Polymer compositions based on poly(ether ketone ketone) and high glass transition temperature thermoplastic polyimide

Abstract

The invention relates to a composition comprising: a poly(ether ketone), PEKK1; a thermoplastic polyimide having a glass transition temperature greater than or equal to 230 °C, TPI; and optionally, a poly(aryl ether ketone), PAEK, PAEK being distinct from PEKK1. PEKK1 represents at least 50% by weight, relative to the total weight of PEKK1, TPI, and, where applicable, PAEK, of the composition. PAEK is necessarily present when the TPI content is greater than or equal to 20% by weight, and preferably when the TPI content is greater than or equal to 15% by weight, relative to the total weight of PEKK1 and TPI of the composition.

Description

Title of the invention: Polymer compositions based on poly(ether ketone ketone) and high glass transition temperature thermoplastic polyimide. Field of the invention

[0001] The present invention relates to the field of polymer materials, and more particularly to compositions based on poly(etherketone ketone) (PEKK) and thermoplastic polyimides. These compositions are designed to meet the requirements of cutting-edge industrial sectors, including aerospace, automotive, medical, and offshore drilling. Prior art

[0002] Poly(etherketone ketones) are well-known high-performance engineering polymers. They can be used for demanding applications involving high temperatures and / or high mechanical, or even chemical, stresses. They can also be used for applications requiring excellent fire resistance and low emissions of smoke or toxic gases. Finally, they exhibit good biocompatibility. These polymers are found in fields as diverse as aerospace, offshore drilling, automotive, rail, marine, wind energy, sports, construction, electronics, and medical implants. Notwithstanding these advantageous properties, it is sometimes necessary to formulate poly(etherketone ketones) to meet specific requirements. In particular, one might seek to increase the glass transition temperature of the material to broaden the temperature range over which it can be used.This allows the material to retain good mechanical properties up to higher temperatures. Furthermore, it is important that the formulation remains stable over time at these higher temperatures. In the present invention, the inventors focused in particular on performing mechanical tests after subjecting the materials to a prolonged heat treatment at 250°C, which could, for example, be representative of extended use at a service temperature of this order.

[0003] Mixtures of poly(aryl ether ketone) (PAEK) and poly(bisphenol A-co-4-nitrophtal anhydride-co-l,3-phenylenediamine) (PEI) and mixtures of poly(aryl ether ketone) (PAEK) and poly(phenylsulfone) (PPSU) are well known and have been extensively studied. The addition of PEI and / or PPSU generally increases the glass transition temperature of PAEK.

[0004] Document WO23242364 discloses mixtures of PEKK and PEI. Document WO20095268 discloses mixtures of PEEK and PEI. PEI is known for It is miscible with poly(ether ether ketones) (PEEK) and PEKK, even in high proportions of PEI. However, the glass transition temperature of PEI is 217°C, which is insufficient to significantly raise the glass transition temperature of the mixture. Furthermore, the inventors have demonstrated in the present invention that such a material does not retain its mechanical properties after aging at 250°C.

[0005] The prior art also discloses other thermoplastic polyimides besides PEI. Thermoplastic polyimides are polymers characterized by the presence of imide (-CO-N-CO-) bonds in their molecular structure. Document WO2024014123 discloses in Table 2 PEKK compositions with polyimides having a glass transition temperature ranging from 166°C to 233°C (Table 1). The glass transition temperatures are defined therein as a second heating with a heating rate of 20°C / min and a cooling rate of 10°C / min. As with PEI, these glass transition temperatures remain too low, even assuming that these less common polyimides are miscible with PEKK, for the glass transition temperature (Tg) of the material to be sufficiently increased.

[0006] Document EP2899231 describes a separate-phase polymer blend composed of 25 to 85% by weight of a polyetherimide and 15 to 75% by weight of a PAEK. The polymer blend is used in a composite material that also includes a fibrous filler and a mineral filler. The document specifically discloses blends of PEEK and polyimides from the Aurum® range. According to the corresponding technical brochure, the glass transition temperature of the polymers in this range is around 250°C. Although the glass transition temperature of this type of polyimide is sufficiently high, the immiscibility of PEEK and this type of polyimide prevents an increase in the glass transition temperature of the polymer blend. Indeed, the immiscibility of PEEK with Aurum® means that the blend has an initial glass transition temperature corresponding to that of PEEK.It can also be pointed out that the material according to EP2899231 contains as an essential characteristic a fibrous filler material and a mineral filler material, necessary to ensure good mechanical properties of the material.

[0007] Furthermore, a general problem with mixtures of a semi-crystalline polymer with any other polymer, amorphous or semi-crystalline, is that this other polymer tends to disrupt the crystalline phases of the semi-crystalline polymer, resulting in a slowing of the crystallization rate of the semi-crystalline polymer in the mixture. A challenge when formulating a mixture of poly(etherketoneketone) and polyimide is therefore to maintain a crystallization rate comparable to that of poly(etherketoneketone) alone, so that The mixture can be used in the same processing methods and under conditions comparable to those of poly(etherketoneketone) alone. For example, a challenge when formulating a mixture of poly(etherketoneketone) and polyimide may be maintaining a good crystallization rate so that the mixture can be used in a process with a rapid cycle time, particularly in an injection molding process. Summary of the invention

[0008] The present invention relates to a composition comprising: • a poly(ether ketone ketone), PEKK1; • a thermoplastic polyimide having a glass transition temperature greater than or equal to 230 °C, TPI; and • possibly, a poly(aryl ether ketone), PAEK, PAEK being distinct from PEKK1;

[0009] in which: • PEKK1 representing at least 50% by weight, relative to the total weight of PEKK1, TPI and, where applicable, PAEK, of the composition, and • PAEK is required to be present when the TPI content is greater than or equal to 20% by weight, and preferably when the TPI content is greater than or equal to 15% by weight, relative to the total weight of PEKK1 and TPI in the composition.

