Fluoroelastomer compounds for sealing elements

Abstract

Disclosed polymer compositions include a fluoroelastic matrix and a fluoro-filler. The fluoroelastic matrix includes a fluoroelastomer and the fluoro-filler includes a fluorinated carbon-based molecule. An amount of the fluoro-filler is dispersed within the fluoroelastic matrix. The polymer compositions are used to form sealing elements having an annular body to withstand harsh environments.

Description

1 / 11 “FLUOROELASTOMER COMPOUNDS FOR SEALING ELEMENTS” Background of the Invention Fluoroelastomers are frequently used in the production of sealing elements and other components in industrial applications due to their thermal resistance, chemical resistance, strength, and other material properties. The term "fluoroelastomer" is generally used to refer to synthetic rubbers that contain fluorine in their molecular structure. Fluoroelastomeric materials are commonly produced with vinylidene fluoride (VDF), hexafluoropropylene (HFP), perfluoromethyl vinyl ether (PMVE), tetrafluoroethylene (TFE), propylene (P), and / or other monomers. For example, fluoroelastic materials used in hydrocarbon recovery system components may include VDF-based copolymers such as Kautschuk Fluorine Material (FKM), TFE / P polymers (FEPM), and perfluoroelastomers (FFKM), to name a few.

[0002] Fluoroelastomers have been used in hydrocarbon recovery system components, such as in packers, blowout preventers, sealing rings, gaskets, electrical insulators, pressure seals for fluids, and many other oilfield and downhole elements. In such applications, polymers may be exposed to harsh environments, such as harsh chemical and mechanical underground environments, which tend to unacceptably reduce the service life and reliability of the polymers. Furthermore, while fluoroelastomers may provide some basic strength and high-temperature resistance in acidic environments (containing hydrogen sulfide (H2S)), fluoroelastomer components may be the first to fail under high levels of dynamic stress.

[0003] Consequently, there is still a need to improve the reliability and service life of polymeric components used in oilfield environments, such as protective sleeves, sealing elements, pressure seals, valve seals, eruption prevention components, cable shielding and sheathing, among others. Summary of the Invention

[0004] This summary is provided to present a selection of concepts that are further described in the detailed description. This summary is not intended to identify the main features or essential characteristics of Petition 870250067995, dated 04 / 08 / 2025, pages 53 / 68 2 / 11 matter claimed, nor should it be used as an aid to limit the scope of the matter claimed.

[0005] In one aspect, the embodiments disclosed herein relate to fluoroelastomer composites that are made of a fluoroelastic matrix of a fluoroelastomer and an amount of fluorofiller material dispersed in the fluoroelastic matrix, wherein the fluorofiller material includes a fluorinated carbon-based molecule.

[0006] In another aspect, the embodiments disclosed herein refer to polymeric components that are made, at least in part, of fluoroelastomer composites made of a fluorofiller material dispersed in a fluoroelastic matrix.

[0007] Other aspects and advantages of the claimed material will be evident from the following description and the appended claims. Brief Description of the Drawings

[0008] The figures are not necessarily to scale, and certain features and views of the figures may be presented on an exaggerated scale for clarification purposes.

[0009] Figure 1 shows a drilling system having at least one component in accordance with the embodiments of the present disclosure.

[0010] Figure 2 shows an example of an annular eruption preventer with an annular seal according to the embodiments of the present disclosure.

[0011] Figure 3 shows an example of a variable hole seal according to the embodiments of the present disclosure.

[0012] Figure 4 shows an example of a shutter sealing element according to the embodiments of the present disclosure.

[0013] Figure 5 shows an example of a sealing ring according to the embodiments of the present disclosure.

[0014] Figure 6 shows an exemplary fluoroelastomer composite according to the embodiments of the present disclosure. Detailed Description of the Invention

[0015] The modalities of this disclosure are described in detail below, with reference to the accompanying figures. In the detailed description that follows, several specific details are presented to provide a more comprehensive understanding. Petition 870250067995, dated 04 / 08 / 2025, pages 54 / 68 3 / 11 of the claimed subject matter. However, it will be evident to the expert in the field that the described modalities can be practiced without these specific details. In other cases, well-known characteristics have not been described in detail to avoid unnecessarily complicating the description.

