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
  • C04B24/26—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
  • 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
  • C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
  • C08F216/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
  • C08F216/14—Monomers containing only one unsaturated aliphatic radical
  • C08F216/16—Monomers containing no hetero atoms other than the ether oxygen
  • C08F216/18—Acyclic compounds
  • C08F216/20—Monomers containing three or more carbon atoms in the unsaturated aliphatic radical
• • 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
  • C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
  • C08F216/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
  • C08F216/14—Monomers containing only one unsaturated aliphatic radical
  • C08F216/1416—Monomers containing oxygen in addition to the ether oxygen, e.g. allyl glycidyl ether
  • C08F216/1425—Monomers containing side chains of polyether groups
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
  • C04B14/02—Granular materials, e.g. microballoons
  • C04B14/04—Silica-rich materials; Silicates
  • C04B14/06—Quartz; Sand
• • 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
  • C04B24/16—Sulfur-containing compounds
  • C04B24/161—Macromolecular compounds comprising sulfonate or sulfate groups
  • C04B24/163—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds
• • 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
  • C04B24/16—Sulfur-containing compounds
  • C04B24/161—Macromolecular compounds comprising sulfonate or sulfate groups
  • C04B24/163—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C04B24/165—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds 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
  • 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
  • C04B24/2664—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of ethylenically unsaturated dicarboxylic acid polymers, e.g. maleic anhydride copolymers
  • C04B24/267—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of ethylenically unsaturated dicarboxylic acid polymers, e.g. maleic anhydride copolymers 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
  • 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
  • C04B24/2688—Copolymers containing at least three different monomers
  • C04B24/2694—Copolymers containing at least three different monomers 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
  • C04B28/04—Portland cements
• • 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
  • C08F2/00—Processes of polymerisation
  • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
• • 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
  • C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/04—Acids; Metal salts or ammonium salts thereof
  • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
• • 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
  • C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
  • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
  • C08F220/285—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety
• • 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
  • C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/52—Amides or imides
  • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
  • C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
  • C08F220/585—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine and containing other heteroatoms, e.g. 2-acrylamido-2-methylpropane sulfonic acid [AMPS]
• • 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
  • C04B2103/0062—Cross-linked 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
  • C04B2103/302—Water reducers
• • 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
  • C04B2103/308—Slump-loss preventing agents
• • 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
  • 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
  • C04B2103/50—Defoamers, air detrainers
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
  • Y02W30/00—Technologies for solid waste management
  • Y02W30/50—Reuse, recycling or recovery technologies
  • Y02W30/91—Use of waste materials as fillers for mortars or concrete

Definitions

• the invention relates to a copolymer obtained by a polymerization reaction using an anionic monomer and two polyethoxylated monomers.
• the invention also relates to a composition comprising this copolymer as well as to a process for its preparation and its use as a superplasticizer of a hydraulic binder composition.
• the copolymer according to the invention is advantageously used in the technical field of mortars, concretes, plasters or other compositions based on compounds or hydraulic binders, especially cement or plaster.
• Such compositions can advantageously be used in the fields of construction, public works or the exploitation of hydrocarbons.
• the dispersing compounds of hydraulic binders are usually used for their ability to modify the rheology of the medium in which they are present, in particular for their ability to control the workability of this medium.
• Workability is generally defined as the property of a composition comprising a hydraulic binder, in particular of a slag or of a cement or mortar grout or else of a concrete, for example a ready-to-use concrete. or precast concrete, to remain manageable for as long as possible.
• controlling the workability makes it possible to transport or move the aqueous composition comprising the hydraulic binder, for example during transport or movement from one reservoir to another reservoir.
• Handling also makes it possible to control the storage conditions of such an aqueous composition. It also makes it possible to be able to pump, or even to pump easily, this composition. Controlling the workability of such a composition therefore makes it possible to improve the conditions of use thereof, in particular to increase its duration of use under satisfactory or effective conditions.
• the workability of an aqueous composition comprising a hydraulic binder can be evaluated by measuring the fluidity time of the hydraulic binder.
• the hydraulic binder or the superplasticizer should make it possible to obtain a composition having a controlled and stable viscosity and, preferably, a stable viscosity over a prolonged period.
• improving the workability of aqueous hydraulic compositions comprising a hydraulic binder should be possible for compositions comprising a small amount of water.
