WO2022136574A1 - Procédé d'inertage d'argiles dans des compositions hydrauliques destinées à la construction - Google Patents
Procédé d'inertage d'argiles dans des compositions hydrauliques destinées à la construction Download PDFInfo
- Publication number
- WO2022136574A1 WO2022136574A1 PCT/EP2021/087350 EP2021087350W WO2022136574A1 WO 2022136574 A1 WO2022136574 A1 WO 2022136574A1 EP 2021087350 W EP2021087350 W EP 2021087350W WO 2022136574 A1 WO2022136574 A1 WO 2022136574A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- acrylamide
- water
- monomeric
- vinylformamide
- units
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 32
- 238000010276 construction Methods 0.000 title claims abstract description 14
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 43
- ZQXSMRAEXCEDJD-UHFFFAOYSA-N n-ethenylformamide Chemical compound C=CNC=O ZQXSMRAEXCEDJD-UHFFFAOYSA-N 0.000 claims abstract description 33
- UYMKPFRHYYNDTL-UHFFFAOYSA-N ethenamine Chemical compound NC=C UYMKPFRHYYNDTL-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000000178 monomer Substances 0.000 claims abstract description 28
- 239000000126 substance Substances 0.000 claims abstract description 24
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 23
- 229920003169 water-soluble polymer Polymers 0.000 claims abstract description 23
- 239000000470 constituent Substances 0.000 claims abstract description 9
- 229920000642 polymer Polymers 0.000 claims description 67
- 230000008569 process Effects 0.000 claims description 23
- 239000004927 clay Substances 0.000 claims description 21
- 230000002209 hydrophobic effect Effects 0.000 claims description 17
- 229920001577 copolymer Polymers 0.000 claims description 10
- 239000004567 concrete Substances 0.000 claims description 8
- 229920002401 polyacrylamide Polymers 0.000 claims description 8
- 239000008030 superplasticizer Substances 0.000 claims description 6
- 229920001897 terpolymer Polymers 0.000 claims description 6
- WHNPOQXWAMXPTA-UHFFFAOYSA-N 3-methylbut-2-enamide Chemical compound CC(C)=CC(N)=O WHNPOQXWAMXPTA-UHFFFAOYSA-N 0.000 claims description 5
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 4
- 239000004570 mortar (masonry) Substances 0.000 claims description 4
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 2
- GASMGDMKGYYAHY-UHFFFAOYSA-N 2-methylidenehexanamide Chemical compound CCCCC(=C)C(N)=O GASMGDMKGYYAHY-UHFFFAOYSA-N 0.000 claims description 2
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 2
- 150000003926 acrylamides Chemical class 0.000 claims description 2
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 claims description 2
- 229920001519 homopolymer Polymers 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 11
- 238000006116 polymerization reaction Methods 0.000 description 11
- 125000002091 cationic group Chemical group 0.000 description 8
- 229920006317 cationic polymer Polymers 0.000 description 8
- 150000001805 chlorine compounds Chemical class 0.000 description 7
- 239000004568 cement Substances 0.000 description 6
- 239000004576 sand Substances 0.000 description 6
- 125000000129 anionic group Chemical group 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- -1 polyethylene Polymers 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000010526 radical polymerization reaction Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 230000002787 reinforcement Effects 0.000 description 3
- 230000007480 spreading Effects 0.000 description 3
- 238000003892 spreading Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 235000019738 Limestone Nutrition 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 239000006028 limestone Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- ZKYCLDTVJCJYIB-UHFFFAOYSA-N 2-methylidenedecanamide Chemical compound CCCCCCCCC(=C)C(N)=O ZKYCLDTVJCJYIB-UHFFFAOYSA-N 0.000 description 1
- ZAWQXWZJKKICSZ-UHFFFAOYSA-N 3,3-dimethyl-2-methylidenebutanamide Chemical compound CC(C)(C)C(=C)C(N)=O ZAWQXWZJKKICSZ-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 229920005372 Plexiglas® Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229910001294 Reinforcing steel Inorganic materials 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 230000016571 aggressive behavior Effects 0.000 description 1
- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 1
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 description 1
- 239000002168 alkylating agent Substances 0.000 description 1
- 229940100198 alkylating agent Drugs 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 150000001767 cationic compounds Chemical class 0.000 description 1
- 210000001520 comb Anatomy 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000005265 dialkylamine group Chemical group 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- DENRZWYUOJLTMF-UHFFFAOYSA-N diethyl sulfate Chemical compound CCOS(=O)(=O)OCC DENRZWYUOJLTMF-UHFFFAOYSA-N 0.000 description 1
