly preferably of hydroxyl-terminated polydimethylsiloxanes, and silanes with monovalent, SiC-bonded, nitrogen-containing hydrocarbon radicals, such as aminoalkyl groups, can be produced.
  • polydimethylsiloxanes terminated with OH groups preference is given to siloxanes having molecular weights M n (number average) of from 500 to 1 000 000 g / mol, in particular ders preferably from 1 000 to 100 000 g / mol, in particular from 2 000 to 10 000 g / mol used.
  • the number-average molar mass M n is in the context of the present invention by means of Size Exclusion Chromatography (SEC) against polystyrene standard, in THF, at 60 ° C, flow rate 1.2 ml / min and detection with RI (refractive index detector ) on a column set Styragel HR3-HR4-HR5-HR5 from Waters Corp. US determined ei ⁇ nem injection volume of 100 ⁇ .
  • SEC Size Exclusion Chromatography
  • Silanes with monovalent, SiC-bonded, Sick fabric aufwei ⁇ send hydrocarbon radicals are preferably H 2 N (CH 2) 3 ⁇ Si (OCH 3) 3, H 2 N (CH 2) 3 -Si (OC 2 H 5) 3 .
  • H 2 N (CH 2 ) 2 NH (CH 2 ) 3 -Si (OC 2 H 5 ) 3 or H 2 N (CH 2 ) 2 NH (CH 2 ) 3 -Si (OCH 3 ) 2 CH 3 are particularly preferred .
  • the siloxanes (B2) have a viscosity at 25 ° C of preferably 10 to 10,000 mm 2 / s, more preferably 15 to 500 mm 2 / s.
  • the siloxanes (B2) preferably have a nitrogen content of 0.5 to 10 wt .-%, particularly preferably from 1 to 6 wt .-%, on.
  • Component (B) of the combination ⁇ reduction is used in the invention there are preferably siloxane (B2).
  • compositions used according to the invention contain component (B) in amounts of preferably 1 to 80 parts by weight, particularly preferably 5 to 40 parts by weight, in each case based on 100 parts by weight of component (A).
  • optionally used acid (C) mineralization mineral acids such as sulfuric acid, hydrochloric acid and phosphoric acids, and organic acids such as carboxylic acids having 1 to 10 carbons ⁇ atoms.
  • organic acids more preferably carboxylic acids ⁇ having 2 to 6 carbon atoms, in particular Essigkla ⁇ acid or propionic acid.
  • compositions used according to the invention contain acids (C), these are amounts of preferably 0.2 to 20 parts by weight, more preferably 1 to 10 parts by weight, in each case based on 100 parts by weight of component (A).
  • Acid (C) is preferably used when siloxanes (B2) are used as component (B) in the compositions used according to the invention.
  • emulsifiers (D) it is possible to use all emulsifiers which have hitherto been used for the preparation of siloxane dispersions.
  • emulsifiers (D) can be used anionic, non ⁇ ionic, cationic and amphoteric surfactants or their Mix ⁇ gen.
  • polymeric compounds which have emulsifying properties such as polyvinyl alcohols, in particular polyvinyl alcohols having a saponification degree of 75-95%.
  • the optionally used component (D) are preferably nonionic emulsifiers or mixtures of nonionic emulsifiers and ionic emulsifiers.
  • nonionic emulsifiers (D) used according to the invention are sorbitan fatty acid esters, ethoxylated sorbitan fatty acid esters, ethoxylated fatty acids, ethoxylated linear or branched alcohols having 10 to 20 carbon atoms, ethoxylated alkylphenols, pentaerythritol fatty acid esters, glycerol esters and alkylpolyglycosides.
  • nonionic emulsifiers (D) to sorbitan fatty acid esters, ethoxylated sorbitan fatty ⁇ ester, ethoxylated fatty acids, ethoxylated linear or branched alcohols having 10 to 20 carbon atoms or ethoxy ⁇ profiled triglycerides.
  • the inventively used together ⁇ men experienceer contain no ethoxylated alkylphenols, as these well-known ingly are not environmentally friendly.
  • nonionic emulsifiers are used as component (D), it may be just one type of nonionic emulsifier or a mixture of several nonionic emulsifiers. Preferably, at least one nonionic
  • Emulsifier (D) has an HLB value of greater than or equal to 12, in particular greater than or equal to 14.
  • component (D) are mixtures of nonionic emulsifiers, of which at least one
  • Emulsifier has an HLB value greater than or equal to 12.
