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WO2013101702A1 - Matériaux dégradables à plusieurs composants et application - Google Patents

Matériaux dégradables à plusieurs composants et application Download PDF

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Publication number
WO2013101702A1
WO2013101702A1 PCT/US2012/071147 US2012071147W WO2013101702A1 WO 2013101702 A1 WO2013101702 A1 WO 2013101702A1 US 2012071147 W US2012071147 W US 2012071147W WO 2013101702 A1 WO2013101702 A1 WO 2013101702A1
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WO
WIPO (PCT)
Prior art keywords
fiber
degradable
pla
water
fibers
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
PCT/US2012/071147
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English (en)
Inventor
S. Sherry ZHU
Huilin Tu
Vadim Kamil'evich Khlestkin
Miranda AMARANTE
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.)
Schlumberger Canada Ltd
Services Petroliers Schlumberger SA
Schlumberger Technology BV
Schlumberger Technology Corp
Schlumberger Holdings Ltd
Prad Research and Development Ltd
Original Assignee
Schlumberger Canada Ltd
Services Petroliers Schlumberger SA
Schlumberger Technology BV
Schlumberger Technology Corp
Schlumberger Holdings Ltd
Prad Research and Development Ltd
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 Schlumberger Canada Ltd, Services Petroliers Schlumberger SA, Schlumberger Technology BV, Schlumberger Technology Corp, Schlumberger Holdings Ltd, Prad Research and Development Ltd filed Critical Schlumberger Canada Ltd
Priority to US14/369,451 priority Critical patent/US20140374106A1/en
Priority to CA2861854A priority patent/CA2861854C/fr
Priority to BR112014016046A priority patent/BR112014016046A8/pt
Priority to CN201280068242.3A priority patent/CN104080960A/zh
Priority to AU2012362642A priority patent/AU2012362642A1/en
Priority to MX2014007816A priority patent/MX2014007816A/es
Publication of WO2013101702A1 publication Critical patent/WO2013101702A1/fr
Anticipated expiration legal-status Critical
Priority to AU2017218922A priority patent/AU2017218922A1/en
Ceased legal-status Critical Current

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Classifications

    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/14—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyester as constituent
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
    • D01D5/30—Conjugate filaments; Spinnerette packs therefor
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • 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
    • E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
    • E21B43/16—Enhanced recovery methods for obtaining hydrocarbons
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2401/00—Physical properties
    • D10B2401/12—Physical properties biodegradable
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2505/00—Industrial
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2916—Rod, strand, filament or fiber including boron or compound thereof [not as steel]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2929—Bicomponent, conjugate, composite or collateral fibers or filaments [i.e., coextruded sheath-core or side-by-side type]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2929—Bicomponent, conjugate, composite or collateral fibers or filaments [i.e., coextruded sheath-core or side-by-side type]
    • Y10T428/2931—Fibers or filaments nonconcentric [e.g., side-by-side or eccentric, etc.]