[0010] Advantageously, the TPI content is less than or equal to 40% by weight, preferably less than or equal to 35% by weight, preferably still less than or equal to 30% by weight and preferably still less than or equal to 25% by weight, the percentages being expressed by weight relative to the total weight of PEKK1 and TPI of the composition.

[0011] Advantageously, the TPI does not include sulfone and / or isopropylidene groups.

[0012] Advantageously, PEKK1 comprises terephthalate (T) and isophthalate (I) units, the T:I molar ratio ranging from 55:45 to 89:11, and preferably from 72:28 to 85:15.

[0013] Advantageously, PAEK, when present in the composition, is selected from: • a poly(ether ether ketone), PEEK; • a poly(ether ketone), PEK; • a poly(ether ketone ether ketone ketone), PEKEKK; • a poly(ether ketone ketone) having a T / I ratio higher than that of PEKK1 and / or a lower viscosity index than that of PEKK1, PEKK2; and • any mixture of at least two of these polymers.

[0014] According to another embodiment, the PAEK is a PEEK.

[0015] Advantageously, the PAEK content represents from 0.1% to 20% by weight, of Preference of 1% to 18% by weight, and more preferably of 5% to 15% by weight, relative to the total weight of PEKK1, TPI and PAEK in the composition.

[0016] Advantageously, the TPI comprises repeating units of general formula (I):

[0017] [Chem.l] (I),

[0018] in which: • X represents a monocyclic or polycyclic tetravalent group, saturated, unsaturated or aromatic, substituted or unsubstituted, comprising from 5 to 50 carbon atoms and possibly one or more heteroatoms; and • Ri represents a linear, branched or cyclic divalent radical, substituted or unsubstituted, comprising from 2 to 50 carbon atoms, preferably from 6 to 36 carbon atoms, and possibly comprising one or more heteroatoms.

[0019] Preferably, in formula (I), Ri corresponds to the general formula (III):

[0020] [Chem.2] o..... RJ RK (III),

[0021] wherein Q represents a direct bond or a radical selected from the group consisting of -O-, -C(O)-, -OYO-, alkylenes comprising from 1 to 6 carbon atoms, and cycloalkylenes comprising from 4 to 8 carbon atoms, where Y represents a group of general formula (IIIA) or (IIIB):

[0022] [Chem.3] (IIIA),

[0023] [Chem.4] Ro RP (inB),

[0024] wherein Z represents a direct bond or a radical selected from the group consisting of -O-, -C(O)-, alkylenes comprising from 1 to 6 carbon atoms, and cycloalkylenes comprising from 4 to 8 carbon atoms, and

[0025] for formulas (II), (IIIA) and (IIIB), wherein each group Rj, Rk, Rb Ro and Rp is, independently of each other, a hydrocarbon group comprising from 1 to 10 carbon atoms and possibly comprising one or more heteroatoms, each index j, k, l, o and p being an integer from 0 to 4 and representing a number of substitution groups on a ring.

[0026] According to a preferred embodiment, the TPI comprises repeating units of general formula (IV):

[0027] [Chem.5] (IV)

[0028] According to another preferred embodiment, the TPI comprises repeating units of general formula (V):

[0029] [Chem.6] (V)

[0030] According to one embodiment, the composition described above, and in more detail below, further comprises one or more fillers and / or one or more functional additives.

[0031] The invention also relates to an article made from the composition as described above and in detail below.

[0032] The invention also relates to a method of manufacturing said article, the method comprising at least one step of injection molding or extrusion of a composition according to the invention.

[0033] The Applicant has developed polymer blends comprising a PEKK (referred to in the invention as PEKK1) as the main polymer, a polyimide having a glass transition temperature Tg greater than or equal to 230°C (referred to in the invention as TPI), and in certain embodiments a poly(aryl ether ketone) distinct from PEKK1 (referred to in the invention as PAEK). These blends offer significant advantages in terms of good polymer miscibility, thermal stability, and crystallization rate.

[0034] The Applicant has observed that PEKK offers significantly better miscibility with TPI than PEEK at an equivalent TPI ratio. Thus, by selecting a polyimide with a Tg greater than or equal to 230°C, the resulting mixture has a glass transition temperature that guarantees good mechanical properties up to higher service temperatures.

[0035] Furthermore, the compositions according to the invention are thermally stable and retain their mechanical properties, even after high-temperature aging, for example at 250°C or higher. In particular, these compositions are more stable than comparative compositions comprising PEKK1 and a polyimide having a lower glass transition temperature than the TPIs according to the invention.

[0036] This precise choice of polymers – PEKK1 as the main component, TPI, and possibly PAEK – optimizes polymer compatibility, crystallization, and the thermal stability of the mixture. It also ensures good processability of the mixture. Detailed description Definitions:

[0037] The miscibility of the polymers of the invention refers to the ability of two or more polymers to mix homogeneously at the molecular level to form a single phase. When two polymers are miscible, they interact well enough to prevent phase separation.

[0038] Miscibility can be assessed by the presence of a single glass transition temperature (Tg) in a mixture. If a single Tg peak is observed, this indicates that the polymers are miscible and form a homogeneous phase. Conversely, if two distinct Tg peaks appear, this means that the polymers are immiscible or partially miscible, forming distinct phases within the material.

