Poly(ether ketone ketone) polymer blends

Abstract

The present invention relates to blends of poly(ether ketone ketone) (PEKK) polymers, and in particular to specific blends composed 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, which have a lower melting point than conventional PEKK polymers while maintaining high crystallinity and fast crystallization behavior; methods for their production; and their use in various fields.

Description

[Technical Field]

[0001] This application claims priority to U.S. Provisional Patent Application No. 63 / 038,100, filed June 11, 2020, and European Patent Application Publication No. 20194026.9, filed September 2, 2020, the entire contents of each of which are incorporated herein by reference for all purposes.

[0002] The present invention relates to blends of poly(ether ketone ketone) (PEKK) polymers, and in particular to certain blends that have lower melting points than conventional PEKK polymers while maintaining high crystallinity and fast crystallization behavior, as well as methods for their production and their use in various fields. [Background technology]

[0003] Poly(ether ketone ketone) ("PEKK") polymers are well-established materials that have been used in relatively extreme conditions. In particular, due to the high crystallinity and high melting point of PEKK polymers, they have excellent thermal, physical, and mechanical properties. Such properties make PEKK polymers desirable not only in a wide range of demanding application situations, including, but not limited to, aerospace and oil and gas drilling, but also as thermoplastic matrices in composite structures.

[0004] In particular, PEKK, with a nominal T / I molar ratio of approximately 70 / 30, is a well-established and proven matrix resin for thermoplastic continuous fiber composites. It is available from several suppliers and can be produced either by an electrophilic process, which essentially involves the electrophilic substitution of a mixture of iso- / terephthalic acid chlorides on phenoxy-terminated aromatic monomers with a Friedel-Crafts-assisted, Al-containing Lewis acid catalyst, or by a nucleophilic route, which essentially involves the polycondensation of dihydroxy- and difluorobenzoyl-containing aromatic compounds and / or hydroxyl-fluorobenzoyl-containing aromatic compounds. While there are clear differences due to the inevitable characteristics of their respective synthetic routes in their microstructures, both "electrophilic" PEKK ("ePEKK") and "nucleophilic" PEKK ("nPEKK") impart an excellent combination of strength, stiffness, heat resistance, and chemical resistance to composite laminate panels and other consolidated articles based on pre-impregnated sheets and tapes (prepregs).

[0005] Nevertheless, the same high crystallinity and high melting point that provide many of the benefits of PEKK polymers also present difficulties in processing. As a result, industries that manufacture and use such PEKK polymers, especially in composite structures, are seeking lower melting point (T) polymers that allow for easier and more tolerant manufacturing, energy savings, and faster manufacturing cycle times. m In fact, the T / I ratio of PEKK, which is nominally about 70 / 30, is m The T of the PEKK polymer is approximately 340°C. Considering that semi-crystalline thermoplastics require melt processing temperatures at least 40°C above their melting points, the plastic temperature must reach at least 380°C in order to properly manufacture this PEKK-based composite. Therefore, the T of the PEKK polymer is required to lower the melt processing temperature. m Therefore, one of the constraints imposed by this long-felt industrial need is the ability to achieve a T of up to 330°C without detrimentally affecting all the other advantageous properties of PEKK.m while also (i) achieving a T m and (ii) a rapid crystallization rate (crystallization temperature, T) such that when the material is cooled from the melt at a rate of 20°C / min, substantially no further "cold" crystallization occurs on subsequent heating. c The goal of this study is to provide a PEKK material that exhibits a high crystallinity (as indicated by the formula "low temperature"), and this lack of "low temperature" crystallization indicates that in rapid cycle melt manufacturing, the "as-molded" material already develops all of its inherent crystallinity upon cooling, and does not undergo further crystallization upon subsequent exposure to heat (e.g., during its use) that could result in internal tensions, distortion, or other undesirable phenomena. Additionally, and perhaps more importantly, complete crystallization during the conventional manufacturing cooling cycle is necessary to ensure that the composite material can achieve its full chemical and environmental resistance over the service life of the part.

[0006] Blend-based approaches to modifying the properties of polyaryletherketone polymers have been pursued in the prior art.

[0007] Within this scenario, US Patent Application Publication No. 2015 / 0259530 describes blends aimed at lowering the "cold crystallization temperature" defined therein. Since the availability of a large temperature window between crystallization and melting is held to be an important process parameter for 3D printing, the objective of such blends is therefore to lower the temperature at which crystallization occurs upon heating, prior to the actual melt phase transition. This document proposes blending PEKK copolymers of various T / I ratios and viscosities to achieve a balance of toughness, crystallinity, and thermal capabilities, thereby providing the intended 3D printing processability. This example illustrates a blend of two electrophilic PEKKs, commercially available under the trade name KEPSTAN®, which differ significantly in T / I content (20 mol % T% content difference). Such blends, consistent with the intended purpose of the solution provided therein, have been shown to have "cold crystallization" behavior, even though the individual e-PEKKs used differ significantly in T / I ratio, which to some extent prevents co-crystallization behavior. Indeed, the blends exemplified hereby, after being cooled from the melt at 10°C / min, were shown to have a non-zero crystallization exotherm upon further heating (thereby termed "cold crystallization"), so that despite very slow cooling rates, the blends still exhibit the ability to further crystallize, as an indication that their crystallization kinetics are hindered to some extent.

