Polyaryletherketone copolymer blends

Abstract

The present invention relates to polymer blends based on PEDEK-PEEK copolymers, which, due to the predominance of PEDEK-type units in the copolymer (PEDEK-PEEK) and due to the blend with polyphenylsulfone polymer (PPSU), are effective in providing an excellent combination of improved strength and modulus at high temperatures with improved ductility, and which possess beneficial partial miscibility behavior that is unexpected and advantageous not only for retaining similar high temperature resistance of the polymer (PPSU) component, but also for avoiding phase separation and / or slowing down of crystallization rate and loss of high temperature performance.

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to earlier U.S. Provisional Patent Application No. 62 / 932,739, filed November 8, 2019, the entire contents of which are incorporated herein by reference for all purposes.

[0002] The present invention relates to novel compositions of polyaryletherketone copolymers and polyphenylsulfone polymers having improved heat resistance and mechanical properties, methods for their production and their use in various fields such as oil and gas exploration and extraction. [Background technology]

[0003] Polyaryletherketone-based materials are known as high performance plastics with high heat resistance and are used for many industrial applications requiring resistance to extreme conditions.

[0004] In particular, oil and gas exploration requires materials that can withstand high temperatures and pressures and maintain the required performance after prolonged exposure to said extreme pressure and temperature conditions, especially to highly reactive chemicals present in the downhole environment including salt water, hydrocarbons, CO2, H2S, etc.

[0005] Thus, in this field, polyetheretherketone (PEEK), having characteristic repeating units of the formula -O-Ph-O-Ph-CO-Ph-, where Ph=para-phenylene, has found wide utility due to its crystalline melting point of about 340° C., which allows for acceptable processing, although its glass transition temperature of about 150° C. somewhat limits its ability to withstand continuous operation at temperatures above 150° C.

[0006] In the art, copolymers containing a mixture of the units -O-Ph-O-Ph-CO-Ph-(PEEK) and -O-Ph-Ph-O-Ph-CO-Ph-(PEDEK) have been proposed in an attempt to provide a material with an increased Tg over PEEK while exhibiting acceptable processing properties.

[0007] For example, WO 2018 / 086873 discloses PEDEK-PEEK copolymers with high temperature resistance and excellent chemical resistance and mechanical properties. However, the glass transition temperature (Tg) of about 170°C limits their use in very high temperature applications (e.g., above 170°C). Although the crystallinity of PEDEK-PEEK allows use above 170°C, the strength and modulus of elasticity are significantly reduced at these high temperatures. Currently, some applications require the chemical resistance and other properties of PEDEK-PEEK copolymers, but require even greater mechanical stiffness and strength at temperatures above 170°C than can be provided by PEDEK-PEEK copolymers. Although the present specification broadly envisions possible combinations of the PEDEK-rich PEDEK-PEEK copolymers provided herein with various other polymer-based materials, including sulfone polymers, it is concomitantly recognized that the unique advantageous properties resulting from the manner in which these blends are made are not associated.

[0008] Therefore, due to the limitations of these PEDEK-PEEK copolymers, there is an unmet need for polyaryletherketone-based materials that can provide higher temperature performance and improved mechanical properties than can be achieved with PEDEK-PEEK copolymers.

[0009] Blending different polymers to create new materials with varying thermal, mechanical and impact properties without chemical modification is an approach that has already been pursued in the area of ​​polyaryletherketones. In addition, physical properties can be altered by blending by modifying the crystallization behavior of one or more of the blend components.

[0010] For example, blending polyphenylsulfone polymers (PPSU) into PEEK polymers to at least partially improve the mechanical properties of PEEK in certain temperature ranges has been known for decades. In particular, PEEK / PPSU blends are disclosed in US Patent Publication No. 10,119,023. Further, for example, WO 2014 / 177392 discloses the use of certain PEEK / PPSU blends for lining pipelines used in oil and gas related operations, and in particular teaches that such blends have higher heat deflection temperatures (e.g., HDT of about 181° C. for PEEK / PPSU blends, 75 / 25 wt / wt), demonstrating better thermal-mechanical stability than the reference PEEK liner. Thus, it is widely recognized in the art that PEEK / PPSU blends exhibit improved mechanical properties over PEEK at temperatures in the range of about 150-190° C., although there is a trade-off between mechanical and chemical resistance above the glass transition temperature of the blend due to the higher amorphous content.

[0011] Thus, there is a continuing need in the art for polyaryletherketone polymers that have an advantageous combination of thermal rating / performance and chemical resistance, while maintaining exceptional mechanical performance, particularly to provide materials suitable for use in highly demanding applications such as oil and gas exploration and extraction.

[0012] The polymer blends of PEDEK-rich PEDEK-PEEK copolymers and PPSU according to the present invention address this unmet need.

[0013] Generally, WO 2019 / 053239, which relates to the use of a powder blend of (i) a PEEK type material having at least 50% units of the formula -O-Ph-O-Ph-CO-Ph- (PEEK units) and (ii) a poly(arylethersulfone) polymer in a selective laser sintering (SLS) process, discloses that (i) the PEEK type material may be a PEEK copolymer, which may optionally further contain small amounts of units of the formula -O-Ph-Ph-O-Ph-CO-Ph- (i.e. PEDEK units), and (ii) the poly(arylethersulfone) polymer may be a PEEK copolymer having a formula: [ka] It is further taught that the repeat unit may be PPSU. According to these teachings, blending poly(aryl ether sulfone)s into PEEK-based materials improves the recyclability and thermal stability of the powdered blends under SLS processing conditions without affecting the expected performance of PEEK, such as toughness. Applicant has now found that compounding such PEEK-rich PEEK-PEDEK copolymers with sulfone polymers, particularly PPSU, is not effective to obtain the desired high temperature behavior, and such addition fails to provide valuable performance improvements at high temperatures. Summary of the Invention

[0014] Therefore, a first object of the present invention is a composition [composition (C)], at least one polyaryletherketone copolymer [copolymer (PEDEK-PEEK)], - Formula (I): [ka] Repeating units (R PEEK ), and - Formula (II): [ka] Repeating units (R PEDEK) (In the above formulas (I) and (II), each of R′ and R″ is equal to or different from each other and, in each occurrence, is a C1-C aryl group optionally containing one or more heteroatoms. 12 groups; sulfonic acid and sulfonate groups; phosphonic acid and phosphonate groups; amine and quaternary ammonium groups; each of j' and k'' is equal to or different from each other and, at each occurrence, is independently selected from 0 and an integer from 1 to 4. The molar ratio (R PEDEK ):(R PEEK ) the repeating unit (R PEEK ) and the repeating unit of formula (II) (R PEDEK ) at least one polyaryletherketone copolymer comprising [copolymer (PEDEK-PEEK)]; at least one sulfone polymer [polymer (SP)], (PS-1) More than 50 mol% of all repeating units of formula (P-1): [ka] (In the formula, - Each R PPSU are equal to or different from one another in each occurrence and are independently selected from the group consisting of halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkyl sulfonate, alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine, and quaternary ammonium; - each d, in each occurrence, is equal to or different from one another and is independently selected from 0, 1, 2, 3 and 4, preferably 0; Repeating units (R PPSU ) containing polyphenylsulfone polymer [polymer (PPSU)]; and (PS-2) More than 50 mol% of all repeating units of formula (P-2): [ka] (In the formula, - Each R PESU are equal to or different from one another, in each occurrence, and are independently selected from the group consisting of halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkyl sulfonate, alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine, and quaternary ammonium; - each e, at each occurrence, is equal to or different from one another and is independently selected from 0, 1, 2, 3 and 4, preferably 0; Repeating units (R PESU ) containing polyethersulfone polymer [polymer (PESU)] At least one sulfone polymer [polymer (SP)] selected from the group consisting of and a composition (C) comprising:

[0015] The invention further relates to a process for preparing said composition (C), which comprises blending said copolymer (PEDEK-PEEK) with said polymer (SP) in the molten state.

[0016] The present invention further relates to a method for producing parts contained in equipment used in the recovery of oil and gas, in particular comprising molding these parts from the inventive composition (C) as detailed above.