[0039] A glass transition temperature (Tg) corresponds to a temperature at which a polymer passes from a rigid and glassy state to a more flexible and rubbery state. The glass transition temperature (Tg) is / are generally determined by techniques such as dynamic mechanical analysis (DMA) or differential scanning calorimetry (DSC).

[0040] The Tg of a single polymer, particularly TPI, is preferably determined by DSC, according to ISO 11357-2:2020. It is measured at mid-height of the glass transition on the thermogram obtained under a nitrogen atmosphere and during a second heating according to the following thermal cycle:

[0041] - heats at 10°C / min up to a temperature typically of about 30°C above of the extrapolated final melting temperature (for Aurum® PL500A and Aurum® PL450C, approximately 420°C);

[0042] - cooling at 20°C / min up to a temperature of 20°C;

[0043] - temperature plateau at 20°C for 5 min;

[0044] - heats at 10°C / min up to a temperature typically of about 30°C above of the extrapolated final melting temperature (for Aurum® PL500A and Aurum® PL450C, approximately 420°C).

[0045] The Tg of a polymer blend, or where applicable the single Tg of a polymer blend, in particular that of the polymer blend(s) of the compositions according to the invention or that of the compositions according to the invention comprising such blends, is preferably determined by DMA, according to ISO 6721-11. The Tg of a single semi-crystalline polymer can also be determined by DMA, in particular for the purpose of comparison with the Tg or Tgs of a polymer blend comprising this semi-crystalline polymer as a constituent. Type IA dumbbells (see ISO 527-2:2012) obtained by injection molding, then dried for 24 hours at 130°C, and finally heat-treated for 4 hours at 260°C are used for this measurement. This measurement is carried out under a nitrogen atmosphere following the following thermal profile: cooled to 0°C, temperature maintained at 0°C for 10 minutes, then heated at 2°C / min.The Tg(DMA) or Tg(DMA) correspond to the maximum(s) of the tangent of the phase angle delta (noted tan ô, corresponding to the ratio viscous modulus / elastic modulus, noted E” / E’) at 1Hz.

[0046] A semi-crystalline polymer is a polymer that possesses, or is capable of possessing, crystalline domains. Crystalline domains form when polymer chains align in an ordered manner, creating regular structures called crystallites. However, if cooling is rapid, crystallization may not occur, and the polymer remains in an amorphous state.

[0047] The crystallization temperature (Te) corresponds to the temperature at which the polymer chains begin to organize into crystalline structures upon cooling from the molten state. Te is preferably measured by DSC under a nitrogen atmosphere. It corresponds to the peak temperature of the exotherm on the thermogram recorded during the first cooling, according to the following thermal cycle:

[0048] - heats at 20°C / min up to 420°C;

[0049] - first cooling at 20°C / min or 60°C / min up to a temperature

[0050] of 20°C (measurement of Te);

[0051] - temperature plateau at 20°C for 5 min;

[0052] - second heating at 20°C / min up to 420°C (measurement of the enthalpy of fusion in second heating).

[0053] In this invention, the Te is used to compare the expected crystallization rates between one polymer or polymer blend and another polymer or polymer blend. A higher Te generally indicates that the polymer or polymer blend will begin to crystallize earlier upon cooling. Another, alternative or complementary, way to assess the crystallization rate is to measure the enthalpy of fusion on the second heating. A higher enthalpy of fusion generally indicates that the polymer or polymer blend crystallizes more during the first cooling and / or the first part of the second heating.

[0054] In this description, unless otherwise specified, any range of numerical values ​​expressed by a lower and upper limit explicitly includes those limits, as well as all intermediate values ​​and subranges between those limits. For example, a range from "X to Y" means that the value can be X, Y, or any intermediate value. The PEKK1

[0055] The composition of the present invention comprises more than 50% by weight of poly(etherketone ketone). In the invention, this poly(etherketone ketone) is referred to by the abbreviation PEKK1. Thus, the composition of the present invention comprises more than 50% by weight of PEKK1, relative to the total weight of PEKK1, TPI, and, where applicable, PAEK, in the composition.

[0056] Preferably, the composition comprises at least 55% by weight of PEKK1, preferably between 60 and 95% by weight, and more preferably between 70% and 90% by weight, relative to the total weight of PEKK1, TPI and where applicable PAEK of the composition.

[0057] PEKK1 is advantageously essentially composed of, or consisting of, repeating units derived from terephthaloyl chloride and isophthaloyl chloride, which respectively form terephthalate (T) and isophthalate (I) units in the polymer chain. These units are based on phenylene groups linked by ether and ketone bonds.

[0058] The terephthalate (T) units comprise a 1,4-phenylene group, and can be represented by the following formula (VI):

[0059] [Chem.7] (VI).

[0060] Isophthalate (I) units comprise a 1,3-phenylene group, and can be represented by the following formula (VII):

[0061] [Chem.8] (VII).

[0062] The molar ratio of T / I units in PEKK1 can vary between 20:80 and 80:20. In some embodiments, this T / I molar ratio is preferably between 55:45 and 89:11, and more specifically between 72:28 and 85:15.

[0063] Preferably, PEKK1 has a glass transition temperature between 150 °C and 180 °C, preferably between 160 °C and 170 °C.

[0064] Advantageously, PEKK1 has a viscosity index at 25 °C, in an aqueous solution of sulfuric acid at 96% by mass, according to ISO 307:2019 applied to a poly(aryl ether ketone), of 0.5 to 2.0 dl / g, and preferably of 0.7 to 1.4 dl / g. The TPI

[0065] The thermoplastic polyimide used in the composition according to the invention has a glass transition temperature, Tg, greater than or equal to 230°C. In the invention, this thermoplastic polyimide is referred to by the abbreviation TPI.

