EP2788300A1 - Procédé de préparation d'accélérateurs de durcissement pour des compositions de liants minérales - Google Patents

Procédé de préparation d'accélérateurs de durcissement pour des compositions de liants minérales

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Publication number
EP2788300A1
EP2788300A1 EP12795001.2A EP12795001A EP2788300A1 EP 2788300 A1 EP2788300 A1 EP 2788300A1 EP 12795001 A EP12795001 A EP 12795001A EP 2788300 A1 EP2788300 A1 EP 2788300A1
Authority
EP
European Patent Office
Prior art keywords
calcium
compound
acid
cvl
setting
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.)
Pending
Application number
EP12795001.2A
Other languages
German (de)
English (en)
Inventor
Franz Wombacher
Beat Marazzani
Christian BÜRGE
Christophe Kurz
Gilbert Mäder
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 EP12795001.2A priority Critical patent/EP2788300A1/fr
Publication of EP2788300A1 publication Critical patent/EP2788300A1/fr
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
    • C04B22/08—Acids or salts thereof
    • C04B22/085—Acids or salts thereof containing nitrogen in the anion, e.g. nitrites
    • 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
    • C04B12/00—Cements not provided for in groups C04B7/00 - C04B11/00
    • C04B12/04—Alkali metal or ammonium silicate cements ; Alkyl silicate cements; Silica sol cements; Soluble silicate cements
    • 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
    • C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B14/02—Granular materials, e.g. microballoons
    • C04B14/04—Silica-rich materials; Silicates
    • C04B14/06—Quartz; Sand
    • C04B14/062—Microsilica, e.g. colloïdal silica
    • 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
    • C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
    • C04B22/08—Acids or salts thereof
    • C04B22/12—Acids or salts thereof containing halogen in the anion
    • C04B22/126—Fluorine compounds, e.g. silico-fluorine 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
    • C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
    • C04B22/08—Acids or salts thereof
    • C04B22/12—Acids or salts thereof containing halogen in the anion
    • C04B22/128—Bromine 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
    • C04B28/04—Portland cements
    • 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
    • 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
    • C04B40/0042—Powdery mixtures
    • 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
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/10—Accelerators; Activators
    • C04B2103/12—Set accelerators
    • 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
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/10—Accelerators; Activators
    • C04B2103/14—Hardening accelerators

Definitions

  • the invention relates to a process for the preparation of a setting and hardening accelerator for mineral binders comprising a step of reacting a calcium compound CV with a silicon compound SV. Further, the invention relates to a setting and hardening accelerator and a binder composition containing such an accelerator. In addition, the invention relates to the use of a setting and hardening accelerator for improving the early compressive strength of mineral binders. State of the art
  • WO 2010/026155 A1 Construction Research & Technology GmbH
  • an accelerator composition which is prepared by precipitation reaction of a calcium compound and a silicon compound in the presence of a water-soluble comb polymer acting as a plasticizer.
  • accelerating additives generally do not yet provide a satisfactory alternative to heat or steam treatment.
  • additives based on calcium compounds and silicon compounds act to accelerate setting and hardening, they often have the disadvantage that their consistency is so highly viscous that their preparation and use, in particular dosage, elaborately designed.
  • the object of the present invention is therefore to provide improved accelerating additives and processes for their preparation.
  • the accelerating additives should, in particular, have the lowest possible viscosity, be as easy as possible to produce and, moreover, have a high storage stability and, if possible, not adversely affect the processability of concrete and mortar.
  • the processes for preparing the accelerating additives should be kept as simple as possible and be as economical as possible. Surprisingly, it has been found that this can be achieved by the process according to claim 1.
  • the core of the invention is the addition of an acidic compound having a molecular weight of at most 200 g / mol, in particular 40-100 g / mol.
  • the setting and hardening accelerators prepared in this way have a lower viscosity and at the same time a high storage stability by the addition of the acidic compound in comparison with conventional accelerators.
  • accelerators according to the invention in mortar or concrete produced therewith exhibit an advantageous slump and good early compressive strengths.
  • the production process according to the invention can be kept relatively simple and allows the use of inexpensive raw materials available worldwide in sufficient quantities, which benefits the economy.
