Blends of poly(ether ketone ketone) polymers

Abstract

The present invention relates to blends of poly(ether ketone ketone) (PEKK) polymers, in particular certain blends endowed with lower melting point than traditional PEKK polymers but maintaining high crystallinity and fast crystallization behavior, consisting of a major amount of a first nucleophilic PEKK having a first T / I ratio and a minor amount of a second PEKK having a second T / I ratio higher than the first T / I ratio; to methods for their manufacture and to their use in various fields.

Description

[0001] This application claims priority to U.S. provisional application 63 / 038,100 filed June 11, 2020 and European patent application 20194026.9 filed September 2, 2020, the entire contents of each of which are incorporated by reference into this application for all purposes. TECHNICAL FIELD

[0002] The present invention relates to blends of poly(ether ketone ketone) (PEKK) polymers, in particular certain blends endowed with lower melting points than traditional PEKK polymers, while maintaining high crystallinity and fast crystallization behavior; to methods of making the same and to uses thereof in various fields. BACKGROUND

[0003] Poly(ether ketone ketone) (“PEKK”) polymers are well-known materials that have been used under relatively extreme conditions. Notably, due to their high crystallinity and high melting temperatures, PEKK polymers have excellent thermal, physical and mechanical properties. Such properties make PEKK polymers desirable in a wide range of demanding application environments including, but not limited to, aerospace and oil and gas drilling, but also as thermoplastic matrices of composite structures.

[0004] Notably, PEKK having a nominal T / I molar ratio of about 70 / 30 is a well-known and proven matrix resin for thermoplastic continuous fiber composites, which can be sourced from several suppliers and produced through a electrophilic route - mainly involving Friedel-Crafts assisted electrophilic substitution of a mixture of Al-containing Lewis acid catalyzed chlorides of isophthalic and terephthalic acids on phenoxy-terminated aromatic monomers; or through a nucleophilic route - mainly involving polycondensation of dihydroxy- and difluorobenzoyl- containing aromatic compounds and / or hydroxy-fluorobenzoyl-containing aromatic compounds. Despite the evident differences in their respective microstructure due to the unavoidable distinctive features of the synthetic routes, both “electrophilic” PEKK (“ePEKK”) and “nucleophilic” PEKK (“nPEKK”) provide excellent combinations of strength, stiffness, heat and chemical resistance to composite laminates and other consolidated articles based on their pre-impregnated sheets and tapes (prepregs).

[0005] However, the same high crystallinity and high melting temperatures that provide many benefits of PEKK polymers also present difficulties in processing. Thus, there is a need in the industry that makes and uses such PEKK polymers, particularly in composite structures, to provide PEKK alternatives having lower melting temperatures (T m ) that would allow easier and more forgiving fabrication, energy savings and faster production cycle times. Indeed, Tm approximately 340°C. Considering that semi-crystalline thermoplastics require a melt processing temperature at least about 40°C higher than the melting temperature, in order to be properly fabricated, the plastic temperature must reach at least 380°C in order to properly fabricate a composite based on this PEKK. Therefore, there is a need to reduce the T m , in order to reduce the melt fabrication temperature, and possibly allow melt processing at temperatures of 360°C or even lower. Therefore, one of the constraints imposed by this long-standing industrial need is to provide a PEKK material with a T m , without adversely affecting all the other advantageous properties of PEKK, while additionally providing a fast crystallization rate (as evidenced by the crystallization temperature T c , (i) for a given T / I ratio of the PEKK polymer, crystallization occurs at a temperature closer to T m , (ii) once the material is cooled from the melt at a rate of 20°C / min, substantially no further "cold" crystallization occurs in the subsequent heating, which indicates that in fast cycle melt fabrication, the "as-molded" material has developed all its inherent crystallization upon cooling, and will not undergo any further crystallization phenomena that can lead to internal tensions, deformations or other unwanted phenomena in its subsequent heating (for example during its use). Moreover, and perhaps more importantly, full crystallization is required during the regular fabrication cooling cycle, to ensure that the composite material is able to exhibit its full potential of chemical and environmental resistance during the use of the part.

[0006] Blending-based approaches have been explored in the prior art to modify the properties of polyaryletherketone polymers.

[0007] In this context, US 2015 / 0259530 describes blends aimed at reducing the "cold crystallization temperature" thus defined: the blends thus provided have the purpose of reducing the temperature at which crystallization occurs upon heating before the actual melt phase transition, as the availability of a large temperature window between crystallization and melting is left in which to play as a key process parameter for 3D printing. The document suggests formulating PEKK copolymers of different T / I ratios and viscosities, to achieve a balance between toughness, crystallinity and thermal performance, and thus provide the expected 3D printing processability. The document exemplifies a blend of two electrophilic PEKKs, which are marketed under the trade names Commercially available, their T / I content is significantly different (20 mol. % difference in T % content). In line with the intended purpose of the solution thus offered, such blends show a "cold crystallization" behavior, despite the fact that the individual e-PEKKs used are significantly different in T / I ratio, and thus somewhat hinder the co-crystallization behavior. Indeed, the blends thus exemplified, once cooled down from the molten state at 10 °C / min, show a non-zero crystallization exotherm upon further heating (thus referred to as "cold crystallization"), thus showing that, despite the very slow cooling rate, the blends have the ability to further crystallize, which indicates that their crystallization rate is somewhat hindered.

[0008] Thus, while such blends can be useful in the field of use of additive manufacturing, such blends do not meet the above listed requirements for effectively being used as a matrix for thermoplastic composite parts, particularly those made by fast cycle fabrication, in view of the fact that the materials are intended to be kept in a heated building chamber for very long processing times. SUMMARY

[0009] The present invention provides PEKK compositions that combine low melting point with significantly increased crystallization rate and crystallinity levels (higher than expected for a given total tere / iso (T / I) ratio in the PEKK composition). The compositions are obtained by blending a first PEKK made by nucleophilic process with an appropriate amount of a second PEKK (as detailed below) and optionally an inorganic nucleating agent, to obtain a PEKK composition that advantageously exhibits T m ≤ 330 °C, while exhibiting a higher crystallization rate than expected for the T / I content of the PEKK composition. These compositions also exhibit a practical level of crystallinity, as evidenced by a heat of fusion of 25 J / g or more. The compositions combine fast cycle times for composite fabrication with improved economics, with lower energy consumption. The high crystallinity levels in these compositions ensure robust chemical resistance in composite structures using them. These compositions, the methods to achieve their attributes, and their end uses in thermoplastic composite applications are the subject of the present application.

[0010] The present invention provides a composition [composition (C)] comprising:

[0011] - a major amount of a first PEKK polymer [polymer (PEKK 低 )] comprising recurring units (R T ) and recurring units (R I ), having a first molar content of units (R T ) [(T 低 )] and a first molar content of units (R I ) [(I低 )], wherein and So a first T / I ratio [(T / I) 低 ] is defined, wherein wherein the repeat unit (R T ) is represented by formula (T):

[0012]

[0013] and the repeat unit (R I ) is represented by formula (I):

[0014]

[0015] wherein:

[0016] -R 1 and R 2 are each independently in each occurrence selected from the group consisting of alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkyl sulfonate, alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine, and quaternary ammonium; and

[0017] i and j are each independently in each occurrence an integer ranging from 0 to 4; and

[0018] a small amount of a second PEKK polymer [polymer (PEKK 高 )] comprising said repeat unit (R I ) and said repeat unit (R T ) having a second mole content of units (R T ) [(T 高 )] and a second mole content of units (R I ) [(I 高 )], wherein and So a second T / I ratio [(T / I) 高 ] is defined, wherein

[0019] wherein polymer (PEKK 低 ) is a nucleophilic PEKK; and

[0020] wherein the (T / I) 低 of the PEKK 低 is lower than the (T / I) 高 of the PEKK 高 ; and

[0021] wherein the following inequality is satisfied:

[0022] T 高 -T 低 ≤17mol.%.

[0023] The compositions of the present invention advantageously have the following characteristics:

[0024] - Melting temperature less than or equal to 330℃ (T m );

[0025] -Heat of fusion exceeding 25 J / g (ΔH) f );

[0026] - No crystallization peak ("cold crystallization peak") was observed during heating in the second DSC heating scan; and

[0027] - Melting temperature (T) determined in the second DSC heating scan m (in °C) and the crystallization temperature (T) determined in the first DSC cooling scan. c The relationship between (in °C) and (in terms of temperature) satisfies the following inequality:

[0028] T c ≥1.3716×T m -190℃

[0029] Where T m T c ΔH f The absence of cold crystallization peaks was measured according to ASTM D3418-03, E1356-03, E793-06, and E794-06 standards using differential scanning calorimetry (DSC), with a heating and cooling rate of 20°C / min, scanning from 30°C to 400°C.

[0030] The present invention further relates to the use of the compositions detailed above in various fields of application, notably including as thermoplastic matrices in composite structures. Attached Figure Description

[0031] Figure 1 This is a bubble diagram, where, for comparison of the PEKK copolymer (transparent bubbles) and the blend of the present invention (dark bubbles), the center of the bubble provides a T-shape. c (in °C) with T m A graph showing the change (in °C), while the size of the bubble represents ΔH. f (in J / g), further specified as a label for the bubbles. Detailed Implementation

[0032] As described, the compositions of the present invention comprise polymers (PEKK). 低 ) and polymers (PEKK) 高), collectively referred to as poly(PEKK). As noted, the poly(PEKK) comprises repeating units (R T ) and repeating units (R I ), respectively, as detailed above.

[0033] According to an embodiment, R 1 and R 2 , at each position in the above formulae (T) and (I), are independently selected from the group consisting of C1-C 12 moieties optionally comprising one or more than one heteroatom; sulfonic acid and sulfonate groups; phosphonic acid and phosphonate groups; amines and quaternary ammonium groups.

[0034] According to another embodiment, for each R 1 and R 2 group, i and j are zero. In other words, both repeating units (R T ) and (R I ) are unsubstituted. According to this embodiment, the repeating units (R T ) and (R I ) are represented by formulae (T’) and (I’), respectively:

[0035]

[0036] According to another embodiment, the poly(PEKK) comprises repeating units (R T ) and repeating units (R I ) as detailed above, in a combined amount of at least 50 mol.%, based on the total number of moles in the poly(PEKK).