- YGANSGVIUGARFR-UHFFFAOYSA-N dipotassium dioxosilane oxo(oxoalumanyloxy)alumane oxygen(2-) Chemical compound [O--].[K+].[K+].O=[Si]=O.O=[Al]O[Al]=O YGANSGVIUGARFR-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical group C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229910052900 illite Inorganic materials 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 235000012243 magnesium silicates Nutrition 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 238000000569 multi-angle light scattering Methods 0.000 description 1
- 229910052627 muscovite Inorganic materials 0.000 description 1
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 description 1
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 1
- GORGQKRVQGXVEB-UHFFFAOYSA-N n-ethenyl-n-ethylacetamide Chemical compound CCN(C=C)C(C)=O GORGQKRVQGXVEB-UHFFFAOYSA-N 0.000 description 1
- PNLUGRYDUHRLOF-UHFFFAOYSA-N n-ethenyl-n-methylacetamide Chemical compound C=CN(C)C(C)=O PNLUGRYDUHRLOF-UHFFFAOYSA-N 0.000 description 1
- OFESGEKAXKKFQT-UHFFFAOYSA-N n-ethenyl-n-methylformamide Chemical compound C=CN(C)C=O OFESGEKAXKKFQT-UHFFFAOYSA-N 0.000 description 1
- RQAKESSLMFZVMC-UHFFFAOYSA-N n-ethenylacetamide Chemical compound CC(=O)NC=C RQAKESSLMFZVMC-UHFFFAOYSA-N 0.000 description 1
- HAZULKRCTMKQAS-UHFFFAOYSA-N n-ethenylbutanamide Chemical compound CCCC(=O)NC=C HAZULKRCTMKQAS-UHFFFAOYSA-N 0.000 description 1
- VGIBGUSAECPPNB-UHFFFAOYSA-L nonaaluminum;magnesium;tripotassium;1,3-dioxido-2,4,5-trioxa-1,3-disilabicyclo[1.1.1]pentane;iron(2+);oxygen(2-);fluoride;hydroxide Chemical compound [OH-].[O-2].[O-2].[O-2].[O-2].[O-2].[F-].[Mg+2].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[K+].[K+].[K+].[Fe+2].O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2 VGIBGUSAECPPNB-UHFFFAOYSA-L 0.000 description 1
- 150000002892 organic cations Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052615 phyllosilicate Inorganic materials 0.000 description 1
- 229920005646 polycarboxylate Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 238000012673 precipitation polymerization Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- CRWJEUDFKNYSBX-UHFFFAOYSA-N sodium;hypobromite Chemical compound [Na+].Br[O-] CRWJEUDFKNYSBX-UHFFFAOYSA-N 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2652—Nitrogen containing polymers, e.g. polyacrylamides, polyacrylonitriles
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B14/02—Granular materials, e.g. microballoons
- C04B14/04—Silica-rich materials; Silicates
- C04B14/10—Clay
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
- C04B28/04—Portland cements
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F18/00—Homopolymers and 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 acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
- C08F18/22—Esters containing nitrogen
-
- 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
- C08F20/00—Homopolymers and 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
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/52—Amides or imides
- C08F20/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F20/56—Acrylamide; Methacrylamide
-
- 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
- C08F26/00—Homopolymers and 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 a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F26/02—Homopolymers and 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 a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a single or double bond to nitrogen
-
- 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
- C04B2103/0052—Hydrophobic polymers
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/32—Superplasticisers
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/10—Compositions or ingredients thereof characterised by the absence or the very low content of a specific material
- C04B2111/1062—Halogen free or very low halogen-content materials
Definitions
- TITLE Process for inerting clays in hydraulic compositions intended for construction
- the present invention relates to a process for inerting clays in hydraulic compositions intended for construction.
- Hydraulic compositions intended for construction such as for example cementitious compositions, contain aggregates and in particular sands whose quality is variable.
- the scarcity of these materials sometimes forces those skilled in the art to turn to rock crushing.
- there is a decrease in the quality of the aggregates which contain in particular a substantial quantity of clays, some of which are swelling, that is to say that they will become hydrated by absorbing a very large quantity of water on both their outer and inner surface by expanding their inter-leaf space.
- These variations are the cause of significant fluctuations in the properties of hydraulic compositions such as rheological properties in the fresh state that are not appropriate until the embrittlement of the structures in the hardened state, thus posing obvious safety problems.