• an important aspect of the invention resides in the provision of an aqueous composition comprising a hydraulic binder having efficient workability. Handling control should not lead to alteration of other properties, especially mechanical properties, especially at young ages.
• aqueous compositions comprising a hydraulic binder can be evaluated by measuring the slump, for example according to standard EN 12350-2. In fact, sagging and handling are proportional.
• Slump retention is also a property to be controlled for aqueous compositions comprising a hydraulic binder.
• Another aspect of the invention relates to obtaining an aqueous formulation comprising a hydraulic binder making it possible to limit or reduce shrinkage during drying.
• Improvement in the properties of aqueous formulations comprising a hydraulic binder should be obtained without modifying the setting of the formulation, in particular without delaying this setting.
• aqueous formulations comprising a hydraulic binder should also have a water / hydraulic binder, generally water / cement or W / C, weight ratio that is as low as possible, without however undergoing an alteration in their properties.
• An effect also sought after for aqueous formulations comprising a hydraulic binder is to make it possible to control the quantity of air occluded in the material resulting from the setting of this formulation, thus making it possible to avoid or reduce the presence of agent defoamer within the hydraulic formulation.
• the aqueous formulations comprising a hydraulic binder should make it possible to improve the mechanical properties of the materials obtained, in particular their mechanical properties at young ages, properties which can be evaluated by measuring the evolution over time of the resistance to water. the compression.
• the compounds used for the preparation of aqueous formulations comprising a hydraulic binder should be used in reduced doses. They should also have high or even total compatibility with the other components of aqueous formulations comprising a hydraulic binder, in particular by being miscible in all proportions with these other components, in order to avoid or limit the risks of segregation of the components of the aqueous formulation. comprising a hydraulic binder.
• Document WO-2019/020936 also describes an aqueous composition comprising a copolymer obtained by a polymerization reaction in the presence of sodium hypophosphite which uses an anionic carboxylic and unsaturated monomer and a hydrophobic vinyl monomer.
• dispersing compounds or superplasticizing agents which can be used in aqueous formulations comprising a hydraulic binder.
• these compounds do not make it possible to provide a solution to the problems encountered.
• these compounds do not make it possible to maintain a good degree of initial fluidity of the aqueous formulations comprising a hydraulic binder in which they are incorporated, while at the same time maintaining their workability and without altering their mechanical properties, nor causing segregation phenomena.
• the invention makes it possible to provide a solution to all or part of the problems encountered with polymers of the state of the art.
• the invention makes it possible to obtain copolymers by a particularly efficient preparation process, for example with regard to controlling the temperature of the polymerization reaction.
• it is essential to be able to have preparation processes which make it possible to dispense with maintaining the reaction medium at low temperature used during the polymerization reactions known from the state of the art.
• the copolymers prepared can comprise residues of the comonomers in proportions which are identical or close to the proportions of the monomers used, thus ensuring stability of the composition of the copolymer.
• terpolymers or polymers resulting from the reaction of three different monomers, the properties of which are improved.
• the choice of monomers having different chain lengths makes it possible to confer particular properties on the polymers prepared. This choice is particularly useful during the preparation of comb terpolymers whose length of the pendant chains can be modulated. The properties of these polymers, in particular of these terpolymers, can then be controlled in a particularly efficient manner.
• the invention provides a copolymer whose polymolecularity index Ip , determined by Steric Exclusion Chromatography (CES), is less than 3 , obtained by at least one radical polymerization reaction in water, at a temperature ranging from from 10 to 90 ° C, and in the presence:
• CES Steric Exclusion Chromatography
• - X independently represents H, Na or K
• - R independently represents a Ci-Cs-alkyl group
• - L 1 independently represents an OE group or a combination of OE and OP groups
• - n independently represents an integer or decimal between 20 and 100;
• - EO independently represents an oxy-ethylene group
• - OP independently represents an oxy-propylene group
• - L 2 independently represents an OE group or a combination of
• - m independently represents an integer or decimal between 20 and 100;
• - EO independently represents an oxy-ethylene group
• - OP independently represents an oxy-propylene group
• - L 3 independently represents an OE group or a combination of OE and OP groups
• - u independently represents an integer or decimal between 22 and 150;
• - EO independently represents an oxy-ethylene group
• - OP independently represents an oxy-propylene group
• - R 1 independently represents H or CH3;
• - L 4 independently represents an OE group
• - EO independently represents an oxy-ethylene group
• - v independently represents an integer or decimal between 50 and 150;
• - L 5 independently represents an OE group
• - EO independently represents an oxy-ethylene group
• - L 6 independently represents an OE group or a combination of
• - 1 independently represents an integer or decimal between 50 and 150;
• - EO independently represents an oxy-ethylene group
• - OP independently represents an oxy-propylene group
• the set of monomers (c) comprising a total number of OE and PO groups which is 1.3 to 2.5 times greater than the total number of OE and PO groups of all the monomers (b).
