WO2004067470A1 - Composition comprenant un liant hydraulique et un latex possedant un groupement fonctionnel sulfonate, sulfonique ou sulfobetaine - Google Patents

Composition comprenant un liant hydraulique et un latex possedant un groupement fonctionnel sulfonate, sulfonique ou sulfobetaine Download PDF

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WO2004067470A1
WO2004067470A1 PCT/EP2004/000680 EP2004000680W WO2004067470A1 WO 2004067470 A1 WO2004067470 A1 WO 2004067470A1 EP 2004000680 W EP2004000680 W EP 2004000680W WO 2004067470 A1 WO2004067470 A1 WO 2004067470A1
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Prior art keywords
monomer
composition according
composition
latex
chosen
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PCT/EP2004/000680
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English (en)
Inventor
Pascal Chapon
Sylvie Touzet
Sylvaine Le Roy Delage
Jonathan Phipps
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Rhodia Chimie
Services Petroliers Schlumberger
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Publication of WO2004067470A1 publication Critical patent/WO2004067470A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
    • 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
    • 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
    • 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
    • C04B24/2676—Polystyrenes
    • 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

Definitions

  • the present invention relates to a composition
  • a composition comprising at least one hydraulic binder and at least one latex having a sulfonate, sulfonic or sulfobetaine functional group, and water.
  • the composition is of use in particular in the construction and civil engineering fields.
  • the composition also relates to techniques for drilling oil, gas, water, geothermal or analogous wells or more specifically the invention also relates to cementing compositions very particularly suited to the cementing of areas which may be subjected to extreme dynamic stresses.
  • the cement compositions and the resulting hardened materials have to respectively exhibit appropriate rheological and mechanical properties.
  • the compositions do not comprise only a binder material, the reaction of which with water gives a hardened product, but also various additives, the role of which is to improve various mechanical and/or rheological characteristics.
  • the mechanical characteristics to which very particular attention is paid include the ultimate strength, which is the representation of the strength of the material when it is subjected to a mechanical stress.
  • Another mechanical characteristic is the modulus of elasticity, which represents the stiffness of the material. The lower the modulus, the greater the flexibility of the material, which means that the material has high capabilities to withstand deformations of the ground.
  • latices which are known additives of cement compositions and are very often styrene-butadiene copolymers, reduce the ultimate strength and the Young's modulus.
  • a cement composition comprising at least one hydraulic binder, of at least one latex exhibiting a mean size of less than 400 nm which is prepared by polymerization from monomers, polymerizable by the radical route, chosen from at least one aromatic monomer (i) , optionally at least one monomer (ii) comprising at least one vinyl ester and/or amide functional group and at least one functional monomer (iii) comprising a sulfonate, sulfonic or sulfobetaine group, and water.
  • the use of the latices as just defined makes it possible to reduce the value of the Young' s modulus while not greatly damaging the ultimate strength. Furthermore, the ratio of the ultimate flexural modulus to the value of its Young' s modulus is increased.
  • the cement composition forming the subject matter of the use according to the invention comprises at least one latex exhibiting a mean size of less than 400 nm which is prepared by polymerization of monomers, polymerizable by the radical route, chosen from at least one aromatic monomer (i) , optionally at least one monomer (ii) comprising at least one ester and/or amide functional group and at least one functional monomer (iii) comprising a sulfonate, sulfonic or sulfobetaine group.
  • the monomer (i) from which the latex is obtained is more particularly chosen from monomers exhibiting at least one aromatic radical, optionally substituted by one or more alkyl radicals, and an ethylenic unsaturation, preferably from monomers of vinylaromatic type optionally exhibiting a halogen atom.
