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EP2563820A1 - Polymères vinyliques synthétiques dégradables hydrosolubles et procédés associés - Google Patents

Polymères vinyliques synthétiques dégradables hydrosolubles et procédés associés

Info

Publication number
EP2563820A1
EP2563820A1 EP11720827A EP11720827A EP2563820A1 EP 2563820 A1 EP2563820 A1 EP 2563820A1 EP 11720827 A EP11720827 A EP 11720827A EP 11720827 A EP11720827 A EP 11720827A EP 2563820 A1 EP2563820 A1 EP 2563820A1
Authority
EP
European Patent Office
Prior art keywords
water
group
poly
degradable synthetic
soluble degradable
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.)
Withdrawn
Application number
EP11720827A
Other languages
German (de)
English (en)
Inventor
Alexander Bismarck
Emilia M. Kot
Rajesh K. Saini
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.)
Halliburton Energy Services Inc
Original Assignee
Halliburton Energy Services Inc
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
Priority claimed from US12/771,961 external-priority patent/US9334338B2/en
Priority claimed from US12/771,973 external-priority patent/US8772205B2/en
Application filed by Halliburton Energy Services Inc filed Critical Halliburton Energy Services Inc
Publication of EP2563820A1 publication Critical patent/EP2563820A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/04—Polymerisation in solution
    • C08F2/10—Aqueous solvent
    • 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
    • C08F4/00—Polymerisation catalysts
    • C08F4/40—Redox systems
    • 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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/50—Partial depolymerisation
    • 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
    • C09K8/66—Compositions based on water or polar solvents
    • C09K8/68—Compositions based on water or polar solvents containing organic 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
    • C09K8/62—Compositions for forming crevices or fractures
    • C09K8/66—Compositions based on water or polar solvents
    • C09K8/68—Compositions based on water or polar solvents containing organic compounds
    • C09K8/685—Compositions based on water or polar solvents containing organic compounds containing cross-linking agents
    • 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
    • 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
    • C09K8/887—Compositions based on water or polar solvents containing organic compounds macromolecular compounds containing cross-linking 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
    • C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
    • C08F2800/10—Copolymer characterised by the proportions of the comonomers expressed as molar percentages
    • 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
    • C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
    • C08F2800/20—Copolymer characterised by the proportions of the comonomers expressed as weight or mass percentages
    • 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
    • C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
    • C09K2208/28—Friction or drag reducing additives

Definitions

  • the present invention relates to water-soluble degradable synthetic vinyl polymers and methods of use thereof in subterranean applications. More specifically, at least in some embodiments, the present invention relates to water-soluble degradable synthetic vinyl polymers having at least one labile group in the backbone of the polymer, and methods of use thereof in subterranean applications.
  • Water-soluble polymers are used in a wide range of industries and products. For example, they may be used as rheology modifiers, stabilizers, and emulsifiers in a variety of products. They are also used in detergents, shampoos, food products, skin lotions, textiles, paints and in the pharmaceutical and oil industry as viscosifiers, flocculants, drag reducing agents, or mobility control fluids. Additionally, water-soluble polymers play an important role in the production of oil and gas. They are used in treatment fluids in various applications such as fracturing, drilling, completion, and work-over applications. Oftentimes, such water-soluble polymers are used as viscosifiers in such application.
  • these subterranean treatment fluids comprise viscosifying agents that comprise natural polysaccharides such as guar, cellulose, xanthan, and the like or water- soluble polymers synthetic polymers that have hydrocarbon backbones, which are generally thought to not be degradable due to their resistance to hydrolysis, oxidative cleavage, temperature or enzymatic attack.
  • the polymer In these subterranean applications, it is preferable for the polymer to be removed from the formation after its use has been exploited.
  • aqueous crosslinked gels that are generally prepared from viscosifying agents are used to fracture formations and transport proppant into those fractures. After placement of the proppant in the fracture(s), it is preferable for the polymer that made up the crosslinked gel to be broken in some way for recovery of a lower viscosity fluid.
  • oxidative breakers or enzymes is a common method that is used to break such polymers to reduce the viscosity of the fluid for recovery.
  • Oxidative breakers may be dissolved in the fluid, but may be lost due to fluid loss as the gel loses water into the porous oil-containing rock of the formation. To circumvent this type of problem, an excess of the oxidative breakers may be used or a fluid loss control agent may be used, which may not be desirable. In some instances, the addition of an oxidative breaker may prematurely decrease the viscosity of the fluid, and thus more polymer may be needed to transport the proppants (which is undesirable).
  • Enzymes are specific to the substrates in which they are effective and there is a diffusion limitation on the movement of enzymes through a crosslinked gel system. Enzymes also have a narrow temperature and pH range where they are effective.
  • Enzymes lose their activity as temperature is raised and most of the enzymes are ineffective above 60°C. Enzymes are also ineffective at extreme pH values and oftentimes work best under neutral conditions. Most of the fluids used in oil-field applications have a pH of 8 and above where the effectiveness of enzymes is low. Furthermore, oxidative breakers may be dissolved in the fluid, but may be lost due to fluid loss as the gel loses water into the porous oil-containing rock of the formation.