  • the proportion of emulsifiers (D) with an HLB value is greater or equal to 12 in the emulsifier mixture (D) preferably at least 30 wt. -%.
  • the HLB reflects the balance between hydrophilic and hydrophobic groups ⁇ an emulsifier.
  • the definition of the HLB value and methods for their determination are general ⁇ my known and are described in Journal of Colloid and Interface Sci ⁇ ence 298 (2006) 441-450 and the literature cited there be ⁇ wrote.
  • anionic emulsifiers (D) may e.g. Alklysulfonate, alkyl sulfates and alkyl phosphates are used.
  • Examples of cationic emulsifiers (D) are all known quaternary ammonium compounds containing at least one substituted or unsubstituted hydrocarbon radical having Minim ⁇ least 10 carbon atoms wear as Dodecyldimethylammonium- chloride, tetradecyltrimethylammonium bromide, Stearyltrimethylam- ammonium chloride, distearyldimethylammonium chloride, cetyltrimethylammonium methylammonium, Behenyltrimethylammoniumbromid, Dedecyl- benzyldimethylammonium chloride and benzyltrimethylammonium chloride.
  • component (D) cationic emulsifiers ⁇ the so are the preferred aryl or alkyltrimethylammonium salts such as stearyltrimethylammonium chloride or cetyltrimethylammonium chloride, particularly preferably Benzyltrialkylammoniumsal- ze, in particular trimethyl or Trimethylbenzylammiumchlorid benzylammoniummethosulfat.
  • aryl or alkyltrimethylammonium salts such as stearyltrimethylammonium chloride or cetyltrimethylammonium chloride, particularly preferably Benzyltrialkylammoniumsal- ze, in particular trimethyl or Trimethylbenzylammiumchlorid benzylammoniummethosulfat.
  • quaternary imidazolinium compounds which contain at least one substituted or unsubstituted hydrocarbon radical having at least 10 carbon atoms.
  • menge component (D) menge component (D)
  • these are the amounts are preferably 0.1 to 15 parts by weight, particularly be ⁇ vorzugt 0.3 to 8 parts by weight, based on 100 weight parts component Ge ⁇ ( A).
  • Emulsifier (D) is preferably used when silicone resins (B1) are used as component (B) in the compositions used according to the invention.
  • the use of Emul gator ⁇ (D) is then preferably dispensed when in the compositions employed in this invention as component (B) siloxanes (B2) are used.
  • the water used as component (E) may be any type of water such as natural waters such as rainwater, groundwater, spring water, river water and seawater, chemical waters such as demineralized water, distilled or (repeatedly) redistilled water , DHW ⁇ water or mineral water act.
  • compositions used in the invention contain component (E) in amounts of preferably 50 to 99.99 wt .-%, preferably 80 to be ⁇ Sonders 99.9 .-%, each based on the total amount of the composition.
  • component (E) in amounts of preferably 50 to 99.99 wt .-%, preferably 80 to be ⁇ Sonders 99.9 .-%, each based on the total amount of the composition.
  • Particularly preferred in the inventive method highly diluted compositions having a water content (E) of 92 to 99.9 wt .-%.
  • the further components (F) optionally used according to the invention may be all additives which have hitherto been used in aqueous dispersions, such as, for example, Thickeners, organosilicon compounds which are different from components (A) and (B), substances for adjusting the pH, fragrances, dyes, pigments such as iron oxide, alcohols, antifreeze agents such as glycols and glycollides, or preservatives.
  • optionally used thickeners (F) are polyacrylic acid, polyacrylates, cellulose ethers such as carboxymethylcellulose and hydroxyethylcellulose, natural gums such as xanthan gum and polyurethanes.
  • organosilicon compounds (F) are tetraethoxysilane, trimethylmethoxysilane, aminopropyltriethoxysilane and aminopropylmethyldimethoxysilane.
  • Periods to ensure buffer systems such as salts of acetic acid, salts of phosphoric acid, salts of Zitronen Text ⁇ re in each case in combination with the free acid can be used depending on the desired pH.
  • the composition according to the invention contains ethanol and / or methanol as component (F) in amounts of preferably 0.00001 to 1% by weight, especially preferred. is from 0.0001 to 0.5 wt .-%.