[0008] As a result, while such blends have found utility for use in additive manufacturing applications, the materials are intended to remain in the heated build chamber for very long processing times, and such blends do not meet the requirements listed above for effective use as a plastic composite material, particularly as a matrix for composite parts manufactured by rapid cycles. Summary of the Invention

[0009] The present invention provides PEKK compositions that combine a significantly increased crystallization rate and level of crystallinity, higher than would be expected for a given total tele / iso (T / I) ratio in the PEKK composition, with a low melting point. The compositions are prepared by blending a first PEKK produced by a nucleophilic process with appropriate amounts of a second PEKK and optional inorganic nucleating agent, as detailed below, to produce a PEKK composition that exhibits a higher crystallization rate than would be expected for the T / I content of the PEKK composition, while maintaining a T of 330°C or less. m These compositions also exhibit practical levels of crystallinity as evidenced by heats of fusion of 25 J / g or greater. The compositions combine fast manufacturing cycle times for composite fabrication with improved economics associated with lower energy consumption. The high level of crystallinity in these compositions ensures robust chemical resistance in composite structures utilizing them. These compositions, methods for achieving their properties, and their end use in thermoplastic composite applications are the subject of this application.

[0010] The present invention provides - Repeating unit (R T ) and repeating units (R I ) and the unit (R T ) first molar content [(T low )] and units (R I ) first molar content [(I low a major amount of a first PEKK polymer [polymer (PEKK)]; low )],

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[0011] The compositions of the present invention advantageously have the following characteristics: Melting point below 330℃ (T m ); Heat of fusion (ΔH) of more than 25 J / g f ); · Absence of a crystallization peak upon heating ("cold crystallization peak") in the second DSC heating scan; Melting point (T in °C) determined by the second DSC heating scan m ) and the crystallization temperature (T in °C) determined by the first DSC cooling scan. c ) satisfies the following inequality: T c ≧1.3716×T m -190℃ (In the formula, T m , T c , ΔH f , and the absence of a low-temperature crystallization peak is measured by differential scanning calorimetry (DSC) in accordance with ASTM D3418-03, E1356-03, E793-06, E794-06 standards in a sweep from 30°C to 400°C, applying a heating and cooling rate of 20°C / min.

[0012] The invention further relates to the use of the compositions detailed above in various fields of use, in particular involving a thermoplastic matrix in composite structures. [Brief explanation of the drawings]

[0013] [Figure 1] 1 is a bubble chart showing a plot of Tc (°C) as a function of Tm (°C) for both comparative PEKK copolymers (white bubbles) and inventive blends (black bubbles), with bubble sizes representing ΔHf (J / g), which is also provided explicitly as a label on the bubble. DETAILED DESCRIPTION OF THE INVENTION

[0014] As mentioned above, the composition of the present invention is a polymer (PEKK low ) and polymer (PEKK high ), which are collectively referred to as polymer (PEKK). As mentioned above, polymer (PEKK) comprises repeating units (R T ) and repeating units (R I ) respectively.

[0015] According to one embodiment, R 1 and R 2 is a C1-C group optionally containing one or more heteroatoms; sulfonic acid and sulfonate groups; phosphonic acid and phosphonate groups; amine and quaternary ammonium groups at each position in the above formulas (T) and (I). 12 The amino acid sequence is independently selected from the group consisting of:

[0016] According to another embodiment, i and j are each R 1 and R 2 In other words, the repeating unit (R T ) and (R I ) are both unsubstituted. According to this embodiment, the repeating units (R T ) and (R I ) are represented by the formulas (T') and (I'), respectively: [ka] .

[0017] According to another embodiment, the polymer (PEKK) comprises the repeating units (R T ) and repeating units (R I ) in a combined amount of at least 50 mole % based on the total number of moles of polymer (PEKK).

[0018] The polymer (PEKK) contains the repeating units (R T ) and repeating units (R I ), which may contain a small amount of repeating units different from the repeating units (R PAEK The repeating unit (R PAEK ) can usually be selected from the group consisting of the following formulae (JA) to (JO): [ka] [ka] [ka] (In the formula, each R', whether equal to or different from one another, is selected from the group consisting of halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkyl sulfonate, alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine, and quaternary ammonium; j' is zero or an integer from 0 to 4).

[0019] Repeating unit (R PAEK In the repeat unit, each phenylene moiety may independently have a 1,2-, 1,4-, or 1,3-bond to another moiety in the repeat unit different from R'. Preferably, the phenylene moieties have a 1,3- or 1,4-bond, more preferably a 1,4-bond.

[0020] Furthermore, the repeating unit (R PAEK ), j' is zero at each occurrence, ie, the phenylene moiety does not have any substituents other than those that allow for attachment in the main chain of the polymer.

[0021] Preferred repeating units (R PAEK ) is therefore selected from the following formulae (J'-A) to (J'-O): [ka] [ka]

[0022] The repeating unit (R T ) and (R I ) and a repeating unit (R PAEK Although a polymer (PEKK) containing the repeating unit (R(R PAEK It is understood that the amount of (PEKK) is limited and is preferably at most 40 mol %, more preferably at most 30 mol %, more preferably at most 20 mol %, even more preferably at most 10 mol %, and most preferably at most 5 mol %, based on the total number of moles of polymer (PEKK).

[0023] Thus, according to one embodiment, 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 repeat units in the polymer (PEKK) are the repeat units (R T ) and (R I), where the mole percent is based on the total number of moles in the polymer (PEKK). The term "substantially all," when used in connection with constituting the repeat units of the polymer (PEKK), is intended to indicate that small amounts of spurious / defective repeat units may be present, for example, in amounts less than 1 mole percent, preferably less than 0.5 mole percent, and more preferably less than 0.1 mole percent. The repeat units (R T ) and (R I If no repeating units other than the unit (R T ) and (R I ), which is a preferred embodiment of the present invention.

