Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • 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
  • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
  • C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
  • C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
• • 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
  • 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
  • C04B24/243—Phosphorus-containing polymers
  • C04B24/246—Phosphorus-containing polymers 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
  • C04B24/2641—Polyacrylates; Polymethacrylates
  • C04B24/2647—Polyacrylates; Polymethacrylates containing polyether side chains
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • 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
  • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
  • C04B24/24—Macromolecular compounds
  • C04B24/28—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • C04B24/32—Polyethers, e.g. alkylphenol polyglycolether
• • C—CHEMISTRY; METALLURGY
  • 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
• • 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
  • 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
  • C08F216/125—Monomers containing two or more unsaturated aliphatic radicals, e.g. trimethylolpropane triallyl ether or pentaerythritol triallyl ether

Definitions

• the present invention relates to novel copolymers and their use as water-reducing agents in hydraulic compositions, such as concrete and mortar compositions.
• compositions are intended for all construction markets.
• the hydraulic compositions generally comprise various chemical additives for improving their properties.
• the agents known as “water-reducing agents”, also known as “dispersing agents”, “fluidifying agents”, “plasticizing agents” or “superplasticizers”, have the function of improving the state of dispersion of the particles minerals in the compositions.
• These chemical agents lead to a decrease in the water content of the hydraulic compositions, which makes it possible to improve the performance of these compositions, and in particular their mechanical strength.
• dispersing agents for hydraulic compositions. These agents differ in their chemical composition and the properties they induce in the compositions containing them. Historically, the first compounds proposed as dispersing agents have been lignosulfonates as described in US 3,772,045. Polycondensates of formaldehyde and naphthalene or melanin sulfonates were then used as illustrated in US 3,359,225 and US 4,258,790.
• WO 97/39037 describes the synthesis of comb-type polymers, which can be used as water-reducing agents in cements, by polymerization starting from an acrylic monomer and a polyether macromonomer, such as an oxyethylene and oxypropylene (meth) acrylate.
• CN 1148329C also proposes, as dispersing agents for cements, copolymers obtained by polymerization from a monomer of the monocarboxylic acid type, such as (meth) acrylic acid; and a polyalkylene glycol ether monomer in which the proportion of ethoxylated units is at least 90 mol% of all the alkoxylated units, preferably a polyethylene glycol ether.
• a monomer of the monocarboxylic acid type such as (meth) acrylic acid
• a polyalkylene glycol ether monomer in which the proportion of ethoxylated units is at least 90 mol% of all the alkoxylated units, preferably a polyethylene glycol ether.
• JP 2006/282414 relates to a high strength cement developer. It contains, as essential components, (a) glycerol or a glycerol derivative and (b) a polycarboxylic acid-based copolymer having a polyoxyalkylene-type compound on a side chain.
• US 6,211,317 discloses emulsion copolymers of unsaturated carboxylic acid derivatives, oxyalkylene alkenyl glycol ethers, unsaturated dicarboximides or amides and vinyl monomers. They are described for use as additives for hydraulic binders, especially cement.
• KR 10086040 discloses polyalkylene ether-based unsaturated monomer copolymers supplemented with at least two alkylene glycols and (meth) acrylate monomers. It describes their use as cement additives.
• the present invention aims to provide new dispersing agents to access a better reduction of the water content of hydraulic compositions, without impairing their fluidity or maneuverability.
• the present invention relates, according to a first aspect, to a copolymer obtained by polymerization from a monomer mixture comprising:
• At least one anionic monomer (a) comprising a polymerizable unsaturated functional group and a carboxylic group
• H 2 C C (- R 1) - (CH 2 ) P - O - [(EO) - (PO) m ] - H (I)
• Ri represents a hydrogen atom or a CH 3 group
• [(EO) n - (PO) m] represents a polyalkoxylated chain consisting of ethoxylated units EO and propoxylated units PO, divided into blocks, alternating or statistical,
• n and n represent integers varying between 1 and 250, the sum of m and n being greater than or equal to 10, provided that the molar proportion of the ethoxylated units in the polyalkoxylated chain (n) / (m + n) is greater than or equal to 10; equal to 70% and strictly less than 90%.
