EP1945589A1 - Utilisation et procede pour diminuer la corrosion - Google Patents

Utilisation et procede pour diminuer la corrosion

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Publication number
EP1945589A1
EP1945589A1 EP06819238A EP06819238A EP1945589A1 EP 1945589 A1 EP1945589 A1 EP 1945589A1 EP 06819238 A EP06819238 A EP 06819238A EP 06819238 A EP06819238 A EP 06819238A EP 1945589 A1 EP1945589 A1 EP 1945589A1
Authority
EP
European Patent Office
Prior art keywords
radical
use according
composition
butyl
concrete
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Withdrawn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
EP06819238A
Other languages
German (de)
English (en)
Inventor
Urs Mäder
Franz Wombacher
Beat Marazzani
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.)
Sika Technology AG
Original Assignee
Sika Technology 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 Sika Technology AG filed Critical Sika Technology AG
Priority to EP06819238A priority Critical patent/EP1945589A1/fr
Publication of EP1945589A1 publication Critical patent/EP1945589A1/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Withdrawn legal-status Critical Current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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • 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
    • C04B41/60—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only artificial stone
    • C04B41/61—Coating or impregnation
    • C04B41/62—Coating or impregnation with organic materials
    • C04B41/64—Compounds having one or more carbon-to-metal of carbon-to-silicon linkages
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D35/00—Pliable tubular containers adapted to be permanently or temporarily deformed to expel contents, e.g. collapsible tubes for toothpaste or other plastic or semi-liquid material; Holders therefor
    • B65D35/14—Pliable tubular containers adapted to be permanently or temporarily deformed to expel contents, e.g. collapsible tubes for toothpaste or other plastic or semi-liquid material; Holders therefor with linings or inserts
    • B65D35/16—Pliable tubular containers adapted to be permanently or temporarily deformed to expel contents, e.g. collapsible tubes for toothpaste or other plastic or semi-liquid material; Holders therefor with linings or inserts for minimising or preventing corrosion of body
    • 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
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/40—Compounds containing silicon, titanium or zirconium or other organo-metallic compounds; Organo-clays; Organo-inorganic complexes
    • C04B24/42—Organo-silicon compounds
    • 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
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
    • 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
    • C04B41/46—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
    • 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/14—Nitrogen-containing compounds
    • C23F11/141—Amines; Quaternary ammonium compounds
    • C23F11/142—Hydroxy amines
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/173—Macromolecular compounds
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04C—STRUCTURAL ELEMENTS; BUILDING MATERIALS
    • E04C5/00—Reinforcing elements, e.g. for concrete; Auxiliary elements therefor
    • E04C5/01—Reinforcing elements of metal, e.g. with non-structural coatings
    • E04C5/015—Anti-corrosion coatings or treating compositions, e.g. containing waterglass or based on another metal
    • 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
    • C04B2111/20—Resistance against chemical, physical or biological attack
    • C04B2111/26—Corrosion of reinforcement resistance
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31652—Of asbestos
    • Y10T428/31663—As siloxane, silicone or silane

Definitions

  • the invention relates to the field of corrosion inhibition of steel reinforcements in concrete structures. More particularly, the invention relates to the use of a composition comprising aminoalcohol-modified polyorganosiloxanes to reduce corrosion on reinforcing steel of concrete structures, and to a method of reducing corrosion of reinforcing bars of concrete structures.
  • Steel as a reinforcing agent in buildings is widely used.
  • reinforcing steel The steel is introduced into a hydraulically setting material and reinforces this.
  • the steel is used in particular strand-shaped, in particular as rods or grids, for use, and is often referred to by the skilled person as a reinforcing iron.
  • reinforced concrete Of particular importance is reinforced concrete.
  • the corrosion of steel, which is present in hydraulically hardened materials, is of great economic importance.
  • the corrosion of the steel core reduces its strength and thus the strength of the concrete.
  • the corrosion products such as iron oxides or iron oxide hydrates have a larger volume than the non-corroded steel itself. As a result, create stresses in the concrete, which can lead to cracks or chipping of whole pieces.
  • Concrete structures can be rehabilitated by superficially removing or blasting concrete and exposing the steel reinforcement.
  • the steel reinforcement can then after removal of corrosion products, for example by sandblasting, with corrosion inhibitors or Treated corrosion-containing products and finally covered with concrete or a repair mortar, or reprofiled, are.
