WO2025156206A1 - Procédé de production de copolymères d'éther de polycarboxylate sous forme de poudre - Google Patents

Procédé de production de copolymères d'éther de polycarboxylate sous forme de poudre

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Publication number
WO2025156206A1
WO2025156206A1 PCT/CN2024/074057 CN2024074057W WO2025156206A1 WO 2025156206 A1 WO2025156206 A1 WO 2025156206A1 CN 2024074057 W CN2024074057 W CN 2024074057W WO 2025156206 A1 WO2025156206 A1 WO 2025156206A1
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WO
WIPO (PCT)
Prior art keywords
aqueous solution
copolymer
process according
mineral binder
binder composition
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
PCT/CN2024/074057
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English (en)
Inventor
Qing Zhang
Jiali ZHU
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 PCT/CN2024/074057 priority Critical patent/WO2025156206A1/fr
Priority to PCT/EP2025/051758 priority patent/WO2025157973A1/fr
Publication of WO2025156206A1 publication Critical patent/WO2025156206A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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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
    • 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
    • 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
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/40—Surface-active agents, dispersants
    • C04B2103/408—Dispersants

Definitions

  • the present invention relates to the process for the production of a powdered dispersant comprising polycarboxylate ether copolymers derived from high molecular weight macromolecules.
  • the present invention also relates to use of such powdered dispersant to increase the early strength and/or to reduce the setting time of a mineral binder composition.
  • Copolymers of ethylenically unsaturated carboxylic acids and ethylenically unsaturated alcohol alkoxylates have been known for many years as dispersion aids for aqueous dispersions, especially for aqueous dispersions of mineral binders. Such copolymers are frequently being called polycarboxylate ethers (PCE) .
  • PCE act as superplasticizers for mineral binders, especially cement, and reduce the water needed to achieve a certain level of fluidity of a given uncured mineral binder composition. A reduction of water in mineral binder compositions, especially in cementitious compositions, is desirable as it leads to less segregation of solid components in the uncured composition and to an increased compressive strength of the cured composition.
  • PCE of various structures and their use as dispersants for mineral binders are well known, for example from EP2687497B1 (Kao Corporation) , WO2010/085425 (W. R. Grace and Company) , and WO2014/139857 (Sika Technology AG) .
  • PCE in a solid form for use in a powdered dispersant for mineral binders has been disclosed in patent literature, for example WO2021/148365A1 (Sika Technology AG) and WO2020/192735A1 (Sika Technology AG) .
  • WO2021/148365A1 Sika Technology AG
  • WO2020/192735A1 Sika Technology AG
  • PCE copolymers can be easily spray-dried into powder.
  • the PCE comprises polyether side chains of high molecular weight such as Mw of 4000 g/mol or higher
  • spray-drying thereof is only possible if additional mineral carrier materials are being added before spray-drying, even where the pH of the PCE solution is adjusted to high values, e.g. higher than 9, before spray-drying.
  • powdered dispersants can be easily obtained by spray drying an aqueous solution of polycarboxylate ether copolymers of different molecular weight.
  • a polycarboxylate ether copolymers of lower molecular weight it was possible to overcome difficulties typically encountered when spray drying a polycarboxylate ether copolymer of higher molecular weight.
  • the present invention relates to a process for the production of a powdered dispersant P, said process comprising the steps of:
  • R 2 H, C1-C12 alkyl
  • a independently of each other is an alkylene group with 2 –8 C atoms
  • R u H, CH 3 ,
  • R w H, CH 3 ,
  • M is selected from H, alkali metal, alkali earth metal, ammonium or organic ammonium group, and having the molar ratios of the monomers (I) : (II) in the range of 1 –5 : 1 –30, preferably 1 –3 : 5 –15, most preferably 1 –1.5 : 1.5 –8.
  • R 1 H, CH 3 ,
  • R 2 H, C1-C12 alkyl
  • a independently of each other is an alkylene group with 2 –8 C atoms
  • n 40 –60, preferably 50 –60, most preferably 50 –55,
  • R w H, CH3,
  • M is selected from H, alkali metal, alkali earth metal, ammonium or organic ammonium group, and having the molar ratios of the monomers (I) : (II) in the range of 1 –5 : 1 –30, preferably 1 –3 : 5 –15, most preferably 1 –1.5 : 1.5 –8.
