WO2011072021A2 - Composition de polymère, composition gonflable comprenant la composition de polymère et articles comprenant la composition gonflable - Google Patents

Composition de polymère, composition gonflable comprenant la composition de polymère et articles comprenant la composition gonflable Download PDF

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Publication number
WO2011072021A2
WO2011072021A2 PCT/US2010/059478 US2010059478W WO2011072021A2 WO 2011072021 A2 WO2011072021 A2 WO 2011072021A2 US 2010059478 W US2010059478 W US 2010059478W WO 2011072021 A2 WO2011072021 A2 WO 2011072021A2
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Prior art keywords
phr
polymer
composition
sealing element
swellable
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PCT/US2010/059478
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English (en)
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WO2011072021A3 (fr
Inventor
James R. Korte
John Thurston
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Baker Hughes Incorporated
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Priority to AU2010328212A priority Critical patent/AU2010328212B2/en
Priority to CA2783341A priority patent/CA2783341C/fr
Priority to NO20120600A priority patent/NO346917B1/no
Priority to GB1209356.3A priority patent/GB2488075B/en
Publication of WO2011072021A2 publication Critical patent/WO2011072021A2/fr
Publication of WO2011072021A3 publication Critical patent/WO2011072021A3/fr

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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L24/00—Surgical adhesives or cements; Adhesives for colostomy devices
    • A61L24/04—Surgical adhesives or cements; Adhesives for colostomy devices containing macromolecular materials
    • A61L24/043—Mixtures of macromolecular materials
    • 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
    • C09K8/44—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells containing organic binders only
    • 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
    • C09K8/504—Compositions based on water or polar solvents
    • C09K8/506—Compositions based on water or polar solvents containing organic compounds
    • C09K8/508—Compositions based on water or polar solvents containing organic compounds macromolecular 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
    • C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L24/00—Surgical adhesives or cements; Adhesives for colostomy devices
    • A61L24/04—Surgical adhesives or cements; Adhesives for colostomy devices containing macromolecular materials
    • A61L24/10—Polypeptides; Proteins
    • A61L24/106—Fibrin; Fibrinogen
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/28—Materials for coating prostheses
    • A61L27/34—Macromolecular materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00—Compositions of unspecified rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L31/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid; Compositions of derivatives of such polymers
    • C08L31/02—Homopolymers or copolymers of esters of monocarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or 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 of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or 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 of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or 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 of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/24—Homopolymers or copolymers of amides or imides
    • C08L33/26—Homopolymers or copolymers of acrylamide or methacrylamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/02—Copolymers with acrylonitrile
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
    • 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
    • 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
    • C09K8/422—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells specially adapted for sealing expandable pipes, e.g. of the non-hardening type
    • 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
    • C09K8/426—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells for plugging
    • 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
    • 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
    • E21B33/12—Packers; Plugs
    • E21B33/1208—Packers; Plugs characterised by the construction of the sealing or packing means
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2420/00—Materials or methods for coatings medical devices
    • A61L2420/04—Coatings containing a composite material such as inorganic/organic, i.e. material comprising different phases
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/01—Hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or 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 of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or 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 of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/18—Homopolymers or copolymers of nitriles
    • C08L33/20—Homopolymers or copolymers of acrylonitrile