  • This method is used mainly in cases of advanced corrosion of the reinforcing steel (in case of excessive cross-sectional loss this is to be replaced by new reinforcing steel) and concrete spalling, as well as presence of higher chloride concentrations in the steel reinforcement covering concrete layer. This procedure is very complicated and causes considerable costs.
  • EP-A-0 177 824 describes a hydrophobing agent of resinous organopolysiloxanes and organic solvents as well as layered silicates.
  • paints are hydrophobic, but not corrosion inhibiting, and have the disadvantage of being easily damaged, for example, by mechanical interference, UV rays or acid rain, which results in the chloride ions still penetrating the concrete over time can penetrate and lead to corrosion on the steel inserts.
  • EP-A-1 308 428 describes an agent based on alkylalkoxysilane or alkylalkoxysiloxane for reducing the corrosion currents on steel reinforcements in concrete.
  • the Si atom is exclusively connected by Si-alkylene bridges, that is to say by a Si-C bond, with substituents carrying the amino function.
  • a solution of the corrosion inhibitor is applied or sprayed onto the concrete surface several times in succession, the corrosion inhibitor penetrating the surface.
  • such a composition contains only a low concentration of migratory corrosion inhibitor.
  • the composition must be applied in a very large amount and in a large number of operations, which is uneconomical and very labor-intensive.
  • the object of the present invention is therefore to provide compositions for the reduction of the corrosion of steel reinforcements, which overcome the disadvantages of the prior art. Surprisingly, it has been found that this object can be achieved by a use according to the independent claims. In addition, such compositions have excellent processability and high stability. These compositions containing polyorganosiloxanes have the great advantage of combining the properties of corrosion inhibition and hydrophobization. A concrete treated with it is treated on the surface, or in a layer on the surface, hydro- phobicized and on the other hand amino alcohol is split off, which penetrates into the concrete and protects the reinforcing steel from corrosion.
  • the present invention relates to compositions and their use for reducing corrosion on steel reinforcements of steel structures.
  • composition here contains at least one polyorganosiloxane S which has at least 4 repeat units of the general formula (I).
  • B 1 here represents either H, an alkyl or aryl radical having up to 18 C atoms or a radical of the general formula (II)
  • X 1 and X 2 independently of one another represent O, S or NR 4
  • a 1 , R 2 , R 3 and R 4 are each independently
  • R 5 , R 5 and R 6 independently of one another are an unbranched or branched alkylene radical having 1 to 8 C atoms.
  • z and p independently represent the values O, 1, 2 or 3.
  • m is 0 or an integer value of 1 to 10 and q is 0 or an integer value of 1 to 10.
  • polyorganosiloxane S is at least 1 radical of the general formula (II), at least one alkoxy or aryloxy having up to 18 carbon atoms and at least one repeat unit of the general formula (I) in which the silicon atom is bonded to 3 oxygen atoms present.
  • the silicon atom is tetravalent and dashed lines symbolize the junctions with the other residues. If z, respectively p, is greater than 1, different ones can be used
  • Residues A 1 , and B 1 be present.
  • the nitrogen-function-bearing radicals of the general formula (II) are attached to the silicon by an oxygen atom bound. This results in a dramatically altered reactivity of this bond, for example, in terms of hydrolyzability.
  • a 1 may be hydrocarbon radicals, and are preferably aliphatic linear or branched or cycloaliphatic radicals or phenyl radicals. This preferably has 1 to 10, in particular 1 or 8 carbon atoms. Particularly preferred hydrocarbon radicals are phenyl, n-butyl, isobutyl, n-propyl, iso-propyl, ethyl, iso-octyl, n-octyl and methyl radicals. Particularly preferably, A 1 is a hydrocarbon radical which is selected from the group consisting of the group methyl, n-octyl and iso-octyl.
  • hydrocarbon radicals A 1 are radicals containing heteroatoms and may have functional groups selected from the group consisting of mercapto group, isocyanato group, wherein the isocyanato may be optionally blocked to protect against chemical reactions, hydroxy group, epoxy group, morpholino, piperazino, primary , secondary or tertiary amino groups having one or more nitrogen atoms, wherein the nitrogen atoms may be substituted by hydrogen or monovalent aromatic, aliphatic or cycloaliphatic hydrocarbon radicals, carboxylic acid group, carboxylic anhydride group, aldehyde group, urethane group, urea group, phosphonic acid monoester group, phosphonic acid diester group, phosphonic acid group, methacryloyloxy group, Acryloyloxy- group and mixtures thereof.
