Polyaryletherketone copolymer blends

Abstract

The present invention relates to novel compositions of polyaryletherketone copolymers and polyetherimides having improved heat resistance and mechanical properties, to a method for producing same and to their use in various fields.

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to earlier U.S. Provisional Patent Application No. 62 / 932767, filed November 8, 2019, and to earlier European Patent Application Publication No. 20153006.0, filed January 21, 2020, 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 polyetherimides having improved heat resistance and mechanical properties, to a process for their preparation and to their use in various fields, in particular as thermoplastic matrices for continuous fiber composites. [Background technology]

[0003] Polyaryletherketone materials are known as high-performance plastics with high heat resistance that are used for many industrial applications where resistance to extreme conditions is required.

[0004] For example, oil and gas exploration (O&G) requires materials that can withstand high temperatures and pressures and maintain the required performance when exposed to extreme pressure and temperature conditions for extended periods, especially to aggressive chemicals present in the downhole environment, including saltwater, hydrocarbons, CO2, H2S, etc.

[0005] Furthermore, in areas where thermoplastic composites are used, such as O&G, aerospace, and automotive, the matrix is ​​similarly required to withstand high temperature conditions, but in addition, fast crystallization rates are required due to the processing peculiarities of thermoplastic composites.

[0006] 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.

[0007] Therefore, it offers better T than PEEK while still exhibiting acceptable processing characteristics. g In an attempt to provide a material with high viscosity, 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.

[0008] In this field, WO 2018 / 086873 discloses PEDEK-PEEK copolymers containing a high percentage of PEDEK, which have high temperature resistance, excellent chemical resistance and mechanical properties. However, their use in high temperature applications is hindered by the glass transition temperature (T) of about 170°C. g ) Due to the crystallinity of PEDEK-PEEK, it can be used above 170°C, but its strength and modulus decrease significantly 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.

[0009] Therefore, due to these limitations of PEDEK-PEEK copolymers, there is an unmet need for polyaryletherketone-based materials that can provide higher temperature capabilities and improved mechanical properties than can be achieved with PEDEK-PEEK copolymers.

[0010] Blending different polymers to create novel materials with varying thermal, mechanical, and impact properties without chemical modification is an approach that has already been pursued in the area of ​​polyaryletherketones. Additionally, physical properties can be altered by blending by modifying the crystallization behavior of one or more blend components.

[0011] For example, blending polyetherimide (PEI) into PEEK polymers has been known for decades to improve, at least to some extent, the mechanical properties of PEEK over a specific temperature range. Nevertheless, the usefulness of this blend is limited by the complete miscibility of PEI with PEEK. This miscibility significantly reduces the crystallinity and crystallization rate of PEEK, making such blends impractical for injection molding processing, and the disproportionate reduction in crystallinity leads to T g For these reasons, PEEK / PEI blends have not yet found significant commercial applications, despite being widely known and studied for decades.

[0012] 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, to provide a material suitable for use in highly demanding applications, particularly as a matrix for thermoplastic continuous fiber composites.

[0013] The polymer blends of PEDEK-rich PEDEK-PEEK copolymers and PEI according to the present invention address this unmet need.

[0014] WO 2019 / 053238, which generally relates to the use of a powder blend of (i) a PEEK-type material having at least 50 mol % units of the formula -O-Ph-O-Ph-CO-Ph- (PEEK units) and (ii) poly(etherimide) (PEI) in a selective laser sintering (SLS) process, further teaches that the PEEK-type material can optionally be a PEEK copolymer further containing a small amount of units of the formula -O-Ph-Ph-O-Ph-CO-Ph- (i.e., PEDEK units). According to these teachings, blending PEI into a PEEK polymer improves the recyclability and thermal stability of the powder blend under SLS processing conditions. However, the applicant has found that incorporating PEI into such PEEK-rich PEEK-PEDEK copolymers is ineffective in achieving the desired behavior. In particular, as shown by the embodiments and non-embodiments, the addition of PEI to comparative PEEK-rich PEEK-PEDEK copolymers slows the crystallization rate, a finding quite contrary to that associated with the compositions of the present invention. Summary of the Invention

[0015] 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 1-hydroxy group optionally containing one or more heteroatoms. 12groups; 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, in each occurrence, is independently selected from 0 and an integer from 1 to 4; The repeating units are in a molar ratio (R PEDEK ):(R PEEK ) included in at least one polyaryletherketone copolymer [copolymer (PEDEK-PEEK)] comprising: at least one poly(etherimide) polymer [polymer (PEI)], comprising at least 50 mole %, based on the total number of moles in the polymer, of repeating units (R PEI at least one poly(etherimide) polymer [polymer (PEI)] containing The composition (C) comprises:

[0016] The present invention further relates to a method for producing said composition (C), which comprises blending said copolymer (PEDEK-PEEK) with said polymer (PEI) in the melt.

[0017] The present invention further relates to methods for producing thermoplastic composites and / or parts contained in devices useful in various fields, in particular by molding these parts from the inventive composition (C) detailed above.

[0018] The applicant has found that the composition (C) of the present invention detailed above is effective in obtaining excellent strength and stiffness at high temperatures due to the predominance of PEDEK type units in the copolymer (PEDEK-PEEK) and due to the blend with the polymer (PEI).