[0016] The embodiments of this disclosure generally relate to fluoroelastomer composites and components manufactured from them. Components made from fluoroelastomer composites according to the embodiments of this disclosure may include sealing elements, such as those used in hydrocarbon recovery systems, and other components subject to aggressive environments. For example, components used in environments rich in hydrogen sulfide (acidic environments), such as sealing elements used in drilling operations exposed to hydrogen sulfide, can be produced with the fluoroelastomer composites described herein. In other embodiments, the fluoroelastomer composites according to the embodiments of this disclosure can be used to produce polymeric components in other industries, such as the automotive industry (e.g., for seals used in automobiles) and for hose applications.

[0017] According to embodiments of the present disclosure, fluoroelastomer composites may include fluorofillers dispersed in a fluoroelastic matrix. As used in the present invention, a fluorofiller refers to a filler material that has been modified to include fluorine (F). Examples of fluoroelastic matrix material and fluorofillers are described below. Fluoroelastic Matrix

[0018] Fluoroelastic matrix materials include fluoroelastomers made from fluorinated carbon-based monomers. Examples of monomers that can be used to form a fluoroelastic matrix include, but are not limited to, ethylene hexafluoropropylene (E) (HFP), perfluoromethyl vinyl ether (PMVE), propylene (P), tetrafluoroethylene (TFE), and vinylidene fluoride (VDF). The chemical composition (e.g., type of monomer used), the fluorine content (e.g., degree of fluorination), and / or the crosslinking mechanism of the fluoroelastic matrix can be varied to provide variable overall material properties.

[0019] For example, the fluoroelastic matrix material used to form fluoroelastic composites for components of recovery systems. Petition 870250067995, dated 04 / 08 / 2025, pages 55 / 68 4 / 11 hydrocarbons may include VDF-based copolymers, such as fluoroelastomers classified as “FKM” by ASTM D1418 (fluorinated polymethylene-type rubbers that use vinylidene fluoride as a comonomer and have fluoro, allyl, perfluoroalkyl, or perfluoroalkoxy substituent groups in the polymer chain), TFE / P polymers (FEPM), and perfluoroelastomers (FFKM).

[0020] The fluoroelastic base material FKM can be selected from among the five types classified in ASTM D1418, including VDF and HFP dipolymers (Type 1), VDF, HFP and TFE terpolymers (Type 2), VDF, TFE and a fluorinated vinyl ether terpolymers (Type 3), P, TFE and VDF terpolymers (Type 4) and VDF, HFP, TFE, E and a fluorinated vinyl ether pentapolymers (Type 5).

[0021] Tetrafluoroethylene propylene (FEPM, TFE / P) is a partially fluorinated polymer composed of propylene and tetrafluoroethylene monomers, which can be crosslinked using a variety of curing agents, such as peroxides. The structure of the condensed FEPM polymer is shown below. -(CF2CF2)n-(CH2CHCH3)m

[0022] Perfluoroelastomers (FFKM) are the elastomeric form of polytetrafluoroethylene (PTFE) and have a fluorinated main structure. As shown in the condensed polymer structure of FFKM below, FFKM includes copolymers of tetrafluoroethylene and a perfluorinated ether, such as perfluoromethyl vinyl ether (PMVE). -(CF2CF2)a-(CF2CFORf)b

[0023] As presented, the main structure of FFKM includes oxygen atoms that are part of the ether groups, which confer elasticity. Depending on the type of ether (indicated by the length of the side chain), the fluorine content in FFKM can vary. To vulcanize FFKM, small amounts of a crosslinkable monomer (CSM) can be introduced, such as cyanofunctional vinyl ethers. Fluorofilling

[0024] According to embodiments of this disclosure, fluorofillers may include a carbon-based starting filler material that has been modified to include fluorine (F). For example, carbon-based molecules such as carbon black, graphene, and carbon nanotubes may be fluorinated to have a fluorine atom compounded with them. In one or more embodiments, the material Petition 870250067995, dated 04 / 08 / 2025, pp. 56 / 68 5 / 11 of the starting filler can be nanoscale carbon-based molecules, which can vary in size, for example, between 1 and 500 nm in diameter.