  • Preferred amino-containing radicals A 1 have the general formula (V).
  • R 11 here is a divalent to C-C hydrocarbon radical, in particular C 2 -, C 3 -, C 4 -, C 5 - or C 6 -hydrocarbon radical, preferably a propylene radical, is.
  • R 12 and R 13 independently of one another represent a hydrogen atom or an optionally fluorine-, chlorine- or bromine-substituted d- to C 18-
  • Hydrocarbon radical preferably C 2 -, C 3 -, C 4 -, C 5 - or C 6 -hydrocarbon radical, which optionally has cycloaliphatic or aromatic moieties.
  • c stands for a value of 2, 3, 3, 5, or 6, in particular of 2
  • d stands for 0 or a value of 1, 2, 3 or 4, in particular of 0 or 1.
  • B 1 may be an alkyl or aryl radical.
  • Preferred alkyl or aryl radicals are aliphatic, linear or branched or cycloaliphatic radicals or phenyloxy radicals bonded to the silicon atom via an oxygen atom.
  • the radicals B 1 preferably have 1 to 6, in particular 1 to 3 carbon atoms.
  • Particularly preferred radicals B 1 are ethyl or methyl.
  • B 1 may be a radical of the formula (II).
  • R 6 represents an ethylene, propylene, isopropylene or -C (CH 3 ) 2-CH 2 - or a polyethylene or polypropylene.
  • R 6 represents an alkylene radical of the formula (III)
  • n is an integer value of 1 to 10, in particular from 1 to 4.
  • N is particularly preferably 2.
  • R 2 and / or R 3 are methyl, ethyl, isopropyl, n-propyl, isobutyl, n-butyl, isopentyl, n-pentyl or linear or branched hexyl, heptyl or octyl. Particularly preferred are methyl, ethyl or n-butyl.
  • R 2 and / or R 3 is H or a linear or branched aliphatic radical having 1 to 12 carbon atoms, in particular methyl, ethyl, n-propyl, iso-
  • R 2 is H and R 3 is a linear or branched aliphatic radical having 1 to 12
  • Carbon atoms in particular methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl or tert-butyl. Particularly preferred are methyl, ethyl or n-butyl.
  • the at least 4 repeat units of the formula (I) may be the same or different, independently of each other, as long as the conditions formulated above for the polyorganosiloxane S are fulfilled.
  • the polyorganosiloxanes S may have, in addition to the 4 recurring units of the general formula (I), further siloxane repeating units.
  • the further siloxane repeating units preferably contain radicals which are selected from the group consisting of hydrogen, hydroxyl, methyl and phenyl radicals.
  • Preferred polyorganosiloxanes S are those which contain at least 0.5 percent by weight, but not more than 60 percent by weight of radicals OB 1 . Particularly preferred are those polyorganosiloxanes S containing at least 1 percent by weight, but not more than 50 percent by weight based on the weight of the polyorganosiloxane S radicals B 1 . Preferably in the polyorganosiloxane S at least 70 mole percent, in particular at least 90 mole percent of the radicals B 1 radicals of the general formula (II).
  • the molecular weights of the preferred polyorganosiloxanes S have a molecular weight average Mw , which is from 500 to 5000, particularly preferably from 600 to 3500, g / mol.
  • the preferred polyorganosiloxanes S are at least 10 mol%, in particular at least 50 mol%, of so-called T units, where T units are those in which the Si atom is bonded to three oxygen atoms, irrespective of whether the oxygen atom links two Si atoms together or is part of a hydroxy, alkoxy or aryloxy radical OB 1 .
  • the further repeating units are preferably D units or M units, that is to say those in which the Si atom is bonded to two oxygen atoms (D unit) or has a bond to only one oxygen atom (M unit).
  • the polyorganosiloxanes S can be obtained by a reaction of polyorganosiloxanes C containing hydrolyzable groups and which are composed of at least 4 repeat units of the general formula (VI)
  • the radical R 1 hereby means an alkoxy or aryloxy radical with up to
  • the radicals A 1 , R 2 , R 4 , R 5 , R 5 ' , R 6 , X 1 , X 2 , p, z, m and q have the above meanings.