[0024] Polymer (PEKK low ) is a nucleophilic PEKK, which is a polymer (PEKK low ) is produced by polycondensation of dihydroxy- and difluorobenzoyl-containing aromatic compounds and / or hydroxylfluorobenzoyl-containing aromatic compounds. low The nucleophilic character of the polymer (PEKK) is particularly evidenced by the presence of fluorine, usually in an amount greater than 100 ppm, preferably greater than 200 ppm, and more preferably greater than 300 ppm. Such organically bound fluorine is an inevitable feature of the use of fluorine-containing monomers. low Further evidence of the nucleophilic character of ) is indicated by the substantial absence of Al residues, i.e., the Al content is typically less than 50 ppm, preferably less than 25 ppm, and more preferably less than 10 ppm. The Al and F content can be conveniently determined by elemental analysis, such as ICP-OES analysis for Al and combustion ion chromatography for fluorine.

[0025] Due to its nucleophilic properties, the polymer (PEKK low) are also characterized by low volatility. The amount of volatiles can be determined using thermogravimetric analysis (TGA) according to ASTM D3850 method; the temperature T at which a predetermined amount of volatile material (e.g., 1% or 2% by weight) leaves the sample is called the temperature. d is determined by gradually heating the sample from 30 to 800 °C under nitrogen using a heating rate of 10 °C / min. The thermal decomposition temperature of 1 wt% is T d In one embodiment of the present invention, the polymer (PEKK low ) has a T of at least 500°C, preferably at least 505°C, more preferably at least 510°C, as measured by thermogravimetric analysis according to ASTM D3850, heating from 30°C to 800°C under nitrogen using a heating rate of 10°C / min. d (1%).

[0026] Applicant has surprisingly found that the beneficial effects of the present invention are achieved by at least one polymer (PEKK low ) are the particularly advantageous features mentioned above (F content, Al content, T d (1%)), and preferably the polymer (PEKK low ) and polymer (PEKK high ) are both nucleophilic PEKK, and therefore the polymer (PEKK high ) and polymer (PEKK low ) with the advantageous features (F content, Al content, T d Without being bound by this theory, the applicant believes that the unique microstructure of the polymer (PEKK) achieved by the nucleophilic synthetic route (e.g., the absence of "regioselective" errors and / or branching phenomena, which may occur, although rare, in the electrophilic synthetic route) allows for the unique and advantageous thermal behavior achieved by the blends of the present invention.

[0027] As mentioned above, in the composition of the present invention, PEKK low (T / I) low is PEKK high (T / I) highLower than polymer (PEKK low ) is preferably at least 50 / 50, preferably at least 54 / 46, more preferably at least 56 / 44, and most preferably at least 57 / 43 (T / I) low , and / or (T / I) of up to 64 / 36, preferably up to 63 / 37, more preferably up to 62 / 38 low Included in 57 / 43~62 / 38 (T / I) low Polymer (PEKK) low ) have been found to be particularly advantageous for use in the blends of the present invention.

[0028] As mentioned above, the polymer (PEKK high ) is also preferably a nucleophilic PEKK, which is high ) also means that it is produced by polycondensation of dihydroxy- and difluorobenzoyl-containing aromatic compounds and / or hydroxylfluorobenzoyl-containing aromatic compounds and therefore advantageously has a fluorine content of typically more than 100 ppm, preferably more than 200 ppm, more preferably more than 300 ppm, and / or an Al content of typically less than 50 ppm, preferably less than 25 ppm, more preferably less than 10 ppm.

[0029] Polymer (PEKK high ) is preferably at least 65 / 35, preferably at least 66 / 34, more preferably at least 67 / 33 (T / I) high , and / or (T / I) of up to 75 / 25, preferably up to 73 / 27, more preferably up to 72 / 28 high Included in 67 / 33~72 / 28 (T / I) high Polymer (PEKK) high ) have been found to be particularly advantageous for use in the blends of the present invention.

[0030] Furthermore, in the compositions of the present invention, the following inequality is satisfied: T high -T low ≦17 mol%. Therefore, a specific T lowA specific polymer (PEKK low Depending on the selection of the appropriate polymer (PEKK high )T high The choice of T is therefore limited, and vice versa. Without being bound by this theory, applicants believe that the co-crystallization phenomenon that ultimately accounts for the advantageous thermal properties of the blends of the present invention can be achieved only if the proportions of T units in the polymers PEKK are moderately different.

[0031] Furthermore, the polymer (PEKK) of the composition of the present invention low ) and polymer (PEKK high ), preferably T high -T low ≦16 mol %, more preferably T high -T low ≦15 mol%. Polymer (PEKK low ) and polymer (PEKK high ) is usually T high -T low ≧3 mol%, more preferably T high -T low ≧4 mol%, more preferably T high -T low It is further understood that the T content varies such that it is ≧5 mole %.

[0032] T high -T low The polymer (PEKK) low ) and polymer (PEKK high ) have been used to obtain blends with particularly advantageous properties.

[0033] The composition is a polymer (PEKK) low ) and a secondary component amount of polymer (PEKK high The terms "major component amount" and "minor component amount" have their commonly understood meanings. low ) amount of polymer (PEKK high ) amount.