  • a first aspect of the present invention relates to a process for the preparation of a setting and hardening accelerator for mineral binders comprising the steps: a) reaction of a calcium compound CV with a silicon compound SV, and b) addition of an acidic compound having a molecular weight of at most 200 g / mol, in particular 40-100 g / mol.
  • the calcium compound as well as the silicon compound are labeled CV or SV only for readability. This marking is in no way limiting.
  • the steps a) and b) can generally be carried out in any desired sequence.
  • a binder which reacts in the presence of water in a hydration reaction to solid hydrates or hydrate phases. This can be, for example, a hydraulic binder (eg cement or hydraulic lime), a latent hydraulic binder (eg slag), a pozzolanic binder (eg fly ash) or a non-hydraulic binder (eg gypsum or white lime).
  • cementitious binder or a “cementitious binder composition” is especially a binder or a binder composition in an amount of at least 5% by weight, in particular at least 20% by weight, preferably at least 50% by weight Special at least 75 wt .-%, cement understood.
  • the mineral binder or binder composition contains a hydraulic binder, preferably cement.
  • a hydraulic binder preferably cement.
  • Portland cement in particular of the type CEM I (according to standard EN 197-1).
  • a proportion of the hydraulic binder in the total mineral binder is advantageously at least 5 wt .-%, in particular at least 20 wt .-%, preferably at least 50 wt .-%, in particular at least 75 wt .-%.
  • the mineral binder consists of 100% hydraulic binder, in particular cement.
  • the binder composition contains other binders in addition to or instead of a hydraulic binder.
  • binders in particular latent hydraulic binders and / or pozzolanic binders.
  • Suitable latent hydraulic and / or pozzolanic binders are, for example, slag, fly ash and / or silica fume.
  • the binder composition may contain inert substances such as limestone flour, quartz powder and / or pigments.
  • the mineral binder contains from 5 to 95% by weight, in particular from 20 to 50% by weight, of latently hydraulic and / or pozzolanic binders.
  • ears compressive strength is meant in the present context in particular a compressive strength after 24 hours. The compressive strengths are defined in particular in accordance with EN 12390-3.
  • an “acidic compound” is especially a compound which, if added to pure water, is capable of lowering its pH.
  • the acidic compound is a proton donor.
  • a pK s value of the acidic compound is in particular ⁇ 8.
  • the pK s value represents the negative decadic logarithm of the acid constant K s .
  • the acidic compound does not comprise a polymeric compound.
  • the acidic compound does not comprise a phosphoric acid ester. Such compounds have proved disadvantageous in the present context.
  • step a) the reaction of the calcium compound CV with the silicon compound SV takes place in the presence of a solvent.
  • Suitable solvents are, for example, water, alcohols and / or polyalcohols, in particular glycol, glycerol, ethanol or isopropanol. Water is the most preferred solvent.
  • the reaction of the calcium compound CV with the silicon compound SV therefore takes place in step a) in the presence of water, in particular in aqueous solution.
  • the reaction in step a) comprises in particular a precipitation reaction between the calcium compound CV and the silicon compound SV.
  • the calcium compound CV is reacted with the silicon compound SV in particular to form a calcium silicate hydrate suspension.
  • the calcium compound CV is introduced in the form of a solution CVL containing the calcium compound CV, in particular an aqueous solution CVL containing the calcium compound CV.
  • the solution CVL containing the calcium compound CV contains the calcium compound CV, a solvent and optionally further substances.
  • the solution CVL containing the calcium compound CV is also referred to below as "calcium solution CVL".
  • water is used as the solvent.
  • a concentration of the calcium compound CV in the calcium solution CVL is advantageously in the range of 5 to 80 wt .-%, in particular 30 to 70 wt .-%, more preferably 40 to 60 wt .-%.
  • the silicon compound SV is advantageously introduced in the form of a solution SVL containing the silicon compound SV, in particular an aqueous solution SVL containing the silicon compound SV.
  • the solution SVL containing the silicon compound SV contains the silicon compound SV, a solvent and optionally further substances. In particular, water is used as the solvent.
  • the solution SVL containing the silicon compound SV is also referred to below as "silicon solution SVL".
  • a concentration of the silicon compound SV in the silicon solution SVL is advantageously in the range of 5 to 60% by weight, in particular 10 to 50% by weight, more preferably 10 to 40% by weight.
  • the Caiciumates CVL and the silicon solution SVL are presented here in particular separately from each other.