  • the amounts of alcohol mentioned usually form during the preparation of the composition used according to the invention and / or during their storage.
  • the composition according to the invention contains no further component (F) other than alcohols.
  • compositions used according to the invention are preferably those containing
  • compositions used are those comprising
  • compositions used according to the invention preferably contain no components which exceed components (A) to (F) and their reaction products.
  • the components used according to the invention may each be one type of such a component as well as a mixture of at least two types of a respective component.
  • compositions used according to the invention are preferably dispersions, such as emulsions and suspensions, more preferably emulsions.
  • the preparation of the aqueous compositions used according to the invention can be carried out by processes known per se. Usually, the preparation is carried out by simply stirring all components in any order at temperatures of preferably 1 to 50 ° C and optionally subsequent homogenization.
  • the compositions are those which are prepared by, in a first step, the components (A), (B), optionally (C) and, if appropriate, (D) in a suitable mixer, For example, a flask or kettle, homogeneously mixed and then 0.5 to 4 hours at Tempe ⁇ temperatures of 60 to 140 ° C, preferably from 80 to 130 ° C, heated, and in a second step he ⁇ held in the first step mixture is emulsified with water (e), optionally (D) and, where appropriate, ⁇ (F).
  • a suitable mixer For example, a flask or kettle, homogeneously mixed and then 0.5 to 4 hours at Tempe ⁇ temperatures of 60 to 140 ° C, preferably from 80 to 130 ° C, heated, and in a second step he ⁇ held in the first step mixture is emulsified with water (e), optionally (D) and, where appropriate, ⁇ (F).
  • the emulsion obtained in the second process step can be diluted with further water, it also being possible to add further substances (F).
  • the dispersions used according to the invention are preferably milky, white to beige liquids.
  • compositions used according to the invention have a solids content, ie a content of non-volatile compounds (for example determined according to ASTM D 5095) of preferably 0.006 to 40% by weight, particularly preferably 0.06 to 18% by weight.
  • compositions used according to the invention have a viscosity of preferably 0.5 to 10,000 mm 2 / s, in particular from 1 to 1,000 mm 2 / s, each measured at 25 ° C according to the above-mentioned test method.
  • calcined clay molded bodies are to be understood as meaning all shaped bodies which pass through
  • the clay-containing Materia ⁇ lien may contain other ingredients in addition to clay, such as sand and Zu- whippers.
  • the fired Tonform redesignurgial Pottery particularly preferably roof tiles, facing bricks, cladding, flow or pots, particularly preferably by tiles or Fas ⁇ sadenziegel.
  • the fired clay moldings used according to the invention may be uncoated or coated, e.g. with a engobe.
  • ⁇ hang a generic term for a low-viscosity clay mineral mass, which is used for coloring or coating ceramic products. This may be, for example, slip; Engobes, unlike glazes, do not form a protective layer for the ceramic product.
  • the fired clay moldings are brought into contact with the aqueous composition, the composition penetrating partially or completely into the moldings.
  • the compositions are applied by conventional and previously known methods of distribution onto the surface of the shaped bodies, such as e.g. by brushing, spraying, knife-coating, rolling, pouring, filling, dipping and rolling.
  • the compositions penetrate into the capillaries of the moldings and dry there.
  • the inventive waterproofing the water treatment is drastically reduced would take the form of the body, which the thermal conductivity ⁇ ability lowers, but also prevents the destruction of the materials by the influence of frost and thaw cycles or salt.