  • the polyorganosiloxane C is at least one alkoxy or aryloxy having up to 18 carbon atoms and at least one repeat unit of the general formula (VI), in which the silicon atom is bonded to 3 oxygen atoms, but contrary to the polyorganosiloxane S, no radical of the general formula ( II) available.
  • suitable amino alcohols of the formula (VII) are examples of suitable amino alcohols of the formula (VII)
  • polyoxyalkylenediols in particular polyethylene glycols or polypropylene glycols
  • Preferred primary amino alcohols are ethanolamine, 1-amino-2-propanol, 2-amino-1-propanol, 2-amino-2-methyl-propanol and 2- (2-aminoethoxy) ethanol.
  • Preferred secondary amino alcohols are N-methyl-ethanolamine, N-methyl-1-amino-2-propanol, N-methyl-2-amino-1-propanol, N-methyl-2- (2-aminoethoxy) -ethanol; N-ethyl-ethanolamine, N-ethyl-1-amino-2-propanol, N-ethyl-2-amino-1-propanol, N-ethyl-2- (2-aminoethoxy) -ethanol; N-butyl-ethanolamine, N-n-butyl-1-amino-2-propanol, N-n-butyl-2-amino-1-propanol, N-n-butyl-2- (2-aminoethoxy) -ethanol.
  • Preferred teritäary amino alcohols are N, N-dimethyl-ethanolamine, N, N-dimethyl-1-amino-2-propanol, N, N-dimethyl-2-amino-1-propanol, N, N-dimethyl-2- (2 -aminoethoxy) ethanol, N, N, N'-trimethyl-aminoethylethanolamine; N 1 N-diethyl-ethanolamine, N, N-diethyl-1 -amino-2-propanol, N, N-diethyl-2-amino-1-propanol, N, N-diethyl-2- (2-aminoethoxy ) -ethanol, N, N, N'-triethyl-aminoethyl-ethanolamine; N, N-di-n-butylethanolamine, N, N-di-n-butyl-1-amino-2-propanol, N, N-di-n-butyl
  • the polyorganosiloxanes C are compounds known to the person skilled in the art and can be prepared in a known manner, as described, for example, in Andreas Tomanek, "Silicones and Technology", ed. Wacker Chemie GmbH, Carl Hanser Verlag, Kunststoff, 1990, pp. 24-25. is described.
  • the reaction of the polyorganosiloxane C with an aminoalcohol of the formula (VII) is preferably carried out as completely as possible, that is, in the Essentially as far as possible no unreacted amino alcohol is present in the reaction product.
  • bases such as alkoxides are used for the reaction.
  • Cleavage products formed during the reaction such as, for example, alcohols, are preferably separated off from the reaction mixture by applying a vacuum, if appropriate at elevated temperature, in order to achieve as complete a conversion as possible.
  • composition may consist only of the polyorganosiloxane S or contain other compounds.
  • further constituents are, in particular, on the one hand
  • the composition in addition to the polyorganosiloxane S, the composition furthermore contains at least one organosilane of the formula (IV)
  • the radical R 7 here is H or an alkyl or aryl radical having up to 18 C atoms or a radical of the formula (II).
  • the radical R 8 here is H or an alkyl or aryl radical having up to 18 C atoms and A 2 is a radical as is possible for A 1 .
  • the radical A 2 may be the same or different from A 1 .
  • a is a value of 0.1 or 2. If there are several radicals R 7 (ie a ⁇ 2), these radicals can be identical or different, independently of one another.
  • Organosilanes in which A 2 is an alkyl radical having 3 to 12 C atoms, in particular having 5 to 9 C atoms, are particularly suitable.
  • organosilanes in which a has a value of 0.
  • Preferred such silanes are pentyltrimethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, isooctyltrimethoxysilane, decyltrimethoxy silane and dodecyltrimethoxysilane, in particular octyltrimethoxysilane and iso-octyltrimethoxysilane and their ethoxy variants.
  • organosilanes in particular those of the formula (IV), in particular with ethyl as R 7 , to polyorganosiloxanes.
  • organosilanes in particular those of the formula (IV), in particular with ethyl as R 7
  • penetration is much faster. This is particularly advantageous when several wet-in-wet applications are performed.
