WO2015071584A1 - Agent retenteur de fluidite pour compositions hydrauliques compatible avec agent reducteur d'eau de type polymere peigne - Google Patents
Agent retenteur de fluidite pour compositions hydrauliques compatible avec agent reducteur d'eau de type polymere peigne Download PDFInfo
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- WO2015071584A1 WO2015071584A1 PCT/FR2014/052871 FR2014052871W WO2015071584A1 WO 2015071584 A1 WO2015071584 A1 WO 2015071584A1 FR 2014052871 W FR2014052871 W FR 2014052871W WO 2015071584 A1 WO2015071584 A1 WO 2015071584A1
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- 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
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- 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
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- 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
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- 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
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- 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
- C08F220/62—Monocarboxylic acids having ten or more carbon atoms; Derivatives thereof
- C08F220/68—Esters
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- 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
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
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- 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
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- 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
Definitions
- the present invention relates to the technical field of hydraulic compositions, for example concrete and mortar compositions. Such compositions are intended for all construction markets. More specifically, the present patent application relates to additives used in such hydraulic compositions.
- the hydraulic compositions generally comprise various chemical additives for improving their properties.
- a chemical agent is generally used whose function is to improve the state of dispersion of the mineral particles within the composition.
- This chemical agent is indifferently called “dispersing agent”, “fluidifying agent”, “water reducing agent”, “plasticizing agent” or “superplasticizer”. This chemical agent makes it possible to reduce the water content of the hydraulic compositions, which makes it possible to improve the performance of the hydraulic compositions, including the mechanical strength.
- dispersing agents for hydraulic compositions. These agents differ in their chemical composition and the properties they induce in the compositions containing them.
- the slump is measured in accordance with the EN 12350-2 standard.
- the workability of a concrete is an important property that conditions its implementation, for example for the filling of a formwork. It is evaluated right after its manufacture, as well as at specific times after manufacture, this which makes it possible to evaluate the workability over time, also called retention of fluidity ("slump retention" in English), as well as the limited period of workability after manufacture.
- ready-mix concrete (BPE), another category of concrete that has maneuverability values of the order of 50 mm to 200 mm.
- a proposed solution for increasing the workability of the concrete consists in overdosing the quantity of dispersing agents used. This solution, very practical, nevertheless leads to a loss of stability and homogeneity of the formulation, which negatively impacts the performance of the concrete (segregation).
- Another solution is to use setting retarding agents, in accordance with the standard ADJUVANT NF EN 934-2. As soon as the anhydrous cement has been mixed with the water, which may be additive, the hydration starts and the properties of the paste thus obtained change over time. After a while, the crystals become more important, the mixture has changed viscosity and stiffens.
- fluidity retentive agents are also proposed to ensure maneuverability for a prolonged time.
- WO 2007/047407 describes a method for increasing the workability of combining three additives: an initial fluidity increasing agent, a fluidity retaining agent and an agent that controls the response of the agent increasing the initial fluidity when the first two agents are added to said composition.
- the document WO 97/48656 describes the use of a copolymer-type agent which confers an initial fluidity on a hydraulic composition such as a cement paste, a mortar or concrete and, moreover, makes it possible to maintain the fluidity of the composition.
- This concrete mixing agent consists of a copolymer consisting of (a) an ethylenically unsaturated monomer having from 25 to 300 moles of C2-C3 oxyalkylene groups, (b) an ethylenically unsaturated monomer of the alkyl, alkenyl or hydroxyalkyl ester type and optionally (c) an ethylenically unsaturated carboxylic acid or a salt thereof, said copolymer comprising a high proportion of monomers (b).
- Such a copolymer is presented as allowing an excellent balance between initial fluidity and fluidity retention, these properties being adjusted according to the molecular weight of the copolymer.
- EP 2 147 901 discloses a dispersion-maintaining agent for hydraulic compositions, without initial fluidity, comprising structural units based on ethylenically unsaturated carboxylate. This agent does not comprise an ethylenically unsaturated carboxylic acid group which, according to this document, confers an initial fluidity on the copolymer.
- EP 1 655 272 A1 discloses cement additives useful as superplasticizers which increase the workability of cement. These additives confer initial fluidity and fluidity retention.
- additives necessarily consist of the following three monomers: (I) ethylenically unsaturated poly (alkylene glycol) ether monomers having from 25 to 300 units of C2-C3 oxyalkylene groups, (II) monomers alkyl esters with ethylenic unsaturation and comprising from 1 to 4 ethylene / propylene glycol units and (III) monomers comprising two optionally oxyalkylated ethylenic unsaturations.
- the document WO 2010/064098 (Coatex) describes the use of a combination of comb polymers as an agent improving the workability of an aqueous formulation based on hydraulic binders, one having hydrophilic side chains and the other of chains. hydrophobic sides.
- EP 0 612 702 A1 discloses superplasticizer type additives consisting of methacrylic acid monomers, poly (ethylene glycol) monoethyl ether methacrylate and poly (ethylene glycol) dimethacrylate as crosslinking agent. This document gives no indication of the molecular weight of the additives described. None of the solutions presented in these documents are completely satisfactory.
- An object of the present invention is to provide a copolymer agent for hydraulic compositions whose essential property fluidity retention.