[0019] Without being bound by this theory, Applicants believe that the addition of a polymer (PEI) to a copolymer (PEDEK-PEEK) surprisingly results in a partially miscible blend, or in other words, a highly compatible blend, resulting in improved strength and stiffness at elevated temperatures compared to pure PEDEK-PEEK copolymers and PEEK / PEI blends. The partially miscible behavior of PEDEK-PEEK copolymer blends with PEI is evidenced by the glass transition temperatures (T) obtained from dynamic mechanical analysis (DMA) measurements. g ), which is unexpected and advantageous, and is particularly evidenced by measurements of high temperature (T g This promotes improved mechanical properties at higher temperatures (including higher temperatures). This also allows the blend to be melt-processed as a single homogeneous blend, especially over certain compositional ranges (e.g., up to 35 wt.% PEI). This eliminates potential complications associated with many heterogeneous two-phase blends, which can exhibit unstable and variable phase domain sizes and morphologies, often leading to variability in the blend's physical and mechanical properties. Finally, while it is well known that adding PEI to PEEK slows the crystallization of PEEK (due to the complete miscibility of the two polymers), blending PEEK-PEK copolymers with PEI increases the rate of crystallization, which is beneficial for efficient processing in injection molding and other operations, including the production and fabrication of thermoplastic continuous fiber composites and parts. DETAILED DESCRIPTION OF THE INVENTION

[0020] 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 containing (RPEDEK ):(R PEEK ) in the molar ratio of the repeating units (R PEDEK ) and (R PEEK ) is included.

[0021] In the copolymer (PEDEK-PEEK), the repeating unit (R PEDEK ) and (R PEEK ) 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.

[0022] The copolymer (PEDEK-PEEK) is composed of the repeating units (R PEEK ) and (R PEDEK ) and a different repeating unit (R PAEK In such cases, the repeating unit (R PAEK The amount of repeating units (R PEEK ) and (R PEDEK ) is present in an amount of at least 95 mole % based on the total number of moles of repeat units in the copolymer (PEDEK-PEEK).

[0023] The copolymer (PEDEK-PEEK) contains repeating units (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] [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; each j' is equal to or different from one another and, in 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.

[0024] Nevertheless, the copolymer (PEDEK-PEEK) contains the repeating units (R PEEK ) and (R PEDEK The phrase "consisting essentially of" in reference to copolymer (PEDEK-PEEK) is intended to indicate that defects, end groups, and monomeric impurities may be incorporated into copolymer (PEDEK-PEEK) in small amounts, advantageously without adversely affecting the performance of the same in the blends of the present invention.

[0025] The repeating unit (R PEEK In the repeating units (R), the link between the phenyl groups is usually in the para position of each of the phenyl rings. Furthermore, it is generally preferred that each j' is zero, or in other words, that each of the phenyl rings does not have any further substituents in addition to the catenary ether group or ketone bridging group. According to these preferred embodiments, the repeating units (R PEEK ) conforms to formula (Ia). [ka]

[0026] Similarly, the repeating unit (R PEDEKIn the repeating units (R), the link between the phenyl groups is usually in the para position of each of the phenyl rings. Furthermore, it is generally preferred that each k" is zero, or in other words, that each of the phenyl rings does not have any further substituents in addition to the catenary ether group or ketone bridging group. According to these preferred embodiments, the repeating units (R PEDEK ) conforms to formula (IIb). [ka]

[0027] Poly(ether imide) [polymer (PEI)] As described above, the polymer (PEI) comprises repeating units (R ) containing at least one aromatic ring, at least one imide group (itself and / or its amic acid form), and at least one ether group, at least 50 mol % based on the total number of moles in the polymer. PEI ) is a polymer containing repeating units (R PEI ) may optionally further comprise at least one amide group that is not included in the amic acid form of the imide group.

[0028] Usually, the repeating unit (R PEI ) are represented by the following formulae (I), (II), (III), (IV), (V) and mixtures thereof: [ka] (In the formula, Ar is a tetravalent aromatic moiety and is selected from the group consisting of substituted or unsubstituted, saturated, unsaturated or aromatic monocyclic and polycyclic groups having 5 to 50 carbon atoms; Ar' is a trivalent aromatic moiety and is selected from the group consisting of substituted, unsubstituted, saturated, unsaturated aromatic monocyclic and aromatic polycyclic groups having 5 to 50 C atoms; and - R, for example, (a) Aromatic hydrocarbon radicals having 6 to 20 carbon atoms and their halogenated derivatives; (b) a straight-chain or branched-chain alkylene radical having 2 to 20 carbon atoms; (c) a cycloalkylene radical having 3 to 20 carbon atoms; and (d) Formula (VI): [ka] (In the formula, - Y is alkylene of 1 to 6 carbon atoms, such as -C(CH3)2 and -C n H 2n - (n is an integer of 1 to 6); perfluoroalkylene of 1 to 6 carbon atoms, such as -C(CF3)2 and -C n F 2n -(n is an integer from 1 to 6); cycloalkylene of 4 to 8 carbon atoms; alkylidene of 1 to 6 carbon atoms; cycloalkylidene of 4 to 8 carbon atoms; -O-; -S-; -C(O)-; -SO2-; -SO-, and R″ is selected from the group consisting of hydrogen, halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkaline earth metal sulfonate, alkaline earth metal sulfonate, alkyl sulfonate, alkaline earth metal phosphonate, alkaline earth metal phosphonate, alkyl phosphonate, amine and quaternary ammonium, and - i is independently for each R" zero or an integer ranging from 1 to 4. Divalent radical of and wherein the substituted and unsubstituted divalent organic radicals are selected from the group consisting of: provided that at least one of Ar, Ar', and R contains at least one ether group, and that the ether group is present in the polymer chain backbone. is selected from the group consisting of:

[0029] In the above formula, Ar typically has the formula: [ka] (In the formula, X is a divalent moiety having a divalent bond at the 3,3', 3,4', 4,3'' or 4,4' positions and is an alkylene of 1 to 6 carbon atoms, such as -C(CH3)2 and -C n H 2n - (n is an integer of 1 to 6); perfluoroalkylene of 1 to 6 carbon atoms, such as -C(CF3)2 and -C n F 2n -(n is an integer from 1 to 6); cycloalkylene of 4 to 8 carbon atoms; alkylidene of 1 to 6 carbon atoms; cycloalkylidene of 4 to 8 carbon atoms; -O-; -S-; -C(O)-; -SO2-; -SO-; or X is a group of formula -O-Ar"-O-, where Ar" is an aromatic moiety selected from the group consisting of substituted or unsubstituted, saturated, unsaturated or aromatic monocyclic and polycyclic groups having 5 to 50 carbon atoms. is selected from the group consisting of:

