EP3052579A1 - Block polymers for fluid loss control - Google Patents

Block polymers for fluid loss control

Info

Publication number
EP3052579A1
EP3052579A1 EP14780519.6A EP14780519A EP3052579A1 EP 3052579 A1 EP3052579 A1 EP 3052579A1 EP 14780519 A EP14780519 A EP 14780519A EP 3052579 A1 EP3052579 A1 EP 3052579A1
Authority
EP
European Patent Office
Prior art keywords
block
units
fluid
particles
polymer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
EP14780519.6A
Other languages
German (de)
French (fr)
Inventor
Arnaud Cadix
David James Wilson
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Rhodia Operations SAS
Original Assignee
Rhodia Operations SAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Rhodia Operations SAS filed Critical Rhodia Operations SAS
Priority to EP20183217.7A priority Critical patent/EP3770231A1/en
Publication of EP3052579A1 publication Critical patent/EP3052579A1/en
Ceased legal-status Critical Current

Links

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
    • C04B24/2688—Copolymers containing at least three different monomers
    • 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
    • C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
    • C04B20/10—Coating or impregnating
    • C04B20/1018—Coating or impregnating with organic materials
    • C04B20/1029—Macromolecular compounds
    • C04B20/1033—Macromolecular compounds 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
    • 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
    • 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
    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
    • C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/02—Well-drilling compositions
    • C09K8/03—Specific additives for general use in well-drilling compositions
    • C09K8/035—Organic additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/42—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells
    • C09K8/46—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells containing inorganic binders, e.g. Portland cement
    • C09K8/467—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells containing inorganic binders, e.g. Portland cement containing additives for specific purposes
    • C09K8/487—Fluid loss control additives; Additives for reducing or preventing circulation loss
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/60—Compositions for stimulating production by acting on the underground formation
    • C09K8/62—Compositions for forming crevices or fractures
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/60—Compositions for stimulating production by acting on the underground formation
    • C09K8/84—Compositions based on water or polar solvents
    • C09K8/845—Compositions based on water or polar solvents containing inorganic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/60—Compositions for stimulating production by acting on the underground formation
    • C09K8/84—Compositions based on water or polar solvents
    • C09K8/86—Compositions based on water or polar solvents containing organic compounds
    • C09K8/88—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
    • C09K8/882—Compositions based on water or polar solvents containing organic compounds macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • E—FIXED CONSTRUCTIONS
    • E21—EARTH OR ROCK DRILLING; MINING
    • E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B33/00—Sealing or packing boreholes or wells
    • E21B33/10—Sealing or packing boreholes or wells in the borehole
    • E21B33/13—Methods or devices for cementing, for plugging holes, crevices or the like
    • E21B33/14—Methods or devices for cementing, for plugging holes, crevices or the like for cementing casings into boreholes
    • 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
    • C04B2103/46—Water-loss or fluid-loss reducers, hygroscopic or hydrophilic agents, water retention agents
    • 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
    • C08F2438/00—Living radical polymerisation
    • C08F2438/03—Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]

Definitions

  • the present invention relates to the field of petroleum extraction. More specifically, it relates to agents providing a control effect of the filtrate in fluids injected under pressure in underground formations.
  • underground formation In the field of petroleum extraction, many stages are conducted by injecting fluids under pressure into underground formations.
  • underground formation is understood in its broadest sense and includes both a rock containing hydrocarbons, especially oil, that the different layers of rock crossed to access this oil rock and ensure the extraction of hydrocarbons.
  • rock is used to designate any type of material constituting a solid subterranean formation, whether the material constituting it is a rock or not, strictly speaking.
  • oil rock is used here as a synonym for "oil reservoir” and refers to any underground formation containing hydrocarbons, especially oil, whatever the nature of the material containing these hydrocarbons (rock or sand by example).
  • drilling fluids for completing and reconditioning wells, in particular drilling fluids, whether they are used to access the oil rock or to drill the reservoir itself. the same is true (“drill in”) or the fracturing fluids, or even the completion fluids, the fluids of control or reconditioning ("workover fluids”) or the ring fluids or fluids of "packer”.
  • a specific case is that of petroleum cement grouts, which are used for the cementation of the annulus of the oil wells according to a method well known per se, described for example in Le Forage by JP Nguyen (Technip 1993). These oil cement grouts are injected under pressure into the interior of a metal casing (casing) introduced into the borehole of the oil wells and then rise, under the effect of pressure by the so-called “annular” space ( “Annulus”) located between the casing and the borehole then take and harden in this ring, thus ensuring the stability of the well being drilled.
  • casing metal casing
  • Annulus annulus
  • the loss of fluid may further induce a quick setting of the cement, before the annular space is cemented, which can, among other things, weaken the structure of the well and impair its seal.
  • agents for controlling the filtrate of the aforementioned type have been proposed, which notably include cellulose derivatives (for example, hydroxyethylcellulose) or else AMPS-based copolymers such as those described, for example, in US 4,632,186 or US 4,515,635.
  • cellulose derivatives for example, hydroxyethylcellulose
  • AMPS-based copolymers such as those described, for example, in US 4,632,186 or US 4,515,635.
  • These additives are not always fully adapted to ensure, in practice, effective limitation of fluid loss.
  • the presence of other additives can inhibit the effect of agents used to ensure control of the filtrate.
  • the above filtrate control agents generally see their properties degrade.
  • An object of the present invention is to provide novel filtrate control agents for pressurized fluids in subterranean formations, which are well suited in practice.
  • the present invention proposes the use of particular copolymers, which are capable of ensuring a control effect of the filtrate when they are used with particles with which they associate, these particles possibly being particles present in the within the underground formation; and / or cement particles in the case of a fluid used in cementing; and / or particles injected into subterranean formations with the copolymers.
  • the subject of the present invention is the use, as control agent, of the filtrate in a fluid (F) injected under pressure into an underground formation
  • said fluid (F) comprises solid particles (p) and / or is contacted with solid particles (p) within the subterranean formation following its injection,
  • a block polymer (P) comprising:
  • the specific polymer used in the context of the present invention by the presence of the two specific blocks (A) and (B) is found to provide a particularly effective control effect of the fluid: the presence of the block (A) ensures anchoring of the polymer on the particles, and the presence of the long block (B), of high and soluble size, schematically ensures a local increase effect of the viscosity of the fluid (F) around the particles.
  • the interaction between the short block (A) and the particles (p) is as strong as possible and, advantageously, that this interaction is irreversible.
  • the short block (A) of a polymer (P) useful according to the invention comprises:
  • At least one chemical group forming at least one bond of ionic, covalent or iono-covalent type between the polymer and the particle;
  • a plurality of chemical groups each forming at least one hydrogen and / or Van der Waals bond between the polymer and the particle, all of these bonds together forming a global binding of force at least in the range of that of an ionic type bond; , covalent, iono-covalent.
  • the strong interactions between particles and polymers also make it possible, if necessary, to use the polymer (P) in the presence of additives which usually impair the effectiveness of the filtrate control agents.
  • the polymers (P) as employed according to the invention can be used in most fluid formulations intended to be injected into petroleum rocks, in particular petroleum cement slurries comprising dispersant-type additives or retardant agents as well as in drilling and fracturing fluids.
  • the fluid (F) injected comprises the polymer (P) but does not comprise solid particles (p), and it encounters said particles (p) within the subterranean formation following its injection .
  • the association between particles and polymers is then in situ.
  • a fluid may for example be injected during a drilling operation, and rock cuttings formed during drilling then act as particles (p) in situ.
  • the injected fluid (F) comprises, before the injection, at least a part, and in general all, of the particles (p) associated with the polymer (P), it being understood that it may possibly meet other particles (p) within the subterranean formation.
  • the polymer (P) and the particles (p) are mixed during the formulation of the fluid (F), at the place of operation or upstream, typically by adding the particles (p), to the dry state or optionally in the dispersed state, to a composition comprising the polymer (P) in solution.
  • the fluid (F) may for example be a petroleum cement slurry, which is prepared by adding cement powder as particles (p) in an aqueous composition comprising the polymer (P) in solution .
  • the fluid (F) is manufactured, advantageously at the place of operation, from a composition (premix) prepared upstream (hereinafter referred to as "blend") comprising the polymer (P) and at least a portion of the particles (p), generally in a dispersing liquid.
  • blend a composition (premix) prepared upstream (hereinafter referred to as "blend") comprising the polymer (P) and at least a portion of the particles (p), generally in a dispersing liquid.
  • this blend is mixed with the other constituents of the fluid (F).
  • the polymer (P) incidentally has the non-negligible advantage of improving the dispersibility and suspension of the particles (p).
  • the polymer (P) associated with the particles (p) can be used primarily as dispersant and stabilizer of the dispersion of the particles (p), while at the same time ensuring a carrier effect. filtrate control.
  • the subject of the present invention is certain particular block polymers which can be used according to the invention, which have been developed by the inventors specifically for this application.
  • the invention also relates to the fluids for injection under pressure in a petroleum rock or a wellbore comprising these specific block polymers, as well as blends for the preparation of these fluids comprising these polymers in combination with particles (p).
  • Fluid (F) and long block (B) are also relates to the fluids for injection under pressure in a petroleum rock or a wellbore comprising these specific block polymers, as well as blends for the preparation of these fluids comprising these polymers in combination with particles (p).
  • fluid is meant, within the meaning of the description any medium, homogeneous or not, comprising a liquid or viscous carrier optionally carrying a dispersed phase, liquid or gelled, and / or solid particles, said medium being generally pumpable by means pressurized injection devices used in the application under consideration.
  • liquid or viscous vector of the fluid (F) is meant the fluid itself; or the solvent in the case where the fluid comprises dissolved compounds and / or the continuous phase in the case where the fluid contains dispersed elements (droplets of liquid or gelled dispersed phase, solid particles, etc.).
  • the nature of the fluid (F) and the long block (B) of the polymers (P) used according to the present invention can vary to a large extent, subject to the compatibility of the liquid or viscous fluid medium (F) and the block long (B).
  • a long block (B) of hydrophilic nature is used when the liquid or viscous vector present in the fluid (F) is hydrophilic in nature; conversely, when the liquid or viscous fluid vector (F) is hydrophobic, a long block (B) of hydrophobic nature is used.
  • the long block (B) of the polymers useful according to the invention is specifically soluble in the fluid (F).
  • the long block (B) taken alone can be dissolved in the liquid or viscous fluid vector (F).
  • the long block (B) is soluble at 25 ° C. and 1% by weight in the liquid or viscous fluid medium (F).
  • the concept of "solubility at 25 ° C” implies only that a more or less viscous or gelled solution can be obtained which, at 25 ° C., does not lead to precipitation. This notion does not exclude that the dissolution of the block (B) may involve preheating above 25 ° C to obtain this solution.
  • the concept of "solubility at 25 ° C” implies the possibility of forming a solution that does not precipitate at 25 ° C, and not the possibility of forming at 25 ° C a solution that does not precipitate.
  • the long block (B) develops the least possible interaction, or even no interaction, with the particles (p). It is also preferable that the long block (B) of the polymers (P) useful according to the invention develops fewer interactions with the particles than the short block (A). In any case, the block (A) and the block (B) have distinct compositions. This means that:
  • Blocks (A) and (B) comprise distinct monomeric units; or
  • At least some of the monomers present on the block (A) are not present on the block (B); and / or at least some of the monomers present on the block (B) are not present on the block (A)
  • Block (A) and block (B) comprise the same monomer units, but in different proportions.
  • the fluid (F) is an aqueous fluid.
  • aqueous is meant herein that the fluid comprises as a liquid or viscous carrier water, either as a sole constituent of the liquid or viscous carrier, or in combination with other water-soluble solvents.
  • the water advantageously remains the majority solvent in the liquid or viscous vector, advantageously present in a proportion of at least 50% by weight. mass, or even at least 75% by weight relative to the total mass of solvents in the liquid or viscous carrier.
  • the block (B) is advantageously a block of hydrophilic nature.
  • block of hydrophilic nature is meant here a polymer block which, in the isolated state, is soluble in pure water at a rate of 1% by weight at 25 ° C. (the dissolution may possibly involve heating ), forming a more or less viscous solution, even gelled, but without precipitate formation at 25 ° C.
  • the hydrophilic block (B) used when the fluid (F) is an aqueous fluid is constituted at least predominantly by monomer units selected from the group consisting of the monomer units U 1 to U 5 defined below, and the mixtures of these monomeric units: monomeric units U1: monomeric units comprising an acrylamide functional group, especially dimethylacrylamide (DMA) or even (meth) acrylamide, morpholine N-oxide acrylamide, diacetone acrylamide; the block (B) advantageously comprises monomer units of this type monomer units U2: monomeric units comprising a sulphonic acid or sulphonate functional group, including in particular 3-sulphopropyl (meth) acrylate units, 2-propene-1-sulphonic acid, Sodium 1-allyloxy-2-hydroxypropyl sulphonate (COPS1), especially 2-acrylamido-2-methylpropanesulphonic acid (AMPS), (meth) allyl sulphonate, sodium vinyl sulphonate, sodium
  • tetrahydrofurfuryl acrylate vinyl acetamide, vinyl pyrrolidone, N-vinylpiperidone, N-vinyl caprolactam, N-vinyl-5-methyl-2-pyrrolidone, N-vinyl-5-ethyl-2-pyrrolidone, N-vinyl-6 -methyl-2-piperidone, N-vinyl-6-ethyl-2-piperidone, N-vinyl-7-methyl-2-caprolactam, N-vinyl-7-ethyl-2-caprolactam.
  • monomer units U4 monomer units carrying ammonium groups, especially esters of mono- or dicarboxylic acids [alpha], [beta] -ethylenically unsaturated with amino alcohols, such as N, N-dimethylaminomethyl (meth) acrylate, N N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N-diethylaminopropyl (meth) acrylate and N, N-dimethylaminocyclohexyl (meth) acrylate;
  • amides of [alpha], [beta] -ethylenically unsaturated mono- or di-carboxylic acids with diamines having at least one primary or secondary amine group such as N- [2- (dimethylamino) ethyl] acrylamide, N [ 2- (dimethylamino) ethyl] methacrylamide, N- [3- (dimethylamino) propyl] acrylamide, N- [3- (dimethylamino) propyl] methacrylamide, N- [4- (dimethylamino) butyl] acrylamide, N- [4] [N- [2- (diethylamino) ethyl] acrylamide, N- [4- (dimethylamino) cyclohexyl] acrylamide, N- [4- (dimethylamino) cyclohexyl] methacrylamide
  • ⁇ , ⁇ -diallylamines and N, N-diallyl-N-alkylamines including especially 3-sulfopropyldimethyl-3-methacrylamidopropylammonium, N- (2-methacryloyloxyethyl) -N, N-dimethyl-N- (3-sulfopropyl) ammoniumbetaine, N- (2-1- (3-sulfo-propyl) -2-vinylpyridinium-betaine, and N- (2-1- (3-sulfopropyl) -4-vinylpyridinium betaine monomer units U5 monomeric acrylate units, bearing COOH or COO- , including in particular acrylic acid, methacrylic acid, ethacrylic acid, [alpha] -chloroacrylic acid, crotonic acid, maleic acid, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic acid, fumaric
  • the block (B) of hydrophilic nature used when the fluid (F) is an aqueous fluid consists essentially or even exc monomeric units of the above-mentioned type, in which, in the abovementioned units, the acid groups may be wholly or partly in the form of a free acid and / or in the form of a salt for example of potassium, sodium or ammonium (form neutralized).
  • polymer or polymer block consisting at least predominantly of monomeric units refers to a (block) homopolymer or copolymer resulting from the polymerization of a monomer mixture including monomers x, this (block) homopolymer or copolymer comprising less than 25 mol%, preferably less than 15% and even more preferably less than 10 mol% of monomer units other than the 'x' units.
  • polymer or polymer block consisting essentially of monomer units 'x' for its part means, within the meaning of the present description, a (block) homopolymer or copolymer consisting at least predominantly of monomer units 'x' of the type above, more specifically comprising less than 5 mol%, preferably less than 2% and even more preferably less than 1 mol% of monomer units other than 'x' units.
  • the hydrophilic block (B) used when the fluid (F) is an aqueous fluid may comprise hydrophobic monomers in small proportions, typically at least 0, 05%, including at least 0.1%, or at least 0.5%, where applicable; this content of hydrophobic monomers preferably remains below 10%, for example less than 5%, especially less than 3%, or even 2%, these percentages being expressed by weight relative to the total mass of monomer units in the block (B).
  • hydrophobic monomers of this type can typically (but not exclusively) be selected from alkyl acrylates (such as methyl acrylate); styrene; alkyl methacrylates; and / or vinyl acetate.
  • the long block (B) present in the polymers employed according to the present invention also has a sufficiently high mass to ensure the control effect of the desired filtrate.
  • the block (B) typically has a weight average molecular weight greater than 100,000 g / mol, preferably greater than 150,000 g / mol, for example greater than 200,000 g / mol, especially greater than 250,000 g / mol. g / mol, especially when the block (B) is of one of the aforementioned types.
  • this weight average molecular weight is most often less than 3,000,000 g / mol (and typically between 150,000 and 2,000,000 g / mol), but higher masses can be envisaged in absolute terms, except in the particular case of a fluid (F) used in the context of a cementing operation, where it is preferable that the mass
  • the weight average molecular weight of the long block (B) remains less than 1,000,000 g / mol, and advantageously less than 800,000 g / mol.
  • the block (B) has a weight average molecular weight of between 10,000 and 100,000 g / mol, preferably at least 20,000 g / mol, for example from less than 25,000 g / mol, this weight average molecular weight typically being less than 90,000, for example less than 75,000, or even less than 50,000.
  • An estimate of the weight average molecular weight of the long block (B) can be measured by steric exclusion chromatography and mass measurement using external calibration with relative ethylene oxide (CES) standards, which leads to a slightly increased value of the weight average molecular weight designated in the present description by Mw (relative CES).
  • CES relative ethylene oxide
  • This Mw (relative CES) is typically measured under the following conditions:
  • Mobile phase Mixture of 80% by weight of deionized water supplemented with 0.1 M NaNO 3 and 20% by weight of acetonitrile.
  • Sample concentration about 0.5% by mass of dry matter in the mobile phase
  • the Mw (relative CES) of the long block (B) of the polymers (P) which are useful according to the invention is generally greater than or equal to 125 000 g / mol, preferably greater than or equal to 150 000 g / mol, this Mw (CES relative) being typically between 200,000 and 2,500,000 g / mol, especially between 250,000 and 2,000,000 g / mol. According to a more particular embodiment, it may be less than 125,000 g / mol, for example between 12,500 and 100,000 g / mol.
  • the Mw (relative CES) of the long block (B) of the polymers (P) typically (but not exclusively) between 25,000 and 900 000 g / mol, for example between 250,000 and 900,000 g / mol.
  • the Mw (relative CES) of the polymer (P) is measured, which, because of the low mass of the block (A) also represents a fairly good approximation, increased, of the mass average molecular weight of the block (B). ).
  • the Mw (relative CES) of the polymer (P) is in general greater than or equal to 15,000 g / mol, and for example greater than or equal to 150,000 g / mol, preferably greater than or equal to 200,000 g / mol, example greater than or equal to 300,000 g / mol, in particular greater than or equal to 400,000 g / mol, this Mw (relative CES) of the polymer (P) being typically between 200,000 g / mol and 2,500,000 g / mol, in particular between 250,000 g / mol and 2,000,000 g / mol. It is more particularly between 25,000 and 900,000 g / mol, for example between 250,000 g / mol and 800,000 g / mol in the case of a fluid (F) used in the context of a cementing operation.
  • the block (B) is advantageously a block of hydrophilic nature, preferably comprising U1 units of the aforementioned type, in particular dimethylacrylamide DMA units, possibly, but not necessarily, in combination with U2 units, in particular acrylamidomethylpropanesulphonic acid units (AMPS) ), optionally wholly or partly in sulphonate form, for example in the form of its sodium salt.
  • U1 units of the aforementioned type in particular dimethylacrylamide DMA units, possibly, but not necessarily, in combination with U2 units, in particular acrylamidomethylpropanesulphonic acid units (AMPS) ), optionally wholly or partly in sulphonate form, for example in the form of its sodium salt.
  • AMPS acrylamidomethylpropanesulphonic acid units
  • the block (B) consists at least predominantly (for example essentially, or exclusively) of a mixture of DMA and AMPS units, with a DMA AMPS molar ratio, for example between 60/40 and 90/10, especially between 75/25 and 85/15 and typically of the order of 80/20.
  • Block (B) typically has a weight average molecular weight of between 150,000 and 750,000 g / mol, preferably between 200,000 and 700,000 g / mol.
  • the block (B) may have a weight average molecular weight of between 15,000 and 150,000 g / mol, preferably between 20,000 and 100,000 g / mol.