• the total number by weight of the EO and PO groups of all the monomers (c) is 1.3 to 2.5 times greater than the total number by weight of EO and PO groups of all the monomers (b).
• the monomers (c) comprise a total number of EO and PO groups which is 1.4 to 2.5 times greater than the total number of EO and PO groups of the monomers (b).
• the copolymer of the invention characterized by such ratios makes it possible to significantly reduce the amount of water in a hydraulic binder composition.
• the monomers used during the preparation of the copolymer according to the invention comprise OE groups or else comprise a combination of OE groups and OP groups.
• EO represents an oxy-ethylene group. It is a group of formula -CH2-CH2O-.
• OP represents an oxy-propylene group. It is a group of formula -CH 2 CH (CH 3 ) 0- or else a group of formula -CH (CH3) CH20-.
• the total number of OE groups is strictly greater than the total number of OP groups.
• the proportion by weight of the number of EO groups and of the number of OP groups ranges from 98/2 to 52/48, preferably from 85/15 to 55/45, more preferably from 80/20 to 60 / 40 or from 75/25 to 65/35, in particular 70/30.
• the conditions for preparing the copolymer according to the invention are particularly advantageous. In fact, these conditions for preparing the copolymer according to the invention make it possible to reduce or avoid the formation of homopolymer of the monomer (a). Very advantageously, the copolymer according to the invention does not comprise a homopolymer of monomer (a). Also very advantageously, the copolymer according to the invention does not comprise a copolymer of the monomers (a). According to the invention, these copolymers of monomers (a) are copolymers of several different monomers (a); they do not include monomer (b) or monomer (c).
• the copolymer according to the invention comprises a reduced, low or very low quantity by weight of homopolymer of monomer (a) relative to the quantity by dry weight of copolymer of monomers (a), (b) and ( vs). Also advantageously, the copolymer according to the invention comprises a reduced, low or very low quantity by weight of copolymer of monomers (a) relative to the quantity by dry weight of copolymer of monomers (a), (b) and ( vs).
• the absence or presence of a reduced, low or very low quantity of homopolymer of monomer (a) or of copolymer of monomers (a) makes it possible to avoid or limit the risk of inhibition of crystallization of concrete when the copolymer according to the invention is used for its plasticizing properties in a concrete formulation.
• a homopolymer of monomer (a) or a copolymer of monomers (a) has dispersing properties of particles of mineral matter and can therefore disrupt or inhibit crystallization within a concrete formulation. The properties of the concrete formulation or of the final material prepared from the concrete formulation can then be modified or altered.
• the invention makes it possible to prepare a copolymer from the monomers (a), (b) and (c) while controlling the polymerization reaction of the monomers (a), (b) and (c) ).
• the invention therefore makes it possible to obtain an aqueous composition comprising a very small amount of residual monomer (a) relative to the amount by dry weight of copolymer.
• the presence of residual monomer (a) in a copolymer can disrupt or inhibit crystallization within a concrete formulation.
• the copolymer according to the invention comprises less than 2000 ppm by weight or less than 1500 ppm by weight, preferably less than 1000 ppm by weight or less than 500 ppm by weight, in particular less than 200 ppm by weight or less than 100 ppm by weight of residual monomer (a) based on the dry weight amount of copolymer.
• the amount of residual monomers is measured according to techniques known as such, for example by High Pressure Liquid Chromatography (HPLC) or in English “High Performance Liquid Chromatography” (HPLC).
• the constituent components of the mixture are separated on a stationary phase and detected by a UV detector. After calibrating the detector, it is possible, for example from the area of the peak corresponding to the acrylic compound, to obtain the quantity of residual (meth) acrylic acid.
• the quantities of monomers (a), (b) and (c) used can vary quite widely.