[0030] In the above formula, Ar' is typically a group of the formula: [ka] (In the formula, X is a divalent moiety having a divalent bond at the 3,3', 3,4', 4,3'' or 4,4' positions and is an alkylene of 1 to 6 carbon atoms, such as -C(CH3)2 and -C n H 2n - (n is an integer of 1 to 6); perfluoroalkylene of 1 to 6 carbon atoms, such as -C(CF3)2 and -C n F 2n-(n is an integer from 1 to 6); cycloalkylene of 4 to 8 carbon atoms; alkylidene of 1 to 6 carbon atoms; cycloalkylidene of 4 to 8 carbon atoms; -O-; -S-; -C(O)-; -SO2-; -SO-; or X is a group of formula -O-Ar"-O-, where Ar" is an aromatic moiety selected from the group consisting of substituted or unsubstituted, saturated, unsaturated or aromatic monocyclic and polycyclic groups having 5 to 50 carbon atoms. is selected from the group consisting of:

[0031] Typically, at least 50 mol%, at least 60 mol%, at least 70 mol%, at least 80 mol%, at least 90 mol%, at least 95 mol%, at least 99 mol% or all of the repeat units in the polymer (PEI) are repeat units (R PEI )

[0032] According to a particular embodiment, the polymer (PEI) comprises at least 50 mole % of a compound of formula (VII), based on the total number of moles in the polymer: [ka] (In the formula, - R, for example, (a) Aromatic hydrocarbon radicals having 6 to 20 carbon atoms and their halogenated derivatives; (b) a straight-chain or branched-chain alkylene radical having 2 to 20 carbon atoms; (c) a cycloalkylene radical having 3 to 20 carbon atoms; and (d) Formula (VI): [ka] (In the formula, - Y is alkylene of 1 to 6 carbon atoms, such as -C(CH3)2 and -C n H 2n- (n is an integer of 1 to 6); perfluoroalkylene of 1 to 6 carbon atoms, such as -C(CF3)2 and -C n F 2n -(n is an integer from 1 to 6); cycloalkylene of 4 to 8 carbon atoms; alkylidene of 1 to 6 carbon atoms; cycloalkylidene of 4 to 8 carbon atoms; -O-; -S-; -C(O)-; -SO2-; -SO-, and R″ is selected from the group consisting of hydrogen, halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkaline earth metal sulfonate, alkaline earth metal sulfonate, alkyl sulfonate, alkaline earth metal phosphonate, alkaline earth metal phosphonate, alkyl phosphonate, amine and quaternary ammonium, and - i is independently for each R" zero or an integer ranging from 1 to 4. Divalent radical of and wherein the substituted and unsubstituted divalent organic radicals are selected from the group consisting of: provided that at least one of Ar, Ar′, and R comprises at least one ether group, and that the ether group is present in the polymer chain backbone; T can be either -O- or -O-Ar''-O-; wherein the divalent bond of the -O- or -O-Ar''-O- group can be in the 3,3', 3,4', 4,3' or 4,4' positions, and Ar'' is an aromatic moiety selected from the group consisting of substituted or unsubstituted, saturated, unsaturated or aromatic monocyclic and polycyclic groups having 5 to 50 carbon atoms, such as a substituted or unsubstituted phenylene, a substituted or unsubstituted cyclohexyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthalene group, or a moiety containing two substituted or unsubstituted phenylenes. Repeating units (R PEI ) is a polymer containing

[0033] According to certain embodiments of the present disclosure, Ar″ is of the general formula (VI) detailed above, for example, Ar″ is of the formula (XIX): [ka] It is of the type.

[0034] The polymer (PEI) according to this preferred embodiment is prepared by reacting a diamino compound of formula H2N-R-NH2(XX) (wherein R is as previously defined) with a diamino compound of formula (XXI): [ka] where T is as previously defined. They can be prepared by any of the methods well known to those skilled in the art, including reaction of any of the above with an aromatic bis(ether anhydride).

[0035] Generally, this preparation can be carried out at temperatures ranging from 20°C to 250°C in solvents such as o-dichlorobenzene, m-cresol / toluene, N,N-dimethylacetamide.

[0036] Alternatively, these polymers (PEI) can be prepared by simultaneously melt polymerizing any dianhydride of formula (XXI) and any diamino compound of formula (XX) while heating the mixture of these components at an elevated temperature.

[0037] Examples of the aromatic bis(ether acid anhydride) of formula (XXI) include: 2,2-bis[4-(2,3-dicarboxyphenoxy)phenyl]propane dianhydride; 4,4'-bis(2,3-dicarboxyphenoxy)diphenyl ether dianhydride; 1,3-bis(2,3-dicarboxyphenoxy)benzene dianhydride; 4,4'-bis(2,3-dicarboxyphenoxy)diphenyl sulfide dianhydride; 1,4-bis(2,3-dicarboxyphenoxy)benzene dianhydride; 4,4'-bis(2,3-dicarboxyphenoxy)benzophenone dianhydride; 4,4'-bis(2,3-dicarboxyphenoxy)diphenylsulfone dianhydride; 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride; 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl ether dianhydride; 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride; 1,3-bis(3,4-dicarboxyphenoxy)benzene dianhydride; 1,4-bis(3,4-dicarboxyphenoxy)benzene dianhydride; 4,4'-bis(3,4-dicarboxyphenoxy)benzophenone dianhydride; 4-(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)diphenyl-2,2-propane dianhydride; and Mixtures of such dianhydrides Examples include:

[0038] The organic diamine of formula (XX) is selected from the group consisting of m-phenylenediamine, p-phenylenediamine, 2,2-bis(p-aminophenyl)propane, 4,4'-diaminodiphenyl-methane, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl ether, 1,5-diaminonaphthalene, 3,3'-dimethylbenzidine, 3,3'-dimethoxybenzidine, and mixtures thereof; preferably, the organic diamine of formula (XX) is selected from the group consisting of m-phenylenediamine and p-phenylenediamine, and mixtures thereof.