- Another object of the present invention is to provide a copolymer which does not provide initial fluidity when it is within a hydraulic composition.
- Another object of the present invention is to provide a fluidity retentive agent which is totally compatible with a water-reducing agent of the comb polymer type having at least one hydrophilic side chain, that is to say to propose an agent fluidity retainer which is miscible in all proportions with such a water reducing agent and which has no impact on the initial fluidity of the formulation at standard doses.
- Another object of the present invention is to provide a workability agent which has an optimization of its characteristics of initial fluidity and fluidity retention.
- the fluid-retaining agent according to the invention of particular composition, compatible with a comb-type water-reducing agent having at least one hydrophilic side chain and the handling agent consisting of a combination of this retaining agent.
- fluidity and a particular water reducing agent make it possible to respond to all of these objects.
- Another object of the present invention is to provide an additive which makes it possible to obtain a homogeneous composition, that is to say which does not lead to a segregation of the materials within the composition.
- a first object of the invention consists of a fluidity retentive agent for hydraulic compositions, said agent not being a water-reducing agent, consisting of a copolymer obtained by polymerization:
- At least one macromonomer comprising a polymerizable unsaturated functional group and a polyalkoxylated chain, consisting of at least one alkoxylated unit, for example at least 10 alkoxylated units, and
- copolymer having a molecular weight greater than 400,000 g / mol.
- the flow-retaining agent according to the invention is a concrete admixture incorporated at the time of mixing concrete at a dose less than or equal to 5% by weight / weight of the cement content of the concrete, in order to modify the properties of the mixture. fresh and / or hardened condition.
- the agent according to the invention makes it possible to extend the handling time of a hydraulic composition, for example a concrete. Furthermore, if it is important to extend the handling time of a concrete, this must not be done at the expense of the performance of the concrete during curing or in the cured state (in particular the initial or final mechanical strengths sought), or the rate of entrained air in the hydraulic compositions.
- the fluid retention agent according to the invention is not a water reducing agent or a high water reducing agent.
- a "water reducing agent” or a “plasticizer” is an agent which, in accordance with the ADJUVANT standard NF EN 934-2, allows a water reduction for the adjoining concrete> 5% compared to the control concrete.
- a "high water reducer” or “superplasticizer” is an adjuvant that allows water reduction for adjuvanted concrete> 12% over control concrete.
- the fluidity retentive agent according to the invention does not meet these characteristics.
- the fluid retention agent according to the invention is completely compatible with a water reducing agent, plasticizer or superplasticizer. This makes it possible to formulate the hydraulic compositions adapted to each structure, without having to adjust the amounts of one or the other of the additives to obtain a desired profile of initial fluidity and maintenance of the maneuverability over time.
- the flow-retaining agent according to the invention is also not a setting-retarding agent according to the standard ADJUVANT NF EN 934-2.
- the agent according to the invention does not affect the hydration stage of the cement when it comes into contact with the other constituents of the concrete or the mortar and / or the crystallization step of the constituents of the cement. It has no influence on resistance at young ages of structures, for example resistance to 1 day or 7 days.
- the fluidity-retaining agents according to the invention make it possible to obtain homogeneous compositions, whereas these same agents, with a molecular weight of the order of 100,000 to 150,000 g / mol, , lead to a segregation of materials within the composition. Such a meaning is not acceptable because it is likely to have a negative impact on the performance of the compositions containing them.
- the retention agent according to the present invention is derived from the polymerization of monomers a), b) and c).
- monomers a), b) and c) can be present in the copolymer, alone or in a mixture of two or more entities.
- the monomer a) can be in acid form, for example carboxylic acid, and / or in salt form, for example carboxylate.
- the copolymer comprises, for example, one or more crosslinking monomers c). According to one embodiment, it comprises a single crosslinking monomer. According to another embodiment, it comprises two crosslinking monomers.
- the crosslinking monomer (s) is (are) used to generate a copolymer in the form of a three-dimensional network.
- a monomer which is a polyunsaturated compound is used as crosslinking monomer c). This compound may comprise two, three or more ethylenic unsaturations.
- the crosslinking monomer may have a hydrophilic, hydrophobic or amphiphilic character.
- di (meth) acrylate compounds such as polyalkylene glycol di (meth) acrylate, especially polypropylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, di (meth) ) polyethylene glycol acrylate, triethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,6-butylene glycol di (meth) acrylate, di (meth) acrylate 1,6-hexanediol, neopentyl glycol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, but also 2,2'-bis (4- (acryloxypropyloxyphenyl) propane, 2,2'-bis (4- (acryloxydiethoxy-phenyl) propane and zinc acrylate, tri (meth) acrylate compounds such as trimethylolpropane tri (meth) acrylate, tri
- crosslinking monomers may be prepared by an esterification reaction of a polyol with an unsaturated anhydride such as maleic anhydride or itaconic anhydride or by an addition reaction with an isocyanate such as 3 isopropenyl-dimethylbenzene isocyanate.
- the following unsaturated compounds which crosslink by means of their pendant carboxyl groups may also be used: polyhaloalkanols such as 1,3-dichloroisopropanol and 1,3-dibromoisopropanol; haloepoxyalkanes such as epichlorohydrin, epibromohydrin, 2-methyl epichlorohydrin and epiiodohydrin; polyglycidyl ethers such as 1,4-butanediol diglycidyl ether, glycerin-1,3-diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, polypropylene glycol diglycidyl ether, bisphenol A- epichlorohydrin epoxy resin and mixtures.
