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
  • C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
• • 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
  • C04B24/12—Nitrogen containing compounds organic derivatives of hydrazine
  • C04B24/122—Hydroxy amines
• • 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
  • C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
  • C04B40/0028—Aspects relating to the mixing step of the mortar preparation
  • C04B40/0039—Premixtures of ingredients
• • 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

Definitions

• the invention relates to the field of corrosion inhibitors on steel, in particular on steel shuttering in prefabricated elements or on reinforcing steel for concrete constructions.
• the invention relates especially to a composition comprising at least one plasticizer for a hydraulically setting composition and at least one amino alcohol selected from the group consisting of 2-amino-2-methyl-1-propanol and N-aminopropylmonomethylethanolamine.
• Steel shuttering are molds for casting concrete into which fresh concrete for producing concrete components, also known as prefabricated elements, is introduced. After curing of the concrete, the steel shuttering is normally removed again.
• the corrosion of steel shuttering represents a great problem and can lead to a reduction in the quality of the concrete, in particular the surface quality of the concrete, and, for example, to undesirable traces of rust on visible concrete.
• a concrete release agent also known as forming oil
• forming oils have the disadvantage that they have only a limited ability to suppress corrosion and thus rust formation and also that they have to be applied individually to each piece of steel shuttering before each use, which is both uneconomical and environmentally polluting.
• steel as reinforcement in constructions is widespread.
• Steel-reinforced concrete is of particular importance.
• the steel is introduced into a hydraulically setting material and reinforces this.
• the steel is used particularly in elongated form, especially as rods or grids, and is also frequently referred to as reinforcement or armoring iron by those skilled in the art.
• the corrosion of steel present in hydraulically setting materials is of great economic importance. Corrosion of the steel inlays reduces their strength and thus the strength of the concrete.
• the corrosion products such as iron oxides or iron oxide hydrates have a greater volume than the uncorroded steel itself. This results in stresses in the concrete which can lead to cracks or splitting off of entire pieces.
• concrete plasticizers have been known for a long time.
• this concrete plasticizer is added as additive to the cement or to the cement before milling and leads to a high degree of plasticization or reduction of the water requirement of the concrete or mortar produced therefrom.
• compositions for reducing corrosion, in particular on steel shuttering or on reinforcing steel which overcome the disadvantages of the prior art. It has now surprisingly been found that a composition comprising at least one plasticizer for a hydraulically setting composition and at least one amino alcohol selected from the group consisting of 2-amino-2-methyl-1-propanol and N-aminopropylmonomethylethanolamine is highly suitable for preventing or reducing corrosion on steel shuttering or on reinforcing steel. In addition, such compositions have excellent processability and a high stability.
• the present invention relates to a composition
• a composition comprising or consisting of at least one plasticizer for a hydraulically setting composition and at least one amino alcohol selected from the group consisting of 2-amino-2-methyl-1-propanol and N-aminopropylmonomethylethanolamine.
• Particular preference is given to a composition comprising or consisting of at least one plasticizer and 2-amino-2-methyl-1-propanol.
• N-Aminopropylmonomethylethanolamine is also referred to as 2-[(3-aminopropyl)methylamino]ethanol (CAS No. 41999-70-6).
• the at least one amino alcohol of the composition according to the invention is 2-amino-2-methyl-1-propanol or N-aminopropylmonomethylethanolamine or a mixture of 2-amino-2-methyl-1-propanol and N-aminopropylmonomethylethanolamine.
• plasticizers are ones which are suitable for plasticizing a hydraulically setting composition or reducing its water requirement.
• plasticizers includes superplasticizers which are frequently also referred to as fluidizers.
• the plasticizer comprises or consists of polycarboxylate, preferably polycarboxylate ether (PCE).
• the polycarboxylate preferably comprises or consists of at least one polymer A of the formula (I).
• the symbols M each represent, independently of one another, H + , an alkali metal ion, alkaline earth metal ion, divalent or trivalent metal ion, ammonium ion or organic ammonium group.
• the term “independently of one another” in each case means that a substituent can have different possible meanings in the same molecule.
• carboxyl groups and sodium carboxylate groups can be simultaneously present in the polymer A of the formula (I), i.e. the radicals R 1 can in this case be H + and Na + independently of one another.
• substituents R are each, independently of one another, hydrogen or methyl.
• the polymer A is a substituted poly(acrylate), poly(methacrylate) or poly((meth)acrylate).