[0034] Typically, the polymer (PEKK) in the composition of the present invention low ) and polymer (PEKK high ) 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 at most 99 / 1, preferably at most 97 / 3, even more preferably at most 96 / 4.

[0035] As previously mentioned, the compositions of the present invention advantageously comprise: Melting point below 330℃ (T m ); Heat of fusion (ΔH) of more than 25 J / g f ); · Absence of a crystallization peak upon heating ("cold crystallization peak") in the second DSC heating scan; Melting point (T in °C) determined by the second DSC heating scan m ) and the crystallization temperature (T in °C) determined by the first DSC cooling scan. c ) satisfies the following inequality: T c ≧1.3716×T m -190℃ (In the formula, T m , T c , ΔH f , and the absence of a low-temperature crystallization peak is measured by differential scanning calorimetry (DSC) in accordance with ASTM D3418-03, E1356-03, E793-06, E794-06 standards in a sweep from 300°C to 400°C, applying a heating and cooling rate of 20°C / min.

[0036] As far as determining the presence / absence of a cold crystallization peak is concerned, it is understood that if an exothermic peak of more than 0.5 J / g preceding the melting onset temperature is not detected by DSC in the second heating scan, this represents the absence of a cold crystallization peak. Typically, for compositions of the present invention, substantially no exothermic peak is detected by DSC in the second heating scan, meaning that no detectable energy release is observed within the sensitivity limits of the instrument.

[0037] The molecular weight of the composition (C) of the present invention can be adjusted depending on the intended field of use. In particular, when the composition (C) is intended to be used as a thermoplastic matrix for a composite structure, it is generally understood that the molecular weight of the composition (C) is adjusted so as to obtain an MFI in the range of 60 to 120 g / 10 min, measured according to ASTM D1238 at a temperature of 340 to 360°C under a piston load of 8.4 kg as defined in the examples.

[0038] Furthermore, especially when composition (C) is intended to be used as a tie layer (also known as a binder film) in a multilayer assembly, the molecular weight of composition (C) is adjusted so as to obtain an MFI in the range of 15 to 50 g / 10 min, measured according to ASTM D1238 at a temperature of 340 to 360°C under a piston load of 8.4 kg as defined in the examples.

[0039] According to a particular embodiment, the composition of the invention further comprises at least one nitride (NI) of an element having an electronegativity (ε) between 1.3 and 2.5.

[0040] The electronegativity values ​​(ε) are found in particular in the "Handbook of Chemistry and Physics", CRC Press, 64th edition, pages B-65 to B-158.

[0041] Within the context of the present invention, the expression "at least one nitride (NI)" is intended to mean one or more nitrides (NI). Mixtures of nitrides (NI) can be advantageously used for the purposes of the present invention.

[0042] Non-limiting examples of nitrides (NI) of elements having an electronegativity (ε) of 1.3 to 2.5 are described in particular in the "Handbook of Chemistry and Physics", CRC Press, 64th edition, pages B-65 to B-158. The symbol in brackets is that ascribed to the nitride in question by the CRC Handbook, while ε denotes the electronegativity of the element from which the nitride is derived. Nitrides of elements (NI) having an electronegativity (ε) of 1.3 to 2.5 that are suitable for the purposes of the present invention are, inter alia, aluminum nitride (AlN, a45, ε=1.5), antimony nitride (SbN, a271, ε=1.9), beryllium nitride (Be3N2, b123, ε=1.5), boron nitride (BN, b203, ε=2.0), chromium nitride (CrN, c406, ε=1.6), copper nitride (Cu3N, c615, ε=1.9), gallium nitride (GaN, g41, ε=1.6), trigermanium dinitride (Ge3N2, g82, ε=1.8), trigermanium tetranitride (Ge3N4, g83, ε=1.8), hafnium nitride ( Iron nitrides such as HfN, h7, ε=1.3), Fe4N (i151, ε=1.8) and Fe2N or Fe4N2 (i152, ε=1.8), mercury nitride (Hg3N2, m221, ε=1.9), niobium nitride (n109, ε=1.6), silicon nitride (Si3N4, s109, ε=1.8), tantalum nitride (TaN, t7, ε=1.5), titanium nitride (Ti3N4, t249, ε=1.5), tungsten dinitride (WN2, t278, ε=1.7), vanadium nitride (VN, v15, ε=1.6), zinc nitride (Zn3N2, z50, ε=1.6) and zirconium nitride (ZrN, z105, ε=1.4).

[0043] Preferred nitrides (NI) for use in the compositions of the present invention are nitrides of elements having an electronegativity of preferably at least 1.6, more preferably at least 1.8, and / or preferably at most 2.2.

[0044] Moreover, the nitride (NI) is preferably selected from the nitrides of elements selected from groups IIIa, IVa, IVb, Va, Vb, VIa, VIb, VIIb and VIII of the periodic table of the elements, more preferably from the nitrides of elements of group IIIa of the periodic table of the elements.

[0045] Particularly good results are obtained when the nitride (NI) is boron nitride, which is the preferred nitride (NI).

[0046] Among the different crystalline forms of boron nitride, it is preferred to use hexagonal boron nitride in the composition according to the present embodiment.

[0047] Typically, the average particle size of the nitrides (NI) is advantageously 30 μm or less, preferably 20 μm or less, more preferably 18 μm or less, more preferably 10 μm or less, and / or preferably at least 0.05 μm, at least 0.1 μm, more preferably at least 0.2 μm or more, at least 1 μm or more.