[0039] According to a particularly preferred embodiment, the polymer (PEI) comprises at least 50 mole % of a compound of formula (XXIII) or (XXIV), based on the total number of moles in the polymer: [ka] (RPEI) in the imide form or its corresponding amic acid form, and mixtures thereof.

[0040] In preferred embodiments, at least 50 mol%, at least 60 mol%, at least 70 mol%, at least 80 mol%, at least 90 mol%, at least 95 mol%, at least 99 mol% or all of the repeat units in the PEI are repeat units of formula (XXIII) or (XXIV) (R PEI )

[0041] Such aromatic polyimides are commercially available, among others, from Sabic Innovative Plastics as ULTEM® polyetherimides.

[0042] Composition containing copolymer (PEDEK-PEEK) and polymer (PEI) Composition (C) comprises at least one copolymer (PEDEK-PEEK); it may comprise one or more copolymers (PEDEK-PEEK), for example a number of 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 thereof.

[0043] Likewise, composition (C) comprises at least one copolymer (PEI): it may comprise one or more polymers (PEI), for example a number of polymers (PEI) 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] Composition (C) may comprise the copolymer (PEDEK-PEEK) detailed above in an amount of at least 40%, preferably at least 50%, more preferably at least 60%, or even at least 65% by weight based on the total weight of copolymer (PEDEK-PEEK) and polymer (PEI) and / or in an amount of up to 95%, preferably up to 90% by weight based on the total weight of copolymer (PEDEK-PEEK) and polymer (PEI).

[0045] Conversely, composition (C) may comprise the polymer (PEI) detailed above in an amount of less than 60%, less than 50%, less than 40% or less than 35% by weight based on the total weight of copolymer (PEDEK-PEEK) and polymer (PEI) and / or in an amount of at least 5%, preferably 10%, by weight based on the total weight of copolymer (PEDEK-PEEK) and polymer (PEI).

[0046] Particularly preferred are compositions (C) in which the copolymer (PEDEK-PEEK) is present in a large amount relative to the blend of the copolymer (PEDEK-PEEK) and the polymer (PEI), and according to these preferred embodiments, the composition (C) comprises: - the copolymers (PEDEK-PEEK) detailed above in an amount by weight of more than 50%, preferably at least 60%, more preferably at least 65%, based on the total weight of the copolymer (PEDEK-PEEK) and the polymer (PEI) and / or in an amount by weight of up to 95%, preferably up to 90%, based on the total weight of the copolymer (PEDEK-PEEK) and the polymer (PEI); - polymer (PEI) as detailed above, in an amount of less than 50%, preferably at most 40%, more preferably at most 35% by weight based on the total weight of copolymer (PEDEK-PEEK) and polymer (PEI) and / or in an amount of at least 5%, preferably at least 10% by weight based on the total weight of copolymer (PEDEK-PEEK) and polymer (PEI); Includes:

[0047] Good results were obtained with a composition (C) containing 60-90% copolymer (PEDEK-PEEK) and 10-40% polymer (PEI) based on the total weight of copolymer (PEDEK-PEEK) and polymer (PEI).

[0048] According to a particular embodiment, composition (C) comprises the copolymer (PEDEK-PEEK) and polymer (PEI) detailed above in a combined amount by weight 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 composition (C) consists essentially of the copolymer (PEDEK-PEEK) and polymer (PEI) 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 (PEI) detailed above are present in an amount of up to 1% by weight, based on the total weight of composition (C), so as not to substantially alter the advantageous properties of the composition.

[0049] Nevertheless, composition (C) often contains additional components in addition to the copolymer (PEDEK-PEEK) and the polymer (PEI).Accordingly, according to another particular embodiment, composition (C) comprises, in addition to the copolymer (PEDEK-PEEK) and the polymer (PEI), at least one additional component, advantageously in an amount of at least 10% by weight and at most 60% by weight, based on the total weight of composition (C).

[0050] 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 fibres or as continuous fibres, including in the form of fabrics.

[0051] 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, nanomaterials (single-walled or multi-walled carbon nanotubes, carbon nanofibers, graphene, nanoclays such as montmorillonite, etc.) Even more preferably, it is selected from mica, kaolin, calcium silicate, magnesium carbonate, glass fibers, carbon fibers, 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. These include those described in Additives for Plastics Handbook, 2004, Vol. nd Included are chopped strand A-, E-, C-, D-, S-, T-, and R-glass fibers as described in John Murphy, Chapter 5.2.3, pp. 43-48, of the 1990 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 oval or rectangular cross-section.

[0055] When 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 be made, in particular, of glass fibers made from E-glass or S-glass.

[0056] In another embodiment of the present invention, the reinforcing filler is carbon fiber.

[0057] The term "carbon fiber" as used herein is intended to include graphitized, partially graphitized, and non-graphitized carbon reinforcing fibers or mixtures thereof. Carbon fibers useful in 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 in the present invention can also be obtained from pitch-based materials. The term "graphite fiber" is intended to mean carbon fibers obtained by high-temperature pyrolysis (above 2000°C) of carbon fibers, in which the carbon atoms are positioned in a manner similar to the graphite structure. Carbon fibers useful in the present invention are preferably selected from the group consisting of PAN-based carbon fibers, pitch-based carbon fibers, graphite fibers, and mixtures thereof.

[0058] The weight of said reinforcing filler 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).

[0059] Preferably, the reinforcing filler is present in an amount ranging from 10 to 60% by weight, preferably from 20 to 50% by weight, preferably from 25 to 45% by weight, most preferably from 25 to 35% by weight, based on the total weight of composition (C).