[0017] The applicant has found that the composition (C) of the present invention detailed above is effective in providing an excellent combination of improved strength and modulus at high temperatures and improved ductility due to the predominance of PEDEK type units in the copolymer (PEDEK-PEEK) and due to the blend with the polymer (SP). Furthermore, the blend exhibits a reduced viscosity that makes processing easier compared to the PEDEK-PEEK copolymer itself. Thus, the composition (C) of the present invention is suitable for the manufacture of molded articles that require a combination of high temperature performance, high ductility and impact resistance, chemical resistance, and high flow during processing. In particular, there has been a long-standing need for melt-processable and chemically resistant materials that can withstand higher temperatures and pressures in oil and gas drilling and production applications, and the composition (C) of the present invention meets such an unmet need. In addition, the compositions of the present invention are equipped with beneficial partial miscibility behavior that is unexpected and advantageous, not only to retain similar high temperature resistance of the polymer (PPSU) component, but also to avoid phase separation (as sometimes associated with complete immiscibility) and / or reduced crystallization rate and reduced high temperature performance (as sometimes associated with complete miscibility). In other words, very limited partial miscibility is sufficient to effectively compatibilize the blend while remaining largely immiscible. [Brief description of the drawings]

[0018] [Figure 1] 1 is a sketch of tensile elongation at break data for representative examples based on PEDEK-PEEK copolymers with a high PEDEK content and a control based on PEEK-PEDEK copolymers with a high PEEK content, all containing the same amount of pure PPSU. [Diagram 2] 1 is a sketch of the Dynatup peak energy of a representative example based on a PEDEK-PEEK copolymer with a PEDEK-rich content, and a control based on a PEEK-PEDEK copolymer with a PEEK-rich content, all containing the same amount of pure PPSU. [Diagram 3]The trend of melt viscosity as a function of shear rate at 400° C. is shown (data in Table 2). C1 is pure PEDEK-PEEK copolymer, E2 is a polymer blend according to the invention which is a 40 / 60 blend of PPSU and PEDEK-PEEK copolymer, and CE1 is a 37 / 63 blend of PPSU / PEEK. The viscosity of the composition according to the invention is reduced compared to that of the pure PEDEK-PEEK copolymer. [Figure 4] The tensile elongation at break and Dynatup impact resistance trends of blend compositions prepared according to the present invention are shown (data in Table 1). [Diagram 5] The high temperature flexural strength trends of blend compositions prepared according to the present invention are shown (data in Table 1). [Figure 6] The high temperature flexural strength trends of comparative blend compositions containing PSU as the sulfone polymer are shown (data in Table 2). [Figure 7] 1 shows a schematic diagram of a drilling rig apparatus. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0019] Copolymer (PEDEK-PEEK) The copolymer (PEDEK-PEEK) has a molar ratio (R PEDEK ):(R PEEK ) in which the repeating unit (R PEDEK ) and (R PEEK A copolymer (PEDEK-PEEK) that has been found to be particularly advantageous is one having a (R PEDEK ):(R PEEK ) in the molar ratio of repeating units (R PEDEK ) and (R PEEK )

[0020] In the copolymer (PEDEK-PEEK), the repeating unit (R PEDEK ) and (RPEEK ) is usually at least 70 mol %, preferably at least 80 mol %, even more preferably at least 90 mol %, and most preferably at least 95 mol %, based on the total number of moles of repeating units.

[0021] The copolymer (PEDEK-PEEK) is composed of the repeating units (R PEEK ) and (R PEDEK ) and a different repeating unit (R PAEK In such a case, the repeat unit (R PAEK The amount of the repeating unit (R PEEK ) and (R PEDEK ) is present in an amount of at least 95 mole % based on the total moles of repeat units in the copolymer (PEDEK-PEEK).

[0022] The repeating unit (R PEEK ) and (R PEDEK ) and a different repeating unit (R PAEK ) are present, these repeating units (R PAEK ) are usually expressed by the following formulas (KA) to (KM): [ka] [ka] (In each of the above formulas (KA) to (KM), each R' is equal to or different from each other and, in each occurrence, is a C1 to C6 alkyl group optionally containing one or more heteroatoms. 12 groups; sulfonic acid and sulfonate groups; phosphonic acid and phosphonate groups; amine and quaternary ammonium groups; and each of j' is equal to or different from one another and, at each occurrence, is independently selected from 0 and an integer from 1 to 4, preferably j' is equal to zero. Follow one of the following:

[0023] Nevertheless, the copolymer (PEDEK-PEEK) contains the repeating units (R PEEK ) and (R PEDEK The phrase "consisting essentially of" in reference to the copolymer (PEDEK-PEEK) is intended to indicate that defects, end groups and monomeric impurities may be incorporated into the copolymer (PEDEK-PEEK) in small amounts, advantageously without adversely affecting the performance of the same in the blends of the present invention.

[0024] The repeating unit (R PEEK In the repeat units (R PEEK ) conforms to formula (Ia). [ka]

[0025] Similarly, the repeating unit (R PEDEK In the repeating units (R PEDEK ) conforms to formula (IIb). [ka]

[0026] Polyphenylsulfone polymer [Polymer (PPSU)] As described above, the polyphenylsulfone polymer [polymer (PPSU)] has more than 50 mol % of the above-mentioned formula (P-1): [ka] Repeating units (R PPSU ).

[0027] Preferably, each d in formula (P-1) is zero. In other words, the repeating unit (R PPSU ) is preferably represented by the formula: [ka] is a unit of.

[0028] The polymer (PPSU) contains less than 50 mol % of the repeating units (R PPSU ) may contain different repeat units.

[0029] In particular, the polymer (PPSU) contains the repeating unit (R PPSU ), formula (P-3): -Ar 1 -(T'-Ar 2 ) n -O-Ar 3 -SO2-[Ar 4 -(T-Ar 2 ) n -SO2] m -Ar 5 -O-(P-3) (In the formula, - Ar 1 , Ar 2 , Ar 3 , Ar 4 and Ar 5 are equal or different from each other and in each occurrence and are independently an aromatic substituted or unsubstituted mononuclear or polynuclear group; each T and T' are equal or different from each other and in each occurrence and are independently a bond or a divalent radical optionally containing one or more heteroatoms; preferably T' is a bond, -CH2-, -C(O)-, -C(CH3)2-, -C(CF3)2-, -C(=CCl2)-, -SO2-, -C(CH3)(CH2CH2COOH)- and a group of the formula: [ka] is selected from the group consisting of the groups - n and m are equal to or different from each other and are independently zero or an integer from 1 to 5. Repeating units (R PAES ).

[0030] Preferably, in formula (P-2), T is a bond, -CH2-, -C(O)-, -C(CH3)2-, -C(CF3)2-, -C(=CCl2)-, -C(CH3)(CH2CH2COOH)-, and the formula: [ka] is selected from the group consisting of the groups:

[0031] Repeating unit (R PAES ) is a repeating unit (R PPSU ) different from the following formulas (SA)~(SD): [ka] (In the formula, - each R' is equal to or different from one another and is selected from the group consisting of halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkyl sulfonate, alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine and quaternary ammonium; - each j' is equal to or different from one another and is independently zero or an integer from 1 to 4; - T and T' are equal to or different from each other and are a bond or a divalent radical optionally containing one or more heteroatoms; preferably T' is a bond, -CH2-, -C(O)-, -C(CH3)2-, -C(CF3)2-, -C(=CCl2)-, -C(CH3)(CH2CH2COOH)-, -SO2- and a group of the formula: [ka] is selected from the group consisting of the groups Preferably, T is selected from the group consisting of a bond, -CH2-, -C(O)-, -C(CH3)2-, -C(CF3)2-, -C(=CCl2)-, -C(CH3)(CH2CH2COOH) and the formula: [ka] (selected from the group consisting of the groups It can be particularly selected from the group consisting of:

[0032] Repeating unit (R PAES ) are represented by the formulas (i) to (iv) and (j) to (jjj) detailed below: [ka] and mixtures thereof.

[0033] Preferably, at least 60 mol %, more preferably at least 70 mol %, even more preferably at least 80 mol %, and most preferably at least 90 mol % of the repeat units of the polymer (PPSU) are the repeat units (R PPSU ) in the polymer (PPSU). PPSU Excellent results have been obtained when the polymer is essentially free of repeat units other than 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62,

[0034] Polyethersulfone polymer [Polymer (PESU)] As described above, the polyethersulfone polymer [polymer (PESU)] has more than 50 mol % of the repeating units of the formula (P-2): [ka] Repeating units (R PESU ).

[0035] Preferably, each e in formula (P-2) is zero. In other words, the repeating unit (R PESU ) is preferably represented by the formula: [ka] is a unit of.

[0036] The polymer (PESU) contains less than 50 mol % of the repeating units (R PESU ) may contain different repeat units.

[0037] In particular, the polymer (PESU) has a repeating unit (RPESU) different from the repeating unit (RPESU) described above, and has the formula (P-3) detailed above: -Ar 1 -(T'-Ar 2 ) n -O-Ar 3 -SO2-[Ar 4 -(T-Ar 2 ) n -SO2] m -Ar 5 -O- (P-3) The compound may include a repeat unit (RPAES) conforming to the following formula:

[0038] Repeating unit (R PAES ) is a repeating unit (R PESU ), which may in particular be selected from the group consisting of those of formulae (SA) to (SD) already detailed above.