  • the latex is obtained at least from styrene.
  • the latex can optionally be obtained from a second type of unsaturated monomer comprising an ester and/or amide functional group.
  • the monomers (ii) exhibiting at least one ester functional group if they are present, they are chosen from C ⁇ -C 18 esters, preferably Ci-C ⁇ esters, of acrylic or methacrylic acid, and their N-substituted derivatives, or from vinyl esters of C 2 -C 10 carboxylic acid.
  • Examples of such monomers include in particular methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, stearyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, di (tert-butyl) aminoethyl (meth) acrylate, vinyl acetate, vinyl versatate, vinyl propionate, vinyl pivalate, vinyl neononanoate or vinyl neodecanoate, alone or as mixtures .
  • the latex participating in the cement composition according to the invention comprises a monomer of (meth) acrylate type.
  • the monomers (ii) exhibiting at least one amide functional group if they are present, they are usually chosen from acrylamide or methacrylamide, or their derivatives.
  • the latex employed in the cement composition of the invention additionally comprises at least one monomer (iii) having a functional group of the sulfonate, sulfonic or sulfobetaine type. More particularly, said monomer (iii) is chosen from unsaturated monomers comprising at least one linear or nonlinear aliphatic radical comprising 2 to 12 carbon atoms, optionally interrupted by at least one heteroatom, and/or at least one aromatic or alkylaromatic radical, it being possible for said aromatic radical to comprise a heteroatom and it being possible for said aromatic radical to be substituted by at least one halogen atom.
  • the monomer (iii) can be present in the acid form or in the form of an alkali metal, alkaline earth metal or ammonium salt.
  • the alkali metal salts are sodium or potassium salts.
  • the ammonium salts they are of the NR 4 + type in which the R radicals, which are identical or different, represent hydrogen atoms or alkyl radicals comprising 1 to 4 carbon atoms, optionally carrying a hydroxyl group.
  • the monomer (iii) is chosen from styrenesulfonic acid, vinylxylenesulfonic acid, vinylsulfonic acid, vinylbenzenesulfonic acid, vinyltoluenesulfonic acid, vinylchlorobenzenesulfonic acid, vinylnaphthalenesulfonic acid, acry1amidomethyl- propanesulfonic acid, sulfopropyl (meth) acrylic acid, 2-sulfoethylene (meth) acrylic acid or ⁇ -acrylamido- methylpropanesulfonic acid, alone or as mixtures, in the acid form or in the form of salts .
  • suitable monomers (iii) of suitable monomers (iii) , of monomers of sulfobetaine type, such as ethyldimethylammoniumpropylsulfonate (meth) acrylate, propyldimethylammoniumsulfopropyl (methy) acrylamide or dimethylammoniumpropylsulfonate vinylpyridinium.
  • sulfobetaine type such as ethyldimethylammoniumpropylsulfonate (meth) acrylate, propyldimethylammoniumsulfopropyl (methy) acrylamide or dimethylammoniumpropylsulfonate vinylpyridinium.
  • sulfobetaine type such as ethyldimethylammoniumpropylsulfonate (meth) acrylate, propyldimethylammoniumsulfopropyl (methy) acrylamide or dimethyl
  • the carboxylic monomers are more particularly unsaturated mono- or dicarboxylic acids comprising 2 to 12 carbon atoms with at least one of the carboxyl groups being free, that is to say being found either in the acid form or in the form of an alkali metal or ammonium salt .
  • Unsaturated ethylenic mono-, di- and tricarboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, aconitic acid or acrylamidoglycolic acid, are suitable for the implementation of the invention.
  • Monoalkyl esters of dicarboxylic acids of the type mentioned with alkanols preferably having 1 to 4 carbon atoms and their N-substituted derivatives can also be used.
  • the monomers (iii) can also optionally be partially substituted by a monomer of the type of the vinylnitriles.
  • vinylnitriles comprising 3 to 12 carbon atoms may be suitable, with preferably acrylonitrile and met acrylonitrile .
  • Such monomers can be aromatic or nonaromatic hydrocarbonaceous monomers, such as divinylbenzene, or monomers derived from (meth) acrylic acid, such as, for example, ethylene glycol di (meth) acrylate, trimethylolpropane trimethacrylate or glycidyl (meth) acrylate, or alternatively vinyl and acrylic silanes .
  • aromatic or nonaromatic hydrocarbonaceous monomers such as divinylbenzene