[0066] The Tg of TPI, polymer alone, is determined by differential scanning calorimetry (DSC) in second heating with temperature ramps of 10°C / min and a cooling ramp of 20°C / min, under nitrogen atmosphere and corresponds to the value at half the glass transition.

[0067] According to some preferred embodiments, the TPI has a glass transition temperature greater than or equal to 240°C. According to some preferred embodiments, the TPI may have a Tg greater than or equal to 245°C, or even greater than or equal to 250°C.

[0068] Advantageously, the TPI content is less than or equal to 40% by weight, preferably less than or equal to 35% by weight, preferably even less than or equal to 30% by weight and preferably less than or equal to 25% by weight, relative to the total weight in PEKK1 and TPI of the composition according to the invention.

[0069] According to one embodiment, TPI represents between 5% and 40% by weight, preferably between 10% and 30% by weight, relative to the total weight of PEKK1 and TPI in the composition according to the invention.

[0070] Advantageously, the TPI comprises repeating units corresponding to the general formula (I):

[0071] [Chem.9] (I)

[0072] in which • X represents a monocyclic or polycyclic tetravalent group, saturated, unsaturated, or aromatic, comprising from 5 to 50 carbon atoms; and possibly one or more heteroatoms such as oxygen, nitrogen, or sulfur, and • RI represents a linear, branched or cyclic divalent radical, substituted or unsubstituted, comprising from 2 to 50 carbon atoms, preferably from 6 to 36 carbon atoms, and possibly one or more heteroatoms such as oxygen, nitrogen or sulfur.

[0073] Advantageously, the repeating units of the TPI do not include sulfone groups (-SO2-) or isopropylidene groups (-C(CH3)2-).

[0074] Advantageously, the TPI comprises at least 50% by weight, preferably at least 70% by weight, preferably still 90% by weight of repeating units of formula (I).

[0075] According to one embodiment, the TPI is essentially made up of repetitive units of formula (I).

[0076] According to one embodiment, X comprises less than 30 carbon atoms, preferably less than 20 carbon atoms, and even more preferably less than 18 carbon atoms.

[0077] Advantageously, X does not include an isopropylidene group.

[0078] According to a first variant, X is a benzene ring.

[0079] In a second embodiment, X is an aromatic polycyclic group comprising 10 to 18 carbon atoms.

[0080] According to this second variant, X is preferably chosen from biphenyl, benzophenone, chrysene, phenanthrene, naphthalene or anthracene, possibly substituted.

[0081] According to a preferred embodiment, X is a biphenyl.

[0082] According to another preferred embodiment, X is a benzophenone.

[0083] Advantageously, Ri is a monocyclic or polycyclic group, saturated, unsaturated or aromatic, comprising from 6 to 36 carbon atoms; and may include one or more heteroatoms such as oxygen, nitrogen and / or sulfur.

[0084] Advantageously, Ri does not include a sulfone group.

[0085] Advantageously, Ri comprises less than 30 carbon atoms, preferably less than 24 carbon atoms, and even more preferably less than 18 carbon atoms.

[0086] According to a first variant, Ri corresponds to the general formula (II):

[0087] [Chem. 10] Ri (ii)

[0088] wherein Ri represents one or more hydrocarbon groups comprising from 1 to 20 carbon atoms, optionally including one or more heteroatoms, the index i being an integer from 0 to 4 representing the number of substitution groups on a ring. Preferably, i is equal to 0.

[0089] Advantageously, according to this first variant, the bonds between the Ri group and the imide groups in the repeating unit of the TPI are in position 1,3 or 1,4 of the cycle of formula (II).

[0090] According to a second variant, Ri corresponds to the following general formula (III):

[0091] [Chem. 11] (III)

[0092] in which Q represents a direct bond or a radical selected from the group consisting of -O-, -C(O)-, -OYO-, alkylenes comprising from 1 to 6 carbon atoms, and cycloalkylenes comprising from 4 to 8 carbon atoms, where Y represents a group of general formula (IIIA) or (IIIB):

[0093] [Chem. 12] (IIIA)

[0094] [Chem. 13] (IIIB)

[0095] in which • Z represents a direct bond or a radical selected from the group consisting of -O-, -C(O)-, alkylenes comprising 1 to 6 carbon atoms, and cycloalkylenes comprising 4 to 8 carbon atoms, and • each group Rj, Rk, Rb Ro and Rp is a hydrocarbon group comprising from 1 to 10 carbon atoms and possibly including one or more heteroatoms, each index j, k, l, o and p being an integer from 0 to 4 and representing a number of substitution groups on a ring.

[0096] Advantageously, according to this second variant, the bonds between the Ri group and the imide groups in the repeating unit of the TPI are in meta or para position of the cycles of the general formula (III).

[0097] According to a preferred embodiment of the invention, the TPI comprises, preferably consists essentially of, repeating units of general formula (IV):

[0098] [Chem. 14] (IV).

[0099] Examples of TPIs having such a structure include polymers available under the trade name AURUM® (Mitsui Chemicals).

[0100] According to another preferred embodiment of the invention, the TPI comprises, preferably consists essentially of, repeating units of formula (V):

[0101] [Chem. 15] (V).

[0102] Examples of TPIs having such a structure include polymers available under the trade name TPI Lare (NASA).

[0103] Advantageously, the TPI used in this invention has a molecular weight suitable for the requirements of industrial processes such as injection molding or extrusion.