[0037] The poly(PEKK) can comprise a small amount of repeating units different from the repeating units (R T ) and (R I ) as detailed above and can optionally consist of the group of repeating units (R PAEK ) comprising an Ar-C(O)-Ar’ group, wherein Ar and Ar’, equal to or different from each other, are aromatic groups. The repeating units (R PAEK ) can generally be selected from the group consisting of formulae (J-A) to (J-O) below:

[0038]

[0039]

[0040]

[0041] wherein:

[0042] Each R' may be the same as or different from the others, and is selected from the group consisting of: halogens, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali metal sulfonate or alkaline earth metal sulfonate, alkyl sulfonate, alkali metal phosphonate or alkaline earth metal phosphonate, alkyl phosphonate, amine, and quaternary ammonium.

[0043] j' is zero or an integer from 0 to 4.

[0044] In the repeating unit (R) PAEK In the repeating unit, the corresponding phenylene moiety may independently have 1,2-, 1,4-, or 1,3- bonds to other moiety in the repeating unit that are different from R'. Preferably, the phenylene moiety has 1,3- or 1,4- bonds, more preferably it has 1,4- bonds.

[0045] Furthermore, in the repeating unit (R) PAEK In ), j' is zero each time it appears, meaning that the phenylene moiety has no other substituents besides those substituents in the polymer backbone that enable bonding.

[0046] Therefore, the preferred repeating unit (R) PAEK ) is selected from those having the formulas (J'-A) to (J'-O) as described below:

[0047]

[0048]

[0049] Although it is possible to use units that are different from repeating units (R) T ) and (R I The repeating unit (R) as detailed above PAEK The polymer (PEKK) is generally understood to be preferred, but the preferred polymers (PEKK) are those in which the repeating unit (R) is... PAEK The amount of ) is limited, and is preferably up to 40 mol.%, more preferably up to 30 mol.%, more preferably up to 20 mol.%, even more preferably up to 10 mol.%, even more preferably up to 5 mol.%, where mol.% is based on the total number of moles in the polymer (PEKK).

[0050] Therefore, according to the embodiments, the repeating units in 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 substantially all of the polymers (PEKK) are repeating units (R). T ) and (R I), as detailed above, mol. % is based on the total number of moles in the polymer (PEKK). When used in conjunction with the constituent repeating units of the polymer (PEKK), the expression "substantially all" is intended to indicate that there can be a small amount of spurious / defective repeating units, for example in an amount of less than 1 mol. %, preferably less than 0.5 mol. %, more preferably less than 0.1 mol. %. When no other repeating units than (R T ) and (R I ) are detected in the polymer (PEKK), the polymer will be considered as a polymer (PEKK) wherein all units are units (R T ) and (R I ), which is a preferred embodiment of the present application.

[0051] The polymer (PEKK 低 ) is a nucleophilic PEKK, which means that the polymer (PEKK 低 ) is produced by polycondensation of dihydroxyl and difluorobenzoyl containing aromatic compounds and / or hydroxyl-fluorobenzoyl containing aromatic compounds. The nucleophilic character of the polymer (PEKK 低 ) is notably evidenced by the presence of fluorine, the amount of which is typically in excess of 100 ppm, preferably in excess of 200 ppm, even more preferably in excess of 300 ppm. This organically bound fluorine is an unavoidable distinctive feature of the use of fluorine containing monomers. Further evidence of the nucleophilic character of the polymer (PEKK 低 ) is provided by the substantial absence of Al residuals, that is to say the Al content is typically below 50 ppm, preferably below 25 ppm, more preferably 10 ppm. The Al and F content is conveniently determined by elemental analysis, ICP-OES analysis for Al and combustion-ion chromatography for fluorine.

[0052] Due to its nucleophilic character, the polymer (PEKK 低 ) is further characterized by a low volatile content. The amount of volatiles can be determined according to ASTM D3850 method using thermogravimetric analysis (TGA); the temperature T d at which a determined amount of volatile material, for example 1 wt. % or 2 wt. %, leaves the sample is determined by gradually heating the sample from 30 °C to 800 °C under nitrogen using a heating rate of 10 °C / min. The thermal decomposition temperature at 1 wt. % is referred to as T d (1 %). In embodiments of the present application, the polymer (PEKK 低 ) has a T d (1 %) of at least 500 °C, preferably at least 505 °C, more preferably at least 510 °C as measured according to ASTM D3850 by thermogravimetric analysis under nitrogen using a heating rate of 10 °C / min from 30 °C to 800 °C.

[0053] The Applicant has surprisingly found that the advantageous effects of the present application can be achieved alone when at least the polymer (PEKK 低 ) is a nucleophilic PEKK - having the above noted advantageous features (F content, Al content, T d (1%) - and preferably when both the polymer (PEKK 低 ) and the polymer (PEKK 高 ) are nucleophilic PEKKs - so that also the polymer (PEKK 高 ) has the above noted advantageous features (F content, Al content, T 低 (1%) in combination with the polymer (PEKK d ); without being bound to this theory, the Applicant believes that the particular microstructure of the polymer (PEKK) obtained through the nucleophilic synthesis route (including notably the absence of "regioselectivity" errors and / or branching phenomena, which although rare, can occur in electrophilic synthesis routes) enables the particular advantageous thermal behavior achieved through the blends of the present application.

[0054] As noted, in the compositions of the present application, wherein the polymer (PEKK 低 ) has a (T / I) 低 lower than the (T / I) 高 of the polymer (PEKK 高 ); the polymer (PEKK 低 ) preferably has a (T / I) 低 of at least 50 / 50, preferably at least 54 / 46, more preferably at least 56 / 44, most preferably at least 57 / 43 and / or a (T / I) 低 of at most 64 / 36, preferably at most 63 / 37, more preferably at most 62 / 38. It has been found that polymers (PEKK 低 ) having a (T / I) 低 comprised between 57 / 43 and 62 / 38 are particularly advantageous for use in the blends of the present application.

[0055] As noted, preferably the polymer (PEKK 高 ) is also a nucleophilic PEKK, meaning that the polymer (PEKK 高 ) is also produced through polycondensation of dihydroxy and difluorobenzoyl containing aromatic compounds and / or hydroxy-fluorobenzoyl containing aromatic compounds and therefore advantageously has a fluorine content typically exceeding 100 ppm, preferably exceeding 200 ppm, even more preferably exceeding 300 ppm and / or an Al content typically lower than 50 ppm, preferably lower than 25 ppm, more preferably 10 ppm.

[0056] The polymer (PEKK 高Preferably, it has a (T / I) ratio of at least 65 / 35, more preferably at least 66 / 34, and even more preferably at least 67 / 33. 高 ; and / or up to 75 / 25, preferably up to 73 / 27, more preferably up to 72 / 28 (T / I) 高 It has been found that (T / I) is included between 67 / 33 and 72 / 28. 高 polymer (PEKK) 高 This is particularly advantageous for use in blends of the present invention.

[0057] Furthermore, in the compositions of the present invention, the following inequality is satisfied: T 高 -T 低 ≤17 mol.%. Therefore, it depends on having a certain T 低 Specific polymers (PEKK) 低 The selection of a suitable polymer (PEKK) 高 ) of T 高 The choice is therefore limited, and vice versa. Unbound by this theory, the applicant believes that a potential co-crystallization phenomenon that ultimately leads to the favorable thermal properties of the blends of the present invention can be achieved only when the polymer PEKK differs in a moderate manner in the fraction of T units.

[0058] Furthermore, the polymer (PEKK) of the composition of the present invention 低 ) and polymers (PEKK) 高 )Optimization makes T 高 -T 低 ≤16mol.%, more preferably T 高 -T 低 ≤15 mol.%. It should be further understood that the polymer (PEKK) 低 ) and polymers (PEKK) 高 Overall, this makes T 高 -T 低 ≥3 mol.%, more preferably T 高 -T 低 ≥4 mol.%, or even better T 高 -T 低 The ≥5 mol.% method differs in its T content.

[0059] Polymer (PEKK) has been used 低 ) and polymers (PEKK) 高 (makes T) 高 -T 低 It is noteworthy that blends with advantageous properties were obtained from approximately 10 to approximately 13 mol.%.

[0060] The composition contains a major amount of polymer (PEKK) 低) and a small amount of a polymer (PEKK 高 ). The expressions "major amount" and "small amount" have the usual understood meaning, that is to say that the amount of polymer (PEKK 低 ) exceeds the amount of polymer (PEKK 高 ).

[0061] Generally, the weight ratio between polymer (PEKK 低 ) and polymer (PEKK 高 ) in the composition of the application is advantageously at least 60 / 40, preferably at least 65 / 35, more preferably at least 70 / 30, even more preferably at least 75 / 25 and / or it is at most 99 / 1, preferably at most 97 / 3, even more preferably at most 96 / 4.

[0062] As mentioned, the composition of the application advantageously has:

[0063] - a melting temperature (T m ) less than or equal to 330°C;

[0064] - a heat of fusion (AH f ) greater than 25 J / g;

[0065] - no crystallization peak upon heating in the second DSC heating scan ("cold crystallization peak"); and

[0066] - a relationship between the melting temperature (T m ) determined in the second DSC heating scan, in °C, and the crystallization temperature (T c ) determined in the first DSC cooling scan, in °C, which satisfies the following inequality:

[0067] T c ≥ 1.3716 x T m - 190°C,

[0068] where T m , T c , AH f and the absence of cold crystallization peak are measured by differential scanning calorimetry (DSC) according to the ASTM D3418-03, E1356-03, E793-06, E794-06 standards, with a heating and cooling rate of 20°C / min, in a scan from 300°C to 400°C.

[0069] As for the determination of the presence / absence of a cold crystallization peak, it is understood that when no exothermic peak of more than 0.5 J / g before the onset of melting is detected by DSC in the second heating scan, this represents the absence of a cold crystallization peak. Generally, in the composition of the application, no exothermic peak is substantially detected by DSC in the second heating scan, which means that no detectable release of energy is observed within the sensitivity limit of the instrument.