- polyhaloalkanols such as 1,3-dichlorois
- the present invention also relates to a fluidity retentive agent for hydraulic compositions, said agent not being a water-reducing agent (according to the standard ADJUVANT NF EN 934-2) consisting of a copolymer obtained by polymerization of:
- [(EO) m - (OP) n - (OB) p ] represents a polyalkoxylated chain consisting of alkoxylated units, divided into blocks, alternating or random, chosen from ethoxylated units EO, propoxylated units OP and butoxylated units OB , m, n and p represent, independently of each other, 0 or an integer ranging between 1 and 250 (inclusive), the sum of m, n and p being between 10 and 250,
- R f represents a radical containing a polymerizable unsaturated functional group
- R f ' represents hydrogen or an alkyl group having from 1 to 4 carbon atoms and
- said copolymer having a molecular weight greater than 400,000 g / mol as determined by CES.
- said retention agent is a copolymer obtained by polymerization of monomers b), in which R f represents a radical containing a polymerizable unsaturated functional group and a carboxylic group.
- said melt-retaining agent is a copolymer obtained by polymerization of monomers b) and c), in which the polymerizable unsaturated functional groups, independently of one another, are chosen from the group consisting of acrylic esters, methacrylic esters, maleic esters, itaconic esters, crotonic esters and a mixture of these esters.
- said fluidity retentive agent is a copolymer obtained by polymerization of monomers a) selected from the group consisting of acrylic acid, methacrylic acid, maleic acid, itaconic acid, acid, and the like. crotonic and a mixture of these monomers.
- said retention agent is a copolymer obtained by copolymerization of two or more different monomers a).
- it may be a mixture of acrylic acid monomers and methacrylic acid monomers, a mixture of maleic acid monomers, acrylic acid and methacrylic acid.
- said retention agent is a copolymer with a molecular weight greater than 400 000 g / mol obtained by copolymerization of:
- At least one anionic monomer selected from the group consisting of acrylic acid, methacrylic acid, maleic acid, itaconic acid, crotonic acid and a mixture of these monomers,
- [(EO) m - (OP) n - (OB) p ] represents a polyalkoxylated chain consisting of alkoxylated units, divided into blocks, alternating or random, chosen from ethoxylated units EO, propoxylated units OP and butoxylated units OB , m, n and p represent, independently of one another, 0 or an integer ranging between 1 and 250 (inclusive), the sum of m, n and p being between 10 and 250,
- R f represents a radical selected from the group consisting of acrylic esters, methacrylic esters, maleic esters, itaconic esters, croquant esters and a mixture of these esters,
- R f ' represents hydrogen or an alkyl group having from 1 to 4 carbon atoms and
- At least one nonionic crosslinking monomer comprising at least two radicals selected from the group consisting of acrylic esters, methacrylic esters, maleic esters, itaconic esters, crotonic esters and a mixture of these esters.
- said retention agent is a copolymer obtained by copolymerization of monomers a) chosen from the group consisting of acrylic acid, methacrylic acid and a mixture of these monomers.
- said retention agent is a copolymer obtained by polymerization of monomers b) and c), in which the polymerizable unsaturated functional groups, independently of one another, are chosen from the group consisting of acrylic esters, methacrylic esters and a mixture of these esters.
- the retention agent according to the invention consists of a copolymer obtained by polymerization of: a) one or two anionic monomers chosen from the group consisting of acrylic acid, methacrylic acid and a mixture of these monomers,
- [(EO) m - (OP) n - (OB) p ] represents a polyalkoxylated chain consisting of alkoxylated units, divided into blocks, alternating or random, chosen from ethoxylated units EO, propoxylated units OP and butoxylated units OB , m, n and p represent, independently of one another, 0 or an integer ranging between 1 and 250 (inclusive), the sum of m, n and p being between 10 and 250,
- Rf represents a radical selected from the group consisting of acrylic esters, methacrylic esters and a mixture of these esters,
- Rf ' represents hydrogen or an alkyl group having from 1 to 4 carbon atoms and
- At least one nonionic crosslinking monomer comprising at least two radicals selected from the group consisting of acrylic esters, methacrylic esters and a mixture of these esters.
- the flow-retaining agent according to the invention consists of a copolymer obtained by polymerization of:
- the anionic monomers according to a) can be used in a mass proportion varying between 0.5 and 40% by weight according to one aspect of the invention, between 5 and 30% by weight according to another aspect of the invention and between 7 and 25% by weight according to still another aspect of the invention, the percentage being based on the total weight of all the monomers which constitute the retention agent according to the invention.
- the copolymer is obtained by polymerization of 0.5 to 40% by weight of two or more anionic monomers.
- the copolymer is obtained by polymerizing from 0.5 to 40% by weight of two anionic monomers selected from the group consisting of acrylic acid, methacrylic acid, maleic acid, itaconic acid and the like. tonic acid.
- poly (alkylene glycol) is meant a polymer of an alkylene glycol derived from an olefinic oxide.
- the macromonomers of formula (I) comprise a poly (alkylene glycol) chain.