[0104] PEKK1 is completely miscible up to a TPI content of at least 20% by weight, relative to the total weight of PEKK1 and TPI. This miscibility results in the presence of a single glass transition temperature.

[0105] Advantageously, the glass transition temperature of the composition comprising PEKK1 and TPI according to the invention is higher than that of PEKK1, polymer alone, and lower than that of TPI, polymer alone.

[0106] Advantageously, the glass transition temperature of the composition comprising PEKK1 and TPI according to the invention is higher than that of PEKK1 by at least 2°C, preferably higher by at least 5°C, preferably even higher by at least 10°C. The PAEK

[0107] According to one embodiment, the composition of the invention comprises PEKK1, TPI, and a poly(aryl ether ketone) distinct from PEKK1. In the invention, this poly(aryl ether ketone) distinct from PEKK1 is referred to by the abbreviation PAEK.

[0108] The addition of this PAEK is particularly advantageous at high TPI contents to increase the crystallization rate of the composition. More specifically, the composition according to the invention and according to these embodiments, comprising PEKK1, TPI and PAEK, makes it possible to obtain a composition having a higher crystallization rate than a reference composition comprising only PEKK1 and TPI, at the same proportion of TPI relative to the total weight of TPI and total poly(aryl ether ketone) in the composition (i.e. in particular PEKK1 for the reference composition and PEKK1 and PAEK for the composition according to the invention).

[0109] PAEK is mandatory in the composition according to the invention when the TPI content is greater than or equal to 20% by weight, relative to the total weight of PEKK1 and TPI in the composition. According to preferred embodiments, the composition comprises PAEK when the TPI content is greater than or equal to 15% by weight, relative to the total weight of PEKK1 and TPI in the composition.

[0110] According to some embodiments, the composition includes PAEK when the TPI content is greater than or equal to 10% by weight, relative to the total weight of PEKK1 and TPI in the composition. The composition may also include PAEK when the TPI content is less than or equal to 10% by weight, relative to the total weight of PEKK1 and TPI in the composition. However, in these embodiments, the need to increase the crystallization rate of the composition is generally less pronounced.

[0111] The PAEK used advantageously has a higher crystallization temperature than the PEKK1 polymer alone.

[0112] According to one embodiment, the PAEK is chosen from: - a poly(ether ether ketone) (PEEK); - a poly(ether ketone) (PEK); - a poly(ether ketone ether ketone ketone) (PEKEKK); - a poly(ether ketone ketone) (PEKK2) having a T / I ratio higher than that of PEKK1 and / or a lower viscosity index than that of PEKK1; and - any mixture of at least two of these polymers.

[0113] These PAEK polymers can be used alone or in mixtures to vary the mechanical properties and / or the crystallization rate of the composition.

[0114] For the present invention, the term "PEEK" designates a polymer in which more than 50% by moles, preferably more than 75% by moles, and even more preferably more than 90% by moles of the repeating units are repeating units corresponding to formula (VIII):

[0115] [Chem. 16] (VIII).

[0116] For the present invention, the term "PEK" designates a polymer in which more than 50% by moles, preferably more than 75% by moles, more preferably still more than 90% by moles of the repeating units are repeating units corresponding to formula (IX):

[0117] [Chem. 17] (IX).

[0118] For the present invention, the term "PEKEKK" designates a polymer of which more than 50% by moles, preferably more than 75% by moles, preferably even more than 90 % in moles of repeating units are repeating units corresponding to the formula (X):

[0119] [Chem.18] (X).

[0120] PAEK can also be a poly(ether ketone ketone) distinct from PEKK1, and denoted in the present invention PEKK2.

[0121] PEKK2 may have a T / I ratio higher than that of PEKKL. According to some embodiments, PEKK1 may comprise terephthalate (T) units and isophthalate (I) units and a T:I molar ratio ranging from 65:35 to 72:28, and PEKK2 may comprise terephthalate (T) units and isophthalate (I) units, and a T:I molar ratio strictly greater than 72:28.

[0122] PEKK 2 may have a viscosity index at 25 °C, in a 96% by mass aqueous sulfuric acid solution, according to ISO 307:2019 applied to a poly(aryl ether ketone), lower than that of PEKKL. According to certain embodiments, PEKK 1 may have a viscosity index at 25 °C, in a 96% by mass aqueous sulfuric acid solution, according to ISO 307:2019 applied to a poly(aryl ether ketone). The viscosity index of PEKK 2 may, in particular, be less than or equal to 0.7 dl / g, or even less than or equal to 0.5 dl / g.

[0123] Advantageously, PAEK represents between 0.1% and 20% by weight, preferably between 1% and 18% by weight, preferably again between 5% and 15% by weight relative to the total weight of PEKK1, TPI and PAEK in the composition.

[0124] According to some embodiments, PAEK may represent between 0.1% and 1% by weight, or between 1% and 2% by weight, or between 2% and 3% by weight, or between 4% and 5% by weight, or between 5% and 10% by weight, or between 10% and 12% by weight, or between 12% and 15% by weight, or between 15% and 18% by weight, or between 18% and 20% by weight, relative to the total weight of PEKK1, TPI and PAEK in the composition.

[0125] According to a preferred embodiment, the PAEK present in the composition according to the invention is PEEK. The PEEK advantageously represents between 0.1% and 15% by weight, preferably between 1% and 12% by weight, and even more preferably between 5% and 10% by weight relative to the total weight of PEKK1, TPI, and PEEK in the composition. According to some embodiments, the PEEK may represent between 0.1% and 1% by weight, or between 1% and 5% by weight, or between 5% and 10% by weight, or between 10% and 12% by weight, or between 12% and 15% by weight, relative to the total weight of PEKK1, TPI, and PEEK in the composition.

