Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
  • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
  • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/04—Homopolymers or copolymers of esters
  • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
  • C04B40/0028—Aspects relating to the mixing step of the mortar preparation
  • C04B40/0039—Premixtures of ingredients
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B16/00—Use of organic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of organic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
  • C04B16/04—Macromolecular compounds
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
  • C08F290/04—Polymers provided for in subclasses C08C or C08F
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/04—Homopolymers or copolymers of esters
• • 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
  • C04B2103/0045—Polymers chosen for their physico-chemical characteristics
  • C04B2103/0049—Water-swellable polymers
  • C04B2103/005—Alkali-swellable polymers
• • 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
  • C04B2103/32—Superplasticisers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group

Definitions

• the present invention relates to the sector of additives which are used in aqueous formulations based on hydraulic binders, such as cements, concretes or mortars, in order to improve their workability.
• hydraulic binders such as cements, concretes or mortars.
• the most efficient of these handling agents are today polymers of comb structure, having a backbone of (meth) acrylic nature on which are grafted monomers having hydrophilic functions of the alkoxy or hydroxy polyakylene glycol type. These polymers are hereinafter referred to as "hydrophilic (meth) acrylic comb polymers".
• the present invention which is based on the combination of these (meth) acrylic comb polymers having a monomer grafted with a hydrophilic function, with an associative acrylic thickener type ASE (soluble alkali emulsion), makes it possible to overcome this disadvantage advantageously. It is therefore possible to maintain the workability of an aqueous formulation based on hydraulic binders, without segregation phenomenon or loss of mechanical properties and for periods longer than 3 hours.
• ASE soluble alkali emulsion
• the fluidizing effect plays against the mechanism of dispersion: the distribution of constituents is no longer homogeneous in the formulation, which negatively impacts its mechanical properties.
• the initial fluidifying power is so marked that it leads to segregation that is to say to a physical separation of the various constituents of the medium.
• This problem is reported in WO 2007/047407.
• the fluidifying agents of the prior art, and in particular the hydrophilic comb (meth) acrylic polymers one skilled in the art has been able to develop alternative solutions, so as to obtain a satisfactory initial fluidifying power and good maneuverability over time, without undesirable effects of loss of mechanical properties or segregation.
• the document WO 2007/047407 proposes the obvious solution of adding to the formulation a setting retarding agent, which is not without posing new problems: the agent constitutes as such a new additive to be added in the formulation, its dosage must be optimized according to the amount of plasticizer used, and the resulting handling is no longer stable beyond two hours.
• Hydrophilic comb (meth) acrylic according to the prior art and acrylic associative thickeners of the ASE type.
• ASE (Alkali Swellable Emulsion) thickeners are emulsion thickeners which are copolymers of (meth) acrylic acid with an ester of these acids.
• HASE Hydrophilic Swellable Emulsion
• HASE Hydrophilic Swellable Emulsion
• the mechanisms of action of these products differ.
• the polymers of the ASE type in the form of dispersions in the acidic state, become soluble only in the neutralized state. By neutralizing the medium, an ion repulsion mechanism is induced between the different carboxylate groups carried by the polymer chain. These ionized groups polarize a large quantity of water molecules, which causes the viscosity of the medium to increase.
• the HASE-type polymers involve interactions between their hydrophobic groups, which also contributes to thickening the medium.
• a first object of the invention is the use as an agent improving the workability of an aqueous formulation based on hydraulic binders:
• this use as an agent improving the workability of an aqueous formulation based on hydraulic binders is also characterized in that said comb copolymer a) and said acrylic polymer b) are introduced separately into said aqueous formulation.
• this use as an agent improving the workability of an aqueous formulation based on hydraulic binders is also characterized in that said comb copolymer a) and said acrylic polymer b), are introduced in the form of a mixture.
• the mixture has a solids content of between 10% and 50% of its total weight.