Definitions

  • Degradable materials have many uses in our society, ranging from making degradable plastic bags, diapers, and water bottles, to making degradable excipients for drug delivery and degradable implants for surgical use, to a wide variety of industrial uses, such as in remediation, agriculture, and oil and gas production.
  • degradable materials have been used for fluid loss control, for diversion, and as temporary plugs in downhole applications of oil and gas production.
  • degradable materials used in such ways include rock salt, graded rock salt, benzoic acid flakes, wax beads, wax buttons, oil-soluble resin material, etc.
  • degradable materials In addition to filling and blocking fractures and permeable zones right in the reservoir, degradable materials have also been used to form consolidated plugs in wellbores that will degrade after use, eliminating the need for retrieval.
  • the current disclosure relates to multicomponent fibers that have accelerated degradation in water in low temperature conditions, and their various industrial, medical and consumer product uses. Such materials are especially useful for uses in subterranean wells in oil and gas production. In some embodiments, the compositions of materials have accelerated degradation even at Ultra Low Temperature (“ULT”) ( ⁇ 60°C) in subterranean formations.
  • ULT Ultra Low Temperature
  • the multicomponent fibers comprise components that degrade at different rates in water, or water soluble components in combination with water degradable components, or hydrocarbon soluble components in combination with water degradable components. Some of the multicomponent fibers described herein lost more than 60% weight at temperatures below 60°C in water within a week.
  • the degradable materials described herein have a variety of uses, e.g., to make consumer products such as plastic grocery bags and diaper liners, and also medical uses as implants, bandages, sutures, or drug delivery materials.
  • our main interest for such material lies in oil and gas production, and other geological, mining, agriculture or remediation uses.
  • Embodiments of the current application can be used in various operations servicing subterranean wells.
  • materials of the current application can be applied to proppant flowback control, transportation of proppant, diversion in hydraulic fracturing, carbonate acidizing, and flow channeling in proppant pack.
  • Materials of the current application can also be added to drilling fluids to help minimize lost circulation, and added to cement to improve the flexural strength of the set cement.
  • materials of the current application may form a temporary plug in a fracture, a perforation, a wellbore or more than one of the locations in a well to allow some downhole operations, and the plug then degrades or dissolves after a selected time, such that the plug disappears.
  • the materials can even be formed into solid plugs for temporary uses to plug wellbore equipment.
  • the time frame for the fiber to degrade to remove the fiber plugs is dependent on the choice of fibers (polymers) and on wellbore temperatures. However, the materials of the invention degrade in water at 60°C in less than a month. Degradation can be accelerated with additives, with reactive fillers or with acids or bases in the injection fluid.
  • multicomponent composite fibers having components that degrade at different rates in water, or having water soluble components (sheath or core, sea or one side) in combination with water degradable components, or having hydrocarbon soluble component (core, island or one side) in combination with water degradable components.
  • multicomponent fibers may be processable, have comparable strength and stiffness to mono-component PLA fibers, and contain locally concentrated reactive fillers and other additives that promote fast degradation in water at low temperatures (T ⁇ 60°C) in subterranean wells.
  • Materials that are suitable for the current application include, but are not limited to, polymers that are capable of being degraded (break down to oligomers or monomers) in aqueous environment.
  • the polymer degradation in water is measurable by the decrease of molecular weight of the polymer (measured by drying and weighing, or by gel permeation chromatography), and the weight loss of the solid polymers over a period of time from a few hours, to a few days, weeks and months depending on the temperatures, the pH of the water, the nature of the polymers and whether the presence of a catalyst.
  • degradation can also be assessed by permeability, such that the polymer degrades or solubilizes enough to allow fluid flow.
  • Examples of the suitable, degradable polymers for the degradable composites include, but are not limited to, aliphatic polyesters, poly(lactic acid), poly(e- caprolactone), poly(glycolic acid) (PGA), poly(lactic-co-glycolic acid) (PLGA), poly(hydroxyl ester ether), poly(hydroxybutyrate), poly(anhydride), polycarbonate, poly(amino acid), poly(ethylene oxide), poly(phosphazene), polyether ester, polyester amide, polyamides, sulfonated polyesters, poly(ethylene adipate) (PEA), polyhydroxyalkanoate (PHA), poly(ethylene terephtalate) (PET), poly(butylene terephthalate) (PBT), Poly(trimethylene terephthalate) (PTT), poly(ethylene naphthalate) (PEN) and copolymers, blends, derivatives or combination of any of these degradable polymers.
  • aliphatic polyesters poly(lactic
  • the degradable polymers are poly(lactic acids), poly(e- caprolactones), poly(glycolic acids) (PGA), and poly(lactic-co-glycolic acids) (PLGA).