[0039] Repeating unit (R PAES ) represents the formulas (i) to (iv) as well as (j), (jjj) and (jv): [ka] The repeat units may be selected from the group consisting of:

[0040] Preferably, at least 60 mol %, more preferably at least 70 mol %, even more preferably at least 80 mol %, and most preferably at least 90 mol % of the repeat units of the polymer (PESU) are the repeat units (R PESU ) in the polymer (PESU). PESU Excellent results have been obtained when the polymer is essentially free of repeat units other than 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62,

[0041] Composition comprising copolymer (PEDEK-PEEK) and polymer (SP) Composition (C) comprises at least one copolymer (PEDEK-PEEK); it may comprise one or more copolymers (PEDEK-PEEK), for example multiple copolymers (PEDEK-PEEK), which may differ due to their respective molecular weights (RV, MV...), or due to the nature of their repeating units, or due to some other parameter, or for reasons including a combination of these.

[0042] Composition (C) comprises at least one polymer (SP) selected from the group consisting of polymer (PPSU) and polymer (PESU) detailed above, i.e. composition (C) may comprise only one polymer (SP), which may be the above-mentioned polymer (PPSU) or polymer (PESU), or may comprise multiple polymers, each of which may be independently selected from polymer (PPSU) and polymer (PESU), such as multiple polymers (PPSU), multiple polymers (PESU), or a combination of one or more polymers (PPSU) and one or more polymers (PESU).

[0043] In a particular embodiment, the composition (C) comprises at least one polymer (PPSU): it may comprise one or more polymers (PPSU), for example multiple copolymers (PPSU), which may differ due to their respective molecular weights (RV, MV...), or due to the nature of their repeating units, or due to some other parameter, or for reasons including a combination of these.

[0044] In a particular embodiment, the composition (C) comprises at least one polymer (PESU): it may comprise one or more polymers (PESU), for example multiple copolymers (PESU), which may differ due to their respective molecular weights (RV, MV...), or due to the nature of their repeating units, or due to some other parameter, or for reasons including a combination of these.

[0045] Composition (C) may comprise copolymer (PEDEK-PEEK) and polymer (SP) in a weight ratio of 5 / 95 to 95 / 5 or preferably in a weight ratio of 10 / 90 to 90 / 10.

[0046] Depending on the intended field of use, the weight ratio between the copolymer (PEDEK-PEEK) and the polymer (SP) can be adjusted, taking into account the beneficial effects of the present invention, for example a synergistic enhancement of the properties can be achieved over the entire range of the composition.

[0047] For example, polymer (SP) may be present in an amount of at least 10%, at least 20%, at least 30%, or even at least 35% by weight based on the combined weight of copolymer (PEDEK-PEEK) and polymer (SP).

[0048] Conversely, composition (C) may comprise the polymer (SP) detailed above in an amount of less than 90%, less than 70%, less than 60% or less than 50% by weight based on the total weight of copolymer (PEDEK-PEEK) and polymer (SP).

[0049] According to another preferred embodiment, the composition (C) comprises the copolymer (PEDEK-PEEK) and polymer (SP) detailed above in a combined amount of at least 90%, if not at least 95%, based on the total weight of said composition (C). Furthermore, an embodiment is provided in which the composition (C) consists essentially of the copolymer (PEDEK-PEEK) and polymer (SP) detailed above. For the purposes of the present invention, the expression "consisting essentially of" should be understood to mean that any additional components different from the copolymer (PEDEK-PEEK) and polymer (SP) detailed above are present in an amount of up to 1% by weight, based on the total weight of the composition (C), so as not to substantially alter the advantageous properties of the composition.

[0050] Nevertheless, composition (C) often contains additional components in addition to the copolymer (PEDEK-PEEK) and the polymer (SP).

[0051] Composition (C) may further comprise, for example, at least one reinforcing filler. Reinforcing fillers are well known to those skilled in the art. They are preferably selected from fibrous and particulate fillers. Fibrous fillers can be added to composition (C) as chopped fibers or as continuous fibers, including in the form of fabrics. More preferably, the reinforcing filler is selected from inorganic fillers (talc, mica, kaolin, calcium carbonate, calcium silicate, magnesium carbonate, boron nitride, etc.), glass fibers, carbon fibers, synthetic polymer fibers, aramid fibers, aluminum fibers, titanium fibers, magnesium fibers, boron carbide fibers, rock wool fibers, steel fibers, wollastonite, etc. Even more preferably, it is selected from mica, kaolin, calcium silicate, magnesium carbonate, glass fibers, carbon fibers and wollastonite, etc.

[0052] Preferably, the filler is selected from fibrous fillers. A particular class of fibrous fillers consists of whiskers, i.e. single crystal fibers made from various raw materials such as Al2O3, SiC, BC, Fe and Ni.

[0053] In one embodiment of the present invention, the reinforcing filler is selected from wollastonite and glass fiber. Among fibrous fillers, glass fiber is preferred. They are described in Additives for Plastics Handbook, 2000, Vol. 2, No. 1, pp. 211-215, 2000; nd Examples of such fibers include chopped strand A-, E-, C-, D-, S-, T-, and R-glass fibers as described in the John Murphy, Chapter 5.2.3, p. 43-48 edition.

[0054] The glass fibers that may optionally be included in the polymer composition (C) may have a circular or non-circular cross-section, such as an elliptical or rectangular cross-section.

[0055] If the glass fibers used have a circular cross section, they preferably have an average glass fiber diameter of 3 to 30 μm, particularly preferably 5 to 12 μm. Various types of glass fibers with a circular cross section are available on the market depending on the type of glass from which they are produced. Mention may in particular be made of glass fibers made from E-glass or S-glass.

[0056] Good results have been obtained with standard E-glass materials having non-circular cross sections.Excellent results have been obtained when round cross section S-glass fibers are used to reinforce the polymer composition, especially when using round cross section fibers (E-glass or S-glass) with a diameter of 6 μm.

[0057] In another embodiment of the present invention, the reinforcing filler is carbon fiber.

[0058] The term "carbon fibers" as used herein is intended to include graphitized, partially graphitized and non-graphitized carbon reinforcing fibers or mixtures thereof. Carbon fibers useful for the present invention can be advantageously obtained by heat treatment and pyrolysis of different polymer precursors, such as, for example, rayon, polyacrylonitrile (PAN), aromatic polyamides or phenolic resins. Carbon fibers useful for the present invention can also be obtained from pitch-based materials. The term "graphite fibers" is intended to refer to carbon fibers obtained by high temperature pyrolysis (above 2000°C) of carbon fibers, the carbon atoms being arranged in a manner similar to the graphite structure. Carbon fibers useful for the present invention are preferably selected from the group consisting of PAN-based carbon fibers, pitch-based carbon fibers, graphite fibers and mixtures thereof.

[0059] The weight of said reinforcing fillers is advantageously less than 60% by weight, more preferably less than 50% by weight, even more preferably less than 45% by weight and most preferably less than 35% by weight, based on the total weight of composition (C).

[0060] Preferably, the reinforcing filler is present in an amount in the range of 10 to 60% by weight, preferably 20 to 50% by weight, preferably 25 to 45% by weight, most preferably 25 to 35% by weight, based on the total weight of composition (C).

[0061] The reinforcing fillers can be nanomaterials such as single or multi-walled carbon nanotubes, carbon nanofibers, graphene, nanoclays such as montmorillonite or any other nanofillers known in the art.

[0062] Composition (C) may optionally contain: (i) colorants, especially dyes; (ii) pigments, especially titanium dioxide, zinc sulfide and zinc oxide; (iii) light stabilizers, e.g. UV stabilizers; (iv) heat stabilizers; (v) antioxidants, especially organic phosphites and phosphonites; (vi) acid scavengers; (vii) processing aids; (viii) crystallization nucleating agents; (ix) internal and / or external lubricants; (x) flame retardants; (xi) smoke suppressants; (x) antistatic agents; (xii) antifungals; (xiii) antifungals; (xiv) antifungals; (xv ... It may further comprise one or more additional components (I) different from the reinforcing fillers and copolymers (PEDEK-PEEK) and polymers (SP) detailed above, generally selected from the group consisting of i) antiblocking agents, (xii) conductive additives, especially carbon black and carbon nanofibrils, (xiii) plasticizers, (xiv) flow control agents, (xv) bulking agents, (xvi) metal deactivators, and combinations comprising one or more of the foregoing additives.

[0063] When one or more additional components (I) are present, their total weight based on the total weight of the polymer composition (C) is usually less than 20%, preferably less than 10%, more preferably less than 5%, even more preferably less than 2%.

[0064] According to certain embodiments, composition (C) may comprise the copolymer (PEDEK-PEEK) and polymer (SP) detailed above in combination with one or more additional polymeric components, such as polyarylether polymers (e.g., PEEK, PEK, PEKK, etc.) different from the copolymer (PEDEK-PEEK) and polyarylsulfides.