• the polymerization reaction implements, relative to the total amount of monomers:
• the polymerization reaction implements, relative to the total amount of monomers:
• the copolymer according to the invention comprises, relative to the total amount of monomers:
• the copolymer according to the invention comprises, relative to the total amount of monomers:
• the polymerization reaction can implement one or more of the monomers (a), (b) and (c).
• the polymerization reaction uses a monomer (a), a monomer (b) and a monomer (c).
• the polymerization reaction uses a monomer (a), a monomer (b) and two monomers (c).
• the polymerization reaction uses one monomer (a), two monomers (b) and one monomer (c).
• the copolymer of the invention is a copolymer obtained by polymerization of at least one monomer (a), at least one monomer (b) chosen from a compound (b1) and a compound ( b2) and at least one monomer (c) selected from a monomer (cl), a monomer (c2) and a monomer (c4). More preferably according to the invention, the copolymer according to the invention is a copolymer obtained by polymerization of at least one monomer (a), at least one compound (b1) and at least one monomer (c) chosen from a monomer (cl) and a monomer (c2).
• the invention comprises the implementation of a radical polymerization reaction in water of acrylic acid alone or in combination with at least one other monomer chosen from methacrylic acid, maleic acid, maleic anhydride, itaconic acid, 2- acid. acrylamido-2-methylpropane sulfonic, 2-acrylamido-2-methylpropane sulfonic, vinylsulfonic acid, 2- (methacryloyloxy) -ethanesulfonic acid,
• the monomer (a) is acrylic acid alone or else acrylic acid combined with another monomer (a) chosen from methacrylic acid, itaconic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-acrylamido -2- methylpropane sulfonic acid, vinylsulfonic acid, 2- (methacryloyloxy) - ethanesulfonic acid, 2- (methacryloyloxy) ethanesulfonic, sodium methallyl sulfonate, styrene sulfonate and their salts.
• the monomer (a) is acrylic acid alone or else acrylic acid combined with another monomer (a) chosen from methacrylic acid, maleic acid, maleic anhydride and 2-acrylamido-2-methylpropanesulfonic acid. , their salts and their combinations. Much more preferably, the monomer (a) is acrylic acid alone.
• acrylic acid can be used in the form of free acrylic acid or else in the form of an acrylic acid salt, for example a sodium salt. It can also be implemented in the form of a combination of free acrylic acid and a salt of acrylic acid, for example a sodium salt.
• the invention also comprises the use of at least one monomer (b) chosen from a monomer (b1), a monomer (b2) and their combinations.
• the preferred monomer (b) is monomer (b1).
• the preferred monomer (b1) is a compound of formula (I) in which n independently represents an integer or decimal between 10 and 120 or between 20 and 120.
• the more preferred monomer (b1) is a compound of formula (I) in which n independently represents an integer or decimal between 25 and 95 or between 40 and 85, in particular between 40 and 60 or between 65 and 85.
• a particularly preferred monomer (b1) is the monomer (b la) of formula (I) in which, n represents approximately 53 and L 1 represents EO.
• Another particularly preferred monomer (bl) is the monomer (blb) of formula (I) in which n represents about 78 and L 1 represents EO.
• the preferred monomer (b2) is a compound of formula (II) in which m independently represents an integer or decimal between 10 and 120 or between 20 and 120.
• the more preferred monomer (b2) is a compound of formula (II) in which m independently represents an integer or decimal between 25 and 95 or between 40 and 85, in particular between 40 and 60 or between 65 and 85.
• the invention also comprises the use of at least one monomer (c) chosen from a monomer (cl), a monomer (c2), a monomer (c3), a monomer (c4) and combinations thereof.
• Preferred monomers (c) are monomers (c1) and (c2) and their combinations.
• the preferred monomer (c1) is a compound of formula (III) in which u independently represents an integer or decimal between 25 and 170 or between 30 and 160.
• the more preferred monomer (c1) is a compound of formula (III) wherein u independently represents an integer or decimal between 50 and 150.
• the preferred monomer (c2) is a compound of formula (IV) in which v independently represents an integer or decimal between 70 and 140.
• the preferred monomer (c3) is a compound of formula (V) in which w independently represents an integer or decimal between 90 and 140.
• the preferred monomer (c4) is a compound of formula (VI) in which t independently represents an integer or decimal between 70 and 140.