  • the presentation of the calcium compound CV and the silicon compound SV in the form of solutions makes it possible, in particular, to simplify process control and monitoring.
  • the cadmium solution CVL and the silicon solution SVL are only labeled with CVL or SVL for readability. This identification is by no means limiting.
  • the calcium solution CVL is added to the silicon solution SVL and / or the silicon solution SVL to the calcium solution CVL during the process.
  • the metering takes place in particular continuously and / or stepwise.
  • the Caiciumates CVL can be mixed with the silicon solution SVL.
  • step a) preferably takes place in a liquid-phase reactor.
  • the liquid phase reactor is in particular selected from the group consisting of Sulzer mixer reactor, reactor with external recirculation, cascade reactor, loop reactor, rotor-stator mixer and stirred reactor instead.
  • Preferred liquid-phase reactors are in particular stirred reactors and static mixers.
  • step a) is carried out at a temperature of -10-90 ° C, a pH of 6-12 and a pressure of 0.8-20 bar. Under certain circumstances, it may also be expedient to carry out step a) under an inert gas atmosphere, for example N 2 atmosphere, in order to reduce undesirable side reactions with reactive air constituents.
  • an inert gas atmosphere for example N 2 atmosphere
  • the addition of the acidic compound may take place before and / or during and / or after step a).
  • the acidic compound is added before and / or during step a).
  • the viscosity of the prepared setting and hardening accelerators can be reduced.
  • the addition of the acidic compound prior to step a) also contributes to an advantageous processability and setting time of binder compositions containing accelerators produced in this way.
  • the acidic compound is added before step a).
  • the acidic compound is admixed with a calcium chloride solution CVL and / or a silicon solution SVL.
  • Particularly advantageous is the admixing of the acidic compound in the Caiciumates CVL.
  • at least 50% by weight of the acidic compound, especially the entire amount of the acidic compound is added to the calcium chloride solution CVL.
  • the acidic compound is presented in this case in particular as part of the calcium chloride solution CVL together with the calcium compound CV.
  • the acidic compound in the calcium solution CVL can generally be dissolved relatively well, without precipitating solids or phase separations. This is usually only partially the case in the case of the silicon solution SLV.
  • the acid compound after step a may also be advantageous to add the acid compound after step a). This can potentially simplify the manufacturing process. It is also possible to add a first part of the acidic compound before step a) and another part of the acidic compound during and / or after step a). Furthermore, the acidic compound, eg dissolved in water or in pure form, even during the mixing of the calcium solution CVL and the silicon solution SVL be added separately.
  • the calcium compound CV is in particular selected from the group consisting of calcium chloride, calcium nitrate, calcium formate, calcium acetate, calcium bicarbonate, calcium bromide, calcium citrate, calcium chlorate, calcium hydroxide, calcium oxide, calcium hypochlorite, calcium iodates, calcium iodide, calcium lactate, calcium nitrite, calcium phosphate, calcium propionate, calcium sulphate, calcium sulphate hemihydrate, calcium sulphate dihydrate, calcium sulphide, calcium tartrate, calcium gluconate, calcium sulphamate, calcium maleate, calcium fumarate, calcium adipate and calcium aluminate.
  • the calcium compound CV is preferably a calcium compound which is readily soluble in water, most preferably calcium nitrate, calcium acetate and calcium sulphamate.
  • the silicon compound SV is advantageously selected from the group consisting of sodium silicate, potassium silicate, lithium silicate, water glass, silicic acid, sodium metasilicate, potassium metasilicate, disodium metasilicate, dipotassium metasilicates, silica, disodium disilicate and disodium trisilicate.
  • the silicon compound SV is a water-soluble silicon compound, most preferred are water glasses, especially sodium silicate and potassium silicate.
  • water glass in the present document from the melt flow solidified water-soluble salts of silicas, especially potassium and sodium silicates or their aqueous solutions are understood, as described in CD Römpp Chemie Lexikon, version 1 .0, Georg Thieme Verlag, Stuttgart 1995.
  • the calcium compound CV is calcium nitrate and the silicon compound SV is sodium silicate.
  • a proportion of the acidic compound per se is advantageously from 0.01 to 12% by weight, preferably from 1 to 8% by weight, more preferably from 2 to 7% by weight, based on the total weight of the setting and hardening accelerator.