  • organosilane it is easy to adjust the concentration of polyorganosiloxane S, and thus the concentration of amino alcohol, which is split off upon penetration, to the particular needs of the application.
  • Preferred such silanes are pentyltrimethoxysilane, hexylthmethoxysilane, octyltrimethoxysilane, isooctylthymethoxysilane, decyltrimethoxysilane and dodecyltrimethoxysilane, in particular octyltrimethoxysilane and isooctylthymethoxysilane.
  • Formula (II) can be prepared by the same method as has already been described for the polyorganosiloxanes S.
  • the provided amino alcohol is implemented as fully as possible.
  • the reaction products of octyltrimethoxysilane with aminoethanol may be mentioned here:
  • the composition in addition to the polyorganosiloxane S, also contains at least one hydraulically setting binder.
  • the hydraulically setting binder is especially a mineral binder such as cement, gypsum, fly ash or slag, as well as additives.
  • Preferred hydraulic binders comprise at least one cement, in particular at least one cement according to Euronorm EN 197 or calcium sulfate, in the form of anhydrite, hemihydrate or dihydrate gypsum; or calcium hydroxide.
  • Portland cements, sulfoaluminate cements and high-alumina cements, in particular Portland cement, are preferred. Cements of cements can lead to particularly good properties.
  • Cementitious rapid binders which preferably contain at least one high-alumina cement or some other source of aluminate, such as, for example, aluminous clinker, and optionally, are used for rapid curing Calcium sulfate, in the form of anhydrite, hemihydrate or dihydrate gypsum; and / or calcium hydroxide.
  • the composition may range from low viscosity to high viscosity, i. pasty or gelatinous form.
  • the composition is preferably low-viscosity and readily penetrable.
  • the composition preferably has a viscosity of from 1 to 100 mPas, more preferably from 1 to 50 mPas, even more preferably from 1 to 20 mPas or from 5 to 10 mPas.
  • the composition can be formulated depending on the use as a low or high viscosity emulsion or solution.
  • the composition can be added as an aqueous emulsion or solution to the concrete mixing water to ensure the most homogeneous possible distribution.
  • Particularly suitable for application to a reinforced concrete surface are compositions which are sufficiently viscous that they can be applied in a few operations, preferably in one operation, even on vertical surfaces in an amount of more than 100 g / m 2 , in particular from 100 to 400 g / m 2 . can be applied by drainage without major product losses.
  • the composition may contain additional components such as solvents, dyes, luminescent agents, diluents, water, emulsifiers, thickeners, thixotropic agents, corrosion inhibitors or a mixture thereof.
  • solvents are alcohols, preferably methanol, ethanol, propanol, isopropanol, butanol, higher alcohols, such as ethylene glycol, glycerol, polyether polyols, such as polyethylene glycols and ether alcohols, such as butylglycol, methoxypropanol, and alkylpolyethylene glycols, but also aldehydes, esters, Ethers, amides or ketones, in particular acetone, methyl ethyl ketone, hydrocarbons, in particular methyl esters, ethyl esters, isopropyl esters, heptane, cyclohexane, xylene, toluene, white spirit and mixtures thereof.
  • composition described above is perfectly suitable for application to concrete surfaces, and which penetrates well into those concrete layers in which the steel reinforcements are usually present.
  • a composition is well suited to reduce or prevent corrosion of the steel reinforcement.
  • the present invention therefore relates to the use of the described composition for reducing corrosion on steel reinforcements of reinforced concrete structures.
  • the invention relates to a method for reducing or reducing corrosion on steel reinforcements of reinforced concrete structures, wherein the composition is preferably applied to a reinforced concrete surface.
  • the application of the composition can advantageously be done by spraying, brushing, spraying, pouring, brushing or rolling and as needed a tool such as brush, airless spray, Druck Boulevardsprüh réelle, paint roller, spray can or the like can be used.
  • the composition is in an amount of 50 to 2000 g / m 2 , preferably from 100 to 1000 g / m 2 , more preferably from 150 to 500 g / m 2, most preferably from 200 to 300 g / m 2 to the reinforced concrete surface applied.
  • the composition is applied in multiple layers, preferably in two, three or four layers, especially if the desired amount of active agent can not be applied in a single operation due to low absorbency of the substrate or the nature of the composition.