  • Poly(lactic acids) can be produced either by direct condensation of lactic acids or by catalytic ring-opening polymerization of cyclic lactides, or can be commercially provided.
  • Lactic acid often produced commercially through bacterial fermentation, is a chiral molecule and has two optical active isomers: the D isomer and the L isomer.
  • the D isomer content in the PLA determines the crystallinity of the PLA polymer.
  • Fully amorphous PLA incudes relatively high D content (>20%) where highly crystalline PLA contains less than 2% D isomer.
  • Examples of the amorphous PLA resins include 6060D, 6302D, or 4060D resins from Natureworks.
  • Examples of crystalline PLA resins include 620 ID or 6202D resins from Natureworks.
  • the matrix polymer in the degradable composites may comprise only the amorphous, only the crystalline PLA, or the blend of amorphous and crystalline PLA.
  • a PLA polymer blend can be a simple mechanical mixture of molten amorphous and crystalline PLA polymers.
  • a reactive filler such as a base, metal oxide, or other catalysts can be included inside the fibers to accelerate degradation through fast water diffusion and fast kinetics.
  • the additives can provide metal ions (Zn 2+ , Mg 2+ , etc.) that may act as Lewis acids and enhance ester bond cleavage as well. Thus, such additives can assist in controlling the rate of degradation.
  • the reactive fillers may include, but are not limited to, bases or base precursors that generate hydroxide ions or other strong nucleophiles when in contact with water.
  • the reactive fillers improve both the rate of water penetration into the fibers and the rate of ester hydrolysis through the catalytic effect of nucleophiles.
  • Examples of reactive fillers include, but are not limited to, Ca(OH) 2 , Mg(OH) 2 , CaC0 3 , Borax, MgO, CaO, ZnO, O, CuO, AI2O 3 , and other bases or compounds that can convert to bases when in contact with water.
  • the reactive fillers in the multicomponent fibers can be surrounded by another component of polymer.
  • the fibers can be used in applications in both neutral and acid solution without undesired interference from the reactive fillers.
  • the fillers are contained on the outside and e.g., acid is used to accelerate degradation.
  • the reactive fillers are dispersed uniformly in at least one of the polymer components.
  • the concentration of the reactive fillers may be the same (evenly distributed reactive fillers in the fibers) or may be different in each polymer component so that the reactive fillers are locally concentrated in certain parts of the fibers.
  • the materials of the current application may be in the shape of rods, particles, beads, films and fibers.
  • a solid plug or other shape can be formed, for example by pressing.
  • Fabrics and woven mats can also be made with the fibers.
  • multicomponent fibers are made from extruding two or more polymers from the same spinneret with both polymers contained within the same filament.
  • polymers with different properties can be tailored into the same filament with any desired cross sectional shapes or geometries.
  • two or more polymer components can be joined, combined, united or bonded to form a unitary fiber body.
  • Multicomponent fibers can be classified by their fiber cross-section structures as side-by-side, sheath-core, islands-in-the-sea and citrus fibers or segmented-pie cross- section types, and various combinations thereof.
  • FIG. 1 and 2 show the examples of cross sections of multicomponent fibers.
  • Polymer resins with different morphology, melting temperatures, dissolution and degradation kinetics may also be designed into multicomponent fibers to achieve the optimum degradation, tensile strength and dimension stability (minimum shrinkage) at given temperatures in water.
  • Fibers can also include other types of additives in addition to reactive fillers, for example to impart color, flexibility, or other desirable properties.
  • the particle sizes of the various additives may be in the range of 10 nm to several hundred nanometers. Reactive fillers with larger total surface area may result in faster degradation at the given temperatures compared to bigger fillers with smaller total surface area.
  • the loading of the various fillers as a weight percentage of the total composite can be in the range of 0-10% or 0.2% to 4% in fibers, depending on the choice of fillers, their molecular weight and the process condition.
  • Each filler can be used alone or combined with other fillers and additives.
  • the most preferred fillers for developing degradable/soluble bicomponent fibers are ZnO and the combination of ZnO with a small amount of other fillers, such as MgO, salts, waxes, plasticizers, and hydrophilic polymers such as ethylene vinyl alcohol (EVOH) or polyvinyl alcohol (PVOH).
  • multicomponent fibers what is meant is that a fiber has at least two different components therein, and such components are at least partially adjacent each other, although many configurations thereof are possible. The term does not include fibers where the components are intimately admixed or blended, however.
  • bicomponent fibers what is meant is that a fiber has two different components therein that are adjacent.
  • degradable polymer what is meant is a polymer that can be degraded in water at 60°C in 30 days or less, preferably in two weeks, or a week or less.
  • degraded is at least a 50% reduction in dry weight or if assessed downhole by flowthrough at least a 50% increase in flow.
  • hydrocarbon soluble polymer is a polymer that is soluble in petroleum hydrocarbons in 30 days or less, preferably in two weeks or in a week or less.