  • a proportion of the acidic compound is in particular 1-12% by weight, preferably 2-8% by weight, more preferably 3-6% by weight. , based on the total weight of the setting and hardening accelerator.
  • a proportion of the acidic compound is in particular 0.1-8% by weight, preferably 0.3-5% by weight, based on the total weight of the setting accelerator and hardening accelerator.
  • the proportions of the acidic compound are particularly optimal if the setting and hardening accelerator is an aqueous suspension having a solids content of 5 to 50 wt.%, In particular 10 to 30 wt.%, Especially 15 to 25 wt.
  • the proportions of the acidic compound can be adjusted accordingly.
  • the acidic compound has a pK s value of -2-8, in particular 1-7, preferably 1-5. In acidic compounds having a plurality of acid groups and / or acidic protons, the lowest pK s value is decisive.
  • the acidic compound comprises or is nitric acid, sulfamic acid, methanesulfonic acid, formic acid, acetic acid, fumaric acid, oxalic acid, maleic acid, maleic anhydride, glycolic acid and / or lactic acid.
  • nitric acid, sulfamic acid, formic acid and / or acetic acid generally form readily soluble Ca salts, which is advantageous in the present context.
  • such acids have little delay in the setting and hardening process of mortar and concrete compositions.
  • these acids have a relatively low molecular weight per acid group, so that it is sufficient for optimal effect to use relatively small amounts.
  • the acidic compound is an organic acid, in particular a monocarboxylic acid. Preferred are
  • Formic acid and / or acetic acid Very particular preference is acetic acid.
  • Such acids are in particular non-corrosive and are very advantageous with regard to the effects according to the invention.
  • the calcium compound CV or calcium solution CVL is prepared with the aid of an acidic compound, in particular more acidic compound is added in step b) than is necessary for the salt formation of the calcium salt.
  • the acidic compound is used with an excess of> 5 mol%, in particular> 10 mol%, in particular> 20 mol%, based on the amount of acidic compound required for the preparation of the calcium compound.
  • the calcium compound CV or the calcium solution CVL has a pH ⁇ 7, preferably ⁇ 6, more preferably ⁇ 5, in particular ⁇ 4, in particular ⁇ 3.
  • the silicon compound SV or the silicon solution SVL has in particular a pH> 7, preferably> 9, particularly preferably> 10, in particular> 1 1, in particular> 12.
  • the reaction of the calcium compound CV with the silicon compound SV or step a) of the process advantageously takes place at a pH of 6 to 12, in particular 7 to 12, preferably 7 to 11, particularly preferably 9 to 10.5.
  • the reaction of the calcium compound CV with the silicon compound SV or step a) of the process takes place in the absence of a hydraulic binder and / or in the absence of a cementitious binder and / or in the absence of cement.
  • a proportion of such substances during the reaction ⁇ 10 wt .-%, preferably ⁇ 5 wt .-%, especially ⁇ 1 wt .-%, particularly preferably ⁇ 0.5 wt .-% or ⁇ 0.1 wt .-% is. In particular, no such substances are present during the reaction.
  • a possible mixing with such substances takes place in particular only when using the prepared setting and hardening accelerator, which in particular takes place delayed in time and / or spatially separated from the preparation of the setting and hardening accelerator.
  • a pH after preparation of the setting and hardening accelerator is in the range from 7 to 12, in particular 7 to 11, preferably 9 to 10.5.
  • Such accelerators have proven to be optimal with regard to viscosity, spread and early compressive strengths.
  • the viscosity after the preparation of the setting and hardening accelerator is advantageously in the range from 10 to 2000 mPas, in particular from 50 to 1000 mPas. Such accelerators are particularly efficient to produce and easy to dose and use and have a high storage stability.
  • the viscosity is determined in particular at a temperature of 23 ° C.
  • the viscosity is preferably determined using a rotary viscometer, in particular a rotary viscometer from Brookfield Model RVT, at 100 rpm.
  • the setting and hardening accelerators prepared by the process according to the invention are particularly stable on storage, preferably for several days, particularly preferably for several weeks, especially for several months.
  • step c) is comminution by stirred mills, roller mills, colloid mills, rotor-stator mixers and / or homogenizers, preferably by homogenizers.
  • Step c) is preferably carried out after step a) and after step b).