• the mixture has a dry weight content of comb copolymer a) of between 5% and 95%, preferably between 10% and 90% of its total dry matter.
• m, n, p and q are integers and m, n, p are less than 150, q is greater than 0 and at least one of m, n and p is nonzero,
• R is a radical containing a polymerizable unsaturated functional group, preferably belonging to the vinyl group as well as to the group of acrylic, methacrylic and maleic esters, as well as to the group of unsaturated urethanes such as acrylurethane, methacrylurethane, ⁇ - ⁇ -dimethyl- isopropenylbenzylurethane, allylurethane, as well as the group of substituted or unsubstituted allylic or vinyl ethers, or else the group of ethylenically unsaturated amides or imides,
• R 1 and R 2 are identical or different and represent hydrogen atoms or alkyl groups
• R ' represents hydrogen or a hydrocarbon radical having 1 to 40 carbon atoms, or an ionic or ionizable group such as a phosphate, a phosphonate, a sulphate, a sulphonate, a carboxylic acid, or an amine primary, secondary or tertiary, or a quaternary ammonium, or mixtures thereof,
• a3) from 0% to 50% of at least one monomer different from the monomers a1) and a2), and which is preferably an ester, an amide, an ether, a styrene monomer, a cationic monomer, a sulfonated monomer, a monomer phosphated, and which is very preferably ethyl acrylate.
• acrylic polymers b) of the ASE type consist of (meth) acrylic acid and an ester of these acids.
• the comb copolymer a) and the acrylic polymer b) are obtained by radical polymerization in solution, in direct or inverse emulsion, in suspension or precipitation in solvents, in the presence of catalytic systems and agents. transfer or by controlled radical polymerization and preferably by controlled polymerization with nitroxides (NMP) or cobaloxymes, by radical atom transfer polymerization (ATRP), by controlled radical polymerization with sulfur derivatives, selected from carbamates , dithioesters or trithiocarbonates (RAFT) or xanthates.
• NMP nitroxides
• ATRP radical atom transfer polymerization
• sulfur derivatives selected from carbamates , dithioesters or trithiocarbonates (RAFT) or xanthates.
• This use is also characterized in that the comb copolymer a) and the acrylic polymer b) are distilled, after polymerization.
• This use is also characterized in that the comb copolymer a) and the acrylic polymer b) are separated into several phases, according to static or dynamic separation processes, with one or more polar solvents preferentially belonging to the group consisting of water, methanol, ethanol, propanol, isopropanol, butanols, acetone, tetrahydrofuran or mixtures thereof
• This use is also characterized in that the comb copolymer a) and the acrylic polymer b) are totally or partially neutralized by one or more neutralization agents having a monovalent or polyvalent cation, said agents being preferably chosen from ammonia or from hydroxides and / or oxides of calcium, of magnesium, or from hydroxides of sodium, potassium or lithium, or from primary, secondary or tertiary aliphatic and / or cyclic amines, such as preferentially stearylamine, ethanolamines (mono-, di-, triethanolamine), mono and diethylamine, cyclohexylamine, methylcyclohexylamine, aminomethylpropanol, morpholine, and preferably in that the neutralizing agent is selected from triethanolamine and sodium hydroxide.
• neutralization agents having a monovalent or polyvalent cation
• This use as an agent improving the workability of an aqueous formulation based on hydraulic binders is also characterized in that said formulation is a cement, a mortar, a concrete or a grout, and preferably a concrete.
• said aqueous formulation based on hydraulic binders contains from 0.1% to 2%, preferentially from 0.2% to 1%, very preferably from 0.4% to 0.8% by dry weight of components a) and b) relative to the dry weight of hydraulic binder.