  • an excess of oxidants may be used or a fluid loss control agent may be used.
  • the use of enzymes and oxidants and enzymes may not guarantee the complete degradation of the polymer system, irrespective of the use of additional fluid loss control agents.
  • the incomplete degradation of the polymer system used can lead to deposition of polymeric materials onto the oil-bearing rock surfaces within the formation, eventually impeding production. Additionally, an incomplete degradation can lead to an ineffective reduction in the viscosity of the fracturing fluid to the level needed to deposit the proppant and return the fluid back to the surface.
  • the present invention relates to water-soluble degradable synthetic vinyl polymers and methods of use thereof in subterranean applications. More specifically, the present invention relates to water-soluble degradable synthetic vinyl polymers having at least one labile group in the backbone of the polymer, and methods of use thereof in subterranean applications.
  • a water-soluble degradable synthetic vinyl polymer with labile group in its backbone made by a redox polymerization, the redox polymerization reaction comprising these reactants: a macroinitiator that comprises a labile link, an oxidizing metal ion, and a vinyl monomer.
  • the present invention provides a micelle having an outer layer comprising a water-soluble degradable synthetic vinyl polymer with labile group in its backbone and an enclosed chemical.
  • the present invention provides an emulsion comprising an external phase, an internal phase, and an emulsion stabilizer that comprises a water- soluble degradable synthetic vinyl polymer with a labile group in its backbone.
  • the present invention provides a process for polymerizing one or more vinyl monomers to form a water-soluble degradable synthetic vinyl polymer, the process comprising: contacting the vinyl monomer with a macroinitiator comprising a labile group and an oxidizing metal ion under redox polymerization conditions to produce a water-soluble degradable synthetic vinyl polymer with a labile group in its backbone.
  • the present invention provides a subterranean treatment fluid comprising: an aqueous fluid; and a water-soluble degradable synthetic vinyl polymer having a labile link in its backbone.
  • the present invention provides a method comprising: providing a treatment fluid comprising a water-soluble degradable synthetic vinyl polymer having a labile link in its backbone; and placing the treatment fluid in a subterranean formation.
  • the invention also provides the use of a polymer according to the invention as an emulsion stabiliser, to form a micelle, or in a subterranean treatment fluid.
  • Figure 1 illustrates a stable emulsion formed with a water-soluble degradable synthetic vinyl polymer of the present invention.
  • Figure 2A is an H 1 - NMR spectrum of L-cystine recorded in D 2 0.
  • Figure 2B is an H 1 - NMR spectra of PAM initiated from L-cystine recorded in D20.
  • Figure 2C is a structure of L-cystine and PAM initiated from L-cystine.
  • Figure 3 shows the relative viscosity of the PAM initiated from L-cystine after addition of DL-threitol over time.
  • Figures 4A, 4B and 4C show H'-NMR spectra of VA-086, commercial poly(acrylamide) and poly(acrylamide) initiated by redox initiation using the Ce(IV) V A-086 redox pair were recorded in D 2 0.
  • Figure 5 is a DSC thermogram relating to a DSC analysis of PAM with azo-functionalities in the backbone.
  • Figures 7A and 7B are H'-NMR spectra of poly(acrylonitrile) and poly(acrylamide)-block-poly(acrylonitrile) synthesized using poly(acrylamide) with thermo- sensitive azo groups in the backbone.
  • Figure 8 illustrates a GPC chromatogram of PAM containing azo groups before and after being subjected to 86°C for various times as described in the Examples section.
  • Figure 9 illustrates the percentage of drag reduction as a function of polymer concentration for both PAM initiated from PEO and PAM with azo groups built in the polymer backbone as described in the Examples section.
  • Figure 10 is an FT-IR spectra of poly(caprolactone) diol, poly(acrylamide) and their copolymers.
  • Figure 1 1 contains four H'-NMR spectra of (a) poly(caprolactone) diol 530 in d 6 -acetone, (b) poly(acryl amide) in D 2 0, (c) poly(acrylamide-co-caprolactone) sample 2 in D 2 0, and (d) chemical structure of poly(acrylamide-co-caprolactone).
  • Figures 12A-12E illustrate emulsions as described in the Examples section.
  • the present invention relates to water-soluble degradable synthetic vinyl polymers and methods of use thereof in subterranean applications. More specifically, the present invention relates to water-soluble degradable synthetic vinyl polymers having at least one labile group in the backbone of the polymer, and methods of use thereof in subterranean applications.
  • water-soluble degradable synthetic vinyl polymers and methods of the present invention are discussed or eluded to herein, one advantage is that these water-soluble degradable synthetic vinyl polymers can be tailored to degrade at a desired point in time and/or under desired conditions (e.g., downhole conditions), taking into account the conditions encountered in a given subterranean application.
  • desired conditions e.g., downhole conditions
  • the degradabihty of the water-soluble degradable synthetic vinyl polymers may be tailored for wells of different temperature conditions from room temperature to very high temperature. This allows for relatively complete degradabihty of the polymer when used downhole, resulting in less potential for formation damage.