Definitions

  • REPackerTM reactive element packer One example of swellable seals in the art is known commercially as a Reactive Element Packer or REPackerTM reactive element packer, available from Baker Oil Tools, Houston Texas. REPackers are commercial isolation tools that use elastomer swelling technology to provide a barrier in surrounding member/open hole and surrounding
  • Such packers may have a water reactive section, an oil reactive section, or both.
  • a water reactive section may include water-absorbing particles incorporated in nitrile-based polymer. These particles swell via absorbing water, which in turn expands the rubber without being physically absorbed into the rubber matrix, which can adversely affect properties.
  • an oil reactive section may include hydrocarbon- absorbing rubbers and polymers, in which uptake of the hydrocarbon by the polymer causes swelling and lubricates and decreases the mechanical strength of the polymer chain as it expands.
  • a polymer composition including a base polymer comprising a hydrocarbon rubber, an acrylic copolymer, and a refined oil in which the acrylic polymer is dispersed.
  • the polymer composition is swellable when treated with an aqueous medium, non-aqueous medium, or both.
  • a sealing element for a flow channel includes an expandable section filled with a swellable composition that swells when treated with a swelling material.
  • a method of sealing a well hole includes inserting the sealing element into a well, and introducing a swelling material into the expandable section.
  • FIG. 1 is a cross-sectional schematic view of an exemplary annular sealing element
  • FIG. 2 is a cross-sectional schematic view of a packer having an annular sealing element and an inlet valve.
  • a polymer composition for a swellable composition which combines an oil swellable base polymer and an acrylic polymer dispersion in a refined oil, can be swelled by treatment of the polymer composition with either an aqueous medium, non-aqueous medium, or both (e.g., wellbore fluids such as water, brine, hydrocarbons, drilling mud, or a combination of these).
  • an aqueous medium e.g., wellbore fluids such as water, brine, hydrocarbons, drilling mud, or a combination of these.
  • the polymer composition includes an oil swellable base polymer, an acrylate copolymer, and a refined oil.
  • refined oil each refers to a petroleum distillate fraction of hydrocarbons of 15 to 40 carbon atoms.
  • the refined oil may be aromatic or non-aromatic.
  • a useful base polymer is a hydrocarbon rubber which swells in the presence of refined oils.
  • Hydrocarbon rubbers, such as those embodied herein, may include those based on elastomeric diene monomers such as 1,3 -butadiene or isoprene (as found in natural rubbers), and may be homo-or copolymers.
  • the base polymer may also be a copolymer.
  • polymer comprises polymers of one monomer, copolymers, terpolymers and polymeric forms of more than one type of monomer.
  • copolymer may indicate the presence of two or more monomers, and may therefore also encompass the terms terpolymer, tetrapolymer, pentapolymer, and the like, and therefore the terms polymer and copolymer should not be construed as limiting to the use of only one or two monomers respectively, unless otherwise specified.
  • terpolymer is used herein, this term refers to the presence of three monomers in the polymer unless otherwise specified.
  • the base polymer may be a random or block copolymer. Where a random copolymer is used, the monomers are substantially randomly dispersed in the polymer. Where a block copolymer is used, the block copolymer may be a diblock copolymer, a triblock copolymer, a diblock terpolymer, or the like. It will be understood that each block may be a homopolymer or random copolymer.
  • the oil swellable base polymer comprises polyethylenes, polypropylenes, poly(ethylene-co-propylene), polyamides, polyesters, polyurethanes, polyvinylchlorides, and rubbers such as ethylene-propylene-diene monomer (EPDM) rubber, butadiene rubber, styrene-butadiene rubber, butyl rubber, natural rubber, or a combination comprising at least one of the foregoing.
  • EPDM ethylene-propylene-diene monomer
  • the base polymer is ethylene-propylene-diene monomer (EPDM) rubber, butadiene rubber, styrene-butadiene rubber, butyl rubber, natural rubber, or a combination comprising at least one of the foregoing.
  • EPDM ethylene-propylene-diene monomer
  • the base polymer is EPDM.
  • the polymer composition also includes an acrylic copolymer of hydrophilic acrylic monomers.
  • a dispersion of such a polymer in a medium, such as in a refined oil or oil/water emulsion, is also referred to herein as a liquid dispersed polymer (LDP).
  • LDP liquid dispersed polymer
  • a useful acrylic copolymer for an LDP includes an acidic monomer such as, for example, acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, or a combination comprising at least one of these.
  • the acidic monomer is acrylic acid or methacrylic acid.
  • the acrylic copolymer also includes a polar hydrophilic monomer, and in particular, an amide monomer.
  • exemplary amide monomers include acrylamide; N-alkyl acrylamides such as N-methylacrylamide, ⁇ , ⁇ -dimethylacrylamide, N-ethylacrylamide, N,N- diethylacrylamide, or N-hydroxyethylacrylamide; methacrylamide; N-alkyl methacrylalmides such as N-methylmethacrylamide, ⁇ , ⁇ -dimethylmethacrylamide, N-ethylmethacrylamide, N,N- diethylmethacrylamide, N-hydroxyethylmethacrylamide, or N,N- dihydroxyethylmethacrylamide; maleimide; N-alkylmaleimides such as N-methylmaleimide, N- ethylmaleimide, N-phenylmaleimide, and the like; or a combination comprising at least one of the foregoing.
  • the amide monomer is acrylamide or methacrylamide.
  • the acrylic copolymer includes the acidic monomer and the amide monomer in a weight ratio of 99:1 to 1:99, specifically 95:5 to 5:95, and more specifically 90:10 to 10:90.
