EP4065537A1 - Copolymères ramifiés utiliés en tant qu'additifs pour la réduction de la viscosité de compositions de liant minéral - Google Patents

Copolymères ramifiés utiliés en tant qu'additifs pour la réduction de la viscosité de compositions de liant minéral

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Publication number
EP4065537A1
EP4065537A1 EP20808466.5A EP20808466A EP4065537A1 EP 4065537 A1 EP4065537 A1 EP 4065537A1 EP 20808466 A EP20808466 A EP 20808466A EP 4065537 A1 EP4065537 A1 EP 4065537A1
Authority
EP
European Patent Office
Prior art keywords
mineral binder
particularly preferably
copolymers
alkyl
range
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
EP20808466.5A
Other languages
German (de)
English (en)
Inventor
Jürg WEIDMANN
Jörg ZIMMERMANN
Lukas Frunz
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
Publication of EP4065537A1 publication Critical patent/EP4065537A1/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
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/24—Macromolecular compounds
    • C04B24/28—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B24/32—Polyethers, e.g. alkylphenol polyglycolether
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/24—Macromolecular compounds
    • C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B24/2641—Polyacrylates; Polymethacrylates
    • C04B24/2647—Polyacrylates; Polymethacrylates containing polyether side chains
    • 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
    • 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
    • C04B28/021—Ash cements, e.g. fly ash cements ; Cements based on incineration residues, e.g. alkali-activated slags from waste incineration ; Kiln dust 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
    • C08G65/22—Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring
    • C08G65/24—Epihalohydrins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
    • C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
    • C08G65/2609—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2618—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2618—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen
    • C08G65/2621—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen containing amine groups
    • C08G65/2624—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen containing amine groups containing aliphatic amine groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2618—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen
    • C08G65/2633—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen the other compounds containing amide groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides
    • 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
    • C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
    • C04B2103/34—Flow improvers
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00034—Physico-chemical characteristics of the mixtures
    • C04B2111/00103—Self-compacting mixtures

Definitions

  • the invention relates to the use of branched copolymers as additives for increasing the flow rate and for reducing the viscosity of a mineral binder composition.
  • Another aspect of the invention relates to a mineral binder composition and a cured molded body containing the branched copolymer.
  • Dispersants or superplasticizers are used in the construction industry as liquefiers or water-reducing agents for binder compositions such as concrete, mortar, cement, plaster and lime.
  • Organic polymers which are added to the mixing water or added as a solid to the binder compositions, are generally used as dispersants.
  • dispersants are generally used as dispersants.
  • the choice and dosage of a suitable dispersant depends in particular on the specific composition, the processing technique or the intended use of the binder composition. Especially with special binder compositions, such as special concretes or special mortars, this is a demanding task.
  • Special concretes include, in particular, concretes with a low
  • Ratio of water / mineral binder are produced, i.e. contain little water in relation to the mineral binder.
  • Such concretes are in particular high-strength concretes (high performance conrete - HPC), ultra-high-strength concretes (ultra high performance conrete - UH PC) and / or self-compacting concretes (self-compacting concrete - SCC).
  • a major advantage of SCC is that it flows quickly and without segregation, purely due to gravity, fills cavities automatically and ventilates without applying compression energy. A vibration like conventional concrete is therefore not necessary. Self-compacting concrete is therefore particularly advantageous when high installation capacities are required, with demanding geometric shapes, with close-meshed reinforcement, with low component thicknesses or in situations in which the application of additional compaction energy is difficult or impossible.
  • PCE polycarboxylate ethers
  • EP 2 986580 therefore describes the use of special PCEs to increase the flow rate and / or to reduce the viscosity of mineral binder compositions.
  • the comb polymers are characterized by a low molar mass of the side chain and a low molar ratio of side chains to acid groups in the polymer backbone.
  • these PCE also reduce the water requirement of mineral binders and have a retarding effect.
  • WO 2010/112775 describes branched polyethers with phosphonic acid end groups, the branching taking place through the incorporation of a nitrogen group into the polymer structure.
  • the polyethers described reduce the viscosity of fresh concrete.
  • these polyethers usually have to be dosed in high amounts, especially in the case of concretes with a low w / w ratio, and yet have little influence on the flow limits or that Have flow rate and often have strong retarding and water-reducing properties.
  • EP 2 964 586 describes copolymers as dispersants for mineral binders, the copolymers containing units which are derived from (i) an ethylenically unsaturated acid and (ii) an ethylenically unsaturated, branched polyether macromonomer.
  • These dispersants have the disadvantage that they are made using epichlorohydrin, which is difficult to handle.
  • these copolymers often lead to an undesirable additional entry of air and also to a reduction in the water requirement of the mineral binder.