  • the block (B) typically has a Mw (relative GPC) of between 200,000 and 800,000, preferably between 250,000 and 900,000 g / mol, for example 300,000 to 600,000 g / mol, the polymer (P) having in general a Mw (relative CES) included in these ranges.
  • the block (B) may alternatively have a Mw (relative GPC) of between 20,000 and 200,000, preferably between 25,000 and 180,000 g / mol, for example 30,000 and 150,000 g / mol, the polymer (P) having in general a Mw (relative CES) included in these ranges.
  • the long block (B) used when the fluid (F) is a petroleum cement slurry is typically a DMA / AMPS statistical block, with a DMA / AMPS molar ratio between 75/25 and 85/15 (typically of the order of 80/20), and a Mw (GPC-MALS) of between 20,000 and 7,500,000, in particular between 200,000 and 750,000, for example between 400,000 and 600,000.
  • particle in the sense in which it is used in the present description is not confined to that of individualized particles. It refers more generally to solid entities dispersible within a fluid, in the form of objects (individual particles, aggregates, etc.) whose dimensions are less than 5 mm, preferably 2 mm, for example less than 1 mm.
  • the nature of the particles (p) and the short block (A) of the polymers (P) used according to the present invention can vary to a large extent, provided that the block (A) interacts with the particles (p) and leads to an immobilization, preferably irreversible, of polymer (P) on the surface of the particles (p).
  • the block (A) generally comprises monomer units carrying groups developing with the particles (p) stronger interactions than the long block (B).
  • the particles (p) are mineral particles introduced into the fluid (F) or with which the fluid (F) comes into contact following its injection. These particles (p) are then typically particles of cement, calcium carbonate, clay, barite, silica, sand or carbon black.
  • the block (A) is preferably constituted at least predominantly (and preferably essentially, if not exclusively) by monomer units chosen from the preferential groups defined below, to be adapted case by case as a function of the nature of the particles (p). :
  • the block (A) may in particular consist at least in the majority (and preferably essentially or exclusively) of:
  • the block (B) is then typically constituted at least predominantly (and preferably substantially, or even exclusively) by units U1 and / or U2 of the aforementioned type
  • the block (A) may in particular be constituted at least predominantly (and preferably substantially, if not exclusively) by:
  • the block (B) is then typically constituted at least predominantly (and preferably essentially, if not exclusively) by units U1 and / or U2 and / or U5 of the aforementioned type
  • the block (A) may in particular be constituted at least predominantly (and preferably substantially or exclusively) by
  • the block (B) is then typically constituted at least predominantly (and preferably essentially, if not exclusively) by units U1 and / or U2 of the aforementioned type for particles (p) of carbon black, the block (A) can in particular be constituted at least predominantly (and preferably essentially or exclusively) by hydrophobic units U8, including in particular
  • the block (B) is then typically constituted at least predominantly (and preferably substantially, if not exclusively) by units of units U1 and / or U2 and / or U5 of the aforementioned type
  • the short block (A) present in the polymers employed according to the present invention has, in general, a weight average molecular weight of between 500 and 30,000 g / mol, for example between 1000 and 25,000 g. / mol and especially when the block (A) is of one of the aforementioned types.
  • the short block (A) is a poly (acrylic acid) homopolymer block of weight average molecular weight ranging from 1 000 to 20,000 g / mol.
  • the weight-average molecular mass of the short block (A) can be measured in particular by gel permeation chromatography followed by multi-angle light scattering (GPC-MALS) analysis.
  • Polymers useful according to the present invention are particular polymers, which comprise at least two blocks of very different size, including a block (B) of large size.
  • the polymers (P) are preferably prepared by controlled radical polymerization, which allows to finely control the size of the two blocks.
  • the controlled radical polymerization technique is a well-known technique which, using a polymerization control agent, makes it possible to obtain controlled mass polymers, in particular block polymers which can be controlled at the same time. the architecture and size of each block.
  • the polymers (P) useful according to the invention may be polymers of the type prepared according to a process comprising the following steps:
  • the ethylenically unsaturated monomers which are identical or different, chosen for the constitution of the block (B) or of the block (A) -;
  • step (E1) a source of free radicals adapted to the polymerization of said monomers; and the polymer obtained at the end of step (E1), which acts as a control agent for the radical polymerization and on which the block (B) -respectively the block (A) is grafted.
  • the size of the polymer block in formation is controlled by the monomer / control agent molar ratio corresponding to the initial quantity of monomers relative to the amount of control agent: schematically, all the chains grow from each of the present control agents and the monomers are distributed evenly over all the growing chains.
  • the monomer / control agent molar ratio thus dictates the degree of polymerization of the block synthesized in each of the steps, and thus makes it possible to define the theoretical average molecular weight expected for each of the blocks.
  • the molar monomer / control agent ratios in steps (E1) and (E2) are chosen so that:
  • the theoretical number average molecular weight of the block (A) is between 250 and 25,000 g / mol, preferably between 500 and 15,000 g / mol, especially between 1,000 and 10,000 g / mol.
  • the theoretical number average molecular weight of the block (B) is between 70,000 and 5,000,000 g / mol, preferably between 80,000 and 3,000,000 g / mol, especially between 90,000 and 2,000,000 g / mol. .
  • this theoretical number average molecular weight of the block (B) is more preferably between 90,000 and 1,000,000 g / mol, advantageously between 100,000 and 500,000 g / mol.
  • the block (B) can advantageously be prepared in step (E2) by bringing into contact: the ethylenically unsaturated monomers, which are identical or different, chosen for forming the block (B);
  • This polymerization technique allows access to blocks (B) of large size.
  • the synthesis of the block (B) can be carried out under the polymerization conditions described in the application WO 2012/042167.
  • the block (B) when the block (B) is hydrophilic, the block (B) can be synthesized by contacting, within an aqueous medium (M) in which the block (B) formed is not soluble:
  • the ethylenically unsaturated monomers which are identical or different, chosen for the constitution of the block (B), chosen to be soluble in the aqueous medium (M)
  • a reactive stabilizer which comprises:
  • a group (G) ensuring a living character and controlled to the radical polymerization of step (E), such as, for example, a group carrying a thiocarbonylthio group -S (C S) -
  • the conditions to be used in the aforementioned polymerization steps can be those typically used in controlled radical polymerizations.
  • step (E) of the process of the invention any source of free radicals known per se. It can be for example one of the following initiators:
  • hydrogen peroxides such as tertiary butyl hydroperoxide, cumene hydroperoxide, t-butyl peroxyacetate, t-butyl peroxybenzoate, t-butylperoxyoctoate, t-butylperoxynethodecanoate and t-butylperoxyisobutarate; , lauroyl peroxide, t-amylperoxypivalte, t-butylperoxypivalate, dicumyl peroxide, benzoyl peroxide, potassium persulfate, ammonium persulfate, azo compounds such as: 2-2'-azobis (isobutyronitrile), 2,2'-azobis (2-butanenitrile), 4,4'-azobis (4-pentanoic acid), 1,1 ' azobis (cyclohexane-carbonitrile), 2- (t-butylazo) -2-cyanopropane, 2,2'-azo
  • alkali metal bisulfite such as sodium metabisulphite
  • alkali metal persulfates in combination with an arylphosphinic acid, such as benzene phosphonic acid and the like, and reducing sugars.
  • an arylphosphinic acid such as benzene phosphonic acid and the like
  • a radical initiator of the redox type which has the advantage of not requiring heating of the reaction medium (no thermal initiation), which allows better still manage the exotherm of the reaction.
  • the source of free radicals employed can typically be selected from redox initiators conventionally used in radical polymerization, typically not requiring heating for their thermal initiation. It is typically a mixture of at least one oxidizing agent with at least one reducing agent.
  • the oxidizing agent present in the redox system is preferably a water-soluble agent.
  • This oxidizing agent may for example be chosen from peroxides, such as: hydrogen peroxide, tertiary butyl hydroperoxide, cumene hydroperoxide, t-butyl peroxyacetate, t-butylperoxybenzoate, t -butylperoxyoctoate, the butylperoxynéodécanoate, t-butylperoxyisobutarate, lauroyl peroxide, t-amylperoxypivalte, t-butylperoxypivalate, dicumyl peroxide, benzoyl peroxide; sodium persulfate, potassium persulfate, ammonium persulfate, or even potassium bromate.
  • peroxides such as: hydrogen peroxide, tertiary butyl hydroperoxide, cumene hydroperoxide, t-butyl
  • the reducing agent present in the redox system is also preferably a water-soluble agent.
  • This reducing agent can typically be selected from sodium formaldehyde sulfoxylate (especially in its dihydrate form, known as Rongalit or in the form of an anhydride), ascorbic acid, erythorbic acid, sulphites, bisulphites or metasulfites (in particular sulphites, bisulphites or metasulfites of alkali metals), nitrilotrispropionamides, and tertiary amines and ethanolamines (preferably water-soluble).
  • Possible redox systems include combinations such as:
  • alkali metal bisulfite such as sodium metabisulphite
  • arylphosphinic acid such as benzene phosphonic acid and the like, and reducing sugars.
  • An interesting redox system includes (and preferably consists of), for example, the combination of ammonium persulfate and sodium formaldehyde sulfoxylate.
  • reaction medium of step (E) is free of copper.
  • a copper complexing agent such as EDTA.
  • control agent used in the synthesis steps of the blocks (A) and (B) can vary to a large extent.
  • control agent may carry several thiocarbonylthio groups.
  • control agent used in step (E2) is a living polymer resulting from step (E1). It can also be envisaged that the control agent of step (E1) is derived from a previous step (E0) in which the radical polymerization of a composition comprising:
  • an initiator of radical polymerization source of free radicals.
  • control agent adapted to the synthesis of the polymer (P) useful according to the invention advantageously corresponds to the formula (A) below:
  • the groups R 1 or Z when substituted, may be substituted with optionally substituted phenyl groups, optionally substituted aromatic groups, saturated or unsaturated carbon rings, saturated or unsaturated heterocycles, or alkyloxycarbonyl or aryloxycarbonyl groups ( -COOR), carboxy (-COOH), acyloxy (-O2CR), carbamoyl (-CONR2), cyano (-CN), alkylcarbonyl, alkylarylcarbonyl, arylcarbonyl, arylalkylcarbonyl, phthalimido, maleimido, succinimido, amidino, guanidimo, hydroxy (-OH ), amino (-NR2), halogen, perfluoroalkyl C n F 2n + 1, allyl, epoxy, alkoxy (-OR), S-alkyl, S-aryl, groups having a hydrophilic or ionic character such as alkali metal salts of carboxylic acids, alkali metal salts
  • R 1 is a substituted or unsubstituted alkyl group, preferably substituted.
  • the optionally substituted alkyl, acyl, aryl, aralkyl or alkyne groups generally have 1 to 20 carbon atoms, preferably 1 to 12, and more preferably 1 to 9 carbon atoms. They can be linear or branched. They may also be substituted by oxygen atoms, in particular esters, sulfur or nitrogen atoms.
  • alkyl radicals mention may especially be made of the methyl, ethyl, propyl, butyl, pentyl, isopropyl, tert-butyl, pentyl, hexyl, octyl, decyl or dodecyl radical.
  • the alkyne groups are radicals generally of 2 to 10 carbon atoms, they have at least one acetylenic unsaturation, such as the acetylenyl radical.
  • the acyl group is a radical generally having from 1 to 20 carbon atoms with a carbonyl group.
  • aryl radicals there may be mentioned the phenyl radical, optionally substituted in particular by a nitro or hydroxyl function.
  • aralkyl radicals mention may especially be made of the benzyl or phenethyl radical, optionally substituted in particular by a nitro or hydroxyl function.
  • R 1 or Z is a polymer chain
  • this polymer chain may be derived from a radical or ionic polymerization or from a polycondensation.
  • control agents xanthates, trithiocarbonates, dithiocarbamates, or dithiocarbazates.
  • 0ethyl-S- (1-methoxycarbonylethyl) xanthate of formula (CH 3 CH (CO 2 CH 3 )) S (C S) OEt.
  • Polymers (P) useful according to the invention generally comprise only blocks (B) and (A). These are typically diblock polymers (A) - (B), but polymers comprising more blocks are possible, in particular copolymers comprising a long block (B) on which are grafted two or more short blocks (triblock polymers of type (A) - (B) - (A) in particular), or else copolymers comprising a block spacer between the block (B) and the block (A) variants that you think are reasonable?
  • Some of the useful polymers according to the present invention are polymers which, to the knowledge of the inventors, have never been described in the past.
  • These polymers include in particular block polymers containing, preferably as single blocks:
  • At least a first block at least predominantly (and preferably substantially, or exclusively) constituted by acrylic acid units, of weight average molecular weight between 500 and 30,000 g / mol, in particular between 1,000 and 20,000; and
  • a second p block (DMA / AMPS) at least predominantly (and preferably essentially, if not exclusively) constituted by a statistical mixture of DMA and AMPS units, with a DMA / AMPS molar ratio of between 60/40 and 90/10; having a molecular weight greater than 150 000 g / mol, typically between 200 000 and 2 000 000 g / mol and especially between 250 000 and 750 000 g / mol.
  • aqueous fluids for injection under pressure in a petroleum rock in particular drilling fluids and fracturing fluids, comprising them in association with mineral particles, as well as blends for the preparation of these fluids.
  • the polymers useful according to the invention can be used in almost all fluids used in petroleum extraction and potentially subject to fluid loss.
  • the fluid (F) is a petroleum cement slurry, which comprises the polymer (P) as an additive.
  • the polymer (P) associated with the particles present in cement, provides the control effect of the filtrate during cementation.
  • the fluid (F) is a drilling fluid or a fracturing fluid, which comprises the polymer (P) associated with particles (p).
  • the particles (p) are then most often introduced together with the polymer in the fluid (F) before the injection of the fluid.
  • the polymer then generally ensures a stabilization of the dispersion of the particles in the fluid (F), while maintaining in suspension in the fluid at least a portion of the particles (p).
  • concentrations of polymer and particles to be employed in these different fluids are to be adapted case by case according to the intended application and the desired rheology.
  • the flask was then placed in an oil bath thermostated at 60 ° C, and the reaction medium was stirred for 4 hours at 60 ° C.
  • Blocks A1 to A4 prepared as indicated in paragraph 1 .1 were used in their reaction medium obtained, without purification, with a mass of polymer m A reported in Table 2 below.
  • the chosen block, in its reaction mixture without purification, was introduced into a 250 ml flask at room temperature, and then NMA (N, N-dimethylacrylamide) was added (in the amounts shown in Table 2 below).
  • NMA N, N-dimethylacrylamide
  • the mixture was degassed by bubbling nitrogen for 20 minutes.
  • To the medium of sodium formaldehyde sulfoxylate was added in the form of a 1.0% by weight aqueous solution, the same mass of this solution being introduced as that of the ammonium persulfate solution (see Table 2).
  • the polymerization reaction was allowed to proceed without stirring for 24 hours at room temperature (20 ° C).
  • the polymerization reaction was then allowed to proceed without stirring for 24 hours at room temperature (20 ° C).
  • diblock polymers P1 to P17 prepared in Examples 1 and the control prepared in Example 2 were used to make petroleum cement slurries having the following formulation:
  • Diblock polymer (20% in aqueous solution):
  • Dispersing agent polymelamine sulfonate (50% aqueous solution)
  • Retarding agent calcium lignosulfonate (48% in aqueous solution)
  • the filtrate control agent is mixed with liquid additives and tap water before incorporation of the cement.
  • the formulation and the filtration test were carried out according to the American Petroleum Institute standard (API recommended for testing items 10B, 2nd edition April 2013).
  • the slurry obtained was conditioned at 88 ° C. for 20 minutes in an atmospheric consistometer (model 1250 supplied by Chandier Engineering Inc.) previously stabilized at this temperature, which allows to simulate the conditions experienced by the cement grout when descending into a well.
  • the filtrate control performance was determined by static filtration at 88 ° C in a 175mL double-opening cell equipped with 325meshx60mesh metal grid (supplied by OFITE Inc., reference 170-45).
  • the performances of the polymers in the cement formulations are reported in Table 4 below:

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Abstract

The present invention relates to the use of a block polymer as fluid loss control agent in a fluid injected under pressure into an oil-bearing rock, where: the fluid comprises solid particles and/or is brought into contact with solid particles within the oil-bearing rock following the injection thereof, the polymer comprises: - a first block which is absorbed onto at least one portion of the particles; and - a second block, having a composition different from that of the first, and having a weight-average molecular mass of greater than 10 000 g/mol, for example greater than 100 000 g/mol, and that is soluble in the fluid.

Description

Polymères séquencés pour le contrôle du filtrat  Sequenced polymers for filtrate control
La présente invention a trait au domaine de l'extraction pétrolière. Plus précisément, elle concerne des agents assurant un effet de contrôle du filtrat dans des fluides injectés sous pression dans des formations souterraines. The present invention relates to the field of petroleum extraction. More specifically, it relates to agents providing a control effect of the filtrate in fluids injected under pressure in underground formations.
Dans le domaine de l'extraction pétrolière, de nombreuses étapes sont conduites en injectant des fluides sous pression au sein de formations souterraines. Dans la présente description, la notion de « formation souterraine » s'entend dans son acception la plus large et inclut aussi bien une roche contenant des hydrocarbures, notamment du pétrole, que les différentes couches de roche traversées pour accéder à cette roche pétrolifère et assurer l'extraction des hydrocarbures. Au sens de la présente description, la notion de « roche » est utilisée pour désigner tout type de matériau constitutif d'une formation souterraine solide, que le matériau la constituant soit, ou non, une roche à proprement parler. Ainsi, en particulier, l'expression « roche pétrolifère » est employée ici comme synonyme de « réservoir pétrolifère » et désigne toute formation souterraine contenant des hydrocarbures, notamment du pétrole, quelle que soit la nature du matériau contenant ces hydrocarbures (roche ou sable par exemple). In the field of petroleum extraction, many stages are conducted by injecting fluids under pressure into underground formations. In the present description, the notion of "underground formation" is understood in its broadest sense and includes both a rock containing hydrocarbons, especially oil, that the different layers of rock crossed to access this oil rock and ensure the extraction of hydrocarbons. For the purposes of the present description, the term "rock" is used to designate any type of material constituting a solid subterranean formation, whether the material constituting it is a rock or not, strictly speaking. Thus, in particular, the term "oil rock" is used here as a synonym for "oil reservoir" and refers to any underground formation containing hydrocarbons, especially oil, whatever the nature of the material containing these hydrocarbons (rock or sand by example).
Parmi les fluides injectés sous pression dans des formations souterraines, on peut notamment citer les différents fluides de complétion et reconditionnement des puits, notamment les fluides de forage , qu'ils soient utilisés pour accéder à la roche pétrolière ou bien pour forer le réservoir lui-même (« drill in ») ou bien les fluides de fracturation, ou bien encore les fluides de complétion, les fluides de contrôle ou de reconditionnement (« workover fluids ») ou les fluides d'annulaire ou fluides de « packer ». Among the fluids injected under pressure in subterranean formations, mention may be made of the various fluids for completing and reconditioning wells, in particular drilling fluids, whether they are used to access the oil rock or to drill the reservoir itself. the same is true ("drill in") or the fracturing fluids, or even the completion fluids, the fluids of control or reconditioning ("workover fluids") or the ring fluids or fluids of "packer".
Un cas spécifique est celui des coulis de ciment pétrolier, qui sont employés pour la cimentation de l'annulaire des puits pétroliers selon une méthode bien connue en soi, décrite par exemple dans Le Forage par J.P Nguyen (Editions Technip 1993). Ces coulis de ciment pétroliers sont injectés sous pression dans l'intérieur d'un tubage métallique (cuvelage) introduit dans le trou de forage des puits de pétrole puis remontent, sous l'effet de la pression par l'espace dit « annulaire » (« annulus » en anglais) situé entre le cuvelage et le trou de forage puis prennent et durcissent dans cet annulaire, assurant ainsi la stabilité du puits en cours de forage. Au sein d'un puits d'extraction pétrolière, la mise en contact du fluide sous pression et de la formation souterraine (qui présente le plus souvent une porosité plus ou moins élevée, voire des fissures) induit un effet dit de « perte de fluide » dit également de « filtrat » (phénomène désigné par le terme de « fluid loss » en anglais) : le liquide présent dans le fluide a tendance à pénétrer dans la roche constitutive de la formation souterraine, ce qui peut endommager le puits, voire nuire à son intégrité. Lorsque ces fluides employés sous pression contiennent des composés insolubles (ce qui est très souvent le cas, notamment pour les coulis de ciment pétrolier ou bien les fluides de forages ou de fracturation comprenant des polymères), l'effet de perte de fluide induit en parallèle une concentration du fluide, ce qui peut conduire à une augmentation de viscosité affectant la mobilité du fluide. A specific case is that of petroleum cement grouts, which are used for the cementation of the annulus of the oil wells according to a method well known per se, described for example in Le Forage by JP Nguyen (Technip 1993). These oil cement grouts are injected under pressure into the interior of a metal casing (casing) introduced into the borehole of the oil wells and then rise, under the effect of pressure by the so-called "annular" space ( "Annulus") located between the casing and the borehole then take and harden in this ring, thus ensuring the stability of the well being drilled. In a petroleum extraction well, the contact between the pressurized fluid and the underground formation (which usually has a greater or lesser porosity, or even cracks) induces a so-called "fluid loss" effect. Also known as "filtrate" (a phenomenon referred to as "fluid loss"): the fluid present in the fluid tends to penetrate into the constituent rock of the subterranean formation, which can damage the well or even harm to his integrity. When these fluids used under pressure contain insoluble compounds (which is very often the case, especially for petroleum cement grouts or drilling or fracturing fluids comprising polymers), the effect of loss of fluid induced in parallel a concentration of the fluid, which can lead to an increase in viscosity affecting the mobility of the fluid.
