EP2205539A1 - Additif pulvérulent et son procédé de préparation - Google Patents

Additif pulvérulent et son procédé de préparation

Info

Publication number
EP2205539A1
EP2205539A1 EP08839614A EP08839614A EP2205539A1 EP 2205539 A1 EP2205539 A1 EP 2205539A1 EP 08839614 A EP08839614 A EP 08839614A EP 08839614 A EP08839614 A EP 08839614A EP 2205539 A1 EP2205539 A1 EP 2205539A1
Authority
EP
European Patent Office
Prior art keywords
additive
layer
inner layer
innermost layer
layers
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Withdrawn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
EP08839614A
Other languages
German (de)
English (en)
Inventor
Urs Mäder
Norman Blank
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 EP08839614A priority Critical patent/EP2205539A1/fr
Publication of EP2205539A1 publication Critical patent/EP2205539A1/fr
Withdrawn legal-status Critical Current

Links

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
    • C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
    • C04B20/10—Coating or impregnating
    • C04B20/12—Multiple coating or impregnating
    • 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
    • C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
    • C04B20/10—Coating or impregnating
    • C04B20/1018—Coating or impregnating with organic materials
    • 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
    • C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
    • C04B20/10—Coating or impregnating
    • C04B20/1018—Coating or impregnating with organic materials
    • C04B20/1029—Macromolecular compounds
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/91—Use of waste materials as fillers for mortars or concrete