• a copolymer as defined above comprising at least units derived from the anionic monomers (a) and units derived from the monomers (b) of formula (I), is referred to more simply in the following text under the name " copolymer according to the invention ".
• the copolymers according to the invention can be used as adjuvants in hydraulic compositions as "water-reducing agents", and even as “agents”. high water reducers ".
• water-reducing agent or "plasticizer” is understood to mean an agent which, in accordance with the standard ADJUVANT NF EN 934-2, allows a reduction of water for the admixed concrete. at least 5% compared to the control concrete.
• a “high water reducer” or “superplasticizer” is an adjuvant that provides a water reduction for the adjoining concrete of at least 12% over the control concrete.
• this water reduction is not at the expense of the performance of the hydraulic composition, for example concrete, including its fluidity or maneuverability.
• the copolymers according to the invention make it possible, with the same maneuverability, to reduce the water content of a given hydraulic composition, such as a concrete.
• the dispersant properties of the water-reducing agent in the hydraulic composition can be evaluated by measuring the slump (or "slump" in English), in accordance with the EN 12350 standard. -2.
• Other characteristics, advantages and modes of application of the copolymer according to the invention will emerge more clearly on reading the description and the example which will follow, given by way of illustration and not limitation.
• the copolymer according to the invention is obtained by polymerization from at least:
• H 2 C C (- R 1) - (CH 2 ) P - O - [(EO) - (PO) m ] - H (I)
• Ri represents a hydrogen atom or a CH 3 group
• p 1 or 2;
• [(EO) n - (PO) m] represents a polyalkoxylated chain consisting of ethoxylated units EO and propoxylated units PO, divided into blocks, alternating or statistical,
• m and n represent integers varying between 1 and 250, the sum of m and n being greater than or equal to 10, provided that the molar proportion of the ethoxylated units in the polyalkoxylated chain (n) / (m + n) is greater than or equal to 10; equal to 70% and strictly less than 90%.
• the copolymer according to the invention may optionally comprise other polymerizable monomers.
• the optional monomers optionally used in the composition of the copolymer of the invention may be of varied nature, as detailed in the rest of the text.
• said anionic monomers (a) and said monomers (b) of formula (I) may represent more than 80 mol%, in particular more than 90 mol%, and more particularly greater than 95 mol%, of the total number of mol constituent monomers of the copolymer.
• the copolymer according to the invention consists solely of units derived from the monomers (a) and (b).
• the copolymer according to the invention can be obtained by polymerization from a monomer mixture formed of one or more anionic monomers (a) and one or more monomers (b) of formula (I).
• the distribution of the units deriving from the monomers (a) and those deriving from the monomers (b) in the copolymer according to the invention can be of block, alternating or statistical type. According to one embodiment, it is a statistical or alternating distribution. According to another embodiment, it is a block-type distribution.
• the copolymer according to the invention can be obtained by polymerization from a monomer mixture consisting of:
• At least one anionic monomer (a) comprising a polymerizable unsaturated functional group and a carboxylic group
• H 2 C C (- R 1) - (CH 2 ) P - O - [(EO) - (PO) m ] - H (I)
• Ri represents a hydrogen atom or a C3 ⁇ 4 group
• p 1 or 2;
• [(EO) n - (PO) m] represents a polyalkoxylated chain consisting of ethoxylated units EO and propoxylated units PO, divided into blocks, alternating or statistical, m and n represent integers varying between 1 and 250, the sum of m and n being greater than or equal to 10, provided that the molar proportion of the ethoxylated units in the polyalkoxylated chain (n) / (m + n) is greater than or equal to 10; equal to 70% and strictly less than 90%.
• the amounts of monomers (a) and (b) used then correspond to 100% by weight of the total amounts of monomers forming the copolymer according to the invention.
• the anionic monomers (a) used in the composition of the copolymer according to the invention may be more particularly chosen from acrylic acid, methacrylic acid, maleic acid, itaconic acid, crotonic acid and mixtures of these monomers.
• the monomer or monomers (a) may be in acid form, for example carboxylic acid and / or salt form, for example carboxylate.
• a single or a mixture of several different monomers (a) can enter into the composition of the copolymer according to the invention.
• it may be a mixture of acrylic acid monomers and methacrylic acid monomers or a mixture of monomers of maleic acid, acrylic acid and methacrylic acid.