  • monomeric units of general structure (I) of copolymers A and B carry mixtures of ethylene oxide groups, propylene oxide groups, and/or butylene oxide groups, for example a mixture of ethylene oxide and propylene oxide groups or a mixture of ethylene oxide and butylene oxide groups.
  • groups (A) in the general structure of copolymers A and copolymers B are ethylene groups.
  • Monomeric unit of structure II of copolymers A and B preferably is selected from acrylic acid and/or methacrylic acid.
  • further monomeric units might be contained in the structure of copolymer A selected from styrene, ⁇ -methylstyrene, vinylacetate, isobutylene, diisobutylene, cyclopentadiene, ethylene, propylene, N-vinylpyrrolidone, acrylamide, methacrylamide, methylvinylether, ethylvinylether, allylsulfonic acid, acrylamidomethylpropene sulfonic acid, styrene sulfonic acid, butadiene, acrylonitrile and sodium methylallyl sulfonate.
  • copolymer A selected from styrene, ⁇ -methylstyrene, vinylacetate, isobutylene, diisobutylene, cyclopentadiene, ethylene, propylene, N-vinylpyrrolidone, acrylamide, methacrylamide, methylvinylether, ethy
  • Copolymers of the present invention are obtained by copolymerization of the respective monomers.
  • Copolymerization is a process known to the person skilled in the art.
  • radical polymerization of different monomers is preferred. Suitable conditions for a radical polymerization are for example described in example 1-1 of EP 1103570 (Nippon Shokubai Chem Ind) .
  • Copolymers of the present invention can be statistical copolymers or have a block-wise or gradient arrangement of the monomers. Statistical copolymers are preferred.
  • the molecular weight (Mw) of a copolymer of the present invention can be measured by GPC using PEG as a standard and may be in the range of 5000 –200000 g/mol, preferably 10000 –150000 g/mol.
  • a higher molecular weight within the present context especially is a molecular weight Mw of more than 4000 g/mol, preferably more than 5000 g/mol.
  • a polycarboxylate ether copolymer of high molecular weight Mw thus especially has a molecular weight Mw of at least 4000 g/mol, preferably at least 5000 g/mol.
  • a low molecular weight Mw within the present context means a molecular weight Mw of not more than 3000 g/mol, preferably not more than 2500 g/mol.
  • a polycarboxylate ether copolymer of low molecular weight Mw thus especially has a molecular weight Mw of not more than 3000 g/mol, preferably not more than 2500 g/mol.
  • copolymers of the present invention can be in the form of a dispersion or a solution in a liquid, preferably in water. According to further embodiments, copolymers of the present invention can be in the form of a powder.
  • Powders can be preferred for example, where the copolymers of the present invention are to be mixed with other dry ingredients to form dry concrete or dry mortars.
  • the shelf life of such dry concrete or dry mortar can be improved if the copolymer of the present invention is used therein in powder form.
  • a “dry mortar” within the context of the present invention refers to a composition containing at least one mineral binder as described above and typically aggregates and additives selected from the group of plasticizers, superplasticizers, rheology modifiers, retarders, air-entrainers, de-aerating agents, corrosion inhibitors, fibers, synthetic organic polymers, expansion producing additives, pigments, strength enhancers, waterproofing additives, alkali-aggregate reaction inhibitors, chromate reducers, and/or anti-microbial agents.
  • a dry mortar may contain a small amount of water.
  • a dry mortar has a solid consistency, especially a powdered consistency. Dry mortars are typically pre-batched at a factory and delivered to a job site. Dry mortars can be formulated to be used as repair mortar for concrete, as screeds, renders, coatings, putties, grouts or water plugs, as well as for waterproofing or fireproofing applications.
  • Means to produce powders of copolymers of the present invention are not particularly limited and are known to the person skilled in the art per se. Such means include spray drying, oven drying, flaking, etc.
  • Spray-drying is a known method for producing a dry powder from a liquid by spraying in combination with rapidly drying the solution. Drying can be performed with a hot gas, preferably hot air or hot nitrogen. It is possible that the hot gas is blown in the same direction as the sprayed liquid. It is likewise possible that the hot gas is blown in the opposite direction as the sprayed liquid.