  • monomers derived from (meth) acrylic acid such as, for example, ethylene glycol di (meth) acrylate, trimethylolpropane trimethacrylate or glycidyl (meth) acrylate, or alternatively vinyl and acrylic silanes .
  • the abovementioned monomers (v) are used in amounts generally of between 0.1 and 5% by weight of the other monomers (i) to (iv) .
  • the monomer (s) (i) /monomer (s) (ii) molar ratio is more particularly between 0/100, limit excluded, and 100/0.
  • the monomer (s) (i) /monomer (s) (ii) molar ratio is between 70/30 and 100/0, or between 0/100, limit excluded, and 30/70.
  • the monomer (s) (i) /monomer (s) (ii) molar ratio is between 20/80 and 60/40.
  • said molar ratio is between 99.5/0.5 and 95/5, more preferably still between 99/1 and 97/3.
  • the monomer (s) (iii) /monomer (s) (iv) molar ratio is between 20/80 and 80/20, preferably between 50/50 and 80/20.
  • the mean size of the latex participating in the cement composition according to the invention is less than 400 nm and preferably between 15 nm and less than 400 nm. It should be pointed out that the mean size can be measured by quasielastic light scattering using a device of Mastersizer 1000 type from Malvern, or by laser diffraction, for example with a device of Coulter LS 230 type.
  • the latex exhibits a mean size of between 60 and less than 400 nm. Preferably, the mean size is between 60 and 350 nm.
  • the latex can be composed of a single entity or of a mixture of several latices, the mean size of which is within the range indicated above.
  • the latex present in the cement composition according to the invention is composed of a blend of one or more latices (60 ⁇ 400 nm) and of one or more nanolatices (15 ⁇ 60 nm) .
  • the latex or latices exhibit (s) a mean size of between 15 and less than 60 nm.
  • the composition of the two, latex and nanolatex is the same or different.
  • nanolatex corresponding to a homopolymer of one of the monomers (i) and (ii) which is mentioned in the context of the description of the latex.
  • the nanolatex if it is employed, is obtained by polymerization of at least two monomers chosen from the abovementioned monomers (i) to (v) .
  • the monomers from which it is obtained are chosen at least from the monomers (ii) and/or (ii) and (iii) .
  • the proportion of latex with respect to a nanolatex can vary within a wide range.
  • the latex/nanolatex proportion by weight is between 20/80 and 80/20, preferably between 30/70 and 70/30.
  • the latices and nanolatices are prepared in a way conventional in the field.
  • the latex can be produced by aqueous emulsion polymerization of the monomers (i) to (ii) , if appropriate (iv) and (v) , in the presence of at least one radical initiator and preferably in the presence of a transfer agent, for example of the mercaptan type, with a concentration of monomers in the reaction medium generally of between 20 and 60% by weight .
  • Any type of free radical initiator conventional in emulsion polymerization may be suitable .
  • initiators comprise hydroperoxides, such as aqueous hydrogen peroxide solution or diisopropylbenzene hydroperoxide, sodium, potassium or ammonium persulfates, and cationic initiators, such as azobis (isobutyronitrile) or 4,4'- azobis (4-cyanovaleric acid).
  • hydroperoxides such as aqueous hydrogen peroxide solution or diisopropylbenzene hydroperoxide, sodium, potassium or ammonium persulfates
  • cationic initiators such as azobis (isobutyronitrile) or 4,4'- azobis (4-cyanovaleric acid).
  • intiators can be used in combination with a reducing agent, such as, for example, bisulfite.
  • a reducing agent such as, for example, bisulfite.
  • the amount generally lies between 0.05 and 2% by weight with respect to the amount of the monomers .
  • the polymerization temperature a function of the initiator employed, is generally between 50 °C and 100°C, preferably between 50°C and 70°C.
  • Stabilization of the particles is provided, if necessary, by any known system for colloidal stabilization, such as anionic, cationic, amphoteric and nonionic emulsifiers.
  • the anionic emulsifiers are, for example, alkaline alkyl sulfates, alkylsulfonates, alkylarylsulfonates and alkyl phosphates; dialkyl sulfosuccinates; or sodium, potassium or ammonium salts of saturated or unsaturated fatty acids.
  • Examples of cationic emulsifiers are alkylpyridinium or alkylammonium salts, such as N-ethyldodecylammonium chloride or bromide or cetylammonium chloride or bromide. Mention is in particular made, as nonionic emulsifiers, of polyoxyethylenated and/or polyoxypropylenated derivatives of fatty alcohols, fatty acids or alkylphenols . '