  • the water-soluble degradable synthetic vinyl polymers of the present invention degrade into smaller pieces that are much more soluble in water and may be produced back easily, and therefore, are believed to not accumulate or plug the formation. Further, these water-soluble degradable synthetic vinyl polymers may be crosslinked if desired to provide increased viscosity for some subterranean treatment fluids, e.g., fracturing fluids, "frac-pack" fluids, gravel packing fluids, fluid loss control pills, friction reducers, viscous sweeps, fluid loss particles, rheological modifiers, and the like. Additionally, it is believed that these polymers do not present the same sort of impurity deposition issues that natural polymers can. A further advantage is that filter cakes formed by these polymers can self destruct.
  • treatment refers to any subterranean operation that uses a fluid in conjunction with a desired function and/or for a desired purpose.
  • treatment does not imply any particular action by the fluid or any particular component thereof.
  • degradation and/or “degradable” refer to the conversion of materials into smaller components, intermediates, or end products.
  • the water-soluble degradable synthetic vinyl polymers of the present invention comprise at least one labile link in their polymer backbone that can be tailored to make the polymers degrade at a desired time and/or at desired conditions.
  • the term "water- soluble degradable synthetic vinyl polymer” as used herein refers to a synthetic vinyl polymer that has at least one labile link in its backbone structure that imparts degradability to the synthetic vinyl polymer.
  • the backbone structures of the water-soluble degradable synthetic vinyl polymers of the present invention are formed from vinyl monomers.
  • vinyl monomer refers to a monomer that has a double bond that is capable of free radical polymerization. Suitable examples include, but are not limited to, acrylamide and vinyl monomers.
  • Suitable monomers may include, but are not limited to, acrylamide, vinyl acetate, 2-acrylamido-2-methylpropane sulfonic acid, N,N-dimethylacrylamide, vinyl pyrrolidone, dimethylaminoethyl methacrylate, acrylic acid, dimethylaminopropylmethacrylamide, vinyl amine, vinyl acetate, trimethylammoniumethyl methacrylate chloride, methacrylamide, hydroxyethyl acrylate, vinyl sulfonic acid, vinyl phosphonic acid, vinylbenzene sulfonic acid, methacrylic acid, vinyl caprolactam, N- vinylformamide, diallyl amine, ⁇ , ⁇ -diallylacetamide, dimethyldiallyl ammonium halide, itaconic acid, styrene sulfonic acid, methacrylamidoethyltrimethyl ammonium halide, quaternary salt derivatives of acrylamide, and quaternary salt derivative
  • labile groups into the polymer backbone of the polymer allows tailoring of the degradation condition and kinetics. Multiple labile links may be present due to termination of the polymerization by disproportionation.
  • a variety of labile groups can be included in the backbone for various conditions. For example, an amide group in the backbone will give high temperature stability. An ester group in the backbone will give slightly less stability at higher temperatures than an amide group. Groups can also be added in the backbone to degrade at very low temperatures for application in low temperature wells. Incorporation of orthoester group, for example, in the backbone will give stability at high pH (>8) and degrade quickly at low pH ( ⁇ 8). Similarly acetal, carbonate, and other labile groups can be included to get the desired degradable properties. Polymers with these sorts of groups should degrade to small polymers that should not accumulate, for example, in aquatic species such as shrimp or fish.
  • These labile links may comprise any suitable labile group that is sufficiently water soluble. These include, but are not limited to, ester groups, amide groups, carbonate groups, azo groups, disulfide groups, orthoester groups, acetal groups, etherester groups, ether groups, silyl groups, phosphazine groups, urethane groups, esteramide groups, etheramide groups, anhydride groups, and any derivative or combination thereof.
  • the labile links may be derived from oligomeric or short chain molecules that include, but are not limited to, poly( anhydrides); poly(orthoesters); orthoesters; poly(lactic acids); poly(glycolic acids); poly(caprolactones); poly(hydroxybutyrates); polyphosphazenes; poly(carbonates); polyacetals; polyetheresters; polyesteramides; polycyanoacrylates; polyurethanes; polyacrylates; any derivative, copolymer, or combination thereof.
  • the labile links may be derived from a hydrophilic polymeric block comprising at least one compound selected from the group consisting of: a poly(alkylene glycol); a poly(alcohol) made by the hydrolysis of poly(vinyl acetate); poly(vinyl pyrrolidone); a polysaccharide; a chitin; a chitosan; a protein; a poly( amino acid); a poly(alkylene oxide); a poly(amide); a poly(acid); a polyol; and any derivative, copolymer, or combination thereof.
  • a hydrophilic polymeric block comprising at least one compound selected from the group consisting of: a poly(alkylene glycol); a poly(alcohol) made by the hydrolysis of poly(vinyl acetate); poly(vinyl pyrrolidone); a polysaccharide; a chitin; a chitosan; a protein; a poly( amino acid
  • azo-based labile groups may be preferred because of their thermal, chemical, photochemical, and biological properties.