  • the liquid is dispersed with a spray nozzle or an atomizer, the inlet being preferably in the upper part of a spray tower.
  • the dried powder can be separated from the hot gas by means of a cyclone.
  • the aqueous solution of copolymers is pre-heated before entering the spray dryer. If no gas is used for the drying, the copolymer solution can be introduced into the spray dryer at a pressure of between 0.2 and 40 MPa. If a gas is used for the drying, the copolymer solution can be introduced into the spray dryer at ambient pressure. Preferably, drying is carried out with hot air or hot nitrogen, preferably the gas is blown in the same direction as the sprayed liquid.
  • the spray-drying may be carried out at an inlet temperature between 90 and 300°C, preferably between 100 and 200°C, more preferably between 110 and 150°C, especially between 110 and 120°C. A lower inlet temperature has the advantage of lower energy consumption as well as lower tendency for degradation of the copolymers.
  • the outlet temperature may be between 55 and 200°C, preferably between 60 and 150°C, more preferably between 65 and 100°C.
  • the aqueous solution of copolymers can be entered into the spray-dryer by any means known to the person skilled in the art such as nozzles, atomizers, or centrifuges. Any spray-dryer known to the person skilled in the art is suitable to produce a powdered dispersant P of the present invention.
  • the size of the spray-dryer can be selected according to the intended throughput.
  • the step (v) is performed at a spray-dry inlet temperature of not more than 150°C, preferably not more than 120°C.
  • the spray-drying process can be performed continuously or discontinuously.
  • concentration of the PCE-type copolymer in the aqueous solution prior to spray-drying there is no particular limitation as to the concentration of the PCE-type copolymer in the aqueous solution prior to spray-drying. It can, however, be preferred to use an aqueous solution with a concentration of the PCE-type copolymer of at least 20 wt. %, more preferably at least 40 wt. %, and up to 75 wt. %, each based on the total weight of said aqueous solution.
  • the weight ratio of copolymers A/B in the mixed aqueous solution is between 0.5/1 and 15/1, preferably between 1/1 and 11/1, more preferably between 1.5/1 and 9/1, most preferably between 3/1 and 8/1, especially between 6/1 and 7/1.
  • the weight ratio of copolymers A/B is 1: 1.
  • steps (i) – (iv) are done in the same reactor.
  • the pH of the aqueous solution of the copolymers A and B is adjusted to >7, preferably >9, especially >10 prior to spray-drying.
  • Such pH of the aqueous solution of the copolymers used for spray-drying leads to a finer particle size of the powdered dispersant P of the present invention and to a powder with less tendency for caking.
  • a pH ⁇ 7 of the aqueous solution of the copolymers leads to increased stickiness and caking during spray-drying.
  • the pH of the aqueous solution of the copolymers is adjusted according to the number n of repeating units -[AO] -. As the number n increases, the pH needs to be increased to prevent stickiness and caking during spray-drying.
  • the number n is between 90 and 115 and the pH is adjusted to at least 10.
  • the number n is between 50 and 55 and the pH is adjusted to at least 10.
  • the pH is adjusted by the addition of oxides or hydroxides of alkali metals, alkali earth metals or mixtures thereof.
  • the pH of the aqueous solution of the copolymers is adjusted in step (iv) by the addition of LiOH, NaOH, KOH, Mg (OH) 2 , Ca (OH) 2 or mixtures thereof.
  • the base added in step (iv) is NaOH and that the pH is between 12 and 13.
  • the powdered dispersant P may be converted into another solid forms, for example by pressing.
  • the inventive powdered dispersant P may also take the form of a granulate, a shaped block, a tablet or the like.
  • a powdered dispersant P of the present invention shows an alkaline reaction with water.
  • a powdered dispersant P of the present invention can be fully redispersed in water.
  • Such a redispersion in water with a concentration of a powdered dispersant P of the present invention of 40 w% has a pH of at least 8, preferably of at least 10, especially of at least 11.
  • the present invention relates to a mineral binder composition
  • a mineral binder composition comprising a powdered dispersant P, obtainable in a process as described above.
  • the mineral binder composition described above comprises
  • composition described above is characterized in that a mineral binder composition additionally comprises water.
  • a mineral binder composition within the present context is a composition comprising at least one mineral binder.