[0048] The average particle size of the nitride (NI) is preferably 1 μm to 20 μm, more preferably 2 μm to 18 μm, and more preferably 2 μm to 10 μm.

[0049] An average nitride (NI) particle size of about 2.5 μm has given particularly good results, and in particular boron nitride having such an average particle size has been found to be particularly effective.

[0050] The average particle size of the nitrides (NI) can be determined, for example, by light scattering (dynamic or laser) using the respective equipment from Malvern (Mastersizer Micro or 3000) or by means of sieve analysis according to DIN 53196.

[0051] According to these or other embodiments, the compositions of the present invention comprise a polymer (PEKK low ) and polymer (PEKK high ), and in some cases in addition to the nitride (NI), may contain one or more additional components.

[0052] Such ingredients may be advantageously 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, antiblocking agents, thermally and electrically and magnetically conductive materials (i.e. materials that may be useful for induction heating), and reinforcing fibrous and non-fibrous additives.

[0053] These aforementioned optional ingredients are well known to those skilled in the art.

[0054] Non-limiting examples of colorants include water-soluble dyes, oil-soluble dyes, water-insoluble color lakes, and mixtures thereof.

[0055] Non-limiting examples of pigments include titanium dioxide, zinc sulfide, and zinc oxide.

[0056] Non-limiting examples of light stabilizers include UV absorbers and hindered amine light stabilizers.

[0057] Non-limiting examples of antioxidants include organic phosphites and phosphonites.

[0058] Non-limiting examples of conductive additives include carbon black and carbon nanofibrils.

[0059] Non-limiting examples of reinforcing fibrous additives include glass fiber, carbon fiber, and wollastonite.

[0060] The glass fibers optionally contained in the polymer composition (C) may be prepared according to Additives for Plastics Handbook, 2000. ndThe glass fibers may be selected from the group consisting of chopped strand type A, type E, type C, type D, type S, type T, and type R glass fibers as described in Chapter 5.2.3, pages 43-48 of the John Murphy, 1999 edition. The glass fibers may have a circular or non-circular cross section (such as an elliptical or rectangular cross section). If the glass fibers used have a circular cross section, they preferably have an average fiber diameter of 3 to 30 μm, particularly preferably 5 to 12 μm. Different types of glass fibers with circular cross sections are available on the market depending on the type of glass from which they are produced.

[0061] The term "carbon fiber" as used herein is intended to include graphitized, partially graphitized, and non-graphitized carbon reinforcing fibers or mixtures thereof. Carbon fibers useful in the present invention can be advantageously obtained by heat treatment and pyrolysis of different polymer precursors, such as, for example, rayon, polyacrylonitrile (PAN), aromatic polyamides, or phenolic resins. Carbon fibers useful in the present invention can also be obtained from pitch-based materials. The term "graphite fiber" is intended to refer to carbon fibers obtained by high-temperature pyrolysis (above 2000°C) of carbon fibers, in which the carbon atoms are arranged in a manner similar to the graphite structure. Carbon fibers useful in the present invention are preferably selected from the group consisting of PAN-based carbon fibers, pitch-based carbon fibers, graphite fibers, and mixtures thereof. Carbon nanofibers and single-walled and multi-walled carbon nanotubes can also be used as reinforcing additives as part of the compositions of the present invention.

[0062] Non-limiting examples of non-fibrous reinforcing additives include talc, mica, kaolin, calcium carbonate, calcium silicate, magnesium carbonate. Non-fibrous reinforcing additives that can be used also include graphite and graphene (sometimes called nanographite or graphite nanoplatelets, GNPs).

[0063] According to a particular embodiment, the polymer (PEKK low ) and polymer (PEKKhigh ) is advantageously at least 60% by weight, preferably at least 70% by weight, more preferably at least 80% by weight, more preferably at least 85% by weight and most preferably at least 90% by weight, based on the total weight of the composition (C) of the invention.

[0064] According to a particular embodiment, the composition (C) of the invention comprises a polymer (PEKK low ) and polymer (PEKK high In other words, the composition (C) of the present invention according to these embodiments does not typically contain any other polyaryletherketone polymer [polymer (PAEK)] other than the polymer (PEKK). low ) but polymer (PEKK high ) and more than 50 mol % of the repeating units are Ar * -C(O)-Ar * A repeating unit (R * PAEK ) polymer (Ar * and Ar * The repeating units (R ′) of the polymer (PAEK) are substantially free of repeating units (R ′) which are the same or different and are aromatic groups. * PAEK ) is an optional repeating unit (R PAEK ) has the same characteristics as already mentioned above.

[0065] When used, the total weight of nitrides (NI) in composition (C) of the present invention is advantageously at least about 0.1 wt. %, usually 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 composition (C).

[0066] If additional optional components are present in composition (C) of the present invention, the total weight of the optional components, based on the total weight of composition (C), is advantageously at least 0.1 wt.-%, preferably at least 0.5 wt.-%, more preferably at least 1 wt.-%, even more preferably at least 2 wt.-%, and / or at most 30 wt.-%, preferably less than 20 wt.-%, more preferably less than 10 wt.-%, even more preferably less than 5 wt.-%, based on the total weight of composition (C).

[0067] According to a particular embodiment, the composition (C) of the invention is made from the above-mentioned polymer (PEKK low ) and polymer (PEKK high For the purposes of the present invention, the expression "essentially consisting of" should be understood to mean that any additional components other than those listed are present in an amount of up to 1% by weight, preferably up to 0.5% by weight, based on the total weight of composition (C), so as not to substantially alter the advantageous properties of the composition.