- a hydraulic composition is characterized by its water/hydraulic binder ratio. This ratio depends in particular on the strength and durability of the finished material. The lower the ratio, the better the strength and durability. To reduce this ratio, superplasticizers are used. However, the clays present in the aggregates trap both water and these superplasticizers, which leads to a loss of implementation performance, overconsumption of adjuvant and difficult control of their dosage because of variations linked to clays in aggregates.
- Synthetic polymers have therefore been developed in order to inert clays and avoid these problems.
- Document WO 98/58887 proposes the use of agents modifying the activity of clays to limit the absorption of superplasticizers of the EO/PO type by these clays and thus to increase the performance of cements and concretes.
- the document proposes in particular the use of inorganic or organic cations, including cationic polymers such as optionally alkoxylated quaternary polyamines.
- Document WO 2006/032785 proposes using cationic polymers having a charge density greater than 0.5 meq/g, in particular cationic polymers obtained by condensation of epichlorohydrin with a dialkylamine.
- inert clay polymers described in the prior art are cationic and research has focused on polymers with an increasingly high degree of cationicity in order to optimize performance.
- these cationic polymers have quaternary ammonium functions and contain high levels of chloride, which poses numerous problems.
- Chlorides are at the origin of attacks on cementitious matrices affecting their mechanical resistance. In addition to this physico-chemical aggression suffered by the matrix, there is the damage linked to the corrosion of the metal reinforcements, thus increasing the risk of degradation of the structures.
- the depassivation of reinforcing steel begins when the chloride ions reach a critical concentration at the level of the first layer of reinforcement, after having passed through the concrete cover.
- This critical concentration is currently very often standardized throughout the world in concrete formulations at rates sometimes lower than 0.2% of chlorides relative to the mass of the cement, values set by scientific knowledge, observation and experience. .
- Document WO 2018/054991 relates to a process for obtaining polymers of high cationic density having a reduced chloride content. These cationic polymers can be used in compositions based on mineral binders to inhibit clays. However, they still contain too much chloride and do not cannot meet standard requirements. The existing solutions are therefore not satisfactory.
- the problem that the invention proposes to solve is to provide a clay inerting agent for hydraulic compositions intended for construction with improved performance and containing no chloride.
- the invention is based on the observation that water-soluble polymers of specific chemical nature and having a specific molecular weight offer an improvement in the inerting performance of clays in hydraulic compositions intended for construction and also make it possible to meet normative requirements because they do not do not contain chloride.
- the present invention it is possible to achieve environmental objectives inherent in new technical innovations.
- the polymers lead to a reduction in polymer consumption thanks to better performance.
- the polymers of the invention do not contain chloride, which results not only in obtaining stronger construction materials, but above all this allows the environmental level to drastically reduce the waste and pollution of water usually required for washing sands and aggregates on filter belts. This allows this resource to be preserved for more noble purposes and avoids contamination of the environment by polluted water.
- the monomers used in the polymers of the invention have a lower carbon footprint than the monomers used in the polymers of the prior art Indeed, they consist of only 3 carbons, which is the minimum to have a polymer functional (except polyethylene) and are produced in a short circuit compared to oil. Both in terms of their composition and their application benefits, these polymers are therefore more virtuous for the environment and its users.
- the present invention relates to a process for inerting clays in hydraulic compositions intended for construction, said process comprising a step consisting in adding to the hydraulic composition or to one of its constituents at least one clay inerting agent , characterized in that the clay inerting agent is a water-soluble polymer comprising acrylamide, and/or vinylamine, and/or vinylformamide monomeric units, and optionally monomeric units of a chemical nature different from the aforesaid chemical natures, and characterized in that its weight-average molecular weight is between Mw L and Mw H, such that:
- the polymers of the invention are chosen from:
- the clay inert can be a composition comprising at least two water-soluble polymers according to the invention.
- the water-soluble polymer according to the invention is preferably nonionic, i. e.it does not contain any anionic or cationic charge.
- the water-soluble polymer according to the invention does not contain chloride ions.
- the invention also relates to a hydraulic composition intended for construction comprising aggregates, at least one superplasticizer, and at least one clay inerting agent as described in the invention.
- water-soluble polymer is understood to mean a polymer which gives an aqueous solution when it is dissolved with stirring at 25° C. and with a concentration of 20 gL ⁇ 1 in water.
- polyacrylamide means a polymer comprising monomeric acrylamide units
- polyvinylamine means a polymer comprising monomeric vinylamine units
- polyvinylformamide means a polymer comprising monomeric vinylformamide units.
- superplasticizer is understood to mean polymers making it possible to reduce the quantity of water in order to maintain in the hydraulic composition a high degree of slump, for example a high fluidity over a prolonged period of time.