• a particularly preferred monomer (c1) is the monomer (cia) of formula (III) in which u represents approximately 112, L 3 represents EO and R 1 represents H.
• acrylic acid monomer (bl) and monomer (cl), in particular acrylic acid, monomer (b la) and monomer (cia) or else acrylic acid, monomer (blb) and the monomer (cia);
• acrylic acid monomer (bl), monomer (cl) and monomer (c2), in particular acrylic acid, monomer (bla), monomer (cia) and monomer (c2) or else acrylic acid, monomer (blb), monomer (cia) and monomer (c2).
• the copolymer according to the invention can also be prepared from a polymerization reaction also using a non-monomer.
• ionic comprising at least one polymerizable olefinic unsaturation, preferably at least one polymerizable ethylenic unsaturation and in particular a polymerizable vinyl function, more preferably a nonionic monomer chosen from esters of an acid comprising at least one monocarboxylic acid function, in particular an ester an acid chosen from acrylic acid, methacrylic acid, and mixtures thereof, for example hydroxyethylacrylate, hydroxypropylacrylate, hydroxyethylmethacrylate, hydroxypropylmethacrylate.
• the preparation of the copolymer according to the invention uses at least one compound which generates radicals which is particular. It is preferably chosen from hydrogen peroxide, ammonium persulfate, sodium persulfate, potassium persulfate, their mixtures or their associations with an ion chosen from Fe n , Fe m , Cu 1 , Cu 11 .
• the Fe 11 , Fe 111 , Cu 1 or Cu n ions can be implemented using of at least one compound selected from iron sulphate, hydrated iron sulphate, iron sulphate hemihydrate, iron sulphate heptahydrate, iron carbonate, hydrated iron carbonate, iron carbonate hemihydrate, iron chloride, carbonate copper, hydrated copper carbonate, hemihydrate copper carbonate, copper acetate, copper sulfate, copper sulfate pentahydrate, copper hydroxide, copper halide.
• the particular radical-generating compound is more preferably chosen from hydrogen peroxide, ammonium persulfate, sodium persulfate, potassium persulfate, very particularly sodium persulfate.
• the polymerization reaction can implement one or more compounds (i) or one or more compounds (ii).
• the polymerization reaction uses a single compound (i) or else a single compound (ii) or else a compound (i) and a compound (ii).
• the polymerization reaction is carried out in the absence of sodium bisulphite and more preferably in the absence of sodium bisulphite associated with a compound (ii).
• the preparation of the aqueous composition according to the invention implements a radical polymerization reaction which is carried out in water in the presence of at least one compound (i) comprising phosphorus at oxidation degree I.
• the polymerization reaction uses a mineral compound (i). More preferably according to the invention, the polymerization reaction uses a compound (i) chosen from hypophosphorous acid (H 3 PO 2 ), a derivative of hypophosphorous acid (H 3 PO 2 ).
• the polymerization reaction uses a compound (i) comprising at least one hypophosphite ion (H 2 PO 2 ), more preferably a compound (i) chosen from sodium hypophosphite (PhPChNa) , potassium hypophosphite (H 2 PO 2 K), calcium hypophosphite ([PbPChkCa) and their mixtures. Particularly preferred is sodium hypophosphite (PbPCLNa).
• the polymerization reaction according to the invention can also implement at least one compound (ii) of formula (A) in which X independently represents H, Na or K and R independently represents a Ci-Cs-alkyl group.
• compound (ii) is a compound of formula (A) in which R represents a C 1 -C 3 -alkyl group, preferably a methyl group, and X represents H.
• compound of formula (A) preferred according to the invention is disodium trithiocarbonate dipropionate (DPTTC - CAS number 86470-33-2).
• the compound (ii) is used in an amount by weight ranging from 0.05 to 5% by weight, relative to the amount of monomers.
• the polymerization reaction uses the compound (ii) of formula (A) in an amount of 0.05 to 4% by weight, from 0.05 to 3% by weight, of 0.05 to 2% by weight, from 0.5 to 4% by weight, from 0.5 to 3% by weight, from 0.5 to 2% by weight, from 1 to 4% by weight, from 1 to 3% by weight, from 1 to 2% by weight relative to the amount of monomers.
• the copolymer according to the invention has a polymolecularity index Ip of less than 3.
• the polymolecularity index Ip ranges from 1.5 to 3, more preferably from 1.5 to 2.8, although more preferably from 1.5 to 2.5.