Dans le cas particulier d'un coulis de ciment, la perte de fluide peut en outre induire une prise trop rapide du ciment, avant que l'espace de l'annulaire soit cimenté, ce qui peut, entre autres, fragiliser la structure du puits et nuire à son étanchéité.  In the particular case of a cement slurry, the loss of fluid may further induce a quick setting of the cement, before the annular space is cemented, which can, among other things, weaken the structure of the well and impair its seal.
Pour plus de détails concernant l'effet de perte de fluide et ses effets en cimentation, on pourra notamment se reporter à Well Cementing, E.B. Nelson (Elsevier, 1990).  For more details on the effect of fluid loss and its effects in cementing, one can refer to Well Cementing, E. B. Nelson (Elsevier, 1990).
En vue d'inhiber le phénomène de perte de fluide, il a été décrit un certain nombre d'additifs qui permettent de limiter (voir d'empêcher totalement dans certains cas) la fuite du liquide présent dans le fluide vers la roche avec laquelle il entre en contact. Ces additifs, dits « agents de contrôle du filtrat » (ou « fluid loss control agents » en anglais) permettent en général d'obtenir, en parallèle, un effet de contrôle de la migration de gaz, à savoir une isolation du fluide vis-à-vis des gaz contenus dans la roche (gaz dont il convient d'éviter qu'ils ne pénètrent le fluide notamment dans le cas de coulis de ciment, ces gaz ayant tendance à fragiliser le ciment en cours de prise.  In order to inhibit the phenomenon of loss of fluid, a number of additives have been described which make it possible to limit (see to totally prevent in certain cases) the leakage of the liquid present in the fluid towards the rock with which it to be in contact. These additives, called "filtrate control agents" (or "fluid loss control agents" in English), generally make it possible to obtain, in parallel, a control effect on the migration of gases, namely an isolation of the fluid vis- with respect to the gases contained in the rock (gas which should be prevented from entering the fluid especially in the case of cement grout, these gases tend to weaken the cement during setting.
Divers agents de contrôle du filtrat du type précité ont été proposés, qui incluent notamment des dérivés cellulosiques (hydroxyéthylcellulose, par exemple) ou bien encore des copolymères à base d'AMPS comme ceux décrits par exemple dans US 4,632,186 ou US 4,515,635. Ces additifs ne sont pas toujours pleinement adaptés pour assurer, en pratique, une limitation efficace de la perte de fluide. En particulier, et c'est notamment le cas dans le domaine des coulis de ciment pétrolier, la présence d'autres additifs peut inhiber l'effet des agents employés pour assurer le contrôle du filtrat. En particulier, en présence de certains agents dispersants ou agents retardateurs de prise, les agents de contrôle du filtrat précités voient en général leurs propriétés se dégrader. Un but de la présente invention est de fournir de nouveaux agents de contrôle du filtrat pour des fluides injectés sous pression dans des formations souterraines, qui soient bien adaptés en pratique. Various agents for controlling the filtrate of the aforementioned type have been proposed, which notably include cellulose derivatives (for example, hydroxyethylcellulose) or else AMPS-based copolymers such as those described, for example, in US 4,632,186 or US 4,515,635. These additives are not always fully adapted to ensure, in practice, effective limitation of fluid loss. In particular, and this is particularly the case in the field of petroleum cement grouts, the presence of other additives can inhibit the effect of agents used to ensure control of the filtrate. In particular, in the presence of certain dispersing agents or setting retarding agents, the above filtrate control agents generally see their properties degrade. An object of the present invention is to provide novel filtrate control agents for pressurized fluids in subterranean formations, which are well suited in practice.
A cet effet, la présente invention propose d'utiliser des copolymères particuliers, qui sont propres à assurer un effet de contrôle du filtrat lorsqu'ils sont employés avec des particules, avec lesquelles ils s'associent, ces particules pouvant être des particules présentes au sein de la formation souterraine ; et/ou des particules de ciment dans le cas d'un fluide employé en cimentation ; et/ou des particules injectées au sein de formations souterraines avec les copolymères. Plus précisément, selon un premier aspect, la présente invention a pour objet l'utilisation, à titre d'agent de contrôle du filtrat dans un fluide (F) injecté sous pression dans une formation souterraine For this purpose, the present invention proposes the use of particular copolymers, which are capable of ensuring a control effect of the filtrate when they are used with particles with which they associate, these particles possibly being particles present in the within the underground formation; and / or cement particles in the case of a fluid used in cementing; and / or particles injected into subterranean formations with the copolymers. More specifically, according to a first aspect, the subject of the present invention is the use, as control agent, of the filtrate in a fluid (F) injected under pressure into an underground formation
où ledit fluide (F) comprend des particules solides (p) et/ou est mis en contact avec des particules solides (p) au sein de la formation souterraine suite à son injection, wherein said fluid (F) comprises solid particles (p) and / or is contacted with solid particles (p) within the subterranean formation following its injection,
d'un polymère séquencé (P) comprenant : a block polymer (P) comprising:
- un premier bloc (A), dit aussi ci-après « bloc court », de masse moléculaire moyenne en poids typiquement inférieure à 30 000 g/mol, qui s'adsorbe, de préférence irréversiblement, sur au moins une partie des particules (p); et  a first block (A), also hereinafter referred to as "short block", of weight average molecular weight, typically less than 30,000 g / mol, which is adsorbed, preferably irreversibly, on at least a portion of the particles ( p); and
- un deuxième bloc (B), dit aussi ci-après «bloc long », de composition distincte de celle dudit premier bloc et de masse moléculaire moyenne en poids supérieure à a second block (B), also hereinafter referred to as "long block", of composition distinct from that of said first block and of weight average molecular mass greater than
10 000 g/mol, par exemple supérieure à 100 000 g/mol, et soluble dans le fluide (F). 10,000 g / mol, for example greater than 100,000 g / mol, and soluble in the fluid (F).
Le polymère spécifique employé dans le cadre de la présente invention, de par la présence des deux blocs spécifiques (A) et (B) s'avère fournir un effet de contrôle du fluide particulièrement efficace : la présence du bloc (A) assure un ancrage du polymère sur les particules, et la présence du bloc long (B), de taille élevée et soluble, assure schématiquement un effet d'augmentation locale de la viscosité du fluide (F) autour des particules. The specific polymer used in the context of the present invention, by the presence of the two specific blocks (A) and (B) is found to provide a particularly effective control effect of the fluid: the presence of the block (A) ensures anchoring of the polymer on the particles, and the presence of the long block (B), of high and soluble size, schematically ensures a local increase effect of the viscosity of the fluid (F) around the particles.
On obtient ainsi, à la surface des particules (p), la formation d'une couche polymère à base des blocs longs (B) ancrés sur les particules à l'aide des blocs (A), l'association particules/polymères ainsi réalisée formant en quelque sorte un « bouchon » de taille suffisante au niveau des porosités de la roche, qui permet de limiter, voire de bloquer totalement, le phénomène de filtrat. Thus, on the surface of the particles (p), the formation of a polymer layer based on the long blocks (B) anchored on the particles using the blocks (A), the particle / polymer association thus produced forming a kind of "plug" of sufficient size at the level of the porosities of the rock, which makes it possible to limit or even totally block the phenomenon of filtrate.
Il est à noter que l'emploi de polymères à base de blocs longs (B) uniquement n'assurerait pas un contrôle du filtrat selon l'invention, qui nécessite un ancrage des blocs longs (B) sur les particules (p) via les blocs courts (A), comme cela est illustré dans les exemples donnés à la fin de la présente description. It should be noted that the use of polymers based on long blocks (B) alone would not ensure control of the filtrate according to the invention, which requires anchoring the long blocks (B) on the particles (p) via the short blocks (A), as illustrated in the examples given at the end of the present description.
Notamment pour que cet ancrage soit le plus efficace possible, il est préférable que l'interaction entre le bloc court (A) et les particules (p) soit la plus forte possible et, avantageusement, que cette interaction soit irréversible. De préférence, le bloc court (A) d'un polymère (P) utile selon l'invention comporte : In particular, for this anchoring to be as effective as possible, it is preferable that the interaction between the short block (A) and the particles (p) is as strong as possible and, advantageously, that this interaction is irreversible. Preferably, the short block (A) of a polymer (P) useful according to the invention comprises:
• au moins un groupement chimique formant au moins une liaison de type ionique, covalente ou iono-covalente entre polymère et particule ; et/ou At least one chemical group forming at least one bond of ionic, covalent or iono-covalent type between the polymer and the particle; and or
• plusieurs groupements chimiques formant chacun au moins une liaisons hydrogène et/ou de Van der Waals entre polymère et particule, l'ensemble de ces liaisons formant ensemble une liaison globale de force au moins dans la gamme de celle d'une liaison de type ionique, covalente, iono-covalente.  A plurality of chemical groups each forming at least one hydrogen and / or Van der Waals bond between the polymer and the particle, all of these bonds together forming a global binding of force at least in the range of that of an ionic type bond; , covalent, iono-covalent.
Les interactions fortes entre particules et polymères permettent en outre, au besoin, d'employer le polymère (P) en présence d'additifs qui, habituellement, nuisent à l'efficacité des agents de contrôle du filtrat. En particulier, les polymères (P) tels qu'employés selon l'invention peuvent être mis en œuvre dans la plupart des formulations de fluides destinés à être injectés dans des roches pétrolières, notamment des coulis de ciment pétrolier comprenant des additifs de type dispersants ou agents retardateur de prise aussi bien que dans des fluides de forage et de fracturation. The strong interactions between particles and polymers also make it possible, if necessary, to use the polymer (P) in the presence of additives which usually impair the effectiveness of the filtrate control agents. In particular, the polymers (P) as employed according to the invention can be used in most fluid formulations intended to be injected into petroleum rocks, in particular petroleum cement slurries comprising dispersant-type additives or retardant agents as well as in drilling and fracturing fluids.
Selon une première variante de l'invention, le fluide (F) injecté comprend le polymère (P) mais ne comprend pas de particules solides (p), et il rencontre lesdites particules (p) au sein de la formation souterraine suite à son injection. L'association entre particules et polymères se fait alors in situ. Un tel fluide peut par exemple être injecté lors d'une opération de forage, et les déblais de roche formés lors du forage assurent alors le rôle des particules (p) in situ. Selon une variante alternative, le fluide (F) injecté comporte avant l'injection au moins une partie, et en général la totalité, des particules (p) associées au polymère (P), étant entendu qu'il peut éventuellement rencontrer d'autres particules (p) au sein de la formation souterraine. Deux modes sont notamment envisageables dans ce cadre : According to a first variant of the invention, the fluid (F) injected comprises the polymer (P) but does not comprise solid particles (p), and it encounters said particles (p) within the subterranean formation following its injection . The association between particles and polymers is then in situ. Such a fluid may for example be injected during a drilling operation, and rock cuttings formed during drilling then act as particles (p) in situ. According to an alternative variant, the injected fluid (F) comprises, before the injection, at least a part, and in general all, of the particles (p) associated with the polymer (P), it being understood that it may possibly meet other particles (p) within the subterranean formation. Two modes can be envisaged in this context:
- mode 1 : le polymère (P) et les particules (p) sont mélangés lors de la formulation du fluide (F), sur le lieu de l'exploitation ou en amont, typiquement en additionnant les particules (p), à l'état sec ou éventuellement à l'état dispersé, à une composition comprenant le polymère (P) en solution. Selon cette variante, le fluide (F) peut par exemple être un coulis de ciment pétrolier, que l'on prépare en ajoutant de la poudre de ciment à titre de particules (p) dans une composition aqueuse comprenant le polymère (P) en solution. mode 1: the polymer (P) and the particles (p) are mixed during the formulation of the fluid (F), at the place of operation or upstream, typically by adding the particles (p), to the dry state or optionally in the dispersed state, to a composition comprising the polymer (P) in solution. According to this variant, the fluid (F) may for example be a petroleum cement slurry, which is prepared by adding cement powder as particles (p) in an aqueous composition comprising the polymer (P) in solution .
- mode 2 : le fluide (F) est fabriqué, avantageusement sur le lieu de l'exploitation, à partir d'une composition (pré-mélange) préparée en amont (désignée ci-après par le terme de « blend ») comprenant le polymère (P) et au moins une partie des particules (p), en général au sein d'un liquide dispersant. Pour former le fluide (F), ce blend est mélangé aux autres constituants du fluide (F). mode 2: the fluid (F) is manufactured, advantageously at the place of operation, from a composition (premix) prepared upstream (hereinafter referred to as "blend") comprising the polymer (P) and at least a portion of the particles (p), generally in a dispersing liquid. To form the fluid (F), this blend is mixed with the other constituents of the fluid (F).
Dans le cadre de ces modes 1 et 2, le polymère (P) présente accessoirement l'avantage non négligeable d'améliorer la dispersibilité et la mise en suspension des particules (p). Dans certains modes de réalisation, les polymères (P) associés aux particules (p) peuvent être employés principalement en tant qu'agent dispersant et stabilisant de la dispersion des particules (p), en assurant dans le même temps un effet d'agent de contrôle du filtrat. In the context of these modes 1 and 2, the polymer (P) incidentally has the non-negligible advantage of improving the dispersibility and suspension of the particles (p). In some embodiments, the polymer (P) associated with the particles (p) can be used primarily as dispersant and stabilizer of the dispersion of the particles (p), while at the same time ensuring a carrier effect. filtrate control.
Selon un autre aspect, la présente invention a pour objet certains polymères séquencés particuliers utilisables selon l'invention, qui ont été développés par les inventeurs spécifiquement pour cette application. According to another aspect, the subject of the present invention is certain particular block polymers which can be used according to the invention, which have been developed by the inventors specifically for this application.
L'invention a également pour objet les fluides pour injection sous pression au sein d'une roche pétrolière ou d'un puits de forage comprenant ces polymères séquencés spécifiques, ainsi que les blends pour la préparation de ces fluides comprenant ces polymères en association à des particules (p). Différents avantages et modes de réalisation particuliers de l'invention vont maintenant être décrits plus en détails. Le fluide (F) et le bloc long (B) The invention also relates to the fluids for injection under pressure in a petroleum rock or a wellbore comprising these specific block polymers, as well as blends for the preparation of these fluids comprising these polymers in combination with particles (p). Various advantages and particular embodiments of the invention will now be described in more detail. Fluid (F) and long block (B)
Par « fluide », on entend, au sens de la description tout milieu, homogène ou non, comprenant un vecteur liquide ou visqueux transportant éventuellement une phase dispersée, liquide ou gélifiée, et/ou des particules solides, ledit milieu étant globalement pompable au moyen des dispositifs d'injection sous pression utilisés dans l'application considérée. By "fluid" is meant, within the meaning of the description any medium, homogeneous or not, comprising a liquid or viscous carrier optionally carrying a dispersed phase, liquid or gelled, and / or solid particles, said medium being generally pumpable by means pressurized injection devices used in the application under consideration.
Par « vecteur liquide ou visqueux» du fluide (F), on entend le fluide lui-même ; ou bien le solvant dans le cas où le fluide comprend des composés dissous et/ou la phase continue dans le cas où le fluide contient des éléments dispersés (gouttelettes de phase dispersée liquide ou gélifiée, particules solides...). By "liquid or viscous vector" of the fluid (F) is meant the fluid itself; or the solvent in the case where the fluid comprises dissolved compounds and / or the continuous phase in the case where the fluid contains dispersed elements (droplets of liquid or gelled dispersed phase, solid particles, etc.).
La nature du fluide (F) et du bloc long (B) des polymères (P) utilisés selon la présente invention peut varier en une assez large mesure, sous réserve de la compatibilité du vecteur liquide ou visqueux du fluide (F) et du bloc long (B). En particulier, on emploie un bloc long (B) de nature hydrophile lorsque le vecteur liquide ou visqueux présent dans le fluide (F) est de nature hydrophile ; inversement, lorsque le vecteur liquide ou visqueux du fluide (F) est hydrophobe, on emploie un bloc long (B) de nature hydrophobe. The nature of the fluid (F) and the long block (B) of the polymers (P) used according to the present invention can vary to a large extent, subject to the compatibility of the liquid or viscous fluid medium (F) and the block long (B). In particular, a long block (B) of hydrophilic nature is used when the liquid or viscous vector present in the fluid (F) is hydrophilic in nature; conversely, when the liquid or viscous fluid vector (F) is hydrophobic, a long block (B) of hydrophobic nature is used.
Le bloc long (B) des polymères utiles selon l'invention est spécifiquement soluble dans le fluide (F). On entend par là que le bloc long (B) pris isolément peut être dissous dans le vecteur liquide ou visqueux du fluide (F). De préférence, le bloc long (B) est soluble à 25°C et à 1 % en masse dans le vecteur liquide ou visqueux du fluide (F). La notion de « solubilité à 25°C » implique uniquement qu'on peut obtenir une solution plus ou moins visqueuse, voire gélifiée qui, à 25°C, ne conduit pas à une précipitation. Cette notion n'exclut pas que la mise en solution du bloc (B) puisse impliquer un chauffage préalable à plus de 25°C pour obtenir cette solution. En d'autres termes, la notion de « solubilité à 25°C » implique la possibilité de former une solution qui ne précipite pas à 25°C, et non pas la possibilité de former à 25°C une solution qui ne précipite pas. The long block (B) of the polymers useful according to the invention is specifically soluble in the fluid (F). By this is meant that the long block (B) taken alone can be dissolved in the liquid or viscous fluid vector (F). Preferably, the long block (B) is soluble at 25 ° C. and 1% by weight in the liquid or viscous fluid medium (F). The concept of "solubility at 25 ° C" implies only that a more or less viscous or gelled solution can be obtained which, at 25 ° C., does not lead to precipitation. This notion does not exclude that the dissolution of the block (B) may involve preheating above 25 ° C to obtain this solution. In other words, the concept of "solubility at 25 ° C" implies the possibility of forming a solution that does not precipitate at 25 ° C, and not the possibility of forming at 25 ° C a solution that does not precipitate.
Par ailleurs, il est préférable que le bloc long (B) développe le moins possible d'interactions, voire pas du tout d'interactions, avec les particules (p). Il est par ailleurs préférable que le bloc long (B) des polymères (P) utiles selon l'invention développe moins d'interactions avec les particules que le bloc court (A). En tout état de cause, le bloc (A) et le bloc (B) ont des compositions distinctes. On entend par là que: Furthermore, it is preferable that the long block (B) develops the least possible interaction, or even no interaction, with the particles (p). It is also preferable that the long block (B) of the polymers (P) useful according to the invention develops fewer interactions with the particles than the short block (A). In any case, the block (A) and the block (B) have distinct compositions. This means that:
• les blocs (A) et (B) comprennent des unités monomères distinctes ; ou  Blocks (A) and (B) comprise distinct monomeric units; or
« au moins certains des monomères présents sur le bloc (A) ne sont pas présents sur le bloc (B); et/ou au moins certains des monomères présents sur le bloc (B) ne sont pas présents sur le bloc (A)  At least some of the monomers present on the block (A) are not present on the block (B); and / or at least some of the monomers present on the block (B) are not present on the block (A)
ou  or
• le bloc (A) et le bloc (B) comprennent les mêmes unités monomères, mais dans des proportions distinctes.  Block (A) and block (B) comprise the same monomer units, but in different proportions.
