Fluoroelastomer compounds for sealing elements

Abstract

The disclosed polymer composition includes a fluorine-containing elastomeric matrix and a fluorine-containing filler. The fluorine-containing elastomeric matrix includes a fluorine-containing elastomer and the fluorine-containing filler includes a fluorinated carbon-based molecule. An amount of the fluorine-containing filler is dispersed in the fluorine-containing elastomeric matrix. A polymer composition is used to form a sealing element having an annular body to withstand harsh environments.

Description

Background Technology

[0001] Due to their heat resistance, chemical resistance, strength, and other material properties, fluorinated elastomers are frequently used in the manufacture of sealing elements and other components for industrial applications. The term "fluorinated elastomer" is generally used to refer to synthetic rubbers whose molecular structure contains fluorine. Fluorinated elastomer materials are typically made from monomers of vinylidene fluoride (VDF), hexafluoropropylene (HFP), perfluoromethyl vinyl ether (PMVE), tetrafluoroethylene (TFE), propylene (P), and / or other materials. For example, fluorinated elastomers used in components of hydrocarbon recovery systems may contain VDF-based copolymers such as fluororubber (FKM), TFE / P polymer (FEPM), and perfluoroelastomer (FFKM).

[0002] Fluorinated elastomers have been used in components of hydrocarbon recovery systems, such as packer elements, blowout preventer elements, O-rings, gaskets, electrical insulators, pressure sealing elements for fluids, and many other oilfield and downhole components. In these applications, the polymers can be exposed to harsh environments, such as severe chemical and mechanical underground conditions, which often unacceptably degrade the polymer's lifespan and reliability. Furthermore, while fluorinated elastomers can provide some resistance to alkalis and high temperatures in acidic environments (containing hydrogen sulfide (H₂S)), fluorinated elastomer components may be among the first to fail under high levels of dynamic stress.

[0003] Therefore, there is still a need to improve the reliability and lifespan of polymer components used in oilfield environments, such as protective bags, packer elements, pressure seals, valve seals, blowout preventer components, cable shielding and sheathing. Summary of the Invention

[0004] This overview is provided to introduce a range of concepts, which are further described in detail below. This overview is not intended to identify key or essential features of the claimed subject matter, nor is it intended to be used as an aid to limiting the scope of the claimed subject matter.

[0005] In one aspect, the embodiments disclosed herein relate to a fluorinated elastomer composite material made of a fluorinated elastomer matrix and a certain amount of fluorinated filler material dispersed in the fluorinated elastomer matrix, wherein the fluorinated filler material comprises fluorinated carbon-based molecules.

[0006] In another aspect, the embodiments disclosed herein relate to a polymer component made at least in part of a fluorinated elastomer composite material made of a fluorinated filler material dispersed in a fluorinated elastomer matrix.

[0007] Other aspects and advantages will become apparent from the following description and the appended claims. Attached Figure Description

[0008] The accompanying drawings are not necessarily drawn to scale, and for clarity, certain features and perspectives in the drawings may be shown at scale.

[0009] Figure 1 A drilling system having at least one component is shown according to an embodiment of the present disclosure.

[0010] Figure 2 An example of an annular blowout preventer with an annular seal according to an embodiment of the present disclosure is shown.

[0011] Figure 3 An example of a variable orifice seal according to an embodiment of this disclosure is shown.

[0012] Figure 4 An example of a packer sealing element according to an embodiment of this disclosure is shown.

[0013] Figure 5 An example of an O-ring according to an embodiment of this disclosure is shown.

[0014] Figure 6 An example of a fluorinated elastomer composite material according to an embodiment of the present disclosure is shown. Detailed Implementation

[0015] Embodiments of this disclosure are described in detail below with reference to the accompanying drawings. In the following detailed description, numerous specific details are set forth to provide a more thorough understanding of the claimed subject matter. However, it will be apparent to those skilled in the art that the embodiments can be practiced without these specific details. In other instances, well-known features have not been described in detail to avoid unnecessarily complicating the description.