Definitions

  • the invention is based on a powdery additive according to the preamble of the first claim.
  • the invention is also based on a process for the preparation of a powdery additive according to the preamble of the method claim.
  • Admixtures have long been known and can have various functions such as air entrainers, retarders, accelerators, stabilizers, chromate reducers, Einpress Anlagenn, foaming agents, sealants, recycling aids, liquefiers and flow agents. These additives can be used liquid or dried as a powder and are used in particular in hydraulic binders.
  • Polycondensates such as sulfonated naphthalene condensates, sulfonated melamine condensates, lignin sulfonates are used as plasticizers to improve the processability and the time-dependent flow behavior of hydraulic binders such as cement, mortar, gypsum and concrete.
  • These water-reducing agents are capable of improving the flowability of such blends, but such flowability can not normally be maintained for a sufficiently long period of time. When As a result, additional amounts of water-reducing agents must be added at certain intervals. However, this multiple dosing is not desirable because it is technically difficult to perform.
  • EP 0 845 444 A1 discloses a concrete additive which comprises a mixture of a lignosulfonate and a water-soluble copolymer of vinyl acetate and an N-substituted maleamic acid and which serves as superplasticizer.
  • the mixture of lignin sulfonate and copolymer to prevent the lignin sulfonate must be added at several intervals. This approach gives good results, but the consumption of the components is relatively high.
  • Polyalkylene glycol carboxylates in the following polycarboxylates, have been used for some years as dispersants for aqueous dispersions. They dramatically reduce the water content of these dispersions, especially in hydraulic binder systems. Originally, these polymers were prepared in aqueous solution and used as aqueous polymer solutions. The disadvantage of these solutions, however, are high transport costs, since a high proportion of solvent must be transported, further it can lead to bacterial attack, resulting in a limited shelf life.
  • polycarboxylates are used as powders, either by drying the polycarboxylates present in aqueous solution or by the preparation of solid polycarboxylates, for example from WO 03/080714 A1.
  • Such powders, or solids have the technical advantage over aqueous solutions that significantly lower costs are incurred during transport, the storage stability is significantly higher because of lower biological infestation or lower cleavage of possible ester bonds in the modified polycarboxylates and the sensitivity to frost is significantly reduced.
  • Such polycarboxylates show in many respects the better properties than previous liquefiers. However, since these polycarboxylates can be relatively expensive, attempts are made to admit as little as possible of them. Likewise, not all required properties of only a polycarboxylate or mixtures thereof, so that other suitable liquefier must be used
  • the invention has for its object to provide an additive in a powdery additive of the type mentioned above, which avoids the disadvantages mentioned above, i. to provide an inexpensive additive, which is not in several
  • the core of the invention is therefore that the powdery particles of the additive have one or more inner layer (s) and an outer layer of a material which acts as an additive.
  • Condenser can be used, through which the basic liquefaction is achieved. This is preferably absorbed faster than the inner layer (s).
  • the outer layer dissolves first and gives a first liquefaction until homogeneous mixture.
  • the active sites of the hydraulic binder, the cement grain are saturated. This requires less of the inner layer and thus increases the efficiency of the inner layer. If the inner layer is a more expensive condenser, much cheaper additives can be produced over the conventional method. Continue by achieved a better distribution of the condenser in the hydraulic binder and there are no local overdoses, also by a time delay of the mode of action can be achieved.
  • air entrainers, retarders, accelerators, stabilizers, chromate reducers, injection aids, foaming agents, sealants, recycling aids as inner layer or inner layers of the multilayer powder can thus be introduced into the hydraulic binder.
  • Fig. 2 shows schematically the dissolution rate of the admixture of Fig. 1;
  • FIG. 4 shows schematically the dissolution rate of the additive according to FIG. 3.
  • an additive is prepared having at least two layers of condensers.
  • Fig. 1 such an additive 1, which has two layers, is shown schematically. It has at least one inner layer with a first one
  • the outer second condenser 3 and then the inner first condenser 2 are dissolved according to the dissolution diagram in Fig. 2, first. In a transitional area, both condensers can be released together.
  • the layers shown in Fig. 1 and the other figures show only a schematic representation.
  • the thickness and shape of the layers is arbitrary and in particular the thickness is adapted to the corresponding amount of material to be dispensed.
  • the layers need not be closed, so that in part the inner layers can lie directly on the surface.
  • plasticizer and plasticizer for hydraulic binders such as concrete, mortar and gypsum
  • plasticizer and plasticizer for hydraulic binders such as concrete, mortar and gypsum
  • naphthalene sulfonate, lignin sulfonate, melamine sulfonate, polycarboxylates, polyacrylates, etc. may be used.
  • Naphthalene sulfonate has the variants sodium naphthalene sulfonate, calcium naphthalene sulfonate and causes very good liquefaction and gives high early strength.
  • Such products are known to the person skilled in the art and are described, for example, in US Pat. No. 3,537,869 and EP 0 214 412 A1.
  • Lignosulfonate is a waste product of the cellulose industry, variants are sodium lignosulfonate, calcium lignin sulfonate, magnesium lignosulfonate.
  • Lignosulfonate is made from cellulose by hydrolysis and sulfonation. Lignosulfonate causes a good liquefaction at low dosage, the residual sugar may have a retarding effect.
  • Such products are known in the art and described for example in DE 32 04 326 A1.
  • Melamine sulphonate also has a very good liquefaction. Such products are known to the person skilled in the art and are described, for example, in DE 1 671 017 OS.
  • Particularly preferred high-performance plasticizers and flow agents consist of polycarboxylates.
  • Polycarboxylates are comb polymers which consist of a main chain to which carboxylic acid groups are bonded as free acids or in the form of their salts, and side chains of polyalkylene oxide.
  • Such polycarboxylates are known per se, for example from EP 1 136 508 A1, EP 1 138 696 A1 and EP 1 138 697 A1 of the Applicant. The disclosure of these polycarboxylates is included below.
  • Such polycarboxylates are sold under the name ViscoCrete ®.
  • the polyalkylene oxide or polyalkylene glycol side chains may be attached to the backbone via ester linkage, amide linkage or ether linkage.
  • other functional or non-functional groups may be attached to the main chain.
  • Such comb polymers can be prepared for example by Copolymehsation of unsaturated mono- or di-carboxylic acids with unsaturated carboxylic acid esters, unsaturated carboxylic acid amides, allyl ethers or vinyl ethers.
  • the carboxylic acids in the finished comb polymer can be present in the form of their free acid or completely or partially in the form of their salts.
  • the comb polymers can also be prepared by polymer-analogous reactions.
  • a polymer which is latent or free Carboxyl groups containing one or more compounds which contain amine or hydroxyl functions are reacted under conditions which lead to partial amidation or esterification of the carboxyl groups.
  • the polyalkylene glycol of the side chain is based on polymerized epoxide-containing compounds, such as ethylene oxide, propylene oxide, 1-butene oxide, phenylethylene oxide, etc.