  • Aromatic azo-groups confer biodegradability.
  • Aliphatic azo-groups are thermally cleavable creating free radicals.
  • redox polymerization is the preferred mechanism.
  • These labile links are incorporated within the backbone structure of the polymer through suitable redox polymerization reactions.
  • Macroinitiators i.e., reducing agents that comprise the labile links
  • the polymerization proceeds through a redox initiated free radical polymerization of the vinyl monomers with the incorporation of at least one macroinitiator into the polymer backbone.
  • multiple macroinitiators may be incorporated into a polymer molecule, resulting in the presence of at least one labile link in the polymer backbone.
  • the redox polymerization method can be tuned to achieve the desired molecular weight by controlling the time, concentration of the monomers, and methodology, for example, by using micellar polymerization. Examples of achievable molecular weights range from about 500,000 to about 15,000,000 or higher for some polymers.
  • the polymerization can be carried out at low temperatures, and second, the polymerization gives high molecular weight polymers at a high yield, resulting in polymers having suitable molecular weights for subterranean applications. It is believed that these advantages are due to the very short induction period of the oxidation pair and low activation energy associated with the reaction (e.g., 40-80kJmor').
  • Another potential advantage is that a wide array of oxidizing ions and reducing agents can be used, which provides a range of options to incorporate any desired degradable reducing agent. This way, high molecular weight polymers can be produced with tailored degradability.
  • an oxidizing metal ion is used to activate the macroinitiator to create the radical, (such as water-soluble cerium (IV), manganese (III), copper (II), vanadium (V), cobalt (III), chromium(VI), and iron (III) and reducing agents (such as alcohols, diols, aldeydes, amines, acids, and amides) generate free radicals, which initiate polymerization. If using chromium, one should be mindful of using a high concentration, and the potential for toxicity concerns to arise.
  • the reducing agent also comprises the labile group, and at least two reducing groups.
  • the reducing groups comprise hydroxides, aldehydes, amines, or acids, in the molecule at two ends of the macroinitiator to incorporate the labile group in the backbone.
  • the labile groups that we described before should have these types of groups at the end to make them behave as macroinitiators.
  • Nonlimiting examples of suitable macroinitiators comprising labile groups include poly(caprolactone)diol (Formula 1 below), which has ester groups that hydrolyze to provide degradability; 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)priopionamide] (Formula 2 below), which has an amide group that provides degradability; and L-cystine (Formula 3), which has a disulfide link, which provides degradability.
  • the resultant water-soluble degradable synthetic vinyl polymer can degrade by an action chosen from the group consisting of: oxidation, reducing agent, photo-degradation, thermal degradation, hydrolysis, and microbial degradation.
  • the rates at which the water-soluble degradable synthetic vinyl polymers of the present invention degrade are dependent on at least the type of labile group, composition, sequence, length, molecular geometry, molecular weight, stereochemistry, hydrophilicity, hydrophobicity, and additives.
  • the environment to which the degradable water-soluble degradable synthetic vinyl polymer is subjected may affect how it degrades, e.g., temperature, presence of moisture, oxygen, microorganisms, enzymes, pH, and the like.
  • These water-soluble degradable synthetic vinyl polymers of the present may be crosslinked.
  • suitable crosslinking agents include metal crosslinking agent (e.g., Zr ion, Ti ion, Al ion, Cr ion and B ion).
  • the preferred crosslinking agent may be determined by the type of functional groups present in the polymer. A carboxylate labile link would dictate that Zr ion and/or Al ion may be preferred. Hydroxyl groups dictate the preferred use of Zr ions and/or B ions.
  • covalent crosslinking can also be achieved. This may be accomplished by using reactive bifunctional compounds to crosslink the polymer. Suitable reactive bifunctional compounds include, but are not limited to, epichlorohydrin and glyoxal.
  • the water-soluble degradable synthetic vinyl polymers of the present invention may be used to form micelles for the encapsulation of certain chemicals, such as oxidizers, chelators, activators, acid-precursors, and the like, for a delayed release delivery.
  • any chemical included within the micelle is referred to as "enclosed chemical.”
  • a micelle may comprise an outer surface that comprises a water-soluble degradable synthetic vinyl polymer of the present invention and an enclosed chemical.
  • Such micelles may be useful in the delayed delivery of the enclosed chemical to a desired application.
  • the aqueous treatment fluids of the present invention generally comprise an aqueous fluid, and a water-soluble degradable synthetic vinyl polymer of the present invention that comprises a labile link in the backbone.
  • These fluids may be used in any applicable subterranean treatment application.
  • Such subterranean treatments include, but are not limited to, stimulation treatments (e.g., fracturing treatments, acidizing treatments, etc.) and completion operations. They may also be used as gelling agents in some fluids, for example, in gelled fluid pills that are used downhole (e.g., fluid loss pills).
  • Fluids incorporating the water-soluble degradable synthetic vinyl polymers of the present invention should degrade under downhole conditions.