[0060] The reinforcing filler can be a nanomaterial such as single-walled or multi-walled carbon nanotubes, carbon nanofibers, graphene, nanoclays such as montmorillonite, or any other nanofiller known in the art.

[0061] Composition (C) may optionally further comprise one or more additional components (I) different from the reinforcing fillers and copolymer (PEDEK-PEEK) and polymer (PEI) detailed above, typically selected from the group consisting of: (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 nucleators; (ix) internal and / or external lubricants; (x) flame retardants; (xi) smoke suppressants; (x) antistatic agents; (xi) antiblocking agents; (xii) conductive additives, especially carbon black and carbon nanofibers; (xiii) plasticizers; (xiv) flow modifiers; (xv) extenders; (xvi) metal deactivators; and combinations comprising one or more of the foregoing additives.

[0062] When one or more additional components (I) are present, their total weight, based on the total weight of the polymer composition (C), is typically less than 20%, preferably less than 10%, more preferably less than 5%, and even more preferably less than 2%.

[0063] According to certain embodiments, composition (C) may comprise the copolymers (PEDEK-PEEK) and polymers (PEI) detailed above in combination with one or more additional polymeric components, such as copolymers (PEDEK-PEEK) and different polyarylether polymers (e.g., PEEK, PEK, PEKK, PEKEKK, etc.); polymers (PEI) such as polyamideimides and different polyimide polymers; sulfone polymers, polyarylsulfides, etc.

[0064] Nevertheless, it is understood that composition (C) is typically a composition based on copolymer (PEDEK-PEEK) and polymer (PEI). Generally speaking, this means that the combined weight of copolymer (PEDEK-PEEK) and polymer (PEI) exceeds the weight of any other polymeric components that may be contained therein.

[0065] According to another embodiment, the copolymer (PEDEK-PEEK) and polymer (PEI) detailed above are the only polymeric components in composition (C).

[0066] 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.

[0067] Composition (C) can be prepared by a variety of methods involving intimately mixing at least one copolymer (PEDEK-PEEK), at least one polymer (PEI), optionally a reinforcing filler, 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.

[0068] Typically, the dry mixing of the copolymers (PEDEK-PEEK) and polymers (PEI) 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 (PEI), and optionally reinforcing fillers and optionally additional components (I).

[0069] Alternatively, the intimate mixing of the at least one copolymer (PEDEK-PEEK), at least one polymer (PEI), optionally a reinforcing filler and optionally additional component (I) desired in composition (C) is carried out by tumble blending based on a single or multiple shaft rotation mechanism to obtain a physical mixture.

[0070] Alternatively, the copolymer (PEDEK-PEEK), the polymer (PEI), optionally a reinforcing filler and optionally an additional component (I) are slurry mixed by first slurrying the copolymer (PEDEK-PEEK), the polymer (PEI), optionally a reinforcing filler and optionally an additional component (I) in powder form as detailed above in a suitable liquid, for example methanol, using a stirrer, followed by removing the liquid by filtration to obtain a powder mixture of at least one copolymer (PEDEK-PEEK), at least one polymer (PEI), optionally a reinforcing filler and optionally an additional component (I).

[0071] In another embodiment, the copolymer (PEDEK-PEEK), polymer (PEI), optionally a 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, diphenyl sulfone.

[0072] Following the physical mixing step by one of the techniques described above, the physical mixture of at least one copolymer (PEDEK-PEEK), at least one polymer (PEI), optionally a reinforcing filler and optionally additional component (I), in particular the resulting powder mixture, is typically melt-fabricated by methods known in the art, including in particular melt-fabrication processes such as compression molding, injection molding, extrusion, etc., to provide molded articles, in particular parts, useful for use in various fields.

[0073] The physical mixture thus obtained, particularly the powder mixture obtained, can comprise the copolymer (PEDEK-PEEK), polymer (PEI), reinforcing filler, and optionally other components (I) detailed above in the weight ratios detailed above, or can 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) and polymer (PEI), reinforcing filler, and optionally other components (I) detailed above. For example, the resulting physical mixture can be extruded into a stock shape, such as a slab or rod, from which a final part can be machined. Alternatively, the physical mixture can be compression molded or injection molded into a finished part or stock shape from which a finished part can be machined.

[0074] The composition of the present invention can also be produced by melt-kneading. Composition (C) can be produced by further melt-kneading the powder mixture described above. Alternatively, melt-kneading can directly affect the copolymer (PEDEK-PEEK) and polymer (PEI) described above, the reinforcing filler described above, and optionally other components (I). In such cases, the copolymer (PEDEK-PEEK) and polymer (PEI) can be fed to the melt-kneading apparatus in the form of pellets or powder, with pellets being the preferred form to ensure stable feeding. Conventional melt-kneading equipment can be used, such as co-rotating and counter-rotating extruders, single-screw extruders, co-kneaders, disk-pack processors, and various other types of extrusion equipment. Preferably, an extruder, more preferably a twin-screw extruder, can be used.

[0075] If necessary, the design of the kneading screw, such as flight pitch and width, clearance, length, and operating conditions, are advantageously selected so that sufficient heat and mechanical energy is supplied to advantageously completely melt the mixture (e.g., a preformed powder mixture) or the components detailed above and advantageously obtain a uniform distribution of the various components. Once optimal mixing between the bulk polymer component and the filler component is achieved, it is advantageously possible to obtain strand extrudates of the composition (C) of the present invention. The strand extrudates of the composition (C) can be chopped into pieces, for example, by a rotating cutting knife, after a cooling period 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 production of molded articles of different shapes and sizes.

[0076] Composition (C) can 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.