[0065] Nevertheless, it is understood that composition (C) is typically a composition based on copolymer (PEDEK-PEEK) and polymer (SP). Generally speaking, this means that the combined weight of copolymer (PEDEK-PEEK) and polymer (SP) exceeds the amount of the weight of any other polymeric components that may be contained therein.

[0066] According to another embodiment, the copolymer (PEDEK-PEEK) and polymer (SP) detailed above are the only polymeric components in composition (C).

[0067] The expression "polymeric component" should be understood according to its ordinary meaning, i.e. to include compounds characterized by repeating linking units, typically having a molecular weight of 2000 or greater.

[0068] According to certain embodiments, the polymer (SP) is a polymer (PPSU) and the composition (C) may comprise said polymer (PPSU) in an amount of at least 10%, at least 20%, at least 30% or even at least 35% by weight based on the total weight of the copolymer (PEDEK-PEEK) and the polymer (PPSU). In these embodiments, the composition (C) may comprise the polymer (PPSU) detailed above in an amount of less than 90%, less than 70%, less than 60% or less than 50% by weight based on the total weight of the copolymer (PEDEK-PEEK) and the polymer (PPSU). All the features detailed above related to the composition (C) comprising the polymer (SP) and the copolymer (PEDEK-PEEK) are characteristic of the embodiments mentioned herein, wherein the polymer (SP) is a polymer (PPSU). A particularly advantageous embodiment is a composition (C) comprising copolymer (PEDEK-PEEK) in an amount of 60-90% and polymer (PPSU) in an amount of 10-40%, based on the total weight of copolymer (PEDEK-PEEK) and polymer (PPSU).

[0069] According to another embodiment, the polymer (SP) is a polymer (PESU) and the composition (C) may comprise said polymer (PESU) in an amount of at least 10%, at least 20%, at least 30% or even at least 35% by weight based on the total weight of the copolymer (PEDEK-PEEK) and the polymer (PESU). In these embodiments, the composition (C) may comprise the polymer (PESU) detailed above in an amount of less than 90%, less than 70%, less than 60% or less than 50% by weight based on the total weight of the copolymer (PEDEK-PEEK) and the polymer (PESU). All the characteristics detailed above related to the composition (C) comprising the polymer (SP) and the copolymer (PEDEK-PEEK) are similar characteristics to the embodiment mentioned here, in which the polymer (SP) is a polymer (PESU). Another particularly advantageous embodiment is a composition (C) comprising copolymer (PEDEK-PEEK) in an amount of 60-90% and polymer (PESU) in an amount of 10-40%, based on the total weight of copolymer (PEDEK-PEEK) and polymer (PESU).

[0070] Composition (C) can be prepared by various methods involving intimately mixing at least one copolymer (PEDEK-PEEK) as detailed above, at least one polymer (SP), optionally reinforcing fillers and optionally additional components (I) desired in the polymer-based material, for example by dry mixing, suspension mixing, slurry mixing, solution mixing, melt mixing and any combination thereof, in particular a combination of dry mixing and melt mixing.

[0071] Typically, the dry mixing of the copolymers (PEDEK-PEEK) and polymers (SP) detailed above, preferably in powder form, and optionally reinforcing fillers and optionally additional components (I), is carried out by using high intensity mixers, in particular Henschel type mixers and ribbon mixers, to obtain a physical mixture, in particular a powder mixture of at least one copolymer (PEDEK-PEEK) and at least one polymer (SP) and optionally reinforcing fillers and optionally additional components (I).

[0072] Alternatively, the intimate mixing of the at least one copolymer (PEDEK-PEEK), at least one polymer (SP), optionally reinforcing fillers and optionally additional components (I) desired in composition (C) is carried out by tumble blending based on single or multiple shaft rotation mechanisms to obtain a physical mixture.

[0073] Alternatively, the slurry mixing of the copolymer (PEDEK-PEEK), the polymer (SP), optionally reinforcing fillers and optionally additional component (I) is carried out by first slurrying the copolymer (PEDEK-PEEK) and the polymer (SP) in powder form as detailed above, and optionally reinforcing fillers and optionally additional component (I), in a suitable liquid, for example methanol, using a stirrer, followed by removing the liquid by filtration to obtain at least one copolymer (PEDEK-PEEK), at least one polymer (SP), optionally reinforcing fillers and optionally additional component (I).

[0074] In another embodiment, the copolymer (PEDEK-PEEK), polymer (SP), optionally reinforcing filler and optionally additional component (I) as detailed above are solution mixed using a stirrer in a suitable solvent or solvent blend, such as, for example, diphenylsulfone, benzophenone, 4-chlorophenol, 2-chlorophenol, meta-cresol, etc. Diphenylsulfone and 4-chlorophenol are most preferred.

[0075] Following the physical mixing step according to one of the techniques mentioned above, the physical mixture of at least one copolymer (PEDEK-PEEK), at least one polymer (SP), optionally reinforcing fillers and optionally additional components (I), in particular the resulting powder mixture, is typically melt manufactured by methods known in the art, including in particular melt manufacturing processes such as compression molding, injection molding, extrusion, etc., to provide molded articles, in particular parts of oil and gas recovery articles or finished oil and gas recovery articles as described in more detail below.

[0076] The physical mixture thus obtained, in particular the powder mixture thus obtained, may comprise the copolymer (PEDEK-PEEK), polymer (SP), reinforcing filler and optionally other components (I) as detailed above in the weight ratios detailed above, or may be a concentrated mixture that is used as a masterbatch and then diluted in a subsequent processing step with additional amounts of the copolymer (PEDEK-PEEK), polymer (SP), reinforcing filler and optionally other components (I) as detailed above. For example, the physical mixture thus obtained may be extruded into stock shapes such as slabs or rods from which final parts can be machined. Alternatively, the physical mixture may be compression molded or injection molded into finished parts or stock shapes of the oil and gas recovery article from which finished parts of the oil and gas recovery article can be machined.

[0077] It is also possible to prepare the composition of the present invention by melt kneading. The composition (C) can be prepared by further melt kneading the powder mixture described above. As an alternative, the melt kneading can directly affect the copolymer (PEDEK-PEEK) and polymer (SP) detailed above, the reinforcing filler detailed above and optionally other components (I). In such a case, the copolymer (PEDEK-PEEK) and polymer (SP) can be fed in the form of pellets or in the form of powder fed to the melt kneading device, with pellets being the preferred form to ensure a stable feed. Conventional melt kneading devices such as co-rotating and counter-rotating extruders, single screw extruders, co-kneaders, disc pack processors and various other types of extrusion devices can be used. Preferably, an extruder, more preferably a twin screw extruder, can be used.

[0078] If necessary, the design of the kneading screw, such as flight pitch and width, clearance, length, as well as the operating conditions, are advantageously selected so that sufficient heat and mechanical energy is provided to advantageously completely melt the mixture (e.g. preformed powder mixture) or the components detailed above and advantageously obtain a homogeneous distribution of the various components. When optimal mixing is achieved between the bulk polymer component and the filler component, it is advantageously possible to obtain a strand extrudate of the composition (C) of the present invention. The strand extrudate of the composition (C) can be chopped, for example by a rotating cutting knife, after a cooling time on a conveyor equipped with water spray. As a result, the composition (C) can be provided in the form of pellets or beads, which can then be further used by different processing techniques, in particular for the manufacture of molded articles of different shapes and sizes.

[0079] Composition (C) may further be provided in the form of a powder (e.g., by grinding, milling and / or sieving) or filaments (e.g., produced by extrusion) for use in additive manufacturing, such as processing by selective laser sintering or fused filament manufacturing.

[0080] In some embodiments, composition (C) can be used to produce a composite material comprising a polymer matrix made from composition (C) and a plurality of fibers embedded therein. The composite material comprising a matrix of composition (C) can be provided in the form of a substantially two-dimensional material, such as a sheet or tape, having one dimension (thickness or height) significantly smaller than the other two dimensions (width and length). In certain preferred embodiments, the composite material comprising a matrix of composition (C) can be provided in the form of a substantially two-dimensional material, such as a sheet or tape, having one dimension (thickness or height) significantly smaller than the other two dimensions (width and length). - composite materials comprising one or more plies of impregnated fabrics, including but not limited to nonwovens such as mats, multiaxial fabrics, woven or braided fabrics; and - unidirectional (continuous or discontinuous) fibre reinforced tapes or prepregs, preferably with aligned fibres; and - Multidirectional fibre reinforced tape or prepreg comprising multiple layers of fibre reinforced tape or prepreg is selected from the group consisting of:

[0081] The fabrics and fibers used in the composite materials described above can be of any type, although it is preferred to use carbon fabrics and fibers, especially to provide unidirectional tapes of continuous carbon fibers.

[0082] molded article Another object of the invention is a molded article comprising the composition (C) detailed above.

[0083] Composition (C) as detailed above may be processed by conventional melt processing techniques, including in particular extrusion, injection molding and compression molding, to provide shaped articles.