[0070] The molecular weight of the composition (C) of the application can be adjusted according to the target field of use. In particular, it is worth noting that when the composition (C) is intended to be used as a thermoplastic matrix of a composite structure, it is generally understood that the molecular weight of the composition (C) will be adjusted to obtain an MFI, measured according to ASTM D1238, under a piston load of 8.4 kg, as defined in the examples, at a temperature of 340°C to 360°C, in the range of 60 to 120 g / 10 min.

[0071] Furthermore, it is worth noting that when the composition (C) is intended to be used as a bonding layer (also known as adhesive film) in a multilayer assembly, the molecular weight of the composition (C) will be adjusted to obtain an MFI, measured according to ASTM D1238, under a piston load of 8.4 kg, as defined in the examples, at a temperature of 340°C to 360°C, in the range of 15 to 50 g / 10 min.

[0072] According to certain embodiments, the composition of the application further comprises at least one nitride (NI) of an element having an electronegativity (ε) from 1.3 to 2.5.

[0073] The electronegativity value (ε) is notably listed in the "Handbook of Chemistry and Physics", CRC Press, 64th edition, pages B-65 to B-158.

[0074] The expression "at least one nitride (NI)" in the context of the present application is intended to mean one or more than one nitride (NI). A mixture of nitrides (NI) can advantageously be used for the purposes of the present application.

[0075] Non-limiting example values of nitrides (NI) of elements having an electronegativity (e) from 1.3 to 2.5 are notably listed in the "Handbook of Chemistry and Physics", CRC Press, 64th edition, pages B-65 to B-158. The code in brackets is the code attributed by the CRC Handbook to the concerned nitride, while e represents the electronegativity of the element from which the nitride derives. Thus, the nitrides (NI) of elements having an electronegativity (e) from 1.3 to 2.5, which are suitable for the purposes of the present invention, are notably aluminum nitride (AIN, a45, e = 1.5), antimony nitride (SbN, a271, e = 1.9), beryllium nitride (Be3N2, b123, e = 1.5), boron nitride (BN, b203, e = 2.0), chromium nitride (CrN, c406, e = 1.6), copper nitride (Cu3N, c615, e = 1.9), gallium nitride (GaN, g41, e = 1.6), germanium trinitride (Ge3N2, g82, e = 1.8), germanium tetranitride (Ge3N4, g83, e = 1.8), hafnium nitride (HfN, h7, e = 1.3), iron nitride like Fe4N (i151, e = 1.8) and Fe2N or Fe4N2 (i152, e = 1.8), mercury nitride (Hg3N2, m221, e = 1.9), niobium nitride (n109, e = 1.6), silicon nitride (Si3N4, s109, e = 1.8), tantalum nitride (TaN, t7, e = 1.5), titanium nitride (Ti3N4, t249, e = 1.5), tungsten dinitride (WN2, t278, e = 1.7), vanadium nitride (VN, v15, e = 1.6), zinc nitride (Zn3N2, z50, e = 1.6) and zirconium nitride (ZrN, z105, e = 1.4).

[0076] The preferred nitrides (NI) for the composition of the present invention are nitrides of elements having an electronegativity preferably of at least 1.6, and more preferably of at least 1.8 and / or preferably of at most 2.2.

[0077] Furthermore, the nitrides (NI) are preferably nitrides of elements selected from the groups IIIa, IVa, IVb, Va, Vb, Via, VIb, VIIb and VIII of the Periodic Table of the Elements, and more preferably nitrides of elements selected from the group IIIa of the Periodic Table of the Elements.

[0078] Particularly good results have been obtained when the nitride (NI) is boron nitride, which is the preferred nitride (NI).

[0079] Among the different crystalline forms of boron nitride, hexagonal boron nitride is preferred for use in the composition according to this embodiment.

[0080] Generally, the average particle size of the nitride (NI) is advantageously equal to or lower than 30 pm, preferably equal to or lower than 20 pm, more preferably equal to or lower than 18 pm, more preferably equal to or lower than 10 pm, and / or preferably equal to or at least 0.05 pm, equal to or at least 0.1 pm, more preferably equal to or at least 0.2 pm, equal to or at least 1 pm.

[0081] The average particle size of the nitride (NI) is preferably from 1 pm to 20 pm, more preferably from 2 pm to 18 pm, more preferably from 2 pm to 10 pm.

[0082] An average particle size of the nitride (NI) of about 2.5 pm gives particularly good results. In particular, it has been found that boron nitride with this average particle size is particularly effective.

[0083] The average particle size of the nitride (NI) can be measured according to DIN 53196 by light scattering techniques (dynamic or laser) using for example a corresponding equipment from company Malvern (Mastersizer Micro or 3000) or using sieve analysis.

[0084] According to these or other embodiments, the composition of the application can comprise one or more than one additional ingredient, in addition to the polymer (PEKK 低 ) and the polymer (PEKK 高 ), and possibly in addition to the nitride (NI).

[0085] Such ingredients can advantageously be notably selected from the group consisting of colorants, pigments, light stabilizers, heat stabilizers, antioxidants, acid scavengers, processing aids, crystallization nucleating agents, internal and / or external lubricants, flame retardants, smoke suppressants, antistatic agents, anticaking agents, thermally, electrically and magnetically conductive materials (i.e. materials that can contribute to inductive heating), and reinforcing fiber additives and reinforcing non-fiber additives.

[0086] These above-mentioned optional ingredients are generally known to the person skilled in the art.

[0087] As non-limiting examples of colorants, water-soluble dyes, oil-soluble dyes, water-insoluble colored lakes, and mixtures thereof can be mentioned.

[0088] As non-limiting examples of pigments, titanium dioxide, zinc sulfide and zinc oxide can be mentioned.

[0089] As non-limiting examples of light stabilizers, UV absorbers and hindered amine light stabilizers can be mentioned.

[0090] As non-limiting examples of antioxidants, organic phosphites and phosphonites can be mentioned.

[0091] As non-limiting examples of electrically conductive additives, carbon black and carbon nanoscale filaments can be mentioned.

[0092] As non-limiting examples of reinforcing fibrous additives, glass fibers, carbon fibers and wollastonite can be mentioned.

[0093] The glass fibers optionally comprised in the polymer composition (C) can be selected from the group consisting of short cut fibers A-, E-, C-, D-, S-, T- and R-glass fibers, as described in the chapter 5.2.3, pages 43-48 of the Additives for Plastics Handbook, 2ndEdition, by John Murphy. The glass fibers can have a circular cross-section or a non-circular cross-section, such as an elliptical or rectangular cross-section. When the glass fibers used have a circular cross-section, they preferably have an average fiber diameter of 3 to 30 pm and particularly preferably of 5 to 12 pm. Different kinds of glass fibers having a circular cross-section are available on the market, depending on the type of glass from which they are made.

[0094] As used herein, the term "carbon fibers" is intended to include graphitized, partially graphitized, as well as non-graphitized carbon reinforcing fibers or mixtures thereof. Carbon fibers useful in the present application can advantageously be obtained by heat treatment and pyrolysis of different polymeric precursors such as, for example, rayon, polyacrylonitrile (PAN), aromatic polyamide, or phenol-formaldehyde resin; carbon fibers useful in the present application can also be obtained from pitch materials. The term "graphite fibers" is intended to mean carbon fibers obtained by high temperature pyrolysis (higher than 2000°C) of carbon fibers, in which carbon atoms are arranged in a similar way to the graphite structure. Carbon fibers useful in the present application are preferably selected from the group consisting of PAN-based carbon fibers, pitch-based carbon fibers, graphite fibers, and mixtures thereof. Carbon nanofibers and single- and multi-walled carbon nanotubes can also be used as reinforcing additives as part of the compositions of the present application.

[0095] As non-limiting examples of reinforcing non-fibrous additives, talc, mica, kaolin, calcium carbonate, calcium silicate, magnesium carbonate can be mentioned. Non-fibrous reinforcing additives that can be used also include graphite and graphene (in some cases referred to as nanographite or graphene nanoplatelets, GNPs).

[0096] According to certain embodiments, the total weight of the polymers (PEKK 低 ) and (PEKK 高 ) is advantageously equal to or higher than 60 wt.%, preferably equal to or higher than 70 wt.%, more preferably equal to or higher than 80 wt.%, more preferably equal to or higher than 85 wt.%, most preferably equal to or higher than 90 wt.%, based on the total weight of the composition (C) of the present application.

[0097] According to certain embodiments, the composition (C) of the application does not comprise any other polyaryletherketone polymer [polymer (PAEK)] than the polymer (PEKK 低 ) and the polymer (PEKK 高 ). In other words, the composition (C) of the application according to these embodiments is generally substantially free of any polymer comprising recurring units more than 50% in mole of which are recurring units (R PAEK ) comprising an Ar*-C(0)-Ar*’ group (with Ar* and Ar*’, equal to or different from each other, being aromatic groups), which polymer is not the polymer (PEKK 低 ) or the polymer (PEKK 高 ). The recurring units (R PAEK ) of the polymer (PAEK) have the same features as already described above in connection with the optional recurring units (R PAEK ) of the polymer (PEKK).

[0098] When used, the total weight of the nitride (NI) in the composition (C) of the application is advantageously at least about 0.1 wt.%, typically at least about 0.2 wt.%, preferably at least about 0.3 wt.%, more preferably at least about 0.5 wt.% and / or at most about 10 wt.%, preferably at most about 8 wt.%, more preferably at most about 5 wt.% and even more preferably at most about 3 wt.%, based on the total weight of the composition (C).

[0099] When additional optional ingredients are present in the composition (C) of the application, the total weight of the optional ingredients is advantageously equal to or higher than 0.1 wt.%, preferably equal to or higher than 0.5 wt.%, more preferably equal to or higher than 1 wt.% and even more preferably equal to or higher than 2 wt.% and / or equal to or lower than 30 wt.%, preferably lower than 20 wt.%, more preferably lower than 10 wt.% and even more preferably lower than 5 wt.%, based on the total weight of the composition (C).