[0077] 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. Typically, the fibers are continuous fibers, which can be provided in the form of unidirectional fiber strands or as woven or nonwoven mats or fabrics. Composite materials comprising a matrix of composition (C) can be provided in the form of substantially two-dimensional materials, such as sheets and tapes, with one dimension (thickness or height) significantly smaller than the other two dimensions (width and length). In certain preferred embodiments, composite materials comprising a matrix of composition (C) can be provided in the form of: - 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) fiber-reinforced tapes or prepregs, preferably with aligned fibers; and - multidirectional fiber reinforced tape or prepreg comprising multiple layers of fiber reinforced tape or prepreg is selected from the group consisting of:

[0078] 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 or reinforced multidirectional fibers.

[0079] molded article Another subject of the present invention is a shaped article comprising the composition (C) detailed above.

[0080] Composition (C) as detailed above can be processed by conventional melt processing techniques, including, inter alia, extrusion, injection molding and compression molding, to provide shaped articles.

[0081] Thus, the molded article of the present invention may be an extruded shape, preferably selected from the group consisting of a rod, a slab, a tube, a pipe or a profile, or may be an injection molded article.

[0082] According to certain embodiments, the shaped article is in the form of a substantially two-dimensional article, for example, a part in which one dimension (thickness or height) is significantly smaller than the other two characteristic dimensions (width and length), such as, among others, films, sheaths and sheets.

[0083] 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, possibly including undercuts, inserts, etc.

[0084] 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, and semiconductor manufacturing.

[0085] The ability to process the compositions of the present invention into thin films without phase separation or segregation also enables the use of composition (C) for the production of ultra-thin films, e.g., having a thickness of less than 25 μm, which are particularly useful as speaker diaphragm films.

[0086] According to a particular embodiment, the molded article made 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 manufacturing.

[0087] To the extent that the disclosure of any patents, patent applications, and publications incorporated herein by reference contradicts the statements of this application to the extent that the term may be unclear, the statements of this application shall control.

[0088] The present invention will now be further described with reference to the following examples, the purpose of which is merely illustrative and is not intended to limit the scope of the invention. [Example]

[0089] Materials used The copolymer (PEDEK-PEEK) used in these examples was derived from the polycondensation of 4,4'-difluorobenzophenone (DFBP), 4,4'-dihydroxydiphenyl (also known as biphenol), and hydroquinone. This copolymer contains a high percentage of biphenol residues relative to the hydroquinone moieties in the total stoichiometric amount of biphenol in the polymerization. PEDEK represents the polymer repeat unit resulting from the polycondensation of biphenol and 4,4'-difluorobenzophenone. While copolymers (PEDEK-PEEK) that can be used in the practice of this invention can vary in the molar ratio of PEDEK repeat units to PEEK repeat units within the polymer backbone, the examples used copolymers with a PEDEK-PEEK molar ratio of 75:25 (hereinafter referred to as PEDEK-PEEK copolymer). The PEDEK-PEEK copolymer exhibited a rheological constant of 0.01% at 420°C and 1000 s when measured using a capillary rheometer according to ASTM D3835. -1 It has a melt viscosity of 310 Pa·s.

[0090] For comparative examples, similar PEEK-rich PEEK-PEDEK copolymers were also used, which contained a higher proportion of PEEK repeat units relative to PEDEK repeat units. The PEEK-rich PEEK-PEDEK copolymers (hereafter PEEK-PEDEK copolymers) used in the comparative examples below had PEEK-PEDEK molar ratios of 70-30 and 80-20, and exhibited a rheological melting point of 370°C and 1000 s when measured using a capillary rheometer according to ASTM D3835. -1 The melt viscosities are 200 Pa·s and 190 Pa·s, respectively.

[0091] The polymer (PEI) used was SABIC's ULTEM® 1000 PEI, a standard grade of PEI for general-purpose extrusion and injection molding applications. This grade is reported by the manufacturer to have a melt flow rate of approximately 9 g / 10 min, as measured using a melt indexer according to ASTM D1238 at 377°C with a 6.6 kg weight.

[0092] The PEEK grade used was KetaSpire® KT-820NT 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 1000 s when measured using a capillary rheometer according to ASTM D3835. -1 It has a melt viscosity in the range of 380 to 500 Pa·s.

[0093] Preparation of formulations Polymer blends according to the present invention were prepared by melt compounding using a 26 mm Coperion® co-rotating, partially intermeshing twin-screw extruder with a 48:1 L / D ratio. The extruder had 12 barrel sections, with barrel sections 2 through 12 heated to temperature settings of 390°C (for the PEDEK-PEEK and PEI blends), 380°C (for the PEEK and PEI blends), or 335°C (for the PEEK-PEDEK and PEI blends). The die temperature was also set at 390°C (for the PEDEK-PEEK and PEI blends), 380°C (for the PEEK and PEI blends), or 345°C (for the PEEK-PEDEK and PEI blends). Different temperature settings were used for melt compounding of each polyketone resin due to the different melt temperatures and different target ranges of processing conditions. The extruder was operated at a throughput rate of 30 lb / hr (13.6 kg / hr) and a screw speed of 200 rpm, and the extruder torque reading was maintained in the range of approximately 60-85% during compounding for all compositions. A vacuum vent was applied to barrel section 10 during compounding at a vacuum level greater than 25 in Hg to remove moisture and any residual volatiles from the compound. The extrudate from each run was stranded, cooled in a water trough, and then pelletized into pellets approximately 2.7 mm in diameter and 3.0 mm long.

[0094] Compound 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 and 2) 5-inch x 0.5-inch x 0.125-inch flexural bars. Except for PEEK / PEI formulations composed of 30% or more PEI, the injection-molded specimens were annealed in an oven at 230°C for 2 hours before testing. Because injection-molded specimens of PEEK / PEI formulations containing 30% or more PEI exhibited significant warpage when annealed at 230°C, these specimens were annealed at 200°C for 2 hours before testing. To reduce warpage during the annealing process, the parts were annealed between two flat, 0.5-inch thick glass plates.