[0084] The molded articles of the present invention are preferably selected from the group consisting of: (i) extruded shapes, preferably selected from the group consisting of rods, slabs, tubes, pipes or profiles; and (ii) injection molded articles.

[0085] According to certain embodiments, the shaped article is in the form of a substantially two-dimensional article, e.g., a part having one dimension (thickness or height) that is significantly smaller than the other two characteristic dimensions (width and length), such as, for example, films, sheaths and sheets, among others.

[0086] According to another embodiment, the molded article is provided as a three-dimensional part that extends substantially in three dimensions of space in a similar manner, for example in the form of a complex shaped part having concave or convex portions that may include undercuts, inserts, etc.

[0087] Potential applications include electrostatic discharge (ESD) components for semiconductor and IC chip manufacturing, electrical and electronic equipment, wire and cable insulation, high performance films, medical and pharmaceutical components, and durable components for a variety of industries in automotive, aerospace, semiconductor manufacturing.

[0088] According to a particular embodiment, the molded article produced from the composition (C) detailed above is provided as part of an electrostatic discharge (ESD) protection device, which may be designed, for example, to be connected to a semiconductor wafer intended for chip manufacture.

[0089] According to a particular embodiment, the shaped article made from the composition (C) detailed above is provided as a part of an article for oil and gas recovery.

[0090] Use of copolymers (PEDEK-PEEK) in O&G The invention further relates to a method for producing a part included in an apparatus used in oil and gas recovery, comprising molding the part from composition (C). Molding can be achieved by any melt processing technique, including in particular extrusion, injection molding, compression molding, etc.

[0091] An article for oil and gas recovery comprising at least one part made from the composition (C) detailed above is yet another object of the present invention.

[0092] For purposes of the present invention, the term "oil and gas recovery article" is intended to mean any article designed to be conveniently used in oil and gas recovery applications, especially at high pressure (HP) / high temperature (HT) conditions.

[0093] For clarity, the term "part of an oil and gas recovery article" is intended to denote a component or portion that, in combination with others, constitutes an entire oil and gas recovery article. Thus, exterior coatings of an oil and gas recovery article are included within this scope. Thus, at least one part of an oil and gas recovery article according to the present invention may be a coating.

[0094] Representative examples of oil and gas recovery applications include, but are not limited to, (i) the drilling and completion of deep, higher temperature, higher pressure oil and gas wells, as particularly described in U.S. Pat. No. 5,662,170, the entire disclosure of which is incorporated herein by reference; (ii) oil and gas recovery processes that are traditionally subdivided into three stages, namely, the primary oil recovery stage, the secondary or assisted oil recovery stage, and the tertiary or enhanced oil recovery stage; (iii) gas gathering and oil processing applications; and (iv) complex transportation of gas and oil from said deep, higher temperature, higher pressure wells to refineries and the like.

[0095] All these applications mentioned herein above are well known to those skilled in the art and should be understood in their common sense.

[0096] Non-limiting examples of oil and gas recovery articles useful in the present invention include drilling systems; drilling rigs; compressor systems, particularly as described in U.S. Patent Application Publication No. 2010239441 (the entire disclosure of which is incorporated herein by reference); pump systems; motor systems, sensors such as reservoir sensors; control systems such as temperature and / or pressure; stimulation and flow control systems; liner hanger systems, particularly as described in U.S. Patent No. 6,655,456 (the entire disclosure of which is incorporated herein by reference); packer systems, particularly as described in U.S. Patent No. 7,874,356 (the entire disclosure of which is incorporated herein by reference); pipe systems, valve systems, tubing systems, casing systems, and the like.

[0097] All these systems mentioned herein above are well known to those skilled in the art and should be understood in a common sense.

[0098] The term "drilling rig" means a structural housing equipment used to drill an oil well or a natural gas extraction well, which may comprise a single item or may comprise two or more components. Typically, the components of a drilling rig include, but are not limited to, mud tanks, shale shakers, mud pumps, drill pipe, drill bits, drill lines, and electrical cable trays.

[0099] Non-limiting examples of pump systems useful in the present invention are jet pump systems, submersible pump systems, particularly submersible electric pumps and beam pumps as described in U.S. Pat. No. 6,863,124, the entire disclosure of which is incorporated herein by reference.

[0100] A non-limiting example of a motor system useful in the present invention is a mud motor assembly, particularly as described in U.S. Patent Application Publication No. 2012234603, the entire disclosure of which is incorporated herein by reference.

[0101] Non-limiting examples of pipe systems useful in the present invention include pipes including rigid and flexible pipes, flexible risers, pipe-in-pipe, pipe liners, subsea jumpers, spools and umbilicals.

[0102] Typical flexible pipes are described, by way of example, in WO 01 / 61232, US 6,123,114 and US 6,085,799, the entire disclosures of which are incorporated herein by reference. Such flexible pipes can be used in particular for the transport of fluids which experience very high or very different water pressures over the length of the pipe, and can take the form of flexible risers, for example, which run from the seabed to installations at or near the surface, but they can also be used generally as pipes for transporting liquids or gases between various pieces of equipment, or as pipes laid deep on the seabed, or as pipes between pieces of equipment near the surface.

[0103] Preferred pipe systems are pipes, flexible risers and pipe liners.

[0104] The term "valve" means any device for stopping or controlling the flow of a liquid, gas, or any other substance through a passageway, pipe, inlet, outlet, etc. Non-limiting examples of valve systems useful in the present invention include choke valves, thermal expansion valves, check valves, ball valves, butterfly valves, diaphragm valves, gate valves, globe valves, knife valves, needle valves, pinch valves, piston valves, plug valves, poppet valves, spool valves, pressure reducing valves, sampling valves, and safety valves, among others.

[0105] At least one part of the oil and gas recovery article according to the present invention may be selected from a large list of articles such as mounting parts; seals, in particular seal rings, preferably backup seal rings, fasteners, etc.; snap-fit ​​parts; mutually movable parts; functional elements, operating elements; tracking elements; adjustment elements; carrier elements; frame elements; films; switches; connectors; wires, cables; bearings, housings, compressor components such as compressor valves and compressor plates and any other structural parts other than housings used in oil and gas recovery articles, such as shafts, shells, pistons, etc.

[0106] In particular, composition (C) is highly suitable for the manufacture of seals, fasteners, cables, electrical connectors and housing parts for oil and gas recovery articles.

[0107] In a preferred embodiment, at least one part of the article for oil and gas recovery according to the invention is advantageously a housing, a seal, an electrical connector or a cable for oil and gas recovery.

[0108] The cables may be wires that, inter alia, electrically connect different parts within an oil and gas recovery article, such as connecting different electrical connectors, connecting tools to connectors, equipment or other tools, connecting equipment to connectors, other equipment or tools, or connecting power sources to connectors, equipment or tools. Cables may also be advantageously used to carry signals to computer systems.

[0109] In a particularly preferred embodiment, the cable is a coated wire.

[0110] "Oil and gas recovery housing" means one or more of the back cover, front cover, frame, and / or backbone of an oil and gas recovery article. The housing may be a single item or may include two or more components. "Backbone" means a structural component to which other components of the oil and gas recovery article are attached. The backbone may be an internal component that is not visible or only partially visible from the exterior of the oil and gas recovery article.

[0111] Exemplary fasteners are described, for example, in WO 2010 / 112435 (the disclosure of which is incorporated herein by reference in its entirety) and include, but are not limited to, threaded fasteners such as bolts, nuts, screws, headless set screws, scribets, threaded studs and threaded bushings; and non-threaded fasteners such as pins, retaining rings, rivets, brackets and fastener washers, among others.

[0112] Sealing of oil and gas recovery article components is critical and it can be said that seals are used in all types of oil and gas recovery articles, as well as in oil and gas recovery articles that remain in-hole after well completion, testing and production. Thus, the seals need to withstand these harsh conditions mentioned above practically indefinitely. It is important to mention that, with the exception of electronics, the seals can be considered the most vulnerable part of the oil and gas recovery article.

[0113] In one embodiment of the invention, at least a portion of the oil and gas recovery article is a seal system, said seal system being selected from the group consisting of metallic seals, elastomeric seals, metal-metal seals, and elastomeric and metal-metal seals.

[0114] Seal systems are typically used in drill bits, motor systems, particularly mud motors, reservoir sensors, stimulation and flow control systems, pump systems, particularly submersible electric pumps, packers, liner hangers, tubing, casings, and the like.

[0115] Representative examples of sealing systems include, but are not limited to, sealing rings such as C-rings, E-rings, O-rings, U-rings, spring loaded C-rings, backup rings, fastener seals, piston seals, gask-O-sals, integral seals, and labyrinth seals, among others.

[0116] In a particularly preferred embodiment, at least one part of the oil and gas recovery article according to the invention is a seal ring, preferably a back-up seal ring.