- these superplasticizers are carbon chain polymers such as polycarboxylates comprising oxyalkylated side chains such as ethoxy or propoxy.
- nonionic polymer is understood to mean a polymer which does not comprise any cationic or anionic charge on its polymer chain.
- hydraulic composition is intended to define any composition having a hydraulic setting, and most particularly mortars, concretes and cementitious compositions intended for the field of construction.
- one of its constituents when this expression refers to the hydraulic composition, we mean the classic constituents of a hydraulic composition and which are known to those skilled in the art, such as aggregates (sand, limestone, ...), superplasticizers, as well as hydraulic binders such as cementitious binders, for example mortar or concrete.
- aggregates is meant to define aggregates of a variable particle size such as sand, gravel. They can be of any mineral, limestone, siliceous or silico-calcareous or other nature.
- the aggregates described in the context of the present invention, such as sand for example, comprise clays.
- clays is understood to denote aluminum and/or magnesium silicates, in particular phyllosilicates with a sheet structure, typically spaced apart by about 7 to about 14 Angstroms. However, this term also covers clays of other types, in particular amorphous clays. Mention may be made, among the clays frequently encountered in aggregates, in particular of montmorillonite, illite, kaolinite and muscovite.
- the proportion of monomeric units of acrylamide, and/or vinylamine, and/or vinylformamide in the water-soluble polymer according to the invention is preferably at least 70% molar relative to the total of monomeric units of the polymer, more preferably of at least 80% mol, more preferably at least 90% mol, even more preferably at least 95% mol.
- the polymer according to the invention may comprise monomeric units of a chemical nature different from the abovementioned chemical natures.
- said chemical natures reference is made to acrylamide, vinylformamide and vinylamine.
- These monomeric units of different chemical nature can be monomeric units of hydrophobic nature, monomeric cationic units, monomeric anionic units, monomeric zwitterionic units, preferably monomeric units of hydrophobic nature.
- the polymer according to the invention advantageously comprises only acrylamide and/or vinylamine and/or vinylformamide monomer units, and optionally hydrophobic monomer units.
- the water-soluble polymer is preferably selected from acrylamide homopolymers, homopolyvinylamines, homopolyvinylformamides, more preferably homopolyvinylamines, homopolyvinylformamides.
- the acrylamide/vinylamine copolymers advantageously comprise only acrylamide and vinylamine monomer units.
- the acrylamide/vinylformamide copolymers advantageously comprise only acrylamide and vinylformamide monomer units.
- the vinylamine/vinylformamide copolymers advantageously comprise only vinylamine/vinylformamide monomer units.
- Acrylamide/vinylamine/vinylformamide terpolymers advantageously comprise only acrylamide, vinylamine and vinylformamide monomer units.
- the polymers according to the invention additionally and advantageously comprise hydrophobic monomer units.
- the proportions of the monomeric acrylamide, vinylamine and/or vinylormamide units may be adjusted by those skilled in the art.
- the polymers according to the invention can advantageously comprise between 0.001 and 20% molar of monomeric units of hydrophobic nature, preferentially between 0.1 and 15% molar, and more preferentially between 0.1 and 10% molar.
- the monomers having a hydrophobic nature are preferably chosen from the group consisting of esters of (meth)acrylic acid having an alkyl, hydroxyalkyl, arylalkyl, propoxylated, ethoxylated, or ethoxylated and propoxylated chain; (meth)acrylamide derivatives having an alkyl, hydroxyalkyl, arylalkyl propoxylated, ethoxylated, ethoxylated and propoxylated, or dialkyl chain; alkyl aryl sulfonates.
- They are preferably chosen from hydroxyethylacrylate, ethylhexyl acrylate, hydroxypropylacrylate, butylacrylate, propylacrylate, dimethylacrylamide, butylacrylamide, terbutylacrylamide.
- hydrophobic monomers in the polymer according to the invention makes it possible to improve the performance over a wider dosage range, thus allowing greater flexibility in the use of the clay inertants according to the invention on the sites processing, whether in the quarry for aggregates, or on the production sites of hydraulic compositions.
- a person skilled in the art knows how to adjust the dosage to obtain optimum performance.
- the Mannich products obtained by reaction of formaldehyde and dimethylamine on a polymer comprising monomeric acrylamide units also form part of the polymers according to the invention. Typically these polymers do not contain chloride ions. These products can be protonated by adding a non-chlorinated alkylating agent, preferably diethyl sulphate.
- the molecular weight of the Mannich products according to the invention is between Mw L and Mw H.