  • the object of the present invention is to provide additives for mineral binder compositions, in particular for concretes or mortars with a low w / w ratio, which allow a targeted increase in the flow rate and a reduction in the viscosity of mineral binder compositions. If possible, further properties of the mineral binder compositions, in particular the slump, the slump or the flow limit, should remain unchanged.
  • the additive should also preferably be usable together with other additives, in particular with liquefiers such as PCE. It has surprisingly been found that this object can be achieved through the use of copolymers as additives according to claim 1.
  • the present invention therefore relates to the use of copolymers as additives to increase the flow rate and to reduce the viscosity in mineral binder compositions, wherein the copolymers can be prepared in a multistage process comprising the steps
  • step 3 optional reaction of the reaction product from step 2) with an alkoxylating agent.
  • a particular advantage of the use of copolymers according to the invention as additives in mineral binder compositions is the increase in the flow rate or the reduction in the viscosity of the compositions with almost unchanged slump or slump compared to mineral binder compositions without the copolymer according to the invention but otherwise the same composition.
  • the increase in the flow rate or the reduction in the viscosity can be achieved with an almost unchanged slump and / or slump in mineral binder compositions with a low w / w ratio.
  • copolymers according to the invention are less segregation or separation of the constituents of the mineral binder composition, less undesirable air entry, and the copolymers do not have any significant water-reducing capacity.
  • the latter is particularly important, since copolymers according to the invention are so with known ones Water reducing agents, for example super liquefiers such as lignosulphonates, polynaphthalene sulphonates, polymelmamine sulphonates and / or polycarboxylate ethers, can be combined in existing recipes without having to adjust the dosage of the water reducing agent.
  • copolymers according to the invention are distinguished by a simple one
  • a first aspect of the invention relates to the use of copolymers as additives to increase the flow rate and to reduce the viscosity of mineral binder compositions, the copolymers being produced in a multistage process comprising the steps
  • a copolymer according to the invention increases the flow rate of the mineral binder composition and reduces its viscosity.
  • copolymers according to the invention do not, or at least not significantly, contribute to reducing the water requirement of the mineral binder composition.
  • a reduction in the flow time or funnel flow time in accordance with DIN EN 12350-9 and / or a reduction in the flow time in accordance with JSCE-F 541-1999 is used as a measure of the reduction in viscosity.
  • Another measure for the reduction in viscosity is in the present case an increase in the flow rate measured in accordance with Swiss standard SIA 262.238 or as tsoo in accordance with Japanese standard JIS A1150.
  • An increased flow rate therefore means a lower viscosity of a mineral binder composition.
  • the term water requirement is understood to mean the amount of water that is required to set a certain slump, measured in accordance with the DIN EN 12350-5 standard, for a given binder composition.
  • a mineral binder composition made up with water which contains these copolymers accordingly shows an increased flow rate and lower viscosity but no additional increase in the slump, in each case in comparison with the same mineral binder composition used with the same Amount of water has been made up, but does not contain any copolymer.
  • the composition flows faster after addition of the inventive copolymer and has a lower viscosity than an analogous composition that does not contain the copolymer, or than an analogous composition that contains a copolymer not according to the invention, such as a polycarboxylate ether (PCE) .
  • PCE polycarboxylate ether
  • the copolymer When used according to the invention and at a dosage of 0.01-10% by weight, in particular 0.1-7% by weight or 0.2-5% by weight, based in each case on the total weight of mineral binder, the copolymer preferably influences the slump according to DIN EN 12350-5 and / or the slump according to DIN EN 12350-2 of the mineral binder composition by less than 15%, in particular less than 10%, preferably less than 5%, in particular less than 3% or less than 2%.
  • Copolymers according to the invention can be prepared in a multistage process comprising the steps
  • reaction product from step 1) with glycidol or epichlorohydrin or a mixture of glycidol and an alkoxylating agent or a mixture of epichlorohydrin and an alkoxylating agent, 3 ) optional reaction of the reaction product from step 2) with a
  • the individual steps of the process are preferably carried out in succession without isolating or purifying the intermediate products.
  • the reaction conditions of steps 1) to 3) can vary.
  • the reaction temperature, the pressure and / or the type and amount of catalyst used in steps 1) to 3) can be different. In general, however, it is preferred if the reaction temperature, the pressure and the type and amount of catalyst used in steps 1) to 3) are the same.
  • the reaction temperature can vary in the range between 80.degree. C.-180.degree. C., in particular 100.degree. C.-140.degree.
  • the pressure is preferably in the range from 1 to 5 bar, in particular in the range from 1 to 3 bar.
  • the individual steps of the process are preferably carried out under catalysis.
  • Suitable catalysts for the alkoxylations of steps 1) to 3) are known per se to the person skilled in the art.