  • step c) leads to an average particle size of the reaction product of ⁇ 2000 nm. This is particularly advantageous for the early strength resulting from the accelerator.
  • the method comprises the addition of at least one further hardening accelerating substance.
  • the further hardening-accelerating substance particularly advantageously comprises one or more of the following representatives: a) one or more amino alcohols b) one or more alkali metal and / or alkaline earth metal nitrates c) one or more alkali metal and / or alkaline earth metal nitrites d) one or more alkali and / or alkaline earth thiocyanates, in particular sodium thiocyanate e) one or more cc-hydroxycarboxylic acids, in particular lactic acid f) one or more alkali metal and / or alkaline earth metal halides, in particular sodium chloride and / or calcium chloride g) glycerol and / or glycerol derivatives h) one or more glycols and / or glycol derivatives i)
  • the at least one further hardening accelerating substance comprises at least one aminoalcohol.
  • Diethanolamine and / or N-methyldiethanolamine are particularly preferred.
  • Very particular preference is given to N-methyldiethanolamine.
  • a proportion of the at least one further hardening accelerating substance, in particular an aminoalcohol, is advantageously 1-15% by weight, preferably 3-12% by weight, more preferably 6-11% by weight, based on the total weight of the setting agent and hardening accelerator.
  • the proportions of the at least one further hardening accelerating substance are particularly optimal if the setting and hardening accelerator is an aqueous suspension having a solids content of 5 to 50 wt.%, In particular 5 to 30 wt.%, Especially 15 to 25 wt. represents.
  • the at least one further hardening accelerating substance is mixed with advantage before step a) of the calcium chloride solution CVL.
  • a good miscibility of the further hardening accelerating substance with the components of the calcium chloride solution CVL is given.
  • the further hardening accelerating substance can also be added to the silicon solution SVL, for example, or it is added only after step a), in particular after step a) and after step b).
  • the method further comprises a step for adding a thickening agent, in particular selected from the group consisting of cellulose ethers, polysaccharides, starch derivatives, polyvinyl alcohols, polyacrylates, latex, guar gum, alginates and polyacrylamides.
  • a thickening agent in particular selected from the group consisting of cellulose ethers, polysaccharides, starch derivatives, polyvinyl alcohols, polyacrylates, latex, guar gum, alginates and polyacrylamides.
  • a thickening agent in particular selected from the group consisting of cellulose ethers, polysaccharides, starch derivatives, polyvinyl alcohols, polyacrylates, latex, guar gum, alginates and polyacrylamides.
  • Such thickeners have proven to be compatible with the other components of the accelerator and allow to adjust the viscosity of the accelerator targeted.
  • the addition of the thickener can in principle be carried out at any time in the process.
  • the method further comprises a step for adding an additive, in particular a concrete additive and / or a mortar additive.
  • the at least one additive in particular comprises a pH regulator, a defoamer, a dye, a preservative, a flow agent, a dispersant, a retarder, an air entraining agent, a shrinkage reducer and / or a corrosion inhibitor and / or mixtures thereof.
  • the addition of the additive can in principle be done at any time in the process. However, it is usually advantageous to add after step a), in particular after step a) and after step b) or c).
  • the at least one additive comprises a flow agent.
  • a flow agent This specifically includes a polycarboxylate, especially a polycarboxylate tether.
  • the flow agent is a comb polymer comprising a polycarboxylate backbone with attached polyether side chains. The side chains are bonded to the polycarboxylate backbone, in particular via ester, ether and / or amide groups.
  • Such comb polymers are also sold commercially by Sika für AG under the trade name series ViscoCrete®.
  • flow agents in the form of lignin sulfonates, sulfonated naphthalene-formaldehyde condensates, sulfonated vinyl copolymers, allyl ether-maleic acid copolymers and / or sulfonated melamine-formaldehyde condensates.
  • the addition of the flow agent is advantageously carried out after step a), in particular after step a) and after step b) or c).