- the polymers according to the invention preferably do not contain any cationic or anionic charge at the pH of use of the product, which is generally between 10 and 13. Preferably, they do not contain any cationic, anionic or zwitterionic monomeric unit.
- the weight-average molecular weight of the polymer according to the invention is expressed in daltons, and is between Mw L and Mw H, such that
- the weight-average molecular weight of the polymer according to the invention is included in the range [Mw L - Mw H], Mw L consisting of the lower limit value of this range while Mw H consists of the upper limit value of this beach.
- the polymer comprises several types of monomeric units of different chemical nature from the monomeric units of acrylamide, vinylamine, vinylformamide, then the monomeric proportion [MO] is equal to the sum of the proportions of these monomeric units of different chemical nature.
- the polymer comprises, for example, 90 mol% of acrylamide monomeric units, 5 mol% of butylacrylate monomeric units, and 5 mol% of dimethylacrylamide monomeric units
- [MO] is equal to 10 mol%
- Mw L is equal to 2900 daltons
- Mw H is equal to 65000 daltons.
- the water-soluble polymer according to the invention comprises at least 80 molar % of acrylamide monomeric units, then its weight-average molecular weight is preferably between 2.5*Mw L and 0.8*Mw H, more preferably between 3.3*Mw L and 0.6 *Mw H, these preferred ranges therefore constituting weight-average molecular weight ranges that are more restricted than the range [Mw L - Mw H] mentioned above.
- the polymer according to the invention is an acrylamide homopolymer
- its weight-average molecular weight is preferably between 7,500 and 40,000 daltons, more preferably between 10,000 and 30,000 daltons.
- the water-soluble polymer according to the invention comprises at least 80% molar of vinylamide and/or vinylformamide monomeric units, then its weight-average molecular weight is preferably between 2*Mw L and 5/6 (five sixths) *Mw H , more preferentially between 5*Mw L and 2/3 (two thirds) 'Mw H, these preferred ranges therefore constituting weight-average molecular weight ranges that are more restricted than the aforementioned range [Mw L - Mw H].
- the polymer according to the invention is a homopolyvinylamide or a homopolyvinylformamide, its weight-average molecular weight is preferably between 7,500 and 40,000 daltons, more preferably between 10,000 and 30,000 daltons.
- the polymer can have a linear, branched, star (star-shaped), comb (comb-shaped), dendritic or block structure.
- the polymer is advantageously linear or structured, preferably linear.
- structured polymer is meant a non-linear polymer which has side chains.
- the polymer does not require the development of a particular polymerization process. Indeed, it can be obtained according to all the polymerization techniques well known to those skilled in the art. It can in particular be a question of polymerization in solution; gel polymerization; precipitation polymerization; emulsion polymerization (aqueous or reverse); suspension polymerization; reactive extrusion polymerization; water-in-water polymerization; or micellar polymerization.
- the polymerization is generally a free radical polymerization, preferably by solution polymerization.
- Free radical polymerization includes free radical polymerization using UV, azo, redox or thermal initiators as well as controlled radical polymerization (CRP) techniques or matrix polymerization techniques.
- CRP controlled radical polymerization
- a particularly advantageous technique for the manufacture of the polymers of the invention is RAFT (Reversible Addition-Fragmentation Chain Transfer) polymerization, which makes it possible to synthesize polymers of controlled architecture (block polymers, stars, combs, etc.) of low polydispersity and of high functionality.
- RAFT Reversible Addition-Fragmentation Chain Transfer
- Polyvinylamines can be obtained by:
- Examples of monomers of formula (I) include in particular N-vinylformamide, N-vinyl-N-methylformamide, N-vinylacetamide, N-vinyl-N-methylacetamide, N-Vinyl-N-ethylacetamide, N -vinyl-propianamide, and N-vinyl-N-methylpropianamide and N-vinylbutyramide.
- the preferred monomer being N-vinylformamide.
- These monomers of formula (I) can be used alone or copolymerized with other monomers in the broad sense such as acrylamide or hydrophobic monomers, provided that the latter are not sensitive to hydrolysis.
- Polyvinylamines are preferentially obtained by hydrolysis reaction, preferentially basic, of polyvinylformamide.
- the polyvinylformamides are obtained according to methods known to those skilled in the art.
- GPC Gel permeation chromatography
- the polymer clay inerting agent can be used in different forms, preferably in the form of an aqueous solution, preferably comprising between 1 and 50% by weight of the inerting agent. It can be added by pouring or by spraying into the hydraulic composition or into one of its constituents.