  • water soluble polymer is a polymer that dissolves in water in 30 days or less, preferably in two weeks or in a week or less.
  • FIG. 1 Examples of sheath-core (1 and 2), islands-in-the-sea (3 and 4) and segmented-pie (5 and 6) cross-section types.
  • FIG. 2 Cross-section of various side-by-side multicomponent fibers.
  • FIG. 3. Schematic view of Fibers 1 in Table 1.
  • FIG. 4A-D Schematic views of bicomponent fibers consisting of degradable polymer and water soluble polymer.
  • FIG. 5A-B Schematic views of bicomponent fibers consisting of degradable polymer and oil soluble polymer.
  • FIG. 6A-B The optical images of the bicomponent fibers.
  • FIG. 7 The degradation of the bicomponent fibers, Bi-50S/50C (vertical hatching) and Bi-75S/25C (horizontal hatching) having different rations of core versus sheath material, at 60°C in water over 14 or 21 days.
  • FIG. 8 The degradation profiles of the bicomponent fibers, Bi-50S/50C (star) and Bi-50S/50C-ZnO (4%) (circle), at 60°C in water versus time in days.
  • FIG. 9 Influence of additives on the degradation rate of PLA fibers at 60°C for 48 hours.
  • the PLA fibers were provided by Nature Works.
  • FIG. 10A-B A: SEM image of as-spun PLA/G-PVOH (8042p) bicomponent fiber with a sheath:core ratio at 31%:69%.
  • B The optical image of the cross-section of the same PLA/G-PVOH sheath-core fiber.
  • FIG. 12A-B SEM images of PLA/G-PVOH fibers after 7 days in deionized (DI) water at 49°C (A) and 60°C (B).
  • FIG. 13 Photograph of glass vials containing 0.25g of Evatane® 28-05 (left) and Evatane® 28-40 (right) in 8 ml of octane. Both resins dissolved in octane at 38°C after 5 hours.
  • composition used/disclosed herein can also comprise some components other than those cited.
  • the polymer components can be arranged to form a core-sheath configurations shown as 1 and 2 cross section in FIG. 1, island-sea with up to 360 islands (3 and 4 cross section in FIG. 1), and segmented pie (4-64 segments) shown as 5 and 6 cross-section in FIG. 1.
  • FIG. 2 shows the examples of side-by-side multicomponent fibers comprising different polymers or similar polymers with different melting points, degradation kinetics and physical properties.
  • Each component of a multicomponent fiber may occupy 10-90% of the weight of the entire fiber, or 25-75%, or 50-50% or any range in between.
  • the components can be regular or irregular in shape or cross-section, and components can be symmetrically or asymmetrically placed (e.g., a core can be off-center).
  • the reactive filler can be in one component or the other, or in all components, as needed for degradation kinetics, strength and the actual application.
  • Reactive fillers can comprise 0-10% or 0.2-4% of the component to which it is added. More can be used if needed for particular applications.
  • PLA Poly(lactic acid)
  • PLA poly(lactic acid)
  • the selection of the PLA resin is based on their melting temperatures, the rate of water penetration, and the degradation kinetics, all of which correlate to the crystallinity of PLA polymers.
  • PLA with the melting point of 125-135°C is an amorphous polymer that degrades faster than semi-crystalline PLA with the melting point at 160- 170°C.
  • Fibers 1, 2 and 3 all have semi-crystalline PLA polymer as the core and amorphous PLA polymer as the sheath.
  • the core provides the stiffness and strength, and the sheath component absorbs water and can rapidly degrade at given temperatures.
  • Fiber 1 has reactive fillers in the core only, and loading of the filler is up to 10% of the core polymer (FIG. 3).
  • reactive fillers e.g., up to 10%
  • Fiber 3 has reactive fillers only in the sheath component (e.g., up to 10%).
  • the weight % of sheath component in Fibers 1 , 2 and 3 may be around 50-90%.
  • Fibers 4, 5 and 6 The configuration of Fibers 4, 5 and 6 is reversed with amorphous PLA as the core and semi-crystalline PLA as the sheath, but the components are otherwise the same as that of Fibers 1 , 2 and 3.
  • the configuration of Fibers 4, 5 and 6 allows the fibers to maintain stiffness and flocculation (fiber network in water to support proppant) for longer time and only break down at the later stage of degradation.
  • the core component in Fibers 4, 5 and 6 may contain up to 10% reactive fillers, or the sheath up to 10%, or both.
  • the weight % of the sheath component in Fibers 4, 5 and 6 may be around 10-50%, or be the same as above depending on the desired characteristics.
  • Tables 2 and 3 show additional examples, where the configuration of the components is in an island sea configuration (Table 2), or a side-by-side configuration (Table 3). Segmented pie configuration and combinations of configurations are also possible. All the PLA polymers in Tables 1 , 2, 3 and 4 have a Glass Transition Temperature (T g ) in the range of 55-60°C. Table 2. Examples of polymers and fillers in degradable island-sea PLA fibers
  • the degradable polymers may be used to construct the sheath and the water soluble polymers may be used as the core (FIG. 4A).
  • the hydrophobic, degradable polymeric sheath provides a layer of protection from moisture for longer shelf life
  • the water soluble core provides mechanical strength to the fibers that should help to maintain the performance properties including proppant settling, bridging and plugging.
  • the core with fast dissolution kinetics will dissolve first to result in a hollow degradable fiber with very thin wall ( ⁇ 2 ⁇ ) which then degrades or even breaks down to small particles in the down-hole high pressure environment.
  • the water soluble polymers may be used to form sheath, sea, or one side of the multicomponent fibers, and degradable polyesters may be used to form core, island or the other side of the multicomponent fibers (FIG. 4B).