[0095] The following ASTM test methods were used to evaluate the compositions. D638: Tensile Properties (Test Speed ​​= 2.0 in / min) D790: Bending properties D256: Notched Izod impact properties

[0096] Dynamic mechanical analysis (DMA) was performed on injection-molded specimens (cut from the center of ASTM Type I tensile bars) in the torsion mode. A dynamic temperature sweep from 50 to 300 °C was performed at a frequency of 10.0 rad / s and a strain amplitude of 0.05%.

[0097] Differential scanning calorimetry (DSC) was performed on the blends at various cooling rates to evaluate the effect of adding PEI to PEEK and to PEDEK-PEEK and PEEK-PEDEK copolymers on the crystallization time. DSC tests were performed according to ASTM method D3418. The crystallization time was calculated according to the following formula:

number

[0098] [Table 1]

[0099] [Table 2]

[0100] The tensile and flexural property data in Table 1 show that the polymer blend compositions according to the present invention (E1-E6) exhibit superior strength and stiffness at 175° C. compared to the pure PEDEK-PEEK copolymer control (C1). Additionally, the notched Izod impact data in Table 1 show that the polymer blend compositions according to the present invention (E1-E6) exhibit superior notched Izod impact strength compared to the pure PEDEK-PEEK copolymer control (C1).

[0101] [Table 3]

[0102] Consideration of the tensile and flexural data in Table 2 for the comparative PEEK / PEI blends shows that the polymer blend compositions according to the present invention exhibit higher strength and stiffness at 175°C than similar PEEK / PEI polymer blends.

[0103] Considering the notched Izod impact data in Table 2 for the comparative PEEK / PEI blends, it is also observed that at PEI concentrations above 10 wt%, the polymer blend compositions according to the present invention exhibit higher notched Izod impact strength than similar PEEK / PEI polymer blends. Furthermore, the data in Table 2 show that the addition of PEI to PEEK decreases the notched Izod impact strength, while the addition of PEI to PEDEK-PEEK copolymers increases the notched Izod impact strength.

[0104] The glass transition temperatures (T g ) data show that PEEK / PEI polymer blends exhibit a single T gat all concentrations investigated, while some blends of PEDEK-PEEK copolymer with PEI exhibited the T of pure PEI or pure PEDEK-PEEK copolymer. g Although slightly different, the two T g This observation indicates partial miscibility of PEI and PEDEK-PEEK copolymers, which is a surprising and beneficial result. Unlike fully miscible blends, partially miscible blends exhibit a higher T of the PEI-rich phase. g The lower T of the partially miscible blend corresponds to the PEDEK-PEEK copolymer-rich phase, improving high-temperature performance. g was estimated to be the inflection point of the asymmetric shoulder occurring near and before the maximum of the DMA loss tangent versus temperature curve for PEI concentrations of 35 wt % and above.

[0105] [Table 4]

[0106] Table 3 shows mechanical property data for comparative examples consisting of blends of PEI and PEEK-rich PEEK-PEDEK copolymers. For demonstration purposes, blends were formulated consisting of copolymers with two different molar ratios of PEEK and PEDEK moieties. For a given PEI concentration, the polymer blend compositions according to the present invention were shown to exhibit higher strength and stiffness at 175°C than the comparative blend formulations in Table 3. Furthermore, the comparative examples in Table 3 exhibit lower ductility at ambient temperatures than the blends according to the present invention, as evidenced by the reduced tensile elongation at break.

[0107] [Table 5]

[0108] [Table 6]

[0109] Table 4 shows storage modulus measurements from DMA tests in the torsion mode at temperatures between 180°C and 200°C. The results demonstrate that the stiffness at elevated temperatures of representative polymer blends according to the present invention exceeds not only the pure PEDEK-PEEK copolymer control, but also the comparative examples of similar PEEK / PEI blends and similar PEI and PEEK-PEDEK copolymer blends. More specifically, the addition of PEI to PEEK or PEEK-PEDEK results in a slight improvement or even a decrease in stiffness (lower storage modulus), while the addition of PEI to PEDEK-PEEK copolymer can significantly improve stiffness under comparable conditions.

[0110] [Table 7]

[0111] [Table 8]

[0112] [Table 9]

[0113] Table 5 shows crystallization data from DSC for exemplary formulations according to the present invention, as well as related controls and comparative examples. While adding PEI to PEEK significantly lowers the crystallization temperature, making the blends more difficult and time-consuming to process by injection molding, Table 5 surprisingly and advantageously shows that blending PEI with PEDEK-PEEK copolymer only slightly lowers the crystallization temperature of pure PEDEK-PEEK copolymer. Furthermore, Table 5 shows that blending PEI with PEEK or PEEK-PEDEK has the detrimental effect of increasing crystallization time compared to the pure PEEK or PEEK-PEDEK controls, and even completely eliminates evidence of crystallization under certain conditions. In contrast, adding PEI to PEDEK-PEEK copolymer surprisingly and advantageously reduces crystallization time. This result suggests that blends of PEDEK-PEEK copolymer with PEI crystallize faster than pure PEDEK-PEEK copolymer. Faster crystallization time is advantageous for efficient injection molding processing.

Claims

1. A composition [composition (C)] comprising: at least one polyaryletherketone copolymer [copolymer (PEDEK-PEEK)], Formula (I): 【Chemical 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, at 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; and each of j' and k'' is equal to or different from one another and, in 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 poly(etherimide) polymer [polymer (PEI)], comprising at least 50 mol %, based on the total number of moles in the polymer, of repeating units (R ＰＥＩ at least one poly(etherimide) polymer [polymer (PEI)] comprising and the copolymer (PEDEK-PEEK) detailed above is present in an amount of at least 65% by weight based on the total weight of the copolymer (PEDEK-PEEK) and the polymer (PEI) [Composition (C)].