Selon un mode de réalisation bien adapté, le fluide (F) est un fluide aqueux. Par « aqueux », on entend ici que le fluide comprend à titre de vecteur liquide ou visqueux de l'eau, soit à titre d'unique constituant du vecteur liquide ou visqueux, soit en association avec d'autres solvants hydrosolubles. En cas de présence de solvants autres que l'eau dans le vecteur liquide ou visqueux du fluide (F), l'eau reste avantageusement le solvant majoritaire au sein du vecteur liquide ou visqueux, présent avantageusement à raison d'au moins 50% en masse, voire d'au moins 75% en masse par rapport à la masse totale des solvants dans le vecteur liquide ou visqueux. Lorsque le fluide (F) est un fluide aqueux, le bloc (B) est avantageusement un bloc de nature hydrophile. Par « bloc de nature hydrophile », on entend ici un bloc polymère qui, à l'état isolé, est soluble dans l'eau pure à raison de 1 % en masse à 25°C (la mise en solution pouvant éventuellement impliquer un chauffage), en formant une solution plus ou moins visqueuse, voire gélifiée, mais sans formation de précipité à 25°C. Avantageusement, le bloc (B) de nature hydrophile employé lorsque le fluide (F) est un fluide aqueux est constitué au moins majoritairement par des unités monomères choisies dans le groupe consistant en les unités monomères U 1 à U5 définies ci-après, et les mélanges de ces unités monomères : unités monomères U1 : unités monomères comprenant un groupement fonctionnel acrylamide, notamment diméthylacrylamide (DMA) ou bien encore (méth)acrylamide, morpholine N-oxide acrylamide, diacétone acrylamide ; le bloc (B) comprend avantageusement des unités monomères de ce type unités monomères U2 : unités monomères comprenant un groupement fonctionnel acide sulfonique ou sulfonate, incluant notamment les unités (méth)acrylate de 3-sulfopropyle, acide 2-propène-1 -sulfonique, 1 -allyloxy-2 hydroxypropyle sulfonate de sodium (COPS1 ), notament acide 2-acrylamido-2- méthyle propane sulfonique (AMPS), sulfonate de (méth)allyle, vinyle sulfonate de sodium, sodium styrène sulfonate, 3-sulfopropyldiméthyl-3- méthacrylamidopropylammonium, N-(2-méthacryloyloxyéthyl)-N,N-diméthyl-N- (3-sulfopropyl)ammoniumbétaine, N-(2-1 -(3-sulfopropyl)-2- vinylpyridiniumbétaine. unités monomères U3 : unités monomères neutres incluant entre autres : les esters d'acides mono- ou di- carboxyliques [alpha], [beta]-éthyléniquement insaturés avec des alcanediols en C2-C30 ou des polyéthyleneglycol, par exemple les 2-hydroxyéthylacrylate, 2-hydroxyéthylméthacrylate, 2- hydroxyéthyléthacrylate, 2-hydroxypropylacrylate, 2- hydroxypropylméthacrylate, 3-hydroxypropyl acrylate, 3- hydroxypropylméthacrylate, 3-hydroxybutylacrylate, 3-hydroxybutyl méthacrylate, 4-hydroxybutylacrylate, 4-hydroxybutylméthacrylate, 6-hydroxy hexylacrylate, 6-hydroxyhexylméthacrylate, 3-hydroxy-2-éthylhexyl acrylate, 3- hydroxy-2-éthylhexylmethacrylate, N-(hydroxyméthyl)acrylamide, N-(2-hydroxy propyl)méthacrylamide, N-hydroxyéthylacrylamide, N-[tris(hydroxyméthyl) méthacrylamide, 4-acryloylmorpholine, 2-N-morpholinoéthyle méthacrylate, méth(acrylate) de polyéthylèneglycol, (méth)acrylate de diéthylène glycol, éthylène glycol méthyl éther (méth)acrylate, acrylate de 2-hydroxyéthyle, acrylate d'hydroxypropyle, acrylate de poly(propylène glycol), acrylate de 2- chloroéthyle, According to a well-adapted embodiment, the fluid (F) is an aqueous fluid. By "aqueous" is meant herein that the fluid comprises as a liquid or viscous carrier water, either as a sole constituent of the liquid or viscous carrier, or in combination with other water-soluble solvents. In the case of the presence of solvents other than water in the liquid or viscous fluid medium (F), the water advantageously remains the majority solvent in the liquid or viscous vector, advantageously present in a proportion of at least 50% by weight. mass, or even at least 75% by weight relative to the total mass of solvents in the liquid or viscous carrier. When the fluid (F) is an aqueous fluid, the block (B) is advantageously a block of hydrophilic nature. By "block of hydrophilic nature" is meant here a polymer block which, in the isolated state, is soluble in pure water at a rate of 1% by weight at 25 ° C. (the dissolution may possibly involve heating ), forming a more or less viscous solution, even gelled, but without precipitate formation at 25 ° C. Advantageously, the hydrophilic block (B) used when the fluid (F) is an aqueous fluid is constituted at least predominantly by monomer units selected from the group consisting of the monomer units U 1 to U 5 defined below, and the mixtures of these monomeric units: monomeric units U1: monomeric units comprising an acrylamide functional group, especially dimethylacrylamide (DMA) or even (meth) acrylamide, morpholine N-oxide acrylamide, diacetone acrylamide; the block (B) advantageously comprises monomer units of this type monomer units U2: monomeric units comprising a sulphonic acid or sulphonate functional group, including in particular 3-sulphopropyl (meth) acrylate units, 2-propene-1-sulphonic acid, Sodium 1-allyloxy-2-hydroxypropyl sulphonate (COPS1), especially 2-acrylamido-2-methylpropanesulphonic acid (AMPS), (meth) allyl sulphonate, sodium vinyl sulphonate, sodium styrene sulphonate, 3-sulphopropyldimethyl-3 methacrylamidopropylammonium, N- (2-methacryloyloxyethyl) -N, N-dimethyl-N- (3-sulfopropyl) ammoniumbetaine, N- (2-1- (3-sulfopropyl) -2-vinylpyridiniumbetaine, U3 monomer units: neutral monomer units including inter alia: [alpha], [beta] -ethylenically unsaturated mono- or di-carboxylic acid esters with C2-C30 alkanediols or polyethylene glycol, for example 2-hydroxyethylacrylate, 2-hydroxyethylmethacrylate, 2-hydroxyethylethacrylate te, 2-hydroxypropylacrylate, 2-hydroxypropylmethacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropylmethacrylate, 3-hydroxybutylacrylate, 3-hydroxybutylmethacrylate, 4-hydroxybutylacrylate, 4-hydroxybutylmethacrylate, 6-hydroxyhexylacrylate, 6-hydroxyhexylmethacrylate, 3-hydroxy-2 ethylhexyl acrylate, 3-hydroxy-2-ethylhexylmethacrylate, N- (hydroxymethyl) acrylamide, N- (2-hydroxypropyl) methacrylamide, N-hydroxyethylacrylamide, N- [tris (hydroxymethyl) methacrylamide, 4-acryloylmorpholine, 2-N- morpholinoethyl methacrylate, polyethylene glycol meth (acrylate), diethylene glycol (meth) acrylate, ethylene glycol methyl ether (meth) acrylate, 2-hydroxyethyl acrylate, hydroxypropyl acrylate, poly (propylene glycol) acrylate, acrylate chloroethyl,
les acrylate de tétrahydrofurfuryle, vinyl acétamide, vinyl pyrrolidone, N-vinyl pipéridone, N-vinyl caprolactam, N-vinyl-5-methyl-2-pyrrolidone, N-vinyl-5- ethyl-2-pyrrolidone, N-vinyl-6-méthyl-2-pipéridone, N-vinyl-6-éthyl-2- pipéridone, N-vinyl-7-méthyl-2-caprolactam, N-vinyl-7-ethyl-2-caprolactame. unités monomères U4 : unités monomères porteuses de groupements ammonium, notamment des esters d'acides mono- ou di- carboxyliques [alpha], [beta]-éthyléniquement insaturés avec des aminoalcools, comme les N,N-diméthylaminométhyl(méth)acrylate, N,N-diméthylaminoéthyl (méth)acrylate, Ν,Ν-diéthylaminoethyl acrylate, N,N-dimethylaminopropyl (méth)acrylate, N,N-diéthylaminopropyl(méth)acrylate et N,N- dimethylaminocyclohexyl (méth)acrylate ; tetrahydrofurfuryl acrylate, vinyl acetamide, vinyl pyrrolidone, N-vinylpiperidone, N-vinyl caprolactam, N-vinyl-5-methyl-2-pyrrolidone, N-vinyl-5-ethyl-2-pyrrolidone, N-vinyl-6 -methyl-2-piperidone, N-vinyl-6-ethyl-2-piperidone, N-vinyl-7-methyl-2-caprolactam, N-vinyl-7-ethyl-2-caprolactam. monomer units U4: monomer units carrying ammonium groups, especially esters of mono- or dicarboxylic acids [alpha], [beta] -ethylenically unsaturated with amino alcohols, such as N, N-dimethylaminomethyl (meth) acrylate, N N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N-diethylaminopropyl (meth) acrylate and N, N-dimethylaminocyclohexyl (meth) acrylate;
amides d'acides mono- ou di- carboxyliques [alpha], [beta]-éthyléniquement insaturés avec des diamines ayant au moins un groupe aminé primaire ou secondaire, tels que les N-[2-(diméthylamino)ethyl]acrylamide, N[2-(dimethyl amino)ethyl]methacrylamide, N-[3-(diméthylamino)propyl]acrylamide, N-[3- (diméthylamino)propyl]methacrylamide, N-[4-(diméthylamino)butyl]acrylamide, N-[4-(diméthylamino)butyl]méthacrylamide, N-[2-(diethylamino)ethyl] acrylamide, N-[4-(dimethylamino)cyclohexyl]acrylamide, N-[4-(dimethylamino) cyclohexyl]méthacrylamide  amides of [alpha], [beta] -ethylenically unsaturated mono- or di-carboxylic acids with diamines having at least one primary or secondary amine group, such as N- [2- (dimethylamino) ethyl] acrylamide, N [ 2- (dimethylamino) ethyl] methacrylamide, N- [3- (dimethylamino) propyl] acrylamide, N- [3- (dimethylamino) propyl] methacrylamide, N- [4- (dimethylamino) butyl] acrylamide, N- [4] [N- [2- (diethylamino) ethyl] acrylamide, N- [4- (dimethylamino) cyclohexyl] acrylamide, N- [4- (dimethylamino) cyclohexyl] methacrylamide
Ν,Ν-diallylamines et N,N-diallyl-N-alkylamines incluant notamment les 3- sulfopropyldiméthyl-3-méthacrylamidopropylammonium, N-(2-méthacryloyl oxyéthyl)-N,N-diméthyl-N-(3-sulfopropyl)ammoniumbétaine, N-(2-1 -(3-sulfo propyl)-2-vinylpyridiniumbétaine, et N-(2-1 -(3-sulfopropyl)-4-vinylpyridinium bétaine unités monomères U5 unités monomères acrylate, porteuses de groupement COOH ou COO-, incluant notamment l'acide acrylique, l'acide méthacrylique, l'acide éthacrylique, l'acide [alpha]-chloro-acrylique, l'acide crotonique, l'acide maléique, l'acide itaconique, l'acide citraconique, l'acide mésaconique, l'acide glutaconique, l'acide aconitique, l'acide fumarique ; les monoesters d'acide dicarboxylique monoéthyléniquement insaturés en C4-C10 et de préf rence en C4 à C6, comme le maléate de monométhyle. Selon un mode de réalisation possible, le bloc (B) de nature hydrophile employé lorsque le fluide (F) est un fluide aqueux est constitué essentiellement, voire exclusivement, par des unités monomères du type précités, où, dans les unités précitées, les groupes acides peuvent être en tout ou partie sous la forme d'acide libre et/ou sous forme de sel par exemple de potassium, sodium ou ammonium (forme neutralisée). Au sens où elle est employée dans la présente description, l'expression « polymère ou bloc polymère constitué au moins majoritairement par des unités monomères 'x' » désigne un (bloc) homopolymère ou copolymère résultant de la polymérisation d'un mélange de monomères incluant des monomères x, ce (bloc) homopolymère ou copolymère comprenant moins de 25% en mole, de préférence moins de 15% et encore plus avantageusement moins de 10% en mole d'unités monomères autres que les unités 'x'. Ν, Ν-diallylamines and N, N-diallyl-N-alkylamines including especially 3-sulfopropyldimethyl-3-methacrylamidopropylammonium, N- (2-methacryloyloxyethyl) -N, N-dimethyl-N- (3-sulfopropyl) ammoniumbetaine, N- (2-1- (3-sulfo-propyl) -2-vinylpyridinium-betaine, and N- (2-1- (3-sulfopropyl) -4-vinylpyridinium betaine monomer units U5 monomeric acrylate units, bearing COOH or COO- , including in particular acrylic acid, methacrylic acid, ethacrylic acid, [alpha] -chloroacrylic acid, crotonic acid, maleic acid, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic acid, fumaric acid, monoethylenically unsaturated C4-C10 and preferably C4-C6 dicarboxylic acid monoesters, such as monomethyl maleate. possible embodiment, the block (B) of hydrophilic nature used when the fluid (F) is an aqueous fluid consists essentially or even exc monomeric units of the above-mentioned type, in which, in the abovementioned units, the acid groups may be wholly or partly in the form of a free acid and / or in the form of a salt for example of potassium, sodium or ammonium (form neutralized). As used herein, the term "polymer or polymer block consisting at least predominantly of monomeric units" refers to a (block) homopolymer or copolymer resulting from the polymerization of a monomer mixture including monomers x, this (block) homopolymer or copolymer comprising less than 25 mol%, preferably less than 15% and even more preferably less than 10 mol% of monomer units other than the 'x' units.
L'expression « polymère ou bloc polymère constitué essentiellement par des unités monomères 'x' » désigne quant à elle, au sens de la présente description, un (bloc) homopolymère ou copolymère constitué au moins majoritairement par des unités monomères 'x' du type précité, comprenant plus spécifiquement moins de 5% en mole, de préférence moins de 2% et encore plus avantageusement moins de 1 % en mole d'unités monomères autres que les unités 'x'. The expression "polymer or polymer block consisting essentially of monomer units 'x'" for its part means, within the meaning of the present description, a (block) homopolymer or copolymer consisting at least predominantly of monomer units 'x' of the type above, more specifically comprising less than 5 mol%, preferably less than 2% and even more preferably less than 1 mol% of monomer units other than 'x' units.
Selon un mode de réalisation particulier, compatibles avec les modes précédents, le bloc (B) de nature hydrophile employé lorsque le fluide (F) est un fluide aqueux peut comprendre des monomères hydrophobes en faibles proportions, typiquement à raison d'au moins 0,05%, notamment au moins 0,1 %, voire au moins 0,5%, le cas échéant ; cette teneur en monomères hydrophobes restant de préférence inférieure à 10 %, par exemple inférieure à 5%, notamment moins inférieure à 3%,voire à 2%, ces pourcentages étant exprimés en masse par rapport à la masse totale d'unité monomères dans le bloc (B). Lorsque des monomères hydrophobes de ce type sont présents, ils peuvent typiquement (mais non limitativement) être choisis parmi les acrylates d'alkyle (comme l'acrylate de méthyle) ; le styrène ; les méthacrylates d'alkyle ; et/ou l'acétate de vinyle. According to a particular embodiment, compatible with the preceding modes, the hydrophilic block (B) used when the fluid (F) is an aqueous fluid may comprise hydrophobic monomers in small proportions, typically at least 0, 05%, including at least 0.1%, or at least 0.5%, where applicable; this content of hydrophobic monomers preferably remains below 10%, for example less than 5%, especially less than 3%, or even 2%, these percentages being expressed by weight relative to the total mass of monomer units in the block (B). When hydrophobic monomers of this type are present, they can typically (but not exclusively) be selected from alkyl acrylates (such as methyl acrylate); styrene; alkyl methacrylates; and / or vinyl acetate.
Le bloc long (B) présent dans les polymères employés selon la présente invention a par ailleurs une masse suffisamment élevée pour assurer l'effet de contrôle du filtrat recherché. A cet effet, le bloc (B) a typiquement une masse moléculaire moyenne en poids supérieure à 100 000 g/mol, de préférence supérieure à 150 000 g/mol, par exemple supérieur à 200 000 g/mol, notamment supérieur à 250 000 g/mol, et ce notamment lorsque le bloc (B) est de l'un des types précités. En pratique, cette masse moléculaire moyenne en poids reste le plus souvent inférieure à 3 000 000 g/mol (et typiquement comprise entre 150 000 et 2 000 0000 g/mol), mais des masses plus élevées peuvent être envisagées dans l'absolu, hormis dans le cas particulier d'un fluide (F) utilisé dans le cadre d'une opération de cimentation, où il est préférable que la masse moléculaire moyenne en poids du bloc long (B) reste inférieure à 1 000 000 g/mol, et avantageusement inférieure à 800 000 g/mol. The long block (B) present in the polymers employed according to the present invention also has a sufficiently high mass to ensure the control effect of the desired filtrate. For this purpose, the block (B) typically has a weight average molecular weight greater than 100,000 g / mol, preferably greater than 150,000 g / mol, for example greater than 200,000 g / mol, especially greater than 250,000 g / mol. g / mol, especially when the block (B) is of one of the aforementioned types. In practice, this weight average molecular weight is most often less than 3,000,000 g / mol (and typically between 150,000 and 2,000,000 g / mol), but higher masses can be envisaged in absolute terms, except in the particular case of a fluid (F) used in the context of a cementing operation, where it is preferable that the mass The weight average molecular weight of the long block (B) remains less than 1,000,000 g / mol, and advantageously less than 800,000 g / mol.
Dans le cadre de la présente invention, il a par ailleurs été mis en évidence, que, de façon surprenante, l'effet de contrôle du filtrat recherché est obtenu pour des blocs (B) ayant une masse moléculaire moyenne en poids plus faible que 100 000 g/mol. Ainsi, selon un mode de réalisation particulier, le bloc (B) a une masse moléculaire moyenne en poids comprise entre 10 000 et à 100 000 g/mol, de préférence d'au moins 20 000 g/mol, par exemple d'au moins 25 000 g/mol, cette masse moléculaire moyenne en poids pouvant typiquement être inférieure à 90 000, par exemple inférieure à 75 000, voire inférieure à 50 000 . In the context of the present invention, it has moreover been demonstrated that, surprisingly, the control effect of the desired filtrate is obtained for blocks (B) having a weight average molecular weight of less than 100 000 g / mol. Thus, according to a particular embodiment, the block (B) has a weight average molecular weight of between 10,000 and 100,000 g / mol, preferably at least 20,000 g / mol, for example from less than 25,000 g / mol, this weight average molecular weight typically being less than 90,000, for example less than 75,000, or even less than 50,000.
Une estimation de la masse moléculaire moyenne en poids du bloc long (B) peut être mesurée par une chromatographie d'exclusion stérique et mesure de masse utilisant une calibration externe avec des étalons de polyoxyde d'éthylène (CES relative), ce qui conduit à une valeur légèrement majorée de la masse moléculaire moyenne en poids désignée dans la présente description par Mw(CES relative). An estimate of the weight average molecular weight of the long block (B) can be measured by steric exclusion chromatography and mass measurement using external calibration with relative ethylene oxide (CES) standards, which leads to a slightly increased value of the weight average molecular weight designated in the present description by Mw (relative CES).
Cette Mw(CES relative) est typiquement mesurée dans les conditions suivantes : This Mw (relative CES) is typically measured under the following conditions:
Phase mobile :Mélange de 80% en masse d'eau désionisée additionnée de 0,1 M NaN03 et 20% en masse d'acetonitrile,. Mobile phase: Mixture of 80% by weight of deionized water supplemented with 0.1 M NaNO 3 and 20% by weight of acetonitrile.
Débit : 1 ml/min Colonnes : Shodex OHpak SB 806 MHQ (3 colonnes de 30 cm) Flow rate: 1 ml / min Columns: Shodex OHpak SB 806 MHQ (3 columns of 30 cm)
Détection: Indice de réfraction (détecteur de concentration Agilent) Detection: Refractive index (Agilent concentration detector)
Concentration des échantillons: environ 0,5 % en masse de matière sèche dans la phase mobile Sample concentration: about 0.5% by mass of dry matter in the mobile phase
Injection: 100 ul Injection: 100 ul
Référence interne: éthyleneglycol Internal reference: ethylene glycol
Etalonnage : polyoxyde d'ethylene PEO La Mw(CES relative) du bloc long (B) des polymères (P) utiles selon l'invention est en général supérieure ou égale à 125 000 g/mol de préférence supérieure ou égale à 150 000 g/mol, cette Mw(CES relative) étant typiquement entre 200 000 et 2 500 000 g/mol, notamment entre 250 000 et 2 000 000 g/mol. Selon un mode de réalisation plus particulier, elle peut être inférieure à 125 000 g/mol , par exemple comprise entre 12 500 et 100 000 g/mol. Calibration: PEO ethylene oxide The Mw (relative CES) of the long block (B) of the polymers (P) which are useful according to the invention is generally greater than or equal to 125 000 g / mol, preferably greater than or equal to 150 000 g / mol, this Mw (CES relative) being typically between 200,000 and 2,500,000 g / mol, especially between 250,000 and 2,000,000 g / mol. According to a more particular embodiment, it may be less than 125,000 g / mol, for example between 12,500 and 100,000 g / mol.