  • the degradable polymers as the core provide the mechanical strength, stiffness, and process-ability for the multicomponent fibers
  • the water soluble polymer as the sheath dissolves rapidly in water at ULT, which effectively reduces the degradable portion to only 10-50% of total weight.
  • the water soluble polymers may occupy 50-90% of the fibers in order to take the most advantage of their fast dissolution kinetics at ULT.
  • the PVOH/PLA bicomponent fiber made herein takes much less time to reach the same weight loss% at the same degradation time and temperature compared to the degradation of a monocomponent PLA fiber, because the degradable polymer with slow degradation kinetics (several weeks to degrade) only accounts for 10-50% of the total weight of the fibers and the water soluble polymer with fast dissolution kinetics (several hours to dissolve) accounts for the major component of the multicomponent fiber.
  • Poly(lactic acid) PLA
  • poly(glycolic acid) PGA
  • poly(caprolacton) PCL
  • polybutylene succinate polymers and polybutylene succinate-co-adipate polymers and copolymer or blends thereof are examples of polymers for the degradable polyester components.
  • the specific choice of the water soluble polymer for constructing the multicomponent fibers is based on the application temperatures. For example, if the wellbore temperature is at 38°C or lower, AQ 38 or Nichago G-polymer may be used as one of the components in a bicomponent fiber.
  • Reactive fillers and other additives that can accelerate degradation may be placed in the degradable polyesters to improve the degradation of the polyester, and the loading is up to 10% (FIG. 4C).
  • placing reactive fillers in water soluble polymers may provide a caustic aqueous environment that may facilitate rapid degradation of the polyesters (FIG. 4D).
  • FIG. 5A-B Another approach is to construct multicomponent fibers in which the first polymer component provides stiffness and strength, where the second polymer dissolves in hydrocarbons at low temperatures.
  • the first polymer in the fibers will partially degrade in water first during the stages of hydraulic fracturing, and the second polymer will dissolve in hydrocarbons during the production stage.
  • the first degradable polymer could occupy the sheath, the sea or one side of a bicomponent fiber, and the hydrocarbon soluble polymer occupies the core, the island or the other side of a bicomponent fiber.
  • Polyolefins such as polyprolylene PP or polyethylene PE), ethylene vinyl acetate (EVA), modified EVA and copolymers and blends thereof are good choices for the hydrocarbon soluble polymers, and specific selection of the polymer depends on the application temperatures.
  • the water degradable composite may form the sheath (core-sheath), sea (island-sea), minor side (side-by-side), and the hydrocarbon soluble polymers form the core, island and the major side of the multicomponent fibers.
  • the weight ratio of water degradable composite and hydrocarbon soluble polymers is in the range of 10:90 to 90: 10 depending on the desired resulting physical properties (stiffness and tensile) of the fibers and the application temperatures.
  • Fillers increase the porosity of the fibers, and can also facilitate faster dissolution.
  • the loading of the fillers inside any of the fibers herein described also depends on the desired physical properties of the fibers (inorganic fillers reduce the tensile strength of the fibers).
  • the process-ability of spinning composite fibers (fibers with inorganic fillers) also puts constraints on the loading of the fillers.
  • adhesion-promoting monomer or reactive functional polymers may be needed for better compatibility between the polymer matrix and the inorganic fillers.
  • the choice of adhesion-promoting monomers includes silane based adhesion promoters (Silquest® brand, for example), maleated or acid functionalized polymers (DuPont Fusabond®, and Optim® E-117), and alkyl phosphate esters (Zelec® brand, for example).
  • the choice of the adhesion promoters is determined by the choice of the fillers, and the loading of the adhesion promoters is the range of 0.5-5% of the total polymers.
  • additives include organic carboxylic acid, carboxylic acid ester, metal salts of organic carboxylic acid, multicarboxylic acid, fatty acid esters, metal salts of fatty acid, fatty acid esters, fatty acid ethers, fatty acid amides, sulfonamides, polysiloxanes, organophosphorous compound, Al(OH) 3 , quaternary ammonium compounds, silver base inorganic agents, carbon black, metal oxide pigments, dyes, silanes, titanate etc.
  • Table 4 shows the spinning conditions and Table 5 shows the composition and tensile strength of the sheath-core bicomponent fibers that were actually made.
  • the amorphous PLA 6060D occupied the sheath component that facilitated fast water absorption and degradation, and the crystalline 620 ID resin occupied the core that provided stiffness and strength.
  • Table 4 The extruder zone temperatures for the bicomponent PLA fibers
  • the samples are named according to their type (e.g., Bi for bicomponent) and sheath/core ratio (e.g., 50S/50C is 50% of each), and finally reactive filler is indicated at the end.
  • Bi-75S/25C is 75% sheath surrounding a 25% core
  • Bi- 50S/50C-ZnO is 50/50 sheath/core with ZnO added, in this case to the core.