- the hydraulic composition preferably contains a cementitious binder. It is preferably a mortar or a concrete. It will preferably contain between 20 and 90% by weight of aggregates, between 0.01 and 1% by weight of superplasticizer relative to the dry base of the composition.
- the other ingredients of the hydraulic composition are the ingredients usually encountered for the manufacture of such compositions. The method of preparing the hydraulic composition will be made according to the knowledge of the person skilled in the art.
- the inerting agent according to the invention is added to the hydraulic composition, it is added during the preparation of the composition at any stage of its preparation. Its implementation is easy and poses no difficulty in mixing.
- this addition is carried out prior to the addition of this constituent in the hydraulic composition. This may involve, for example, the addition of the inerting agent in the aggregates intended for the preparation of hydraulic compositions.
- the aggregates are brought into contact with the inerting agent, preferably by mixing the whole during or after the treatment in order to ensure a good distribution of the composition and to obtain a homogeneously treated material.
- aggregates with a clay content of 0.1 to 2% by weight will be treated.
- the aggregate will preferably be dry (moisture less than 10% by weight) at the time of processing.
- the aggregate will preferably be processed in the quarry.
- the inerting agent is preferably used in an appropriate amount to ensure complete inerting of the clays present in the aggregates or in the hydraulic composition.
- the treatment of an aggregate is generally satisfactory with a dosage of 2 to 200 ppm of inerting agent relative to the weight of aggregate. Those skilled in the art know how to adjust the dosage to obtain optimum performance.
- inerting agent allows, as previously explained, an improvement in the inhibition of clays while offering a chloride-free solution thus meeting the normative requirements and market expectations. It allows in the long term to participate in a reduction of the phenomena of corrosion of metals, in the reduction of the attack of the cementitious matrix, and thus in the increase of the durability of the works.
- the polymers according to the invention detailed in the examples do not contain chlorides.
- the processes for obtaining the polymers are described below.
- Acrylamide homopolymers are obtained by a solution polymerization process in deionized water.
- the amount of transfer agent is adjusted to achieve the molar masses described in Table 1.
- Homopolyvinylamines are obtained by alkaline hydrolysis of a poly(N-vinylformamide) following a solution polymerization process in water. Hydrolysis is quantitative.
- copolymer of acrylamide and vinylamine is obtained by Hofmann degradation of a polyacrylamide in the presence of sodium hypobromite then casting the polyisocyanate in an excess of acid.
- the copolymer of acrylamide and N-vinylformamide is obtained by copolymerization of acrylamide and N-vinylformamide by a solution polymerization process in deionized water.
- the terpolymer of acrylamide, vinylamine and N-vinylformamide is obtained by Hofmann degradation of the copolymer of acrylamide and N-vinylformamide as described above.
- VA Vinylamine EPI/DMA: cationic polymer obtained by polycondensation of epichloridrine and dimethylacrylamide
- the polymer of counterexample 3 contains 26% by weight of chlorides.
- Ciment Portland Le Classic (Lafarge, CEM II - 32.5 R, Cimenterie Le Opera), standardized sand (ciosceni du Littoral) and clay (bara-kade 200, Bentonite Performance Minerals LLC) are added to the bowl of the mixer then mixed at low speed for 15s to homogenize the mixture.
- An aqueous solution of superplasticizer (Floset SH5) and clay inertant is prepared and added over a period of 30 s to the cement mixture with stirring at low speed.
- the paste is then mixed for an additional 5 minutes.
- the water/cement ratio is set at 0.45, the superplasticizer is dosed at 0.5% by mass relative to the weight of cement, the sand/cement ratio is equal to 3.
- the quantity of inertant is dependent on the product tested and is expressed in % of dry product compared to sand.
- the paste is then poured into an inverted cone (Abrams cone) on a Plexiglas plate. This cone is lifted and the dough spreads out. The diameter of the wafer (D) is measured.
- the inert clay polymers of the invention make it possible to obtain performances superior to the counter-examples. In fact, they offer a recovery of at least 50% of the spreading obtained without inertant, whereas this value is less than 50% for the other polymers. In addition, the polymers of the invention make it possible to significantly reduce the dosages while being more effective. Polyvinylamine shows excellent results with more than 60% of the spreading found with dosages below 20 ppm. Polyvinylformamide also shows excellent performance with 100% of the spreading recovered. Finally, it is noted that the cationic polymer of counter-example 3 which contains chlorides (26% by weight) offers a lower performance than the polymers according to the invention which do not contain any.
- polymer of example 4 is compared to the polymers of examples 10 and 12. The same application test as in part 2 is carried out. Polymer dosages vary and performance is shown in Table 3.