[0100] According to certain embodiments, the composition (C) of the application consists essentially of the polymer (PEKK 低 ) and the polymer (PEKK 高 ), as described above. For the purposes of the present application, the expression “consists essentially of’ is understood to mean that any additional components different from those listed are present in an amount of at most 1 wt.%, preferably at most 0.5 wt.%, based on the total weight of the composition (C), so as not to materially alter the advantageous properties of the composition.

[0101] According to other embodiments, as noted above, the composition (C) of the present application consists essentially of the polymer (PEKK 低 ), the polymer (PEKK 高 ), and the nitride (NI).

[0102] According to still other embodiments, the composition (C) of the present application consists essentially of the polymer (PEKK 低 ), the polymer (PEKK 高 ), and one or more additional ingredients (as listed above) other than the nitride (NI). According to these embodiments, as noted above, the composition (C) can include the nitride (NI).

[0103] The composition (C) can be prepared by a variety of methods including intimate mixing of the polymers (PEKK 低 ), (PEKK 高 ), possibly in combination with the nitride (NI) and / or with any optional additional ingredients, as desired in the form of a formulation. For example, dry (or powder) blending, suspension or slurry mixing, solution mixing, melt mixing, or any combination thereof can be used. As used herein, the "other components" of the composition (C) include any other components desired in the composition (C) other than the polymers (PEKK 低 ) and (PEKK 高 ), possibly including the nitride (NI) or any additional optional ingredients listed above.

[0104] The composition (C) can be prepared by a method that includes dissolving the polymers (PEKK 低 ) and (PEKK 高 ), possibly in combination with other components, in a medium that is liquid at the temperature of the dissolution. In practice, this dissolution can be accompanied by heating the polymers (PEKK 低 ) and (PEKK 高 ) in the liquid medium, which can advantageously comprise at least one of diphenyl sulfone, benzophenone, 4-chlorophenol, 2-chlorophenol, and m-cresol. A suitable liquid medium for effectively dissolving the polymers (PEKK 低 ) and (PEKK 高 ) is diphenyl sulfone (DPS), which is liquid above 123°C, or a blend of an organic solvent comprising a major amount of DPS. When using DPS, the mixing is achieved by heating at a temperature of at least 250°C, preferably at least 275°C, more preferably at least 300°C. Good results have been obtained when dissolving the polymers (PEKK 低 ) and (PEKK 高 ) in DPS at a temperature of about 330°C.

[0105] The composition (C) of the present application can be recovered from the liquid medium by standard techniques, including liquid / solid separation, crystallization, extraction, etc.

[0106] When using DPS, the polymers (PEKK 低 ) and (PEKK 高 ) dissolved in the liquid DPS are cooled below the melting point of the DPS in order to obtain a solid, which can be extracted with a mixture of acetone and water, possibly rinsed with an aqueous medium, and finally dried to yield the composition of the present application.

[0107] As an alternative, the composition (C) of the present application can be manufactured, for example, by melt mixing or a combination of powder blending and melt mixing. When the polymers (PEKK 低 ) and (PEKK 高 ) and optional further components are provided in powder form, powder blending is feasible. Typically, powder blending of the polymers (PEKK 低 ) and (PEKK 高 ) as detailed above can be carried out by using high intensity mixers, such as notably Henschel-type mixers and ribbon mixers.

[0108] The composition of the present application can also be manufactured by melt compounding the polymers (PEKK 低 ) and (PEKK 高 ) and optional further components, and / or by further melt compounding a powder mixture as described above. Conventional melt compounding devices can be used, such as co-rotating and counter-rotating extruders, single screw extruders, co-kneaders, disc-pack processors, and various other types of extrusion equipment. Preferably, an extruder, more preferably a twin-screw extruder, can be used.

[0109] If desired, the design of the compounding screw, e.g. pitch and width, gap, length, and operating conditions, will advantageously be chosen such that sufficient heat and mechanical energy is provided to advantageously completely melt the powder mixture or ingredients as detailed above and to advantageously obtain a homogeneous distribution of the different ingredients. Provided that an optimal mixing between the bulk polymer and the filler content is achieved, possibly advantageously a strand extrudate of the composition (C) of the present application is obtained. Such strand extrudate can be cut short after a cooling time on a conveyor with a water spray, for example, by means of a rotating knife, in order to provide the composition (C) in the form of pellets or beads. The pellets or beads of the composition (C) can thus be further used for making parts or composites, or can be milled to provide a powdery composition (C) for powder making techniques.

[0110] Shaped articles and methods of manufacture

[0111] Further embodiments of the present application are shaped articles comprising the inventive composition (C) and methods of manufacturing said shaped articles.

[0112] The shaped article can comprise one or more parts. When the shaped article is a single part, the single part is preferably composed of the inventive composition (C).

[0113] Alternatively, the shaped article can be composed of more than one part, one or more of which is preferably composed of the inventive composition (C). When the more than one part of the shaped article comprises the composition (C), each part can comprise the same polymeric composition or a different polymeric composition as described herein.

[0114] The weight of the inventive composition (C) is preferably greater than 1 %, greater than 5 %, greater than 10 %, preferably greater than 15 %, greater than 20 %, greater than 30 %, greater than 40 %, greater than 50 %, greater than 60 %, greater than 70 %, greater than 80 %, greater than 90 %, greater than 95 %, greater than 99 %, based on the total weight of the shaped article.

[0115] The inventive composition (C) can be very well suited for the manufacture of articles useful in a wide variety of applications. For example, the surprising and advantageous properties of the inventive composition (C) described herein make the inventive composition (C) particularly suitable for use in automotive applications (such as magnet wire coatings in hybrid and electric vehicles), oil and gas applications (such as structural parts of extraction tools, downhole cable coatings, etc.); as structural components of mobile electronic devices (e.g. frames or housings), as thermoplastic matrix for thermoplastic composites used in structural and transportation applications; as adhesive films or adhesives for fusing laminates together, in particular for bonding metal surfaces, (thermoplastic) composite laminate surfaces, aramid film surfaces, prepreg surfaces, etc.; electrostatic powder coatings on metal substrates for corrosion protection and wear resistance, and parts for a wide range of applications produced by additive manufacturing.

[0116] The term "mobile electronic device" is intended to mean any electronic device designed for convenient transport and use at various locations while exchanging / providing data access, e.g. through wireless connections or mobile network connections. Representative examples of mobile electronic devices include mobile telephones, personal digital assistants, notebook computers, tablet computers, radios, cameras and camera accessories, watches, calculators, music players, global positioning system receivers, portable game consoles, hard drives and other electronic storage devices, etc.

[0117] The shaped articles can be selected from a large number of articles such as fittings; such as seals, in particular sealing rings, preferably bearing sealing rings, fasteners and the like; snap-in parts; mutually movable parts; functional elements, operating elements; tracking elements; adjusting elements; carrier elements; frame elements; membranes; switches; connectors; electric wires, electric cables; bearings, housings, compressor parts such as compressor valves and compressor plates, shafts, casings or pistons.

[0118] In particular, the inventive composition (C) is very suitable for use as a coating for electric wires or cables, as a structural part for mobile electronic devices or as a part produced by additive manufacturing. Accordingly, exemplary embodiments also include shaped articles manufactured at least partially by an additive manufacturing process using the above described polymeric composition. Such shaped articles can be used in a variety of end applications such as implantable medical devices, dental prosthetics and stents and complex shaped parts in the aerospace and automotive industries.

[0119] In particular, the inventive composition (C) is very suitable for use as a thermoplastic matrix for continuous fiber reinforced composites.

[0120] In other embodiments, the inventive composition (C) can be used in the form of an adhesive layer positioned between and in contact with a first substrate and a second substrate to ensure a satisfactory adhesion between said substrates, wherein said substrates can notably be metal substrates, thermoplastic composite substrates, aramid film substrates, prepreg substrates.

[0121] The shaped articles described herein can be manufactured from the inventive composition (C) by injection molding, extrusion, compression molding, additive manufacturing (also known as three-dimensional (3D) printing, which for shaped articles can also be referred to as 3D objects or 3D parts), coating, continuous fiber impregnation, and continuous fiber composite lamination / curing or other shaping techniques.

[0122] In some embodiments, the method for manufacturing a shaped article or a part thereof comprises compression molding or injection molding, and a subsequent step of curing the inventive composition (C).

[0123] In some embodiments, the method for manufacturing a shaped article or a part thereof comprises a coating step. For example, the inventive composition (C) can be applied as a coating onto an electric wire by using any suitable coating method, preferably by extrusion coating around the electric wire to form a coated electric wire, preferably a coated magnet wire.

[0124] Exemplary embodiments also relate to methods for manufacturing a shaped article by additive manufacturing, wherein the shaped article is printed from the inventive composition (C) (also referred to as "part material"). These methods include printing a shaped article from a layer of the polymeric composition, as described below.

[0125] Additive manufacturing systems are used to print or otherwise build shaped objects from a digital representation of the shaped object by one or more additive manufacturing techniques. Examples of commercially available additive manufacturing techniques include extrusion-based techniques, selective laser sintering, powder / binder jetting, electron-beam melting, and stereolithography processes. For each of these techniques, the digital representation of the shaped object is initially sliced into multiple horizontal layers. Then, for each layer, a tool path is generated that provides instructions for a particular additive manufacturing system to print the given layer.

[0126] For example, in an extrusion-based additive manufacturing system, a shaped article can be printed from a digital representation of the shaped article in a layer-by-layer manner by extruding and abutting a polymer composition strand. The polymer composition is extruded through an extrusion tip carried by a print head of the system and deposited as a series of roads on a platen in the x-y plane. The extruded material fuses to previously deposited material and solidifies as it cools. The position of the print head relative to the substrate is then incremented along the z-axis (perpendicular to the x-y plane), and the process is repeated to form a shaped article similar to the digital representation. An example of an extrusion-based additive manufacturing system is fused filament fabrication (FFF), also known as fused deposition modeling (FDM). Pellet additive manufacturing (PAM) is an example of a 3D printing method that is capable of printing feedstock as pellets.

[0127] As another example, in a powder-based additive manufacturing system, a powder is locally sintered into a solid part using a laser. A shaped article is produced by sequentially depositing a layer of powder and then laser patterning to sinter an image onto the layer. An example of a powder-based additive manufacturing system is selective laser sintering (SLS).