  • Suitable aqueous fluids that may be used in the present invention include, but are not limited to, fresh water, salt water, brine, seawater, or any combination thereof.
  • the aqueous fluid used may be from any source, provided it does not contain an excess of compounds that may adversely affect the other components used in accordance with this invention or the subterranean formation.
  • the water-soluble degradable synthetic vinyl polymers of the present invention should reduce energy losses due to friction in the aqueous treatment fluids of the present invention.
  • the water-soluble degradable synthetic vinyl polymer of the present invention may reduce energy losses during introduction of the aqueous treatment fluid into a well bore due to friction between the aqueous treatment fluid in turbulent flow and the formation and/or tubular good(s) (e.g., a pipe, coiled tubing, etc.) disposed in the well bore.
  • the water-soluble degradable synthetic vinyl polymers of the present invention should have a molecular weight sufficient to provide a desired level of viscosity, friction reduction, and the like.
  • the weight average molecular weight of the friction reducing copolymers may be in the range of from about 2,5000,000 to about 20,000,000, as determined using intrinsic viscosity measurements.
  • the water-soluble degradable synthetic vinyl polymers of the present invention should be included in the aqueous treatment fluids of the present invention in an amount sufficient to provide the desired viscosity, reduction of friction, etc.
  • a water-soluble degradable synthetic vinyl polymer of the present invention may be present in an amount in the range of from about 0.01% to about 10% by weight of the aqueous treatment fluid.
  • a water-soluble degradable synthetic vinyl polymer of the present invention may be present in an amount in the range of from about 0.025% to about 4% by weight of the aqueous treatment fluid.
  • a friction reduction application generally a longer polymer that can absorb the turbulence in the water thereby reducing friction is advisable.
  • Low molecular weight polymers are not as effective in most instances. However, when the water-soluble degradable synthetic vinyl polymers of the present invention are used in hydraulic fracturing applications, fluid loss control pills, or other applications smaller molecular weight polymers may be sued as they can be crosslinked.
  • an amount of the water-soluble degradable synthetic vinyl polymers of the present invention to include may be about 0.1 gal/Mgal to about 5 gal/Mgal concentration (about 0.01% to about 0.5%), for example, in slick water fracs.
  • Additional additives may be included in the aqueous treatment fluids of the present invention as deemed appropriate by one of ordinary skill in the art, with the benefit of this disclosure.
  • additives include, but are not limited to, corrosion inhibitors, proppant particulates, acids, fluid loss control additives, surfactants, breakers, iron-control inhibitors, scale inhibitors, and clay stabilizers.
  • an acid may be included in the aqueous treatment fluids, among other things, for a matrix or fracture acidizing treatment.
  • proppant particulates may be included in the aqueous treatment fluids to prevent the fracture from closing when the hydraulic pressure is released.
  • the water-soluble degradable synthetic vinyl polymers may be used in a fracturing treatment.
  • a fracturing fluid comprising a water-soluble degradable synthetic vinyl polymer of the present invention is placed in a subterranean formation at a pressure sufficient to create or enhance a fracture in the subterranean formation.
  • the water-soluble degradable synthetic vinyl polymer may be used in an amount of 0.1 about to about 10% by weight.
  • the polymer may be crosslinked with any suitable metal ion or other crosslinking material.
  • the water-soluble degradable synthetic vinyl polymers may be used in a subterranean treatment fluid as a friction reducer.
  • the water-soluble degradable synthetic vinyl polymers may be used in a subterranean treatment fluid as a viscosifier, for example, in a fluid loss pill or a completion fluid.
  • a fluid loss pill the polymer may be crosslinked to achieve a stiff gel thereby not allowing it to penetrate the formation and damage the well bore permeability.
  • the present invention provides a water-soluble degradable synthetic vinyl polymer made by a redox polymerization comprising a reducing agent with a labile group, an oxidizing agent, and a monomer.
  • the present invention provides a process for polymerizing one or more vinyl monomers to form a water-soluble degradable synthetic vinyl polymer, the process comprising: contacting the vinyl monomer or monomers with an oxidizing agent and a macroinitiator comprising a labile link.
  • the present invention provides a subterranean treatment fluid comprising: an aqueous fluid; and a water-soluble degradable synthetic vinyl polymer.
  • the present invention provides a method comprising: providing a treatment fluid comprising a water-soluble degradable synthetic vinyl polymer; and placing the treatment fluid in a subterranean formation.
  • the present invention provides a method comprising: providing a fracturing fluid comprising a water-soluble degradable synthetic vinyl polymer; and placing the fracturing fluid in a subterranean formation at a pressure sufficient to create or enhance a fracture therein.
  • the water-soluble degradable synthetic vinyl polymers of the present invention may be used in a completion fluid, a gravel packing fluid or a drilling fluids (e.g., as a rheology modifier).
  • the water-soluble degradable synthetic vinyl polymers of the present invention may be used in a concentrated form as a diverter.
  • the water-soluble degradable synthetic vinyl polymers of the present invention may be useful in water purification applications.