[0016] Embodiments of this disclosure generally relate to fluorinated elastomer composite materials and components made therefrom. Components made of fluorinated elastomer composite materials according to embodiments of this disclosure may include sealing elements, such as those used in hydrocarbon recovery systems, and other components used in harsh environments. For example, components used in hydrogen sulfide-rich environments (acidic environments), such as sealing elements for drilling operations exposed to hydrogen sulfide, may be made of the fluorinated elastomer composite materials described herein. In other embodiments, the fluorinated elastomer composite materials according to embodiments of this disclosure may be used to manufacture polymer components in other industries, such as in the automotive industry (e.g., for automotive seals) and for hose applications.

[0017] According to embodiments of this disclosure, fluorinated elastomer composite materials may include fluorinated fillers dispersed within a fluorinated elastomer matrix. As used herein, a fluorinated filler refers to a filler material that has been modified to contain fluorine (F). Examples of fluorinated elastomer matrix materials and fluorinated fillers are described below.

[0018] Fluorinated elastic matrix

[0019] Fluorinated elastomer matrix materials comprise fluorinated elastomers made from fluorinated carbon-based monomers. Examples of monomers that can be used to form fluorinated elastomer matrices include, but are not limited to, ethylene (E), hexafluoropropylene (HFP), perfluoromethyl vinyl ether (PMVE), propylene (P), tetrafluoroethylene (TFE), and vinylidene fluoride (VDF). The chemical composition (e.g., type of monomer used), fluorine content (e.g., degree of fluorination), and / or crosslinking mechanism of fluorinated elastomer matrices can be varied to provide a variety of overall material properties.

[0020] For example, the fluorinated elastic matrix material of fluorinated elastic composites used to form components of hydrocarbon recovery systems may contain VDF-based copolymers, such as fluorinated elastomers classified as "FKM" (polymethylene fluororubber, using vinylidene fluoride as a comonomer and having substituted fluorine, allyl, perfluoroalkyl or perfluoroalkoxy groups on the polymer chain) according to ASTM D1418; TFE / P polymer (FEPM) and perfluoro elastomer (FFKM).

[0021] FKM fluorinated elastic matrix materials can be selected from five types classified according to ASTM D1418, including: binary copolymers of VDF and HFP (Type 1), terpolymers of VDF, HFP and TFE (Type 2), terpolymers of VDF, TFE and fluorinated vinyl ethers (Type 3), terpolymers of P, TFE and VDF (Type 4), and pentpolymers of VDF, HFP, TFE, E and fluorinated vinyl ethers (Type 5).

[0022] 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 condensation polymer structure of FEPM is shown below.

[0023] -(CF2CF2) n -(CH2CHCH3) m -

[0024] Perfluoroelastomers (FFKMs) are elastomeric forms of polytetrafluoroethylene (PTFE) and have a fluorinated backbone. As shown in the condensation polymer structure of FFKM below, FFKM comprises copolymers of tetrafluoroethylene and perfluoroethers (such as perfluoromethyl vinyl ether (PMVE)).

[0025] -(CF2CF2) a -(CF2CFORf) b -

[0026] As shown in the structure, the skeleton of FFKM includes oxygen atoms as part of the ether group, which provide elasticity. The fluorine content in FFKM can vary depending on the type of ether (marked by the side chain length). To vulcanize FFKM, small amounts of crosslinkable monomers (CSMs) can be introduced, such as vinyl ethers with cyano functional groups.

[0027] Fluorine filler

[0028] According to embodiments of this disclosure, the fluorinated filler may comprise a carbon-based starting filler material that has been modified to contain fluorine (F). For example, carbon-based molecules, such as carbon black, graphene, and carbon nanotubes, may be fluorinated to incorporate fluorine atoms. In one or more embodiments, the starting filler material may be a nanoscale carbon-based molecule, possibly ranging in size from, for example, in diameter between 1 and 500 nm.