- the polyalkylene glycol chains of the copolymer according to the present invention contain a proportion of ethylene-oxys groups, a proportion of propylene-oxys groups and / or a proportion of butylene-oxys groups.
- the polyalkylene glycol chains according to the present invention may, for example, comprise a major proportion of ethylene-oxys groups in combination with a minor proportion of propylene-oxys groups.
- alkylene glycol polymers include: polyalkylene glycols having an average molecular weight of 1,000, 4,000, 6,000 and 10,000 g / mol; polyethylenes polypropylenes glycols having a percentage of ethylene oxides of between 20 and 80% by weight and a percentage of propylene oxides of between 20 and 80% by weight.
- the macromonomers of formula (I) can be used in a mass proportion varying between 50 and 99% by weight according to one aspect of the invention, between 60 and 95% by weight according to another aspect of the invention and between 70 and 93. % by weight according to still another aspect of the invention, the percentage being based on the total weight of all the monomers which constitute the retention agent according to the invention.
- the crosslinking monomers can be used in a mass proportion varying between 0.05 and 10% by weight according to one aspect of the invention, between 0.5 and 5% by weight according to another aspect of the invention and between 0.5 and 3% by weight according to still another aspect of the invention, the percentage being based on the total weight of all the monomers which constitute the retention agent according to the invention.
- the flow-retaining agent according to the invention does not contain an ethylenically unsaturated monomer of the alkyl, alkenyl or hydroxyalkyl ester type.
- the flow-retaining agent according to the invention does not contain an ethylenically unsaturated poly (alkylene glycol) ether monomer having from 25 to 300 moles of C2-C3 oxyalkylene groups.
- m represents an integer ranging between 1 and 250 (different from 0) and n and p represent, independently of one another, 0 or an integer ranging between 1 and 250 (inclusive),
- n and p being between 10 and 250, for example between 20 and 200 or for example between 40 and 150.
- n and n represent an integer ranging between 1 and 250 (different from 0) and p equals 0,
- n the sum of m and n being between 10 and 250, for example between 20 and 200 or for example between 40 and 150.
- n represents an integer ranging between 10 and 250, for example between 20 and
- n and p are 0.
- the flow-retaining agents according to the invention have a molecular weight greater than 400 000 g / mol. This is an essential feature of the invention.
- the flow-retaining agents according to the invention can, according to a first aspect of the present invention, have a molecular weight of between 450,000 and 800,000 g / mol (inclusive), as determined by CES.
- the flow-retaining agents according to the invention may, according to a second aspect of the present invention, have a molecular weight greater than or equal to 1 500 000 g / mol, as determined by CES.
- the inventors have indeed found that at these molecular weights, that is to say higher than 400 000 g / mol, in addition to the advantageous effect on the handling retention, the concrete or mortar formulations have a high homogeneous appearance, without sedimentation of constituents.
- This is an advantageous technical effect because in the case of sedimentation, the heavier components of the fresh concrete descend by gravity, resulting in segregation, settling of the concrete and the formation of a film of surface water ("bleeding" in English).
- the use of agents of lower molecular weight, of the order of 100,000 to 150,000 g / mol for example leads to segregation of the materials within the composition, which is likely to negatively impact. the performance of concrete or hydraulic compositions containing them.
- the flow-retaining agent according to the invention may be in the form of salts, stoichiometric or otherwise, mixed or not and consisting of alkali metals, alkaline earth metals, amines or quaternary ammoniums. According to one embodiment, the flow-retaining agent according to the invention is in acid form.
- the flow-retaining agent according to the invention is in neutralized form.
- the flow-retaining agent according to the invention is in partially or totally neutralized form.
- the fluid retention agent according to the invention may in particular be a calcium salt, a sodium salt or a diethanolamine salt.
- the flow-retaining agent is neutralized with an ion selected from the group consisting of potassium ion, sodium ion, lithium ion, calcium ion, magnesium ion, ammonium ion and a mixture of these ions.
- the flow-retaining agent according to the invention is in liquid form.
- the additive according to the invention is water-soluble or water-dispersible. Handling agent
- Another subject of the present invention relates to a handling agent for hydraulic compositions, consisting of a compatible mixture of the two following additives:
- a water-reducing agent of the dispersant copolymer type obtained by polymerization of: a) at least one anionic monomer having a saturable polymerizable function and a carboxyl group and
- [(EO) i - (OP) j - (OB) k ] represents a polyalkoxylated chain consisting of alkoxylated units, divided into blocks, alternating or random, chosen from ethoxylated units EO, propoxylated units OP and butoxylated units OB ,
- i, j and k represent, independently of each other, 0 or an integer ranging between 1 to 150 (inclusive), the sum of i, j and k being between 1 and 250,
- R d represents a radical containing a polymerizable unsaturated functional group
- R d ' represents hydrogen or an alkyl group having from 1 to 4 carbon atoms
- said copolymer having a molecular weight of between 20,000 g / mol and 400,000 g / mol.
- the constitutive water-reducing agent of the workability agent according to the invention is a copolymer obtained by polymerization of anionic monomers a) and macromonomers b). It does not include crosslinking monomer.
- the water-reducing agent is a copolymer obtained by direct esterification (or grafting or polyesterification) of a polymer (homopolymer or copolymer) containing carboxylic or anhydride functions.