  • the water-soluble degradable synthetic vinyl polymer may be used in a cementing application to temporarily suspend the cement particles while the cement sets.
  • the water-soluble degradable synthetic vinyl polymers may be used in such cementing operations to control settling and modify the rheology.
  • the water-soluble degradable synthetic vinyl polymers may be used as a rheology modifier in a drilling fluid.
  • the water-soluble degradable synthetic vinyl polymers may be used to make self-degrading fluid loss particles by crosslinking.
  • the water-soluble degradable synthetic vinyl polymers may be used to make self-degrading diverting particles.
  • the water-soluble degradable synthetic vinyl polymers may be used in water purification.
  • the water- soluble degradable synthetic vinyl polymers may be used as chelators for undesired metal ions in fluids that may adversely affect their performance for their desired use.
  • the water-soluble degradable synthetic vinyl polymers may be used in flocculation applications for water treatments and other applications.
  • the water-soluble degradable synthetic vinyl polymers may be used to encapsulate a reactive chemical in the polymer shell.
  • the water-soluble degradable synthetic vinyl polymers of the present invention may be used as emulsion stabilizers.
  • Sample 4 in Figure 1 illustrates a stable emulsion formed with a water water-soluble degradable synthetic vinyl polymer of the present invention as compared to another emulsion stabilized by PAM.
  • an emulsion may comprise an external phase, an internal phase, and an emulsion stabilizer that comprises a water-soluble degradable synthetic vinyl polymer with labile group in the backbone.
  • the external phase is oil- based and the internal phase is aqueous-based.
  • the internal phase is oil-based and the external phase is aqueous-based.
  • a water-soluble degradable synthetic vinyl polymer of the present invention may be present in an amount in the range of from about 0.025% to about 4% by weight of the external phase.
  • Vinyl acetate >99%, from Fluka
  • L-cystine 99%, Acros (available from Acros Organics at www.acros.com)
  • eerie ammonium nitrate 98,5%, Fluka
  • 70% nitric acid Aldrich (available through Sigma Aldrich at www.sigmaaldrich.com)
  • DL-dithiothreitol >99,0%, Fluka
  • Equation 1 Equation 1 where t solutlon is an efflux time of the polymer solution, t solvent in an efflux time of the solvent
  • Protons neighboring carboxylic group can be observed as a multiplet at the region of 3.99-4.04. From polymerization mechanism it can be noticed that chemical environment of the proton B changes once it is within polymer chain, hence only multiplets in the region of 2.98 - 3.12 can be found. Strong peaks in the range 1.2-1.8 ppm and 2.0-2.4 ppm correspond to the protons of the methylene (E) and methine (D) groups of PAM.
  • a eerie solution was prepared by dissolving eerie ammonium nitrate (1/1 to 1/4 molar ratio with respect to hydroxyl end groups of VA-086 - Table 1) in 1 ml of 1M nitric acid. The eerie solution was purged with nitrogen for 1 min, before it was injected into the monomer solution containing VA-086. The whole reaction was carried out in the dark under nitrogen at 26°C for 2 h to 3.5 h. The synthesized product was recovered by precipitation in methanol, which was followed by filtration and multiple washing with methanol in order to remove most of the non-reacted initiator and monomer. Finally, the precipitate was dried to the constant weight over ⁇ 0 5 in a desiccator under reduced pressure. The yield of the reaction Y was determined by gravimetric method:
  • W p is a weight of the precipitated product and W m and Wj are the weights of the monomers and the initiator used, respectively.
  • W m and Wj are the weights of the monomers and the initiator used, respectively.
  • VA - 086 content ⁇ lOO [mol%]
  • Equation 3 where I ]M is the integrating area at 1.06 pmm from CH 3 protons of VA-086 and /, 56 is the integrating area at 1.56 from CH 2 of poly(acrylamide).
  • the polymer was purified further by dialysis in deionized water.
  • a dialysis tube with a molecular weight cut off of 3500 Da (Fisher Scientific) was used.
  • poly(acrylamide) was deionized using poly(ethylene oxide)/Ce(IV) as redox couple and used for drag reduction test and degradation experiment.
  • Poly(ethylene oxide) was chosen as a non-degradable reducing agent.
  • the same polymerization procedure as outlined above was followed in order to produce non-degradable PAM in the same conditions as PAM containing azo-groups in the backbone.
  • 0.1 g (0.05mmol) of poly( ethylene oxide) was used with the same amount of monomers as for the polymerization of acrylamide initiated using VA-086.
  • a eerie solution (0.055 g (0.1 mmol) of Ce(IV) in 1 ml of IN nitric acid) was added to the reaction vessel after purging monomer solution containing reducing agent for 20 min with nitrogen. The whole reaction was carried out in the dark under nitrogen at 35 °C for 2.5 h. The synthesized product was recovered and purified the same way as PAM initiated using VA-086.
  • Thermolysis of PAM containing azo groups was carried out at a temperature of 86°C.
  • the choice of the temperature was based on the decomposition temperature of VA-086.
  • a water solution with a polymer concentration of 2 mg/ml was prepared and 200 ppm of hydroquinone was added in order to scavenge any radicals created.