  • reaction steps 1) to 3) are catalyzed. It is particularly preferred to use the same catalyst for steps 1) to 3) without removing or deactivating it in the meantime.
  • Alkali metal hydroxides and / or alkali metal alcoholates have proven to be particularly suitable catalysts.
  • an alkali metal alcoholate of the alcohol which is also used as starter S is used as the catalyst.
  • sodium alcoholates in particular sodium methoxide or sodium ethoxide, as the catalyst.
  • the starter S is selected from the group consisting of methanol, ethanol, n-propanol, i-propanol, n-butanol, 2-butanol, prenol, isoprenol, n-hexanol, cyclo-hexanol, n-octanol, 2-Ethylhexanol, Lauryl Alcohol, Myristyl Alcohol, Geraniol, Citronellol, Cetyl Alcohol, Stearyl Alcohol, Vinyl Alcohol, Allyl Alcohol, Methallyl Alcohol, Palmitoleyl Alcohol, Oleyl Alcohol, Linoleyl Alcohol, Linolenyl Alcohol, Phenol, Benzyl Alcohol, Butylamine, Ethylamine, Anylamine, Ethylamine, Anylamine, Anylamine Hexylamine,
  • Oleylamine aniline, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, isovaleric acid, caproic acid, 2-ethylhexanoic acid, caprylic acid, Lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, acrylic acid, methacrylic acid, benzoic acid, acrylamide, methacrylamide.
  • alkoxylating agents are compounds which can be converted to polyethers by polymerization. Alkoxylating agents thus cause alkoxylation or the formation of alkylene oxide or polyalkylene oxide units.
  • alkoxylating agents for the purposes of the present invention contain oxirane, oxetane or oxolane structures.
  • Particularly preferred alkoxylating agents are alkylene oxides selected from ethylene oxide, propylene oxide, 1,2-butylene oxide, cyclohexene oxide and / or tetrahydrofuran.
  • the alkoxylating agent is ethylene oxide and / or propylene oxide.
  • steps 1) to 3 It may be preferred to use only one alkoxylating agent in one of steps 1) to 3). In a very preferred embodiment, only one alkoxylating agent, in particular ethylene oxide, is used in steps 1) to 3). However, it is also possible to use two or more alkoxylating agents in steps 1) to 3), either as a mixture or individually in each case in one of steps 1) to 3).
  • the starter S is selected from ethoxylated methanol, ethoxylated ethanol, ethoxylated vinyl alcohol, ethoxylated allyl alcohol, ethoxylated methallyl alcohol, ethoxylated isoprenol, ethoxylated acrylic acid or ethoxylated methacrylic acid.
  • the starter S is very particularly preferably selected from ethoxylated methanol or ethoxylated methallyl alcohol.
  • copolymers according to the invention are produced without the use of epichlorohydrin.
  • the manufacturing process is therefore epichlorohydrin-free.
  • Copolymers according to the invention can therefore preferably be produced in a process comprising the steps:
  • copolymers according to the invention are prepared without the use of epichlorohydrin and with the use of an alcohol as the starter S.
  • the manufacturing process is therefore epichlorohydrin-free.
  • copolymers according to the invention can particularly preferably be prepared in a process comprising the steps:
  • step 3 optional reaction of the reaction product from step 2) with an alkoxylating agent.
  • copolymers according to the invention are prepared without the use of epichlorohydrin and with the use of an amine as the starter S.
  • the manufacturing process is therefore epichlorohydrin-free.
  • Copolymers according to the invention can therefore also be produced particularly preferably in a process comprising the steps:
  • step 3 optional reaction of the reaction product from step 2) with an alkoxylating agent.
  • copolymers according to the invention are prepared without the use of epichlorohydrin and with the use of a carboxylic acid as the starter S.
  • the manufacturing process is therefore epichlorohydrin-free.
  • C1 - C16 is alkyl
  • step 3 optional reaction of the reaction product from step 2) with an alkoxylating agent.
  • copolymers according to the invention are prepared without the use of epichlorohydrin and using an alcohol as starter S, the starter alcohol first being reacted with an alkoxylating agent.
  • the manufacturing process is therefore epichlorohydrin-free.
  • step 3 optional reaction of the reaction product from step 2) with an alkoxylating agent. It is particularly preferred if the process for the preparation of copolymers according to the invention contains a step 3) as described above.
  • A are each independently C1-C10 alkylene, preferably ethylene, propylene and / or butylene,
  • R 2 C1-C16 alkyl
  • B are each independently C1-C10 alkylene, preferably ethylene, propylene and / or butylene,
  • the number of linear structural units (BO) m in the general structure (I) depends on o and q.
  • the number of structural units (BO) m is the same oxq +1.
  • the number of linear structural units (B0) m corresponds to the degree of branching. Since both q and o are in each case> 0, the degree of branching of copolymers according to the invention is at least 2.