• Another subject of the invention consists of an aqueous formulation based on hydraulic binders, containing as improving agent its handling: a) at least one (meth) acrylic comb copolymer having at least one side chain carrying at least one alkoxy hydrophilic group or hydroxy polyalkylene glycol,
• This formulation is also characterized in that said comb copolymer a) consists of, expressed as a percentage by weight of each of its monomers, the sum of these percentages being equal to 100%:
• m, n, p and q are integers and m, n, p are less than 150, q is greater than 0 and at least one of m, n and p is nonzero,
• R is a radical containing a polymerizable unsaturated functional group, preferably belonging to the vinyl group as well as to the group of acrylic, methacrylic and maleic esters, as well as to the group of unsaturated urethanes such as acrylurethane, methacrylurethane, ⁇ - ⁇ -dimethyl- isopropenylbenzylurethane, allylurethane, as well as the group of substituted or unsubstituted allylic or vinyl ethers, or else the group of ethylenically unsaturated amides or imides,
• R 1 and R 2 are identical or different and represent hydrogen atoms or alkyl groups
• - R ' represents hydrogen or a hydrocarbon radical having 1 to 40 carbon atoms, or an ionic or ionizable group such as a phosphate, a phosphonate, a sulphate, a sulphonate, a carboxylic acid, or a primary amine, secondary or tertiary, or a quaternary ammonium, or mixtures thereof.
• a3) from 0% to 50% of at least one monomer different from the monomers a1) and a2), and which is preferably an ester, an amide, an ether, a styrene monomer, a cationic monomer, a sulfonated monomer, a monomer phosphated, and which is very preferably ethyl acrylate.
• This formulation is also characterized in that said acrylic polymers b) of the ASE type consist of (meth) acrylic acid and an ester of these acids, and (meth) acrylic acid, an ester of these acids .
• This formulation is also characterized in that the comb copolymer a) and the acrylic polymer b) can be obtained by radical polymerization in solution, in direct or inverse emulsion, in suspension or precipitation in solvents, in the presence of catalytic systems and transfer agents, or by controlled radical polymerization and preferably by controlled polymerization with nitroxides (NMP) or by cobaloxymes, by radical atom transfer polymerization (ATRP), by sulfur-derived controlled radical polymerization, chosen from carbamates, dithioesters or trithiocarbonates (RAFT) or xanthates.
• NMP nitroxides
• ATRP radical atom transfer polymerization
• RAFT sulfur-derived controlled radical polymerization
• This formulation is also characterized in that the comb copolymer a) and the acrylic polymer b) are distilled after polymerization.
• This formulation is also characterized in that the comb copolymer a) and the acrylic polymer b) are separated into several phases, according to static or dynamic separation processes, with one or more polar solvents belonging to one or more polar solvents. preferentially to the group consisting of water, methanol, ethanol, propanol, isopropanol, butanols, acetone, tetrahydrofuran or their mixtures
• This formulation is also characterized in that the comb copolymer a) and the acrylic polymer b) are totally or partially neutralized by one or more neutralization agents having a monovalent or polyvalent cation, said agents being chosen preferentially from ammonia or among the hydroxides and / or oxides of calcium, of magnesium, or of the hydroxides of sodium, of potassium, of lithium, or of the primary, secondary or tertiary aliphatic and / or cyclic amines and preferably stearylamine, ethanolamines (mono- , di-, triethanolamine), mono and diethylamine, cyclohexylamine, methylcyclohexylamine, amino methylpropanol, morpholine, and preferentially in that the neutralizing agent is selected from triethanolamine and sodium hydroxide .
• the neutralizing agent is selected from triethanolamine and sodium hydroxide .
• This formulation is also characterized in that it is a cement, a mortar, a concrete or a grout, and preferably a concrete.
• This formulation is also characterized in that it contains from 0.1% to 2%, preferably from 0.2% to 1%, very preferably from 0.4% to 0.8% by dry weight of components a) and b) relative to the dry weight of hydraulic binder.
• the molecular weight of the polymers used in the aqueous solutions a) are determined from a technique of a multi-detection steric exclusion chromatography (CES 3D) technique, as indicated in FIG. document FR 2 917 091.