[0029] In one or more embodiments, the starting filler material can be fluorinated by treating or reacting it with a fluorinating agent using direct fluorination, indirect fluorination, or plasma-assisted fluorination methods. Fluorinating agents include, for example, gaseous fluorine (F2), xenon difluoride (XeF2), hydrofluoric acid (HF), tetrafluoromethane (CF4), terbium (IV) fluoride (TbF4), etc. For example, nanoscale starting filler materials can be fluorinated using direct gas fluorination, wherein the fluorinated filler is synthesized in an atmosphere formed by using an F2-containing gas as a fluorinating agent. In some embodiments, the fluorinated filler material can be derived from the starting filler material by replacing one or more hydrogen atoms in the starting filler compound with fluorine.

[0030] In one or more embodiments, the fluorinated filler material may be fluorinated carbon black. Fluorinated carbon black can be formed, for example, by reacting a certain amount of carbon black nanoparticles with gaseous fluorine (F2). The carbon black nanoparticles may be selected from, for example, the N100 and N800 series. When carbon black is fluorinated, fluorine can be covalently bonded to reactive carbon atoms on the surface and subsurface shell of the carbon black particles.

[0031] In some embodiments, the fluorinated filler material may be fluorinated graphene. Fluorinated graphene can be, for example, produced by reacting graphene with a fluorinating agent such as xenon difluoride (XeF2), or by fluorinating graphene (CF2). x ) nIt is formed by chemical exfoliation. In one or more embodiments, fluorinated graphene may have a composition of fluorine ranging from 53 to 65 wt% and carbon ranging from 35 to 47 wt%.

[0032] In some embodiments, the fluorinated filler material may be fluorinated graphene nanotubes. Fluorinated graphene nanotubes may be formed, for example, by reacting a fluorinating agent with a graphene nanotube starting material under high temperature (e.g., above 300℉) conditions.

[0033] According to embodiments of this disclosure, the size of the fluorinated filler material should be at the nanoscale. For example, the fluorinated filler material for forming a fluorinated elastomer composite material according to embodiments of this disclosure may have an average particle size ranging from about 1 nm to about 500 nm. In some embodiments, the fluorinated filler material may have an average particle size ranging from about 50 nm to 600 nm or greater.

[0034] Fluorinated elastomer composites

[0035] Fluorinated elastomer composites according to embodiments of this disclosure can be prepared, for example, by in-situ polymerization, wherein a fluorinated filler material is mixed in a solution of a fluorinated elastomer matrix monomer and the solution is polymerized. In some embodiments, the fluorinated elastomer composite can be prepared by directly mixing a fluorinated filler with a fluorinated elastomer matrix, which may include mixing the fluorinated elastomer with the fluorinated filler at a temperature above the softening point of the fluorinated elastomer without any solution, or mixing the fluorinated elastomer with the fluorinated filler in solution.

[0036] As an example of forming a fluorinated elastomer composite material according to embodiments of the present disclosure, the components of the fluorinated elastomer composite material can be mixed in a Banbury mixer or a roller mill. In some embodiments, the components of the fluorinated elastomer composite material can be mixed in a slurry or solvent serving as a masterbatch for polymerization.

[0037] In some embodiments, one or more types of fluorinated filler materials may be added to a single type of fluorinated elastomer matrix material to form a fluorinated elastomer composite material. In some embodiments, a single type of fluorinated filler material may be added to a mixture of multiple types of fluorinated elastomer matrix materials to form a fluorinated elastomer composite material.

[0038] In one or more embodiments, the fluorinated elastomer composite material may contain a certain amount of fluorinated filler material, for example, ranging from 1 to 60 parts per hundred parts polymer (phr), calculated by dividing the weight of the fluorinated filler by the weight of the fluorinated elastomer and multiplying by 100. In some embodiments, the fluorinated elastomer composite material may contain an amount of fluorinated filler material ranging from 1 to 40 phr. In one or more specific embodiments, the fluorinated elastomer composite material may contain an amount of fluorinated filler material ranging from 5 to 20 phr.