  • a mineral binder in the context of the present invention, is a binder, which in the presence of water reacts in a hydration reaction to form solid hydrates or hydrate phases.
  • This can be, for example, a hydraulic binder (e.g. cement or hydraulic lime) , a latent hydraulic binder (e.g. slag) , a pozzolanic binder (e.g. fly ash) or a nonhydraulic binder (gypsum plaster or white lime) .
  • a cement having a cement clinker content of ⁇ 35 wt. % is of the type CEM I, II, III, IV or V (according to the 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 35 wt. %, especially at least 65 wt. %.
  • the mineral binder consists to an extent of at least 95 wt. %of a hydraulic binder, in particular cement clinker.
  • the mineral binder composition comprises other binders in addition to or instead of a hydraulic binder.
  • binders in addition to or instead of a hydraulic binder.
  • latent hydraulic binders and/or pozzolanic binders are, for example, slag, fly ash, silica dust, silica fume, rice husk shale, burnt shale, trass, and pumice.
  • the mineral binder contains 5-95 wt. %, in particular 5-65 wt. %, especially 15-35 wt. %, of latent hydraulic and/or pozzolanic binders, relative to the total dry weight of the mineral binder.
  • the mineral binder composition may also be based on calcium sulfate and/or lime as a binder.
  • Calcium sulfate is meant to encompass any of anhydrite, alpha-and beta-calcium sulfate hemihydrate, and calcium sulfate dihydrate.
  • Lime is meant to encompass any of hydraulic lime, air lime, and natural hydraulic lime.
  • Gypsum within the present context can be obtained from different sources, such as e.g. gypsum from natural sources, gypsum from flue gas desulphurization (FGD gypsum) , phosphogypsum, pyro gypsum, and/or fluoro gypsum.
  • sources such as e.g. gypsum from natural sources, gypsum from flue gas desulphurization (FGD gypsum) , phosphogypsum, pyro gypsum, and/or fluoro gypsum.
  • the gypsum comprises calcium sulfate dihydrate, calcium sulfate hemihydrate, and/or anhydrite.
  • Calcium sulfate hemihydrate (CaSO 4 ⁇ 0.5 H 2 O) may be present as ⁇ -hemihydrate or ⁇ -hemihydrate.
  • Anhydrite is in particular anhydrite II and/or anhydrite III.
  • Limestone within the present context stands for calcium carbonate (CaCO 3 ) .
  • the chemical composition of limestone is as defined in standard EN 197-1 (2011) .
  • limestone may also stand for magnesium carbonate, dolomite, and or mixtures of magnesium carbonate, dolomite, and/or calcium carbonate.
  • limestone within the present context is a naturally occurring limestone mainly consisting of calcium carbonate (typically calcite and/or aragonite) but typically also containing some magnesium carbonate and/or dolomite.
  • Limestone may also be a naturally occurring marl.
  • Limestone within the present context, in particular is a ground material that is not heat treated. Especially, the limestone is not decarbonated. According to embodiments, the limestone has a Blaine surface of 3’000 –15’000 cm 2 /g. The Blaine surface is measured as described in standard EN 196-6 (2010) .
  • Fly ash within the present context is a fine powder that is a byproduct of burning pulverized coal.
  • Fly ash is a pozzolan. It comprises aluminous and siliceous material.
  • the fly ash is according to standard JIS 6201 (2015) .
  • fly ash according to other standard, such as ASTM C618 (2022) or EN 450-1 (2012) is also suitable.
  • Slag within the present context especially is iron making slag and/or steelmaking slag.
  • Steel making slag within the present context is a by-product from the steelmaking process.
  • Steel making slag is obtained for example in the Thomas process, the Linz-Donawitz process, the Siemens-Martin process or the electric arc furnace when iron is converted to steel.
  • steel making slag of the present invention is a type of slag which has not been additionally treated in the hot state or during the cooling process. More specifically, steel making slag of the present invention preferentially is not treated with any of fluorspar, Na 2 CO 3 , NaHCO 3 , NaOH, NaCl 2 , CaCO 3 , (NH 4 ) 2 CO 3 , NH 4 HCO 3 or by a steam treatment.
  • a very preferred type of steel making slag within the present context is basic oxygen furnace slag (BOF) , also called basic oxygen slag (BOS) .