  • the PLA bicomponent fibers were cut to 6 mm long. A fixed amount of the fibers was immersed in 100 ml of DI water. The bottles were kept at 60°C for 7, 14 and 21 days. After degradation, the residuals were filtered and washed with DI water three times before being dried at 49°C in an oven. The weight loss as a percentage of the total original weight was calculated and used as the degree of degradation. See FIG. 7 and 8.
  • Bi-75S/25C fiber with more amorphous PLA 6060D had more weight loss% than the Bi-50S/50C fiber with less amorphous PLA.
  • the addition of 4% reactive filler, ZnO, in the core resulted in more weight loss% for Bi- 50S/50C-ZnO compared to the similar fiber Bi-50S/50C at the same degradation condition (FIG. 8).
  • PLA fibers were provided by Nature Works. A fixed amount (1.2_mg) of PLA fibers were dispersed in 100 ml of DI water. 50 mmol of water insoluble additive was added to the mixture. The mixture was placed in the oven at 66°C for 48h. After that time, the mixture was cooled down to room temperature, the residues were filtered off, washed with 6% HC1 and DI water, dried at 50°C, and weight determined. The results are shown in FIG. 9, where it can be seen that all additives increased the degree of degradation at 48 hours, especially the combination of ZnO and 4-dimethylaminopyridine.
  • PLA containing both ZnO 4- dimethylaminopyridine only showed slightly higher degradation compared with PLA containing only ZnO fillers.
  • MgO is more effective to accelerate PLA degradation
  • the melt spinning of PLA fibers with MgO as a filler turned out be very challenge even at very low weight% of MgO ( ⁇ 1%). The spinning was interrupted frequently due to fiber breakage.
  • Nichigo G-polymerTM (referred to as G-PVOH in this patent), developed by Nippon Gohsei, is a hydrolyzed copolymer of vinyl acetate and proprietary comonomers.
  • G-PVOH is an amorphous polymer that combines ordinarily conflicting traits of "low crystallinity” and "high hydrogen-bonding strength,” and realizes functions of water solubility at room temperature, low melting points, high stretching characteristics, and a wide temperature gap between the melting point (185°C) and the thermal decomposition temperature (> 220°C) which make it possible to develop fibers and films using conventional melt extrusion processes.
  • NatureWorks amorphous PLA 6060D resin was used to construct the sheath ( ⁇ 30%), and 8042P was used to construct the core (> 70%) of the bicomponent fiber.
  • Table 6 the spinning conditions of the PLA/G-PVOH bicomponent fiber.
  • the SEM image shows the as-spun PLA/G-PVOH fiber (FIG. 10A), and the optical image of the cross-section of the fiber clearly indicates the big core surrounded by a thin layer of sheath polymer (FIG. 10B).
  • the average fiber diameter was 27 ⁇ and the thickness of the sheath was 3 ⁇ with the spinning speed set at 1000 m/m.
  • the degradation of the PLA/G-PVOH bicomponent fiber was conducted in water at different pH (acid, DI water or base buffers) at 49°C and 60°C for 7, 14 and 21 days.
  • the percentage of weight loss (weight loss%) was used to measure the degradation.
  • FIG. 11 shows the weight loss% vs. degradation time and temperature in various pH aqueous solution.
  • the PLA/G-PVOH fibers lost more than 70% weight after only 7 days in DI water or at different buffer solutions (FIG. 11) and form hollow fibers with ⁇ 2 ⁇ thin wall at 49°C (FIG. 12A) and the hollow fiber broke down at 60°C (FIG. 12B).
  • the pH of the solutions in contrast, had little effect on the rate of degradation.
  • the weight loss% is determined by the weight% of water soluble component in the fibers.
  • hydrocarbon soluble polymer is ethylene vinyl acetate.
  • EVA Ethylene vinyl acetate
  • Commercial grades of EVA resins have vinyl content ranging from 9 to 40% and a melt flow index range from 0.3 to 500 dg/min.
  • These specialty thermoplastic polymers are inherently flexible, resilient, and tough, and can be processed using conventional thermoplastic or rubber handling equipment and techniques.
  • the melt spinning process for fibers requires resin melt index in the range of 10 to 45 g/min (ASTM D1238, modified), and Melt Viscosity in the range of 10 to 20 (Pa S) at 190°C temperature.
  • the VA% (vinyl acetate content in the EVA copolymer) impacts the flexibility and the toughness of the resin and the final products. Higher VA% results in more flexible and tougher products.
  • EVA resins DuPont Elvax® 550 and Elvax® 250, and Arkema Evatane® 20-20, 33-15, 28-05 and 28-40, were chosen for the initial trial based on their % of vinyl acetate content and their melt index (ASTM D1238), though EVA resins from other brands and suppliers should be equally useful.
  • EVA polymers may be blended to make homogeneous or heterogeneous blend fibers for optimum process-ability and properties.
  • the choice of the resins for EVA blends is determined by the melting point and the Ring and Ball Softening point of the resins. Blending of EVA resin with other resins for better physical properties of the resultant blend fibers is also under consideration.
  • Polymers other than EVA may be blended with the EVA resin to improve the physical properties of the fibers.
  • the choice of polymers includes polyolefins and polyolefin oligomers (ethylene or propylene), wax, pitch and bitumen.
  • the EVA resins also have good solubility in hydrocarbons at low temperatures.
  • FIG. 13 shows the pictures of Evatane® 28-05 and Evatane® 28-40 resins dissolved in octane at 38°C.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Mining & Mineral Resources (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Fluid Mechanics (AREA)
  • Geochemistry & Mineralogy (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Environmental & Geological Engineering (AREA)
  • Multicomponent Fibers (AREA)