  • the polyether side chain thus consists of polyethylene oxide or polypropylene oxide or a mixed copolymer of ethylene oxide and propylene oxide and has at the free end a hydroxyl group, a primary amino group or an alkyl group having 1 to 20 carbon atoms which is linear, branched or cyclic, preferably a linear alkyl group having 1 to 4 carbon atoms.
  • These polycarboxylates have a molecular weight of 50,000 to 200,000, preferably 8,000 to 100,000, particularly preferably a molecular weight of 10,000 to 80,000.
  • the Cabonklasalze can alkali metal or alkaline earth metal salts or salts of other di- or trivalent metal ions,
  • Ammonium ions organic ammonium groups or mixtures.
  • the polycarboxylate according to the invention consists of four structural units (a, b, c and d) and has the structural formula A.
  • R 3 -NH 2 , -NR 5 R 6 , -OR 7 NR 8 R 9 , wherein R 5 and R 6 are independently a Ci to C 2 o alkyl, cycloalkyl-I or alkylaryl or aryl group or a hydroxyalkyl group , such as hydroxyethyl, hydroxypropyl, hydroxybutyl, or a
  • 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 is a part, to form a morpholine or imidazoline ring, wherein R 7 a C 2 -C 4 -alkylene group and R 8 and R 9 independently of one another a C 1 -C 20 -alkyl-, cycloalkyl-,
  • Alkylaryl or aryl group or a hydroxyalkyl group such as
  • sequence of building blocks a, b, c, d can be block-wise, alternating or random.
  • Polycarboxylates according to the formula A can be imagined to be composed of a main chain of polymerized units of acrylic acid and
  • Methacrylic acid or a mixed copolymer thereof Methacrylic acid or a mixed copolymer thereof.
  • the polyalkylanoxide Side chains are linked to this backbone via ester or amide groups.
  • further groups may be bonded via the ester or amide bond on the main chain of the polycarboxylates, for example alkyl groups, cycloalkyl groups, aromatics, substituted aromatics, hydroxyalkyl groups, dialkylaminoalkyl groups or heterocyclic rings in which the N of the amide group is an ingredient, such as morpholine or imidazole.
  • groups R 3 which are bonded via their N as amides to the main chain are amine radicals which have one or two independent aliphatic, cycloaliphatic or aromatic radicals of 1 to 20 carbon atoms, such as, for example, methyl, ethyl, propyl, isobutyl. Propyl, - butyl, iso-butyl or cyclohexyl radicals. Examples of such amine radicals are dibutylamine or dicyclohexylamine. Further examples are amine radicals with hydroxyalkyl groups such as ethanolamine or diethanolamine.
  • groups R 3 attached via their O as esters to the main chain are aliphatic, cycloaliphatic or aromatic radicals of 1 to 20 carbon atoms, such as methyl, ethyl, propyl, iso-propyl, butyl, iso Butyl or cyclohexyl radicals.
  • Further examples are aminoalcohol radicals such as methyldiethanolamine, triisopropanolamine, triethanolamine, dibutylaminoethanol, diisopropanolamine, diethylaminoethanol, dimethylaminoethanol.
  • the first and second condenser may be of different categories such as polycarboxylate and lignin sulfonate or of the same category, i.
  • polycarboxylate as the first plasticizer in the inner layer and naphthalene sulfonate, lignin sulfonate or melamine sulfonate as second plasticizer in the outer layer Lignosulfonate, used.
  • the sulphonated condenser achieves the basic liquefaction.
  • the lignin sulfonate absorbs faster than the polycarboxylate.
  • the lignosulfonate first dissolves and gives a first liquefaction until homogeneous mixing and the active sites of the cement grain are saturated. This will be less
  • Polycarboxylate needed and thus increases the efficiency of Polycarboxylat.es. Furthermore, a better distribution of the liquefier in the hydraulic binder is achieved, and there are no local overdoses.
  • a further additive with additional layers is shown schematically. It has an outer layer with a second condenser 3, followed by a second intermediate layer 6, followed by the first condenser 2, then a first intermediate layer 5 and completely inside a further layer 4, in the following innermost layer or core called.
  • this multi-layered additive 1 according to the dissolution diagram in Fig. 4, first the outer layer, i. the second condenser 3, then the second intermediate layer 6, then the inner layer, i. the first condenser 2, then the first intermediate layer 5 and optionally, shown in phantom, the innermost layer 4 dissolved.
  • Transition areas can each be released two consecutive layers with each other.
  • first intermediate layer 5 and / or the second intermediate layer 6 and / or the innermost layer 4 can be omitted, or even further layers can be additionally arranged.
  • the additional intermediate layers and the innermost layer can consist of any materials. Particularly preferred are additives such as air entraining agents, retarders, accelerators, stabilizers, chromate reducers, injection aids, foaming agents, sealants, recycling aids and of course plasticizers and flow agents or mixtures of the aforementioned additives.
  • additives such as air entraining agents, retarders, accelerators, stabilizers, chromate reducers, injection aids, foaming agents, sealants, recycling aids and of course plasticizers and flow agents or mixtures of the aforementioned additives.
  • the intermediate layers and the innermost layer can also be made of any other materials, such as polyvinyl alcohol PVA.
  • the intermediate layer serves on the one hand to control the delivery and dissolution of the condenser layers and on the other hand to deliver additional additives in the hydraulic binder.
  • the arrangement of PVA as layer 6 between polycarboxylate as the first condenser layer 2 and lignin sulfonate as the second condenser layer 3 delays the release of the polycarboxylate.
  • any material can be used. These may be the above-mentioned materials or in principle all substances used for the production of the concrete, in particular cement particles. It is also possible to use substances or additives, such as, for example, silica fume, fly ash, light aggregate, slag, fiber materials, e.g. organic such as polypropylene fibers, etc. or inorganic such as basalt, glass, etc. may be used. For example, fly ash of different origin has different adsorption properties and thus has different properties depending on the origin in the concrete. Coating with additives results in identical and more adapted properties, so that the different origin no longer has to be considered.
  • a mineral carrier material as described in WO 00/47533 A1 can also be used as the innermost layer.
  • These support materials can be coated according to the disclosure of WO 00/47533 A1 with a first layer of polycarboxylate and give a free-flowing powder. This is then provided according to the invention with further layers.
  • the methods used to construct the layers are known to the person skilled in the art. Such coating methods are described, for example, in WO2006 / 027363 A1, the disclosure of which is hereby incorporated by reference is.
  • the coating can be done for example in a DC mixer, a countercurrent mixer or a fluidized bed mixer with rotary atomizer.
  • the coated particulate additives according to the invention are prepared, for example, by treating a powdery innermost layer with the coating substances, which as a rule consist of an aqueous solution or suspension of the constituents of this coating substance, and then drying.
  • the coating substances which as a rule consist of an aqueous solution or suspension of the constituents of this coating substance, and then drying.
  • the innermost layers, ie cores, in the fluidized bed are sprayed with the coating material while maintaining a fluidized bed temperature of 30 to 100 ° C. and dried simultaneously or subsequently. If several layers are applied, the aqueous solutions or dispersions of the coating materials are sprayed one after the other.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Soil Conditioners And Soil-Stabilizing Materials (AREA)
  • Package Frames And Binding Bands (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)