  • the aqueous composition is employed in an amount such that the total amount of components (A), (B) and optionally (C) and optionally their reaction products per m 2 of surface to be treated of the calcined clay body is preferably 0.01 to 7.00 g, particularly preferably 0.03 to 3.00 g.
  • the process according to the invention is carried out at temperatures in the range of preferably 0 to 100.degree. C., more preferably 10 to 90.degree.
  • the inventive process is preferably conducted at ambient pressure ⁇ , ie between 900 and 1100 hPa.
  • the inventive method is carried out either immediately after firing the clay molded body or at any time after the preparation of the clay molded body.
  • hydrophobic impregnation according to the invention can also be carried out in fired clay moldings which have already undergone a certain aging process.
  • the treated, fired clay moldings are preferably stored under conditions in which water and other volatile components can evaporate.
  • the process has the advantage that it is efficiently and inexpensively and that the Tonformkör ⁇ are by long term and permanent ge ⁇ protects against the influence of water fired.
  • composition used according to the invention has the advantage that a concentrate can be prepared from the components (A), (B), optionally (C) and optionally (D), which is only in spatial and temporal proximity for use in the finished composition according to the invention diluted with water. This saves transport and storage costs. Also has this con ⁇ centrate the advantage of being very stable in storage.
  • aqueous compositions have the advantage that they are environmentally friendly and dilutable within wide limits.
  • the method according to the invention has the advantage that it impregnates fired clay moldings highly efficiently and without stains.
  • aqueous compositions used according to the invention have the advantage that they can be produced inexpensively and are easy to handle.
  • the inventive method has the advantage that the triessri ⁇ gen compositions show a very good and stable hydrophobic-absorbing impregnation and excellent penetration to the fired TonformMechn.
  • organopolysiloxane has a viscosity of 50 mm 2 / s at 25 ° C and containing 2.9 wt .-% nitrogen.
  • emulsions are prepared from the premix thus obtained by stirring the premix by hand with a spatula in water.
  • the emulsions formed are suitable for at least 30 days to be used as a water repellent. If the emulsion is framed, it must be mixed again briefly before use.
  • the roof tile discolors darkly, whereas the near-surface hydrophobized layer retains its hue.
  • the thickness of this layer can be determined by simple measurement. The results obtained with the two roof tiles previously treated with an identical emulsion are averaged. The thickness of the hydrophobized layer is an important measure of their durability.
  • the assessment of the staining on the surface is carried out by a visual inspection.
  • the tests were carried out in the same way as for the bricks treated with the emulsions E1 to E5 before the tests.
  • Example 2 The procedure described in Example 1 is repeated with the modification that the ready-dilute emulsion is stored for 30 days before application. The results are shown in Table 2.
  • a 54% potassium methylsiliconate (commercially available under the name SILRES BS ® 16 from Wacker Chemie AG, Kunststoff D) is prepared by adding water to ones Wirkstoffkonzentrati- of 1.50 wt .-% 1.00 wt .-% , and diluted to 0.50% by weight. The dilution can be done by simply stirring with the aid of a spatula.
  • Baysilone WA is a hydrophobing emulsion from the company Momen- tive Performance Materials (USA, Columbus, OH 43215), which is awarded for the waterproofing of building and roof tiles.
  • the commercially available emulsion contains an active substance content of 60% by weight. This is diluted by the addition of water to active compound concentrations of 1.50 wt .-%, 1.25 wt .-%, 1.00 wt .-%, 0.75 wt .-% and 0.50 wt .-%.
  • the dilution can be done by simply stirring with the aid of a spatula.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Silicon Polymers (AREA)
  • Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
  • Inorganic Chemistry (AREA)