  • BOF basic oxygen furnace slag
  • BOS basic oxygen slag
  • GGBS also called GGBFS
  • GGBFS GGBFS
  • a ground granulated blast furnace slag (GGBS) within the present context is obtained by quenching molten iron slag from a blast furnace in water or steam, to produce a glassy, granular product that is then dried and ground into a fine powder.
  • the said mineral binder may also comprise clay.
  • Clay minerals within the present context are solid materials composed to at least 30 wt. %, preferably to at least 35 wt. %, especially to at least 75 wt. %, each relative to its dry weight, of clay minerals.
  • Such clay minerals preferably belong to the kaolin group (such as kaolinite, dickite, nacrite or halloysite) , the smectite group (such as montmorillonite, nontronite or saponite) , the vermiculite group, serpentine, palygorskite, sepiolite, chlorite, talc, pyrophyllite, micas (such as biotite muscovite, illite, glauconite, celadonite, and phengite) or mixtures thereof.
  • Clay minerals belonging to the kaolin group, especially kaolinite, and micas, especially muscovite and illite, as well as mixtures thereof are especially preferred.
  • Clays within the present context can be any type of clays, for example crude clays and/or calcined clays.
  • Crude clays are e.g., clay minerals extracted from a quarry, optionally purified and optionally dried.
  • Calcined clays may be for example low-temperature calcined clays and/or high-temperature calcined clays.
  • Low-temperature calcined clays are clays that have been thermally treated at temperatures between 500 –1200°C.
  • High-temperature calcined clays are clay minerals that have been thermally treated at temperatures above 1200°C and typically between 1300 –1400°C.
  • the present invention relates to mineral binders or mineral binder compositions, especially dry mortars, containing a powdered dispersant P of the present invention.
  • the mineral binder is as defined above.
  • the mineral binder composition may take the form, for example, of a dry composition or of a fluid or stiffened binder composition mixed up with mixing water.
  • the mineral binder composition may also take the form of a fully cured mineral binder composition –for example, a shaped body.
  • the mineral binder composition is a dry composition, for example a dry mortar composition. It is therefore preferable, that the mineral binder composition is essentially free of water.
  • the powdered copolymer P contains further ingredients.
  • such further ingredients are selected from at least one of aggregates, fillers and additives.
  • aggregate refers to mineral materials that are non-reactive in the hydration reaction of mineral binders.
  • Aggregates can be any aggregate typically used for cementitious materials such as concrete, mortars, screeds, renders, grouts, coatings, putties or the like. Typical aggregates are for example rock, crushed stone, gravel, slag, limestone, sand, recycled concrete, perlite or vermiculite.
  • Fillers within the present context are mineral additions of low particle size that have no cementitious properties. Typical fillers are finely ground calcium carbonates.
  • Additives can be any typically used in the concrete or mortar industry.
  • Typical additives include plasticizers, thickeners, retarders, air-entrainers, de-aerating agents, defoamers, corrosion inhibitors, anti-caking agents, antioxidants, fibers, synthetic organic polymers, expansion producing additives, pigments, strength enhancers, waterproofing additives, alkali-aggregate reaction inhibitors, chromate reducers, and/or anti-microbial agents.
  • additives are not polycarboxylate comb polymers.
  • Sand within the present context is a naturally occurring granular material composed of finely divided rock or mineral particles. It is available in various forms and sizes. Examples of suitable sand are quartz sand, limestone sand, river sand or crushed aggregates. Suitable sands are for example described in standards ASTM C778 or EN 196-1.
  • Preferred additives are anti-caking agents and antioxidants which stabilize the powder against thermo-oxidative degradation and self-ignition.
  • Suitable anti-caking agents can be any known to the person skilled in the art.
  • examples for anti-caking agents include powdered cellulose, magnesium stearate, calcium carbonate, dolomite, clay, kaolin, vermiculite, bentonite, talc, slag, fly ash, silicates or aluminosilicates, and silicon dioxide, such as for example fumed silica, precipitated silica, silica gels or silica sols.
  • Suitable antioxidants can be any known to the person skilled in the art. Examples for antioxidants are for example disclosed in WO 00/17263 and include alkylated monophenols, alkylated hydrochinones, alkylidene bisphenols, hydroxylated benzyls, phenol-thiodiphenyl ethers, acylaminophenols, phenolic esters, and phenolic amides.