[0128] As another example, carbon fiber composite shaped articles can be prepared using a continuous fiber-reinforced thermoplastic printing (FRTP) process. This process is based on fused deposition modeling (FDM) and prints a combination of fibers and resin.

[0129] Method of manufacturing a composite material

[0130] Further exemplary embodiments relate to methods of manufacturing a composite material, comprising impregnating reinforcing fibers with a matrix of the inventive composition (C) described herein; and to the composite materials obtained therefrom.

[0131] Various methods can be employed in which fibers are impregnated with a matrix of the inventive composition (C), wherein the matrix is in a molten or particulate form, including, for example, powder coating, film lamination, extrusion, pultrusion, aqueous slurry, and melt impregnation, to form a layer in the form of, for example, a sheet or tape of fibers at least partially impregnated with a polymeric matrix. As used herein, “tape” means a strip of material having reinforcing fibers extending in a longitudinal direction, the reinforcing fibers being aligned along a single axis of the strip material.

[0132] The layers of matrix-impregnated fibers can be placed adjacent to one another to form an uncured composite laminate, such as a prepreg. The fiber reinforcement layers of the laminate can be positioned in their respective fiber reinforcements in selected orientations relative to one another.

[0133] The layers can be stacked manually or automatically, for example, by automated tape laying using "pick and place" robots, or advanced fiber placement, in which pre-impregnated fiber tows are heated and compacted in a mold or on a mandrel to form a composite laminate having the desired physical dimensions and fiber orientation.

[0134] The layers of the uncured laminate are typically not fully fused together, and the uncured composite laminate can exhibit a significant void content, for example, greater than 20% by volume as measured by x-ray microtomography. Heat and / or pressure can be applied, or ultrasonic vibration welding can be used, to stabilize the laminate and prevent the layers from moving relative to one another, for example, to form a composite "blank" as an intermediate step to allow handling of the composite laminate prior to curing the composite laminate.

[0135] The composite laminate so formed is subsequently cured, typically by subjecting the composite laminate to heat and pressure, for example, in a mold, to form a shaped fiber-reinforced thermoplastic matrix composite article. If desired, a bonding layer made from the composition (C) of the present invention can be used to adhere the layers of the uncured laminate. Such a bonding layer can be provided in the form of a self-supporting film made from the composition (C) of the present invention, or can be provided in the form of a coating applied to at least one surface of the layers of the uncured composite laminate to be assembled and cured.

[0136] As used herein, "curing" is the process by which the matrix material is softened, the layers of the composite laminate are pressed together, air, moisture, solvents, and other volatiles are pressed out of the laminate, and the adjacent plies of the composite laminate are fused together to form a solid coherent article. Ideally, the cured composite article exhibits minimal, for example, less than 5% by volume, and more typically less than 2% by volume, void content as measured by x-ray microtomography.

[0137] The composite material of the present invention preferably comprises from 20 to 80 wt.% of reinforcing fibers and from 80 to 20 wt.% of the matrix of the composition (C) of the present invention, based on the weight of the composite material.

[0138] Method of manufacturing an assembly

[0139] Further exemplary embodiments relate to a method of manufacturing an assembly comprising a first substrate layer and a second substrate layer, said method comprising positioning and contacting a bonding layer made from the composition (C) of the present application between and with said first substrate and said second substrate; and an assembly obtained therefrom.

[0140] One or both substrate layers connected by the bonding layer can be, for example, a sheet or a film. The substrate layers can be composed of any suitable material, such as, for example, a metal, a plastic (thermoplastic or thermoset), a ceramic or a glass, or of a composite material, notably including composites as described above. The thickness of the film or sheet can be suitably chosen and can be, for example, from about 0.01 to about 10 mm.

[0141] Suitable crystalline and / or high temperature thermoplastics that can be included in the plastic substrate layers include, but are not limited to, polyaryletherketones (such as crystalline polyetherketone (PEK), crystalline polyether ether ketone (PEEK), crystalline polyether ketone ketone (PEKK), polyether ether ether ketone (PEEEK), polyether ether ketone ketone (PEEKK), polyether ketone ether ether ketone (PEKEKK), and polyether ketone ketone ketone (PEKKK)), polyimides, polyetherimides, polyamideimides, polysulfones, polyethersulfones, polyarylethers, polycarbonates, liquid crystalline polymers, polyphenylene sulfides, polyarylenes (polyphenylenes), polyamides, polyphthalamides, polyarylates, and the like.

[0142] In another embodiment, at least one of the first substrate layer or the second substrate layer is metallic, such as a metal sheet, foil, or the like. The substrate can be composed of any suitable metal or metal alloy, such as steel, aluminum, aluminum alloys, copper, gold, silver, and the like.

[0143] The assemblies of the present application can be made in any conventional form by coextrusion, including films, sheets, plaques, tubes, or any other conventional shape obtainable by coextrusion, particularly when the components of the substrate layers are melt processable thermoplastics.

[0144] Compression molding, intermittent matched-die consolidation, twin belt press consolidation, roll forming of composites, transfer molding, and other such techniques can also be used in conjunction with the present application. For example, an assembly can be prepared by placing a sheet or film made from the composition (C) of the present application (corresponding to the desired bonding layer) between a first substrate layer and a second substrate layer, and heating the resulting "sandwich" at a temperature effective to soften at least one of the layers, sufficient to cause it to flow and intimately contact the adjacent layer, thereby forming an adherent bond upon cooling of the assembly. Typically, pressure is desired to be applied to the "sandwich" to enhance the degree of adhesion obtained between the bonding layer and the substrate layers. The assembly can be thermoformed in order to obtain a particular desired shape or profile.

[0145] The assemblies of the present invention can be used in any end-use application for which it is conventional or has been proposed to use such laminates or composites. Representative applications include composites and laminates (including two- and three-dimensional panels and sheets) for aerospace / aircraft, automotive and other vehicles, boats, machinery, heavy equipment, storage tanks, pipes, sporting equipment, tools, biomedical devices (including devices implanted in the human body), architectural components, wind blades, and the like.

[0146] If the disclosure of any patents, patent applications, and publications that are incorporated by reference in the present application conflict in any manner with the description of the present application, then the description of the present application should be controlling.

[0147] Examples

[0148] The present disclosure will now be described in greater detail by reference to the following examples, which are for illustrative purposes only and are not intended to limit the scope of the present disclosure.

[0149] Part I: Synthesis of PEKK polymers and example compositions produced by solution blending

[0150] The following examples illustrate the synthesis of PEKK copolymers, their thermal and mechanical properties.

[0151] Raw materials

[0152] 1,2-dichlorobenzene, terephthaloyl dichloride, isophthaloyl dichloride, 3,5- dichlorobenzoyl chloride, aluminum chloride (AlCl3), methanol were purchased from Sigma Aldrich.

[0153] 1,4-bis(4-phenoxybenzoyl)benzene was prepared according to IN patent 193687 (filed on June 21, 1999 and incorporated herein by reference).

[0154] Diphenyl sulfone (polymeric grade) was obtained from Proviron (99.8% pure).

[0155] Sodium carbonate, light soda, was purchased from Solvay S.A., France and dried before use. Its particle size was such that its d 90 was 130 pm.

[0156] Potassium carbonate having a d 90 <45 pm was purchased from Armand products and dried before use.

[0157] Lithium chloride (anhydrous powder) was purchased from Acros.

[0158] NaH2PO4.2H2O and Na2HPO4 were purchased from Sigma-Aldrich.

[0159] 1,4-Bis(4'-hydroxybenzoyl)benzene (1,4-BHBB) and 1,3-bis(4'-hydroxybenzoyl)benzene (1,3-BHBB) were produced by hydrolysis of 1,4-DFDK and 1,3-DFDK, respectively, following the procedure described in Example 1 of U.S. Patent No. 5,250,738 to Hackenbruch et al. (filed February 24, 1992 and incorporated by reference herein in its entirety). They were purified by recrystallization in DMF / ethanol.

[0160] 1,4-Bis(4'-hydroxybenzoyl)benzene (1,4-BHBB) and 1,3-bis(4'-hydroxybenzoyl)benzene (1,3-BHBB) were produced by hydrolysis of 1,4-DFDK and 1,3-DFDK, respectively, following the procedure described in Example 1 of U.S. Patent No. 5,250,738 to Hackenbruch et al. (filed February 24, 1992 and incorporated by reference herein in its entirety). They were purified by recrystallization in DMF / ethanol.

[0161] Determination of melt flow index

[0162] Melt flow index was determined according to ASTM D1238 at the indicated temperature (340-380 °C, depending on the melting point of the material) with a 3.8 kg weight. The final MFI with an 8.4 kg weight was obtained by multiplying the resulting value by 2.35.

[0163] Determination of glass transition temperature, melting temperature and heat of fusion

[0164] Glass transition temperature T g (midpoint, using the half-height method) and melting temperature T mis determined in the 2nd heating scan in a differential scanning calorimeter (DSC) according to ASTM D3418-03, E1356-03, E793-06, E794-06, further according to the details below. Details of the procedure as used in the present application are as follows: A TA Instruments DSC Q20 is used, with nitrogen as carrier gas (99.998% purity, 50 mL / min). Temperature and heat flow calibration is done using indium. Sample mass is 5 to 7 mg. A hermetically sealed pan is used. Weight is recorded to ±0.01 mg. The heating cycle is:

[0165] • 1st heating scan: 30.00 °C to 400.00 °C at 20.00 °C / min, 1 min isotherm at 400.00 °C;

[0166] • 1st cooling scan: 400.00 °C to 30.00 °C at 20.00 °C / min, 1 min isotherm;

[0167] • 2nd heating scan: 30.00 °C to 400.00 °C at 20.00 °C / min, 1 min isotherm at 400.00 °C.

[0168] Melting temperature Tm m is determined as the peak temperature of the melting endotherm in the 2nd heating scan. The enthalpy of fusion is determined in the 2nd heating scan and is taken as the area under the linear baseline drawn from T g above to the temperature above which the end of the endothermic peak is found. Crystallization temperature Tc c is determined as the peak temperature of the crystallization exotherm in the 1st cooling scan. The presence of cold crystallization is determined from the 2nd heating scan: the presence of an exothermic heat flow exceeding 0.5 J / g before the onset of the endothermic melting peak is taken as clear evidence for the presence of an exothermic before the onset of the endothermic melting peak.