• the copolymer according to the invention is formed from at least acrylic acid and / or methacrylic acid, in particular at least acrylic acid (AA).
• the at least one anionic monomer (a) used in the composition of the copolymer according to the invention are chosen from acrylic acid, methacrylic acid and their mixture.
• said anionic monomer (s) may represent from 50 to 99 mol%, in particular from 60 to 95 mol%, in particular from 70 to 95 mol%, and more particularly from 80 to 90 mol%. of the total number of moles of constituent monomers of the copolymer according to the invention.
• H 2 C C (- Ri) - (CH 2) p - O - [(EO) "- (PO) m ] - H (I) in which:
• Ri represents a hydrogen atom or a CH 3 group
• p 1 or 2;
• [(EO) n - (PO) m] represents a polyalkoxylated chain consisting of EO ethoxylated units and PO propoxylated units;
• n and n represent integers varying between 1 and 250, the sum of m and n being greater than or equal to 10, provided that the molar proportion of the ethoxylated units in the polyalkoxylated chain (n) / (m + n) is greater than or equal to 10; equal to 70% and strictly less than 90%.
• polyalkoxylated chain is meant a chain of poly (alkylene glycol) type.
• poly (alkylene glycol) is meant a polymer of an alkylene glycol derived from an olefinic oxide.
• the poly (alkylene glycol) chain of the monomer (b) according to the invention is formed of ethoxylated (or "ethylene-oxy") units, denoted "EO”, of the formula -CH 2 -CH 2 -O- and of propoxylated units (or “propylene-oxy"), denoted "PO”, of formula -CH 2 -CH (CH 3 ) -O-.
• EO ethoxylated
• PO propoxylated units
• the units EO and PO are divided into blocks.
• the polyalkoxylated chain of the monomer (b) may be of diblock type and be formed of a polyoxyethylene block and a polyoxypropylene block.
• p in formula (I) above is 1.
• the monomer or monomers (b) used in the composition of the copolymer according to the invention correspond to the following formula ( ⁇ ):
• H 2 C C (-Ri) -CH 2 -O- [(EO) "- (PO) m ] - H ( ⁇ )
• R 1, n and m are as previously defined.
• the copolymer according to the invention is formed from at least one monomer (b) of formula (I) or ( ⁇ ) above, in which R 1 represents a methyl group.
• the copolymer according to the invention is formed from at least one monomer (b) of formula (II) below:
• H 2 C C (-CH 3 ) -CH 2 -O- [(EO) "- (PO) m ] -H (II)
• n and m are as defined above.
• the schematic representation "[(EO) n - (PO) m ]" does not presuppose the order of the ethoxylated and propoxylated units of the polyalkoxylated chain.
• the polyalkoxylated chain may have a distribution of units EO and PO block type, statistical or alternating, in particular blocks.
• the copolymer according to the invention is obtained from at least one monomer (b) of formula (III) below:
• the polyalkoxylated chain is formed of a first polyoxyethylene block and a second polyoxypropylene block.
• p in formula (I) above is 2.
• the copolymer according to the invention is formed from at least one monomer (b) of formula (I ") above, in which R 1 represents a methyl group.
• the copolymer according to the invention is formed from at least one monomer (b) of formula (IV) below:
• H 2 C C (-CH 3 ) -CH 2 -CH 2 -O- [(EO) "- (PO) m ] -H (IV) in which n and m are as defined above.
• the schematic representation "[(EO) n - (PO) m ]" does not presuppose the order of the ethoxylated and propoxylated units of the polyalkoxylated chain.
• the polyalkoxylated chain may have a distribution of units EO and PO block type, statistical or alternating, in particular blocks.
• the copolymer according to the invention is obtained from at least one monomer (b) of formula (V) below:
• H 2 C C (-CH 3 ) -CH 2 -CH 2 -O- (EO) - (PO) m - H (V) m and n being as defined above.
• the polyalkoxylated chain is formed of a first polyoxyethylene block and a second polyoxypropylene block.
• the copolymer according to the invention is obtained from at least one mixture of at least one monomer (bi) of formula (I) in which R 1 represents a hydrogen atom and a at least one monomer (b 2 ) of formula (I) in which R 1 represents a methyl group.