  • copolymers according to the invention are not linear copolymers.
  • copolymers according to the invention are not purely linear polyethers.
  • the degree of branching of the copolymer according to the invention is between 2 and 501, preferably between 2 and 200, more preferably between 2 and 100, particularly preferably between 3 and 50, in particular between 5 and 20. It is clear to the person skilled in the art that in the reaction according to step 2 ) of the process according to the invention for the preparation of copolymers different regioisomers can arise. These are regioisomers that arise when the oxirane ring of the glycidol is opened via the various carbon atoms according to one of the chemical reaction equations a) or b) as shown below.
  • copolymers according to the invention are copolymers of the general structure (I) in which
  • R 1 is selected from C1-C18 alkyl, particularly preferably from methyl or ethyl,
  • A are each independently ethylene, propylene and / or butylene, particularly preferably ethylene,
  • B are each, independently of one another, ethylene, propylene and / or butylene, particularly preferably ethylene,
  • R 3 is H
  • m are each, independently of one another, an integer in the range from 0-350, particularly preferably 2-200, very particularly preferably 5-150, in particular 7-30
  • n is an integer in the range from 1-100 , particularly preferably 2-75, very particularly preferably 5-55
  • p 0,
  • q is an integer in the range from 1-10, particularly preferably 2-8, very particularly preferably 4-7
  • o is an integer in the range from 1-50, particularly preferably 3-40, very particularly preferably 6-30, especially 8-20.
  • the number of linear structural units (BO) m in the general structure (I) depends on o and q.
  • the number of structural units (BO) m is equal to oxq +1.
  • the structural elements (AO) and (BO) of the general structure (I) are polyalkylene oxide chains.
  • a proportion of ethylene oxide units in the polyalkylene oxidettes, based on all alkylene oxide units present, is preferably more than 90 mol%, in particular more than 95 mol%, preferably more than 98 mol%, in particular 100 mol%.
  • the polyalkylene oxide chains have no hydrophobic groups, in particular no alkylene oxides having three or more carbon atoms.
  • a high proportion of ethylene oxide units or a low content of alkylene oxides with three or more carbon atoms reduces the risk of undesired air entrainment.
  • the weight average molecular weight (Mw) is determined in the present case by gel permeation chromatography (GPC) with polyethylene glycol (PEG) as the standard. This technique is known per se to the person skilled in the art.
  • Copolymers according to the invention can have a molar mass M w in the range from 200-40-00 g / mol.
  • the parameters n, m, o and p are of the general structure (I) chosen so that the mean molar mass M w of the copolymers is in the range from 200-7500, preferably 500-5000, particularly preferably 1-3500-, very particularly preferably 1500-2500, in particular 2-00--1500.
  • Copolymers of the general structure (I) in which R 1 is a methyl or ethyl unit are particularly preferred.
  • an (AO) m unit or an R 2 -X unit is present in the copolymers.
  • all m are chosen such that the average number of (BO) units on all oxq +1 linear structures is the same in each case.
  • copolymers according to the invention are those copolymers of the general structure (I) in which R 1 is selected from C1-C18 alkyl, particularly preferably from methyl or ethyl,
  • A are each independently ethylene, propylene and / or butylene, particularly preferably ethylene,
  • B are each, independently of one another, ethylene, propylene and / or butylene, particularly preferably ethylene,
  • Such copolymers correspond to the general structure (II) Copolymers of general structure (II) can be prepared in a process comprising the steps
  • copolymers according to the invention are those copolymers of the general structure (I) in which R 1 is selected from C1-C18 alkyl, particularly preferably from methyl or ethyl,
  • X O
  • A are each independently ethylene, propylene and / or butylene, particularly preferably ethylene
  • B are each, independently of one another, ethylene, propylene and / or butylene, particularly preferably ethylene,
  • R 3 is H
  • m are each, independently of one another, an integer in the range from 0-350, particularly preferably 2-200, very particularly preferably 5-150, in particular 7-30
  • n is an integer in the range from 1-100 , particularly preferably 2-75, very particularly preferably 5-55
  • p 0, and o is an integer in the range from 1-50, particularly preferably 3-40, very particularly preferably 6-30, especially 8-20 , and q is at least 2.
  • Such copolymers correspond to the general structure (III)
  • Copolymers of general structure (III) can be prepared in a process comprising the steps
  • Glycidol and an alkoxylating agent preferably ethylene oxide
  • copolymers according to the invention are those copolymers of the general structure (I) in which
  • B are each, independently of one another, ethylene, propylene and / or butylene, particularly preferably ethylene,
  • R2 is C1-C16 alkyl, particularly preferably C2-C4 alkyl, in particular butyl,
  • R 3 is H
  • m are each independently an integer in the range from 0-350, particularly preferably 2-200, very particularly preferably 5-150, especially 7-30
  • o is an integer in the range from 1-50, particularly preferably 3-40, very particularly preferably 6-30, especially 8-20
  • q is at least 2.