[0039] Figure 6 An example fluorinated elastomer composite material 600 according to one or more embodiments disclosed herein is shown. Figure 6 The fluorinated elastomer composite material 600 comprises a fluorinated elastomer matrix 602 and a fluorinated filler 604. In one or more embodiments, the fluorinated elastomer matrix 602 is a fluorinated elastomer 606. As described above, the fluorinated elastomer 606 can be a carbon-based polymer containing fluorine atoms or fluorinated groups attached to a backbone. Additionally, the fluorinated filler 604 described above can be a carbon-based material comprising carbon black, graphene, and carbon nanotubes functionalized with fluorine atoms. In one or more embodiments, the carbon-fluorine surface bonds on the fluorinated filler 604 can improve compatibility with the fluorinated elastomer 606.

[0040] The fluorinated filler 604 can be partially bonded to the fluorinated elastomer 606 via carbon-fluorine surface bonds 612, for example, via covalent bonds. In some embodiments, the fluorinated filler 604 can interact with the fluorinated elastomer 606 via van der Waals forces. In one or more embodiments, when strain 608 is applied to the fluorinated elastomer composite material 600, as... Figure 6 The bond 612 (or van der Waals force) between the fluorinated filler 604 and the fluorinated elastomer 606 shown can provide anchoring points for polymer chain extension. For example, an extended fluorinated elastomer chain 610 is shown after strain 608 is applied to the fluorinated elastomer composite 600. The anchoring of the polymer chain to the fluorinated filler 604 can therefore provide improved strain 608 tolerance and enhanced mechanical properties compared to conventional fluorinated elastomers.

[0041] The carbon-fluorine surface bonds of the fluorinated filler can provide enhanced polymer-filler-fluorinated elastomer matrix interactions in fluorinated elastomer composites according to embodiments of the present disclosure. This enhanced polymer-filler interaction can provide improved mechanical properties compared to conventional fluorinated elastomers, such as increased tear strength and improved fatigue resistance. The resulting improved mechanical properties, compared to conventional fluorinated elastomers, allow the use of fluorinated elastomer composites according to embodiments of the present disclosure to withstand higher temperatures, harsher environments, and for longer durations in such environments.

[0042] Fluorinated elastomer components

[0043] The fluorinated elastomer composite materials according to embodiments of this disclosure can be used to prepare polymer components in a variety of industries, such as hydrocarbon recovery systems, automotive systems, and industrial processing systems. For example, in the oil and gas industry, the fluorinated elastomer composite materials according to embodiments of this disclosure can be used to form packers, annular and variable gate seals, other sealing elements for forming seals around pipelines, gland seals, O-rings and other pressure control sealing elements, well site polymer components, or downhole polymer components. In some embodiments, the fluorinated elastomer composite materials according to embodiments of this disclosure can be used to form hoses, such as connecting hoses or other fluid delivery hoses. In some embodiments, the fluorinated elastomer composite materials according to embodiments of this disclosure can be used to form polymer components for use in or around engines or other mechanical systems that may be exposed to harsh environments (e.g., high temperatures and / or corrosive elements) and dynamic conditions (e.g., sealing stress, rotational motion, etc.).

[0044] Figures 1 to 4 Several examples of systems and components are shown, wherein fluorinated elastomer composite materials according to embodiments of the present disclosure are used to form components. However, after reading this disclosure, those skilled in the art will understand that a wide variety of other components can be formed from fluorinated elastomer composite materials according to embodiments of the present disclosure.