[0068] According to another embodiment, the composition (C) of the invention comprises the above-mentioned polymer (PEKK low ) and polymer (PEKK high ) and nitride (NI).

[0069] According to yet another embodiment, the composition (C) of the present invention comprises a polymer (PEKK low ) and polymer (PEKK high ) and one or more additional components other than the nitrides (NI) listed above. According to these embodiments, composition (C) may include the nitrides (NI) listed above.

[0070] The composition (C) may be a polymer (PEKK) or a mixture thereof, depending on the desired formulation. low ), polymer (PEKK highThe composition (C) can be prepared by a variety of methods, including thoroughly mixing the polymer (PEKK), optionally with a nitride (NI), and / or any of the optional additional components described above. For example, dry (or powder) blending, suspension or slurry blending, solution blending, melt blending, or any combination thereof can be used. The "other components" of the composition (C) herein include the polymer (PEKK), low ) and polymer (PEKK high ), plus any other components desired in composition (C), optionally including nitrides (NI) or any additional optional components listed above.

[0071] The composition (C) is a polymer (PEKK) in a medium that is liquid at the temperature of solubilization. low ) and polymer (PEKK high The polymers can be prepared by a process comprising solubilizing a polymer (PEKK), optionally together with other ingredients, in said liquid medium, which may advantageously comprise at least one of diphenylsulfone, benzophenone, 4-chlorophenol, 2-chlorophenol, and meta-cresol. low ) and polymer (PEKK high ) may involve heating the polymer (PEKK low ) and polymer (PEKK high A suitable liquid medium for effectively solubilizing the polymer (PEKK) is diphenyl sulfone (DPS), which is liquid above 123°C, or a blend of organic solvents containing a major amount of DPS. When DPS is used, mixing is accomplished by heating to a temperature of at least 250°C, preferably at least 275°C, and more preferably at least 300°C. low ) and polymer (PEKK high Good results were obtained when ) was solubilized in DPS at a temperature of about 330°C.

[0072] Composition (C) of the present invention can be recovered from the liquid medium by standard techniques, including liquid / solid separation, crystallization, extraction, and the like.

[0073] When DPS is used, the solubilized polymer (PEKK) in the liquid DPS low ) and polymer (PEKK high ) is cooled below the melting point of DPS to obtain a solid, which, optionally after grinding, is extracted with a mixture of acetone and water, optionally rinsed with an aqueous medium, and finally dried to obtain the composition of the present invention.

[0074] Alternatively, the composition (C) of the present invention can be prepared by, for example, melt blending or a combination of powder blending and melt blending. The powder blend can be a mixture of a polymer (PEKK low ) and polymer (PEKK high ), as well as any other optional ingredients, are provided in powder form. Typically, the polymers detailed above (PEKK low ) and polymer (PEKK high Powder blending with the hydroxybenzoates can be carried out using high intensity mixers, particularly Henschel type mixers and ribbon mixers.

[0075] Polymer (PEKK low ) and polymer (PEKK high The composition of the present invention can also be produced by melt-kneading the powder mixture described above and optional other ingredients, and / or by further melt-kneading the powder mixture described above. Conventional melt-kneading equipment can be used, such as co-rotating and counter-rotating extruders, single-screw extruders, co-kneaders, disk-pack processors, and various other types of extrusion equipment. Preferably, an extruder, more preferably a twin-screw extruder, can be used.

[0076] If necessary, the design of the compounding screw, such as flight pitch and width, clearance, length, and operating conditions, will be advantageously selected to provide sufficient heat and mechanical energy to advantageously completely melt the powder mixture or raw materials as detailed above and advantageously obtain a homogeneous distribution of the different raw materials. Once optimal mixing between the bulk polymer component and the filler component is achieved, it is advantageously possible to obtain strand extrudates of the composition (C) of the present invention. Such strand extrudates can be cooled for a while on a conveyor using a water spray and then chopped, for example, by a rotary cutting knife, to obtain the composition (C) in the form of pellets or beads. Thus, the pellets or beads of the composition (C) can then be further used for the production of parts or composites, or can be crushed to obtain the powder composition (C) for powder production techniques.

[0077] Shaped products and manufacturing methods Additional embodiments of the present invention are shaped articles comprising the composition (C) of the present invention and methods for producing said shaped articles.

[0078] The shaped article may comprise one or more parts. If the shaped article is a single part, the single part is preferably composed of the composition (C) of the invention.

[0079] Alternatively, the shaped article may be composed of two or more parts, one or more of which preferably are composed of composition (C) of the present invention. When two or more parts of the shaped article comprise composition (C), each part may comprise the same or different polymer compositions described herein.

[0080] The weight of composition (C) of the present invention, based on the total weight of the shaped article, is preferably more than 1%, more than 5%, more than 10%, preferably more than 15%, more than 20%, more than 30%, more than 40%, more than 50%, more than 60%, more than 70%, more than 80%, more than 90%, more than 95%, more than 99%.