- inert clay polymers of the invention containing a hydrophobic monomer offer good performance over a wider dosage range, thus allowing greater flexibility in their use at treatment sites, whether either in the quarry for the aggregates, or on the production sites of the hydraulic compositions.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Civil Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Preparation Of Clay, And Manufacture Of Mixtures Containing Clay Or Cement (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
Claims
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP21844709.2A EP4267526A1 (fr) | 2020-12-23 | 2021-12-22 | Procédé d'inertage d'argiles dans des compositions hydrauliques destinées à la construction |
AU2021405735A AU2021405735A1 (en) | 2020-12-23 | 2021-12-22 | Method for inerting clays in hydraulic compositions intended for construction |
MX2023007471A MX2023007471A (es) | 2020-12-23 | 2021-12-22 | Proceso de inertizacion de arcillas en composiciones hidraulicas destinadas a la construccion. |
KR1020237021228A KR20230150254A (ko) | 2020-12-23 | 2021-12-22 | 건설용 수경성 조성물의 점토 불활성화 방법 |
JP2023539752A JP2024502796A (ja) | 2020-12-23 | 2021-12-22 | 建設産業で使用する水硬性組成物中の粘土を不活性化する処理 |
CN202180086290.4A CN116745252A (zh) | 2020-12-23 | 2021-12-22 | 一种在建筑专用水硬性混合物中惰化黏土的方法 |
US18/257,035 US20240034678A1 (en) | 2020-12-23 | 2021-12-22 | Method for inerting clays in hydraulic compositions intended for the construction industry |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR2014074 | 2020-12-23 | ||
FR2014074A FR3118028B1 (fr) | 2020-12-23 | 2020-12-23 | Procédé d'inertage d'argiles dans des compositions hydrauliques destinées à la construction |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2022136574A1 true WO2022136574A1 (fr) | 2022-06-30 |
Family
ID=75108520
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2021/087350 WO2022136574A1 (fr) | 2020-12-23 | 2021-12-22 | Procédé d'inertage d'argiles dans des compositions hydrauliques destinées à la construction |
Country Status (9)
Country | Link |
---|---|
US (1) | US20240034678A1 (fr) |
EP (1) | EP4267526A1 (fr) |
JP (1) | JP2024502796A (fr) |
KR (1) | KR20230150254A (fr) |
CN (1) | CN116745252A (fr) |
AU (1) | AU2021405735A1 (fr) |
FR (1) | FR3118028B1 (fr) |
MX (1) | MX2023007471A (fr) |
WO (1) | WO2022136574A1 (fr) |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4460720A (en) * | 1982-02-17 | 1984-07-17 | W. R. Grace & Co. | Multicomponent concrete superplasticizer |
WO1998058887A1 (fr) | 1997-06-25 | 1998-12-30 | W.R. Grace & Co.-Conn. | Adjuvant et procede destine a optimiser l'ajout d'un superplastifiant d'eo/po a un beton renfermant des agregats d'argile smectique |
WO2006032785A2 (fr) | 2004-09-21 | 2006-03-30 | Lafarge | Procede d'inertage d'impuretes |
WO2013124003A1 (fr) | 2012-02-22 | 2013-08-29 | W R Grace & Co.-Conn | Polyamines fonctionnalisées pour la mitigation de l'argile |
WO2018054991A1 (fr) | 2016-09-21 | 2018-03-29 | S.P.C.M. Sa | Procede d'obtention de polymeres cationiques a teneur reduite en halogenures |
CN108328987A (zh) * | 2018-02-10 | 2018-07-27 | 朱东洋 | 一种聚酯树脂基水泥材料 |
-
2020
- 2020-12-23 FR FR2014074A patent/FR3118028B1/fr active Active
-
2021
- 2021-12-22 JP JP2023539752A patent/JP2024502796A/ja active Pending
- 2021-12-22 KR KR1020237021228A patent/KR20230150254A/ko unknown
- 2021-12-22 CN CN202180086290.4A patent/CN116745252A/zh active Pending
- 2021-12-22 AU AU2021405735A patent/AU2021405735A1/en active Pending
- 2021-12-22 US US18/257,035 patent/US20240034678A1/en active Pending
- 2021-12-22 EP EP21844709.2A patent/EP4267526A1/fr active Pending
- 2021-12-22 MX MX2023007471A patent/MX2023007471A/es unknown
- 2021-12-22 WO PCT/EP2021/087350 patent/WO2022136574A1/fr active Application Filing
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4460720A (en) * | 1982-02-17 | 1984-07-17 | W. R. Grace & Co. | Multicomponent concrete superplasticizer |