• the copolymer according to the invention can be obtained from at least one mixture of at least one monomer (bi ') of formula ( ⁇ ) above, in which R 1 represents a hydrogen atom and from minus one monomer (b 2 ') of formula ( ⁇ ) above, in which R 1 represents a methyl group (in other words, a monomer (b 2 ') of formula (II) above).
• the one or more monomers (bi ') and the monomer or monomers (b 2 ') used in the composition of the copolymer according to the invention can be used in a molar monomer ratio (s). ) (bi ') / monomer (s) (b 2 ') ranging from 10 to 0.01, in particular from 1 to 0.1.
• the copolymer according to the invention can be obtained from at least one mixture of at least one monomer (bi ') of formula ( ⁇ ) mentioned above and at least one monomer ( b 2 ") of formula (I") above.
• the copolymer according to the invention can be obtained from at least one mixture of at least one monomer (bi ') of formula ( ⁇ ) above in which R 1 represents a methyl group (in other words, a monomer ( bi ') of formula (II) above) and at least one monomer (b 2 ") of formula (I") above wherein R 1 represents a methyl group (in other words, a monomer (b 2 ") of formula ( IV) above).
• the molar proportion of the ethoxylated units EO in the polyalkoxylated chain is greater than or equal to 70% and strictly less than 90%.
• the molar proportion of ethoxylated units EO in the polyalkoxylated chain may be between 70% and 88, in particular be greater than or equal to 72, and more particularly greater than or equal to 75%.
• the molar proportion of ethoxylated units EO in the polyalkoxylated chain may be less than or equal to 85, in particular less than or equal to 80%.
• the molar ratio between the ethoxylated units and the propoxylated units of the polyalkoxylated chain may more particularly be between 2.5 and 8, in particular between 2.8 and 7.5 and especially between 3 and 6.
• the total number of ethoxylated and propoxylated units of the polyalkoxylated chain (that is, the sum of m and n) of the monomer (b) is greater than or equal to 10.
• it may be between 10 and 150, in particular between 18 and 110 and more particularly between 20 and 70.
• the polyalkoxylated chain of the monomer (b) according to the invention can thus have a number-average molecular weight of between 450 and 7,500 g / mol, in particular between 900 and 500 g / mol and more particularly between 1,000 and 3,500 g / mol. g / mol.
• the monomers (b) according to the invention can be prepared by techniques known to those skilled in the art, by growing the desired polyalkoxylated chain by polymerization from ethylene oxide monomers and propylene oxide on a allylic or methallyl alcohol.
• the monomer or monomers (b) may represent from 1 to 50 mol%, in particular from 5 to 40 mol%, in particular from 5 to 30 mol% and more particularly from 10 to 20 mol%, total number of moles of constituent monomers of the copolymer according to the invention.
• the monomer or monomers (b) may be used in various forms, in particular in solid form, in particular in the form of powder or flakes, or in liquid form (liquid formed by the monomers (b), or aqueous monomer solution ( b)).
• the monomers (b) are water-soluble.
• the monomer or monomers (b) are used in liquid form, in particular in aqueous solution, this form being particularly suitable for the synthesis of the copolymer according to the invention.
• the molar ratio between the one or more anionic monomers (a) and the monomer or monomers (b) used in the composition of the copolymer according to the invention may be more particularly between 1 and 99, in particular between 2.3 and 19 and more. especially between 4 and 9.
• the copolymer according to the invention can be obtained by polymerization from a monomer mixture comprising, besides said monomer (s) and said monomer (s) (b), one or more additional monomers, other than monomers (a) and (b), denoted "monomers (c)" in the rest of the text.