  • Equation 4 M plo is a peak molecular weight of the polymer before degradation and p(j is a peak molecular weight of the polymer after heating it at 86°C for some time. M p was determined using GPC.
  • Polymer samples for the drag reduction measurements were prepared by dissolving a predetermined amount of PAM in deionized water. In order to obtain good polymer dissolution, samples were shaken at 200 oscillation/min on a shaker tray overnight. Prior to the measurements, the polymer solutions were filtered using a syringe filter with a pore size of 0.45 ⁇ . Sample volume of 17 ml was used always for all drag reduction measurements. The drag reduction efficiency, the percentage drag reduction (%DR), was calculated following the equations above.
  • H'-NMR spectra of the deionized polymers and their initiators were recorded on a 2 channel "DRX-400 Spectrometer" (from Bruker, Germany) using d 6 -DMSO and D 2 0 as a solvent. Chemical shifts were expressed in parts per million (ppm, ⁇ ). Tetramethylsilane (TMS) was used as a generally accepted internal standard.
  • the molecular weight of the deionized polymers were determined by gel permeation chromatography (GPC) "PL-GPC 50" (from Polymer Laboratories, UK) with integrated triple detection system, including refractive index (“PL-RI”), viscometer (“PL-BV 400RT”) and light scattering ("PL-LS”) detectors using two "TSK-Gel” columns (from TOSOH, Japan).
  • GPC gel permeation chromatography
  • PL-RI refractive index
  • PL-BV 400RT viscometer
  • PL-LS light scattering
  • the maximum degradation temperature for PAM with azo functionalities in the backbone was observed at 192°C, whereas for PAM mixed with VA-086 at 164 °C.
  • the shift and the shape of the exothermic peak, in the thermogram of PAM containing azo-functionalities in the backbone, is caused by the different chemical environment due to the covalent incorporation of VA-086 into PAM.
  • VA-086 contains hydroxyl groups on both ends
  • the polymerization of acrylamide was initiated from both sides of the reducing agent, allowing for the incorporation of at least one azo group into the polymer.
  • the number of azo groups in the backbone and hence the molecular weight of the polymer after degradation depends on the termination step of the polymerization. In case of bimolecular recombination one expects at least two azo groups in the polymer backbone, whereas in case of disproportionation or unimolecular termination only one azo group would be incorporated. Peak molecular weight M p and weight average molecular weight M w of PAM containing azo-functionalities during the degradation process are tabulated in Table 3.
  • the M p of the polymer before degradation was around 4,400 kDa.
  • M p decreased to 600 kDa, which was about 14% of the original polymer molecular weight.
  • the molecular weight of the PAM with azo groups in the backbone decreased further but at a lower rate and stabilized when M p of the polymer reached 260 kDa (about 6% of the original molecular weight of the polymer). Based on the molecular weight of the polymer before and after degradation, it can be assumed that about 11 weak links were successfully built in the polymer backbone, which would be about 0.1 1 mol%.
  • azo functional groups may be successfully incorporated into a poly(acrylamide) backbone by redox polymerization using a water-soluble azo initiator 2,2'-azobis[2-methyl-(2-hydroxyethyl) propionamide] (VA-086) as a reducing agent and Ce(IV) as an oxidizing ion.
  • VA-086 water-soluble azo initiator 2,2'-azobis[2-methyl-(2-hydroxyethyl) propionamide]
  • Ce(IV) as an oxidizing ion.
  • H'-NMR spectra of the synthesized polymer confirm the presence of azo functionalities in the polymer backbone. This result was supported by DSC testing where an exothermic peak from the degradation of azo groups can be observed in the PAM initiated from VA-086.
  • the synthesized PAM containing azo groups in the backbone was used as an initiator for the free radical initiator polymerization of acrylonitrile, which resulted in the synthesis of PAM-block-PAN. This also indicates that active azo groups were incorporated into the PAM backbone.
  • PAM with temperature- sensitive azo groups in the backbone can degrade when subjected to a temperature above the degradation temperature of azo groups; in this case 86 °C.
  • Reagents Acrylamide (98%, BDH) was purified by re-crystallisation from methanol (99.5%, Fluka).
  • Other reactants used for the polymerization such as poly(caprolactone)diols with molecular weights M w 530, 1250 and 2000 (99%, Aldrich), vinyl acetate (>99%, Fluka), eerie ammonium nitrate (98,5%, Fluka), sodium dodecyl sulphate (>99%, Aldrich), 70% nitric acid (Aldrich) were used as received.
  • Oxygen free nitrogen was purchased from BOC and deionized water was purified using Option 4 (Elga, UK).
  • reagents such as poly(acrylamide) 5-6 million Da (PAM) (Polysciences, Inc.), sodium nitrate (>98%, BDH), sodium azide (>99%, Fluka), phosphorus pentoxide (>98%, Aldrich) were also used without further purification.
  • D 2 0 (99,96%) and acetone-d 6 (99,9%) was purchased from Merck and used for NMR analysis.