Dans le cas d'un fluide (F) utilisé dans le cadre d'une opération de cimentation, la Mw(CES relative) du bloc long (B) des polymères (P) et typiquement (mais non limitativement) entre 25 000 et 900 000 g/mol, par exemple entre 250 000 et 900 000 g/mol. In the case of a fluid (F) used in the context of a cementing operation, the Mw (relative CES) of the long block (B) of the polymers (P) and typically (but not exclusively) between 25,000 and 900 000 g / mol, for example between 250,000 and 900,000 g / mol.
En pratique, on mesure la Mw(CES relative) du polymère (P), qui, du fait de la faible masse du bloc (A) représente également une assez bonne approximation, majorée, de la masse moléculaire moyenne en masse du bloc (B). La Mw(CES relative) du polymère (P) est en général supérieure ou égale à 15 000 g/mol, et par exemple supérieure ou égale à 150 000 g/mol, de préférence supérieure ou égale à 200 000 g/mol, par exemple supérieure ou égale à 300 000 g/mol, notamment supérieur ou égale à 400 000 g/mol, cette Mw(CES relative) du polymère (P) étant typiquement entre 200 000 g/mol et 2 500 000 g/mol, notamment entre 250 000 g/mol et 2 000 000 g/mol. Elle est plus particulièrement entre 25 000 et 900 000 g/mol, par exemple entre 250 000 g/mol et 800 000 g/mol dans le cas d'un fluide (F) utilisé dans le cadre d'une opération de cimentation. In practice, the Mw (relative CES) of the polymer (P) is measured, which, because of the low mass of the block (A) also represents a fairly good approximation, increased, of the mass average molecular weight of the block (B). ). The Mw (relative CES) of the polymer (P) is in general greater than or equal to 15,000 g / mol, and for example greater than or equal to 150,000 g / mol, preferably greater than or equal to 200,000 g / mol, example greater than or equal to 300,000 g / mol, in particular greater than or equal to 400,000 g / mol, this Mw (relative CES) of the polymer (P) being typically between 200,000 g / mol and 2,500,000 g / mol, in particular between 250,000 g / mol and 2,000,000 g / mol. It is more particularly between 25,000 and 900,000 g / mol, for example between 250,000 g / mol and 800,000 g / mol in the case of a fluid (F) used in the context of a cementing operation.
Dans le cas particulier où le fluide (F) est utilisé dans une opération de cimentation In the particular case where the fluid (F) is used in a cementing operation
(coulis de ciment pétrolier, typiquement) : (petroleum cement grout, typically):
• le bloc (B) est avantageusement un bloc de nature hydrophile, de préférence comprenant des unités U1 du type précité, notamment des unités diméthylacrylamide DMA, éventuellement, mais non nécessairement, en association avec des unités U2, notamment des unités acide acrylamidométhylpropanesulfonique (AMPS), éventuellement en tout ou partie sous forme de sulfonate, par exemple sous la forme de son sel de sodium. The block (B) is advantageously a block of hydrophilic nature, preferably comprising U1 units of the aforementioned type, in particular dimethylacrylamide DMA units, possibly, but not necessarily, in combination with U2 units, in particular acrylamidomethylpropanesulphonic acid units (AMPS) ), optionally wholly or partly in sulphonate form, for example in the form of its sodium salt.
Selon un mode de réalisation particulier, le bloc (B) est constitué au moins majoritairement (par exemple essentiellement, voire exclusivement) par un mélange d'unités DMA et AMPS, avec un rapport molaire DMA AMPS par exemple compris entre 60/40 et 90/10, notamment entre 75/25 et 85/15 et typiquement de l'ordre de 80/20. According to a particular embodiment, the block (B) consists at least predominantly (for example essentially, or exclusively) of a mixture of DMA and AMPS units, with a DMA AMPS molar ratio, for example between 60/40 and 90/10, especially between 75/25 and 85/15 and typically of the order of 80/20.
• le bloc (B) a typiquement une masse moléculaire moyenne en poids comprise entre 150 000 et 750 000 g/mol, de préférence entre 200 000 et 700 000 g/mol. Alternativement, le bloc (B) peut avoir une masse moléculaire moyenne en poids comprise entre 15 000 et 150 000 g/mol, de préférence entre 20 000 et 100 000 g/mol. Block (B) typically has a weight average molecular weight of between 150,000 and 750,000 g / mol, preferably between 200,000 and 700,000 g / mol. Alternatively, the block (B) may have a weight average molecular weight of between 15,000 and 150,000 g / mol, preferably between 20,000 and 100,000 g / mol.
• le bloc (B) a typiquement une Mw(GPC relative) comprise entre 200 000 et 800 000 , de préférence entre 250 000 et 900 000 g/mol , par exemple 300 000 à 600 000 g/mol le polymère (P) ayant en général une Mw(CES relative) comprise dans ces gammes. Le bloc (B) peut alternativement avoir une Mw(GPC relative) comprise entre 20 000 et 200 000 , de préférence entre 25 000 et 180 000 g/mol , par exemple 30 000 et 150 000 g/mol, le polymère (P) ayant en général une Mw(CES relative) comprise dans ces gammes. The block (B) typically has a Mw (relative GPC) of between 200,000 and 800,000, preferably between 250,000 and 900,000 g / mol, for example 300,000 to 600,000 g / mol, the polymer (P) having in general a Mw (relative CES) included in these ranges. The block (B) may alternatively have a Mw (relative GPC) of between 20,000 and 200,000, preferably between 25,000 and 180,000 g / mol, for example 30,000 and 150,000 g / mol, the polymer (P) having in general a Mw (relative CES) included in these ranges.
Le bloc long (B) employé lorsque le fluide (F) est un coulis de ciment pétrolier est typiquement un bloc statistique DMA/AMPS, avec un ratio molaire DMA/AMPS entre 75/25 et 85/15 (typiquement de l'ordre de 80/20), et une Mw(GPC-MALS) comprise entre 20 000 et 7500 000, notamment entre 200 000 et 750 0000, par exemple entre 400 000 et 600 000. The long block (B) used when the fluid (F) is a petroleum cement slurry is typically a DMA / AMPS statistical block, with a DMA / AMPS molar ratio between 75/25 and 85/15 (typically of the order of 80/20), and a Mw (GPC-MALS) of between 20,000 and 7,500,000, in particular between 200,000 and 750,000, for example between 400,000 and 600,000.
Les particules (p) et le bloc court (A) The particles (p) and the short block (A)
La notion de « particule » au sens où elle est employée dans la présente description ne se cantonne pas à celle de particules individualisées. Elle désigne de façon plus générale des entités solides dispersables au sein d'un fluide, sous la forme d'objets (particules individuelles, agrégats ...) dont toutes les dimensions sont inférieures à 5 mm, de préférence à 2 mm, par exemple inférieures à 1 mm. The notion of "particle" in the sense in which it is used in the present description is not confined to that of individualized particles. It refers more generally to solid entities dispersible within a fluid, in the form of objects (individual particles, aggregates, etc.) whose dimensions are less than 5 mm, preferably 2 mm, for example less than 1 mm.
La nature des particules (p) et du bloc court (A) des polymères (P) utilisés selon la présente invention peuvent varier en une assez large mesure, sous réserve que le bloc (A) interagisse avec les particules (p) et conduise à une immobilisation, de préférence irréversible, de polymère (P) sur la surface des particules (p). The nature of the particles (p) and the short block (A) of the polymers (P) used according to the present invention can vary to a large extent, provided that the block (A) interacts with the particles (p) and leads to an immobilization, preferably irreversible, of polymer (P) on the surface of the particles (p).
Pour ce faire, le bloc (A) comprend en général des unités monomères porteuses de groupements développant avec les particules (p) des interactions plus fortes que le bloc long (B). To do this, the block (A) generally comprises monomer units carrying groups developing with the particles (p) stronger interactions than the long block (B).
Selon un mode de réalisation bien adapté, les particules (p) sont des particules minérales introduites au sein du fluide (F) ou avec lesquelles le fluide (F) entre en contact suite à son injection. Ces particules (p) sont alors typiquement des particules de ciment, de carbonate de calcium, d'argile, de barite, de silice, de sable ou de noir de carbone. Selon ce mode de réalisation, le bloc (A) est de préférence constitué au moins majoritairement (et de préférence essentiellement, voire exclusivement) par des unités monomères choisies dans les groupes préférentiels définis ci-après, à adapter au cas par cas en fonction de la nature des particules (p). : According to a well-adapted embodiment, the particles (p) are mineral particles introduced into the fluid (F) or with which the fluid (F) comes into contact following its injection. These particles (p) are then typically particles of cement, calcium carbonate, clay, barite, silica, sand or carbon black. According to this embodiment, the block (A) is preferably constituted at least predominantly (and preferably essentially, if not exclusively) by monomer units chosen from the preferential groups defined below, to be adapted case by case as a function of the nature of the particles (p). :
• pour des particules (p) de carbonate de calcium ou de ciment : le bloc (A) peut notamment être constitué au moins majoritairement (et de préférence essentiellement, voire exclusivement) par : For particles (p) of calcium carbonate or cement: the block (A) may in particular consist at least in the majority (and preferably essentially or exclusively) of:
■ des unités monomères U5 du type précité, avantageusement présentes dans le bloc (A) ; et/ou ■ monomer units U5 of the aforementioned type advantageously present in the block (A); and or
■ des unités monomères U3 du type précité ; et/ou ■ des unités monomères U6 porteuses de groupements phosphate, phosphonate ou phosphinate (sous forme d'acide libre et/ou sous forme saline), comme par exemple des unités phosphate de monoacryloxyéthyle, phosphate de bis(2-méthacryloxyéthyle), les unités monomères introduites en employant les Sipomer PAM 100, 200, 400 ou 5000 disponibles auprès de la société Solvay, l'acide vinylphosphonique, l'acide allylphosphonique, l'acide isopropylphosphonique, le phosphonate de diallyle aminométhylène et leurs sels. ■ monomer units U3 of the aforementioned type; and or ■ carrier U6 monomer units phosphate groups, phosphonate or phosphinate (in free acid form and / or salt form), such as monoacryloxyéthyle phosphate units, phosphate bis (2-methacryloxyethyl) introduced monomer units using Sipomer PAM 100, 200, 400 or 5000 available from Solvay, vinylphosphonic acid, allylphosphonic acid, isopropylphosphonic acid, diallyl aminomethylene phosphonate and their salts.
Le bloc (B) est alors typiquement constitué au moins majoritairement (et de préférence essentiellement, voire exclusivement) par des unités U1 et/ou U2 du type précité The block (B) is then typically constituted at least predominantly (and preferably substantially, or even exclusively) by units U1 and / or U2 of the aforementioned type
• pour des particules (p) de silice ou de sable : le bloc (A) peut notamment être constitué au moins majoritairement (et de préférence essentiellement, voire exclusivement) par : For particles (p) of silica or sand: the block (A) may in particular be constituted at least predominantly (and preferably substantially, if not exclusively) by:
■ des unités monomères U3 du type précité ; et/ou ■ monomer units U3 of the aforementioned type; and or
■ des unités monomères U4 du type précité ; et/ou ■ monomer units U4 of the aforementioned type; and or
■ des unités monomères U7 (méth)acrylate fonctionnalisé par des polydimethylsiloxanes comme le triméthylsiloxy PEG 4-5 methacrylate, ou le(3-trimethoxysilyl)propyl methacrylate ■ U7 of monomer units (meth) acrylate-functionalized polydimethylsiloxanes such as trimethylsiloxy PEG 4-5 methacrylate, or (3-trimethoxysilyl) propyl methacrylate
Le bloc (B) est alors typiquement constitué au moins majoritairement (et de préférence essentiellement, voire exclusivement) par des unités U1 et/ou U2 et/ou U5 du type précité The block (B) is then typically constituted at least predominantly (and preferably essentially, if not exclusively) by units U1 and / or U2 and / or U5 of the aforementioned type
• pour des particules (p) d'argile : le bloc (A) peut notamment être constitué au moins majoritairement (et de préférence essentiellement, voire exclusivement) par For particles (p) of clay: the block (A) may in particular be constituted at least predominantly (and preferably substantially or exclusively) by
■ des unités monomères U4 du type précité ; et/ou ■ monomer units U4 of the aforementioned type; and or
■ des unités monomères U6 du type précité. Le bloc (B) est alors typiquement constitué au moins majoritairement (et de préférence essentiellement, voire exclusivement) par des unités U1 et/ou U2 du type précité pour des particules (p) de noir de carbone le bloc (A) peut notamment être constitué au moins majoritairement (et de préférence essentiellement, voire exclusivement) par des unités U8 hydrophobes, incluant notamment ■ U6 monomer units of the aforementioned type. The block (B) is then typically constituted at least predominantly (and preferably essentially, if not exclusively) by units U1 and / or U2 of the aforementioned type for particles (p) of carbon black, the block (A) can in particular be constituted at least predominantly (and preferably essentially or exclusively) by hydrophobic units U8, including in particular
les esters d'acides mono ou di-carboxylique [alpha], [betaj-éthyléniquement insaturés avec des alcools en C1 -C20, comme par exemple les méthyl (méth)acrylate, méthyl éthacrylate, éthyl (méth)acrylate, éthyl éthacrylate, n-propyl (méth)acrylate, isopropyl (méth)acrylate, n-butyl (méth)acrylate, sec-butyl (méth)acrylate, tert-butyl (méth)acrylate, tert-butyl éthacrylate, n-hexyl (méth)acrylate, n-heptyl (méth)acrylate, n-octyl (méth)acrylate, 1 ,1 ,3,3- tetraméthylbutyl (méth)acrylate, éthylhexyl (méth)acrylate, n-nonyl (méth)acrylate, n-decyl (méth)acrylate, n-undecyl (méth)acrylate, tridecyl(méth)acrylate, myristyl (méth)acrylate, pentadecyl (méth)acrylate, palmityl (méth)acrylate, heptadecyl (méth)acrylate, nonadecyl (méth)acrylate, arachinyl (méth)acrylate, béhényl (méth)acrylate, lignoceryl (méth)acrylate, cérotinyl (méth)acrylate, mélissinyl (méth)acrylate, palmitoléoyl (meth)acrylate, oléyl (méth)acrylate, linoléyl (méth)acrylate, linolényl (méth)acrylate, stéaryl (méth)acrylate, lauryl (méth)acrylate, les mono, di or tristyryl phényl (meth)acrylates éventuellement éthoxylés entre les groupes aromatique et méthacrylate ; et/ou les unités monomères vinylaromatiques comme le styrène, le 2-méthylstyrène, 4-méthylstyrène, 2-(n-butyl)styrène, 4-(n-butyl)styrène, 4-(n-decyl)styrène les unités monomères fluorées, comme les (méth)acrylates d'alkyle perfluorés ou hautement fluorés. esters of mono- or di-carboxylic acids [alpha], [beta-ethylenically unsaturated with C 1 -C 20 alcohols, for example methyl (meth) acrylate, methyl ethacrylate, ethyl (meth) acrylate, ethyl ethacrylate, n propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, tert-butyl ethacrylate, n-hexyl (meth) acrylate, n-heptyl (meth) acrylate, n-octyl (meth) acrylate, 1,1,3,3-tetramethylbutyl (meth) acrylate, ethylhexyl (meth) acrylate, n-nonyl (meth) acrylate, n-decyl (meth) acrylate, n-undecyl (meth) acrylate, tridecyl (meth) acrylate, myristyl (meth) acrylate, pentadecyl (meth) acrylate, palmityl (meth) acrylate, heptadecyl (meth) acrylate, nonadecyl (meth) acrylate, arachinyl (meth) acrylate, behenyl (meth) acrylate, lignoceryl (meth) acrylate, cerotinyl (meth) acrylate, melissinyl (meth) acrylate, palmitoleoyl (meth) acrylate, oleyl (meth) acrylate, linoleyl (meth) acrylate, nolenyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, mono-, di or tristyryl phenyl (meth) acrylates optionally ethoxylated between the aromatic and methacrylate groups; and / or vinylaromatic monomeric units such as styrene, 2-methylstyrene, 4-methylstyrene, 2- (n-butyl) styrene, 4- (n-butyl) styrene, 4- (n-decyl) styrene fluorinated monomeric units such as perfluorinated or highly fluorinated alkyl (meth) acrylates.
Le bloc (B) est alors typiquement constitué au moins majoritairement (et de préférence essentiellement, voire exclusivement) par des unités des unités U1 et/ou U2 et/ou U5 du type précité Quelle que soit sa nature chimique, le bloc court (A) présent dans les polymères employés selon la présente invention a, en général, une masse moléculaire moyenne en poids entre 500 et 30 000 g/mol, par exemple entre 1000 et 25 000 g/mol et ce notamment lorsque le bloc (A) est de l'un des types précités. Selon un mode de réalisation particulièrement intéressant, employé lorsque les particules (p) sont des particules de ciment ou de carbonate de calcium, le bloc court (A) est un bloc homopolymère poly(acide acrylique) de masse moléculaire moyenne en poids allant de 1 000 à 20 000 g/mol. The block (B) is then typically constituted at least predominantly (and preferably substantially, if not exclusively) by units of units U1 and / or U2 and / or U5 of the aforementioned type Whatever its chemical nature, the short block (A) present in the polymers employed according to the present invention has, in general, a weight average molecular weight of between 500 and 30,000 g / mol, for example between 1000 and 25,000 g. / mol and especially when the block (A) is of one of the aforementioned types. According to a particularly advantageous embodiment, used when the particles (p) are particles of cement or calcium carbonate, the short block (A) is a poly (acrylic acid) homopolymer block of weight average molecular weight ranging from 1 000 to 20,000 g / mol.
La masse moléculaire en poids du bloc court (A) peut être mesurée notamment par une chromatographie par perméation de gel suivie d'une analyse par diffusion de la lumière multiangle (GPC-MALS) The weight-average molecular mass of the short block (A) can be measured in particular by gel permeation chromatography followed by multi-angle light scattering (GPC-MALS) analysis.
Les polymères (P) Polymers (P)
Les polymères utiles selon la présente invention sont des polymères particuliers, qui comprennent au moins deux blocs de taille très différente, incluant un bloc (B) de taille élevée. Polymers useful according to the present invention are particular polymers, which comprise at least two blocks of very different size, including a block (B) of large size.
Les polymères (P) sont de préférence préparés par polymérisation radicalaire contrôlée, ce qui permet de contrôler finement la taille des deux blocs. The polymers (P) are preferably prepared by controlled radical polymerization, which allows to finely control the size of the two blocks.
La technique de polymérisation radicalaire contrôlée est une technique bien connue en soi, qui permettent, à l'aide d'agent de contrôle de la polymérisation, d'obtenir des polymères de masses contrôlées et notamment des polymères séquencés dont on peut contrôler à la fois l'architecture et la taille de chacun des blocs.  The controlled radical polymerization technique is a well-known technique which, using a polymerization control agent, makes it possible to obtain controlled mass polymers, in particular block polymers which can be controlled at the same time. the architecture and size of each block.