- a copolymer obtained by direct esterification or grafting or polyesterification
- a polymer homopolymer or copolymer containing carboxylic or anhydride functions.
- Coatex WO 2007/132322 which discloses such a method.
- the handling agent for hydraulic compositions consists of a compatible mixture of the two following additives:
- a water-reducing agent of dispersing copolymer type obtained by functionalization of a homopolymer and / or a copolymer of (meth) acrylic acid by esterification with at least one compound comprising a polyalkoxylated chain consisting of alkoxylated units, divided into blocks, alternating or random, selected from ethoxylated units EO, propoxylated units OP and butoxylated units OB.
- said water-reducing agent is a copolymer obtained by polymerization of macromonomers b) of formula (II) in which the radical R ⁇ j is chosen from the group consisting of acrylic esters, methacrylic esters, maleic esters, itaconic esters, crotonic esters and a mixture of these esters.
- said water-reducing agent is a copolymer obtained by polymerization of macromonomers b) of formula (II) in which the radical Rd is chosen from the group consisting of acrylic esters, methacrylic esters and a mixture of these esters.
- said water-reducing agent is a copolymer obtained by copolymerization of monomers a) selected from the group consisting of acrylic acid, methacrylic acid, maleic acid, itaconic acid, and a mixture of these monomers.
- said water-reducing agent is a copolymer obtained by copolymerization of monomers a) chosen from the group consisting of acrylic acid, methacrylic acid and a mixture of these monomers.
- i represents an integer ranging between 1 and 250 (different from 0) and
- j and k represent, independently of one another, 0 or an integer ranging between 1 and 250 (inclusive),
- i, j and k being between 1 and 250, for example between 10 and 200, or for example between 40 and 150.
- i and j represent an integer ranging between 1 and 250 (different from 0) and k equals 0,
- i and j being between 2 and 250, for example between 10 and 200 or for example between 40 and 150.
- i represents an integer ranging between 1 and 250, for example between 10 and 200 or for example between 40 and 150 and
- the anionic monomers can be used in a mass proportion varying between 0.5 and 30% by weight according to one aspect of the invention, between 1 and 25% by weight according to another aspect of the invention and between 2 and 10% by weight according to still another aspect of the invention, the percentage being based on the total weight of all the monomers which constitute the water reducing agent.
- the macromonomers of formula (II) comprise a poly (alkylene glycol) chain.
- the polyalkylene glycol chains of the copolymer according to the present invention contain a proportion of ethylene-oxys groups, a proportion of propylene-oxys groups and / or a proportion of butylene-oxys groups.
- the polyalkylene glycol chains according to the present invention may, for example, comprise a major proportion of ethylene-oxys groups in combination with a minor proportion of propylene-oxys groups.
- alkylene glycol polymers include: polyalkylene glycols having an average molecular weight of 1,000, 4,000, 6,000 and 10,000 g / mol; polyethylenes polypropylenes glycols having a percentage of ethylene oxides of between 20 and 80% by weight and a percentage of propylene oxides of between 20 and 80% by weight.
- the macromonomers of formula (II) can be used in a mass proportion varying between 70 and 99.5% by weight according to one aspect of the invention, between 75 and 99% by weight according to another aspect of the invention and between 90 and 90% by weight. and 98% by weight according to still another aspect of the invention, the percentage being based on the total weight of all the monomers which make up the water-reducing agent.
- the workability agent for hydraulic compositions according to the invention may consist of a compatible mixture of the flow-retaining agent, as defined above, and of the water-reducing agent in the proportions varying between 1: 0, 1 and 1: 10, for example between 1: 0.2 and 1: 3 or between 1: 0.25 and 1: 1.5 or between 1: 0.25 and 1: 1.
- the fluidity retentive agent makes it possible to extend the handling time of the concrete, in particular when it is added to the composition in combination with the water reducing agent described above. It is a combination of additives having advantageous properties for hydraulic compositions, for example concretes, mortars, glues, coatings or grouts.
- the hydraulic composition is an aqueous formulation containing water, at least one hydraulic binder, at least one fluidity-retaining agent according to the invention and at least one water-reducing agent.
- the hydraulic binder comprises at least one cement, for example a Portland cement.
- aluminous cement type hydraulic binders and a sulfoaluminum calcium cement are also mentioned.
- the dosages of the flow control agent according to the invention and the water-reducing agent depend mainly on the amount of hydraulic binders in the hydraulic composition. Most often, they are expressed in additive dry matter relative to the total hydraulic binder (for example cement in concrete and mortar compositions).
- said hydraulic composition comprises, expressed as a percentage by dry weight of said fluid retention agent relative to the dry weight of cement, from 0.05% to 5% of said fluid retentive agent.
- said hydraulic composition comprises, expressed as a percentage by dry weight of said fluid retention agent relative to the dry weight of cement, from 0.1% to 3% of said fluid retentive agent.
- said hydraulic composition comprises, expressed as a percentage by dry weight of said workability agent relative to the dry weight of cement, from 0.05% to 5% of said workability agent.
- said hydraulic composition comprises, expressed as a percentage by dry weight of said workability agent relative to the dry weight of cement, from 0.1% to 3% of said workability agent.