  • the abovementioned other additives are added before the spray-drying process as this will lead to increased performance of such additives.
  • the additives can be added to the aqueous solution of the PCE-type copolymer prior to spray drying. It is likewise possible to add one or more additives during the spray-drying process, for example via a separate feeding nozzle.
  • the content of such other additives in the powdered copolymer P is less than 5 wt. %, especially less than 1 wt. %, each based on the total weight of said mineral binder composition.
  • the resulting powder product may be sieved in order to remove small agglomerates, which might potentially be formed.
  • a mineral binder or mineral binder composition containing a powdered dispersant P as described above has increased flowability, reduced slump loss and water demand, increased compressive strength, especially at early age, when compared to the same mineral binder or mineral binder composition with a comparative powdered dispersant.
  • the present invention relates to the use of a powdered dispersant P prepared in a process described above to increase the early strength of a mineral binder composition.
  • a powdered dispersant P prepared in a process described above can be used to reduce the water demand of a mineral binder composition.
  • a powdered dispersant P prepared in a process described above can be used to increase the flowability of a mineral binder composition.
  • a powdered dispersant P prepared in a process described above can be used to improve the slump retention of a mineral binder composition.
  • slump retention refers to the ability of a concrete mix to maintain its desired level of workability over a specific period, typically from the time of mixing to the time of placement.
  • Copolymers of the present invention have the effect of retaining the slump and/or slump flow of a mineral binder composition over long periods of time. Especially the slump and/or slump flow of a mineral binder composition comprising an inventive copolymer is retained over longer periods of time as compared to the same mineral binder composition but comprising a polycarboxylate ether type copolymer that is not according to the invention. Thus, copolymers of the present invention are used as an admixture for mineral binder compositions to increase the slump retention and/or slump flow retention thereof.
  • a powdered dispersant P prepared in a process described above can be used to reduce the setting time of a mineral binder composition.
  • Concrete setting time refers to the period it takes for freshly mixed concrete to change from a liquid state to a solid state.
  • Setting time refers to the period it takes for a cementitious material to change from a liquid, workable state to a solid state.
  • the setting time is the time it takes from the addition of mixing water to a dry cementitious material until the mixed, wet cementitious does not show plastic behavior anymore.
  • the setting process involves a chemical reaction known as hydration, where the cement particles react with water to form a solid matrix. This process is crucial for the development of strength and durability in the concrete.
  • There are several methods to measure the concrete setting time e.g., by means of the manual Vicat apparatus according to the standard GB/T 1346 (2011) “Test methods for water requirement of normal consistency, setting time and soundness of the Portland cement” .
  • a powdered dispersant P prepared in a process described above can be used to increase the compressive strength of a mineral binder composition.
  • the polymer powder A2 was prepared as polymer powder A1 above but instead of polymer P1, polymer P2 was used.
  • the polymer powder A3 was prepared as polymer powder A1 above but instead of polymer P1, polymer P3 was used.
  • the polymer powder A4 was prepared as polymer powder A1 above but with 200 g of polymer P4 and without addition of P1.
  • the polymer powder R1 was prepared as polymer powder A1 above but 200 g of polymer P1 was used.
  • the polymer powder R2 was prepared as polymer powder R1 above but 200 g of polymer P2 was used.
  • the polymer powder R3 was prepared as polymer powder R1 above but 200 g of polymer P3 was used.
  • Examples A1, A2, A3 are according to the present invention, while examples A4, R1, R2 and R3 are not according to the present invention.
  • Microconcrete was prepared by mixing 570 g of Portland Cement (Jinfeng P. O 42.5) , 1265 g of sand, 180 g of fly ash type I (according to GB/T 1596-2017) and 245 g of water. The amount of the respective polymer powder as indicated in below table 2, in each case relative to the weight of cement, was added to this mix.
  • Examples M1, M2 and M3 are according to the present invention, while example M-Ref1 is not according to the present invention.
  • the slump flow of the inventive powdered dispersants was generally comparable to the non-inventive powdered dispersants (results not disclosed) .