  • the solution of cerium ammonium nitrate was prepared by mixing an appropriate amount of cerium ammonium nitrate salt with 0.25ml IN HN0 3 .
  • the polymerization solution was purged with nitrogen for 1 min. before and after injecting pre- prepared cerium ammonium nitrate solution.
  • the polymerization was carried out for 2 h. Afterwards the synthesized product was re-precipitated in an access of acetone and then filtered.
  • the precipitate was re-dissolved in water and precipitated in an access of acetone for second time in order to remove most of the un-reacted monomers, poly(caprolactone), and sodium dodecyl sulphate. Afterwards collected product was washed 2-3 times with a small amount of acetone and then filtered. Finally the precipitate was dried to the constant weight over P 2 0 5 in a desiccator under reduced pressure. The yield of the reaction Y was determined by a gravimetric method:
  • H'-NMR measurements were carried out on a 2 channel DRX-400 spectrometer (Bruker, Germany). Deuterated solvents such as D 2 0 and acetone-d 6 were used to dissolve studied polymer. Tetramethylsilane (TMS) was used as a generally accepted internal standard. Chemical shifts are expressed in parts per million (ppm, ⁇ ).
  • the molecular weight of the synthesized polymers was determined using gel permeation chromatography (GPC) PL-GPC 50 (Polymer Laboratories, UK) with integrated triple detection system, including refractive index (PL-RI), viscometer (PL-BV 400RT) and light scattering (PL-LS) detectors using two TSK-Gel columns (TOSOH, Japan).
  • GPC gel permeation chromatography
  • PL-RI refractive index
  • PL-BV 400RT viscometer
  • PL-LS light scattering
  • Poly(acrylamide-co-caprolactone) was synthesized via redox polymerization, where poly(caprolactone)diol and eerie ions were used as a redox couple to initiate polymerization of acrylamide as shown in the in Reaction 3 below.
  • Poly(caprolactone) diol as a hydrophobic polymer does not dissolve in water.
  • One way to introduce poly(caprolactone) diol into an aqueous environment is to use emulsion polymerization. By using surface active agents at the concentration above critical micelle concentration (CMC), surfactants will self assemble to form micelles. Hydrophobic domains should improve the solubility of poly(caprolactone) diol in aqueous solution.
  • hydrophilic hydroxyl groups in the poly(caprolactone) diol should stay attached to the interphase allowing initiation of the polymerization.
  • poly(caprolactone) diols with molecular weight 2000 Da was utilised as an organic reducing agent under the same polymerization condition, decrease in the polymerization yield and molecular weight was observed. It could be related to an increase in the length of poly(caprolactone) chain, hence its hydrophobicity and worse dissolution in surfactant micelles. An additional reason could be a decrease in number of carbons with hydroxyl groups which are available to initiate polymerization.
  • sample 2 and 4 have much smaller molecular weight than samples 3, 5 and 6, which might suggest that poly(caprolactone) diol was present only on the beginning of the polymer chain and thus sensitivity of the NMR technique was too low to detect it once the ration of PCL/P AM is too low.
  • Amphiphilic copolymers can stabilize emulsions (oil/ water phase). The stability of the emulsion depends on the concentration of the copolymer and the content of the hydrophobic part in the copolymers. More hydrophobic copolymers stabilize an emulsion more effectively. Stabilization of hexane/water emulsion with poly(acrylamide-co- caprolactone) is a good indicating experiment to check if poly(caprolactone) diol was indeed successfully built in the polymer backbone. For comparison reasons the same concentration of PAM was prepared to observe its ability to stabilize hexane/water emulsion. The results of the experiment can be seen in Figure 12. Figure 12 shows emulsions stabilized with PAM- co-PCL compared to pure PAM.
  • micellar polymerization of acrylamide initiated from poly(acrylamide) diol/Ce(IV) redox pair may yield poly(acrylamide-co-caprolactone) copolymers.
  • the addition of small amount of vinyl acetate as a comonomer increases both the molecular weight of the polymer and the yield of the polymerization.
  • concentration of SDS was increased.
  • the presence of polycaprolactone diol in the PAM backbone was confirmed by FT-IR and H '-NMR results. Oil in water emulsion were stabilized using synthesized poly(acrylamide- co-caprolactone) proving their amphiphilic character.

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Abstract

Parmi les nombreux modes de réalisation de la présente invention, l'un porte sur un fluide de traitement souterrain comprenant : un fluide aqueux ; et un polymère vinylique synthétique dégradable hydrosoluble ayant une liaison labile dans son squelette. L'invention porte également dans un cas sur un polymère vinylique synthétique dégradable hydrosoluble comprenant un groupe labile dans son squelette formé par une polymérisation redox, la réaction de polymérisation redox comprenant les réactifs suivants : un macroinitiateur qui comprend une liaison labile, un ion métallique oxydant et un monomère vinylique.
EP11720827A 2010-04-30 2011-04-28 Polymères vinyliques synthétiques dégradables hydrosolubles et procédés associés Withdrawn EP2563820A1 (fr)

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