  • the present invention comprises a process wherein the composition is added to the fresh concrete, ie a concrete that has not set yet.
  • the composition is preferably added to the mixing water of the concrete.
  • the composition is preferably added in an amount of 0.2 to 10 wt .-%, preferably 0.5 to 5 wt .-%, more preferably 1 to 3 wt .-% based on the weight of the cement mixture.
  • the present invention therefore also provides a hydraulically setting composition
  • a hydraulic binder in particular a mineral binder such as cement, gypsum, fly ash or slag
  • Preferred hydraulic binders comprise at least one cement, in particular at least one cement according to Euronorm EN 197 or calcium sulfate, in the form of anhydrite, hemihydrate or dihydrate gypsum; or calcium hydroxide.
  • Preference is given to Portland cements, sulfo-aluminate cements and high-alumina cements, in particular Portland cement. Cements of cements can lead to particularly good properties.
  • Cementitious quick-release agents are preferably used for rapid curing, which preferably comprise at least one high-alumina cement or other aluminate source, such as, for example, aluminum-donating clinker, and optionally calcium sulfate, in the form of anhydrite, hemihydrate or dihydrate gypsum; and / or calcium hydroxide.
  • aluminate source such as, for example, aluminum-donating clinker, and optionally calcium sulfate, in the form of anhydrite, hemihydrate or dihydrate gypsum; and / or calcium hydroxide.
  • any liquid or powdered concrete admixtures can be used.
  • Such additives, such as solidification accelerator or condenser, etc. are well known.
  • accelerators which are sold by Sika Nurse AG for example under the trade name Sigunit®.
  • Sika® ViscoCrete® can be used as the plasticizer or retarder.
  • Another object of the present invention is a against
  • Corrosion of steel reinforcement protected concrete structure, which has been treated by a process according to the invention.
  • the concrete structure is advantageously a building of civil engineering, in particular a building or tunnel, a road or a bridge.
  • the polyorganosiloxane S can split off amino alcohol.
  • the polyorganosiloxane penetrates into the concrete.
  • the polyorganosiloxane S separates amino alcohol and can undergo condensation reactions.
  • a hydrophobic layer forms on the surface, in particular in a surface layer of the concrete.
  • the aminoalcohol formed can in turn continue to penetrate into the concrete, so that it is possible to reach reinforcing iron, which are deeper, and to protect against corrosion. It is thus possible with the described method to simultaneously render reinforcing concrete hydrophobic on the surface and to protect reinforcing steel from corrosion.
  • compositions containing polyorganosiloxane S as compared to compositions containing the corresponding aminoalcohol in the corresponding concentration, also have working toxicological and transport advantages, which may result in a more advantageous classification.
  • less volatile amino alcohols are released into the ambient air. This also leads to the particular advantage that the odor load during application is massively reduced.
  • compositions containing polyorganosiloxanes S and / or comparative examples are described below. All percentages are by weight. Unless otherwise stated, all manipulations are carried out at room temperature of 23 ° C and under normal pressure (1013 mbar (abs.)). The devices are commercially available laboratory equipment as they are commercially available from numerous equipment manufacturers.
  • the apparatus further comprises a reflux condenser and an internal thermometer. To the mixture is added 0.86 g of sodium methylate. The mixture is heated until reflux forms (112 ° C internal temperature). It is refluxed for 1 h. Thereafter, the mixture is cooled and exchanged the reflux condenser for a distillation bridge. The mixture is distilled for 3 hours under normal pressure, whereby the internal temperature increases to 135 ° C. Thereafter, a vacuum of 60 mbar and distilled for a further 2 hours under vacuum. This gives a slightly yellowish, clear, slightly viscous liquid with a slight odor.
  • Trimethylaminoethylethanolamine 9.88 mol% 12.6 wt.%
  • 254.94 g of the silicone resin are mixed with 245.06 g of N-methylethanolamine and added 0.25 g of sodium methylate.
  • the preparation of the mixture is carried out under nitrogen purge.
  • the mixture is prepared in the 1 l one-necked round bottom flask of a rotary evaporator.
  • the charged flask is attached to a rotary evaporator.