[0045] exist Figure 1 In the figure, a drilling system 100 is shown, wherein one or more polymer components are made of a fluorinated elastomer composite material according to embodiments of the present disclosure. The drilling system illustrates a variety of devices generally used in drilling operations. The devices shown are not necessarily all used simultaneously in drilling operations, but are merely included together to illustrate their relative arrangement within the drilling system. As shown, the drilling system 100 may include a blowout preventer (BOP) 102 located at the opening of a well 104. A drill string 108 or other tubing may be inserted through the BOP 102 and into the wellbore 106, for example, to drill the drillbore 106 during drilling operations, to generate fluid from the well during production operations, or to perform other downhole operations.

[0046] One or more sealing elements in a BOP, such as annular seals or variable bore ram seals, may be made of fluoroelastomer composite materials according to embodiments of the present disclosure. Figure 2 An example 200 of an annular seal 202 in an annular BOP 204 made entirely of a fluorinated elastomer composite material according to embodiments of the present disclosure is shown. Figure 3An example of a variable aperture gate 300 having a variable gate body 302, a front seal 304 and a top seal 306 is shown, wherein one or both of the front seal 304 and the top seal 306 may be made entirely of a fluoropolymer composite material according to embodiments of the present disclosure.

[0047] Refer again Figure 1 The drilling system 100 may also include one or more packers 110 or plugs for sealing sections of the wellbore. The packers 110 and plugs may include sealing elements of various configurations, which may, for example, be used to seal annular spaces within the wellbore 106 (e.g., the annular space between the drill string 108 and the wellbore) or to seal an entire flow path (e.g., sealing tubing or casing boreholes). Examples of packers 110 and plugs having one or more sealing elements made of a fluoropolymer composite material according to embodiments of this disclosure include permanent plugs, recyclable plugs, bridge plugs, pneumatic packers, hydraulic packers, production packers, recyclable packers, etc. Figure 4 An example of a packer sealing element 400 made entirely of a fluorinated elastomer composite material according to embodiments of the present disclosure is shown.

[0048] A sealing element made entirely of a fluoroelastomer composite material according to embodiments of the present disclosure may include a sealing element having a generally annular body. For example, Figure 2 The annular seal 202 shown and Figure 4 The packer sealing element 400 shown has an annular body formed entirely of a fluorinated elastomer composite material according to embodiments of the present disclosure. Additionally, as... Figure 5 As shown, the O-ring 500 having an annular body can be formed entirely from a fluorinated elastomer composite material according to embodiments of the present disclosure.

[0049] Additionally, in some embodiments, the polymer component may be formed from a variety of polymer materials to provide different material properties to different portions of the component, wherein at least one of the various polymer materials is a fluorinated elastomer composite material according to the embodiments described herein. For example, in some embodiments, the polymer component may be formed from two or more different fluorinated elastomer composite materials according to embodiments of the present disclosure, wherein the different fluorinated elastomer composite materials contain different chemical compositions (e.g., types of monomers used), fluorine content (e.g., degree of fluorination), and / or crosslinking mechanisms.

[0050] Fluorinated elastomer composite materials according to embodiments of this disclosure are particularly suitable for forming sealing elements and other components subjected to harsh environments and / or dynamic stresses. For example, such as Figure 4The packer sealing element 400 and other downhole sealing elements shown can withstand dynamic stresses during operation, such as compressive forces, shear stresses, and / or torsional stresses; and harsh environments, such as downhole pressures and temperatures (e.g., pressures greater than 5000 psi (e.g., in the range of 10,000 psi to 35,000 psi or higher) and temperatures greater than 150℉ (e.g., in the range of 170℉ to 400℉ or higher)). Additionally, fluorinated elastomer composite materials according to embodiments of this disclosure are particularly suitable for forming components for or exposed to acidic environments with high levels of hydrogen sulfide, e.g., hydrogen sulfide levels greater than 30 percent by volume, or 40 percent or more by volume, of the environmental composition.