- This hydraulic composition is, for example, for the manufacture of a grout, a coating, an adhesive, a concrete or a mortar.
- This composition may comprise impurities, for example clays.
- This composition can in particular include latexes, fibers, organic granulates, inorganic aggregates, fillers and / or CaCO 3 .
- Hydraulic compositions for example concrete and mortar compositions, for which the flow-retaining agent according to the invention may be useful may comprise, as hydraulic binder, different types of cements such as CEM I, CEM II, CEM cements. III, EMC V as described in the standard EN 197-1. Of these, CEM I cements do not have additions. It is nevertheless possible to add to these cements slags, fly ash, calcareous fillers, siliceous fillers.
- the concrete compositions may be concrete of classes of different strengths such as C20 / 25 to C100 / 115.
- the hydraulic composition according to the invention comprises from 10 to 90% by weight of hydraulic binder.
- the hydraulic composition according to the invention comprises, relative to the total weight of the composition:
- hydraulic binder comprising a cement
- the hydraulic composition according to the invention can also comprise, in addition, from 10 to 60% by weight of sand.
- the hydraulic composition according to the invention comprises, relative to the total weight of the composition:
- hydraulic binder comprising a cement
- the hydraulic composition according to the invention may, in addition, comprise one or more ingredient (s) following:
- fine or ultra-fine fillers for example calcium carbonate or silica, anti-foam agent,
- the present invention also relates to the use of a fluidity retaining agent according to the present invention, and optionally a water reducing agent according to the present invention, for preparing a hydraulic composition comprising water, a hydraulic binder comprising himself a cement.
- the present invention also relates to the use of a handling agent according to the present invention for preparing a hydraulic composition comprising water, a hydraulic binder itself comprising a cement.
- Said hydraulic composition may, for example, be a ready-mixed concrete.
- said fluid retentive agent and said water reducing agent are introduced separately into said hydraulic composition.
- said fluidity retentive agent and said water-reducing agent are introduced in the form of a mixture into said hydraulic composition.
- the present invention also relates to a copolymer as fluidity retentive agent for hydraulic compositions, said copolymer being obtained by polymerization of: a) at least one anionic monomer comprising a polymerizable unsaturated functional group and a carboxylic group,
- [(EO) m - (OP) n - (OB) p ] represents a polyalkoxylated chain consisting of alkoxylated units, divided into blocks, alternating or random, chosen from ethoxylated units EO, propoxylated units OP and butoxylated units OB , m, n and p represent, independently of each other, 0 or an integer ranging between 1 and 250 (inclusive), the sum of m, n and p being between 10 and 250,
- R f represents a radical containing a polymerizable unsaturated functional group
- R f ' represents hydrogen or an alkyl group having from 1 to 4 carbon atoms and
- copolymer having a molecular weight greater than 400,000 g / mol.
- the present invention relates to the use, as a handling agent for hydraulic compositions, of a combination of a fluidity-retaining agent and a water-reducing agent, said agents being such that:
- the flow-retaining agent is a copolymer obtained by polymerization of:
- [(EO) m - (OP) n - (OB) p ] represents a polyalkoxylated chain consisting of alkoxylated units, divided into blocks, alternating or random, chosen from ethoxylated units EO, propoxylated units OP and butoxylated units OB , m, n and p represent, independently of each other, 0 or an integer ranging between 1 and 250 (inclusive), the sum of m, n and p being between 10 and 250,
- R f represents a radical containing a polymerizable unsaturated functional group and R f 'represents hydrogen or an alkyl group having from 1 to 4 carbon atoms and
- copolymer having a molecular weight greater than 400 000 g / mol
- the water-reducing agent is a copolymer obtained by polymerization of:
- [(OE); - (OP) j - (OB) k ] represents a polyalkoxylated chain consisting of alkoxylated units, divided into alternating or random blocks, chosen from ethoxylated units EO, propoxylated units OP and butoxylated units OB,
- i, j and k represent, independently of each other, 0 or an integer ranging between 1 to 150 (inclusive), the sum of i, j and k being between 1 and 250,
- R d represents a radical containing a polymerizable unsaturated functional group
- R d ' represents hydrogen or an alkyl group having from 1 to 4 carbon atoms
- said copolymer having a molecular weight of between 20,000 g / mol and 400,000 g / mol.
- the molecular weight of the copolymers according to the invention is determined by Steric Exclusion Chromato graphy (CES).
- One such technique uses a WATERS TM brand liquid chromato graphy instrument with two detectors. One of these detectors combines static dynamic light scattering at an angle of 90 ° C with viscometry measured by a VISCOTEK TM MALVERN TM viscometer. The other of these detectors is a WATERS TM refractometric concentration detector.
- This liquid chromatography apparatus is provided with steric exclusion columns appropriately chosen by those skilled in the art in order to separate the different molecular weights of the polymers studied.
- the liquid phase of elution is an aqueous phase containing 1% of KN0 3 .
- the polymerization solution in the eluent of the CES which is a 1% solution of KNO 3
- a 1% solution of KNO 3 is diluted to 0.9% dry.
- filtered at 0.2 ⁇ . 100 ⁇ ⁇ are then injected into the chromatograph (eluent: a 1% solution of KN0 3).