WO1998058887A1 (fr) | 1997-06-25 | 1998-12-30 | W.R. Grace & Co.-Conn. | Adjuvant et procede destine a optimiser l'ajout d'un superplastifiant d'eo/po a un beton renfermant des agregats d'argile smectique |
WO2006032785A2 (fr) | 2004-09-21 | 2006-03-30 | Lafarge | Procede d'inertage d'impuretes |
WO2013124003A1 (fr) | 2012-02-22 | 2013-08-29 | W R Grace & Co.-Conn | Polyamines fonctionnalisées pour la mitigation de l'argile |
WO2018054991A1 (fr) | 2016-09-21 | 2018-03-29 | S.P.C.M. Sa | Procede d'obtention de polymeres cationiques a teneur reduite en halogenures |
CN108328987A (zh) * | 2018-02-10 | 2018-07-27 | 朱东洋 | 一种聚酯树脂基水泥材料 |
Also Published As
Publication number | Publication date |
---|---|
FR3118028B1 (fr) | 2023-12-15 |
MX2023007471A (es) | 2023-09-05 |
US20240034678A1 (en) | 2024-02-01 |
AU2021405735A1 (en) | 2023-07-06 |
KR20230150254A (ko) | 2023-10-30 |
CN116745252A (zh) | 2023-09-12 |
FR3118028A1 (fr) | 2022-06-24 |
AU2021405735A9 (en) | 2024-02-08 |
EP4267526A1 (fr) | 2023-11-01 |
JP2024502796A (ja) | 2024-01-23 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP1799624B1 (fr) | Procede d'inertage d'impuretes | |
EP1984309B1 (fr) | Utilisation d'un adjuvant a titre de plastifiant pour compositions hydrauliques | |
US11548967B2 (en) | Preparation method for polycarboxylate water reducer having regular sequence structure | |
FR2546173A1 (fr) | Composition de revetement et d'etancheification et notamment composition renforcee par des fibres et procede d'amelioration des proprietes de cette composition | |
FR2668773A1 (fr) | Agent de maintien de la rheologie des produits a base de ciment. | |
CN1087613A (zh) | 水硬水泥晶穴减少添加剂及其用法 | |
EP3256426B1 (fr) | Procédé pour le traitement de suspensions de particules solides dans l'eau à l'aide de polymères amphotères | |
EP3515970B1 (fr) | Procede d'obtention de polymeres cationiques a teneur reduite en halogenures | |
WO2022136574A1 (fr) | Procédé d'inertage d'argiles dans des compositions hydrauliques destinées à la construction | |
EP1194390B1 (fr) | Nouveaux agents de type copolymeres acryliques a base d'urethanne pour ameliorer la maniabilite des liants hydrauliques, leur procede de preparation, les liants les contenant et leurs applications | |
WO1985000802A1 (fr) | Composition de beton pour applications sous-marines | |
EP1828257B1 (fr) | Dispersants acryliques hydrosolubles ou hydrodispersibles obtenus par polymerisaton radicalaire controlee | |
FR3118049A1 (fr) | Composition pour préparer un fluide d’injection pour la récupération de pétrole et de gaz | |
FR3069547B1 (fr) | Composition polymerique aqueuse et copolymere | |
EP3658597A1 (fr) | Composition polymérique aqueuse et copolymère | |
FR2828484A1 (fr) | Additifs polymeres pour compositions de ciment destinees a ameliorer l'action interfaciale apres la prise | |
FR3069548A1 (fr) | Composition polymerique aqueuse et copolymere | |
WO2017068288A1 (fr) | Utilisation de polyacrylamide dans une composition hydraulique pour une resistance a la carbonatation amelioree | |
EP3024860A1 (fr) | Viscosifiant a base de particules polymeriques filamenteuses | |
FR2964883A1 (fr) | Procede d'acceleration et/ou d'augmentation du drainage d'eau d'un amas de granulats | |
WO2020260776A1 (fr) | Copolymère et composition de liant hydraulique | |
JPH0517182B2 (fr) |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 21844709 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 18257035 Country of ref document: US |
|
WWE | Wipo information: entry into national phase |
Ref document number: 202180086290.4 Country of ref document: CN |
|
WWE | Wipo information: entry into national phase |
Ref document number: MX/A/2023/007471 Country of ref document: MX |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2023539752 Country of ref document: JP |
|
ENP | Entry into the national phase |
Ref document number: 2021405735 Country of ref document: AU Date of ref document: 20211222 Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 2021844709 Country of ref document: EP Effective date: 20230724 |