[0025] In one or more embodiments, a starting filler material can be fluorinated by treating or reacting the starting filler material with a fluorinating agent, for example, gaseous fluorine (F2), xenon difluoride (XeF2), hydrofluoric acid (HF), tetrafluoromethane (CF4), terbium(IV) fluoride (TbF4), etc., using direct fluorination, indirect fluorination, or plasma-assisted fluorination methods. For example, a nanometric starting filler material can be fluorinated using direct gas fluorination, wherein the fluorofiller is synthesized in a gaseous atmosphere using gas containing F2 as a fluorinating agent. In some embodiments, the fluorofiller can be derived from a starting filler material by replacing one or more hydrogen atoms in the starting filler compound with fluorine.

[0026] In one or more embodiments, the fluorofilling material may be fluorinated carbon black. Fluorinated carbon black may be formed, for example, by the reaction of a quantity of carbon black nanoparticles with gaseous fluorine (F2). Carbon black nanoparticles may be selected, for example, from the N100 and N800 series. When the carbon black is fluorinated, the fluorine may be covalently bonded to reactive carbon atoms in the surface and subsurface layers of the carbon black particles.

[0027] In some embodiments, the fluorofilling material may be fluorographene. Fluorographene may be formed, for example, by reacting graphene with a fluorinating agent such as xenon difluoride (XeF2), or by chemical exfoliation of graphite fluoride (CFx)n. In one or more embodiments, the fluorographene may have a composition of F ranging from 53 to 65 wt% (wt%) and C ranging from 35 to 47 wt% (wt%).

[0028] In some embodiments, the fluorofilling material may be fluorinated graphene nanotubes. Fluorinated graphene nanotubes may be formed, for example, by the reaction of a fluorinating agent with graphene nanotube starting material under elevated temperatures (e.g., above (149 °C (300 °F)).

[0029] According to the embodiments of the present disclosure, the fluorofiller material may be nanometer-sized. For example, the fluorofiller material used to form fluoroelastomer composites according to Petition 870250067995, dated 04 / 08 / 2025, pp. 57 / 68 6 / 11 embodiments of the present disclosure may have an average particle size ranging from about 1 nm to about 500 nm. In some embodiments, the fluorofilling material may have an average particle size ranging from about 50 nm to 600 nm, or more. Fluoroelastomer Composites

[0030] Fluoroelastomer composites according to the embodiments of this disclosure can be produced, for example, by in situ polymerization, wherein the fluorofiller material is mixed in a solution of fluoroelastic matrix monomers, and the solution is polymerized. In some embodiments, fluoroelastomer composites can be produced by direct mixing of the fluorofiller and fluoroelastic matrix, which may include mixing a fluoroelastomer, in the absence of solvents, with fluorofillers above the softening point of the fluoroelastomer or mixing the fluoroelastomer and fluorofillers in a solution.

[0031] As an example of forming fluoroelastomer composites according to the embodiments of this disclosure, the components of a fluoroelastomer composite can be mixed in a Banbury mixer or in a roller mill. In some embodiments, the components of a fluoroelastomer composite can be mixed in a fluid paste or solvent as a base mixture for polymerization.

[0032] In some embodiments, one or more types of fluorofiller material may be added to a single type of fluoroelastic matrix material to form a fluoroelastomer composite. In some embodiments, a single type of fluorofiller material may be added to a mixture of multiple types of fluoroelastic matrix material to form a fluoroelastomer composite.

[0033] In one or more embodiments, fluoroelastomer composites may include an amount of fluorofiller material ranging, for example, from 1 to 60 parts per hundred of polymer (phr), as calculated by dividing the weight of the fluorofiller by the weight of the fluoroelastomer times 100. In some embodiments, fluoroelastomer composites may include an amount of fluorofiller material ranging from 1 to 40 phr. In one or more specific embodiments, fluoroelastomer composites may include an amount of fluorofiller material ranging from 5 to 20 phr. Petition 870250067995, dated 04 / 08 / 2025, pages 58 / 68 7 / 11

[0034] Figure 6 presents an exemplary fluoroelastomer composite 600 according to one or more embodiments disclosed herein. The fluoroelastomer composite 600 in Figure 6 includes a fluoroelastic matrix 602 and a fluorofiller 604. In one or more embodiments, the fluoroelastic matrix 602 is a fluoroelastomer 606. As described above, the fluoroelastomer 606 can be a carbon-based polymer having fluorine atoms or fluorine-containing groups attached to the back chain. Furthermore, the fluorofiller 604 as described above can be a carbon-based material, including carbon black, graphene, and carbon nanotubes functionalized with fluorine atoms. In one or more embodiments, the carbon-fluorine surface bonds in the fluorofiller 604 can improve compatibility with the fluoroelastomer 606.