  • step a) is used as Calciumveitati CV calcium nitrate and this before the reaction in step a) in the form of an aqueous solution containing the calcium compound CV CVL, is presented, and
  • the sodium silicate has a SiO 2 : Na 2 O molar ratio of from 0.1-0.5 and this is initially introduced in the form of an aqueous solution SVL containing the silicon compound SV, and
  • Sodium silicate 0.25-8.0, preferably 0.65-3, in particular 0.75-1.75, and
  • Step b) takes place prior to step a), and the acidic compound is an organic acid having a pK s of 1-7, preferably 1-5, and a monocarboxylic acid, acetic acid being most preferred, and
  • the acidic compound has a proportion of 1 to 8% by weight, more preferably 2 to 7% by weight, based on the total weight of the setting and hardening accelerator, and - Is optionally added a further hardening accelerating substance, in particular an aminoalcohol, wherein N-methyldiethanolamine is preferred.
  • the present invention relates to a setting and hardening accelerator prepared by one of the aforementioned methods.
  • the setting and hardening accelerator is present as a solid or liquid, in particular as a powder or suspension.
  • a suspension preferably has a solids content of 5 to 50% by weight, in particular 10 to 30% by weight, especially 15 to 25% by weight.
  • a powder is preferably free-flowing and / or substantially free of water.
  • the setting and hardening accelerator is preferably substantially free of hydraulic and / or cementitious binders and / or cement.
  • a proportion of deratiger substances ⁇ 10 wt .-%, preferably ⁇ 5 wt .-%, especially ⁇ 1 wt .-%, more preferably ⁇ 0.5 wt .-% or ⁇ 0.1 wt .-% is.
  • the setting and hardening accelerator according to the invention is used in various fields, in particular in concrete and cement technology.
  • the accelerator has particularly good properties as an accelerator for mineral binders, as described above.
  • the accelerator is well processable, among other things, because of its relatively low viscosity.
  • the accelerator can be used to accelerate the setting and hardening of mineral binders, especially hydraulic binders, especially quick-setting cement, as well as mortar or concrete made therefrom.
  • mortar or concrete can be produced which has a high early and final strength.
  • the setting and hardening accelerator according to the invention is thus particularly suitable if the hydraulically setting composition must be able to be loaded or walked over again very quickly after application, for example in road construction or bridge construction, in the prefabrication of concrete elements in precast concrete and precast concrete elements or in slope repair in the case of runways, so that the finished parts can be dismantled, transported can be stacked or biased or the roads or slopes can be traveled.
  • the accelerator according to the invention can be used for the novel use both in liquid and in solid form, both alone or as part of an additive composition.
  • the invention therefore additionally relates to an additive composition in liquid or solid form comprising at least one accelerator according to the invention.
  • additional hardening accelerating substances, flow agents or additives, in particular concrete admixtures and / or mortar additive, may be included.
  • the accelerator or additive composition according to the invention is preferably used in an amount of from 0.01 to 15% by weight, in particular 0.01-10% by weight, preferably 0.2-8% by weight, based on the weight of the mineral binder, of the desired Effect. It is also possible to use several accelerators mixed in order to adapt the desired effect, for example, to specific conditions.
  • the accelerator or the additive composition according to the invention can be present, for example, in the solid or pasty state of matter and can optionally be mixed with a flow agent, which is also present in the solid state, and thus stored or transported for a long time.
  • the accelerator according to the invention or the additive composition containing the accelerator in the solid state of aggregation may also be part of a cement composition, a so-called dry mixture, which can be stored for a long time and is typically packaged in bags or stored in silos and used.
  • the accelerator according to the invention or the additive composition containing the accelerator can also be used for a conventional concrete composition. be added with or shortly before or shortly after the addition of the water.
  • the accelerator or additive composition according to the invention can also be added to the binder and / or to the additives before or after the grinding of the mineral binder and / or of hydraulic additives, e.g. mixed and / or sprayed.
  • the mineral binder may also be at least partially coated with the accelerator or additive containing the accelerator.
  • Another aspect of the present invention relates to a binder composition containing a mineral binder and a setting and hardening accelerator as described above.
  • a flow agent as described above, in particular a polycarboxylate ether is advantageously present.
  • the flow agent with respect to the mineral binder advantageously has a fraction of 0.01-6 wt.%, In particular 0.1-4 wt.%, More preferably 0.2-3 wt.%. Due to the combination of the novel hardening accelerator and the flow agent, the processability of the binder composition can be improved and at the same time higher compressive strengths are achieved. As it has been shown, the flow agent affects the effect of the hardening accelerator hardly or not at all.