  • microemulsion is understood to denote a thermodynamically stable dispersion, in contrast to a dispersion which is only kinetically stable, which coalesces after a certain period of time.
  • Said direct microemulsion being obtained beforehand using an effective amount of an ionic surfactant, either from a direct emulsion stabilized by at least one ionic surfactant or from an inverse emulsion stabilized by at least one nonionic surfactant, the two emulsions, referred to as starting emulsions, being composed of at least one monomer in aqueous dispersion.
  • an ionic surfactant either from a direct emulsion stabilized by at least one ionic surfactant or from an inverse emulsion stabilized by at least one nonionic surfactant
  • the nanolatex can be prepared by incrementally adding to the reactor at least one of the monomers present, capable of polymerizing in aqueous emulsion, and a polymerization initiator and at least one surfactant are added incrementally, so that nanolatex particles with an appropriate particle size are obtained.
  • the content of water in the latex is more particularly between 30 and 80% by weight. It is preferably between 40 and 50% by weight for the latices and between 40 and 75% for the nanolatices.
  • the composition comprises at least one nonionic or anionic surfactant, or their mixture.
  • the surfactant or surfactants are chosen from nonionic surfactants .
  • the following are suitable in particular, alone or as a mixture: optionally alkoxylated fatty alcohols, more particularly comprising from 6 to 22 carbon atoms; optionally alkoxylated mono-, di- and triglycerides ; optionally alkoxylated fatty acids, more particularly comprising from 6 to 22 carbon atoms; - optionally alkoxylated sorbitan esters (cyclized esters of sorbitol with a fatty acid comprising from 10 to 20 carbon atoms) ; optionally alkoxylated fatty amines, more particularly comprising from 6 to 22 carbon atoms; - alkoxylated alkylphenols, more particularly comprising one or two linear or branched alkyl groups having 4 to 12 carbon atoms; polyalkoxylated di- or tristyrylphenols ; alkylpolyglucosides ;
  • the surfactant or surfactants are chosen from anionic surfactants, in the acid form or in the form of alkali metal, ammonium or alkaline earth metal salts. It should be pointed out that the definition of ammonium was given in detail above.
  • alkyl ester sulfonates for example of formula R-CH(S0 3 M) -CH 2 C00R' , where R represents a C 8 -C 20 alkyl radical, preferably a C ⁇ 0 -C ⁇ 6 alkyl radical, R' represents a C 3.
  • -C 6 alkyl radical preferably a C1-C 3 alkyl radical
  • M is a hydrogen atom, an alkali metal (sodium, potassium or 'lithium) or unsubstituted or substituted ammonium (methyl-, dimethyl-, trimethyl- or tetramethylammonium, dimethylpiperidinium, and the like) cation or a cation derived from an alkanolamine
  • R-CH(OS0 3 M) -CH 2 C00R' where R represents a C 8 -C 20 alkyl radical, preferably a C 10 -C ⁇ 6 alkyl radical, R' represents a C ⁇ -C 6 alkyl radical, preferably a C1-C 3 alkyl radical, and M corresponds to the above definition; alkylbenzenesulfonates, more particularly C 9 -C 20 alkylbenzenesulfonates, primary or secondary alkylsulfonates, in particular C 8 -C 22 alkylsulfonates, or alkylglycerolsulfonates; - alkyl sulfates, for example of formula ROSO3M where R represents a C ⁇ 0 -C 24 , preferably C 12 -C 2 o.
  • alkyl or hydroxyalkyl radical corresponds to the definition above; alkyl ether sulfates, for example of formula RO(AO) n S0 3 M where R represents a C ⁇ 0 -C 24 , preferably C12-C20.
  • alkyl or hydroxyalkyl radical AO representing an ethoxylated and/or propoxylated group
  • M corresponds to the definition above
  • alkylamide sulfates for example of formula RCONHROSO 3 M where R represents a C 2 -C 22 alkyl radical, preferably a C 3 -C 2 o alkyl radical, R' represents a C 2 -C 3 alkyl radical and M corresponds to the definition above, and their polyalkoxylated (ethoxylated and/or propoxylated) derivatives; salts of saturated or unsaturated fatty acids, for example such as those of C 8 -C 2 4 fatty acids, preferably of C ⁇ 4 -C 2 o fatty acids, and of an alkali metal, ammonium or alkaline earth metal cation, N-acyl-N-alkyltaurates
  • the content of surfactant in the composition represents 0.5 to 50% by weight, expressed with respect to the weight of latex, preferably 1 to 20% by weight, with respect to the same reference .