• substituents R 1 and R 2 are each, independently of one another, C 1 -C 20 -alkyl, cycloalkyl, alkylaryl or -[AO] n —R 4 .
• A is a C 2 -C 4 -alkylene group and R 4 is a C 1 -C 20 -alkyl, cyclohexyl or alkylaryl group, while n is from 2 to 250, in particular from 8 to 200, particularly preferably from 11 to 150.
• R 3 are each, independently of one another, —NH 2 , —NR 5 R 6 , —OR 7 NR 8 R 9 .
• R 5 and R 6 are each, independently of one another, H or a C 1 -C 20 -alkyl, cycloalkyl or alkylaryl or aryl group or a hydroxyalkyl group or an acetoxyethyl (CH 3 —CO—O—CH 2 —CH 2 —) or hydroxyisopropyl (HO—CH(CH 3 )—CH 2 —) or acetoxyisopropyl group (CH 3 —CO—O—CH(CH 3 )—CH 2 —) or R 5 and R 6 together form a ring of which the nitrogen of —NR 5 R 6 is part so as to build up a morpholine or imidazoline ring.
• substituents R 8 and R 9 are each, independently of one another, a C 1 -C 20 -alkyl, cycloalkyl, alkylaryl, aryl or hydroxyalkyl group and R 7 is a linear or branched C 2 -C 4 -alkylene group, in particular isomers of C 2 -C 4 -alkylenes, preferably ethylene, propylene, isopropylene or —C(CH 3 ) 2 —CH 2 —.
• indices a, b, c and d indicate the molar ratios of these structural elements in the polymer A of the formula (I). These structural elements are present in a ratio of
• a/b/c/d (0.05 ⁇ 0.9)/(0.05 ⁇ 0.9)/(0 ⁇ 0.8)/(0 ⁇ 0.5),
• a/b/c/d (0.1 ⁇ 0.9)/(0.1 ⁇ 0.9)/(0 ⁇ 0.3)/(0 ⁇ 0.06)
• the sum a+b+c+d is preferably greater than 0.
• the proportion of the polymer A of the formula (I) is typically from 10 to 100% by weight, in particular from 25 to 50% by weight, based on the weight of the plasticizer.
• the polymer A can be prepared by free-radical polymerization of the respective monomers
• the polycarboxylic acid is esterified or amidated by means of the appropriate alcohols, amines. Details regarding polymer-analogous reactions are disclosed, for example, in EP 1 138 697 B1 on page 7 line 20 to page 8 line 50, and in the examples therein or in EP 1 061 089 B1 on page 4, line 54 to page 5 line 38 and in the examples therein. In a variant thereof, as is described in EP 1 348 729 A1 on page 3 to page 5 and in the examples thereof, the polymer A can be prepared in the solid state.
• a particularly preferred embodiment of the polymer is that in which c+d>0, in particular d>0.
• radical R 3 —NH—CH 2 —CH 2 —OH, in particular, has been found to be particularly advantageous.
• Such polymers A have a chemically bound ethanolamine which can be split off. The ethanolamine is an extremely efficient corrosion inhibitor. Due to the chemical attachment of the corrosion inhibitor, the odor is greatly reduced compared to the case where it is merely mixed in. Furthermore, it has been found that such polymers A also display significantly greater plasticizing properties.
• the plasticizer of the present composition according to the invention comprises or consists of at least one polysaccharide, vinylic copolymer or at least one sulfonate, preferably on the basis of a lignosulfonate, naphthalenesulfonate or melaminesulfonate.
• the vinylic copolymer is preferably based on a polyvinyl alcohol or polyvinyl ether.
• the plasticizer preferably comprises, consists of or is based on Na, Ca or Mg lignosulfonate, Na, Ca or Mg naphthalenesulfonate, Na or Ca melaminesulfonate or a sulfonated melamine- or naphthalene-formaldehyde condensate. Particular preference is given to Na lignosulfonate or Na naphthalenesulfonate.
• the composition of the invention can contain further additives, preferably a solvent, in particular water.
• the composition of the invention is preferably a dispersion, in particular an aqueous dispersion, or a solution, in particular an aqueous solution.
• Suitable solvents are water and organic solvents. The choice is made according to technical but preferably also ecological considerations, for example toxicity, water hazard classes or biodegradability.
• Particularly useful organic 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 butyl glycol, methoxypropanol and alkylpolyethylene glycols, and 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.