  • the acrylic copolymer consists essentially of the acidic monomer and the amide monomer. In another embodiment, the acrylic copolymer consists of the acidic monomer and amide monomer.
  • the acrylic copolymer may be a solution polymerized copolymer, but is typically an emulsion or suspension polymerized polymer.
  • the acrylic copolymer is an aqueous emulsion polymer having a polymer solids content of 40 to 99 wt , specifically 45 to 95 wt , and more specifically 50 to 90 wt , based on the total weight of the aqueous emulsion polymer.
  • the acrylic copolymer comprises at least one of acrylic acid and methacrylic acid, and at least one of acrylamide and methacrylamide.
  • the acrylic copolymer is a copolymer of acrylic acid and acrylamide.
  • An example of a commercial acrylic copolymer is DPNT06-0124 which is an acrylic acid/acrylamide copolymer dispersion in heavy petroleum naphtha, commercially available from Ciba
  • Additional monomers copolymerizable with the acidic and amide monomers may be included provided the inclusion of these monomers does not significantly adversely affect the desired properties of the swellable composition.
  • Additional monomers that may be included in the acrylic copolymer include, but are not limited to, polar acrylate or acrylic monomers such as those having nitrile functional groups including acrylonitrile,
  • aldehydic monomers such as acrolein, methacrolein, and the like
  • hydroxy-containing monomers such as 2-hydroxyethyl acrylate (HEA), 2-hydroxyethyl methacrylate (HEMA), 2- hydroxypropylacrylate, 2-hydroxypropylmethacrylate, and the like
  • anhydrides such as maleic anhydride, itaconic anhydride, and the like
  • nonpolar acrylate monomers such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, t-butyl acrylate, pentyl acrylate,
  • the additional monomers may be used in an amount of less than or equal to 80 wt , specifically less than 70 wt , and more specifically less than 50 wt , based on the total weight of acidic monomer, amide monomer, and additional monomer in the acrylic copolymer.
  • Cross-linking monomers may also be included.
  • Such cross linking monomers may include, for example, divinyl benzene, ethylene diacrylate, ethylene dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, and the like, or a
  • crosslinkers may be used in amounts of less than or equal to 5 wt , specifically less than or equal to 2 wt , and more specifically less than or equal to 1 wt , based on the total weight of acidic monomer, amide monomer, and additional monomer in the acrylic copolymer.
  • the acrylic copolymer may include combinations of copolymers of acrylic acid and its esters with other materials such as sodium hydroxide, polyacrylamide copolymer, ethylene maleic anhydride copolymer, crosslinked
  • carbomethoxycellulose polyvinyl alcohol copolymers, cross linked polyethylene oxide, or a combination comprising at least one of the foregoing.
  • the acrylic copolymer has a weight average molecular weight of 1,000 to 500,000 g/mol, specifically 10,000 to 300,000 g/mol, and more specifically 20,000 to 100,000 g/mol.
  • the acrylic copolymer may be included in the swellable composition as a suspension in a solvent (e.g., a refined oil as discussed below), as an aqueous emulsion, or may be a mixture of an aqueous emulsion with a refined oil, referred to as discussed hereinabove as an LDP.
  • a solvent e.g., a refined oil as discussed below
  • LDP liquid phase polymer
  • the swellable composition thus further includes a refined oil in which the base polymer and the acrylic polymer are dispersed.
  • the refined oil is as described herein a petroleum distillate fraction and may be any Ci5_ 4 o petroleum fraction useful for swelling the base polymer, where the refined oil has a high affinity for the base polymer and for which the base polymer has a high capacity.
  • the term "high capacity" with respect to the base polymer is where the base polymer can absorb up to 200 phr, specifically 100 to 150 phr, of refined oil based on 100 parts of base polymer and any added fillers.
  • the refined oil may be a naphthenic oil comprising mostly cycloalkanes and having an n-alkane (paraffin) content of less than about 55-60%; a paraffinic oil (sometimes referred to as a heavy naphtha) having an n- alkane content of greater than about 55-60%; an aromatic oil, such as a phthalate oil derived from phthalic anhydride, and including such compounds as, for example di-n-butylphthalate; or a combination comprising at least one of the foregoing.
  • a naphthenic oil comprising mostly cycloalkanes and having an n-alkane (paraffin) content of less than about 55-60%
  • a paraffinic oil sometimes referred to as a heavy naphtha
  • an aromatic oil such as a phthalate oil derived from phthalic anhydride, and including such compounds as, for example di-n-butylphthalate; or a combination comprising at least one of the foregoing.
  • the refined mineral oil is a phthalate oil, a naphthenic oil, a paraffinic oil, or a combination comprising at least one of the foregoing oils.
  • the refined oil is a naphthenic oil, a paraffinic oil, or a combination comprising at least one of the foregoing oils.
  • the acrylic copolymer is dispersed in the refined oil to prepare the LDP.
  • the amount of acrylic copolymer dispersed in refined oil is 20 to 80 wt , specifically 30 to 70 wt , and more specifically 40 to 60 wt , based on the total weight of the acrylic copolymer and refined oil.
  • the acrylic copolymer (as an LDP) is included in the swellable composition in an amount of 30 to 200 parts by weight per 100 parts (also referred to as parts per hundred, abbreviated “phr”) by weight (also referred to as parts per hundred, abbreviated “phr”) of the base polymer.