  • copolymers correspond to the general structure (IV)
  • Alkoxylating agent preferably ethylene oxide.
  • copolymers according to the invention are those copolymers of the general structure (I) in which R 1 is selected from C1-C18 alkyl, particularly preferably from methyl or ethyl,
  • B are each, independently of one another, ethylene, propylene and / or butylene, particularly preferably ethylene,
  • R 2 is C1-C16 alkyl, particularly preferably C2-C4 alkyl, in particular butyl
  • R 3 is H
  • m in each case independently of one another an integer in the range from 0-350, particularly preferably 2-200, very particularly preferably 5 - 150, in particular 7-30
  • o is in each case, independently of one another, an integer in the range from 1 to 50, particularly preferably 3 - 40, very particularly preferably 6-30, especially 8-20.
  • Such copolymers correspond to the general structure (V) (V).
  • Copolymers of general structure (V) can be prepared in a process comprising the steps
  • copolymers according to the invention are those copolymers of the general structure (I) in which
  • R 1 is selected from methyl
  • Such copolymers correspond to the general structure (VI)
  • Copolymers of general structure (VI) can be prepared in a process comprising the steps
  • reaction of the reaction product from step 1) with glycidol 2) reaction of the reaction product from step 1) with glycidol, 3) reaction of the reaction product from step 3) with ethylene oxide.
  • the mineral binder composition is in particular a processable and / or aqueous mineral binder composition.
  • the mineral binder composition contains at least one mineral binder.
  • mineral binder is to be understood in particular as a binder which, in the presence of water, reacts in a hydration reaction to form solid hydrates or hydrate phases.
  • This can for example a hydraulic binding agent (e.g. cement or hydraulic lime), a latent hydraulic binding agent (e.g. slag), a pozzolanic binding agent (e.g. fly ash) or a non-hydraulic binding agent (gypsum or white lime).
  • the mineral binder or the binder composition contains a hydraulic binder, preferably cement.
  • a cement with a cement clinker content of> 35% by weight is particularly preferred.
  • the cement is of the type CEM I, CEM II and / or CEM III, CEM IV or CEM V (according to standard EN 197-1).
  • the mineral binder composition comprises at least one hydraulic binder, preferably cement, in at least 5% by weight, preferably in at least 20% by weight, particularly preferably in at least 35% by weight, very particularly preferably in at least 65% by weight, in particular> 95% by weight, based in each case on the dry matter of the mineral binder composition.
  • the mineral binder or the mineral binder composition contains or essentially consists of other binders.
  • these are in particular latent hydraulic binders and / or pozzolanic binders.
  • Suitable latent hydraulic and / or pozzolanic binders are e.g. slag, fly ash and / or silica dust.
  • the binder composition can also contain inert substances such as limestone, quartz powder and / or pigments.
  • the mineral binder contains 5-95% by weight, in particular 5-65% by weight, particularly preferably 15-35% by weight, based in each case on the total weight of the binder, latent hydraulic and / or pozzolanic binders.
  • Advantageous latent hydraulic and / or pozzolanic binders are slag and / or fly ash.
  • the mineral binder contains a hydraulic binder, in particular cement or cement clinker, and a latent hydraulic and / or pozzolanic binder, preferably slag and / or fly ash.
  • the proportion of the latent hydraulic and / or pozzolanic binder is particularly preferably 5-65% by weight, particularly preferably 15-35% by weight, while at least 35% by weight, especially at least 65% by weight, of the hydraulic Binder are present.
  • the mineral binder composition is preferably a mortar or concrete composition, in particular a mortar or Concrete compositions with a low weight ratio of water to binder (w / b ratio).
  • it is high-strength concrete (HPC), ultra-high-strength concrete (UHPC) or self-compacting concrete (SCC).
  • the mineral binder composition is in particular a processable and / or water-made mineral binder composition.
  • the mineral binder composition accordingly comprises water.
  • a weight ratio of water to binder in the mineral binder composition (w / b ratio) is preferably in the range from 0.18-0.6, particularly preferably 0.2-0.5, very particularly preferably 0.22-0.4, in particular 0.22-0.37, especially 0.22-0.28 or 0.32 - 0.37.
  • the copolymer according to the invention is advantageously present in an amount of 0.01-10% by weight, in particular 0.1-7% by weight or 0.2-5% by weight, based in each case on the total weight of mineral binder.
  • the mineral binder composition contains flour grain, preferably with a proportion of> 250 kg / m 3 , in particular 350-600 kg / m 3 .