[0035] The fluorofiller 604 can be linked to a portion of the fluoroelastomer 606 via a carbon-fluorine surface bond 612, for example, by covalent bonding. In some embodiments, the fluorofiller 604 can interact with the fluoroelastomer 606 via van der Waals forces. In one or more embodiments, when a strain 608 is applied to the fluoroelastomer composite 600, the bonds 612 (or van der Waals forces) between the fluorofiller 604 and the fluoroelastomer 606, as shown in Figure 6, can provide an anchoring point for polymer chain extension. For example, extended fluoroelastomer chains 610 are presented after application of deformation 608 to the fluoroelastomer composite 600. Anchoring polymer chains to the fluorofiller 604 can therefore provide greater resistance to deformation 608 and better mechanical properties compared to conventional fluoroelastomers.

[0036] Carbon-fluorine surface bonds of fluorofillers can provide enhanced polymer-filler interactions with the fluoroelastic matrix in fluoroelastomer composites, according to the embodiments of the present disclosure. Such enhanced polymer-filler interactions can provide improved mechanical properties compared to conventional fluoroelastomers, such as higher tear resistance and greater fatigue resistance. The resulting enhanced mechanical properties allow the use of fluoroelastomer composites according to the embodiments of the present disclosure to withstand higher temperatures, Petition 870250067995, dated 04 / 08 / 2025, pages 59 / 68 8 / 11 more aggressive environments and last longer in those environments, compared to conventional fluoroelastomers. Fluoroelastomer Components

[0037] Fluoroelastomer composites according to the embodiments of this disclosure can be used for the production of polymeric components in various industries, such as hydrocarbon recovery systems, automotive systems, industrial processing systems, and others. For example, in the oil and gas industry, fluoroelastomer composites according to the embodiments of this disclosure can be used to form obturators, annular and variable gate seals, other sealing elements used to form a seal around a pipe, gasket seals, O-rings and other sealing elements for pressure control, polymeric components for wells, or polymeric components for wellheads. In some embodiments, fluoroelastomer composites according to the embodiments of this disclosure can be used to form hoses, such as connecting hoses or other fluid distribution hoses.In some embodiments, fluoroelastomer composites according to embodiments of the present disclosure can be used to form polymeric components used in or around motors or other mechanical systems that may be exposed to aggressive environments (e.g., high temperatures and / or corrosive elements) and dynamic conditions (e.g., sealing stresses, rotational motion, and others).

[0038] Figures 1 to 4 show several examples of systems and components in which fluoroelastomer composites according to the embodiments of this disclosure are used to form the components. However, by reading this disclosure, a person skilled in the art may recognize that various other components can be formed from fluoroelastomer composites according to the embodiments of this disclosure.

[0039] Figure 1 shows a drilling system 100 in which one or more polymeric components are made of a fluoroelastomer composite according to the embodiments of the present disclosure. The drilling system features several pieces of equipment commonly used in drilling operations. The equipment shown is not necessarily all used simultaneously in a drilling operation, but is merely included together for Petition 870250067995, dated 04 / 08 / 2025, pages 60 / 68 9 / 11 present their relative arrangements in a drilling system. As presented, a blowout system 100 may include a blowout preventer (BOP) 102 positioned in a wellbore 104. A drill string 108 or other pipe string may be inserted through the BOP 102 and into the well 106, for example, to drill the well 106 in a drilling operation, to produce well fluids in a production operation, or to perform other downhole operations.

[0040] One or more sealing elements in the BOP, such as an annular seal or a variable bore gate seal, may be made of a fluoroelastomer composite according to the embodiments of the present disclosure. Figure 2 shows an example 200 of an annular seal 202 in an annular BOP 204 that is made entirely of a fluoroelastomer composite according to the embodiments of the present disclosure. Figure 3 shows an example of a variable bore gate 300 having a variable gate body 302, a front seal 304 and a top seal 306, wherein one or both of the front seal 304 and top seal 306 may be made entirely of a fluoroelastomer composite according to the embodiments of the present disclosure.