• the additional monomers (c) may be more particularly chosen from:
• vinylsulphonates in particular sodium styrene sulphonate
• esters having a hydroxyl group for example hydroxyethyl methacrylate (HEMA); hydroxyethyl acrylate; hydroxypropyl methacrylate and hydroxypropyl acrylate;
• HEMA hydroxyethyl methacrylate
• hydroxypropyl methacrylate hydroxypropyl acrylate
• alkylene glycol acrylate or methacrylate phosphates in particular ethylene glycol methacrylate phosphate or ethylene glycol acrylate phosphate;
• phosphonic monomers such as vinylphosphonates and alkyl phosphonates
• [(EO) q - (PO) r - (BO) s ] represents a polyalkoxylated chain consisting of alkoxylated units, divided into blocks, alternating or random, chosen from ethoxylated units EO, propoxylated units PO and butoxylated units B ;
• q, r and s represent, independently of each other, 0 or an integer ranging between 1 and 250, the sum of m, n and p being between 10 and 250;
• R a represents a radical selected from the group consisting of acrylic esters, methacrylic esters and a mixture of these esters;
• R a ' represents hydrogen or an alkyl group having from 1 to 4 carbon atoms
• [(EO) t - (PO) u - (BO) v] represents a polyalkoxylated chain consisting of alkoxylated units, divided into blocks, alternating or random, chosen from the ethoxylated units EO, the propoxylated units PO and the butoxylated units B ;
• t, u and v represent, independently of one another, 0 or an integer ranging between 1 and 250, the sum of m, n and p being between 10 and 250;
• Rb represents a radical selected from the group consisting of acrylic esters, methacrylic esters and a mixture of these esters;
• Rb ' represents an alkyl group having from 8 to 40 carbon atoms, the crosslinking monomers.
• s is equal to 0; and q and r represent an integer ranging between 1 and 250, for example between 10 and 150 or between 10 and 100.
• v is equal to 0; and t and u represent an integer ranging between 1 and 250, for example between 10 and 150 or between 10 and 100.
• the additional monomer (s) (c) may also be chosen from crosslinking monomers.
• the copolymer according to the invention may for example comprise a single crosslinking monomer. According to another embodiment, it comprises two different crosslinking monomers.
• the crosslinking monomer may have a hydrophilic, hydrophobic or amphiphilic character. Examples of these compounds include 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- (acryl
• the crosslinking monomers may be prepared by an esterification reaction of a polyol with an unsaturated anhydride such as maleic anhydride, itaconic anhydride or (meth) acrylic anhydride, or by a reaction of addition with an isocyanate such as 3-isopropenyl-dimethylbenzene isocyanate.
• an unsaturated anhydride such as maleic anhydride, itaconic anhydride or (meth) acrylic anhydride
• an isocyanate such as 3-isopropenyl-dimethylbenzene isocyanate.
• 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.
• the crosslinking monomer is chosen from (meth) acrylates having at least two polymerizable ethylenically unsaturated double bonds (for example prepared by esterification of (meth) acrylic acid with a linear or branched polyol having 2 to 12 carbon atoms and at least two hydroxyl groups), the polyalkenyl polyether having at least two polymerizable ethylenically unsaturated double bonds (for example prepared by etherification of alkenyl halide with a linear or branched polyol having from 2 to 12 carbon atoms and at least two hydroxyl groups) and mixtures of these crosslinking monomers.
• (meth) acrylates having at least two polymerizable ethylenically unsaturated double bonds for example prepared by esterification of (meth) acrylic acid with a linear or branched polyol having 2 to 12 carbon atoms and at least two hydroxyl groups
• the copolymer comprises two crosslinking monomers: said first crosslinking monomer being a (meth) acrylate having at least two polymerizable ethylenically unsaturated double bonds (for example prepared by esterification of (meth) acrylic with a linear or branched polyol having 2 to 12 carbon atoms and at least two hydroxyl groups), and
• said second crosslinking monomer being a polyalkenyl polyether having at least two polymerizable ethylenically unsaturated double bonds (for example prepared by etherification of alkenyl halide with a linear or branched polyol having from 2 to 12 carbon atoms and at least two hydroxyl groups).
• the copolymer comprises two crosslinking monomers of different natures, for example trimethylolpropane tri (meth) acrylate (TMPTA or TMPTMA), and trimethylolpropane diallyl ether (TMPDAE).
• TMPTA trimethylolpropane tri (meth) acrylate
• TMPDAE trimethylolpropane diallyl ether
• the additional monomer content (s) used is adjusted not to alter the desired properties of the copolymer.
• the additional monomer or monomers (c) may represent less than 20 mol%, in particular less than 15 mol%, in particular less than 10 mol% and more particularly less than 5 mol% of the total number of mol of constituent monomers of the copolymer according to the invention.