Des procédés de polymérisation radicalaire contrôlée bien adaptés pour la synthèse des polymères (P) utiles selon l'invention sont les procédés dit RAFT ou MADIX, qui mettent typiquement en œuvre un procédé de transfert réversible par addition- fragmentation employant des agents de contrôle (dits également de transfert réversible), par exemple de type xanthate (composés porteurs de fonctions -SC=SO-). A titre d'exemples de tels procédés, il peut notamment être fait mention de ceux décrits dans WO96/30421 , WO 98/01478, WO 99/35178, WO 98/58974, WO 00/75207, WO 01/42312, WO 99/35177, WO 99/31 144, FR2794464 ou WO 02/26836. Ces procédés dits de « polymérisation radicalaire contrôlée » conduisent de façon bien connue à la formation de chaînes polymères qui croissent sensiblement toutes à la même vitesse, ce qui se traduit par une augmentation sensiblement linéaire des masses moléculaires avec la conversion et une distribution des masses resserrée, avec un nombre de chaînes qui reste typiquement sensiblement fixe pendant toute la durée de la réaction, ce qui permet de contrôler très aisément la masse molaire moyenne du polymère synthétisé (le rapport initial monomère/agent de contrôle définit le degré de polymérisation obtenu pour les chaînes synthétisé). Les chaînes obtenues présentent par ailleurs en général un caractère « vivant » : elles présentent en bout de chaîne le groupement réactif présent sur l'agent de contrôle. On peut de ce fait poursuivre la polymérisation sur la chaîne polymère obtenue, en conservant le caractère contrôlé de la polymérisation, ce qui peut notamment être utilisé pour synthétiser à l'extrémité d'un premier bloc polymère de taille contrôlée un autre bloc de composition différente et également de taille contrôlée . Dans ce cadre, les polymères (P) utiles selon l'invention peuvent être des polymères du type préparés selon un procédé comprenant les étapes suivantes : Controlled radical polymerization processes that are well suited for the synthesis of the polymers (P) that are useful according to the invention are the so-called RAFT or MADIX processes, which typically implement a reversible addition-fragmentation transfer process employing control agents (known as also reversible transfer), for example of xanthate type (compounds bearing -SC = SO- functions). By way of examples of such methods, mention may in particular be made of those described in WO96 / 30421, WO 98/01478, WO 99/35178, WO 98/58974, WO 00/75207, WO 01/42312, WO 99 / 35177, WO 99/31144, FR2794464 or WO 02/26836. These so-called "controlled radical polymerization" processes lead, in a well-known manner, to the formation of polymer chains, all of which grow substantially at the same rate, which results in a substantially linear increase in the molecular weights with the conversion and a narrow mass distribution. with a number of chains which typically remains substantially fixed throughout the duration of the reaction, which makes it possible very easily to control the average molar mass of the synthesized polymer (the initial ratio monomer / control agent defines the degree of polymerization obtained for the synthesized channels). The chains obtained moreover generally have a "living" character: they present at the end of the chain the reactive group present on the control agent. It is thus possible to continue the polymerization on the polymer chain obtained, while preserving the controlled nature of the polymerization, which can notably be used to synthesize at the end of a first polymer block of controlled size another block of different composition. and also of controlled size. In this context, the polymers (P) useful according to the invention may be polymers of the type prepared according to a process comprising the following steps:
(E1 ) on synthétise le bloc (A) -ou plus rarement le bloc (B)- des polymères (P) en mettant en contact en milieu aqueux : (E1) the block (A) - or more rarely the block (B) - polymers (P) are synthesized by bringing into contact in an aqueous medium:
- les monomères éthyléniquement insaturés, identiques ou différents choisis pour la constitution du bloc (A) - respectivement du bloc (B) - ; the ethylenically unsaturated monomers, which are identical or different, chosen for the constitution of the block (A) or block (B) -;
- une source de radicaux libres adaptée à la polymérisation desdits monomères; et a source of free radicals adapted to the polymerization of said monomers; and
- un agent de contrôle de la polymérisation radicalaire, de préférence comprenant un groupe thiocarbonylthio -S(C=S)- ; an agent for controlling the radical polymerization, preferably comprising a thiocarbonylthio group -S (C = S) -;
(E2) on synthétise le bloc (B) - respectivement le bloc (A) - à l'extrémité du bloc (A) - respectivement à l'extrémité du bloc (B) - formé dans l'étape (1 ) en mettant en contact : (E2) the block (B) - the block (A) - at the end of the block (A) - respectively at the end of the block (B) - formed in the step (1) is synthesized by setting contact :
- les monomères éthyléniquement insaturés, identiques ou différents, choisis pour la constitution du bloc (B) - respectivement du bloc (A) -; the ethylenically unsaturated monomers, which are identical or different, chosen for the constitution of the block (B) or of the block (A) -;
- une source de radicaux libres adaptée à la polymérisation desdits monomères; et - le polymère obtenu à l'issue de l'étape (E1 ), qui joue le rôle d'agent de contrôle de la polymérisation radicalaire et sur lequel se greffe le bloc (B) -respectivement le bloc (A). a source of free radicals adapted to the polymerization of said monomers; and the polymer obtained at the end of step (E1), which acts as a control agent for the radical polymerization and on which the block (B) -respectively the block (A) is grafted.
Dans chacune des étapes (E1 ) et (E2), la taille du bloc polymère en formation est contrôlée par le rapport molaire monomère/agent de contrôle correspondant à la quantité initiale de monomères rapportée à la quantité d'agent de contrôle : schématiquement, toutes les châines croissent à partir de chacun des agents de contrôle présent et les monomères se répartissent de façon homogène sur toutes les chaînes en croissance. Le rapport molaire monomère/agent de contrôle dicte de ce fait le degré de polymérisation du bloc synthétisé dans chacune des étapes, et permet donc de définir la masse moléculaire moyenne en nombre théorique attendue pour chacun des blocs. In each of the steps (E1) and (E2), the size of the polymer block in formation is controlled by the monomer / control agent molar ratio corresponding to the initial quantity of monomers relative to the amount of control agent: schematically, all the chains grow from each of the present control agents and the monomers are distributed evenly over all the growing chains. The monomer / control agent molar ratio thus dictates the degree of polymerization of the block synthesized in each of the steps, and thus makes it possible to define the theoretical average molecular weight expected for each of the blocks.
Typiquement, les rapports molaire monomère/agent de contrôle dans les étapes (E1 ) et (E2) sont choisis de façon à ce que : Typically, the molar monomer / control agent ratios in steps (E1) and (E2) are chosen so that:
• La masse moléculaire moyenne en nombre théorique du bloc (A) est comprise entre 250 et 25 000 g/mol, de préférence entre 500 et 15 000 g/mol, notamment entre 1 000 et 10000g/mol. The theoretical number average molecular weight of the block (A) is between 250 and 25,000 g / mol, preferably between 500 and 15,000 g / mol, especially between 1,000 and 10,000 g / mol.
• La masse moléculaire moyenne en nombre théorique du bloc (B) est comprise entre 70 000 et 5 000 000 g/mol, de préférence entre 80 000 et 3 000 000 g/mol, notamment entre 90 000 et 2 000 000 g/mol. Lorsque le polymère est destiné à une opération de cimentation, cette masse moléculaire moyenne en nombre théorique du bloc (B) est plus préférentiellement entre 90 000 et 1 000 000 g/mol, avantageusement entre 100 000 et 500 000 g/mol. The theoretical number average molecular weight of the block (B) is between 70,000 and 5,000,000 g / mol, preferably between 80,000 and 3,000,000 g / mol, especially between 90,000 and 2,000,000 g / mol. . When the polymer is intended for a cementing operation, this theoretical number average molecular weight of the block (B) is more preferably between 90,000 and 1,000,000 g / mol, advantageously between 100,000 and 500,000 g / mol.
Le bloc (B) peut avantageusement être préparé dans l'étape (E2) en mettant en contact : - les monomères éthyléniquement insaturés, identiques ou différents, choisis pour la constitution du bloc (B) ; The block (B) can advantageously be prepared in step (E2) by bringing into contact: the ethylenically unsaturated monomers, which are identical or different, chosen for forming the block (B);
- une source de radicaux libres adaptée à la polymérisation desdits monomères; et a source of free radicals adapted to the polymerization of said monomers; and
- le bloc (A) préparé selon l'étape (E1 ) précitée, qui joue le rôle d'agent de contrôle de la polymérisation radicalaire, de préférence comprenant un groupe thiocarbonylthio - S(C=S)-, et sur lequel se greffe le bloc (B) avec une concentration en monomères au sein du milieu réactionnel de l'étape (E) qui est suffisamment élevée pour induire la gélification du milieu si la polymérisation était conduite en l'absence de l'agent de contrôle. the block (A) prepared according to the above-mentioned step (E1), which acts as a control agent for the radical polymerization, preferably comprising a thiocarbonylthio-S (C = S) - group, and on which is grafted the block (B) with a monomer concentration within the reaction medium of step (E) which is sufficiently high to induce gelation of the medium if the polymerization is conducted in the absence of the control agent.
Cette technique de polymérisation permet d'accéder à des blocs (B) de taille élevées. Avantageusement, la synthèse du bloc (B) peut être réalisée dans les conditions de polymérisaion décrites dans la demande WO 2012/042167. This polymerization technique allows access to blocks (B) of large size. Advantageously, the synthesis of the block (B) can be carried out under the polymerization conditions described in the application WO 2012/042167.
Alternativement, lorsque le bloc (B) est hydrophile, le bloc (B) peut être synthétisé: en mettant en contact, au sein d'un milieu aqueux (M) dans lequel le bloc (B) formé n'est pas soluble : Alternatively, when the block (B) is hydrophilic, the block (B) can be synthesized by contacting, within an aqueous medium (M) in which the block (B) formed is not soluble:
- les monomères éthyléniquement insaturés, identiques ou différents, choisis pour la constitution du bloc (B), choisis solubles dans le milieu aqueux (M)  the ethylenically unsaturated monomers, which are identical or different, chosen for the constitution of the block (B), chosen to be soluble in the aqueous medium (M)
- au moins une source de radicaux libres ; et  at least one source of free radicals; and
- un stabilisant réactif qui comprend :  a reactive stabilizer which comprises:
- une chaîne polymère (CP) soluble dans le milieu (M)  a polymer chain (CP) soluble in the medium (M)
- un groupe (G) assurant un caractère vivant et contrôlé à la polymérisation radicalaire de l'étape (E), tel que, par exemple, un groupe porteur d'un groupe thiocarbonylthio -S(C=S)-  a group (G) ensuring a living character and controlled to the radical polymerization of step (E), such as, for example, a group carrying a thiocarbonylthio group -S (C = S) -
De façon générale, les conditions à mettre en œuvre dans les étapes de polymérisation précitées peuvent être celles typiquement mises en œuvre dans les polymérisations radicalaires contrôlées. In general, the conditions to be used in the aforementioned polymerization steps can be those typically used in controlled radical polymerizations.
En particulier, on peut utiliser dans l'étape (E) du procédé de l'invention toute source de radicaux libres connue en soi. Il peut s'agir par exemple d'un des initiateurs suivants : In particular, it is possible to use in step (E) of the process of the invention any source of free radicals known per se. It can be for example one of the following initiators:
- les peroxydes d'hydrogène tels que : l'hydroperoxyde de butyle tertiaire, l'hydroperoxyde de cumène, le t-butyl-peroxyacétate, le t-butyl-peroxybenzoate, le t- butylperoxyoctoate, le t-butylperoxynéodécanoate, le t-butylperoxyisobutarate, le peroxyde de lauroyle, le t-amylperoxypivalte, le t-butylperoxypivalate, le peroxyde de dicumyl, le peroxyde de benzoyle, le persulfate de potassium, le persulfate d'ammonium, - les composés azoïques tels que : le 2-2'-azobis(isobutyronitrile), le 2,2'-azobis(2- butanenitrile), le 4,4'-azobis(4-acide pentanoïque), le 1 ,1 '-azobis(cyclohexane- carbonitrile), le 2-(t-butylazo)-2-cyanopropane, le 2,2'-azobis[2-méthyl-N-(1 ,1 )- bis(hydroxyméthyl)-2-hydroxyéthyl] propionamide, le 2,2'-azobis(2-méthyl-N- hydroxyéthyl]-propionamide, le dichlorure de 2,2'-azobis(N,N'- diméthylèneisobutyramidine), le dichlorure de 2,2'-azobis (2-amidinopropane), le 2,2'- azobis (Ν,Ν'-diméthylèneisobutyramide), le 2,2'-azobis(2-méthyl-N-[1 ,1 -bis (hydroxyméthyl)-2-hydroxyéthyl] propionamide), le 2,2'-azobis(2-méthyl-N-[1 ,1 -bis (hydroxyméthyl)éthyl] propionamide), le 2,2'-azobis[2-méthyl-N-(2-hydroxyéthyl) propionamide], le 2,2'-azobis(isobutyramide) dihydrate, hydrogen peroxides such as tertiary butyl hydroperoxide, cumene hydroperoxide, t-butyl peroxyacetate, t-butyl peroxybenzoate, t-butylperoxyoctoate, t-butylperoxynethodecanoate and t-butylperoxyisobutarate; , lauroyl peroxide, t-amylperoxypivalte, t-butylperoxypivalate, dicumyl peroxide, benzoyl peroxide, potassium persulfate, ammonium persulfate, azo compounds such as: 2-2'-azobis (isobutyronitrile), 2,2'-azobis (2-butanenitrile), 4,4'-azobis (4-pentanoic acid), 1,1 ' azobis (cyclohexane-carbonitrile), 2- (t-butylazo) -2-cyanopropane, 2,2'-azobis [2-methyl-N- (1,1) -bis (hydroxymethyl) -2-hydroxyethyl] propionamide, 2,2'-azobis (2-methyl-N-hydroxyethyl) -propionamide, 2,2'-azobis (N, N'-dimethyleneisobutyramidine) dichloride, 2,2'-azobis dichloride (2 -amidinopropane), 2,2'-azobis (Ν, Ν'-dimethyleneisobutyramide), 2,2'-azobis (2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide) 2,2'-azobis (2-methyl-N- [1,1-bis (hydroxymethyl) ethyl] propionamide) 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) propionamide] 2,2'-azobis (isobutyramide) dihydrate,
- les systèmes redox comportant des combinaisons telles que :  - redox systems with combinations such as:
- les mélanges de peroxyde d'hydrogène, d'alkyle, peresters, percarbonates et similaires et de n'importe lequel des sels de fer, de sels titaneux, formaldéhyde sulfoxylate de zinc ou formaldéhyde sulfoxylate de sodium, et des sucres réducteurs,  mixtures of hydrogen peroxide, alkyl, peresters, percarbonates and the like and any of the iron salts, titanous salts, zinc formaldehyde sulfoxylate or sodium formaldehyde sulphoxylate, and reducing sugars,
- les persulfates, perborate ou perchlorate de métaux alcalins ou d'ammonium en association avec un bisulfite de métal alcalin, tel que le métabisulfite de sodium, et des sucres réducteurs, et  persulfates, perborate or perchlorate of alkali metals or ammonium in combination with an alkali metal bisulfite, such as sodium metabisulphite, and reducing sugars, and
- les persulfates de métal alcalin en association avec un acide arylphosphinique, tel que l'acide benzène phosphonique et autres similaires, et des sucres réducteurs.  alkali metal persulfates in combination with an arylphosphinic acid, such as benzene phosphonic acid and the like, and reducing sugars.
Notamment dans le cas de polymérisation effectuées en milieu aqueux, il peut d'utiliser un amorceur radicalaire de type redox, qui présente l'avantage de ne pas nécessiter un chauffage du milieu réactionnel (pas d'amorçage thermique), ce qui permet de mieux gérer encore l'exothermie de la réaction. In particular, in the case of polymerization carried out in an aqueous medium, it may be used a radical initiator of the redox type, which has the advantage of not requiring heating of the reaction medium (no thermal initiation), which allows better still manage the exotherm of the reaction.
Ainsi, la source de radicaux libres employée peut typiquement être choisie parmi les amorceurs redox classiquement utilisés en polymérisation radicalaire, typiquement ne nécessitant pas de chauffage pour leur amorçage thermique. Il s'agit typiquement d'un mélange d'au moins un agent oxydant avec au moins un agent réducteur. Thus, the source of free radicals employed can typically be selected from redox initiators conventionally used in radical polymerization, typically not requiring heating for their thermal initiation. It is typically a mixture of at least one oxidizing agent with at least one reducing agent.
L'agent oxydant présent dans le système redox est de préférence un agent hydrosoluble. Cet agent oxydant peut par exemple être choisi parmi les peroxydes, tels que : le peroxyde d'hydrogène, l'hydroperoxyde de butyle tertiaire, l'hydroperoxyde de cumène, le t-butyl-peroxyacétate, le t-butyl-peroxybenzoate, le t-butylperoxyoctoate, le t- butylperoxynéodécanoate, le t-butylperoxyisobutarate, le peroxyde de lauroyle, le t- amylperoxypivalte, le t-butylperoxypivalate, le peroxyde de dicumyl, le peroxyde de benzoyle ; le persulfate de sodium, le persulfate de potassium, le persulfate d'ammonium, ou bien encore le bromate de potassium. L'agent réducteur présent dans le système redox est également, de préférence, un agent hydrosoluble. Cet agent réducteur peut typiquement être choisi parmi le formaldéhyde sulfoxylate de sodium (notamment sous sa forme de dihydrate, connue sous le nom de Rongalit ou sous la forme d'un anhydride), l'acide ascorbique, l'acide érythorbique, les sulfites, bisulfites ou métasulfites (sulfites, bisulfites ou métasulfites de métaux alcalins en particulier), les nitrilotrispropionamides, et les aminés et ethanolamines tertiaires (de préférence hydrosolubles). The oxidizing agent present in the redox system is preferably a water-soluble agent. This oxidizing agent may for example be chosen from peroxides, such as: hydrogen peroxide, tertiary butyl hydroperoxide, cumene hydroperoxide, t-butyl peroxyacetate, t-butylperoxybenzoate, t -butylperoxyoctoate, the butylperoxynéodécanoate, t-butylperoxyisobutarate, lauroyl peroxide, t-amylperoxypivalte, t-butylperoxypivalate, dicumyl peroxide, benzoyl peroxide; sodium persulfate, potassium persulfate, ammonium persulfate, or even potassium bromate. The reducing agent present in the redox system is also preferably a water-soluble agent. This reducing agent can typically be selected from sodium formaldehyde sulfoxylate (especially in its dihydrate form, known as Rongalit or in the form of an anhydride), ascorbic acid, erythorbic acid, sulphites, bisulphites or metasulfites (in particular sulphites, bisulphites or metasulfites of alkali metals), nitrilotrispropionamides, and tertiary amines and ethanolamines (preferably water-soluble).
Des systèmes redox possibles comportent des combinaisons telles que :  Possible redox systems include combinations such as:
- les mélanges de persulfates hydrosolubles avec des aminés tertiaires hydrosolubles,  mixtures of water-soluble persulfates with water-soluble tertiary amines,
- les mélanges de bromates hydrosolubles (bromate de métaux alcalins par exemple) avec des sulfites hydrosolubles (sulfites de métaux alcalins par exemple) ,  mixtures of water-soluble bromates (alkali metal bromate, for example) with water-soluble sulphites (alkali metal sulphites, for example),
- les mélanges de peroxyde d'hydrogène, d'alkyle, peresters, percarbonates et similaires et de n'importe lequel des sels de fer, de sels titaneux, formaldéhyde sulfoxylate de zinc ou formaldéhyde sulfoxylate de sodium, et des sucres réducteurs,  mixtures of hydrogen peroxide, alkyl, peresters, percarbonates and the like and any of the iron salts, titanous salts, zinc formaldehyde sulfoxylate or sodium formaldehyde sulphoxylate, and reducing sugars,
- les persulfates, perborate ou perchlorate de métaux alcalins ou d'ammonium en association avec un bisulfite de métal alcalin, tel que le métabisulfite de sodium, et des sucres réducteurs, et  persulfates, perborate or perchlorate of alkali metals or ammonium in combination with an alkali metal bisulfite, such as sodium metabisulphite, and reducing sugars, and
- les persulfates de métal alcalin en association avec un acide  alkali metal persulfates in combination with an acid
arylphosphinique, tel que l'acide benzène phosphonique et autres similaires, et des sucres réducteurs.  arylphosphinic acid, such as benzene phosphonic acid and the like, and reducing sugars.
Un système redox intéressant comprend (et de préférence consiste en) par exemple l'association de persulfate d'ammonium et de formaldéhyde sulfoxylate de sodium. An interesting redox system includes (and preferably consists of), for example, the combination of ammonium persulfate and sodium formaldehyde sulfoxylate.
De façon générale, et en particulier dans le cas de l'utilisation d'un système redox du type persulfate d'ammonium/formaldéhyde sulfoxylate de sodium, il s'avère préférable que le milieu réactionnel de l'étape (E) soit exempt de cuivre. En cas de présence de cuivre, il est en général souhaitable d'ajouter un complexant du cuivre, tel que de l'EDTA. In general, and particularly in the case of the use of a redox system of the ammonium persulfate / sodium formaldehyde sulfoxylate type, it is preferable to that the reaction medium of step (E) is free of copper. In the case of the presence of copper, it is generally desirable to add a copper complexing agent, such as EDTA.
La nature de l'agent de contrôle mis en œuvre dans les étapes de synthèse des blocs (A) et (B) peut quant à elle varier en une large mesure. The nature of the control agent used in the synthesis steps of the blocks (A) and (B) can vary to a large extent.
Selon une variante intéressante, l'agent de contrôle utilisé est un composé porteur d'un groupe thiocarbonylthio -S(C=S)-. Selon un mode de réalisation particulier, l'agent de contrôle peut être porteur de plusieurs groupes thiocarbonylthio. According to an advantageous variant, the control agent used is a compound carrying a thiocarbonylthio group -S (C = S) -. According to a particular embodiment, the control agent may carry several thiocarbonylthio groups.
Il peut éventuellement s'agir d'une chaîne polymère porteuse d'un tel groupe. Ainsi, l'agent de contrôle employé dans l'étape (E2) est un polymère vivant issu de l'étape (E1 ). On peut de même envisager que l'agent de contrôle de l'étape (E1 ) soit issu d'une étape (E0) préalable dans laquelle on a réalisé la polymérisation radicalaire d'une composition comprenant : It may possibly be a polymer chain bearing such a group. Thus, the control agent used in step (E2) is a living polymer resulting from step (E1). It can also be envisaged that the control agent of step (E1) is derived from a previous step (E0) in which the radical polymerization of a composition comprising:
des monomères éthyléniquement insaturés ;  ethylenically unsaturated monomers;
un agent de contrôle de la polymérisation radicalaire comprenant au moins un groupe thiocarbonylthio -S(C=S)- ; et  a radical polymerization control agent comprising at least one thiocarbonylthio group -S (C = S) -; and
un amorceur de la polymérisation radicalaire (source de radicaux libres).  an initiator of radical polymerization (source of free radicals).