[0041] Referring again to Figure 1, a drilling system 100 may also include one or more packers 110 or plugs used to seal a section of the well. Packers 110 and plugs may include various configurations of sealing elements that may be used, for example, to seal annular spaces in the well 106 (e.g., the annular space between the drill string 108 and the well wall) or to seal an entire flow path (e.g., sealing a pipe or casing). Examples of packers 110 and plugs that may have one or more sealing elements made of a fluoroelastomer composite according to embodiments of the present disclosure include permanent plugs, recoverable plugs, bridging plugs, inflatable packers, hydraulic packers, production packers, recoverable packers, and others.Figure 4 shows an example of a 400 obturator sealing element made entirely of a fluoroelastomer composite according to the embodiments of the present disclosure.

[0042] Sealing elements made entirely of a fluoroelastomer composite according to the embodiments of this disclosure may include sealing elements having a body generally in an annular shape. For example, the Petition 870250067995, dated 04 / 08 / 2025, pages 61 / 68 The annular seal 202 shown in Figure 2 and the obturator sealing element 400 shown in Figure 4 have annular bodies that can be formed entirely of a fluoroelastomer composite according to the embodiments of this disclosure. Furthermore, as shown in Figure 5, a sealing ring 500, which has an annular body, can be formed entirely of a fluoroelastomer composite according to the embodiments of this disclosure.

[0043] Furthermore, in some embodiments, the polymeric components may be formed from multiple polymeric materials to provide different material properties to different portions of the component, wherein at least one of the multiple polymeric materials is a fluoroelastomer composite according to the embodiments described in the present invention. For example, in some embodiments, a polymeric component may be formed from two or more different fluoroelastomer composite materials according to embodiments of the present disclosure, wherein the different fluoroelastomer composites include a different chemical composition (e.g., type of monomer used), fluorine content (e.g., degree of fluorination), and / or crosslinking mechanism.

[0044] Fluoroelastomer composites according to the embodiments of this disclosure may be suitable for forming sealing elements and other components subject to aggressive environments and / or dynamic stresses. For example, the 400 obturator sealing elements, as shown in Figure 4, and other downhole sealing elements may be subject to dynamic stresses such as compressive forces, shear stresses and / or torsional stresses during operation and in aggressive environments such as downhole pressures and temperatures (e.g., pressures exceeding 5,000 psi (e.g., ranging from 10,000 psi to 35,000 psi or more) and temperatures exceeding (65 °C (150 °F)) (e.g., ranging from (77 °C (170 °F)) to (95 °C (204 °C)) or more)).Furthermore, fluoroelastomer composites according to the embodiments of this disclosure may be particularly suitable for forming components used in or exposed to acidic environments with high levels of hydrogen sulfide, for example, exceeding 30% by volume of the environmental composition, or 40% by volume or more.

[0045] Although conventional fluoroelastomers have been used in many oil and gas applications to provide resistance to drilling fluids and corrosive gases, such as hydrogen sulfide, in aggressive environments, Petition 870250067995, dated 04 / 08 / 2025, pages 62 / 68 Conventional fluoroelastomers exhibit inferior mechanical properties, such as tear resistance and fatigue resistance, compared to those obtained with other oil-resistant elastomer compounds used in oil and gas applications, due to their crosslinking mode. By using fluoroelastomer composites according to the embodiments of this disclosure, in which reinforcing fluorofillers are provided in fluoroelastomer compounds, the fluoroelastomer composites can have improved mechanical properties compared to conventional fluoroelastomers, especially at higher temperatures.

[0046] Although the present disclosure has been described in relation to a limited number of embodiments, those skilled in the art who benefit from this disclosure will recognize that other embodiments may be conceived without departing from the scope of the disclosure as described in this invention. Consequently, the scope of the disclosure should be limited only by the appended claims. Petition 870250067995, dated 04 / 08 / 2025, pp. 63 / 68

Claims

1 / 3 CLAIMS 1. Polymer, CHARACTERIZED by comprising: a fluoroelastic matrix comprising a fluoroelastomer, and an amount of fluorofiller dispersed in the fluoroelastic matrix, wherein the fluorofiller comprises a fluorinated carbon-based molecule.