  • the binder composition additionally contains solid aggregates, in particular gravel, sand and / or aggregates. Corresponding binder compositions can be used, for example, as mortar mixtures or concrete mixtures.
  • the binder composition additionally contains water, wherein a weight ratio of water to mineral binder is preferably in the range of 0.25-1.0, in particular 0.3-0.6, preferably 0.35-0.5.
  • a weight ratio of water to mineral binder is preferably in the range of 0.25-1.0, in particular 0.3-0.6, preferably 0.35-0.5.
  • Such binder compositions can be processed directly as mortar mixtures or concrete mixtures.
  • An additional aspect of the present invention relates to a molded article obtainable by curing a binder composition as described above after addition of water.
  • the shaped body produced in this way can have virtually any shape and, for example, part of a building, such as, for example, a building, masonry or bridge.
  • the present invention relates to a process for the preparation of a binder composition wherein the at least one accelerator according to the invention is added separately or premixed as additive composition in solid or liquid form to a mineral binder.
  • the present invention relates to a process for accelerating the setting and hardening of mineral binders and mortar or concrete made therefrom.
  • the hardening accelerator or the additive composition according to the invention can be used to accelerate the hardening of mineral salts. see binder compositions, especially cementitious binder compositions.
  • the mineral binder compositions are defined as described above. Further advantageous embodiments of the invention will become apparent from the following embodiments.
  • Inventive accelerators and comparative compounds were prepared according to the preparation processes 1 and 2 described below, the raw materials used were used in accordance with Chapter 1.
  • Preparation Method 1 is based on the admixture of the acidic compound prior to the reaction of the calcium compound CV with the silicon compound SV.
  • a silicon solution SVL1 was prepared by dissolving 20% by weight of the silicon compound SV of Table 1 in pure water. The resulting solution was stirred for 1 minute. The molar ratio of Si0 2 : Na 2 0 is 1 .2.
  • Table 2 Composition of the prepared Caiciumitesen CVL. All percentages in wt .-%.
  • Table 3 gives an overview of the setting and hardening accelerators produced in this way:
  • Table 3 Overview of the setting and hardening accelerator prepared by preparation process 1. All percentages are in% by weight. The viscosities were determined at a temperature of 23 ° C.
  • the column "base” in Table 3 indicates the silicon solutions SVL and calcium solutions CVL used for the preparation.
  • the proportion of the acidic compound refers to the total weight of the particular setting and hardening accelerator after the preparation.
  • the measurement of viscosities was carried out with a rotary viscometer from Brookfield, model RVT. The measurements were carried out at 100 rpm and a temperature of 23 ° C.
  • the solids content of the setting and hardening accelerators produced was consistently 20% by weight.
  • Preparation Method 2 is based on the admixture of the acidic compound after the reaction of the calcium compound CV with the silicon compound SV.
  • a silicon solution SVL1 was prepared as in Production Method 1.
  • the calium solutions CVL.7 ', CVL.8', CVL.9 'as well as CVL.R2', CVL.R3 ', CVL.R4' and CVL.R5 ' were used as well as the corresponding calcium solutions CVL.7, CVL .8, CVL.9 and CVL.R2, CVL.R3, CVL.R4 and CVL.R5 are prepared without addition of the respective acidic compound.
  • Table 4 Overview of the setting and hardening accelerator prepared according to preparation method 2. All percentages are in% by weight. The viscosities were determined at a temperature of 23 ° C.
  • the solids content of the setting and hardening accelerators produced was consistently 20% by weight.
  • a comparison of the data in Tables 3 and 4 also shows that significantly lower viscosities can be achieved with production method 1 than with production method 2. It is noteworthy, for example, to compare accelerators B.7 and B.7 '.
  • the accelerator B.7 produced according to manufacturing method 1 has has a viscosity of only 80 mPas.
  • the corresponding accelerator B.7 'prepared according to production process 2 has a ten times higher viscosity of 800 mPas.
  • the setting and hardening accelerators B.1 - B.12 and ⁇ .1 '- ⁇ .9' produced according to the invention are stable over several months and change their consistency or viscosity only insignificantly. These accelerators are thus storable for a long time and can be easily used at any time in mortar or concrete compositions.
  • the setting and hardening accelerators for the comparative experiments as well as for the experiments according to the invention were mixed in each case with the mixing water for the mortar mixtures, which was then used to stir the mortar mixtures.