[0126] Advantageously, the PAEK used in this invention has a molecular weight suitable for the requirements of industrial processes such as injection molding or extrusion. Functional fillers or additives

[0127] The compositions according to the invention may include, in addition to the polymers described above, fillers and / or functional additives.

[0128] Among the possible fillers, mention may be made in particular of silica and alumina, nucleating fillers such as mineral fillers, in particular talc, carbon fillers, in particular carbon nanotubes or carbon blacks, ceramic fillers, in particular boron nitride (NB), or metal oxides, in particular ZnO or MgO, and reinforcing fillers, such as glass fibers or carbon fibers.

[0129] Preferably, when the composition includes at least one filler, said at least one filler represents from 2% to 30% by weight relative to the total weight of the composition.

[0130] According to some embodiments, the composition does not include a filler.

[0131] According to some embodiments, the composition does not include a filler nucleating.

[0132] According to some embodiments, the composition does not include a reinforcing filler.

[0133] The compositions according to the invention may also include one or more functional additives selected from pigments, such as titanium dioxide, zinc sulfide and zinc oxide; UV stabilizers; thermal stabilizers; antioxidants, such as phosphites; acid neutralizers; lubricants; flame retardants; antismoke agents; antistatic agents; anti-adhesion agents; conductive fillers such as carbon black.

[0134] Preferably, when the composition includes at least one functional additive, said at least one functional additive represents 5% or less by weight relative to the total weight of the composition.

[0135] According to some embodiments, the composition consists of: • PEKK1, • TPI, • possibly PAEK, and • optionally at least one functional additive.

[0136] According to some embodiments, the composition consists of: • PEKK1, • TPI, • possibly PAEK, • optionally at least one charge, and • optionally at least one functional additive. Preparation of compositions according to the invention

[0137] The compositions according to the invention can be prepared by any known method allowing a homogeneous mixture of polymers and, where appropriate, fillers and / or functional additives to be obtained.

[0138] Suitable methods include, in particular, dry blending or melt blending (extrusion). Preferably, the composition is obtained by melt blending.

[0139] The composition can be prepared in the form of powders or granules, which can then be used to manufacture various objects by conventional processing techniques such as laser sintering, powder coating, injection molding, extrusion, compression and extrusion-compression.

[0140] By way of example, a method for implementing a composition according to the invention may include the following steps: - pre-mix PEKK and TPI, and where applicable PAEK, at room temperature, to form a composition according to the invention; - compound the composition in a twin-screw extruder, preferably at a temperature between 240 °C and 400 °C and granulate it; - mold the granules by injection, preferably at an injection temperature between 360 °C and 400 °C.

[0141] The composition can be adapted, in particular, for use in processes where it is melted and then rapidly cooled, for example, in injection or extrusion processes with air or water cooling. According to certain embodiments, such a composition may have a second heating enthalpy measured by DSC with heating ramps at 20°C / min and a cooling ramp at 60°C / min greater than or equal to 15 J / g, preferably greater than or equal to 20 J / g, and preferably greater than or equal to 25 J / g. The enthalpy of fusion is herein indicated in joules per gram of total polymer content in the composition.

[0142] According to another aspect, the invention relates to an article consisting of the composition according to the invention and obtained by a process such as laser sintering, powder coating, injection molding or extrusion, in particular the extrusion of sheets, plates and coating of wires or metal bars.

[0143] According to another aspect, the invention relates to the use of the compositions according to the invention and / or articles obtained from such compositions in industrial applications requiring high thermal and mechanical resistance, such as aeronautical components, automotive parts, parts of Industrial machinery, components for oil and gas extraction, coatings for electronic and electrical components. In particular, such compositions and / or articles may be used at temperatures, including service temperatures, higher than those generally indicated for PEKK1 alone. Examples

[0144] The following examples illustrate the invention without limiting its scope. 1 / Raw materials:

[0145] - PEKK KEPSTAN®: poly(ether ketone ketone) having a molar ratio It has a T / I ratio of 80 / 20 and a viscosity index at 25°C in a 96% by mass aqueous sulfuric acid solution of 1.2 dl / g. It is commercially available from Arkema. This polymer is used in the examples as "PEKK1" within the meaning of the invention. - Aurum® PL500A and Aurum® PL450C, respectively: thermoplastic polyimides having a glass transition temperature, as measured by DSC in a second heating cycle with heating rates of 10°C / min and a cooling rate of 20°C / min, of 252°C and 253°C, respectively. They are commercially available from Mitsui. These polymers are used in the examples as "TPI" within the meaning of the invention. - ULTEM™ 1000: poly(bisphenol A-co-4-nitrophtal anhydride-co-1,3-phenylenediamine)polyimide (PEI) with a glass transition temperature of 217 °C, according to the corresponding technical data sheet. It is commercially available from Sabic. This polymer is used in the comparative examples because PEI is a polyimide well known to those skilled in the art, generally used to increase the glass transition temperature of PEKK. However, its Tg is too low compared to that of the TPIs used according to the invention. - RADEL® R5000 NT: polyphenylsulfone (PPSU) having a glass transition temperature of 220 °C, as measured by DSC according to the invention, commercially available from Solvay. This polymer is used in the comparative examples because PPSU is a polymer well known to those skilled in the art as a compatible polymer and used in blends with poly(aryl ether ketones). - PEEK 450G™: poly(ether ketone ketone) consisting of the formula repeating unit (VIII). It is commercially available from Victrex. This polymer is used in the examples as "PAEK" within the meaning of the invention. 2 / Preparation of polymer mixtures

[0146] Different polymer compositions were prepared with the polymers and quantities indicated in Table 1. The quantity of each polymer is expressed as a percentage by weight, relative to the total weight of the composition.