Plus généralement, un agent de contrôle adapté à la synthèse du polymère (P) utile selon l'invention répond avantageusement à la formule (A) ci-dessous : More generally, a control agent adapted to the synthesis of the polymer (P) useful according to the invention advantageously corresponds to the formula (A) below:
dans laquelle : in which :
- Z représente : Z represents:
. un atome d'hydrogène,  . a hydrogen atom,
. un atome de Chlore,  . a chlorine atom,
. un radical alkyl éventuellement substitué, aryl éventuellement substitué, . un hétérocycle éventuellement substitué, . an optionally substituted alkyl radical, optionally substituted aryl, . an optionally substituted heterocycle,
. un radical alkylthio éventuellement substitué,  . an optionally substituted alkylthio radical,
. un radical arylthio éventuellement substitué,  . an optionally substituted arylthio radical,
. un radical alkoxy éventuellement substitué,  . an optionally substituted alkoxy radical,
. un radical aryloxy éventuellement substitué,  . an optionally substituted aryloxy radical,
. un radical amino éventuellement substitué,  . an optionally substituted amino radical,
. un radical hydrazine éventuellement substitué,  . an optionally substituted hydrazine radical,
. un radical alkoxycarbonyl éventuellement substitué,  . an optionally substituted alkoxycarbonyl radical,
. un radical aryloxycarbonyl éventuellement substitué,  . an optionally substituted aryloxycarbonyl radical,
. un radical carboxy, acyloxy éventuellement substitué,  . an optionally substituted carboxy, acyloxy radical,
. un radical aroyloxy éventuellement substitué,  . an optionally substituted aroyloxy radical,
. un radical carbamoyie éventuellement substitué,  . an optionally substituted carbamoyl radical,
. un radical cyano,  . a cyano radical,
. un radical dialkyl- ou diaryl-phosphonato,  . a dialkyl- or diaryl-phosphonato radical,
. un radical dialkyl-phosphinato ou diaryl-phosphinato, ou  . a dialkyl phosphinato or diaryl phosphinato radical, or
. une chaîne polymère,  . a polymer chain,
et and
Ri représente :  Ri represents:
. un groupe alkyle, acyle, aryle, aralkyle, alcène ou alcyne éventuellement substitué,  . an optionally substituted alkyl, acyl, aryl, aralkyl, alkene or alkyne group,
. un cycle carboné ou un hétérocycle, saturé ou non, aromatique éventuellement substitué, ou  . a saturated or unsaturated aromatic ring or heterocycle, optionally substituted aromatic, or
. une chaîne polymère.  . a polymer chain.
Les groupes Ri ou Z, lorsqu'ils sont substitués, peuvent l'être par des groupes phényles éventuellement substitués, des groupes aromatiques éventuellement substitués, des cycles carbonés saturés ou non, des hétérocycles saturé ou non, ou des groupes : aikoxycarbonyle ou aryloxycarbonyle (-COOR), carboxy (-COOH), acyloxy (-O2CR), carbamoyie (-CONR2), cyano (-CN), alkylcarbonyle, alkylarylcarbonyle, arylcarbonyle, arylalkylcarbonyle, phtalimido, maleïmido, succinimido, amidino, guanidimo, hydroxy (- OH), amino (-NR2), halogène, perfluoroalkyle CnF2n+i, allyle, époxy, alkoxy (-OR), S- alkyle, S-aryle, des groupes présentant un caractère hydrophile ou ionique tels que les sels alcalins d'acides carboxyliques, les sels alcalins d'acide sulfonique, les chaînes polyoxyde d'alkylène (PEO, POP), les substituants cationiques (sels d'ammonium quaternaires), R représentant un groupe alkyle ou aryle, ou une chaîne polymère. The groups R 1 or Z, when substituted, may be substituted with optionally substituted phenyl groups, optionally substituted aromatic groups, saturated or unsaturated carbon rings, saturated or unsaturated heterocycles, or alkyloxycarbonyl or aryloxycarbonyl groups ( -COOR), carboxy (-COOH), acyloxy (-O2CR), carbamoyl (-CONR2), cyano (-CN), alkylcarbonyl, alkylarylcarbonyl, arylcarbonyl, arylalkylcarbonyl, phthalimido, maleimido, succinimido, amidino, guanidimo, hydroxy (-OH ), amino (-NR2), halogen, perfluoroalkyl C n F 2n + 1, allyl, epoxy, alkoxy (-OR), S-alkyl, S-aryl, groups having a hydrophilic or ionic character such as alkali metal salts of carboxylic acids, alkali metal salts of sulfonic acid, polyalkylene oxide chains (PEO, POP), cationic substituents (quaternary ammonium salts), R representing an alkyl or aryl group, or a polymer chain .
Selon un mode de réalisation particulier, R-ι est un groupe alkyle substitué ou non, de préférence substitué.  According to a particular embodiment, R 1 is a substituted or unsubstituted alkyl group, preferably substituted.
Les groupes alkyle, acyle, aryle, aralkyle ou alcyne éventuellement substitués présentent généralement 1 à 20 atomes de carbone, de préférence 1 à 12, et plus préférentiellement 1 à 9 atomes de carbone. Ils peuvent être linéaires ou ramifiés. Ils peuvent être également substitués par des atomes d'oxygène, sous forme notamment d'esters, des atomes de soufre ou d'azote.  The optionally substituted alkyl, acyl, aryl, aralkyl or alkyne groups generally have 1 to 20 carbon atoms, preferably 1 to 12, and more preferably 1 to 9 carbon atoms. They can be linear or branched. They may also be substituted by oxygen atoms, in particular esters, sulfur or nitrogen atoms.
Parmi les radicaux alkyle, on peut notamment citer le radical méthyle, éthyle, propyle, butyle, pentyle, isopropyle, tert-butyle, pentyle, hexyle, octyle, decyle ou dodécyle.  Among the alkyl radicals, mention may especially be made of the methyl, ethyl, propyl, butyl, pentyl, isopropyl, tert-butyl, pentyl, hexyl, octyl, decyl or dodecyl radical.
Les groupes alcynes sont des radicaux généralement de 2 à 10 atomes de carbone, ils présentent au moins une insaturation acétylénique, tel que le radical acétylenyle.  The alkyne groups are radicals generally of 2 to 10 carbon atoms, they have at least one acetylenic unsaturation, such as the acetylenyl radical.
Le groupe acyle est un radical présentant généralement de 1 à 20 atomes de carbone avec un groupement carbonyle.  The acyl group is a radical generally having from 1 to 20 carbon atoms with a carbonyl group.
Parmi les radicaux aryle, on peut notamment citer le radical phényle, éventuellement substitué notamment par une fonction nitro ou hydroxyle.  Among the aryl radicals, there may be mentioned the phenyl radical, optionally substituted in particular by a nitro or hydroxyl function.
Parmi les radicaux aralkyle, on peut notamment citer le radical benzyle ou phénéthyle, éventuellement substitué notamment par une fonction nitro ou hydroxyle.  Among the aralkyl radicals, mention may especially be made of the benzyl or phenethyl radical, optionally substituted in particular by a nitro or hydroxyl function.
Lorsque Ri ou Z est une chaîne polymère, cette chaîne polymère peut être issue d'une polymérisation radicalaire ou ionique ou issue d'une polycondensation.  When R 1 or Z is a polymer chain, this polymer chain may be derived from a radical or ionic polymerization or from a polycondensation.
Dans le cadre de la présente invention, il est notamment intéressant d'employer à titre d'agents de contrôle des xanthates, des trithiocarbonates, des dithiocarbamates, ou des dithiocarbazates. In the context of the present invention, it is particularly advantageous to use as control agents xanthates, trithiocarbonates, dithiocarbamates, or dithiocarbazates.
Avantageusement, on utilise comme agent de contrôle des composés porteurs d'une fonction xanthate -S(C=S)0-, par exemple porteur d'une fonction O-ethyl xanthate de formule -S(C=S)OCH2CH3, comme par exemple le 0-ethyl-S-(1 -methoxycarbonyl ethyl) xanthate de formule (CH3CH(C02CH3))S(C=S)OEt. Un autre agent de contrôle possible dans l'étape (E) est le dibenzyltrithiocarbonate de formule PhCH2S(C=S)SCH2P (où Ph=phényle). Advantageously, compounds containing a function xanthate -S (C = S) O-, for example bearing an O-ethyl xanthate function of formula -S (C = S) OCH 2 CH 3 , are used as control agent. , for example 0-ethyl-S- (1-methoxycarbonylethyl) xanthate of formula (CH 3 CH (CO 2 CH 3 )) S (C = S) OEt. Another possible control agent in step (E) is dibenzyltrithiocarbonate of formula PhCH 2 S (C = S) SCH 2 P (where Ph = phenyl).
Les polymères (P) utiles selon l'invention comprennent en général uniquement les blocs (B) et (A). Il s'agit typiquement de polymères dibloc (A)-(B), mais des polymères comportant davantage de blocs sont envisageables, notamment des copolymères comportant un bloc long (B) sur lequel sont greffés deux blocs courts ou plus (polymères triblocs de type (A)-(B)-(A) notamment), ou bien encore des copolymères comprenant un bloc espaceur entre le bloc (B) et le bloc (A) variantes qui vous paraissent raisonables ? Certains des polymères utiles selon la présente invention sont des polymères qui, à la connaissance des inventeurs n'ont jamais été décrits par le passé. Polymers (P) useful according to the invention generally comprise only blocks (B) and (A). These are typically diblock polymers (A) - (B), but polymers comprising more blocks are possible, in particular copolymers comprising a long block (B) on which are grafted two or more short blocks (triblock polymers of type (A) - (B) - (A) in particular), or else copolymers comprising a block spacer between the block (B) and the block (A) variants that you think are reasonable? Some of the useful polymers according to the present invention are polymers which, to the knowledge of the inventors, have never been described in the past.
Ces polymères comprennent en particulier les polymères séquencés contenant, de préférence à titre d'uniques blocs : These polymers include in particular block polymers containing, preferably as single blocks:
- au moins un premier bloc pAA au moins majoritairement (et de préférence essentiellement, voire exclusivement) constitué par des unités acide acrylique, de masse moléculaire moyenne en poids entre 500 et 30 000 g/mol, notamment entre 1 000 et 20 000; et  at least a first block at least predominantly (and preferably substantially, or exclusively) constituted by acrylic acid units, of weight average molecular weight between 500 and 30,000 g / mol, in particular between 1,000 and 20,000; and
- un deuxième bloc p( DMA/AMPS) au moins majoritairement (et de préférence essentiellement, voire exclusivement) constitué par un mélange statistique d'unités DMA et AMPS, avec un rapport molaire DMA/AMPS compris entre 60/40 et 90/10, de masse moléculaire en poids supérieure à 150 000 g/mol, typiquement entre 200 000 et 2 000 000 g/mol et notamment entre 250 000 et 750 000 g/mol.  a second p block (DMA / AMPS) at least predominantly (and preferably essentially, if not exclusively) constituted by a statistical mixture of DMA and AMPS units, with a DMA / AMPS molar ratio of between 60/40 and 90/10; having a molecular weight greater than 150 000 g / mol, typically between 200 000 and 2 000 000 g / mol and especially between 250 000 and 750 000 g / mol.
Ces polymères constituent un objet particulier de la présente invention, ainsi que These polymers constitute a particular object of the present invention, as well as
les coulis de ciment pétrolier les comprenant  petroleum cement grouts including them
- les fluides aqueux pour injection sous pression au sein d'une roche pétrolière, notamment les fluides de forage et fluides de fracturation, les comprenant en association avec des particules minérales, ainsi que les blends pour la préparation de ces fluides.. Applications pratiques aqueous fluids for injection under pressure in a petroleum rock, in particular drilling fluids and fracturing fluids, comprising them in association with mineral particles, as well as blends for the preparation of these fluids. Practical applications
Les polymères utiles selon l'invention peuvent être employés dans la quasi-totalité des fluides mis en œuvre en extraction pétrolière et potentiellement sujet à la perte de fluide. Selon un mode de réalisation particulier de l'invention le fluide (F) est un coulis de ciment pétrolier, qui comprend le polymère (P) comme additif. Dans ce cas, le polymère (P), associé aux particules présentes dans ciment, assure l'effet de contrôle du filtrat lors de la cimentation. The polymers useful according to the invention can be used in almost all fluids used in petroleum extraction and potentially subject to fluid loss. According to a particular embodiment of the invention the fluid (F) is a petroleum cement slurry, which comprises the polymer (P) as an additive. In this case, the polymer (P), associated with the particles present in cement, provides the control effect of the filtrate during cementation.
Selon un autre mode de réalisation, le fluide (F) est un fluide de forage ou un fluide de fractu ration, qui comprend le polymère (P) associé à des particules (p). Les particules (p) sont alors le plus souvent introduites conjointement au polymère dans le fluide (F) avant l'injection du fluide. Le polymère assure alors en général une stabilisation de la dispersion des particules dans le fluide (F), en maintenant en suspension dans le fluide au moins une partie des particules (p). Les concentrations en polymère et particules à employer dans ces différents fluides sont à adapter au cas par cas en fonction de l'application visée et de la rhéologie recherchée. According to another embodiment, the fluid (F) is a drilling fluid or a fracturing fluid, which comprises the polymer (P) associated with particles (p). The particles (p) are then most often introduced together with the polymer in the fluid (F) before the injection of the fluid. The polymer then generally ensures a stabilization of the dispersion of the particles in the fluid (F), while maintaining in suspension in the fluid at least a portion of the particles (p). The concentrations of polymer and particles to be employed in these different fluids are to be adapted case by case according to the intended application and the desired rheology.
Différents aspects et avantages de l'invention seront encore illustrés par les exemples ci-après dans lesquels des polymères ont été préparés selon le procédé de l'invention. Various aspects and advantages of the invention will be further illustrated by the following examples in which polymers have been prepared according to the process of the invention.
Exemple 1 : Example 1
Synthèse de copolymères diblocs  Synthesis of diblock copolymers
poly(acide acrylique)-b-poly(N,N-dimethylacrylamide-co-AMPS) 1 .1 : Synthèse de blocs polyfacide acrylique) vivant à terminaision xanthate poly (acrylic acid) -b-poly (N, N-dimethylacrylamide-co-AMPS) 1 .1: Synthesis of acrylic polyfacid blocks) living with terminaision xanthate
(bloc courts A1 à A4) (short block A1 to A4)
Dans un ballon de 250 ml_ à température ambiante, on a introduit 30 g d'acide acrylique, dans un solvant aqueux(à savoir 70 g d'eau distillée pour les blocs A1 -A3 - un mélange de 35 g d'eau distillée et 28 g d'éthanol pour le blocs A4), et du 0-ethyl-S-(1 - methoxycarbonyl ethyl) xanthate de formule (CH3CH(C02CH3))S(C=S)OEt (dans les quantités indiquées donné dans le Tableau 1 ci-dessous, où est également indiqué la valeur de la masse moléculaire ne nombre théorique attendue (Mn, th) calculée par le rapport de la quantité de monomère à la quantité de xanthate) et 312 mg de 2,2'- Azobis(2-methylpropionamidine)di chlorhydrate. Le mélange a été dégazé par bullage d'azote pendant 20 minutes. In a 250 ml flask at room temperature, 30 g of acrylic acid were introduced into an aqueous solvent (ie 70 g of distilled water for A1-A3 blocks - a mixture of 35 g of distilled water and 28 g of ethanol for the A4 block), and 0-ethyl-S- (1-methoxycarbonylethyl) xanthate of formula (CH 3 CH (CO 2 CH 3 )) S (C = S) OEt (in the amounts given in Table 1 below, where is also indicated the value of the expected molecular weight theoretical number (M n , th) calculated by the ratio of the amount of monomer to the amount of xanthate) and 312 mg of 2 2'-Azobis (2-methylpropionamidine) hydrochloride. The mixture was degassed by bubbling nitrogen for 20 minutes.
Le ballon a ensuite été placé dans un bain d'huile thermostaté à 60°C, et le milieu réactionnel a été laissé sous agitation pendant 4 heures à 60°C.  The flask was then placed in an oil bath thermostated at 60 ° C, and the reaction medium was stirred for 4 hours at 60 ° C.
A l'issue de ces quatre heures, la conversion a été déterminée par RMN 1H. At the end of these four hours, the conversion was determined by 1 H NMR.
Une analyse en chromatographie d'exclusion stérique dans un mélange de l'eau et de l'acétonitrile (80/20) additivé de NaN03 (0,1 N) avec un détecteur MALLS dix-huit angles et fournit les valeurs de masse molaire moyenne en poids (Mw) et d'indice de polymolécularité (Mw/Mn) reporté dans le tableau 1 ci-dessous. An analysis in steric exclusion chromatography in a mixture of water and acetonitrile (80/20) additive NaN0 3 (0.1 N) with a detector MALLS eighteen angles and provides molar mass values weight average (M w ) and polymolecularity index (M w / M n ) reported in Table 1 below.
Tableau 1 : blocs A1 -A4 Table 1: Blocks A1-A4
Bloc Mn,th Xanthate Conversion Mw Mw/Mn synthétisé (g) (RMN 1H) (g/mol) Block M n th th Xanthate Conversion M w M w / M n synthesized (g) ( 1 H NMR) (g / mol)
A1 10000 0.624 99.5% 22000 1 .8  A1 10000 0.624 99.5% 22000 1 .8
A2 5000 1 .25 99.7% 10000 1 .7  A2 5000 1 .25 99.7% 10000 1 .7
A3 2500 2.50 99.6% 5000 1 .7  A3 2500 2.50 99.6% 5000 1 .7
A4 1000 6.24 >99.9% 2100 1 .8 1 .2 : Synthèse de copolvmères dibloc à partir des blocs A1 à A5 A4 1000 6.24> 99.9% 2100 1 .8 1 .2: Synthesis of diblock copolymers from blocks A1 to A5
Polymères P1 à P17 Les blocs A1 à A4 préparés comme indiqués dans le paragraphe 1 .1 ont été employés dans leur milieu réactionnel obtenu, sans purification, avec une masse de polymère mA reportée dans le tableau 2 ci-dessous. Le bloc choisi, dans son mélange réactionnel sans purification, a été introduit dans un ballon de 250 mL, à température ambiante, puis on a ajouté (dans des quantités reportées dans le tableau 2 ci-dessous) du N,N- diméthylacrylamide DMA, une solution aqueuse d'AMPS à 50% massique (25% par rapport molaire au quantité de Ν,Ν-diméthylacrylamide), et de l'eau distillée, avec un extrait sec final d'environ 20% massique, et du persulfate d'ammonium en solution aqueuse à 5,0 % en masse. Polymers P1 to P17 Blocks A1 to A4 prepared as indicated in paragraph 1 .1 were used in their reaction medium obtained, without purification, with a mass of polymer m A reported in Table 2 below. The chosen block, in its reaction mixture without purification, was introduced into a 250 ml flask at room temperature, and then NMA (N, N-dimethylacrylamide) was added (in the amounts shown in Table 2 below). an aqueous solution of AMPS at 50% by mass (25% relative to the amount of Ν, Ν-dimethylacrylamide), and distilled water, with a final solids content of approximately 20% by weight, and persulfate of ammonium in aqueous solution at 5.0% by weight.
Le mélange a été dégazé par bullage d'azote pendant 20 minutes. On a ajouté au milieu du formaldéhyde sulfoxylate de sodium, sous forme d'une solution aqueuse à 1 ,0 % en masse, la même masse de cette solution étant introduite que celle de la solution de persulfate d'ammonium (voir Tableau 2).  The mixture was degassed by bubbling nitrogen for 20 minutes. To the medium of sodium formaldehyde sulfoxylate was added in the form of a 1.0% by weight aqueous solution, the same mass of this solution being introduced as that of the ammonium persulfate solution (see Table 2).
On a laissé la réaction de polymérisation se dérouler sans agitation pendant 24 heures à température ambiante (20°C).  The polymerization reaction was allowed to proceed without stirring for 24 hours at room temperature (20 ° C).
A l'issue des 24 heures de réaction, on a mesuré la conversion par RMN 1H (résultats dans le tableau 3). After 24 hours of reaction, the conversion was measured by 1 H NMR (results in Table 3).