[0169] Determination of elemental impurities such as aluminum in polymer compositions by ICP-OES

[0170] Place a clean dry platinum crucible on an analytical balance and zero the balance. Weigh one half to 3 grams of polymer sample into the boat and record the weight to 0.0001 g. Place the sample containing crucible into a muffle furnace (Thermo Scientific Thermolyne F6000 Programmable Furnace). Gradually heat the furnace to 525°C and hold at temperature for 10 hours to dry ash the sample. After ashing, cool the furnace to room temperature and remove the crucible from the furnace and place in a fume hood. Dissolve the ash in dilute hydrochloric acid. Using a polyethylene pipette, transfer the solution to a 25 mL volumetric flask. Rinse the crucible with approximately 5 mL of ultrapure water (R < 18 MΩ cm) twice and add the washings to the volumetric flask to achieve a quantitative transfer. Add ultrapure water in the flask to a total of 25 mL. Place a stopper on top of the flask and shake the contents well to mix.

[0171] The ICP-OES analysis was performed using an inductively coupled plasma emission spectrometer Perkin-Elmer Optima 8300 dual view. The spectrometer was calibrated using a set of NIST traceable multi-element mixed standards with analyte concentrations between 0.0 and 10.0 mg / L. Linear calibration curves were obtained in a series of concentrations with a correlation coefficient better than 0.9999 for each of the 48 analytes. Standards were run before and after every ten samples to ensure instrument stability. Results were reported as the average of three replicates. The concentration of elemental impurities in the sample was calculated with the following formula: A = (B * C) / D

[0172] where:

[0173] A = concentration of element in the sample in mg / kg (= wt. ppm)

[0174] B = element in solution analyzed by ICP-OES in mg / L

[0175] C = volume of solution analyzed by ICP-OES in mL

[0176] D = sample weight used in the procedure in grams.

[0177] Determination of fluorine concentration in polymers by combustion ion chromatography

[0178] For combustion ion chromatography (IC) analysis, a clean, pre-oven dried ceramic sample boat was placed on the analytical balance and the balance was zeroed. Approximately 20 mg of polymer sample was weighed into the boat and the weight was recorded to 0.0001 g. The boat containing the sample was placed in the combustion furnace, which was set to an inlet temperature of 900 °C and an outlet temperature of 1000 °C. The combusted sample and argon carrier gas passed through 18.2 MΩ ultrapure water and was automatically injected into the IC system equipped with a conductivity detector.

[0179] Combustion IC analysis was performed using a Dionex ICS 2100 IC system equipped with a Dionex IonPac AS19 IC column and guard column (or equivalent), a Dionex CRD 200 4mm suppressor (set to 50 mA), and a GA-210 gas absorption cell HF-210 furnace and ABC-210 boat controller, all from Mitsubishi Analytech.

[0180] The elution gradient for this method was as follows:

[0181] 0-10 minutes: 10 mM KOH

[0182] 10-15 minutes: Steady, constant increase to 20 mM KOH

[0183] 15-30 minutes: 20 mM KOH

[0184] The instrument was calibrated using a 3-point calibration from a NIST traceable 7-anion mixture supplied by AllTech, where F - analyte concentrations were between 0.1-3.0 mg / L. Linear calibration curves were obtained over the entire concentration range with a correlation coefficient better than 0.9999 for each analyte. Prior to analyzing any samples, a control sample was run to verify that the machine was operating correctly. The anion concentration in the sample was calculated using the following equation:

[0185] A = (B * C) / D where:

[0186] A = elemental concentration in the sample in mg / kg

[0187] B = anion in the solution analyzed by IC in mg / L

[0188] C = volume of the solution analyzed by IC in mL

[0189] D = sample weight used in the procedure in mg.

[0190] Comparative Preparation Example 1 : Preparation of an electrophilic PEKK (e-PEKK) having T / I = 72 / 28

[0191] In a 2000 mL 4-necked reaction flask, equipped with a stirrer, a dry N2inlet tube, a thermocouple inserted in the reaction medium, and a condenser, 1000 g of 1,2- dichlorobenzene and 40.63 g of 1,4-bis(4-phenoxybenzoyl)benzene were introduced. Then, 7.539 g of terephthaloyl dichloride, 9.716 g of isophthaloyl dichloride and 0.238 g of benzoyl dichloride were added to the reaction mixture under a dry nitrogen purge. The reactor was then cooled to -5°C and 71.88 g of aluminum chloride (AlCl3) were slowly added while keeping the temperature below 5°C. The reaction was maintained at 5°C for 10 minutes, then the temperature of the mixture was increased to 90°C at 5°C / min. The reaction mixture was maintained at 90°C for 30 minutes, then cooled to 30°C. At 30°C, 250 g of methanol were slowly added to maintain the temperature below 60°C. After the addition was completed, the reaction mixture was maintained under stirring for 2 hours, then cooled to 30°C. The solids were then removed by filtration on a Buchner funnel. The wet cake was rinsed on the filter with another 188 g of methanol. The wet cake was then re-slurried in a beaker with 440 g of methanol for 2 hours. The polymer solids were filtered again on a Buchner funnel and the wet cake was rinsed on the filter with 188 g of methanol. The solids were slurried with 470 g of an aqueous hydrochloric acid solution (3.5 wt%) for 2 hours. The solids were then removed by filtration on a Buchner funnel. The wet cake was rinsed on the filter with another 280 g of water. The wet cake was then re-slurried in a beaker with 250 g of a 0.5 N aqueous sodium hydroxide solution for 2 hours. The wet cake was then re-slurried in a beaker with 475 g of water and filtered on a Buchner funnel. The last water washing step was repeated 3 times more. The polymer was then slurried with 0.75 g of an aqueous solution containing 6.6 wt% of NaH2PO4.2H2O and 3.3 wt% of Na2HPO4and dried in a vacuum oven at 180°C for 12 hours. The melt flow index (360°C, 8.4 kg) was 82 g / 10 min.

[0192]

[0193] Comparative Preparation Examples 2 to 4 of e-PEKK with T / I = 60 / 40 and 82 / 18 of different molecular weights

[0194] The same procedure as for Example 1 was followed, but using the amounts of reagents specified in the table below.

[0195] Table 1 : Comparative Preparation Examples 2 to 4

[0196] Preparation Example 5: Synthesis of a nucleophilic PEKK (n-PEKK) 71 / 29 low MV

[0197] In a 500 mL 4-neck reaction flask, equipped with a stirrer, N2inlet tube, Claisen adapter with thermocouple inserted into the reaction medium, and a Dean-Stark trap with condenser and dry-ice trap, 112.50 g of diphenyl sulfone (DPS), 23.054 g of 1,3-BHBB, 16.695 g of 1,4-BHBB, and 41.292 g of 1,4-DFDK were introduced. The contents of the flask were evacuated under vacuum and then filled with high purity nitrogen (containing less than 10 ppm of O2). The reaction mixture was then placed under constant nitrogen purge (60 mL / min). The reaction mixture was slowly heated to 270 °C. At 270 °C, 13.725 g of Na2CO3and 0.078 g of K2CO3were added to the reaction mixture over 60 minutes via a powder dispenser. At the end of the addition, the reaction mixture was heated to 310 °C at 1 °C / minute. After 2 minutes at 310 °C, 1.107 g of 1,4-DFDK was added to the reaction mixture while maintaining the nitrogen purge on the reactor. After 5 minutes, 0.741 g of lithium chloride was added to the reaction mixture. After 10 minutes, an additional 0.402 g of 1,4-DFDK was added to the reactor and the reaction mixture was held at temperature for 15 minutes. An additional charge of 15 g of diphenyl sulfone was added to the reaction mixture which was held under agitation for 15 minutes.

[0198] The reactor contents were then poured from the reactor into a stainless steel pan and cooled. The solid was broken up and ground in a mill (through a 2 mm screen). Diphenyl sulfone and salts were extracted from the mixture with acetone and water at a pH between 1 and 12. 0.67 g of NaH2PO4-2H2O and 0.62 g of Na2HPO4were dissolved in 1200 mL of DI water for the final wash. The powder was then removed from the reactor and dried under vacuum at 120 °C for 12 hours, yielding 72 g of yellow powder.

[0199] Preparation Examples 6 to 13: Synthesis of nucleophilic PEKK (n-PEKK) with variable T / I and / or different melt viscosity (MV)

[0200] The same procedure as Example 5 was followed, but using the amounts of reagents specified in the table below.

[0201] Table 2: Examples of n-PEKK with T / I = 58 / 42 to 69 / 31

[0202]

[0203]

[0204]

[0205]

[0206] General procedure for solution blending of various PEKKs

[0207] In a 500 mL 4-necked reaction flask (fitted with stirrer, N2inlet tube, Claisen adapter with thermocouple inserted into the reaction medium, and condenser), 235.00 g of diphenyl sulfone (DPS) and optional boron nitride (see Table 3) were introduced. The contents of the flask were slowly heated to 330 °C. At 330 °C, a blend of 100 g of polymer powders in the proportions shown in Table 3 was slowly added to the molten DPS through a flex tube. At the end of the addition, the stirring speed was increased to provide good mixing, and the mixture was held at 330 °C for an additional hour.

[0208] The reactor contents were then poured from the reactor into a stainless steel pan and cooled. The solid was broken up and ground in a mill (through a 2 mm screen). Diphenyl sulfone was extracted from the mixture using acetone and water. 0.67 g of NaH2PO4-2H2O and 0.62 g of Na2HPO4were dissolved in 1200 mL of DI water for the final wash. The powder was then removed from the reactor and dried at 120 °C under vacuum for 12 hours, yielding 90-95 g of yellow powder.