[0117] The weight of composition (C) based on the total weight of the oil and gas recovery article is typically greater than 1%, greater than 5%, greater than 10%, preferably greater than 15%, greater than 20%, greater than 30%, greater than 40%, greater than 50%, greater than 60%, greater than 70%, greater than 80%, greater than 90%, greater than 95%, greater than 99%.

[0118] The article for oil and gas recovery may consist of one part, i.e. it is a single-component article, in which case the single part preferably consists of composition (C).

[0119] Alternatively, the oil and gas recovery article may be composed of multiple parts. In that case, either one part or multiple parts of the oil and gas recovery article may be composed of composition (C). If multiple parts of the oil and gas recovery article are composed of composition (C), each of them may be composed of one and the same composition (C). Alternatively, at least two of them may be composed of different compositions (C).

[0120] Another object of the present invention is to provide a method for manufacturing the above-mentioned parts of the oil and gas recovery article. Such a method is not particularly limited. The composition (C) detailed above can be typically processed by injection molding, extrusion molding, compression molding or other molding techniques.

[0121] In one embodiment of the present invention, the method for manufacturing the above-mentioned part of an article for oil and gas recovery or an article for oil and gas recovery comprises a step of compression molding or injection molding and subsequent solidification of the composition (C).

[0122] In another embodiment, the method of manufacturing the above-mentioned part of the oil and gas recovery article or the oil and gas recovery article comprises a coating step.

[0123] For example, composition (C) can be applied as a coating to a wire by using any suitable coating method, preferably by extrusion coating around the wire to form a coated wire.

[0124] Techniques for producing wire coatings are well known in the art.

[0125] In another embodiment of the invention, the above-mentioned part of the article for oil and gas recovery or the method for manufacturing the above-mentioned article for oil and gas recovery comprises machining of structural parts of standard shape in parts of any kind of size and shape. Non-limiting examples of said structural parts of standard shape include, inter alia, plates, rods, slabs, etc. Said structural parts of standard shape can be obtained by extrusion, compression molding or injection molding of the composition (C).

[0126] Method for oil and / or gas recovery using copolymers (PEDEK-PEEK) According to another aspect of the present invention, there is provided herein a method of recovering oil and / or gas comprising using at least one oil and gas recovery article as defined above.

[0127] The method of the present invention is advantageously a method of recovering oil and / or gas from a subterranean formation comprising the use of said oil and gas recovery article.

[0128] The subterranean formation may advantageously be a deep buried reservoir, which may encounter temperatures approaching 300° C. and pressures exceeding 1,500 bar at depths of more than 6,000 meters. The oil and gas article of the present invention has all the necessary requirements and properties to withstand the harsh conditions underground for extended periods of time.

[0129] The method of the invention may advantageously comprise at least one operation selected from the group consisting of: 1. Drilling at least one well for exploring for or developing an oil and / or gas reservoir in a subterranean formation using at least one oil and gas recovery article as defined above; 2. Completing at least one well using at least one oil and gas recovery article as defined above; 3. The transportation of oil and / or gas from underground oil and / or gas reservoirs to the earth's surface.

[0130] The operation of drilling boreholes to explore for or develop oil and / or natural gas reservoirs typically involves the use of drilling rig equipment, which is an embodiment of the oil and gas recovery article defined above.

[0131] FIG. 1 shows a schematic of a drilling rig apparatus. In this apparatus, the drill pipe or string (#5) serves as a conduit for the drilling fluid. It is usually made from joints of hollow tubes connected together and standing vertically in a derrick. The drill bit (#7) apparatus is attached to the end of the drill string, and this bit fragments the rock being drilled. It also contains jets for draining through the drilling fluid. The rotating bed (#6) or top drive (not shown) rotates the drill string with the attached tools and bits.

[0132] The machine section or drawwork section (#13) contains the spools whose main function is to reel the drill line in and out and raise and lower the traveling block.

[0133] Mud pumps (#11) are used to circulate the drilling fluid throughout the system; mud is drawn from a mud tank or mud pit (#9), which serves as a reserve reservoir for the drilling fluid. The mud flows through conduit #14 and through the drill pipe (#5) to the bit (#7). It flows upwards through the borehole carrying the drilling cuttings and is returned to the mud pit where it is extracted through conduit (#12). The shale shaker (#10) separates the drilling cuttings from the drilling fluid before it is pumped back up the borehole.

[0134] The apparatus may further include a device (not shown) located at the wellhead to prevent the unintentional escape of fluids and gases from the borehole.

[0135] Any of the components of the drilling rig detailed above may be an article for oil and gas recovery as detailed above, i.e. may comprise at least a part comprising or made from the composition (C) as defined above.

[0136] The operation of completing a well 2. is an operation that encompasses all the preparation or outfitting operations necessary to bring the geological formation from the well into operation. This primarily includes preparing the bottom hole to the required specifications, operating the production tubing and its associated downhole tools and controls, and performing drilling and stimulation as required. In some cases, it also includes the process of casing and cementing. In every single of these operations, an article comprising at least one part comprising the composition (C) detailed above may be used.

[0137] To the extent that the disclosures of any patents, patent applications, and publications incorporated herein by reference conflict with the statements of this application to the extent that a term may be unclear, this statement shall control.

[0138] The invention will now be described with reference to the following examples, the purpose of which is illustrative only and are not intended to limit the scope of the invention. EXAMPLES

[0139] Materials used The copolymer (PEDEK-PEEK) used in these examples was a copolymer derived from the polycondensation of 4,4'-difluorobenzophenone (DFBP), 4,4'-dihydroxydiphenyl (also known as biphenol), and hydroquinone. This copolymer contains a high number of biphenol residue sites compared to the hydroquinone sites in the total stoichiometric amount of biphenol in the polymerization. PEDEK represents the polymer repeat unit from the polycondensation of biphenol and 4,4'-difluorobenzophenone. The copolymer (PEDEK-PEEK) that can be used in the practice of the invention can vary in the molar ratio of PEDEK repeat units to PEEK repeat units in the polymer backbone, but the examples used a copolymer with a PEDEK / PEEK molar ratio of 75-25 (hereinafter PEDEK-PEEK copolymer). The PEDEK-PEEK copolymer has a melting point of 1000 s at 420°C and 1000 s when measured using a capillary rheometer according to ASTM D3835. -1 It has a melt viscosity of 400 Pa·s.

[0140] For comparative examples, similar PEEK-rich PEEK-PEDEK copolymers were also used, which contained a higher percentage of PEEK repeat units compared to PEDEK repeat units. The PEEK-rich PEEK-PEDEK copolymers used in the comparative examples below (hereinafter PEEK-PEDEK copolymers) had PEEK / PEDEK molar ratios of 70-30 and 80-20, and had a melting point of 370° C. and 1000 s when measured using a capillary rheometer according to ASTM D3835. -1 The melt viscosities of these compounds are 200 Pa·s and 190 Pa·s, respectively.

[0141] The polymer (PPSU) used was Radel® R-5100 NT PPSU natural resin from Solvay Specialty Polymers USA, LLC. This is a standard grade of PPSU for general purpose extrusion and injection molding applications. It has a melt flow rate range of 14-20 g / 10 min as measured using a melt indexer according to ASTM D1238 at 365° C. using a 5.0 kg weight.

[0142] The polymer (PESU) used was Verade® A-201 NT PESU natural resin from Solvay Specialty Polymers USA, LLC. This is a standard grade of PESU for general purpose extrusion and injection molding applications. It has a melt flow rate range of 15-25 g / 10 min as measured using a melt indexer according to ASTM D1238 at 380° C. using a 2.16 kg weight.

[0143] The polymer (PSU) used in the comparative examples was Udel® P-1700 NT PSU natural resin from Solvay Specialty Polymers USA, LLC. This is a standard grade of PSU for general purpose extrusion and injection molding applications. It has a melt flow rate range of 5-9 g / 10 min as measured using a melt indexer according to ASTM D1238 at 343° C. using a 2.16 kg weight.

[0144] The PEEK polymer used in the comparative examples was KetaSpire® KT-820 NT PEEK natural resin from Solvay Specialty Polymers USA, LLC. This is a standard grade of PEEK for general purpose extrusion and injection molding applications. It has a melting point of 400°C and 1000s when measured using a capillary rheometer according to ASTM D3835. -1 It has a melt viscosity of 380 to 500 Pa·s.

[0145] Preparation of Formulations Polymer blends according to the invention were prepared by melt compounding using a 26 mm Coperion® co-rotating partially intermeshing twin screw extruder with a L / D ratio of 48:1. The extruder had 12 barrel sections, with barrel sections 2-12 heated at temperature settings of 390°C. The die temperature was also set at 390°C. The extruder was operated at a throughput rate of 30 lb / hr and a screw speed of 200 rpm, and the extruder torque readings were maintained in the range of 50-70% during compounding of all compositions. A vacuum vent was applied to barrel section 10 during compounding at a vacuum level of greater than 25 inHg to remove moisture and any residual volatiles from the compound. The extrudate from each run was stranded and cooled in a water trough and then pelletized into pellets approximately 2.7 mm in diameter and 3.0 mm in length.