Abstract

La présente invention concerne en général des fibres à plusieurs composants qui ont accéléré la dégradation dans l'eau dans des conditions de basses températures, ainsi que leurs diverses applications dans les domaines industriel, médical et produit de consommation. Lesdits matériaux sont particulièrement utiles dans les puits souterrains dans la production de pétrole et de gaz. Dans certains modes de réalisation, les compositions des matériaux ont accéléré la dégradation même à des températures ultra basses (« ULT ») (≤ 60°C) dans des formations souterraines.
PCT/US2012/071147 2011-12-28 2012-12-21 Matériaux dégradables à plusieurs composants et application Ceased WO2013101702A1 (fr)

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US14/369,451 US20140374106A1 (en) 2011-12-28 2012-12-21 Multicomponent degradable materials and use
CA2861854A CA2861854C (fr) 2011-12-28 2012-12-21 Materiaux degradables a plusieurs composants et application
BR112014016046A BR112014016046A8 (pt) 2011-12-28 2012-12-21 fibra multicomponente degradável, fibra multicomponente, e método de produção de hidrocarbonetos de um reservatório subterrâneo
CN201280068242.3A CN104080960A (zh) 2011-12-28 2012-12-21 多组分可降解材料其及用途
AU2012362642A AU2012362642A1 (en) 2011-12-28 2012-12-21 Multicomponent degradable materials and use
MX2014007816A MX2014007816A (es) 2011-12-28 2012-12-21 Materiales degradables de multiples componentes y su uso.
AU2017218922A AU2017218922A1 (en) 2011-12-28 2017-08-21 Multicomponent degradable materials and use

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015061553A1 (fr) * 2013-10-23 2015-04-30 Schlumberger Canada Limited Développement et caractérisation de réticulé dégradable dans du poly(alcool vinylique)
WO2015061420A1 (fr) * 2013-10-22 2015-04-30 3M Innovative Properties Company Composition de ciment pour puits comprenant des fibres à multicomposants et procédé de cimentation l'utilisant
US20160003022A1 (en) * 2014-07-01 2016-01-07 Research Triangle Institute Cementitious fracture fluid and methods of use thereof
WO2018057500A1 (fr) * 2016-09-20 2018-03-29 Fairmount Santrol Inc. Balles d'obturation dégradables ayant des caractéristiques de solubilité améliorées
WO2019122195A1 (fr) * 2017-12-21 2019-06-27 Beaulieu International Group Nv Tissu biodégradable et utilisation d'un tel tissu
US10808162B2 (en) 2017-11-17 2020-10-20 Fairmount Santrol Inc. Crush resistant buoyant ball sealers
WO2020261035A1 (fr) * 2019-06-26 2020-12-30 3M Innovative Properties Company Procédé de fabrication d'une bande de fibres non tissées, bande de fibres non tissées et fibre à composants multiples
US11193356B2 (en) 2017-03-31 2021-12-07 Schlumberger Technology Corporation Method of generating a fracturing design and method of hydraulic fracturing
WO2021250513A1 (fr) * 2020-06-12 2021-12-16 3M Innovative Properties Company Matériau de pansement et procédés de fabrication et d'utilisation de celui-ci
CN114401703A (zh) * 2019-09-25 2022-04-26 3M创新有限公司 伤口敷料材料及其制造和使用方法

Families Citing this family (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ITMI20112450A1 (it) * 2011-12-30 2013-07-01 Eni Spa Apparato e metodo per monitorare l'integrita' strutturale di una condotta
US11566349B2 (en) 2015-03-27 2023-01-31 The United States Of America As Represented By The Secretary Of The Army High strength 3D-printed polymer structures and methods of formation
US10513653B2 (en) 2015-04-28 2019-12-24 Thru Tubing Solutions, Inc. Flow control in subterranean wells
US10851615B2 (en) 2015-04-28 2020-12-01 Thru Tubing Solutions, Inc. Flow control in subterranean wells
US10774612B2 (en) 2015-04-28 2020-09-15 Thru Tubing Solutions, Inc. Flow control in subterranean wells
US9745820B2 (en) 2015-04-28 2017-08-29 Thru Tubing Solutions, Inc. Plugging device deployment in subterranean wells
US9816341B2 (en) 2015-04-28 2017-11-14 Thru Tubing Solutions, Inc. Plugging devices and deployment in subterranean wells
US10655427B2 (en) 2015-04-28 2020-05-19 Thru Tubing Solutions, Inc. Flow control in subterranean wells
US11466193B2 (en) * 2017-06-15 2022-10-11 Halliburton Energy Services, Inc. Plasticized polyvinyl alcohol diverter materials
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US11767462B2 (en) * 2020-05-22 2023-09-26 Kuraray Co., Ltd. Polyvinyl alcohol-based particulate compositions
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US20230372578A1 (en) * 2020-09-23 2023-11-23 3M Innovative Properties Company Wound Dressing Material and Methods of Making and Using the Same
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US20250237138A1 (en) * 2024-01-18 2025-07-24 Saudi Arabian Oil Company Tracer compositions

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5814404A (en) * 1994-06-03 1998-09-29 Minnesota Mining And Manufacturing Company Degradable multilayer melt blown microfibers
WO2000043579A1 (fr) * 1999-01-25 2000-07-27 3M Innovative Properties Company Microfibres a deux composants
US20020168912A1 (en) * 2001-05-10 2002-11-14 Bond Eric Bryan Multicomponent fibers comprising starch and biodegradable polymers
US20100029161A1 (en) * 2005-06-24 2010-02-04 North Carolina State University Microdenier fibers and fabrics incorporating elastomers or particulate additives
KR20110133798A (ko) * 2010-06-07 2011-12-14 (주)엘지하우시스 직물 표면을 갖는 ｐｌａ 바닥재