  • the presence of the surfactant has the consequence of improving the processing of the composition. Without wishing to be committed to any one theory, it is believed that the surfactant renders the latex compatible with the remainder of the composition.
  • the composition used according to the invention comprises at least one hydraulic binder.
  • any conventional compound capable of reacting and hardening when it is in the presence of water can be used.
  • compounds based on silicon, aluminum, calcium, oxygen and/or sulfur may be suitable for the implementation of the invention.
  • compounds based on calcium silicate (Portland cement) , on pozzolana or on gypsum, hydraulic binders with a high aluminum content, hydraulic binders based on phosphate and hydraulic binders based on calcium silicate are preferred.
  • the composition is such that, per 100 parts by weight of hydraulic binder, the latex is present between 1 and 50 parts by weight, more particularly between 5 and 50 parts by weight, preferably between 10 and 40 parts by weight and more preferably still between 10 and 25 parts by weight.
  • the cement according to the invention can comprise additives which are conventional in the field, for example setting retarders or accelerators, dispersants, antifoam agents, defoamers, rheology modifiers, thickeners, air entrainers, agents which prevent migration of gases, and the like.
  • the cement according to the present invention can comprise fillers.
  • inorganic fillers capable of being used, of calcium carbonate, fly ash, silica, fumed silica, clays (kaolin, metakaolin, bentonite, sepiolite, wollastonite) , mica, feldspar, silicate, glass, titanium dioxide, aluminum or magnesia.
  • Use may in particular be made, as organic filler, of expanded polystyrene.
  • the mean size of inorganic fillers is advantageously less than or equal to 120 ⁇ m, preferably less than or equal to 80 ⁇ m.
  • the content of the fillers in the cement when they are present, varies according to the subsequent applications for which the cement is intended. Likewise, according to whether it is desired to render the cement denser or lighter, inorganic or organic fillers can be employed.
  • the content of fillers represents at most the same weight as the hydraulic binder.
  • the composition can likewise comprise polymer
  • the dimensions of the fibers vary within a wide range and can be between a few tenths to a few tens of millimeters.
  • the water content of the composition according to the invention it can be easily determined by a person skilled in the art. It depends, inter alia, on the rheology and density characteristics desired for the composition.
  • composition can be prepared by any means conventional in the field.
  • the binder, the water, the latex, optionally the surfactant and optionally the conventional additives are brought into contact with stirring.
  • the mixing of the various constituent components is here again carried out in a way conventional in the field.
  • a kneading and, if necessary, a deagglomeration can in particular be carried out .
  • the mixing operation generally takes place at ambient temperature .
  • the composition can be formed, inter alia, by grouting, casting, extrusion or spraying.
  • the consolidated material obtained after the composition has hardened can, for example, be used in the field of the extraction of oil or gas or alternatively in that of construction and civil engineering.
  • composition according to the invention and the material obtained after hardening can very particularly be used in the field of the drilling of wells for the extraction of oil and/or gas.
  • cementing fluids is often used. Such fluids or compositions are described below in more detail.
  • compositions suitable for the field of the drilling of wells for the extraction of oil and/or gas are known. Such compositions are disclosed, for example, in the document EP 0 621 247 and the document WO 01/09056. They comprise, in addition to the latex in accordance with the invention, a hydraulic binder and generally other components.
  • the hydraulic binder is preferably a cement, such as Portland cement.
  • Other binders have been mentioned above.
  • the "other components” include in particular particulate additives (hollow or nonhollow solids) of various sizes and of various chemical natures. According to a specific embodiment, particulate additives have a multimodal size distribution in accordance with the teaching of EP 621 247.