• the copolymer according to the invention can thus be obtained by polymerization from a monomer mixture comprising or even consisting of:
• anionic monomers (a) chosen from acrylic acid, methacrylic acid and mixtures thereof, in particular acrylic acid; and
• the copolymer according to the invention comprises at least units derived from acrylic acid and units deriving from a monomer of formula (II), in particular of formula (III), as described above. .
• the copolymer according to the invention is obtained by polymerization of at least:
• the copolymer according to the invention is obtained by polymerization of at least:
• the copolymer according to the invention is obtained by polymerization of at least:
• the sum of the molar percentages of the monomers (a) and of the monomers (b) is equal to 100%.
• the copolymer consists solely of units derived from the monomers (a) and (b) in the molar proportions indicated.
• the copolymer according to the invention may have a weight average molecular weight Mw of between 15,000 and 250,000 g / mol, in particular between 20,000 and 200,000 g / mol and more particularly between 25,000 and 175,000 g / mol.
• the weight average molecular weight or Mw can be determined by size exclusion chromatography (CES), as described more specifically in the following example.
• the copolymer according to the invention may be in the form of salts, stoichiometric or not, mixed or not, and consisting of alkali metals, alkaline earth metals, amines or quaternary ammoniums.
• the copolymer according to the invention is in acid form.
• the copolymer according to the invention is in neutralized form. According to yet another embodiment, the copolymer according to the invention is in partially or totally neutralized form.
• the copolymer is neutralized with an ion selected from the group consisting of potassium ion, sodium ion, lithium ion, calcium ion, magnesium ion, ammonium ion, the diethanolammonium ion and a mixture of these ions.
• the copolymer according to the invention can be prepared by conventional polymerization techniques from monomers (a), (b) and optionally (c). According to an alternative embodiment, the copolymer according to the invention can be obtained by radical polymerization, in particular by controlled radical polymerization.
• the copolymers according to the invention are particularly effective as water-reducing agents in hydraulic compositions.
• the invention thus relates, in another of its aspects, to the use of a copolymer as defined above as a water-reducing agent in a hydraulic composition.
• the water-reducing agent consists of a copolymer or a mixture of copolymers according to the invention.
• the water-reducing agent can be used in various forms, in particular in liquid form. It may especially be in the form of an aqueous solution of one or more copolymers according to the invention, the dry extract of which may more particularly be between 25 and 65, for example between 30 and 60%. According to yet another of its aspects, the invention relates to a hydraulic composition comprising at least one copolymer according to the invention.
• the hydraulic compositions can be of various kinds. They can be used for the manufacture of a grout, a coating, an adhesive, a concrete or a mortar. They may include impurities, for example clays. These The compositions may include, but are not limited to, latexes, fibers, organic granules, inorganic granulates, fillers and / or CaCO 3 .
• Hydraulic compositions for example concrete and mortar compositions, for which the water-reducing agent according to the invention may be useful, may comprise as hydraulic binder various types of cements, such as, for example, CEM I cements. , CEM II, CEM III, CEM IV and CEM V as described in 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, or calcareous fillers, or siliceous fillers.
• the concrete compositions may be concrete of classes of different strengths, such as C20 / 25 to C100 / 115.
• the hydraulic composition may more particularly be an aqueous formulation comprising, besides said copolymer (s) according to the invention, water and at least one hydraulic binder. It may further optionally include one or more additional additives.
• the hydraulic binder may comprise at least one cement, for example a Portland cement. Mention may also be made, by way of examples, of hydraulic binders of aluminous cement type and sulpho-alumino-calcium cement.
• the hydraulic composition can be for example a ready-mix concrete (BPE or "ready-mix”).
• the hydraulic composition according to the invention may for example comprise from 8 to 75% by weight, for example from 10 to 50% or from 10 to 40% by weight of hydraulic binder, relative to the total weight of the hydraulic composition.
• the water-reducing agent according to the invention may for example be incorporated at the time of mixing the concrete.
• the water-reducing agent according to the invention may be used in a proportion of from 0.05 to 3% by weight of copolymer (s), in particular from 0.25 to 2.5% by weight, relative to total weight of the composition.
• the hydraulic composition according to the invention comprises, relative to the total weight of the composition:
• 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 may comprise, relative to the total weight of the composition:
• a hydraulic composition according to the invention may comprise various ingredients, conventionally used in the field of hydraulic compositions, in particular chosen from sand, gravel, aggregates, fine or ultra-fine fillers, for example calcium carbonate. or silica, defoamers, thickeners, stabilizers, biocides or antibacterials, and accelerators or setters.