- the liquid chromatography apparatus contains an isocratic pump (WATERS TM 515) with a flow rate of 0.8 ml / min.
- the chromatography apparatus also comprises an oven which itself comprises in series the following column system: a precolumn GUARD COLUMN type ULTRAHYDROGEL WATERS TM 6 cm long and 40 mm internal diameter, a linear column type ULTRAHYDROGEL WATERS TM 30 cm long and 7.8 mm inside diameter and two columns ULTRAHYDROGEL 120 ANGSTROM WATERS TM 30 cm long and 7.8 mm inside diameter.
- the detection system consists on the one hand of a RI WATERS TM 410 type refractometric detector and on the other hand a double viscometer detector and light scattering at an angle of 90 ° type 270 DUAL DETECTOR MALVERN TM
- the oven is heated to a temperature of 55 ° C and the refractometer is heated to a temperature of 45 ° C.
- the chromato graphy instrument is calibrated by a single standard of PEO 19k type PolyCAL TM MALVERN TM.
- the cone is placed on a plate moistened with a sponge.
- the cone is then filled with a determined quantity of each of the preparations. The filling lasts 2 minutes. The contents of the cone are packed with a metal rod. ⁇ Measurement of maneuverability in TO
- the concrete is allowed to stand for 45 or 90 minutes, the mixture is again kneaded and the maneuverability is measured with the Abrams cone as indicated above.
- a concrete according to EN 480-1 is prepared by mixing with stirring, standardized sand (0/4), cement (CEM I 52.5N Holcim), gravel 4/11 and 11/22, water and possibly an anti-foaming agent.
- a water-reducing agent and / or a fluid-retaining agent according to the invention is optionally added.
- the proportions of each constituent are given in Table 1 below.
- the exemplary water reducing agent in the following Examples 1-2 and 1-5 is a dispersant copolymer consisting of, based on the total weight of the copolymer:
- the dispersant copolymer has a molecular weight of between 110,000 and 150,000 g / mol and is partially neutralized with NaOH (pH 3-4.5).
- the fluidity retaining agent exemplified in the tests 1-3 to 1-5 below is a copolymer according to the invention, prepared according to the method below.
- DMDO 1,8-dimercapto-3,6-dioxaoctane
- a solution consisting of 0.9 g of ammonium persulfate and 4.4 g of deionized water is prepared.
- the reagents contained in the 3 containers are introduced into the reactor heated to 70 ° C. and with stirring.
- the mixture is then cooked for 2 hours at 67 ° C.
- the fluidity retaining agent exemplified is therefore composed of, based on the total weight of the copolymer:
- Test 1-1 is a negative control. It illustrates a hydraulic composition without adjuvant, that is to say without water reducing agent and fluidity retaining agent according to the invention.
- the use of the water reducing agent reduces the amount of water by 22% in the hydraulic composition by maintaining an initial fluidity similar to that of the negative control.
- the water reducing agent can be qualified as a high water reducer in accordance with the standard ADJUVANT NF EN 934-2 according to which is qualified "high water reducer” or "superplasticizer” an adjuvant that allows a reduction of water. water for the adjoining concrete> 12% compared to the control concrete.
- Tests 1-3 and 1-4 confirm that the exemplary flow-retaining agent is not a water-reducing agent according to the standard ADJUVANT NF EN 934-2 according to which is qualified as “water-reducing agent” or " plasticizer "an adjuvant that allows a water reduction for the adjoining concrete> 5% compared to the control concrete.
- Test 1-5 shows that the combination of a fluid retention agent according to the invention and a high water-reducing agent at the same time allows a water reduction of 22, a good initial fluidity as well as a maintenance of maneuverability over time.
- the resistance at the young ages of the formulation according to test 1-5 is similar to that of the control composition (test 1-2) comprising as sole additive a water-reducing agent. It is thus demonstrated that the flow-retaining agent according to the invention is not a set-retarding agent. It is furthermore confirmed that, in accordance with the standard ADJUVANT NF EN 934-2 (Table 3.1), the resistance values of the adjuvanted concretes (tests 1-2 and 1-5) at 1 day are greater than 140% of the value. resistance of control concrete without adjuvant (test 1-1).
- a concrete according to EN 480-1 is prepared by mixing with stirring, standardized sand (0/4), cement (CEM I 52.5N Holcim), gravel 4/11 and 11/22, water and possibly an anti-foaming agent.
- a water-reducing agent and a flow-retaining agent according to the invention.
- the proportions of each constituent are given in Table 2 below. More specifically, the water reducing agent exemplified in the tests below is a dispersant copolymer identical to that of Example 1.
- Tests 2-1 to 2-4 illustrate various fluidity-retaining agents according to the invention or to the invention. They are prepared according to a procedure similar to that of Example 1 above.
- the fluidity retaining agent exemplified in test 2-1 consists of, based on the total weight of the copolymer:
- the fluidity retaining agent exemplified in test 2-2 consists of, based on the total weight of the copolymer: 8% by weight of acrylic acid monomers,
- the fluidity retaining agent exemplified in test 2-3 consists of, based on the total weight of the copolymer:
- the fluidity retaining agent exemplified in test 2-4 consists of, based on the total weight of the copolymer:
- na the measured maneuverability at a previous time is ⁇ 100 ⁇ 10 mm or the measurement is impossible
- test 2-1 and 2-2 show, moreover, that the combination of the said fluid retention agents according to the invention and a high water reducing agent at the same time allows a good initial fluidity as well as a maintenance maneuverability over time.