  • the compositions can comprise:
  • very large particles mean diameter of greater than 1 mm
  • sand for the glass-making industry or ground waste such as sand for the glass-making industry or ground waste
  • - "large” particles mean diameter of 200-800 ⁇ m
  • silica silica
  • carbonates barium hydroxide, hematites, or iron oxides, carbide or sulfides
  • medium particles (mean diameter of 10-20 ⁇ m) , such as particles of cement or of other hydraulic binders
  • fine particles mean diameter of 0.5-10 ⁇ m) , such as microcements, micro-fly ash, carbonates (marble, chalk, calcite) , blanc fixe, hematites, iron oxides, silica, carbon, sulfides or fine industrial waste
  • very fine particles mean diameter of 0.05-05 ⁇ m
  • ultrastyrene particles mean diamter of 7-50 nm
  • colloidal silicas or aluminas such as colloidal silicas or aluminas.
  • the “other components” can also include adjuvants conventional in the field, such as dispersants, antifreezes, water retainers, hardening accelerators or retarders, or agents for controlling foaming.
  • the composition has a density of 0.9 g/cm 3 to 1.3 g/cm 3 and in that the ratio by volume of the liquid fraction to the solid fraction is from 38% to 50%.
  • the document WO 01/09056 discloses compositions exhibiting this density.
  • compositions advantageously comprise a solid fraction, the composition of which is as follows: 60 to 90% by volume of light particles (with a density of less than 2 g/cm 3 , preferably of less than 0.8 g/cm 3 ), if appropriate hollow, with a size of between 20 and 350 ⁇ m, - 10 to 30% by volume of microcement with a size of between 0.5 and 5 ⁇ m, for example Portland G cement, 0 to 30% by volume of Portland cement, with a size between 20 and 50 ⁇ m, 0 to 30% by volume of gypsum.
  • Example 1 Preparation of a latex
  • Rhodia and 1 120 g of a pre-emulsion defined below are introduced in this order into a three-necked glass reactor with a capacity of 25 liters equipped with a mechanical stirrer. The combined reactants are heated to 80 °C.
  • a the remainder of the pre-emulsion composed of a mixture of 4 468 g of styrene, of 4 690 g of butyl acrylate, of 92.5 g of 2-acrylamide-2-methylpropanesulfonic acid, of 122 g of an anionic surfactant and of 4 440 g of water, is added continuously at 80 °C under nitrogen and with stirring.
  • reaction medium is maintained at 80 °C for a further 2 hours and is then cooled at approximately T 0 + 9h.
  • a latex with the following characteristics is obtained:
  • a slag of Dyckerhoff Class G cement is formulated at a density of 1.92 kg/1 (16 lbm/gal) , i.e. a water/cement ratio by mass of 0.44, with the following additives
  • Rhodasurf CET/5 is a commercial surfactant supplied by Rhodia.
  • the slag has a plastic viscosity of 50 mPa-s and a yield point of 1.4 Pa. These values are clearly within the acceptable range for the cementing of oil or gas wells.
  • the hardened cement test specimen After curing for 7 days at 77 °C and 20.7 MPa, the hardened cement test specimen has an ultimate flexural strength of 12.15 MPa and a flexural Young's modulus of 7 834 MPa. The ratio of the ultimate strength to the modulus is therefore 1.55-10 "3 .
  • Example 3 A slag of Dyckerhoff Class G cement was formulated at a density of 1.92 kg/1 (16 lbm/gal) , i.e. a water/cement ratio by mass of 0.44, with the following additives
  • the slag has a plastic viscosity of 150 mPa-s and a yield point of 19 Pa. These values are within the acceptable range for the cementing of oil or gas wells.
  • the hardened cement test specimen After curing for 7 days at 77 °C and 20.7 MPa, the hardened cement test specimen has an ultimate flexural strength of 7.82 MPa and a flexural Young's modulus of 3 537 MPa. The ratio of the ultimate strength to the modulus is therefore 2.21* 10 "3 .
  • Example 3 Comparative
  • a slag of Dyckerhoff Class G cement was formulated at a density of 1.92 kg/1 (16 lbm/gal) , i.e. a water/cement ratio by mass of 0.44, with the following additives
  • the hardened cement test specimen After curing for 7 days at 77 °C and 20.7 MPa, the hardened cement test specimen has an ultimate flexural strength of 12.74 MPa and a flexural Young's modulus of 9 754 MPa. The ratio of the ultimate strength to the modulus is therefore 1.31-10 "3 .
  • the latex according to the invention makes it possible to increase the flexibility of the cement while, at the same time, increasing the ultimate strength/modulus ratio by 70%.