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

4. The repeating unit (R ＰＥＩ ) are represented by the following formulae (I), (II), (III), (IV), (V) and mixtures thereof: 【Chemistry 7】 (In the formula, Ar is a tetravalent aromatic moiety and is selected from the group consisting of substituted or unsubstituted, saturated, unsaturated or aromatic monocyclic and polycyclic groups having from 5 to 50 carbon atoms; Ar′ is a trivalent aromatic moiety and is selected from the group consisting of substituted, unsubstituted, saturated, unsaturated, aromatic monocyclic and aromatic polycyclic groups having 5 to 50 C atoms; and R is selected from the group consisting of substituted and unsubstituted divalent organic radicals; provided that at least one of Ar, Ar' and R contains at least one ether group, and said ether group is present in the polymer chain backbone. The composition of any one of claims 1 to 3, selected from the group consisting of:

5. (A) The repeating unit (R ＰＥＩ ) is selected from the group consisting of formula (I), (II), (III) and mixtures thereof, wherein Ar is a group of formula: 【Chemistry 9】 (In the formula, X is a divalent moiety having a divalent bond at the 3,3′, 3,4′, 4,3″, or 4,4′ positions and is an alkylene of 1 to 6 carbon atoms, e.g., —C(CH ３ ) ２ and -C ｎ H ２ｎ - (n is an integer from 1 to 6); perfluoroalkylene of 1 to 6 carbon atoms, for example, -C(CF ３ ) ２ and -C ｎ F ２ｎ - (n is an integer from 1 to 6); cycloalkylene of 4 to 8 carbon atoms; alkylidene of 1 to 6 carbon atoms; cycloalkylidene of 4 to 8 carbon atoms; -O-; -S-; -C(O)-; -SO ２ -; -SO-; or X is a group of the formula -O-Ar"-O-, where Ar" is an aromatic moiety selected from the group consisting of substituted or unsubstituted, saturated, unsaturated or aromatic monocyclic and polycyclic groups having from 5 to 50 carbon atoms. or (B) The repeating unit (R ＰＥＩ ) is selected from the group consisting of formula (IV) and (V) and mixtures thereof, wherein Ar′ is a group of formula: 【Chemistry 10】 (In the formula, X is a divalent moiety having a divalent bond at the 3,3′, 3,4′, 4,3″, or 4,4′ positions and is an alkylene of 1 to 6 carbon atoms, e.g., —C(CH ３ ) ２ and -C ｎ H ２ｎ - (n is an integer from 1 to 6); perfluoroalkylene of 1 to 6 carbon atoms, for example, -C(CF ３ ) ２ and -C ｎ F ２ｎ - (n is an integer from 1 to 6); cycloalkylene of 4 to 8 carbon atoms; alkylidene of 1 to 6 carbon atoms; cycloalkylidene of 4 to 8 carbon atoms; -O-; -S-; -C(O)-; -SO ２ -; -SO-; or X is a group of the formula -O-Ar"-O-, where Ar" is an aromatic moiety selected from the group consisting of substituted or unsubstituted, saturated, unsaturated or aromatic monocyclic and polycyclic groups having from 5 to 50 carbon atoms. The composition of claim 4 selected from the group consisting of:

6. The polymer (PEI) comprises at least 50 mole % of a compound of formula (VII), based on the total number of moles in the polymer: 【Chemistry 11】 (In the formula, R is selected from the group consisting of substituted and unsubstituted divalent organic radicals; provided that at least one of Ar, Ar′, and R comprises at least one ether group, and said ether group is present in the polymer chain backbone; T is —O— or —O—Ar″—O—; wherein Ar″ is an aromatic moiety selected from the group consisting of substituted or unsubstituted, saturated, unsaturated or aromatic monocyclic and polycyclic groups having from 5 to 50 carbon atoms. Repeating units (R ＰＥＩ The composition according to any one of claims 1 to 5, which is a polymer comprising:

7. The polymer (PEI) comprises at least 50 mole % of a compound represented by formula (XXIII) or (XXIV), based on the total number of moles in the polymer: 【Chemistry 13】 Repeating units (R ＰＥＩ 7. The composition of claim 1, wherein the polymer comprises 2-(2-methyl-2-propanol)-2-(2-methyl-2-propanol)-1 ...

8. - the copolymer (PEDEK-PEEK) as detailed above, in an amount by weight of up to 95% based on the total weight of said copolymer (PEDEK-PEEK) and polymer (PEI); - polymer (PEI) as detailed above, in an amount of up to 35% by weight based on the total weight of said copolymer (PEDEK-PEEK) and polymer (PEI) and / or in an amount of at least 5% by weight based on the total weight of said copolymer (PEDEK-PEEK) and polymer (PEI); and / or The composition (C) according to any one of claims 1 to 7, comprising the copolymer (PEDEK-PEEK) in an amount of 60 to 90% and the polymer (PEI) in an amount of 10 to 40%, based on the total weight of the copolymer (PEDEK-PEEK) and the polymer (PEI).

9. 9. The composition according to any one of claims 1 to 8, comprising the copolymer (PEDEK / PEEK) and polymer (PEI) as detailed above in an amount by combined weight of at least 90%, if not at least 95%, based on the total weight of 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, said copolymer (PEDEK-PEEK), and said polymer (PEI), generally selected from the group consisting of: (i) colorants, (ii) pigments, (iii) light stabilizers, (iv) heat stabilizers, (v) antioxidants, (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, (xi) antiblocking agents, (xii) conductive additives, (xiii) plasticizers, (xiv) flow modifiers, (xv) extenders, (xvi) metal deactivators, and combinations comprising one or more of the foregoing additives; Composition (C) according to any one of claims 1 to 9, wherein said reinforcing filler is 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 the 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 (PEI).

12. A composite material comprising a matrix of composition (C) according to any one of claims 1 to 10, a composite material comprising one or more plies of impregnated fabric; 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 shaped article comprising the composition (C) according to any one of claims 1 to 10.

14. 14. The shaped article of claim 13 in an extruded shape.

15. 14. The molded article of claim 13, which is an injection molded article.

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