  • the acrylic copolymer is included in an amount of 40 to 180 phr, more specifically 50 to 150 phr, and still more specifically 80 to 140 phr, based on 100 parts of the base polymer.
  • the swelling composition may further include, in addition to the polymer composition, ingredients or components to provide other performance aspects of the swellable composition.
  • ingredients or components to provide other performance aspects of the swellable composition.
  • these additional ingredients/components include fillers, activators, antioxidants, process aids, and curatives.
  • fillers there are various other grades of fillers which may be used alone or in combination, and in lesser or greater amounts that may yield comparable, desirable or improved rubber properties.
  • Suitable fillers include, but are not necessarily limited to, carbon black, silica (silicon dioxide, S1O 2 ), clays, calcium carbonate, bentonite, and the like, and combinations thereof.
  • the proportion of filler may range between about 30 and 100 phr.
  • Suitable activators include, but are not necessarily limited to, magnesium oxide (MgO), zinc oxide (ZnO), zinc stearate, stearic acid and the like and combinations thereof.
  • the proportion of activator may be in the range from about 1-10 phr.
  • Suitable antioxidants include, but are not necessarily limited to, any of the diphenyl amines (e.g. NAUGARD ® antioxidants available from Chemtura Corporation), or any of the mercaptobenzimidazoles (e.g., VANOX ® ZMTI from RT Vanderbilt) and the like and combinations thereof.
  • Suitable process aids include, but are not necessarily limited to, waxes (e.g. VANFRE ® waxes available from R. T. Vanderbilt Company), or process aids such as WB-16 process additive from Strucktol, and the like, and combinations thereof.
  • the antioxidants and the process aids may each be in the range of from about 0.5 to about 5.0 phr.
  • a swelling composition may include 100 phr base polymer (e.g., EPDM), 30 to about 200 phr acrylic copolymer, 0.2 to 15 phr curative, 20 to 100 phr carbon black filler, 20 to 100 phr silica filler, 1 to 10 phr activator, 0.5 to about 5 phr antioxidant, and 0.5 to 5 phr process aid.
  • EPDM phr base polymer
  • acrylic copolymer e.g., ethylene glycol dimethacrylate
  • 0.2 to 15 phr curative 0.2 to 15 phr curative
  • 20 to 100 phr carbon black filler 20 to 100 phr silica filler
  • 1 to 10 phr activator 0.5 to about 5 phr antioxidant, and 0.5 to 5 phr process aid.
  • the polymer composition, and a swelling composition prepared therefrom may be swelled by treatment by an aqueous swelling material such as water or brine, or by treatment with a non-aqueous swelling material, such as a hydrocarbon as described above, drilling mud, or a combination of these.
  • an aqueous swelling material such as water or brine
  • a non-aqueous swelling material such as a hydrocarbon as described above, drilling mud, or a combination of these.
  • the swelling composition disclosed herein may achieve a swelling capacity for the combination of base polymer (e.g., EPDM) and acrylic copolymer in refined oil or water of over 500 volume .
  • base polymer e.g., EPDM
  • the amount of swelling achieved and the rate of swelling depends on physical boundaries and limitations, the viscosity of the refined oil, the salinity of the water, and the temperature.
  • concentration of mono-valent salts e.g. NaCl, KC1
  • co-valent salts e.g., CaCl 2
  • the polymer composition described herein, and the swelling composition prepared therefrom, may be used in a sealing element for a flow channel.
  • an exemplary sealing element is shown in FIG. 1, in which the sealing element 100 includes a channel 110, and an expandable section 120.
  • the sealing element 100 may be annular in design and surrounding the channel 110, or may be of another shape depending on the application.
  • the sealing element 120 comprises an expandable section 120 filled with a swellable composition (not shown) which includes the polymer composition described herein, which swells when treated with a swelling material.
  • the swelling material may be a wellbore fluid including an aqueous medium such as water or brine, a non-aqueous medium such as hydrocarbons, drilling mud, or a combination comprising at least one of the foregoing.
  • the expandable sealing element is changeable in shape and size, so that the sealing element may upon expanding conform to the shape and dimensions of the environment in which it is inserted (such as a borehole, well, or the like).
  • an annular sealing element is included in the structure of a packer and has a through hole running lengthwise through the expandable sealing element containing the swelling material.
  • An exemplary packer is shown in FIG. 2, in which the packer 200 includes a channel 210, an annular expandable section 220, a surrounding member 230 surrounding the channel 210 to encase the expandable section 220.
  • a valve 240 opens into surrounding member 230 to allow introduction of a swelling material to contact expandable section 220.
  • the expandable section 220 of the packer 200 conforms by expanding radially outward, to conform to the outer environment, as well as expanding radially toward the center, to constrict around a production pipe or conduit (not shown) inserted through channel 210 the packer.
  • the sealing element is a bridge plug for sealing off a bore hole completely, and does not include a hole running through the expandable section.
  • An exemplary method of sealing a well hole using the sealing element includes inserting the sealing element into a hole (bore hole or well), and introducing a swelling material into the expandable section.
  • the swelling material may be introduced to the sealing element through a tube or line for introducing the swelling material affixed to a valve attached to the surrounding member.