  • a cement content is in particular between 200-800 kg / m 3 , preferably 320-500 kg / m 3 .
  • the flour grain contains in particular fly ash, metakaolin, silica dust and / or inert rock flour.
  • the flour grain is fine as cement.
  • a maximum grain diameter of the flour e.g. measured by laser granulometry, is below 0.125 mm.
  • the flour grain preferably has a Blaine fineness of at least 1 cm00 cm 2 / g, in particular at least T500 cm 2 / g, preferably at least 2,500 cm 2 / g, even more preferably at least 3,500 cm 2 / g or at least 5 ⁇ 00 cm 2 / g, on.
  • Copolymers according to the invention have little or no water-reducing power. This is advantageous because they can therefore be used in mineral binder compositions known per se which contain water-reducing substances such as superplasticizers, for example, to reduce the viscosity without the need to adjust the amount of superplasticizer or water.
  • the mineral binder composition therefore also contains at least one superplasticizer selected from the group of lignosulphonates, polynaphthalene sulphonates, polymelmamine sulphonates and / or polycarboxylate ethers, in particular at least one polycarboxylate ether.
  • Polycarboxylate ethers are comb polymers with a polycarboxyl backbone and polyalkylene oxide side chains.
  • Preferred polycarboxylate ethers include structural units of the formula VII and structural units of the formula VIII, in which
  • R 4 each independently of one another, is -COOM, -SO2-OM, -0- PO (0M) 2 and / or -PO (OM) 2, preferably -COOM
  • R 5 each independently of one another, is H, -CH2-COOM or an alkyl group of 1 to 5
  • R 6 are H or an alkyl group having 1 to 5 carbon atoms, preferably H,
  • R 7 are H, -COOM or an alkyl group with 1 to 5 carbon atoms, preferably H, or R 4 and R 7 form a ring to form -CO-O-CO- (anhydride),
  • Y in each case independently of one another, is -O- or -NH-
  • R 8 independently of one another, is H, a C 1 to C 2 alkyl group, a cyclohexyl group or a alkylaryl group
  • D C 2 to C 4 alkylene, preferably ethylene.
  • the molar ratio of structural unit VII to structural unit VIII is preferably 0.7-10: 1, more preferably 1-8: 1, in particular 1.5-5: 1.
  • the polycarboxylate ether additionally comprises a structural unit IX.
  • Structural unit IX is preferably derived from monomers selected from the group consisting of alkyl or hydroxyalkyl esters of acrylic or methacrylic acid, vinyl acetate, styrene and N-vinylpyrrolidone.
  • the polycarboxylate ether preferably contains carboxylic acid groups and / or their salts and polyethylene glycol side chains.
  • the polycarboxylate ether is preferably composed of structural units VII, which are derived from ethylenically unsaturated carboxylic acids, in particular unsaturated monocarboxylic acids, or their salts, and structural units VIII, which are derived from ethylenically unsaturated polyalkylene glycols, in particular polyethylene glycols.
  • structural units VII which are derived from ethylenically unsaturated carboxylic acids, in particular unsaturated monocarboxylic acids, or their salts
  • structural units VIII which are derived from ethylenically unsaturated polyalkylene glycols, in particular polyethylene glycols.
  • the polycarboxylate ether contains no further structural units.
  • Superplasticizers in particular polycarboxylate ethers, can be used in mineral binder compositions in 0-10% by weight, preferably 0.1-8% by weight, in particular 0.25-7% by weight, calculated as the dry weight of the superplasticizer, based on the total weight of the binder compositions.
  • the invention therefore relates to the use of a copolymer according to the invention in a mineral binder composition which contains a superplasticizer selected from the group of lignosulphonates, polynaphthalene sulphonates, polymelmamine sulphonates and / or polycarboxylate ethers, in particular at least one polycarboxylate ether.
  • a superplasticizer selected from the group of lignosulphonates, polynaphthalene sulphonates, polymelmamine sulphonates and / or polycarboxylate ethers, in particular at least one polycarboxylate ether.
  • a copolymer according to the invention it is possible to add a copolymer according to the invention as such to a mineral binder composition. However, it is also possible to add a copolymer according to the invention as an aqueous solution or emulsion in water to a mineral binder composition. It is also possible to dissolve or disperse a copolymer according to the invention in an additive, in particular an aqueous additive.
  • Another aspect of the present invention is therefore an additive comprising at least one copolymer produced in a multistage process comprising the steps
  • step 3 optional reaction of the reaction product from step 2) with an alkoxylating agent.
  • the additive can comprise at least one polycarboxylate ether and / or water.
  • the additive can be used as a dispersant for mineral binders, it being possible to achieve a reduction in viscosity and a reduction in water requirements at the same time.