Une analyse en chromatographie d'exclusion stérique dans un mélange de l'eau et de l'acétonitrile (80/20 v/v) additivé de NaN03 (0,1 N) avec un détecteur indice de réfraction fournit les valeurs de masse molaire moyenne en nombre (Mn) et d'indice de polymolécularité (Mw/Mn) qui sont répertoriés dans le Tableau 3: Tableau 2: polymères P1 à P17 : quantités de réactifs employés lors de la synthèse An analysis in steric exclusion chromatography in a mixture of water and acetonitrile (80/20 v / v) additive of NaNO 3 (0.1 N) with a refractive index detector provides molar mass values. number average (M n ) and polymolecularity index (M w / M n ) which are listed in Table 3: Table 2: polymers P1 to P17: quantities of reagents used during the synthesis
meau : masse de l'eau distillée ajoutée, à l'exclusion de l'eau ajoutée dans les autres solution m water : mass of distilled water added, excluding added water in other solutions
rripersuif : masse de la solution aqueuse à 5% massique d'ammonium persulfate ajoutée  rripersuif: mass of the 5% by weight aqueous solution of ammonium persulfate added
rrifss : masse de la solution aqueuse à 1 % massique de formaldéhyde sulfoxylate de sodium Tableau 3 : polymères P1 à P17 rri f ss: mass of the 1% by weight aqueous solution of sodium formaldehyde sulfoxylate Table 3: polymers P1 to P17
Exemple 2 (comparatif) : Example 2 (comparative):
Synthèse d'un polymère monobloc poly(N,N-dimethylacrylamide-co-AMPS)  Synthesis of a poly (N, N-dimethylacrylamide-co-AMPS) monoblock polymer
Dans ballon de 250 ml_ à température ambiante, on a introduit 15.3 g de N,N- diméthylacrylamide, 18 g d'AMPS, 75.6 g d'eau distillée, 1.03 g d'une solution éthanolique à 1 % massique de 0-ethyl-S-(1 -methoxycarbonyl ethyl) xanthate de formule (CH3CH(C02CH3))S(C=S)OEt et 6.0 g d'une solution aqueuse à 5% massique de persulfate d'ammonium. Le mélange a été dégazé par bullage d'azote pendant 20 minutes. On a ensuite ajouté 6.0 g d'une solution aqueuse à 1 % massique de formaldéhyde sulfoxylate de sodium. Les deux solutions aqueuses de persulfate d'ammonium et formaldéhyde sulfoxylate de sodium ont été préalablement dégazées par bullage d'azote.In a 250 ml flask at room temperature, 15.3 g of N, N-dimethylacrylamide, 18 g of AMPS, 75.6 g of distilled water, 1.03 g of a 1% by weight ethanolic solution of 0-ethyl- S- (1-methoxycarbonylethyl) xanthate of formula (CH 3 CH (CO 2 CH 3 )) S (C = S) OEt and 6.0 g of a 5% aqueous solution of ammonium persulfate. The mixture was degassed by bubbling nitrogen for 20 minutes. 6.0 g of a 1% by weight aqueous solution of sodium formaldehyde sulfoxylate was then added. The two aqueous solutions of ammonium persulfate and sodium formaldehyde sulfoxylate were degassed beforehand by bubbling with nitrogen.
On a alors laissé la réaction de polymérisation se dérouler sans agitation pendant 24 heures à température ambiante (20°C). The polymerization reaction was then allowed to proceed without stirring for 24 hours at room temperature (20 ° C).
A l'issue des 24 heures de réaction, on a obtenu une conversion de 99.8% en N,N- diméthylacrylamide et de 99.6% en AMPS, telle que déterminée par RMN 1H. At the end of the 24 hours of reaction, a conversion of 99.8% to N, N-dimethylacrylamide and 99.6% to AMPS was obtained, as determined by 1 H NMR.
Une analyse en chromatographie d'exclusion stérique dans l'eau additivé de NaN03 (0,1 N) avec un détecteur indice de réfraction fournit les valeurs de masse molaire moyenne en nombre (Mn) et d'indice de polymolécularité (Mw/Mn) suivants (relative aux étalons PEO): An analysis in steric exclusion chromatography in water with NaNO 3 additive (0.1 N) with a refractive index detector gives the values of the number-average molecular weight (M n ) and of the polymolecularity index (M w / M n ) following (relative to the PEO standards):
Mw = 1 070 000 g/mol M w = 1,070,000 g / mol
Mw/Mn = 2,8. M w / M n = 2.8.
Exemple 3 Example 3
Evaluation des polymères dibloc dans des coulis de ciment  Evaluation of diblock polymers in cement slurries
Les polymères diblocs P1 à P17 préparés dans les exemples 1 et le témoin préparé dans l'exemple 2 ont été utilisés pour réaliser des coulis de ciment pétrolier ayant la formulation suivante :  The diblock polymers P1 to P17 prepared in Examples 1 and the control prepared in Example 2 were used to make petroleum cement slurries having the following formulation:
Eau de ville : City water :
Polymère dibloc (à 20% en solution aqueuse) :  Diblock polymer (20% in aqueous solution):
Agent dispersant (polymélamine sulfonate) (à 50% en solution aqueuse)  Dispersing agent (polymelamine sulfonate) (50% aqueous solution)
Agent retardant (lignosulfonate de calcium)(à 48% en solution aqueuse) Retarding agent (calcium lignosulfonate) (48% in aqueous solution)
Anti-mousse organique : Organic antifoam:
Ciment Dykheroff black label (API Class G) : Dykheroff black label cement (API Class G):
L'agent de contrôle de filtrat est mélangé aux additifs liquides et à l'eau de ville avant incorporation du ciment. La formulation et le test de filtration ont été réalisés selon la norme de l'American Petroleum Institute (API recommended practice for testing well céments 10B, 2nd édition April 2013). The filtrate control agent is mixed with liquid additives and tap water before incorporation of the cement. The formulation and the filtration test were carried out according to the American Petroleum Institute standard (API recommended for testing items 10B, 2nd edition April 2013).
Après mélange et dispersion de l'ensemble des constituants de la formulation, le coulis obtenu a été conditionné à 88°C pendant 20 minutes dans un consistomètre atmosphérique (modèle 1250 fourni par Chandier Engineering Inc.) préalablement stabilisé à cette température, ce qui permet de simuler les conditions subies par le coulis de ciment lors de la descente dans un puits.  After mixing and dispersing all the constituents of the formulation, the slurry obtained was conditioned at 88 ° C. for 20 minutes in an atmospheric consistometer (model 1250 supplied by Chandier Engineering Inc.) previously stabilized at this temperature, which allows to simulate the conditions experienced by the cement grout when descending into a well.
La performance en contrôle de filtrat a été déterminée par une filtration statique à 88°C dans une cellule double ouverture de capacité 175mL équipée de grille métallique 325meshx60mesh (fourni par OFITE Inc., référence 170-45). Les performances des polymères dans les formulations de ciment sont reportées dans le tableau 4 ci-dessous :  The filtrate control performance was determined by static filtration at 88 ° C in a 175mL double-opening cell equipped with 325meshx60mesh metal grid (supplied by OFITE Inc., reference 170-45). The performances of the polymers in the cement formulations are reported in Table 4 below:
Tableau 4 : performances Table 4: Performance
Polymère testé vol API (ml_) Polymer tested vol API (ml_)
P18 54  P18 54
P17 41  P17 41
P16 40  P16 40
P15 45  P15 45
P14 35.8 P14 35.8
P13 37.9  P13 37.9
P12 193 P12 193
P11 1 13  P11 1 13
P10 72  P10 72
P9 66.2  P9 66.2
P8 59  P8 59
P7 70  P7 70
P6 174 P6 174
P5 131  P5 131
P4 67  P4 67
P3 62  P3 62
P2 68  P2 68
P1 62  P1 62
Exemples Comparatifs : Comparative Examples:
655 Polymère de l'exemple 2 655 Polymer of Example 2
Polymère de l'exemple 2 + bloc A2 Polymer of Example 2 + Block A2
435 435
(composition similaire à celle de P8, avec les (composition similar to that of P8, with the
deux blocs non liés) two unbound blocks)

Claims

REVENDICATIONS
'\ - Utilisation, à titre d'agent de contrôle du filtrat dans un fluide (F) injecté sous pression dans une formation souterraine, Use as control agent of the filtrate in a fluid (F) injected under pressure into an underground formation,
où ledit fluide (F) comprend des particules solides (p) et/ou est mis en contact avec des particules solides (p) au sein de la formation souterraine suite à son injection, wherein said fluid (F) comprises solid particles (p) and / or is contacted with solid particles (p) within the subterranean formation following its injection,
d'un polymère séquencé (P) comprenant : a block polymer (P) comprising:
- un premier bloc (A) qui s'adsorbe sur au moins une partie des particules (p); et a first block (A) which adsorbs on at least a portion of the particles (p); and
- un deuxième bloc (B), de composition distincte de celle dudit premier bloc (A), de masse moléculaire moyenne en poids supérieure à 10 000 g/mol, par exemple supérieure à 100 000 g/mol et soluble dans le fluide (F). a second block (B), of a composition different from that of said first block (A), having a weight average molecular weight greater than 10,000 g / mol, for example greater than 100,000 g / mol and soluble in the fluid (F ).
2. - Utilisation selon la revendication 1 , où le fluide (F) injecté comprend le polymère (P) mais ne comprend pas de particules solides (p), et rencontre lesdites particules (p) au sein de la formation souterraine suite à son injection. 2. - Use according to claim 1, wherein the fluid (F) injected comprises the polymer (P) but does not comprise solid particles (p), and meets said particles (p) in the subterranean formation following its injection .
3. - Utilisation selon la revendication 1 , où le fluide (F) injecté comporte avant l'injection au moins une partie des particules (p) associées au polymère (P), le polymère étant avantageusement employé dans ce cas tant qu'agent dispersant et stabilisant de la dispersion des particules (p). 3. - Use according to claim 1, wherein the fluid (F) injected comprises before injection at least a portion of the particles (p) associated with the polymer (P), the polymer being advantageously used in this case as a dispersing agent and stabilizer of the particle dispersion (p).
4. - Utilisation selon l'une des revendications 1 à 3, où le fluide (F) est un fluide aqueux et où le bloc (B) est un bloc constitué au moins majoritairement par des unités monomères choisies dans le groupe consistant en les unités monomères U1 à U5 définies ci-dessous, et les mélanges de ces unités monomères : unités monomères U1 : unités monomères comprenant un groupement fonctionnel acrylamide unités monomères U2 : unités monomères comprenant un groupement fonctionnel acide sulfonique ou sulfonate 4. - Use according to one of claims 1 to 3, wherein the fluid (F) is an aqueous fluid and wherein the block (B) is a block consisting at least predominantly of monomer units selected from the group consisting of units monomers U1 to U5 defined below, and mixtures of these monomer units: monomeric units U1: monomeric units comprising an acrylamide functional group monomeric units U2: monomeric units comprising a functional group sulfonic acid or sulfonate
unités monomères U3 : unités monomères neutres incluant les esters d'acides mono- ou di- carboxyliques [alpha], [betaj-éthyléniquement insaturés avec des alcanediols en C2-C30 ou des polyéthyleneglycol, et les acrylate de tétrahydrofurfuryle, vinyl acétamide, vinyl pyrrolidone, N-vinyl pipéridone, N- vinyl caprolactam, N-vinyl-5-methyl-2-pyrrolidone, N-vinyl-5-ethyl-2-pyrrolidone, N-vinyl-6-méthyl-2-pipéridone, N-vinyl-6-éthyl-2-pipéridone, N-vinyl-7-méthyl-2- caprolactam, N-vinyl-7-ethyl-2-caprolactame. monomer units U3: neutral monomer units including esters of mono- or dicarboxylic acids [alpha], [beta-ethylenically unsaturated with C2-C30 alkanediols or polyethylene glycol, and acrylates of tetrahydrofurfuryl, vinyl acetamide, vinyl pyrrolidone, N-vinylpiperidone, N-vinyl caprolactam, N-vinyl-5-methyl-2-pyrrolidone, N-vinyl-5-ethyl-2-pyrrolidone, N-vinyl-6-methyl- 2-piperidone, N-vinyl-6-ethyl-2-piperidone, N-vinyl-7-methyl-2-caprolactam, N-vinyl-7-ethyl-2-caprolactam.
- unités monomères U4 : unités monomères porteuses de groupements ammonium, incluant les amides d'acides mono- ou di- carboxyliques [alpha], [beta]-éthyléniquement insaturés avec des diamines ayant au moins un groupe aminé primaire ou secondaire ; les Ν,Ν-diallylamines et N,N-diallyl-N- alkylamines. - unités monomères U5 : unités monomères acrylate, porteuses de groupement U4 monomeric units: monomer units carrying ammonium groups, including amides of [alpha], [beta] -ethylenically unsaturated mono- or dicarboxylic acids with diamines having at least one primary or secondary amine group; Ν, Ν-diallylamines and N, N-diallyl-N-alkylamines. U5 monomeric units: acrylate monomer units, group carriers
COOH ou COO" , le bloc (B) pouvant optionnellement comprendre des monomères hydrophobes en faibles proportions, typiquement à raison de 0,05% à 10% en masse par rapport à la masse totale d'unité monomères dans le bloc (B). COOH or COO " , the block (B) may optionally comprise hydrophobic monomers in small proportions, typically in a proportion of 0.05% to 10% by weight relative to the total mass of monomer units in the block (B).
5.- Utilisation selon l'une des revendications 1 ou 4, où le bloc (B) a une masse moléculaire supérieure à 150 000 g/mol, par exemple entre 200 000 à 3 000 000 g/mol. 5. Use according to one of claims 1 or 4, wherein the block (B) has a molecular weight greater than 150 000 g / mol, for example between 200 000 to 3 000 000 g / mol.
6. - Utilisation selon l'une des revendication 1 à 5, où le bloc (A) a une masse moléculaire moyenne en poids entre 500 et 30 000 g/mol 6. - Use according to one of claims 1 to 5, wherein the block (A) has a weight average molecular weight between 500 and 30 000 g / mol
7. - Utilisation selon l'une des revendications 1 à 6 où : - les particules (p) sont des particules de carbonate de calcium ou de ciment ; et le bloc (A) est constitué au moins majoritairement par des unités monomères U5 (avantageusement présentes) et/ou U3 et/ou U6 ; et 7. - Use according to one of claims 1 to 6 wherein: - the particles (p) are particles of calcium carbonate or cement; and the block (A) consists at least predominantly of monomer units U5 (advantageously present) and / or U3 and / or U6; and
le bloc B est constitué au moins majoritairement par des unités U1 et/ou U2 ; ou - les particules (p) sont des particules de carbonate de silice ou de sable ; et  block B consists at least mainly of units U1 and / or U2; or the particles (p) are particles of silica or sand carbonate; and
le bloc (A) est constitué au moins majoritairement par des unités monomères U3 et/ou U4 et/ou U7 ; et the block (A) consists at least predominantly of monomer units U3 and / or U4 and / or U7; and
le bloc B est constitué au moins majoritairement par des unités U1 et/ou U2 et/ou U5 ; ou block B is constituted at least mainly by units U1 and / or U2 and / or U5; or
- les particules (p) sont des particules d'argile ; et the particles (p) are clay particles; and
le bloc (A) est constitué au moins majoritairement par des unités monomères U4 et/ou U6 ; et the block (A) consists at least predominantly of monomer units U4 and / or U6; and
le bloc B est constitué au moins majoritairement par des unités U1 et/ou U2 ; ou  block B consists at least mainly of units U1 and / or U2; or
- les particules (p) sont des particules de noir de carbone ; et the particles (p) are particles of carbon black; and
le bloc (A) est constitué au moins majoritairement par des unités monomères hydrophobes U8; et the block (A) consists at least predominantly of U8 hydrophobic monomer units; and
le bloc B est constitué au moins majoritairement par des unités U1 et/ou U2 et/ou U5 ; où :  block B is constituted at least mainly by units U1 and / or U2 and / or U5; or :
o les unités monomères U1 à U5 sont telles que définies dans la revendication 4 ;  the monomer units U1 to U5 are as defined in claim 4;
o les unités monomères U6 sont des unités monomères porteuses de groupements phosphate, phosphonate ou phosphinate, sous forme d'acide libre et/ou sous forme saline ,  the monomeric units U6 are monomer units carrying phosphate, phosphonate or phosphinate groups, in free acid form and / or in saline form,
o les unités monomères U7 sont des unités (méth)acrylate fonctionnalisé par des polydimethylsiloxanes  the monomeric units U7 are (meth) acrylate units functionalized with polydimethylsiloxanes
o les unités monomères U8 sont des unités hydrophobes incluant notamment les esters d'acides mono ou di-carboxylique [alpha], [beta]- éthyléniquement insaturés avec des alcools en C1 -C20, les unités monomères vinylaromatiques comme le styrène par exemple, et les unités monomères fluorés.  the monomeric units U8 are hydrophobic units including, in particular, esters of mono or di-carboxylic acids [alpha], [beta] -ethylenically unsaturated with C 1 -C 20 alcohols, vinylaromatic monomer units, for example styrene, and fluorinated monomer units.
8. - Utilisation selon l'une des revendications 1 à 7 où le fluide (F) est un coulis de ciment pétrolier, qui comprend le polymère (P) comme additif. 8. - Use according to one of claims 1 to 7 wherein the fluid (F) is a slurry of petroleum cement, which comprises the polymer (P) as an additive.
9. - Utilisation selon la revendication 8, où : 9. - Use according to claim 8, wherein:
- le bloc (B) comprend des unités monomères U1 comprenant un groupement fonctionnel acrylamide, notamment des unités diméthylacrylamide DMA, et optionnellement des unités U2 comprenant un groupement fonctionnel acide sulfonique ou sulfonate, notamment des unités acide acrylamidométhylpropanesulfonique (AMPS) ; the block (B) comprises monomeric units U1 comprising an acrylamide functional group, especially dimethylacrylamide DMA units, and optionally units U2 comprising a sulphonic acid or sulphonate functional group, especially acrylamidomethylpropanesulphonic acid (AMPS) units;
et and
- le bloc (B) a une masse moléculaire moyenne en poids comprise entre 150 000 et 750 000 g/mol, de préférence entre 200 000 et 700 000 g/mol.  the block (B) has a weight-average molecular weight of between 150,000 and 750,000 g / mol, preferably between 200,000 and 700,000 g / mol.
10. - Utilisation selon l'une des revendications 1 à 7 où le fluide (F) est un fluide de forage ou un fluide de fracturation, qui comprend le polymère (P) associé à des particules10. - Use according to one of claims 1 to 7 wherein the fluid (F) is a drilling fluid or a fracturing fluid, which comprises the polymer (P) associated with particles
(P)- (P) -
1 1 . Utilisation selon l'une des revendications 1 à 10, où le polymère (P) est un polymère préparé par polymérisation radicalaire contrôlée. 1 1. Use according to one of claims 1 to 10, wherein the polymer (P) is a polymer prepared by controlled radical polymerization.
12. Polymère adapté à titre d'additif de contrôle du filtrat qui comprend : 12. Suitable polymer as filtrate control additive which comprises:
- au moins un premier bloc pAA au moins majoritairement constitué par des unités acide acrylique, de masse moléculaire moyenne en poids entre 500 à 30 000 g/mol;  at least one first block pAA at least predominantly constituted by acrylic acid units, of weight average molecular weight between 500 and 30,000 g / mol;
et  and
- un deuxième bloc p(DMA AMPS) au moins constitué par un mélange statistique d'unités DMA et AMPS, avec un rapport molaire DMA/AMPS compris entre 60/40 et 90/10, et de masse moléculaire en poids supérieure à 100 000 g/mol12. Polymère selon la revendication 1 1 , qui est un polymère dibloc ne comprenant que les blocs pAA et p(DMA/AMPS).  a second p block (DMA AMPS) at least consisting of a statistical mixture of DMA and AMPS units, with a DMA / AMPS molar ratio of between 60/40 and 90/10, and a molecular weight greater than 100,000 g / mol12. Polymer according to claim 11, which is a diblock polymer comprising only the pAA and p (DMA / AMPS) blocks.
13. Coulis de ciment pétrolier comprenant un polymère selon la revendication 12. 13. A petroleum cement grout comprising a polymer according to claim 12.
14. Fluide aqueux pour injection sous pression au sein d'une roche pétrolière, notamment fluide de forage ou fluide de fracturation, comprenant des particules minérales associées à un polymère selon la revendication 12. 14. Aqueous fluid for injection under pressure in a petroleum rock, particularly drilling fluid or fracturing fluid, comprising mineral particles associated with a polymer according to claim 12.
15. Mélange (« blend ») pour la préparation d'un fluide selon la revendication 14, comprenant un mélange de particules minérales et d'un polymère selon la revendicationMixture for the preparation of a fluid according to claim 14, comprising a mixture of mineral particles and a polymer according to claim
12. 12.
EP14780519.6A 2013-10-04 2014-10-03 Block polymers for fluid loss control Ceased EP3052579A1 (en)

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