• the copolymer according to the invention is obtained by at least one radical polymerization reaction in water and at a temperature ranging from 10 to 90 ° C, preferably ranging from 30 to 85 ° C, more preferably at a temperature ranging from 40 at 75 ° C or from 50 to 70 ° C, much more preferably from 50 to 68 ° C or from 50 to 65 ° C.
• the copolymer according to the invention can also be characterized by its molecular mass by weight (Mw). Preferably, it has a molecular mass by weight ranging from 8,000 g / mol to 200,000 g / mol or from 10,000 g / mol to 200,000 g / mol or alternatively from 12,000 g / mol to 200,000 g / mol.
• it has a molecular mass by weight ranging from 15,000 g / mol to 150,000 g / mol or from 15,000 g / mol to 120,000 g / mol or else from 15,000 g / mol to 90,000 g / mol or from 15,000 g / mol to 50,000 g / mol.
• the molecular weight and the polymolecularity index of the copolymers is determined by Steric Exclusion Chromatography (CES) or in English “Steric Exclusion Chromatography” (SEC).
• This technique uses a Waters brand liquid chromatography with detector.
• This detector is a Waters brand refractometric concentration detector.
• This liquid chromatography apparatus is fitted with a steric exclusion column in order to separate the different molecular weights of the copolymers studied.
• the liquid elution phase is an aqueous phase adjusted to pH 9.00 by means of 1 N sodium hydroxide containing 0.05 M of NaHCCL, 0.1 M of NaNCh, 0.02 M of triethanolamine and 0.03% of NaN3 .
• the copolymer solution is diluted to 0.9% dryness in the solvent for solubilizing the CES, which corresponds to the liquid phase for eluting the CES to which 0.04% of dimethylformamide is added, which plays a role. the role of flow marker or internal standard. Then, it is filtered at 0.2 ⁇ m. 100 ⁇ L are then injected into the chromatography apparatus (eluent: an aqueous phase adjusted to pH 9.00 with IN sodium hydroxide containing 0.05 M of NaHCCL, 0.1 M of NaNCh, 0.02 M of triethanolamine and 0.03% NaN 3 ).
• the liquid chromatography apparatus contains an isocratic pump (Waters 515) whose flow rate is set at 0.8 mL / min.
• the chromatography apparatus also comprises an oven which itself comprises the following column system as standard: a Guard Column Ultrahydrogel Waters type precolumn 6 cm in length and 40 mm in internal diameter and a linear column of Waters Ultrahydrogel type 30cm in length and 7.8mm inside diameter.
• the detection system consists of an RI Waters 410 type refractometric detector. The oven is brought to a temperature of 60 ° C and the refractometer is brought to a temperature of 45 ° C.
• the copolymer according to the invention is obtained by at least one radical polymerization reaction in water.
• An aqueous composition is then obtained comprising the copolymer according to the invention.
• the water can be separated in order to obtain the copolymer as such, for example in powder form.
• the invention therefore also provides an aqueous composition comprising water and at least one copolymer according to the invention.
• the particular, advantageous or preferred characteristics of the copolymer according to the invention define aqueous compositions according to the invention which are also particular, advantageous or preferred.
• copolymer and the aqueous composition according to the invention have particularly advantageous properties in many technical fields.
• the copolymer or the aqueous composition according to the invention can take different forms. They can therefore be used directly or be used in combination with other ingredients. They can be implemented in different formulations. Preferably, these formulations can be hydraulic binder formulations.
• the invention also relates to a formulation (F1) comprising:
• the invention also relates to a formulation (F2) comprising:
• formulations (Fl) and (F2) according to the invention comprise:
• the formulations (F1) and (F2) according to the invention comprise: - from 0.01 to 4% by dry weight or from 0.01 to 3% by dry weight of copolymer, respectively in the form of at least one aqueous composition according to the invention or in the form of at least one copolymer according to the invention as such;
• formulations (F1) and (F2) according to the invention comprise:
• formulations (F1) and (F2) according to the invention comprise:
• formulations (F1) and (F2) according to the invention comprise water in an amount by weight relative to the amount by weight of hydraulic binder of less than 0.7, less than 0.65 or less. 0.6, preferably less than 0.5 or less than 0.4 or even less than 0.3 or less than 0.2.