[0146] Formulation testing Mechanical properties were tested for all formulations using injection molded 0.125 inch (3.2 mm) thick ASTM specimens consisting of 1) Type I tensile bars, 2) 5 inch x 0.5 inch x 0.125 inch flexure bars, and 3) 4 inch x 4 inch x 0.125 inch plaques for instrumented impact (Dynatup) testing. Control and comparative formulations were also injection molded into the same specimens. Except for the pure PPSU, PESU, and PSU specimens, the injection molded specimens were annealed in an oven prior to testing. The annealing conditions used were 230°C for 2 hours, except for the annealing of the injection molded specimens from the blend compositions containing PSU, where a 200°C for 2 hours annealing condition was used to prevent specimen warping. The molded parts were annealed between two flat 0.5 inch thick glass plates.

[0147] The following ASTM test methods were used in evaluating all compositions: - ASTM D638: Tensile Properties (Test Speed ​​= 2.0 in / min); - ASTM D790: Flexural properties; - ASTM D3763: Instrumented Impact Resistance, also known as Dynatup Impact.

[0148] Melt viscosity was evaluated by capillary rheometry according to ASTM D3835 using a temperature of 400° C., except for a comparative composition containing a PEEK-rich PEEK-PEDEK copolymer, where a temperature of 370° C. was used.

[0149] Dynamic mechanical analysis (DMA) was also performed in torsion mode on the injection molded specimens (cut from the center of ASTM Type I tensile bars). A dynamic temperature sweep from 50°C to 350°C was performed at a frequency of 10.0 rad / s and a strain amplitude of 0.05%.

[0150] Table 1 summarizes the mechanical and thermal properties of exemplary formulations of the present invention.

[0151] [Table 1]

[0152] As shown by the tensile elongation at break data in Table 1, the ductility of PEDEK-PEEK copolymers at ambient conditions is significantly enhanced by the addition of either PPSU or PESU. The ductility of the polymer blends according to the invention is significantly greater than would be predicted from a linear weighted average of the two components. This improvement in ductility is achieved without sacrificing strength or stiffness, as the tensile strength and tensile modulus at ambient temperatures are observed to trend linearly with the concentration ratio of the blends.

[0153] Tensile elongation at break data for representative examples and a control containing pure PPSU is shown in FIG.

[0154] The impact energy of the PEDEK-PEEK copolymer and PPSU blends is also significantly enhanced compared to the pure resin control, as shown by the peak load energy from the Dynatup measurements in Table 1. The measurements all exceed those predicted from a linear weighted average of the two components. Tensile elongation at break and Dynatup impact data for the examples and control are shown in Figure 4, and flexural strength data is shown in Figure 5.

[0155] The addition of PPSU or PESU to PEDEK-PEEK copolymers also improves mechanical properties at high temperatures. The tensile and flexural data at 160°C in Table 1 show that blends of PEDEK-PEEK copolymers and PPSU at 160°C have tensile strength at yield, elongation at yield, and flexural strength that exceed those predicted from the linear weighted average of the two components (see Figures 4 and 5). These improvements in strength and ductility across the PPSU concentration range are achieved without a significant decrease in tensile and flexural modulus at 160°C compared to the linear weighted average of the two components.

[0156] Furthermore, DMA measurements of the polymer blends according to the invention showed that the compositions of the invention exhibit two distinct glass transition temperatures (Tg) over the range of PEDEK-PEEK to PPSU or PESU weight ratios, as shown in Table 1. In addition, for blends with PPSU, the high Tg corresponding to the PPSU-rich phase shifts to lower values ​​with increasing concentration of PEDEK-PEEK copolymer, from 226°C for pure PPSU to about 221-223°C for blends with PPSU-rich in PEDEK-PEEK copolymer, and from 233.4°C for pure PESU to 232.0°C for blends with PESU-rich in PEDEK-PEEK copolymer. This combination of behavior indicates that the blends are partially miscible, which is a surprising and beneficial result. Unlike a fully miscible blend, which would be expected to show a single Tg corresponding to the weighted average of the two components, the partially miscible blends retain the higher Tg of the sulfone polymer-rich phase. Additionally, partially miscible blends are understood to be easier to process than completely immiscible blends, which can be difficult to process or can exhibit phase separation during melt processing, compromising the mechanical properties of the molded parts.

[0157] Table 2 summarizes the mechanical and thermal properties of comparative examples containing PSU as the sulfone polymer in the blend.

[0158] [Table 2]

[0159] The data in Table 2 show that, in contrast to the exemplary blends of the present invention, the addition of PSU to PEDEK-PEEK copolymer does not improve high temperature mechanical properties beyond those predicted from a linear weighted average of the two components. As an example, flexural strength at 160°C as a function of the amount of PEDEK-PEEK copolymer in a blend with PSU is shown in Figure 6.

[0160] Table 3 summarizes the mechanical and thermal properties of comparative examples of blends of PPSU with PEEK-rich PEEK-PEDEK copolymers.

[0161] [Table 3]

[0162] The tensile elongation at break data for the comparative examples in Table 3 are plotted in FIG. 1. Compared to the blends according to the invention, the blends containing the PEEK-PEDEK copolymer with a higher PEEK content have a lower tensile elongation at break, indicating lower ductility. Furthermore, while the tensile elongation at break for the blends according to the invention is significantly higher than would be predicted from a linear weighted average of the two components, FIG. 1 shows that for the comparative blends containing the PEEK-PEDEK copolymer with a higher PEEK content, the tensile elongation at break is much closer to that predicted from a linear weighted average of the two components. Similarly, the impact energy data for the comparative examples in Table 3 are plotted in FIG. 2. Compared to the blends according to the invention, the blends containing the PEEK-PEDEK copolymer with a higher PEEK content have a lower Dynatup peak load energy. Furthermore, the Dynatup peak energies of the blends according to the invention are significantly greater than would be predicted from a linear weighted average of the two components, while in comparative blends containing PEEK-rich PEEK-PEDEK copolymers, the Dynatup peak energies are less than or usually much closer to what would be predicted from a linear weighted average of the two components.

[0163] Table 4 summarizes the melt viscosity data for exemplary formulations of the present invention compared to similar blends based on PEEK.

[0164] [Table 4]

[0165] As shown in Table 4, the melt viscosity of the polymer blends according to the invention exhibits reduced melt viscosity compared to the pure PEDEK-PEEK copolymer control. This reduced melt viscosity facilitates easier processing, especially for injection molding or 3D printing applications of thin walled parts. The melt viscosity data in Table 4 shows that the melt viscosity of the polymer blends according to the invention is between that of the pure PEDEK-PEEK copolymer control and that of a similar PEEK / PPSU blend with similar PPSU concentration. See also the plot of melt viscosity vs. shear rate in Figure 1.

[0166] Table 5 summarizes the melt viscosity data for comparative examples of PPSU blends with PEEK-rich PEEK-PEDEK copolymers.

[0167] [Table 5]

[0168] While Table 4 shows that the addition of PPSU to PEDEK-PEEK beneficially reduces the melt viscosity, the data in Table 5 show that the addition of PPSU to PEEK-PEDEK copolymers increases the melt viscosity, adversely affecting processability.

[0169] [Table 6]

[0170] Table 6 summarizes storage modulus data from DMA at high temperatures (180° C. and 200° C.) for exemplary formulations of the invention compared to similar blends based on either PEEK or PEEK-rich PEEK-PEDEK copolymers having PEEK / PEDEK repeat unit molar ratios of 80-20 or 70-30.

[0171] More specifically, Table 6 shows storage modulus measurements from torsion mode DMA testing at 180°C and 200°C. The data show that the stiffness of the polymer blends according to the invention exceeds that of a pure PEDEK-PEEK copolymer control and a comparative example consisting of a blend of PPSU with either PEEK or a PEEK-rich PEEK-PEDEK copolymer having a molar ratio of PEEK repeat units and PEDEK repeat units of 80-20 or 70-30. Furthermore, the change in storage modulus caused by the addition of PPSU is a more significant improvement when adding PPSU to a PEDEK-rich PEDEK-PEEK copolymer than when adding PPSU to a PEEK-based material or to a PEEK-rich PEEK-PEDEK copolymer. Most surprisingly, the beneficial effects increase in the temperature range of 180-200°C, resulting in the most valuable performance enhancement at higher temperatures.