[0147] The polymers were first pre-mixed at room temperature and then fed into a Haake II twin-screw extruder operating at a throughput of 2 kg / h with a screw rotation speed of 250 rpm. The extruder temperature profile was controlled from 240°C (feed zone) to 400°C (die zone) to ensure melting or softening of the polymer(s).

[0148] The extruded and then granulated polymers were injection molded in a Battenfeld B A800 CDC injection molding machine, with an injection temperature maintained between 365 °C and 385 °C, and a mold temperature set at 255 °C.

[0149] Compositions C3, C4, C6, C7, C11, C13 and C14 are according to the invention. Compositions C11, C2, C8, C9 and C12 are comparative compositions.

[0150] The compositions implemented are presented in Table 1.

[0151] [Table 1]: Compositions according to the invention and comparative compositions (mass proportions) PEKK PEEK4 50G Aurum PL500A Aurum PL450C ULT EM 1000 RADEL R5000 Cl 100 C2 100 C3 81.9 8.1 10 C4 77.3 7.7 15 C6 72.7 7.3 20 C7 72.7 7.3 20 C8 72.7 7.3 20 C9 72.7 7.3 20 Eyelash 90 10 C12 90 10 C13 80 20 C14 80 20

[0152] 3 / Miscibility and glass transition temperature

[0153] The single glass transition temperature or the multiple glass transition temperatures (in the case of total or partial immiscibility) were determined by Dynamic mechanical analysis (DMA) was performed as indicated in the definitions. The tangents (Tg(DMA)) are identified at the maximum of tan θ. The results are presented in Table 2.

[0154] [Table 2]: Glass transition temperature(s) Tg(DMA) Tgl (°C) Tg 2 (°C) Cl 165 C2 179 C3 187 C4 189 C6 193 C7 194 C8 188 C9 187 Cil 187 C12 165 270 C13 189 C14 188

[0155] These results show that PEEK and Aurum PL500A TPI are not miscible, even in small proportions (90 / 10), as evidenced by the presence of two distinct Tgs in the comparative composition C12. The lowest Tg at 165°C corresponds to that of PEEK alone (see composition Cl).

[0156] Conversely, PEKK and TPI, Aurum PL500A or Aurum PL450C, are miscible up to a proportion of at least 20% by weight of TPI relative to the total weight of TPI and PEKK, as evidenced by the presence of a single Tg for compositions Cil, C13 and C14. The Tg measured at a value of 187-189°C is higher than that of PEKK alone (179°C, see composition C2).

[0157] Due to the majority presence of PEKK, the compositions consisting of PEKK, PEEK and TPI (C3 to C7) all have a single Tg, the value of which is higher (187°C, 189°C, 193°C and 194°C) than that of PEKK alone (179°C, see composition C2).

[0158] It should also be noted that the polymers in the PEKK, PEEK, and PEI mixture of comparative composition C8 and the polymers in the PEKK, PEEK, and PPSU mixture of comparative composition C9 are miscible, since only one Tg was observed. The Tg reached is higher than that of PEKK alone or PEEK alone, but it is nevertheless lower than those of compositions C6 and C7. 4 / Crystallization kinetics

[0159] The prepared compositions were analyzed by DSC to determine their crystallization temperature (Te), carried out as indicated in the definitions, with a first cooling at 20°C / min or at 60°C / min.

[0160] After the first controlled cooling, the sample is heated at 20°C / minute up to 420°C to detect the melting of the crystals formed (2nd heating). The area under the endothermic peak recorded during this melting corresponds to the enthalpy of fusion AHf, proportional to the quantity of crystals formed in the polymer mixture.

[0161] The results are presented in Table 3.

[0162] [Table 3]: Crystallization temperatures and enthalpies of fusion 1st type of test 2nd type of test Cooling (207 min) 2nd heating (207 min) Cooling (607 min) 2nd heating (207 min) Te (°C) AHf (J / g of composition) Te (°C) AHf (J / g of composition) C2 283 34.3 266 34.9 C6 282 33.5 258 30.2 C7 281 33.9 256 25.5 C13 257 25.5 245 5.4 C14 261 27.3 238 13.6

[0163] The results obtained by DSC show that compositions comprising PEKK and TPI (Cl3 and Cl4) crystallize much more slowly than PEKK alone (C2), as evidenced by the significant decrease in crystallization temperature and the significant decrease in enthalpy of fusion (AHf). This shows in particular that the addition of TPI in high proportions greatly reduces the crystallization rate compared to PEKK alone.

[0164] On the other hand, compositions comprising PEKK, TPI and PEEK (C6 and C7) have a crystallization rate equal to or comparable to that of PEKK alone (C2), and in all cases, a crystallization rate much higher than that of PEKK and TPI mixtures (C13 and C14)

[0165] The addition of PEEK therefore improves the crystallization kinetics of the PEKK / TPI mixture, which is advantageous for industrial processes requiring rapid implementation cycles. 5 / Thermal aging

[0166] The compositions obtained were used to evaluate their elongation at break after thermal aging on ISO 527-1A type specimens.