• Preferred ranges of the amount of water by weight relative to the amount by weight of hydraulic binder in formulations (F1) and (F2) are from 0.2 to 0.65 or from 0.2 to 0.6 or 0.2 to 0.5 or from 0.3 to 0.65 or from 0.3 to 0.6 or from 0.3 to 0.5.
• the hydraulic or hydrolite binder can be chosen from among cement, mortar, plaster, grout, concrete.
• the cement can be chosen from Portland cement, white Portland cement, artificial cement, blast furnace cement, high strength cement, alumina cement, rapid cement, magnesium phosphate cement, cement based on incineration products, fly ash cement and mixtures thereof.
• hydraulic binders can be chosen from latent hydraulic binders, pozzolanic binders, ash, slag, clinker.
• the plaster can be chosen from gypsum, calcium sulfate dihydrate, calcium sulfate, calcium sulfate hemihydrate, calcium sulfate anhydride and mixtures thereof.
• the aggregate can be selected from sand, coarse aggregate, gravel, crushed stone, slag, recycled aggregate.
• the aggregates are classified into several categories known as such by those skilled in the art, for example according to the French standard XP P 18-540. According to this standard, defining in particular the values d and D, the families of aggregates include:
• fillers are silica fumes or siliceous additions, or limestone additions such as calcium carbonate.
• the adjuvant of formulations (F1) or (F2) can be chosen from an anti-foaming agent, a plasticizer or superplasticizer, an agent for improving workability, a sag reducing agent, air entrainment reducing agent, coloring agent, pigment, water reducing agent, setting retardant, hygroscopy controlling agent, anti-corrosion agent, anti- removal, an inhibitor of silico-alkaline reactions, a water-repellent agent, a foaming agent.
• the particular properties of the aqueous composition according to the invention or of the copolymer according to the invention make it possible to use them in many technical fields, in particular for their properties for controlling or regulating rheology.
• the invention provides a method of modifying the rheology of a hydraulic formulation comprising the addition of at least one aqueous composition according to the invention or of at least one copolymer according to the invention in the hydraulic formulation comprising of water and a hydraulic binder.
• composition according to the invention and of the copolymer are particularly useful in the field of hydraulic formulations.
• the invention therefore provides a method of reducing water from a hydraulic formulation comprising the addition of at least one aqueous composition according to the invention or at least one copolymer according to the invention in a hydraulic formulation.
• the water reduction method is determined according to the ADJUVANT NF EN 934-2 standard.
• the hydraulic formulation is chosen from a hydraulic formulation (Fl) and a hydraulic formulation (F2).
• the water reduction of the hydraulic formulation is determined relative to the amount of water of a hydraulic formulation not comprising a copolymer.
• the water reduction method according to the invention makes it possible to reduce the amount by weight of water in the hydraulic formulation by at least 15%, preferably by at least 20% or d 'at least 25%, more preferably at least 30% relative to the amount of water of a hydraulic formulation not comprising a copolymer.
• the particular, advantageous or preferred characteristics of the hydraulic formulations (F1) and (F2) according to the invention define methods of reducing water from a hydraulic formulation according to the invention which are also particular, advantageous or preferred.
• Example 1 preparation of copolymers according to the invention and of a comparative copolymer
• Example 1.1 copolymer (PI) according to the invention
• the product is cooled and then neutralized by adding an aqueous sodium hydroxide solution at 50% by mass (63 g).
• the aqueous polymeric solution contains less than 3 ppm of dry residual acrylic acid based on the total amount of dry copolymer.
• a copolymer (PI) comprising 15.9% by weight of acrylic acid, 73.1% by weight of monomer (bla) and 11.0% by weight of monomer (cia) is obtained. Its molecular mass Mw is 35,000 g / mol and its polymolecularity index Ip is 1.9.
• Example 1.2 copolymer (P2) according to the invention
• a mixture of water (34.2 g), acrylic acid (57.44 g) and comonomer (cia) with a molecular mass of 5000 g / mol is injected in parallel into the reactor in 50% solution in water (100 g), a mixture of water (34.2 g) and hydrated sodium hypophosphite (12.57 g), and a mixture of water (13.7 g) and sodium persulfate (5.6 g).
• the reactor is then maintained at a temperature of 65 ⁇ 2 ° C. for 1 h.
• the product is cooled and then neutralized by adding an aqueous sodium hydroxide solution at 50% by mass (62.2 g).