  • a vacuum of 300 mbar is applied and the oil bath is then heated to 110 ° C. If the oil bath temperature of 110 0 C is reached, the vacuum is carefully lowered to 60 mbar. To keep the distillation alive, the bath temperature is raised to 140 ° C over 2 hours. After 2 hours no more distillate passes.
  • Example 3 A mixture of 50% by weight of Example 3 and 50% by weight of isooctyltrimethoxysilane by pouring together the two liquid produced. The liquid has remained stable over the entire storage period observed.
  • Example 5 5 A mixture of 66.6% by weight of Example 3 and 33.3
  • Wt .-% iso-octyltrimethoxysilane prepared by pouring together the two liquids.
  • the mixture has a low odor.
  • the liquid has remained stable over the entire storage period observed.
  • Example 2 A mixture of 66.6% by weight of Example 2 and 33.3% by weight of isooctyltrimethoxysilane was prepared by pouring together the two liquids. The mixture has a low odor. The liquid has remained stable over the entire storage period observed.
  • Example 1 A mixture of 66.6% by weight of Example 1 and 33.3% by weight of isooctyltrimethoxysilane was prepared by pouring the two liquids together. The mixture has a low odor. The liquid has remained stable over the entire storage period observed.
  • Example 2 A mixture of 50% by weight of Example 2 and 50% by weight of dipropylene glycol monomethyl ether was prepared by pouring together the two liquids. The mixture has a low odor. The liquid has remained stable over the entire storage period observed.
  • Example 2 A mixture of 55.6% by weight of Example 2 and 44.4% by weight of dipropylene glycol monomethyl ether was prepared by pouring together the two liquids. The mixture has a low odor. The liquid has remained stable over the entire storage period observed.
  • Reference Example 1 Ref. 100% by weight of isooctyltrimethoxysilane.
  • the mixture has a significant odor.
  • the liquid has remained stable over the entire storage period observed.
  • the mixture has a very strong odor.
  • compositions were applied to 3 year old concrete slabs using a brush in the amount shown in Tables 1 and 2.
  • a concrete was used which was produced using the following and water: 11.25 kg Portland cement PC CEM I 42.5 according to standard EN 197-1 0.75 kg limestone filler 24 kg sand 0 - 1.2 mm 15 kg sand 1.2 - 4.0 mm 11.25 kg Sand 4.0 - 8.0 mm 24 kg Sand 8.0 - 16.0 mm
  • SIA 162/1 A (2003) 3.8 g / m 2 h, the water absorption coefficient w, measured according to the standard DIN 52617 (mod. 1996) 720 +/- 80g / m 2 h 0 5 and the air pores Content measured according to standard EN 12350-7 (2000) 3.6%.
  • the plates Prior to application of the compositions, the plates were sawn in two halves of the size 300x148x80 mm. After rinsing with water, the plate-like specimens thus obtained were conditioned for about 2 weeks in a climatic chamber at 23 ° C and 50% relative humidity.
  • the samples were stored for weather-exposed on a flat roof surface for one month and then the corrosion-inhibiting composition to the concrete sample plates.
  • the beading effect of dripped water was evaluated by measuring the contact angle or contact angle. Large contact angles of more than 90 ° indicate good bead-off effects, average to small contact angles of less than 90 ° rather indicate poor bead-off effects (Table 1).
  • the penetration behavior of the hydrophobic compounds was determined by determining the thickness of the hydrophobic zone at the surface. After removal of a core (75mm core bit) and drying of the wall of the hole in the concrete slab, the wall was wetted by means of water. The boundary line from wetting to non-wetting by water was clearly visible. The thickness of the non-wetted hydrophobic zone on the surface indicates the penetration depth of the hydrophobic compounds. With the penetration depth, the water absorption of the concrete decreases while increasing its hydrophobicity.
  • the penetration behavior of the corrosion inhibitor was determined by determining the depth profile, i. by determining the amino alcohol concentrations in different concrete layers of the sample plates, i. a depth of 0-8mm, 11-19mm, 22-30mm, 33-41mm, and 44-52mm, analyzed by ninhydrin color reaction (Table 2).
  • the ninhydrin color reaction was carried out as follows: 1 g of crushed concrete sample from different layers of the concrete sample plate was weighed into a pilling glass, admixed with 1 ml of distilled water, shaken well and left for 30 min. ditched. The liquid was filtered through a 0.45 ⁇ m membrane filter. The extract was prepared in an oven at 120 0 C for 2 h activated TLC plate (TLC finished plates silica gel 60 F 2 54, 20x20cm, Merck Art. No. 105735) was applied to 10 ul in several portions. In between was dried with a hair dryer.