  • the setting and hardening accelerators were each used in a concentration of 4.0% by weight, based on the binder.
  • Sika® ViscoCrete®-3081 S is a comb polymer with Polycarboxylat Weggrat and via ester groups bonded polyalkylene oxide side chains.
  • the flow agent was used in a concentration of 1 .0 wt .-%, based on the binder, and also previously admixed to the mixing water.
  • Table 5 Dry composition of the mortar mixtures used (maximum particle size 8 mm).
  • the cement used was Swiss CEM I 42.5 N Normo 4 [Holcim AG / Siggenthal]) with a Blaine fineness of 3,600 cm 2 / g.
  • the sands, limestone filler and cement were dry blended in a Hobart mixer for 1 minute.
  • the mixing water in which the flow agent PCE (1 .0 wt .-% based on cement) and optionally the hardening accelerator was dissolved or dispersed added and mixed for another 2.5 minutes.
  • the total mixing time wet took 3 minutes each.
  • the water / cement value (w / c value) was consistently 0.4.
  • the test for determining the compressive strength (in N / mm 2 ) was carried out on prisms (40 x 40 x 160 mm) according to standard EN 12390-1 to 12390-4.
  • the spread (ABM) of the mortar was determined according to EN 1015-3.
  • the temperature profile of the mortar mixtures was also recorded to control the hydration or the setting behavior of the mortar mixtures after mixing and the time until the occurrence of the global temperature maximum was determined. 3.5 results
  • Table 6 gives an overview of the effect of the various setting and hardening accelerators B.1 - B.12, R.1 - B.R5, ⁇ .1 '- ⁇ .9' and R.2 '- B.R5' in Mortar mixtures (M.1 - M.12, M.R1 - M.R5, ⁇ .1 '- ⁇ .9', M.R2 '- M.R5') with hardening accelerators.
  • R is a reference sample which does not contain a setting-hardening accelerator, but otherwise has an identical composition as the other mixtures.
  • Table 6 Effect of setting and hardening accelerators.
  • the columns “8 h” and “24 h” indicate the compressive strengths after 8 and 24 hours, respectively.
  • the columns “ ⁇ (8h)” and “ ⁇ (24h)” indicate the percentage change in the respective compressive strength relative to the reference sample R.
  • T the time until the occurrence of the global temperature maximum in hours is indicated.
  • the accelerators B.1 - B.9 and B.1 '- B.9' are opposite to the accelerators B.R2 - B.R5 and B.R2 '- B.R5 '(not according to the invention) almost consistently better.
  • the accelerators B.1-B.9 produced according to production method 1 perform better in comparison with the corresponding accelerators B.1 'to B.9' produced according to production method 2.
  • acetic acid as an acidic compound is an optimal choice. This especially in concentrations of 2-8%, especially at concentrations At 4%.

Abstract

L'invention concerne un procédé de préparation d'un accélérateur de prise et de durcissement pour des liants minéraux, consistant à: a) faire réagir un composé calcium (CV) avec un composé silicium (SV), et b) ajouter une composé acide ayant un poids moléculaire de 200 g/mol au plus, notamment de 40 à 100 g/mol.
EP12795001.2A 2011-12-05 2012-12-05 Procédé de préparation d'accélérateurs de durcissement pour des compositions de liants minérales Pending EP2788300A1 (fr)

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EP11191944 2011-12-05
EP12795001.2A EP2788300A1 (fr) 2011-12-05 2012-12-05 Procédé de préparation d'accélérateurs de durcissement pour des compositions de liants minérales
PCT/EP2012/074501 WO2013083627A1 (fr) 2011-12-05 2012-12-05 Procédé de préparation d'accélérateurs de durcissement pour des compositions de liants minérales

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CO (1) CO6970585A2 (fr)
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RU2617852C9 (ru) 2017-08-30
BR112014009938A2 (pt) 2017-05-02
CN103906720B (zh) 2016-12-14
US9145335B2 (en) 2015-09-29
US20140305345A1 (en) 2014-10-16
RU2014114177A (ru) 2016-02-10
RU2617852C2 (ru) 2017-04-28
BR112014009938B1 (pt) 2021-01-26
WO2013083627A1 (fr) 2013-06-13
CO6970585A2 (es) 2014-06-13
CN103906720A (zh) 2014-07-02

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