[0167] Each specimen was initially annealed in air at 260 °C for a period of 4 hours, so that the changes observed during the aging test could not be attributed to structural changes, such as a change in the degree of crystallinity. Aging was then carried out in air in an oven at 250 °C for a period of 1003 hours, in order to evaluate long-term mechanical stability under severe thermal conditions.

[0168] A tensile test was carried out after initial annealing and after aging using an MTS 810 dynamometer equipped with a mechanical extensometer. The tests were performed at an ambient temperature of 23 °C, with a tensile speed of 50 mm / min, in accordance with the requirements of ISO 527-1. The results obtained are presented in Table 4.

[0169] [Table 4]: Elongation at break after thermal aging Nominal break (initial) (%) Nominal break (after aging) (%) Difference in nominal break after and before aging C2 9 9 0 C3 14 14 0 C4 13 12 -1 C6 12 11 -1 C7 10 12 2 C8 13 4 -9 C9 10 4 -6 C12 12 0 C12 4 Not measured Not measured C13 11 11 0 C14 10 11 1

[0170] Compositions C3 to C7, Cl 1, C13 and C14, are according to the invention. They initially exhibit a higher elongation at break than PEKK alone (Comparison of the nominal (initial) elongation at break of the compositions according to the invention with respect to the nominal (initial) elongation at break of C2). They have aging comparable to that of PEKK alone since the value of the elongation at break varies little or not at all after and before aging. This retention of mechanical properties after aging confirms the good thermal stability of the compositions under demanding conditions of use (high temperature and in air).

[0171] Compositions C8 and C9 are comparative compositions. The elongation at break of these compositions decreases considerably after aging. This suggests that these mixtures are more brittle and less suitable for thermally demanding environments.

[0172] The comparative C12 composition shows a low initial elongation at break. Consequently, no aging was carried out.

Claims

Demands

1. Composition comprising: • a poly(ether ketone), PEKK1; • a thermoplastic polyimide having a glass transition temperature greater than or equal to 230 °C, TPI; and • optionally, a poly(aryl ether ketone), PAEK, PAEK being distinct from PEKK1; wherein: • PEKK1 representing at least 50% by weight, relative to the total weight of PEKK1, TPI and where applicable PAEK, of the composition, and • PAEK being compulsorily present when the TPI content is greater than or equal to 20% by weight, and preferably when the TPI content is greater than or equal to 15% by weight, relative to the total weight of PEKK1 and TPI of the composition.

2. Composition according to claim 1, wherein the TPI content is less than or equal to 40% by weight, preferably less than or equal to 35% by weight, preferably still less than or equal to 30% by weight, and preferably still less than or equal to 25% by weight, relative to the total weight of PEKK1 and TPI of the composition.

3. Composition according to claim 1 or claim 2, wherein the TPI does not comprise a sulfone group and / or does not comprise an isopropylidene group.

4. Composition according to any one of the preceding claims, wherein PEKK1 comprises terephthalate (T) and isophthalate (I) units, the T:I molar ratio ranging from 55:45 to 89:11, and preferably from 72:28 to 85:

15.

5. A composition according to any one of the preceding claims, wherein PAEK is selected from:

6.

7.

8. • a poly(ether ether ketone), PEEK; • a poly(ether ketone), PEK; • a poly(ether ketone ether ketone ketone), PEKEKK; • a poly(ether ketone ketone) having a T / I ratio higher than that of PEKK1 and / or a lower viscosity index than that of PEKK1, PEKK2; and • any mixture of at least two of these polymers. Composition according to claim 5, wherein PAEK is PEEK. Composition according to any one of the preceding claims, wherein the PAEK content represents from 0.1% to 20% by weight, preferably from 1% to 18% by weight, and more preferably from 5% to 15% by weight, relative to the total weight of PEKK1, TPI and PAEK in the composition. Composition according to any one of the preceding claims, wherein the TPI comprises repeating units of general formula (I): [Chem. 19]

9. (I) in which • X represents a monocyclic or polycyclic tetravalent group, saturated, unsaturated or aromatic, substituted or unsubstituted, comprising from 5 to 50 carbon atoms and possibly one or more heteroatoms; and • Ri represents a linear, branched or cyclic divalent radical, substituted or unsubstituted, comprising from 2 to 50 carbon atoms, preferably from 6 to 36 carbon atoms, and possibly comprising one or more heteroatoms. Composition according to claim 8, wherein Ri corresponds to the general formula (III): [Chem.20] (II) in which Q represents a direct bond or a radical selected from the group consisting of -O-, -C(O)-, -OYO-, alkylenes comprising 1 to 6 carbon atoms, and cycloalkylenes comprising 4 to 8 carbon atoms, where Y represents a group of general formula (IIIA) or (IIIB): [Chem.21] AA \ ■ / R, (IIIA) [Chem.22] (IIIB) in which • Z represents a direct bond or a radical selected from the group consisting of -O-, -C(O)-, alkylenes comprising 1 to 6 carbon atoms, and cycloalkylenes comprising 4 to 8 carbon atoms, and • each group Rj, Rk, Rb Ro and Rp is a hydrocarbon group comprising from 1 to 10 carbon atoms and possibly including one or more heteroatoms, each index j, k, l o and p being an integer from 0 to 4 and representing a number of substitution groups on a ring. [Chem.23]

11. (IV) Composition according to claim 9, wherein the TPI comprises repeating units of general formula (V): [Chem.24]

12.

13.

14. (V) Composition according to any one of the preceding claims, further comprising one or more fillers and / or one or more functional additives. Article manufactured from the composition according to any one of claims 1 to 12. Method of manufacturing an article according to claim 13, comprising at least one injection molding or extrusion step of the composition according to any one of claims 1 to 12.