- a concrete according to EN 480-1 is prepared by mixing with stirring, standardized sand (0/4), cement (CEM I 52.5N Holcim), gravel 4/11 and 11/22, water and a water-reducing agent and a flow-retaining agent according to the invention are added at two different doses.
- the proportions of each constituent are given in Table 3 below.
- Tests 3-1 and 3-2 illustrate a fluid retention agent according to the invention. They are prepared according to a procedure similar to that of Example 1 above.
- This agent consists of, based on the total weight of the copolymer:
- Tests 3-3 and 3-4 illustrate a fluidity retaining agent according to the invention. They are prepared according to a procedure similar to that of Example 1 above.
- This agent consists of, based on the total weight of the copolymer: 8.1% by weight of acrylic acid monomers,
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- Engineering & Computer Science (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
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Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US15/035,868 US20160289120A1 (en) | 2013-11-15 | 2014-11-12 | Fluidity-retaining agent for hydraulic compositions, compatible with a water-reducing agent of the comb polymer type |
CN201480062215.4A CN105722804A (zh) | 2013-11-15 | 2014-11-12 | 与梳形聚合物型的减水剂相容的用于水硬性组合物的保坍剂 |
MX2016006306A MX2016006306A (es) | 2013-11-15 | 2014-11-12 | Agente de retencion de fluidez para composiciones hidraulicas, compatible con un agente reductor de agua tipo polimero en peine. |
EP14809482.4A EP3068745A1 (fr) | 2013-11-15 | 2014-11-12 | Agent retenteur de fluidite pour compositions hydrauliques compatible avec agent reducteur d'eau de type polymere peigne |
CA2929307A CA2929307A1 (fr) | 2013-11-15 | 2014-11-12 | Agent retenteur de fluidite pour compositions hydrauliques compatible avec agent reducteur d'eau de type polymere peigne |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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FR1361234 | 2013-11-15 | ||
FR1361234A FR3013350B1 (fr) | 2013-11-15 | 2013-11-15 | Agent retenteur de fluidite pour composition hydraulique compatible avec agent reducteur d'eau de type polymere peigne |
Publications (1)
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WO2015071584A1 true WO2015071584A1 (fr) | 2015-05-21 |
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ID=50424395
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PCT/FR2014/052871 WO2015071584A1 (fr) | 2013-11-15 | 2014-11-12 | Agent retenteur de fluidite pour compositions hydrauliques compatible avec agent reducteur d'eau de type polymere peigne |
Country Status (7)
Country | Link |
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US (1) | US20160289120A1 (fr) |
EP (1) | EP3068745A1 (fr) |
CN (1) | CN105722804A (fr) |
CA (1) | CA2929307A1 (fr) |
FR (1) | FR3013350B1 (fr) |
MX (1) | MX2016006306A (fr) |
WO (1) | WO2015071584A1 (fr) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2018177908A1 (fr) * | 2017-03-30 | 2018-10-04 | Basf Se | Stabilisateur bi-composant pour des suspensions inorganiques |
CN113174019A (zh) * | 2021-05-21 | 2021-07-27 | 山西佳维新材料股份有限公司 | 一种水性环氧酯改性的聚羧酸减水剂及其制备方法和应用 |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR3069546B1 (fr) * | 2017-07-28 | 2020-09-25 | Coatex Sas | Composition polymerique aqueuse et copolymere |
CN112920337B (zh) * | 2021-01-29 | 2022-11-18 | 湖北工业大学 | 一种稳定泵送型保坍剂及其制备方法 |
CN116040975B (zh) * | 2023-01-16 | 2024-08-20 | 杭州构建新型材料有限公司 | 一种抗泥型聚羧酸减水剂及其制备方法 |
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2013
- 2013-11-15 FR FR1361234A patent/FR3013350B1/fr not_active Expired - Fee Related
-
2014
- 2014-11-12 WO PCT/FR2014/052871 patent/WO2015071584A1/fr active Application Filing
- 2014-11-12 EP EP14809482.4A patent/EP3068745A1/fr not_active Withdrawn
- 2014-11-12 MX MX2016006306A patent/MX2016006306A/es unknown
- 2014-11-12 CN CN201480062215.4A patent/CN105722804A/zh active Pending
- 2014-11-12 US US15/035,868 patent/US20160289120A1/en not_active Abandoned
- 2014-11-12 CA CA2929307A patent/CA2929307A1/fr not_active Abandoned
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CN113174019A (zh) * | 2021-05-21 | 2021-07-27 | 山西佳维新材料股份有限公司 | 一种水性环氧酯改性的聚羧酸减水剂及其制备方法和应用 |
Also Published As
Publication number | Publication date |
---|---|
EP3068745A1 (fr) | 2016-09-21 |
MX2016006306A (es) | 2016-09-06 |
CN105722804A (zh) | 2016-06-29 |
FR3013350B1 (fr) | 2016-09-02 |
CA2929307A1 (fr) | 2015-05-21 |
FR3013350A1 (fr) | 2015-05-22 |
US20160289120A1 (en) | 2016-10-06 |
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