[0051] Although conventional fluorinated elastomers have been used in many oil and gas applications to provide resistance to drilling fluids and corrosive gases such as hydrogen sulfide in harsh environments, they exhibit lower mechanical properties, such as tear strength and fatigue resistance, compared to other oil-resistant elastomer compounds used in oil and gas applications due to their crosslinking patterns. By using fluorinated elastomer composites according to embodiments of this disclosure, wherein a reinforcing fluorinated filler is provided in the fluorinated elastomer compound, the mechanical properties of the fluorinated elastomer composites have been improved compared to conventional fluorinated elastomers, especially at higher temperatures.

[0052] While this disclosure has been described with respect to a limited number of embodiments, those skilled in the art who benefit from this disclosure will understand that other embodiments may be designed without departing from the scope of the disclosure described herein. Therefore, the scope of this disclosure should be limited only by the appended claims.

Claims

1. A polymer comprising: Fluorinated elastic matrix, including fluorinated elastomers; and A certain amount of fluorinated filler dispersed in the fluorinated elastic matrix, wherein the fluorinated filler comprises fluorinated carbon-based molecules.

2. The polymer according to claim 1, wherein the fluorinated elastic 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. The polymer according to claim 1, wherein the fluorinated elastic matrix is ​​selected from fluororubber materials (FKM), TFE / P polymers (FEPM), and perfluoroelastomers (FFKM).

4. The polymer according to claim 1, wherein the fluorinated filler is selected from at least one of fluorinated carbon black, fluorinated graphene, and fluorinated carbon nanotubes.

5. The polymer of claim 4, wherein the fluorinated filler comprises fluorinated graphene having a composition of 53 to 65% by weight of fluorine and 35 to 47% by weight of carbon.

6. The polymer of claim 4, wherein the fluorinated filler comprises fluorinated carbon nanotubes formed by reacting a fluorinating agent and graphene nanotubes at a temperature greater than 300℉.

7. The polymer according to claim 1, wherein the average particle size of the fluorinated filler ranges from 1 to 500 nm.

8. The polymer of claim 1, wherein the fluorinated filler comprises a starting filler material, wherein the starting filler material is fluorinated to produce the fluorinated filler.

9. The polymer according to claim 8, wherein 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), and terbium fluoride (IV) (TbF4).

10. The polymer of claim 9, wherein the fluorination step is performed using a direct fluorination, indirect fluorination, or plasma-assisted fluorination method.

11. The polymer of claim 2, wherein the polymer is synthesized by in-situ polymerization of the one or more monomers of the fluorinated elastic matrix and the fluorinated filler.

12. The polymer of claim 1, wherein the polymer is prepared by directly mixing the fluorinated elastomer matrix and the fluorinated filler at a temperature above the softening point of the fluorinated elastomer without any solvent.

13. The polymer according to claim 1, wherein the polymer is prepared by directly mixing the fluorinated elastomer and the fluorinated filler in solution.

14. The polymer of claim 1, wherein the polymer comprises an amount of the fluorinated filler of 1 to 60 phr.

15. A seal comprising: A ring-shaped body made of a fluorinated elastomer composite material, the fluorinated elastomer composite material comprising: Including fluorinated elastomers and fluorinated elastomer matrices; and A certain amount of fluorinated filler dispersed in the fluorinated elastic matrix, wherein the fluorinated filler comprises fluorinated carbon-based molecules.

16. The seal of claim 15, wherein the seal is installed in the blowout preventer.

17. The seal according to claim 15, wherein the fluorinated elastomer is selected from fluororubber materials (FKM), TFE / P polymers (FEPM), and perfluoroelastomers (FFKM).

18. The seal according to claim 15, wherein the fluorinated filler is selected from at least one of fluorinated carbon black, fluorinated graphene, and fluorinated carbon nanotubes.

19. The seal of claim 15, wherein the fluorinated elastomer composite material comprises the fluorinated filler in an amount of 1 to 60 phr.

20. The seal according to claim 15, wherein the average particle size of the fluorinated filler is in the range of 1 to 500 nm.

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