Abstract

L'invention concerne un procédé d'hydrophobisation par imprégnation d'éléments en argile moulés cuits, notamment des tuiles de toit, par traitement des éléments en argile moulés cuits avec des compositions aqueuses contenant : a) des silanes de la formule (I) : RaR1Si(OR2)3-a et/ou leurs hydrolysats partiels comportant 5 atomes de silicium, B) des siloxanes contenant 10 unités ou plus de la formule (II) : R3 bR4 c (OR5) d SiO(4-bcd)/2, les radicaux et les indices ayant la signification donnée dans la revendication 1, éventuellement (C) un acide, éventuellement (D) un émulsifiant, (E) de l'eau et éventuellement (F) d'autres substances.
EP15795139.3A 2014-11-21 2015-11-10 Procédé d'hydrophobisation par imprégnation d'éléments en argile moulés cuits Withdrawn EP3221282A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102014223846.3A DE102014223846A1 (de) 2014-11-21 2014-11-21 Verfahren zur hydrophobierenden Imprägnierung von gebrannten Tonformkörpern
PCT/EP2015/076251 WO2016078976A1 (fr) 2014-11-21 2015-11-10 Procédé d'hydrophobisation par imprégnation d'éléments en argile moulés cuits

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EP3221282A1 true EP3221282A1 (fr) 2017-09-27

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US (1) US10882960B2 (fr)
EP (1) EP3221282A1 (fr)
JP (1) JP6490812B2 (fr)
KR (1) KR101943244B1 (fr)
CN (1) CN107001161B (fr)
DE (1) DE102014223846A1 (fr)
WO (1) WO2016078976A1 (fr)

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JP7039718B2 (ja) * 2018-08-24 2022-03-22 ワッカー ケミー アクチエンゲゼルシャフト 分枝オルガノポリシロキサンの調製方法
KR102187447B1 (ko) * 2018-11-27 2020-12-07 대동산업 주식회사 도자타일용 고유동성 과립분말의 제조방법

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DE3613384C1 (de) 1986-04-21 1988-01-07 Wacker Chemie Gmbh Waessrige Emulsionen von Organopolysiloxan und Verwendung solcher Emulsionen
DE4241727A1 (de) * 1992-12-10 1994-06-16 Wacker Chemie Gmbh In Wasser selbstdispergierende, Organopolysiloxan anhaltende Zusammensetzungen
DE19634500A1 (de) 1996-08-26 1998-03-05 Wacker Chemie Gmbh Zusammensetzungen für die wasser- und ölabweisende Behandlung saugfähiger Materialien
DE19752659A1 (de) 1997-11-27 1999-06-24 Wacker Chemie Gmbh Organosiliciumverbindungenhaltige hydrophobierende Pulver enthaltende Baustoffmassen
GB9726636D0 (en) 1997-12-17 1998-02-18 Dow Corning Method for preparing hydrophobic clay
JP2004251100A (ja) * 2002-12-26 2004-09-09 Kansai Paint Co Ltd 磁器タイル壁面の塗装工法
JP2005000742A (ja) * 2003-06-10 2005-01-06 Clion Co Ltd Ａｌｃパネルの撥水処理方法
DE102005004871A1 (de) * 2005-02-03 2006-08-10 Degussa Ag Hochviskose wässrige Emulsionen von funktionellen Alkoxysilanen, deren kondensierten Oligomeren, Organopolysiloxanen, deren Herstellung und Verwendung zur Oerflächenbehandlung von anorganischen Materialien
DE102005022100A1 (de) * 2005-05-12 2006-11-16 Wacker Chemie Ag Verfahren zur Herstellung von Dispersionen von vernetzten Organopolysiloxanen
JP5158935B2 (ja) 2007-07-09 2013-03-06 旭化成ワッカーシリコーン株式会社 土木建築用吸水防止剤組成物
GB201012661D0 (en) 2010-07-28 2010-09-15 Dow Corning Organosilicon hydrophobing agents
DE102011007006A1 (de) * 2011-04-07 2012-10-11 Wacker Chemie Ag Wässrige Dispersionen von Organosiliciumverbindungen

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Also Published As

Publication number Publication date
JP2018503579A (ja) 2018-02-08
KR101943244B1 (ko) 2019-01-28
CN107001161B (zh) 2020-07-31
JP6490812B2 (ja) 2019-03-27
US20170321015A1 (en) 2017-11-09
DE102014223846A1 (de) 2016-05-25
KR20170086598A (ko) 2017-07-26
US10882960B2 (en) 2021-01-05
CN107001161A (zh) 2017-08-01
WO2016078976A1 (fr) 2016-05-26

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