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Abstract

L'invention concerne une composition comprenant au moins un liant hydraulique et au moins un latex de taille moyenne inférieure à 400 nm, lequel est préparé par polymérisation de monomères pouvant être polymérisés par l'itinéraire radical, choisis parmi au moins un monomère aromatique (i), facultativement au moins un monomère (ii) comprenant au moins un groupement fonctionnel d'éther vinylique et/ou amide et au moins un monomère fonctionnel (iii) comprenant un groupement sulfonate, sulfonique ou sulfobétaïne, ainsi que de l'eau. L'invention concerne également l'utilisation de ce latex dans une composition de liant hydraulique, plus spécifiquement dans un fluide destiné à la cimentation de puits pour l'extraction de pétrole et/ou de gaz.
PCT/EP2004/000680 2003-01-30 2004-01-27 Composition comprenant un liant hydraulique et un latex possedant un groupement fonctionnel sulfonate, sulfonique ou sulfobetaine WO2004067470A1 (fr)

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FR0301054A FR2850647B1 (fr) 2003-01-30 2003-01-30 Composition comprenant un liant hydraulique et un latex possedant un groupement foncitonnel sulfonate, sulfonique ou sulfobetaine
FR03/01054 2003-01-30

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WO2004067470A1 true WO2004067470A1 (fr) 2004-08-12

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WO2013156551A1 (fr) * 2012-04-18 2013-10-24 Rhodia Operations Traitement de formations souterraines par des gels
CN108439872A (zh) * 2018-05-15 2018-08-24 中国石油集团工程技术研究院有限公司 一种抗高温的高强度低弹模高密度水泥浆

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WO1992017417A1 (fr) * 1991-03-26 1992-10-15 The Western Company Of North America Regulation d'un ecoulement gazeux a travers une colonne de ciment
EP0812872A2 (fr) * 1996-06-12 1997-12-17 BASF Aktiengesellschaft Procédé pour préparer des poudres polymères
WO1997048655A1 (fr) * 1996-06-19 1997-12-24 Atlantic Richfield Company Procede et composition de ciment a base de ciment et de boue de forage pour la cimentation d'un forage
US6171386B1 (en) * 1998-01-22 2001-01-09 Benchmark Research& Technology Inc. Cementing compositions, a method of making therefor, and a method for cementing wells
WO2000020350A1 (fr) * 1998-10-06 2000-04-13 Sofitech N.V. Compositions de cimentation et leur utilisation pour cimenter des puits de petrole ou similaires
WO2000034199A1 (fr) * 1998-12-10 2000-06-15 Sofitech N.V. Compositions de cimentation et leur application pour la cimentation de puits de petrole ou similaires
WO2001009056A1 (fr) * 1999-07-29 2001-02-08 Sofitech N.V. Boue de cimentation a faible densite et faible porosite pour puits de petrole ou analogues

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013156551A1 (fr) * 2012-04-18 2013-10-24 Rhodia Operations Traitement de formations souterraines par des gels
FR2989686A1 (fr) * 2012-04-18 2013-10-25 Rhodia Operations Traitement de formations souterraines par des gels
EP3456759A1 (fr) * 2012-04-18 2019-03-20 Rhodia Operations Traitement de formations souterraines par des gels
US10815413B2 (en) 2012-04-18 2020-10-27 Rhodia Operations Treatment of underground formations with gels
CN108439872A (zh) * 2018-05-15 2018-08-24 中国石油集团工程技术研究院有限公司 一种抗高温的高强度低弹模高密度水泥浆

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FR2850647A1 (fr) 2004-08-06

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