[0209] Table 3: Compositions made by solution blending

[0210] Examples 14 CE15 CE16 17 18 19 20 21 Boron nitride pph 1.2 ePEKK Example 1 CP Wt% 15 ePEKK Example 2 CP Wt% 65 85 ePEKK Example 3 CP Wt% ePEKK Example 4 CP Wt% 35 n-PEKK Example 5 P Wt% 15 5 10 15 20 15 n-PEKK Example 6 P Wt% 85 n-PEKK Example 7 P Wt% 95 90 85 80 85

[0211] Thermal properties (DSC at 20 °C / min to 400 °C) of solution blends of copolymers with different T / I ratios (Examples 7-13) and n-PEKK (Examples 17-21) are presented in Table 4. In the table, T g is the glass transition temperature; T m is the melting temperature, T c is the crystallization temperature; Equation 1 is the following inequality: T c ≥ 1.3716*T m - 190 °C; T c * 最小 is the theoretical minimum value T m corresponding to the measured T c in order to satisfy the above inequality, calculated as T c * 最小 = 1.3716*T m - 190 °C. When the measured T c is ≥ Tc 最小 T c ≥ 1.3716 * T m - 190°C, the criterion of equation 1 is labeled as fulfilled [Y (pass)] in table 4. When an exotherm of more than 0.5 J / g is measured, the cold crystallization test is labeled “yes (not passed)”, while when no detectable exotherm is measured, the test result is labeled “no (passed)”.

[0212] Table 4: Thermal properties as determined by DSC

[0213]

[0214] As shown by the data collected above, copolymers PEKK with a lower melting point per se are generally poorly crystalline, exhibit cold crystallization behavior, and have a significant gap between T c and T m (therefore not passed in equation 1) as an indication of slow crystallization rate; copolymers PEKK with a higher melting point per se are inherently poorly processable, and while having a suitable crystallinity, also show a significant gap between T c and T m (therefore not passed in equation 1) as an indication of slow crystallization rate. In contrast, the above data (also plotted in Figure 1 ) very well demonstrate that the blends according to the present application are endowed with a higher T m than copolymers having the same T c , with a heat of fusion AH f of more than 25 J / g, i.e. an acceptably high crystallinity. Therefore, as already explained, this means that the inventive blends allow to reach a better combination of improved processability (as evidenced by their lower T m (kept below 330°C) with faster crystallization rate (as evidenced by higher T c ) and suitable final crystallization fraction (as evidenced by AH f ). Overall, the blends according to the present application exhibit:

[0215] • T m ≤ 330°C

[0216] • heat of fusion AH f > 25 J / g

[0217] • no cold crystallization peak at 2nd heating scan

[0218] • T c satisfying the following equation:

[0219] T c ≥ 1.3716 * T​m -190°C [Equation 1]

[0220] where T m and T c have the meanings indicated above.

[0221] The data provided in Table 5 below further demonstrate that these advantageous effects are only achieved with blends where a nucleophilic PEKK is used. Table 5 compares the properties obtained in Example 14 (blend of nPEKK of Example 6 and nPEKK of Example 5) with the unsatisfactory results achieved with a blend of ePEKK.

[0222] Table 5: Thermal properties as determined by DSC

[0223]

[0224] The data provided in Table 5 below further demonstrate that these advantageous effects are only achieved with blends where a nucleophilic PEKK is used. Table 5 compares the properties obtained in Example 14 (blend of nPEKK of Example 6 and nPEKK of Example 5) with the unsatisfactory results achieved with a blend of ePEKK.

[0225] General procedure for the preparation of the compositions of the application by melt blending

[0226] The compositions in the following set of examples were prepared by melt blending in a twin-screw extruder, the details of which are further described below. The PEKK starting material was an n-PEKK polymer, prepared as described above.

[0227] Raw materials:

[0228] n-PEKK from Example 6P: T / I = 58 / 42 high MV

[0229] n-PEKK from Example 7P: T / I = 58 / 42 low MV

[0230] n-PEKK from Example 9P: T / I = 61 / 39

[0231] n-PEKK from Example 5P: T / I = 71 / 29

[0232] PEEK: KT-880UFP, a low viscosity grade PEEK polymer commercially available from Solvay Specialty Polymers. It has a melt viscosity in the range of 0.12-0.18 kPa-s, as measured according to ASTM D3835 at a temperature of 400 °C and a shear rate of 1000 1 / s, using a capillary die with a length of 3.175 mm and a length of 0.5 mm and having a 120 degree entry angle.

[0233] Boron nitride: S1-SF, a hexagonal boron nitride grade commercially available from 3M Company

[0234] Blend preparation

[0235] All compositions described in this section were prepared by melt blending using a Leistritz 18 mm twin-screw co-rotating intermeshing extruder with a length to diameter ratio (L / D) of 30. The ingredients, all in powder or pellet form, were first tumble blended according to the composition ratios shown in the following example tables in each case. The tumble blending was carried out for about 20 minutes, followed by melt compounding using the extruder described above. The extruder had 6 barrel sections, with barrel sections 2 to 6 being heated. Vacuum venting (vacuum level with > 25 inches of Hg) was applied at barrel section 5 during compounding to purge the compounds of moisture and any possible residual volatiles. In each case, the extrudate was air-cooled in strands on a conveyor belt and fed into a pelletizer which cut it into pellets of approximately 3 mm in diameter and 3 mm in length. The other compounding conditions were as follows: barrel sections 2-6 as well as die section were heated to 360 °C. The extruder was run at a screw speed of about 200 rpm, and the production rate was about 6 lb / h.

[0236] Table 6: Example illustrating blends of PEKK (Example 9P) T / I = 61 / 39 with addition of PEKK of Example 5P compared to addition of another polyaryletherketone polymer

[0237]

[0238] Table 7 Example illustrating addition of boron nitride to a blend of PEKK (Example 6P) T / I = 58 / 42 and PEKK (Example 5P) according to the application, and addition of boron nitride to the PEKK alone as a comparison

[0239]

[0240]

[0241] Table 8 Example of a blend of PEKK (Example 7P) T / I = 58 / 42 and PEKK (Example 5P) according to the application

[0242]

[0243]

[0244] Table 9: Example of a blend of PEKK (Example 7P) T / I = 58 / 42 and PEKK (Example 5P) according to the application

[0245]

[0246]

Claims

1. A composition (C) comprising: - The main amount of the first PEKK polymer [polymer (PEKK)] 低 )], which contains repeating units (R) T ) and repeating unit (R) I ), with unit (R) T The first molar content of [(T)] 低 )] and unit (R) I The first molar content of [(I)] 低 )],in and Therefore, the first T / I ratio is defined as [(T / I)]. 低 ],in And the first PEKK polymer [polymer (PEKK 低 (T / I) has a value between 50 / 50 and 64 / 36. 低 ;where the repeating unit (R) T Equation (T) represents: And repeating unit (R) I Equation (I) represents: in: - R 1 and R 2 In each case, each is independently selected from the group consisting of: alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali metal sulfonate or alkaline earth metal sulfonate, alkyl sulfonate, alkali metal phosphonate or alkaline earth metal phosphonate, alkyl phosphonate, amine, and quaternary ammonium; and - i and j are each independently chosen integers ranging from 0 to 4 in each case; and - Small amount of second PEKK polymer [polymer (PEKK)] 高 )], which includes the repeating unit (R) I ) and the repeating unit (R) T ), with unit (R) T The second molar content of [(T)] 高 )] and unit (R) I The second molar content of [(I)] 高 )],in and Therefore, the second T / I ratio is defined as [(T / I)]. 高 ],in And the second PEKK polymer [polymer (PEKK 高 (T / I) having values ​​between 65 / 35 and 75 / 25 高 ; Among them, polymer (PEKK) 低 It is a nucleophilic PEKK; and Among them, PEKK 低 (T / I) 低 Below this PEKK 高 (T / I) 高 ;and The following inequalities are satisfied: 5 mol.% ≤ T 高 - T 低 ≤ 15 mol.%。 2. The composition (C) according to claim 1, wherein, The composition has the following characteristics: - Melting temperature less than or equal to 330°C (T m ); - Heat of fusion exceeding 25 J / g (ΔH) f ); - No crystallization peak ("cold crystallization peak") was observed during heating in the second DSC heating scan; and - The melting temperature (T) determined during the second DSC heating scan. m (in °C) and the crystallization temperature (T) determined in the first DSC cooling scan. c The relationship between (in °C) and (the two values) satisfies the following inequality: T c ≥ 1.3716 × T m - 190°C, Where T m T c ΔH f The absence of cold crystallization peaks was measured according to ASTM D3418-03, E1356-03, E793-06, and E794-06 standards using differential scanning calorimetry (DSC), with a heating and cooling rate of 20°C / min, scanning from 30°C to 400°C.

3. The composition (C) according to claim 1, wherein, These repeating units (R) T ) and (R I The following are represented by equations (T') and (I'), respectively: (T'), and (I’)。 4. The composition (C) according to any one of claims 1 to 3, wherein, The polymer (PEKK) 低 ) and the polymer (PEKK) 高 These are collectively referred to as polymers (PEKK), and among them: - The polymer (PEKK) contains repeating units (R) T ) and repeating unit (R) I The combined amount of these repeating units is at least 60 mol.%, where mol.% is based on the total number of moles in the polymer (PEKK); and / or - Polymer (PEKK) contains a small number of elements different from repeating units (R). T ) and repeating unit (R) I ), Select repeating units from the following groups: equations (JA) to (JO) below: in: Each R' may be the same as or different from the others, and is selected from the group consisting of: halogens, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali metal sulfonate or alkaline earth metal sulfonate, alkyl sulfonate, alkali metal phosphonate or alkaline earth metal phosphonate, alkyl phosphonate, amine, and quaternary ammonium. j' is zero or an integer from 0 to 4.

5. The composition (C) according to claim 4, wherein the polymer (PEKK) comprises repeating units (R) T ) and repeating unit (R) I The combined amount of these repeating units is at least 70 mol.%, which is based on the total number of moles in the polymer (PEKK).

6. The composition (C) according to claim 4, wherein the polymer (PEKK) comprises repeating units (R) T ) and repeating unit (R) I The combined amount of these repeating units is at least 80 mol.%, which is based on the total number of moles in the polymer (PEKK).