• Preference is given to ethyl acetate, ethanol, isopropanol or heptane, and mixtures thereof.
• water as solvent.
• mixtures of water with alcohols having a proportion of water of more than 50% by weight, preferably more than 65% by weight, in particular more than 80% by weight.
• composition comprising Na lignosulfonate or Na naphthalenesulfonate, 2-amino-2-methyl-1-propanol and water.
• additives as are customary in concrete technology, in particular surface-active substances, stabilizers against heat and light, mold release agents, chromate reducers, dyes, antifoams, accelerators, retardants, further corrosion inhibitors, air-introducing or deaerating substances, pore formers, pumping aids, viscosity regulators, hydrophobicizing agents or thixotropes, shrinkage reducers.
• the proportion of the amino alcohol is from 0.1 to 20% by weight, preferably from 0.5 to 10% by weight, particularly preferably from 1 to 5% by weight, based on the total weight of the composition.
• the proportion of the at least one plasticizer is from 10 to 99.9% by weight, preferably from 50 to 95% by weight, more preferably from 80 to 90% by weight, based on the total weight of the composition.
• the proportion of water or solvent is from 0 to 70% by weight, preferably from 5 to 50% by weight, more preferably from 10 to 40% by weight, based on the total weight of the composition.
• the present invention provides a hydraulically setting composition which comprises or consists of the composition of the invention and also at least one hydraulically setting binder.
• the hydraulically setting binder is preferably a mineral binder such as cement, gypsum plaster, fly ash, fumed silica, slag, slag sand, limestone filler or quicklime.
• Preferred hydraulic binders encompass at least one cement, in particular at least one cement in accordance with European standard EN 197 or calcium sulfate in the form of anhydrite, hemihydrate or dihydrate; or calcium hydroxide. Preference is given to portland cements, sulfoaluminate cements and high-alumina cements, in particular portland cement.
• cements can lead to particularly good properties.
• fast-setting cement-containing binders which preferably contain at least one high-alumina cement or another aluminate source, for example, aluminate-supplying clinker and, if appropriate, calcium sulfate in the form of an anhydrite, hemihydrate or dihydrate; and/or calcium hydroxide.
• cement in particular portland cement, is preferred as constituent of the hydraulic binder. Particular preference is given to a low-chromate cement.
• composition of the invention is preferably added to the hydraulically setting binder so that the proportion of composition of the invention is from 0.1 to 5% by weight, preferably from 0.2 to 2% by weight, particularly preferably from 0.4 to 1.5% by weight, based on the weight of the hydraulically setting binder.
• the composition of the invention is produced by mixing the amino alcohol 2-amino-2-methyl-1-propanol or N-aminopropylmonomethylethanolamine with at least one plasticizer, with it being immaterial whether the amino alcohol is added to the plasticizer or vice versa.
• An aqueous composition or solution is produced by adding water or an organic solvent during production of the plasticizer, in particular in the preparation of the polymer A of the formula (I), or by subsequent mixing of the plasticizer, the amino alcohol or the plasticizer and the amino alcohol with water or an organic solvent. Preference is given to mixing the plasticizer with water or an organic solvent, preferably water, and subsequently adding the amino alcohol.
• the composition of the invention can be present as a clear or opaque solution or as a dispersion, i.e. as emulsion or suspension.
• the composition of the invention is preferably added simultaneously with the make-up water to the hydraulically setting composition, preferably the dry concrete mix, or mixed last into the hydraulically setting composition after addition of the make-up water.
• the present invention provides for the use of the composition of the invention for reducing or preventing corrosion of steel, in particular corrosion on steel shuttering of prefabricated elements or on reinforcing steel of concrete constructions.
• the composition of the invention is particularly useful for reducing or preventing corrosion on steel shuttering used for the production of prefabricated elements.
• the present invention provides for the use of 2-amino-2-methyl-1-propanol and/or N-aminopropylmonomethylethanolamine for reducing or preventing corrosion on steel shuttering of prefabricated elements or on reinforcing steel of concrete constructions.
• the present invention provides a method of reducing corrosion on steel shuttering of prefabricated elements or on steel reinforcement of steel-reinforced concrete constructions, in which the composition of the invention is added to the fresh concrete and the fresh concrete is brought into contact with the steel.
• the present invention further provides a concrete construction which has been protected against corrosion of steel shuttering or against corrosion of steel reinforcement and which comprises at least one composition according to the invention.