Abstract

L'invention se rapporte à un additif pulvérulent (1) destiné notamment à des liants hydrauliques dans lequel les particules de poudre (1) de l'additif présentent une couche interne (2) et une couche externe (3) de matériau agissant comme un additif.
EP08839614A 2007-10-19 2008-10-17 Additif pulvérulent et son procédé de préparation Withdrawn EP2205539A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP08839614A EP2205539A1 (fr) 2007-10-19 2008-10-17 Additif pulvérulent et son procédé de préparation

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP20070118886 EP2050729A1 (fr) 2007-10-19 2007-10-19 Additif en poudre et procédé pour sa préparation
EP08839614A EP2205539A1 (fr) 2007-10-19 2008-10-17 Additif pulvérulent et son procédé de préparation
PCT/EP2008/064020 WO2009050255A1 (fr) 2007-10-19 2008-10-17 Additif pulvérulent et son procédé de préparation

Publications (1)

Publication Number Publication Date
EP2205539A1 true EP2205539A1 (fr) 2010-07-14

Family

ID=38754748

Family Applications (2)

Application Number Title Priority Date Filing Date
EP20070118886 Withdrawn EP2050729A1 (fr) 2007-10-19 2007-10-19 Additif en poudre et procédé pour sa préparation
EP08839614A Withdrawn EP2205539A1 (fr) 2007-10-19 2008-10-17 Additif pulvérulent et son procédé de préparation

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP20070118886 Withdrawn EP2050729A1 (fr) 2007-10-19 2007-10-19 Additif en poudre et procédé pour sa préparation

Country Status (2)

Country Link
EP (2) EP2050729A1 (fr)
WO (1) WO2009050255A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2298710A1 (fr) * 2009-09-21 2011-03-23 Sika Technology AG Additif pour liant minéral
FR2960537A1 (fr) * 2010-05-25 2011-12-02 Francais Ciments Superplastifiant a base de nanoparticules minerales a surface modifiee pour mortier et beton
FR2960538A1 (fr) * 2010-05-25 2011-12-02 Francais Ciments Agent anti-retrait a base de nanoparticules minerales a surface modifiee pour mortier et beton

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2200163B2 (de) * 1972-01-04 1975-06-12 Gebr. Knauf Westdeutsche Gipswerke, 8715 Iphofen Verfahren zur Zugabe von HilfsStoffen zu Trockenmörteln oder Spachtelpulvern
DE10209698A1 (de) * 2002-03-06 2003-09-18 Sachtleben Chemie Gmbh Verfahren zur Herstellung von gecoateten, feinteiligen, anorganischer Festkörpern und deren Verwendung
DE102004006145A1 (de) * 2004-02-07 2005-08-25 Merck Patent Gmbh Partikel mit funktionellem Multilayeraufbau
JP2008512268A (ja) * 2004-09-06 2008-04-24 シーカ・テクノロジー・アーゲー 水硬性組成物のための被覆塩基性材料の製造方法、水硬性組成物のための被覆塩基性材料、水硬性組成物のための添加剤および水硬性組成物の製造方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2009050255A1 *

Also Published As

Publication number Publication date
WO2009050255A1 (fr) 2009-04-23
WO2009050255A9 (fr) 2010-01-21
EP2050729A1 (fr) 2009-04-22

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