7. The composition (C) according to claim 4, wherein the polymer (PEKK) comprises repeating units (R) T ) and repeating unit (R) I The combined amount of these repeating units is at least 90 mol.%, which is based on the total number of moles in the polymer (PEKK).

8. The composition (C) according to claim 4, wherein the polymer (PEKK) comprises repeating units (R) T ) and repeating unit (R) I The combined amount of these repeating units is at least 95 mol.%, which is based on the total number of moles in the polymer (PEKK).

9. The composition (C) according to claim 4, wherein the polymer (PEKK) comprises repeating units (R) T ) and repeating unit (R) I The combined amount of these repeating units is at least 99 mol.%, which is based on the total number of moles in the polymer (PEKK).

10. The composition (C) according to claim 4, wherein substantially all repeating units in these polymers (PEKK) are repeating units (R). T ) and (R I ).

11. The composition (C) according to any one of claims 1 to 3, wherein: - The polymer (PEKK) 低 Contains more than 100 ppm of fluorine and / or less than 50 ppm of Al, wherein the Al and F contents are determined by ICP-OES analysis for Al and combustion-ion chromatography for fluorine; and / or - The polymer (PEKK) 低 It has a 1 wt.% thermal decomposition temperature T of at least 500°C, as measured by thermogravimetric analysis under nitrogen at a heating rate of 10°C / min from 30°C to 800°C according to ASTM D3850. d (1%).

12. The composition (C) according to claim 11, wherein the polymer (PEKK) 低 It contains more than 200 ppm of fluorine.

13. The composition (C) according to claim 11, wherein the polymer (PEKK) 低 It contains more than 300 ppm of fluorine.

14. The composition (C) according to claim 11, wherein the polymer (PEKK) 低 It contains less than 25 ppm of Al.

15. The composition (C) according to claim 11, wherein the polymer (PEKK) 低 It contains less than 10 ppm of Al.

16. The composition (C) according to claim 11, wherein the polymer (PEKK) 低 It has a 1 wt.% thermal decomposition temperature T of at least 505°C, as measured by thermogravimetric analysis under nitrogen at a heating rate of 10°C / min from 30°C to 800°C according to ASTM D3850. d (1%).

17. The composition (C) according to claim 11, wherein the polymer (PEKK) 低 It has a 1 wt.% thermal decomposition temperature T of at least 510°C, as measured by thermogravimetric analysis under nitrogen at a heating rate of 10°C / min from 30°C to 800°C according to ASTM D3850. d (1%).

18. The composition (C) according to claim 1, wherein the polymer (PEKK) 低 It has at least 54 / 46 (T / I) 低 .

19. The composition (C) according to claim 1, wherein the polymer (PEKK) 低 It has at least 56 / 44 (T / I) 低 .

20. The composition (C) according to claim 1, wherein the polymer (PEKK) 低 It has at least 57 / 43 (T / I) 低 .

21. The composition (C) according to claim 1, wherein the polymer (PEKK) 低 It has a maximum of 63 / 37 (T / I) 低 .

22. The composition (C) according to claim 1, wherein the polymer (PEKK) 低 It has a maximum of 62 / 38 (T / I) 低 .

23. The composition (C) according to claim 1, wherein the polymer (PEKK) 低 (T / I) has values ​​between 57 / 43 and 62 / 38. 低 .

24. The composition (C) according to claim 1, wherein the polymer (PEKK) 高 It has at least 66 / 34 (T / I) 高 .

25. The composition (C) according to claim 1, wherein the polymer (PEKK) 高 It has at least 67 / 33 (T / I) 高 .

26. The composition (C) according to claim 1, wherein the polymer (PEKK) 高 It has a maximum of 73 / 27 (T / I) 高 .

27. The composition (C) according to claim 1, wherein the polymer (PEKK) 高 It has a maximum of 72 / 28 (T / I) 高 .

28. The composition (C) according to claim 1, wherein the polymer (PEKK) 高 (T / I) includes those between 67 / 33 and 72 / 28. 高 .

29. The composition (C) according to any one of claims 1 to 3, wherein, The polymer (PEKK) 高 It has a fluorine content of more than 100 ppm and / or an Al content of less than 50 ppm, while the Al and F contents are determined by ICP-OES analysis for Al and combustion-ion chromatography for fluorine.

30. The composition (C) according to claim 29, wherein the polymer (PEKK) 高 It has a fluorine content of over 200 ppm.

31. The composition (C) according to claim 29, wherein the polymer (PEKK) 高 It has a fluorine content of over 300 ppm.

32. The composition (C) according to claim 29, wherein the polymer (PEKK) 高 It has an Al content of less than 25 ppm.

33. The composition (C) according to claim 29, wherein the polymer (PEKK) 高 It has an Al content of less than 10 ppm.

34. The composition (C) according to any one of claims 1 to 3, wherein, Polymer (PEKK) 低 ) and polymers (PEKK) 高 The weight ratio between them is at least 60 / 40 and / or at most 99 / 1.

35. The composition (C) according to claim 34, wherein the polymer (PEKK) 低 ) and polymers (PEKK) 高 The weight ratio between them is at least 65 / 35.

36. The composition (C) according to claim 34, wherein the polymer (PEKK) 低 ) and polymers (PEKK) 高 The weight ratio between them is at least 70 / 30.

37. The composition (C) according to claim 34, wherein the polymer (PEKK) 低 ) and polymers (PEKK) 高 The weight ratio between them is at least 75 / 25.

38. The composition (C) according to claim 34, wherein the polymer (PEKK) 低 ) and polymers (PEKK) 高 The weight ratio between them is at most 97 / 3.

39. The composition (C) according to claim 34, wherein the polymer (PEKK) 低 ) and polymers (PEKK) 高 The weight ratio between them is at most 96 / 4.

40. The composition (C) according to any one of claims 1 to 3, wherein: - The composition further comprises at least one nitride (NI) of an element having an electronegativity (e) from 1.3 to 2.5; and / or - The composition further comprises one or more additional ingredients that are different from nitrides (NI) and are selected from the group consisting of: colorants, pigments, light stabilizers, heat stabilizers, antioxidants, acid scavengers, processing aids, nucleating agents, internal and / or external lubricants, flame retardants, smoke suppressants, antistatic agents, anti-caking agents, thermally, electrically and magnetically conductive materials, fiber-reinforcing additives and non-fiber-reinforcing additives.

41. The composition according to claim 40, wherein, Based on the total weight of the composition (C), the polymer (PEKK) 低 ) and polymers (PEKK) 高 The total weight is equal to or greater than 60 wt.%; and / or - Wherein composition (C) is composed of polymer (PEKK) 低 ) and polymers (PEKK) 高 It does not contain any other polyaryletherketone polymers [polymer (PAEK)] other than that, and polymer (PAEK) is a polymer containing repeating units, wherein more than 50% molar of the repeating units are repeating units containing Ar*-C(O)-Ar*' groups (R*). PAEK ), where Ar* and Ar*', which may be the same as or different from each other, are aromatic groups, and the polymer is not a polymer (PEKK). 低 ) or polymer (PEKK) 高 ); and / or - Wherein composition (C) is essentially composed of polymer (PEKK) 低 ) and polymers (PEKK) 高 Composition; or - Wherein, when used, the total weight of the nitride (NI) in the composition (C) is at least 0.1 wt.% and / or at most 10 wt.% based on the total weight of the composition (C).

42. The composition (C) according to claim 41, wherein, based on the total weight of the composition (C), the polymer (PEKK) 低 ) and polymers (PEKK) 高 The total weight is equal to or greater than 70 wt.%.

43. The composition (C) according to claim 41, wherein, based on the total weight of the composition (C), the polymer (PEKK) 低 ) and polymers (PEKK) 高 The total weight is equal to or greater than 80 wt.%.

44. The composition (C) according to claim 41, wherein, based on the total weight of the composition (C), the polymer (PEKK) 低 ) and polymers (PEKK) 高 The total weight is equal to or greater than 85 wt.%.

45. The composition (C) according to claim 41, wherein, based on the total weight of the composition (C), the polymer (PEKK) 低 ) and polymers (PEKK) 高 The total weight is equal to or greater than 90 wt.%.

46. ​​The composition (C) according to claim 41, wherein, when used, the total weight of the nitride (NI) in the composition (C) is at least 0.2 wt.% based on the total weight of the composition (C).

47. The composition (C) according to claim 41, wherein, when used, the total weight of the nitride (NI) in the composition (C) is at least 0.3 wt.% based on the total weight of the composition (C).

48. The composition (C) according to claim 41, wherein, when used, the total weight of the nitride (NI) in the composition (C) is at least 0.5 wt.% based on the total weight of the composition (C).

49. The composition (C) according to claim 41, wherein, when used, the total weight of the nitride (NI) in the composition (C) is at most 8 wt.% based on the total weight of the composition (C).

50. The composition (C) according to claim 41, wherein, when used, the total weight of the nitride (NI) in the composition (C) is at most 5 wt.% based on the total weight of the composition (C).

51. The composition (C) according to claim 41, wherein, when used, the total weight of the nitride (NI) in the composition (C) is at most 3 wt.% based on the total weight of the composition (C).

52. A method for manufacturing the composition (C) according to any one of claims 1-51, wherein, The method includes mixing the polymer (PEKK) 低 ), polymer (PEKK) 高 ), and optionally other components; wherein the mixing is achieved by dry blending, suspension or slurry mixing, solution mixing, melt mixing or any combination thereof.

53. The method according to claim 52, wherein, The mixing is achieved through powder blending.

54. A molded article comprising the composition (C) according to any one of claims 1 to 51.

55. A method of manufacturing a molded article as claimed in claim 54, the method comprising processing the composition (C) by at least one of injection molding, extrusion, compression molding, additive manufacturing, coating, continuous fiber impregnation, and continuous fiber composite lamination / consolidation or combinations thereof.

56. A method for manufacturing a composite material, the method comprising impregnating reinforcing fibers with a matrix of the composition (C) according to any one of claims 1 to 51.

57. A method of manufacturing an assembly comprising a first substrate layer and a second substrate layer, the method comprising positioning and contacting an adhesive layer made of the composition (C) according to any one of claims 1 to 51 between and with the first substrate and the second substrate.

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