Claims

1. A composition [composition (C)] comprising: at least one polyaryletherketone copolymer [copolymer (PEDEK-PEEK)], - Formula (I): 【Chemistry 1】 Repeating units (R ＰＥＥＫ ), and - Formula (II): 【Chemistry 2】 Repeating units (R ＰＥＤＥＫ ) (In the above formulas (I) and (II), each of R′ and R″ is equal to or different from each other and, in each occurrence, optionally contains one or more heteroatoms. １ ~C １２ groups; sulfonic acid and sulfonate groups; phosphonic acid and phosphonate groups; amine and quaternary ammonium groups; each of j' and k'' is equal to or different from one another and, at each occurrence, is independently selected from 0 and an integer from 1 to 4. and a molar ratio (R ＰＥＤＥＫ ): (R ＰＥＥＫ The repeating unit (R ＰＥＥＫ ) and the repeating unit of formula (II) (R ＰＥＤＥＫ ) At least one polyaryletherketone copolymer [copolymer (PEDEK-PEEK)] comprising: at least one sulfone polymer [polymer (SP)], (PS-1) More than 50 mol% of all repeating units of the formula (P-1): 【Chemistry 3】 (In the formula, - Each R ＰＰＳＵ are equal to or different from one another, in each occurrence, and are independently selected from the group consisting of halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkyl sulfonate, alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine, and quaternary ammonium; each d, at each occurrence, is equal to or different from one another and is independently selected from 0, 1, 2, 3 and 4; Repeating units (R ＰＰＳＵ ), and a polyphenylsulfone polymer [polymer (PPSU)]; (PS-2) More than 50 mol% of all repeating units of the formula (P-2): 【Chemistry 4】 (In the formula, - Each R ＰＥＳＵ are equal to or different from one another, in each occurrence, and are independently selected from the group consisting of halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkyl sulfonate, alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine, and quaternary ammonium; each e, at each occurrence, is equal to or different from one another and is independently selected from 0, 1, 2, 3, and 4; Repeating units (R ＰＥＳＵ ) Polyethersulfone polymer [Polymer (PESU)] At least one sulfone polymer [polymer (SP)] selected from the group consisting of: and the composition (C) comprises a copolymer (PEDEK-PEEK) and a polymer (SP) in a weight ratio of 10 / 90 to 90 / 10.

2. The copolymer (PEDEK-PEEK) has a molar ratio (R ＰＥＤＥＫ ): (R ＰＥＥＫ ) in which the repeating unit (R ＰＥＤＥＫ ) and (R ＰＥＥＫ ) and / or the copolymer (PEDEK-PEEK) comprises the repeating unit (R ＰＥＥＫ ) and (R ＰＥＤＥＫ ) and a repeating unit (R ＰＡＥＫ 10. The composition of claim 1, additionally comprising:

3. In the copolymer (PEDEK-PEEK), the repeating unit (R ＰＥＥＫ In the repeat unit (R ＰＥＤＥＫ 3. Composition (C) according to claim 1 or 2, wherein in (a) and (b), the bonds between the phenyl groups are generally at the para position of each of the phenyl rings, and / or each k'' is zero.

4. The polymer (SP) is at least one polymer (PPSU), and the repeating unit (R ＰＰＳＵ ) has the formula: 【Chemistry 9】 Each polymer (PPSU) has a repeating unit (R ＰＰＳＵ ) or the polymer (PPSU) contains less than 50 mol % of repeat units other than the repeat units (R ＰＰＳＵ ) Formula (P-3): -Ar １ -(T’-Ar ２ ) ｎ -O-Ar ３ -SO ２ -[Ar ４ -(T-Ar ２ ) ｎ -SO ２ ] ｍ -Ar ５ -O- (P-3) (In the formula, - Ar １ , Ar ２ , Ar ３ , Ar ４ and Ar ５ are equal or different from one another and in each occurrence and are independently an aromatic substituted or unsubstituted mononuclear or polynuclear group; each T and T' is equal or different from each other and at each occurrence and is independently a bond or a divalent group optionally containing one or more heteroatoms; n and m are equal to or different from each other and are independently zero or an integer from 1 to 5. Repeating units (R ＰＡＥＳ The composition according to any one of claims 1 to 3, comprising

5. The polymer (SP) is at least one polymer (PESU), and the repeating unit (R ＰＥＳＵ ) has the formula: 【Chemistry 11】 Each polymer (PESU) has a repeating unit (R ＰＥＳＵ ) or the polymer (PESU) contains less than 50 mol % of repeat units (R ＰＥＳＵ ) Formula (P-3): -Ar １ -(T’-Ar ２ ) ｎ -O-Ar ３ -SO ２ -[Ar ４ -(T-Ar ２ ) ｎ -SO ２ ] ｍ -Ar ５ -O- (P-3) (In the formula, - Ar １ , Ar ２ , Ar ３ , Ar ４ and Ar ５ are equal or different from one another and in each occurrence and are independently an aromatic substituted or unsubstituted mononuclear or polynuclear group; each T and T' is equal or different from each other and at each occurrence and is independently a bond or a divalent group optionally containing one or more heteroatoms; n and m are equal to or different from each other and are independently zero or an integer from 1 to 5. Repeating units (R ＰＡＥＳ The composition according to any one of claims 1 to 4, comprising

6. Repeating unit (R ＰＡＥＳ ) are represented by the following formulas (SA) to (SD): 【Chemistry 13】 (In the formula, each R' is equal to or different from one another and is selected from the group consisting of halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkyl sulfonate, alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine and quaternary ammonium; each j' is equal to or different from one another and is independently zero or an integer from 1 to 4; T and T' are equal to or different from each other and are a bond or a divalent radical optionally containing one or more heteroatoms; and / or When the polymer (SP) is a polymer (PPSU), the repeating unit (R ＰＡＥＳ ) is selected from the group consisting of repeating units of formulae (i) to (iv) and (j) to (jjj); when the polymer (SP) is a polymer (PESU), the repeating unit (R ＰＡＥＳ ) represents the formulas (i)-(iv), (j), (jj) and (jv): 【Chemistry 15】 The composition according to claim 4 or 5, wherein the repeating unit is selected from the group consisting of:

7. 7. Composition (C) according to any one of claims 1 to 6, wherein polymer (SP) is present in an amount of at least 10%, at least 20%, at least 30% or even at least 35% by weight based on the total weight of said copolymer (PEDEK-PEEK) and polymer (SP); and / or composition (C) comprises polymer (SP) in an amount of less than 90%, less than 70%, less than 60% or less than 50% by weight based on the total weight of said copolymer (PEDEK-PEEK) and polymer (SP).

8. 8. The composition of claim 7, comprising copolymer (PEDEK-PEEK) in an amount of 60-90% and polymer (PPSU) in an amount of 10-40%, based on the combined weight of copolymer (PEDEK-PEEK) and polymer (PPSU).

9. 9. The composition according to any one of claims 1 to 8, comprising said copolymer (PEDEK-PEEK) and polymer (SP) in an amount of at least 90% by combined weight, if not at least 95%, based on the total weight of said composition (C).

10. at least one reinforcing filler selected from fibrous and particulate fillers, and optionally one or more additional components (I) different from said reinforcing filler and said copolymer (PEDEK-PEEK) generally selected from the group consisting of: (i) colorants, (ii) pigments, (iii) light stabilizers, e.g., UV stabilizers, (iv) heat stabilizers, (v) antioxidants, (vi) acid scavengers, (vii) processing aids, (viii) crystallization nucleators, (ix) internal and / or external lubricants, (x) flame retardants, (xi) smoke suppressants, (x) antistatic agents, (xi) antiblocking agents, (xii) conductive additives, (xiii) plasticizers, (xiv) flow modifiers, (xv) bulking agents, (xvi) metal deactivators, and combinations comprising one or more of the foregoing additives; the weight of said reinforcing fillers is advantageously less than 60% by weight, based on the total weight of said composition (C); and / or Composition (C) according to any one of the preceding claims, wherein said reinforcing fillers are present in an amount ranging from 10 to 60% by weight, based on the total weight of said composition (C).

11. A method for producing a composition (C) according to any one of claims 1 to 10, which involves mixing said at least one copolymer (PEDEK-PEEK), at least one polymer (SP).

12. A composite material comprising a matrix of the composition (C) according to any one of claims 1 to 10, - composite materials comprising one or more plies of impregnated fabrics, including but not limited to nonwovens such as mats, multiaxial fabrics, woven or braided fabrics; and - unidirectional (continuous or discontinuous) fibre reinforced tapes or prepregs; and - Multidirectional fibre-reinforced tapes or prepregs comprising several layers of fibre-reinforced tapes or prepregs A composite material selected from the group consisting of:

13. A molded article comprising a composition (C) according to any one of claims 1 to 10.

14. 14. The molded article of claim 13, selected from the group consisting of parts of electrostatic discharge (ESD) protection devices designed to be connected to semiconductor wafers intended for chip manufacturing.

15. An article for oil and gas recovery comprising at least a part made from the composition (C) according to any one of claims 1 to 10.

16. 20. A method for recovering oil and / or gas comprising using at least one oil and gas recovery article according to claim 15.

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