  • the weight ratio of inventive copolymer to polycarboxylate ether in an aqueous additive is preferably in the range between 0.05: 5-1: 1, preferably 0.1: 3-1: 1, particularly preferably 0.1: 3-1: 3.
  • the invention relates to a composition, in particular a mortar composition, a concrete composition or a cementitious composition, containing at least one copolymer as described above and a mineral binder.
  • the mineral binder is preferably a hydraulic binder, in particular cement, preferably Portland cement.
  • the composition is a high-strength concrete, ultra-high-strength concrete or self-compacting concrete.
  • the copolymer advantageously has a proportion of 0.01-10% by weight, in particular 0.1-7% by weight or 0.2-5% by weight, based on the weight of the mineral binder.
  • the composition contains flour grain, preferably with a proportion of> 350 kg / m 3 , in particular 400-600 kg / m 3 .
  • a cement content is in particular between 320 and 380 kg / m 3 .
  • Another aspect relates to a method for controlling the rheology of mineral binder compositions, in particular HPC, UHPC or SCC, characterized in that at least one copolymer according to the invention is added to the dry mixture of the mineral binder composition and / or the mineral binder composition together with the mixing water, in particular as aqueous Solution or emulsion in the mixing water is added and / or the mineral binder composition is added shortly after the mixing water has been added.
  • the mixing water in particular as aqueous Solution or emulsion in the mixing water is added and / or the mineral binder composition is added shortly after the mixing water has been added.
  • control of the rheology is understood to mean that by adding a copolymer according to the invention, the viscosity, measured in particular as the funnel flow time according to DIN EN 12350-9 and / or the flow time according to JSCE-F 541-1999, of the respective mineral binder composition is reduced, or the flowability is increased, and the slump, measured according to DIN EN 12350-5, and / or the slump, measured according to DIN EN 12350-2, is not significantly changed.
  • control of the rheology is understood here to mean an increase in the flow rate and reduction in the viscosity of a mineral binder composition.
  • control of the rheology is understood to mean an increase in the flow rate and a reduction in viscosity without any significant change in the slump and / or slump of a mineral binder composition.
  • “Dry mix” is understood to mean a mineral binder composition which contains all components of the mineral binder composition except water.
  • a dosage of a copolymer according to the invention of 0.01-10% by weight, in particular 0.1-7% by weight or 0.2-5 %
  • the funnel discharge time according to DIN EN 12350-9 by at least 5%, preferred at least 10%, particularly preferably at least 15% and / or the drainage time according to JSCE-F 541-1999 of the mineral binder composition by at least 10%, preferably at least 15%, particularly preferably at least 25%, in particular at least 30% compared to the funnel drainage time and / or expiration time of an analogous composition which does not contain the copolymer according to the invention.
  • the slump according to DIN EN 12350-5 and / or the slump according to DIN EN 12350-2 of the mineral binder composition by less than 15%, in particular less than 10%, preferred less than 5%, in particular less than 3% or less than 2% compared to the slump and / or slump of an analogous composition which does not contain the copolymer according to the invention.
  • Another aspect relates to a shaped body which can be obtained by curing a mineral binder composition as described above, in particular HPC, UHPC or SCC containing at least one copolymer according to the invention, after adding water.
  • Step 1 4 g (0.074 mol) of sodium methylate are dissolved in 576 g (8 mol) of methallyl alcohol in a reactor which has been inerted with 1 h gas and the mixture is heated to 100.degree. Then 1760 g (40 mol) of ethylene oxide are metered in over 5 hours. The temperature is kept at 100 to 140 ° C and the pressure at 1 to 3 bar. After the metering has ended, the reaction mixture is stirred at 140 ° C. for 2 hours. The mixture is then cooled to 30.degree.
  • Step 2 In a reactor rendered inert with 1 h gas, 123 g (0.42 mol) of the mixture from step 1) are mixed with 0.54 g (0.01 mol) of sodium methylate and heated to 130.degree. Then 93 g (1.26 mol) of glycidol are metered in over a period of 30 minutes. The temperature is kept at 130 to 140 ° C and the pressure at 1 to 3 bar. After the metering has ended, the reaction mixture is stirred at 140 ° C. for 2 hours. It is allowed to cool to 50 ° C.
  • Step 3 After cooling to 50 ° C., 2.2 g (0.04 mol) of sodium methylate are added to the mixture from step 2). The reactor is again rendered inert with N2 gas and heated to 130.degree. Then 628 g (14.27 mol) of ethylene oxide are metered in over 4 hours. The temperature is kept at 130 to 140 ° C and the pressure at 0 to 3 bar. After the metering has ended, the reaction mixture is stirred at 140 ° C. for 3 hours. The mixture is then cooled to 50 ° C. and neutralized with 3.2 g (0.054 mol) of acetic acid. The mixture obtained is the inventive copolymer C-1.