[0081] The composition (C) of the present invention may be suitable for the manufacture of articles useful in a variety of applications. For example, due to the surprisingly advantageous properties of the composition (C) of the present invention described herein, the composition (C) of the present invention is particularly suitable for use in automotive applications such as magnet wire coatings for hybrid and electric vehicles; in oil and gas applications such as structural parts for extraction tools, downhole cable coatings, etc.; as structural components (for example, frameworks and housings) of mobile electronic devices; as a thermoplastic matrix for thermoplastic composites for structural and transportation applications; as a binder film or adhesive for fusing laminates together, especially for joining metal surfaces, (thermoplastic) composite laminate surfaces, aramid film surfaces, prepreg surfaces, etc.; in electrostatic powder coatings on metal substrates for corrosion protection and wear resistance; and in additive manufacturing parts for a variety of applications.

[0082] The term "portable electronic device" is intended to mean any electronic device designed to be conveniently carried and used in various locations while exchanging / providing access to data, for example, via wireless or cellular network connections. Representative examples of portable electronic devices include mobile phones, personal digital assistants, laptop 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, and the like.

[0083] The shaped article may be selected from a large list of articles such as seals, in particular seal rings, preferably backup seal rings, attachment parts such as fasteners; snap-fit ​​parts; inter-moving parts; functional elements, operating elements; tracking elements; adjusting elements; carrier elements; frame elements; films; switches; connectors; wires, cables; bearings, housings, compressor components such as compressor valves and compressor plates, shafts, shells or pistons.

[0084] In particular, the composition (C) of the present invention is well suited for use as a coating for wires or cables, as a structural component for portable electronic devices, or as a component manufactured by additive manufacturing. Accordingly, exemplary embodiments also include shaped articles manufactured at least in part by additive manufacturing methods using the polymer compositions described above. Such shaped articles can be used in a variety of end uses, such as implantable medical devices, dental prosthetics, and brackets and complex shaped parts in the aerospace and automotive industries.

[0085] In particular, the composition (C) of the present invention is well suited for use as a thermoplastic matrix for continuous fiber reinforced composite materials.

[0086] In another embodiment, the composition (C) of the present invention is useful in the form of a tie layer placed between and in contact with a first substrate and a second substrate to ensure satisfactory adhesion between the substrates, which may be metal substrates, thermoplastic composite substrates, aramid film substrates, prepreg substrates, among others.

[0087] The shaped articles described herein can be produced from the composition (C) of the present invention by injection molding, extrusion, compression molding, additive manufacturing (also known as three-dimensional (3D) printing, where the shaped articles may also be referred to as 3D objects or 3D parts), coating, continuous fiber impregnation and continuous fiber composite lamination / consolidation or other molding techniques.

[0088] In some embodiments, the method for producing a shaped article or part thereof comprises a step of compression molding or injection molding the composition (C) of the present invention followed by a step of consolidation.

[0089] In some embodiments, the method of producing a shaped article or a shaped article or part thereof includes a coating step. For example, the composition (C) of the present invention can be applied as a coating to a wire by using any suitable coating method, preferably by extrusion coating around the wire to form a coated wire, preferably a coated magnet wire.

[0090] Exemplary embodiments also relate to a method of making a shaped article by additive manufacturing, where the shaped article is printed from a polymer composition (C) of the present invention, also referred to as a "part material." The method includes printing layers of the shaped article from the polymer composition as described below.

[0091] Additive manufacturing systems are used to print or otherwise construct a feature from a digital representation of the feature 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 feature is first sliced ​​into multiple horizontal layers. For each layer, a tool path is then provided, which instructs a particular additive manufacturing system to print the given layer.

[0092] For example, in an extrusion-based additive manufacturing system, a built article can be printed from a digital representation of the article layer-by-layer by extruding and adjoining strips of polymer composition. The polymer composition is extruded through an extrusion tip carried by the system's print head and deposited as a series of tracks onto a platen in the xy plane. The extruded material fuses with 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 xy plane), and the process is repeated to form a built article similar to the digital representation. One 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 in which feedstock can be printed as pellets.

[0093] As another example, in powder-based additive manufacturing systems, a laser is used to locally sinter powder into a solid part. The part is created by sequentially depositing layers of powder and subsequently sintering an image onto the layers with a laser pattern. An example of a powder-based additive manufacturing system is selective laser sintering (SLS).

[0094] As another example, carbon fiber composite parts can be fabricated using continuous fiber reinforced thermoplastic printing (FRTP), a method based on fused deposition modeling (FDM) that prints a combination of fiber and resin.

[0095] Composite material manufacturing method Additional exemplary embodiments relate to methods for producing composite materials comprising impregnating reinforcing fibers with a matrix of the inventive composition (C) described herein, and the composite materials obtained therefrom.

[0096] For example, various methods can be used to impregnate fibers with a matrix of the composition (C) of the present invention, where the matrix is ​​in either molten or particulate form, such as powder coating, film lamination, extrusion, pultrusion, aqueous slurry, and melt impregnation, to form plies in the form of sheets or tapes of fibers at least partially impregnated with a polymer matrix. As used herein, "tape" means a stripe of material having longitudinally extending reinforcing fibers aligned along a single axis of the stripe material.

[0097] Plies of matrix-impregnated fiber can be placed adjacent to one another to form unconsolidated composite laminates, such as prepregs, in which the fiber reinforced layers can be oriented with the respective fiber reinforcements in a selected direction relative to one another.

[0098] The plies can be laid up manually or automatically, for example, by automated tape layup using "pick and place" robotics, or by advanced fiber placement in which tows of pre-impregnated fibers are heated and compressed into a mold or over a mandrel, to form a composite laminate with the desired physical dimensions and fiber orientation.