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Abstract

L'invention porte sur une composition de polymère qui comprend un polymère de base comprenant un caoutchouc hydrocarboné, un copolymère acrylique et une huile raffinée dans laquelle le polymère acrylique est dispersé. La composition de polymère est gonflable lorsqu'elle est traitée par un milieu aqueux, un milieu non aqueux ou les deux. Un élément de scellement pour un canal d'écoulement comprend une section expansible remplie d'une composition gonflable qui gonfle lorsqu'elle est traitée par une matière de gonflement. La composition gonflable comprend la composition de polymère et le matériau gonflable peut être aqueux, non aqueux ou les deux.
PCT/US2010/059478 2009-12-11 2010-12-08 Composition de polymère, composition gonflable comprenant la composition de polymère et articles comprenant la composition gonflable WO2011072021A2 (fr)

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AU2010328212A AU2010328212B2 (en) 2009-12-11 2010-12-08 Polymer composition, swellable composition comprising the polymer composition, and articles including the swellable composition
CA2783341A CA2783341C (fr) 2009-12-11 2010-12-08 Composition de polymere, composition gonflable comprenant la composition de polymere et articles comprenant la composition gonflable
NO20120600A NO346917B1 (no) 2009-12-11 2010-12-08 Polymersammensetning, svellbar sammensetning omfattende polymersammensetningen og artikler omfattende den svellbare sammensetningen
GB1209356.3A GB2488075B (en) 2009-12-11 2010-12-08 Polymer composition, swellable composition comprising the polymer composition, and articles including the swellable composition

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US12/636,176 2009-12-11
US12/636,176 US9018144B2 (en) 2007-10-01 2009-12-11 Polymer composition, swellable composition comprising the polymer composition, and articles including the swellable composition

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WO2011072021A2 true WO2011072021A2 (fr) 2011-06-16
WO2011072021A3 WO2011072021A3 (fr) 2011-10-20

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US9018144B2 (en) 2015-04-28
US9303200B2 (en) 2016-04-05
US20100147507A1 (en) 2010-06-17
NO346917B1 (no) 2023-02-27
AU2010328212A1 (en) 2012-06-07
GB2488075B (en) 2016-03-09
WO2011072021A3 (fr) 2011-10-20
GB201209356D0 (en) 2012-07-11
CA2835959C (fr) 2015-06-02
GB2488075A (en) 2012-08-15
CA2783341C (fr) 2015-10-20
CA2835959A1 (fr) 2011-06-16
AU2010328212B2 (en) 2013-09-26
US20130306306A1 (en) 2013-11-21
NO20120600A1 (no) 2012-06-14
CA2783341A1 (fr) 2011-06-16

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