  • C-2 takes place analogously to the production of C-1. However, 2513 g of ethylene oxide (57 mol) are metered in to produce C-2 in step 3).
  • C-6 is analogous to the production of C-5. However, 186 g (2.51 mol) glycidol are metered in to produce C-6 in step 2).
  • a dry mix was prepared consisting of 150 g cement (CEM I).
  • a dry mix was prepared consisting of 735 g cement (CEM I 42.5 N from Vigier Holding AG), 28 g microsilica (SikaFume® -HR / -TU, available from Sika für AG), 340 g blast furnace slag (Regen GGBS from Hanson UK) , 203 g limestone (Nekafill 15 from Kalkfabrik Netstal AG) and 2845 g aggregates with a particle size of 0 - 8 mm.
  • the ingredients were dry blended in a Hobart mixer for 30 seconds.
  • the experiments E4 and E5 according to the invention show, in comparison to the experiment V4 not according to the invention, a significantly reduced flow time from the V funnel. This corresponds to an improved flowability or a reduced viscosity.
  • the inventive experiments E6-E11 show that a improved flowability or reduced viscosity can also be achieved if the amount of water is reduced.
  • a dry mixture was produced consisting of 340 g of cement (CEM I 42.5 N from Vigier Holding AG), 851 g of quartz sand and 951 g of gravel. To prepare the dry mix, the ingredients were dry blended in a Hobart mixer for 30 seconds. The additives indicated in Table 4, each dissolved in 170 g of water, were added to this dry mixture. Mixing was continued for 30 seconds at level 1, then mixing was continued for 3.5 minutes at level 2. The slump in accordance with JIS A1150 and the flow rate in accordance with JSCE-F-514 were measured on the concretes obtained. The following table 4 gives an overview of the results.
  • Example 4 The dry mixture from Example 4 was passed through a sieve with a mesh size of 5 mm.

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Abstract

L'invention concerne l'utilisation de copolymères ramifiés de structure générale (I) en tant qu'additifs pour augmenter la vitesse d'écoulement et réduire la viscosité de compositions de liant minéral. Un autre aspect de l'invention concerne des compositions de liant minéral contenant au moins un copolymère ramifié de structure générale (I).
EP20808466.5A 2019-11-29 2020-11-25 Copolymères ramifiés utiliés en tant qu'additifs pour la réduction de la viscosité de compositions de liant minéral Pending EP4065537A1 (fr)

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EP19212573.0A EP3828154A1 (fr) 2019-11-29 2019-11-29 Copolymères ramifiés en tant qu'additifs destinés à la réduction de la viscosité de compositions minérales de liants
PCT/EP2020/083325 WO2021105187A1 (fr) 2019-11-29 2020-11-25 Copolymères ramifiés utiliés en tant qu'additifs pour la réduction de la viscosité de compositions de liant minéral

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EP20808466.5A Pending EP4065537A1 (fr) 2019-11-29 2020-11-25 Copolymères ramifiés utiliés en tant qu'additifs pour la réduction de la viscosité de compositions de liant minéral

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AU2478684A (en) 1983-02-22 1984-08-30 Union Carbide Corporation Branch-copolymers
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DE19947631A1 (de) * 1998-12-22 2000-06-29 Bayer Ag Verfahren zur Herstellung von hochverzweigten Polyolen auf der Basis von Glycidol
JP2007153641A (ja) * 2005-12-01 2007-06-21 Construction Research & Technology Gmbh セメント添加剤およびそれを用いたセメント組成物
FR2944022B1 (fr) 2009-04-02 2011-06-10 Chryso Fluidifiants pour suspensions aqueuses de particules minerales et pates de liant hydraulique
JP2012532975A (ja) * 2009-07-15 2012-12-20 ビーエーエスエフ ソシエタス・ヨーロピア コポリマー、増粘剤としてのその使用及びその製造方法
CN102115516A (zh) * 2010-12-22 2011-07-06 江苏博特新材料有限公司 梳形共聚物水泥分散剂的制备方法、所用单体及所得梳形共聚物水泥分散剂
US9212095B2 (en) * 2011-02-21 2015-12-15 Construction Research & Technology, Gmbh Use of HyperBranched polyether surfactant in cementitious systems
CN102504238B (zh) * 2011-10-10 2014-01-22 江苏博特新材料有限公司 一种不饱和聚醚单体、采用该单体制备的梳形支化共聚物水泥分散剂及其制备方法
EP2774899A1 (fr) 2013-03-06 2014-09-10 Construction Research & Technology GmbH Polycarboxylatéther à chaînes latérales ramifiées
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EP3828154A1 (fr) 2021-06-02
JP2023502866A (ja) 2023-01-26
KR20220107156A (ko) 2022-08-02
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