2. Polymer according to claim 1, CHARACTERIZED in that the fluoroelastic matrix comprises one or more monomers selected from the group consisting of ethylene (E), hexafluoropropylene (HFP), perfluoromethyl vinyl ether (PMVE), propylene (P), tetrafluoroethylene (TFE) and vinylidene fluoride (VDF).

3. Polymer according to claim 1, CHARACTERIZED in that the fluoroelastic matrix is ​​selected from Fluor Kautschuk Material (FKM), TFE / P polymers (FEPM) and perfluoroelastomers (FFKM).

4. Polymer according to claim 1, CHARACTERIZED in that the fluorofiller is selected from at least one of fluorinated carbon black, fluorinated graphene and fluorinated carbon nanotubes.

5. Polymer according to claim 4, CHARACTERIZED in that the fluorofiller comprises fluorinated graphene having a fluorine composition of 53 to 65% by weight and carbon of 35 to 47% by weight.

6. Polymer according to claim 4, CHARACTERIZED in that the fluorofilling comprises fluorinated carbon nanotubes formed by reaction of a fluorinating agent with a graphene nanotube at temperatures above (149 °C (300 °F)).

7. Polymer according to claim 1, CHARACTERIZED in that the fluorofiller has an average particle size ranging from 1 to 500 nm.

8. Polymer according to claim 1, CHARACTERIZED in that the fluorofiller comprises a starting filler material, wherein the starting filler material is fluorinated to produce the fluorofiller.

9. Polymer according to claim 8, CHARACTERIZED in that the starting filler material is fluorinated by treatment or reaction with one or more fluorinating agents selected from the group consisting of gaseous fluorine (F2), xenon difluoride (XeF2), hydrofluoric acid (HF), tetrafluoromethane (CF4), terbium(IV) fluoride (TbF4). Petition 870250067995, dated 04 / 08 / 2025, page 49 / 68 2 / 3 10. Polymer according to claim 9, CHARACTERIZED in that the fluorination step is conducted using direct fluorination, indirect fluorination or plasma-assisted fluorination methods.

11. Polymer according to claim 2, CHARACTERIZED in that the polymer is synthesized by in situ polymerization of one or more fluoroelastic matrix monomers and the fluorofiller.

12. Polymer according to claim 1, CHARACTERIZED in that the polymer is produced by direct mixing of the fluoroelastic matrix and the fluorofiller in the absence of any solvents at a temperature above the softening point of the fluoroelastomer.

13. Polymer according to claim 1, CHARACTERIZED in that the polymer is produced by direct mixing of the fluoroelastic matrix and the fluorofiller in a solution.

14. Polymer according to claim 1, CHARACTERIZED in that the polymer comprises fluorofiller in an amount of 1 to 60 phr.

15. Sealing, CHARACTERIZED by comprising: an annular body made of a fluoroelastomer composite, the fluoroelastomer composite comprising: a fluoroelastic matrix comprising a fluoroelastomer, and an amount of fluorofiller dispersed in the fluoroelastic matrix, wherein the fluorofiller comprises a fluorinated carbon-based molecule.

16. Sealing according to claim 15, CHARACTERIZED in that the seal is fitted into a rupture preventer.

17. Sealing according to claim 15, CHARACTERIZED in that the fluoroelastic matrix is ​​selected from Fluor Kautschuk Material (FKM), TFE / P polymers (FEPM) and perfluoroelastomers (FFKM).

18. Sealing according to claim 15, CHARACTERIZED in that the fluorofiller is selected from at least one of fluorinated carbon black, fluorinated graphene and fluorinated carbon nanotubes.

19. Sealing according to claim 15, CHARACTERIZED in that the fluoroelastomer composite comprises the fluorofiller in an amount of 1 to 60 phr. Petition 870250067995, dated 04 / 08 / 2025, pp. 50 / 68 3 / 3 20. Sealing according to claim 15, CHARACTERIZED in that the fluorofiller has an average particle size ranging from 1 to 500 nm. Petition 870250067995, dated 04 / 08 / 2025, pp. 51 / 68

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