• the present invention also relates to the use of a water reducing agent according to the invention for preparing a hydraulic composition comprising in particular water and a hydraulic binder comprising itself a cement.
• the molecular weight of the copolymers is determined by size exclusion chromatography (CES).
• Such a technique implements a WATERS TM brand liquid chromatography apparatus with two detectors.
• One of these detectors combines the static dynamic scattering of light at a 90 ° angle with viscometry measured by a VISCOTEK TM MALVERN TM viscometer.
• the other detector 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 KNO3, is diluted to 0.9% dry. Then filtered at 0.2 ⁇ . 100 ⁇ ⁇ are then injected into the chromatograph (eluent: a 1% solution of KNO3).
• 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 side of a double viscometer detector and light diffusion at a 270 ° angle of 90 °. DUAL DETECTOR MALVERN. The oven is heated to 55 ° C, and the refractometer is heated to 45 ° C.
• the chromato graphy instrument is calibrated by a single standard of PEO 19k type PolyCAL TM MALVERN TM.
• the copolymer A is obtained by polymerization from a monomer mixture formed of:
• the chemicals used are:
• the product is cooled and then neutralized by addition of 109.4 g of 50% NaOH.
• the copolymer A obtained has a molecular weight, measured as described above, of 160,300 g / mol.
• Copolymer B (in accordance with the invention):
• the copolymer B is obtained by polymerization from a monomer mixture formed of: 83.4 mol% of acrylic acid;
• the chemicals used are:
• the product is cooled and then neutralized by addition of 109.4 g of 50% NaOH.
• the copolymer B obtained has a molecular mass, measured as described above, of 172,500 g / mol.
• the copolymer C is obtained by polymerization from a mixture formed of:
• the copolymer C is prepared according to a procedure similar to that described above for the copolymer B.
• the copolymer C obtained has a molecular weight, measured as described above, of 156,900 g / mol.
• a concrete (350 kg / m 3 ) according to EN 480-1 is prepared by mixing with agitation, standardized sand (0/4), cement (CEM I 52.5N Holcim), gravel 4 / 11 and 11/22, water and an antifoaming agent.
• composition 1 No adjuvant is added to composition 1 (control).
• Formulations 2 to 4 of concrete are supplemented respectively by the solutions of copolymers A, B and C prepared as described above.
• the water / cement weight ratio is adjusted so as to maintain an initial workability similar to that of the control concrete.
• compositions are evaluated for their properties of initial fluidity (maneuverability at T0), air capture and water reduction according to the following protocols. Measurement of the maneuverability at T0:
• the measurement of the initial fluidity is carried out at room temperature, by means of a frustoconical cone, of frustoconical shape, made of galvanized steel, called Abrams cone, according to the EN 12350-2 standard.
• This cone has the following characteristics: Upper diameter: 100 + 2 mm, Lower diameter: 200 + 2 mm, Height: 300 + 2 mm.
• 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.
• the cone is lifted vertically, which leads to the collapse of its contents on the plate.
• Concretes can be classified according to their maneuverability according to EN 206-1.
• the set of hydraulic compositions has a homogeneous appearance, without segregation of the constituents.
• copolymers B and C makes it possible to reduce the quantity of water by 36% and 28% respectively in the hydraulic composition, while maintaining an initial fluidity (handling) similar to that of the negative control.
• copolymers according to the invention can be characterized as "high water reducing agents" in accordance with the standard ADJUVANT NF EN 934-2 according to which is qualified as “high water reducer” or “superplasticizer” an adjuvant that allows a reduction of water for concrete at least 12% higher than the control concrete.
• copolymers B and C make it possible to significantly reduce the quantity of water in the hydraulic composition (respectively 36% and 28%) compared with the use of the copolymer A which is not in accordance with the present invention. invention (15) without affecting the workability of said hydraulic composition.

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• 2015
  • 2015-03-16 FR FR1552129A patent/FR3033794B1/fr active Active
• 2016
  • 2016-03-15 CN CN201680008058.8A patent/CN107207678A/zh active Pending
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