• the aqueous polymeric solution contains less than 3 ppm of dry residual acrylic acid based on the total amount of dry copolymer.
• a copolymer (P2) is obtained comprising 16.0% by weight of acrylic acid, 70.1% by weight of monomer (bla) and 13.9% by weight of monomer (cia). Its molecular mass Mw is 29,000 g / mol and its polymolecularity index Ip is 1.5.
• a mixture of water (34.2 g), acrylic acid (57.44 g) and comonomer (cia) with a molecular mass of 5000 g / mol is injected in parallel into the reactor in 50% solution in water (120 g), a mixture of water (34.2 g) and hydrated sodium hypophosphite (12.57 g), and a mixture of water (13.7 g) and sodium persulfate (5.6 g).
• the reactor is then maintained at a temperature of 65 ⁇ 2 ° C. for 1 h.
• the product is cooled and then neutralized by adding an aqueous sodium hydroxide solution at 50% by mass (62.0 g).
• the aqueous polymeric solution contains less than 3 ppm of dry residual acrylic acid based on the total amount of dry copolymer.
• a copolymer (P3) comprising 16.0% by weight of acrylic acid, 67.2% by weight of monomer (bla) and 16.8% by weight of monomer (cia) is obtained. Its molecular mass Mw is 31,000 g / mol and its polymolecularity index Ip is 1.3.
• Example 1.4 copolymer (P4) according to the invention
• the reactor is kept at a temperature of 65 ⁇ 2 ° C. for 1 h.
• the product is cooled and then neutralized by adding an aqueous sodium hydroxide solution at 50% by mass (63.5 g).
• the aqueous polymeric solution comprises less than 15 ppm of dry residual acrylic acid relative to the total amount of dry copolymer.
• a copolymer (P4) is obtained comprising 15.9% by weight of acrylic acid, 73.1% by weight. weight of monomer (b la) and 11.0% by weight of monomer (cia). Its molecular mass Mw is 110,000 g / mol and its polymolecularity index Ip is 1.4.
• Example 1.5 copolymer (P5) according to the invention
• the product is cooled and then neutralized by adding an aqueous sodium hydroxide solution at 50% by mass (46.3 g).
• the aqueous polymeric solution contains less than 10 ppm of dry residual acrylic acid based on the total amount of dry copolymer.
• a copolymer (P5) comprising 11.9% by weight of acrylic acid, 79.9% by weight of monomer (blb) and 8.2% by weight of monomer (cia) is obtained. Its molecular mass Mw is 39,000 g / mol and its polymolecularity index Ip is 1.6.
• Example 2 evaluation of the reducing power of water in a mortar
• Mortar formulations are prepared according to the procedure: incorporation of the admixture and water in the bowl of a Perrier automatic mixer for standardized cements and mortars,
• FC comparative mortar formulation
• the water-reducing power of the copolymers according to the invention is evaluated using mortar formulations.
• the workability T0 of the mortars formulated with the copolymers according to the invention was evaluated by measuring the spreading diameter (slump flow in English) according to the standard EN 12350-2 adapted to the mortar (Abrams mini-cone).
• the cone filled with formulated mortar is lifted perpendicular to a horizontal plate while carrying out a quarter turn.
• the spread is measured after 5 minutes according to two diameters at 90 ° with a ruler.
• the result of the spreading measurement is the average of the 2 values at ⁇ 1 mm.
• the tests are carried out at 20 ° C.
• the adjuvant dosage is determined so as to achieve a target spread of 220 mm ⁇ 5 mm.
• the dosage is expressed in% by dry weight relative to the weight of the hydraulic binder or of the mixture of hydraulic binders. The results are shown in Table 1.
• copolymers according to the invention makes it possible to reduce the quantity of water by 36% in the hydraulic formulations, while maintaining an initial fluidity. (workability) similar to that of the comparative formulation not comprising a copolymer.
• copolymers according to the invention can therefore be qualified as high water reducing agents according to the ADJUVANT NF EN 934-2 standard. Indeed, they allow a reduction in water for the admixed mortar of at least 12% compared to the control mortar.
• copolymers according to the invention would make it possible to obtain similar results in admixed concrete by reducing the quantity of water by at least 12% relative to a control concrete not comprising a copolymer according to invention.

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• 2019
  • 2019-06-26 FR FR1906925A patent/FR3097865B1/fr active Active
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