• CES 3D multi-detection steric exclusion chromatography
• That of the polymers used in the aqueous solutions b) are determined from a technique of a size exclusion chromatography technique, as indicated in the document FR 2 907 347.
• the polymers used are obtained by polymerization techniques well known to those skilled in the art.
• the first step is to introduce 22 kg of 10/20 type aggregates and 25 kg of 0/4 type sand, mixed in a masonry type concrete mixer (volume of about 100 liters). for 30 seconds.
• the dry materials are mixed for 1 minute.
• the dotted curve with the square symbols is relative to the test 2 according to the prior art where the product is overdosed.
• the solid curve with the round symbols is relative to the test 3 according to the invention which implements two products introduced separately.
• the solid curve with the square symbols is relative to the test 4 according to the invention which implements two products introduced as a mixture.
• R 1 and R 2 denote the methyl group
• R 'de represents hydrogen
• This test illustrates the prior art and implements 0.1 kg of the same aqueous solution as that implemented during test 1. In this case, all of said solution is introduced at the beginning of the test. .
• the dose of product (hydrophilic comb polymer) used is equal to 0.62% by dry weight of copolymer relative to the dry weight of cement: this illustrates an "overdose" test as sometimes practiced in the prior art.
• Figure 2 which is a photo representing the composition at the initial time, once removed the cone of Abraham, it appears a very marked phenomenon of segregation, unacceptable to the skilled person.
• the aqueous solution is introduced initially, in the form of a mixture between solutions a) and b).
• hydrophilic comb copolymer a 0.66% by weight is used relative to the dry weight of cement.
• Tests 3 and 4 do not lead to any segregation phenomenon: they have overdosed the amount of hydrophilic comb copolymer a) used.
• R is the methacrylate function
• R 1 and R 2 denote the methyl group
• R 'de represents hydrogen
• hydrophilic comb copolymer a or 2.0% by dry weight of hydrophilic comb copolymer a) relative to the dry weight of cement.
• R 'de represents hydrogen
• hydrophilic comb copolymer a or 2.0% by dry weight of hydrophilic comb copolymer a) relative to the dry weight of cement.
• R 1 and R 2 denote the methyl group
• R 'de represents hydrogen
• hydrophilic comb copolymer a or 1.0% by dry weight of hydrophilic comb copolymer a) relative to the dry weight of cement.
• hydrophilic comb copolymer a or 1.0% by dry weight of hydrophilic comb copolymer a) relative to the dry weight of cement.
• This test illustrates the invention and uses 0.240 kg of an aqueous solution, containing: a) 90% by weight of the aqueous solution a) used in test No. 5,
• hydrophilic comb copolymer a 0% by dry weight of hydrophilic comb copolymer a) relative to the dry weight of cement.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Ceramic Engineering (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Materials Engineering (AREA)
• Structural Engineering (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Curing Cements, Concrete, And Artificial Stone (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Compositions Of Macromolecular Compounds (AREA)

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• 2008
  • 2008-12-08 FR FR0858346A patent/FR2939428B1/fr not_active Expired - Fee Related
• 2009
  • 2009-11-25 JP JP2011539114A patent/JP5607644B2/ja not_active Expired - Fee Related
  • 2009-11-25 CA CA2740641A patent/CA2740641C/fr not_active Expired - Fee Related
  • 2009-11-25 EP EP09774719A patent/EP2370485A1/fr not_active Withdrawn
  • 2009-11-25 WO PCT/IB2009/007589 patent/WO2010067155A1/fr not_active Ceased
  • 2009-11-25 RU RU2011127994/03A patent/RU2503632C2/ru not_active IP Right Cessation
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  • 2009-11-25 US US13/126,021 patent/US20110207856A1/en not_active Abandoned
  • 2009-11-25 KR KR1020117015644A patent/KR20110112323A/ko not_active Abandoned
• 2011
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