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  • Ceramic Engineering (AREA)
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  • Organic Chemistry (AREA)
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  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

La présente invention concerne le procédé de production d'un dispersant en poudre comprenant des copolymères d'éther de polycarboxylate dérivés de macromolécules de poids moléculaire élevé (≥ 4 000 g/mol). Ces mélanges de copolymères selon l'invention peuvent être séchés par pulvérisation sans formation d'agglomérats. La présente invention concerne également l'utilisation d'un tel dispersant en poudre pour augmenter la résistance précoce et/ou réduire le temps de prise d'une composition de liant minéral.
PCT/CN2024/074057 2024-01-25 2024-01-25 Procédé de production de copolymères d'éther de polycarboxylate sous forme de poudre Pending WO2025156206A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000017263A1 (fr) 1998-09-24 2000-03-30 Skw Bauchemie Gmbh Poudres polymeres hydrosolubles et stabilisees, a base de carboxylates de polyoxyalkyleneglycol et procedes de preparation desdites poudres
EP1103570A2 (fr) 1999-11-29 2001-05-30 Nippon Shokubai Co., Ltd. Copolymère pour compositions de ciment leur procédé de fabrication et utilisation
JP2001302306A (ja) * 2000-04-20 2001-10-31 Nippon Shokubai Co Ltd セメント分散剤
WO2010085425A1 (fr) 2009-01-21 2010-07-29 W. R. Grace & Co.-Conn. Polycarboxylate robuste contenant des liaisons éther pour une préparation par broyage de matières à base de ciment
WO2011089085A1 (fr) * 2010-01-21 2011-07-28 Basf Construction Polymers Gmbh Agent de dispersion
WO2014139857A1 (fr) 2013-03-13 2014-09-18 Sika Technology Ag Utilisation d'éthers de polycarboxylates en combinaison avec d'autres additifs pour le broyage de ciment
EP2687497B1 (fr) 2011-03-15 2018-08-08 Kao Corporation Agent dispersant pour des compositions hydrauliques
WO2020192735A1 (fr) 2019-03-26 2020-10-01 Sika Technology Ag Préparation de poudre de réduction à haute teneur en eau pour mortier sec
WO2021148365A1 (fr) 2020-01-23 2021-07-29 Sika Technology Ag Procédé de préparation d'agents de dispersion sous forme solide et leur utilisation dans des compositions de liant minéral
WO2024012776A1 (fr) * 2022-07-12 2024-01-18 Sika Technology Ag Copolymères de carboxylates et de polyéthers comprenant des chaînes latérales polyéther de longueur différente, et leur utilisation dans des compositions de liants minéraux

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000017263A1 (fr) 1998-09-24 2000-03-30 Skw Bauchemie Gmbh Poudres polymeres hydrosolubles et stabilisees, a base de carboxylates de polyoxyalkyleneglycol et procedes de preparation desdites poudres
EP1103570A2 (fr) 1999-11-29 2001-05-30 Nippon Shokubai Co., Ltd. Copolymère pour compositions de ciment leur procédé de fabrication et utilisation
JP2001302306A (ja) * 2000-04-20 2001-10-31 Nippon Shokubai Co Ltd セメント分散剤
WO2010085425A1 (fr) 2009-01-21 2010-07-29 W. R. Grace & Co.-Conn. Polycarboxylate robuste contenant des liaisons éther pour une préparation par broyage de matières à base de ciment
WO2011089085A1 (fr) * 2010-01-21 2011-07-28 Basf Construction Polymers Gmbh Agent de dispersion
EP2687497B1 (fr) 2011-03-15 2018-08-08 Kao Corporation Agent dispersant pour des compositions hydrauliques
WO2014139857A1 (fr) 2013-03-13 2014-09-18 Sika Technology Ag Utilisation d'éthers de polycarboxylates en combinaison avec d'autres additifs pour le broyage de ciment
WO2020192735A1 (fr) 2019-03-26 2020-10-01 Sika Technology Ag Préparation de poudre de réduction à haute teneur en eau pour mortier sec
WO2021148365A1 (fr) 2020-01-23 2021-07-29 Sika Technology Ag Procédé de préparation d'agents de dispersion sous forme solide et leur utilisation dans des compositions de liant minéral
WO2024012776A1 (fr) * 2022-07-12 2024-01-18 Sika Technology Ag Copolymères de carboxylates et de polyéthers comprenant des chaînes latérales polyéther de longueur différente, et leur utilisation dans des compositions de liants minéraux

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