• the concrete construction is advantageously a building work or a component of an above-ground or underground construction, in particular a building or tunnel, a road or a bridge, in particular a building work which is produced from prefabricated elements.
• the present invention therefore further provides a prefabricated element comprising the composition of the invention.
• the prefabricated element is, for example, a pipe, a wall, ceiling or floor slab, a tubbing element, prop, bridge bearer, bridge segment, binder, a flight of stairs or a platform.
• the present composition according to the invention has the advantage that it simultaneously acts as plasticizer for a hydraulically setting composition and as corrosion inhibitor for steel.
• the corrosion protection is improved further above the corrosion-inhibiting action of the amino alcohol because the use of the plasticizer reduces the amount of make-up water required in the production of concrete and thus decreases the water/cement value (w/c value).
• a further advantage of the composition of the invention is that the corrosion inhibitor can be introduced directly into the hydraulically setting composition and the corrosion inhibitor does not have to be applied to the steel shuttering or steel inlays before the steel shuttering or steel inlays is/are used. This results in improved corrosion protection and a saving of time.
• the polymer A-1 indicated in table 3 was prepared from poly(meth)acrylic acid by polymer-analogous reaction with the corresponding alcohols and amines in a known manner.
• the polymer A is used as an aqueous solution in these examples.
• the polymer content is 40% by weight.
• This aqueous solution is referred to as A-1L.
• concentrations of A-1 indicated in the following tables are in each case based on the content of aqueous solution A-1L.
• R H
• R 1 -PEG1000-OCH 3 :-PEG3000-OCH 3 57.2:42.8 molar ratio
• R 2 EO/PO(50/50)2000-OCH 3
• Corrosion Behavior of Plasticizer and Amino Alcohol on Steel Plates 5% by weight of cement (CEM I 42.5 R) was mixed with 95% by weight of water and this mixture was filtered. This results in “serum”.
• a mixture of serum and amino alcohol or plasticizer or of serum, amino alcohol and plasticizer was then produced and 3 drops of this mixture were in each case applied to a steel plate (20 ⁇ 20 cm, ST 35).
• the amounts of amino alcohol or plasticizer added to the serum are shown in table 4.
• the % figures are in each case the % by weight of aqueous solutions of the amino alcohol or of the plasticizer, based on the total mixture of serum and the aqueous solutions of amino alcohol or of the plasticizer.
• the % figures for the addition are in each case the % by weight of the amino alcohol or of the plasticizer based on the total weight of cement.
• a concrete mixture of the compressive strength class C35/45, the slump class F5 and having a maximum particle size of 16 mm (GK16) and a water/cement value (w/c value) of 0.45 was produced in accordance with EN 934 from 360 kg/m 3 of CEM I 52.5 R.
• the concrete mixture was admixed with plasticizer or with a plasticizer/amino alcohol mixture and the slump was determined in accordance with EN 12350, the air pore content was determined in accordance with EN 12350 and the compressive strength of the cured prisms was determined in accordance with EN 12390.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Ceramic Engineering (AREA)
• Materials Engineering (AREA)
• Structural Engineering (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Inorganic Chemistry (AREA)
• Curing Cements, Concrete, And Artificial Stone (AREA)
• Preventing Corrosion Or Incrustation Of Metals (AREA)
• Building Environments (AREA)

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• 2005
  • 2005-11-23 EP EP05111175A patent/EP1790625A1/fr not_active Withdrawn
• 2006
  • 2006-11-23 AU AU2006316441A patent/AU2006316441A1/en not_active Abandoned
  • 2006-11-23 CN CNA200680046577XA patent/CN101326141A/zh active Pending
  • 2006-11-23 US US12/085,439 patent/US20090218546A1/en not_active Abandoned
  • 2006-11-23 WO PCT/EP2006/068840 patent/WO2007060204A2/fr active Application Filing
  • 2006-11-23 EP EP06819718A patent/EP1963240B1/fr not_active Not-in-force
  • 2006-11-23 JP JP2008541747A patent/JP2009529480A/ja active Pending
  • 2006-11-23 CA CA002630908A patent/CA2630908A1/fr not_active Abandoned
  • 2006-11-23 BR BRPI0618884-2A patent/BRPI0618884A2/pt not_active Application Discontinuation
  • 2006-11-23 KR KR1020087015208A patent/KR20080072062A/ko not_active Application Discontinuation

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