  • the TLC plate was sprayed completely with a spray solution consisting of 0.15 g ninhydrin in 50 ml butanol and 1.5 ml glacial acetic acid (Merck reagent 231) and after further brief drying with a spray solution consisting of 0.1 g ninhydrin in 50 ml ethanol (Merck reagent 231 ) sprayed. Subsequently, the TLC plate was developed for about 1 h at 120 0 C in a drying oven until the evaluation. The identification help became a standard solution. (100ng monoethanolamine / 10 ⁇ l H 2 O) and a blank (distilled water) with applied. A red spot on an orange background means that alkanolamine was detected in the sample layer.
  • amino alcohol detection at a depth of 22-30 mm, where usually the steel reinforcement is located.
  • Table 2 Depth profile analysis (amino alcohol detection) by ninhydrin color reaction. after application.

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Abstract

L'invention concerne l'utilisation d'une composition qui contient un polyorganosiloxane (S), un procédé de diminution de la corrosion sur des armatures d'acier de structures en béton armé ainsi qu'un ouvrage en béton qui est fabriqué en utilisant ces compositions. La composition et le procédé conviennent particulièrement bien pour la rénovation de béton ancien mais également pour inhiber la corrosion des fers d'armature de bétons neufs.
EP06819238A 2005-11-04 2006-11-03 Utilisation et procede pour diminuer la corrosion Withdrawn EP1945589A1 (fr)

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EP05110364 2005-11-04
EP06819238A EP1945589A1 (fr) 2005-11-04 2006-11-03 Utilisation et procede pour diminuer la corrosion
PCT/EP2006/068063 WO2007051833A1 (fr) 2005-11-04 2006-11-03 Utilisation et procede pour diminuer la corrosion

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DE102009007913A1 (de) * 2009-02-06 2010-08-19 Sto Ag Verfahren zum Auftragen einer viskosen, aushärtenden Beschichtungsmasse
BR112013009993A2 (pt) 2010-10-27 2017-07-25 Shell Int Research concreto reforçado com enxofre, e, processo para preparar concreto reforçado com enxofre
GB201207662D0 (en) * 2012-05-02 2012-06-13 Dow Corning Water repellent organopolysiloxane materials
JP6001357B2 (ja) * 2012-06-29 2016-10-05 花王株式会社 水硬性組成物
US8969263B2 (en) * 2012-09-21 2015-03-03 Halliburton Energy Services, Inc. Treatment fluid containing a corrosion inhibitor of a polymer including a silicone and amine group
DE102012221170A1 (de) 2012-11-20 2014-05-22 Evonik Industries Ag Verfahren zur Tiefenimprägnierung von mineralischen Substraten und Verwendung von Organosilanen und/oder Organosilxanen zur Tiefenimprägnierung von mineralischen Substraten
US9581559B2 (en) 2013-08-19 2017-02-28 Board Of Regents, The University Of Texas System Corrosion detection sensor embedded within a concrete structure with a diffusion layer placed over the sacrificial transducer
CN103601527B (zh) * 2013-12-03 2016-01-20 中国建筑材料科学研究总院苏州防水研究院 一种硅烷膏体防护剂及其制备方法
CN104119027B (zh) * 2014-06-25 2015-12-30 芜湖市三兴混凝土外加剂有限公司 缓凝减水剂
JP2016179919A (ja) * 2015-03-24 2016-10-13 信越化学工業株式会社 鉄筋コンクリート用防食剤及び防食方法
EP3165512A1 (fr) 2015-11-06 2017-05-10 Technische Universität München Composition à base de ciment hybride modifiée présentant une meilleure résistance au mouillage
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KR20080072036A (ko) 2008-08-05
WO2007051833A1 (fr) 2007-05-10
CA2628484A1 (fr) 2007-05-10
BRPI0618187A2 (pt) 2011-08-23
JP2009515038A (ja) 2009-04-09
US8012543B2 (en) 2011-09-06
CN101331093A (zh) 2008-12-24
US20090218545A1 (en) 2009-09-03
RU2008122344A (ru) 2009-12-10

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