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3499053B2 (ja) * 1995-07-26 2004-02-23 ユニチカ株式会社 生分解性ポリエステル繊維
US5698322A (en) * 1996-12-02 1997-12-16 Kimberly-Clark Worldwide, Inc. Multicomponent fiber
DE60233264D1 (de) * 2001-06-15 2009-09-17 Kuraray Co Verbundfaser
EP1436113A4 (fr) * 2001-07-23 2008-05-28 Scandus Trading Company L L C Lame de scie pour appareil de scie alternative
CN1239523C (zh) * 2002-12-26 2006-02-01 中国石油化工股份有限公司北京燕山分公司研究院 脱除聚合物溶液中挥发性组分的方法
CN100379800C (zh) * 2003-05-27 2008-04-09 旭化成化学株式会社 可生物降解的树脂膜或片及其制造方法
US7380600B2 (en) * 2004-09-01 2008-06-03 Schlumberger Technology Corporation Degradable material assisted diversion or isolation
US7267170B2 (en) * 2005-01-31 2007-09-11 Halliburton Energy Services, Inc. Self-degrading fibers and associated methods of use and manufacture
US8230936B2 (en) * 2005-08-31 2012-07-31 Schlumberger Technology Corporation Methods of forming acid particle based packers for wellbores
CN101139752B (zh) * 2006-09-06 2014-07-16 远东新世纪股份有限公司 具有生物可分解性的热融着复合纤维
US20110028062A1 (en) * 2008-02-14 2011-02-03 Chester Stephen O Bicomponent fibers, textile sheets and use thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5814404A (en) * 1994-06-03 1998-09-29 Minnesota Mining And Manufacturing Company Degradable multilayer melt blown microfibers
WO2000043579A1 (fr) * 1999-01-25 2000-07-27 3M Innovative Properties Company Microfibres a deux composants
US20020168912A1 (en) * 2001-05-10 2002-11-14 Bond Eric Bryan Multicomponent fibers comprising starch and biodegradable polymers
US20100029161A1 (en) * 2005-06-24 2010-02-04 North Carolina State University Microdenier fibers and fabrics incorporating elastomers or particulate additives
KR20110133798A (ko) * 2010-06-07 2011-12-14 (주)엘지하우시스 직물 표면을 갖는 ｐｌａ 바닥재

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015061420A1 (fr) * 2013-10-22 2015-04-30 3M Innovative Properties Company Composition de ciment pour puits comprenant des fibres à multicomposants et procédé de cimentation l'utilisant
US20160264839A1 (en) * 2013-10-22 2016-09-15 3M Innovative Properties Company Well cement composition including multi-component fibers and method of cementing using the same
WO2015061553A1 (fr) * 2013-10-23 2015-04-30 Schlumberger Canada Limited Développement et caractérisation de réticulé dégradable dans du poly(alcool vinylique)
US20160003022A1 (en) * 2014-07-01 2016-01-07 Research Triangle Institute Cementitious fracture fluid and methods of use thereof
US9567841B2 (en) * 2014-07-01 2017-02-14 Research Triangle Institute Cementitious fracture fluid and methods of use thereof
WO2018057500A1 (fr) * 2016-09-20 2018-03-29 Fairmount Santrol Inc. Balles d'obturation dégradables ayant des caractéristiques de solubilité améliorées
US11193356B2 (en) 2017-03-31 2021-12-07 Schlumberger Technology Corporation Method of generating a fracturing design and method of hydraulic fracturing
US10808162B2 (en) 2017-11-17 2020-10-20 Fairmount Santrol Inc. Crush resistant buoyant ball sealers
WO2019122195A1 (fr) * 2017-12-21 2019-06-27 Beaulieu International Group Nv Tissu biodégradable et utilisation d'un tel tissu
WO2020261035A1 (fr) * 2019-06-26 2020-12-30 3M Innovative Properties Company Procédé de fabrication d'une bande de fibres non tissées, bande de fibres non tissées et fibre à composants multiples
US20220228306A1 (en) * 2019-06-26 2022-07-21 3M Innovative Properties Company Method of making a nonwoven fiber web, nonwoven fiber web, and multi-component fiber
US12000071B2 (en) 2019-06-26 2024-06-04 Solventum Intellectual Properties Company Method of making a nonwoven fiber web, nonwoven fiber web, and multi-component fiber
CN114401703A (zh) * 2019-09-25 2022-04-26 3M创新有限公司 伤口敷料材料及其制造和使用方法
WO2021250513A1 (fr) * 2020-06-12 2021-12-16 3M Innovative Properties Company Matériau de pansement et procédés de fabrication et d'utilisation de celui-ci

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AU2012362642A1 (en) 2014-07-03
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CA2861854C (fr) 2020-03-24
AU2017218922A1 (en) 2017-09-07
BR112014016046A2 (pt) 2017-06-13
US20140374106A1 (en) 2014-12-25
CN104080960A (zh) 2014-10-01

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