[0099] The layers of an unconsolidated laminate are typically not completely fused together, and an unconsolidated composite laminate may exhibit a large void content, for example, greater than 20% by volume, as measured by X-ray microtomography. As an intermediate step to allow handling of the composite laminate prior to its consolidation, heat and / or pressure may be applied or sonic vibration welding may be used to stabilize the laminate and prevent the layers from moving relative to one another, for example, to form a composite "blank."

[0100] The composite laminate so formed is then typically consolidated, for example, by subjecting the composite laminate to heat and pressure in a mold to form a molded fiber-reinforced thermoplastic matrix composite article. If desired, a tie layer made from the composition (C) of the present invention can be used to bond the layers of the unconsolidated laminate. Such a tie layer can be provided as a free-standing film made from the composition (C) of the present invention, or it can be provided in the form of a coating applied to at least one surface of the layers of the unconsolidated composite laminate that are to be assembled and then consolidated.

[0101] As used herein, "consolidation" refers to a process in which the matrix material is softened, the layers of the composite laminate are pressed together, air, moisture, solvents, and other volatiles are forced out of the laminate, and adjacent plies of the composite laminate are fused together to form a solid, coherent article. Ideally, a consolidated composite article exhibits minimal porosity, e.g., less than 5% by volume, more typically less than 2% by volume, as measured by X-ray microtomography.

[0102] The composite material of the present invention preferably contains 20 to 80% by weight of reinforcing fibers and 80 to 20% by weight of the matrix of the composition (C) of the present invention, based on the weight of the composite material.

[0103] Assembly manufacturing method An additional exemplary embodiment relates to a method for producing an assembly comprising a first substrate layer and a second substrate layer, the method comprising placing a bonding layer made from composition (C) of the present invention between and in contact with the first substrate and the second substrate, and the resulting assembly.

[0104] One or both of the substrate layers bonded by the bonding layer may be, for example, a sheet or a thin film. The substrate layer may be made of any suitable material, such as metal, plastic (thermoplastic or thermosetting resin), ceramic, glass, or a composite material, particularly including the composite materials described above. The thickness of the thin film or sheet may be appropriately selected and may be, for example, about 0.01 to about 10 mm.

[0105] Suitable crystalline and / or high temperature thermoplastic resins that may be included in the plastic substrate layer include, but are not limited to, polyaryletherketones (such as crystalline polyetherketone (PEK), crystalline polyetheretherketone (PEEK), crystalline polyetherketoneketone (PEKK), polyetheretheretherketone (PEEEK), polyetheretherketoneketone (PEEKK), polyetherketoneetheretherketone (PEKEKK), and polyetherketoneketoneketone (PEKKK)), polyimides, polyetherimides, polyamideimides, polysulfones, polyethersulfones, polyarylethers, polycarbonates, liquid crystal polymers, polyphenylene sulfides, polyarylenes (polyphenylenes), polyamides, polyphthalamides, polyaromatic esters, and the like.

[0106] In another embodiment, at least one of either the first substrate layer or the second substrate layer is a metal, such as a metal sheet or foil, etc. The substrate may be composed of any suitable metal or metal alloy, such as steel, aluminum, an aluminum alloy, copper, gold, silver, etc.

[0107] The assemblies of the present invention, particularly when the substrate layer components are melt-processable thermoplastic resins, can be produced by coextrusion into any conventional form, including films, plates, sheets, tubes, or any other shape conventionally obtained by coextrusion.

[0108] Compression molding, intermittent matched die consolidation, double-belt press consolidation, composite roll molding, transfer molding, and other such techniques can also be utilized in connection with the present invention. For example, an assembly can be made by placing a sheet or film made from the composition (C) of the present invention (corresponding to the intended tie layer) between a first substrate layer and a second substrate layer, and heating the resulting "sandwich" at a temperature effective to sufficiently soften at least one layer to cause it to flow and adhere to the adjacent layer, thereby forming an adhesive bond when the assembly is cooled. Typically, it is desirable to apply pressure to the "sandwich" to enhance the degree of adhesion achieved between the tie layer and the substrate layer. Thermoforming of the assembly may also be performed to obtain a specific desired shape or configuration.

[0109] The assemblies of the present invention can be used in any end use where such laminates or composites are conventionally used or proposed for use. Typical applications include composites and laminates (such as two-dimensional and three-dimensional panels and sheets) for aerospace / aircraft, automobiles and other vehicles, boats, machinery, heavy equipment, storage tanks, pipes, sporting goods, tools, biomedical devices (such as devices implanted in the human body), building components, wind blades, and the like.

[0110] If the disclosure of any patent, patent application, or publication incorporated herein by reference contradicts the statement of this application to the extent that it may render a term unclear, the statement shall control. [Example]

[0111] The present disclosure will now be described in more detail with reference to the following examples, the purpose of which is illustrative only and is not intended to limit the scope of the present disclosure.

[0112] Section I: Synthesis of PEKK Polymers and Exemplary Compositions Produced by Solution Blending The following examples demonstrate the synthesis of PEKK copolymers and their thermal and mechanical properties.

[0113] raw materials 1,2-Dichlorobenzene, terephthaloyl chloride, isophthaloyl chloride, 3,5-dichlorobenzoyl chloride, aluminum chloride (AlCl3), and methanol were purchased from Sigma Aldrich.

[0114] 1,4-bis(4-phenoxybenzoyl)benzene was prepared according to IN Patent 193687, filed June 21, 1999, which is incorporated herein by reference.

[0115] Diphenyl sulfone (polymer grade) (99.8% purity) was sourced from Proviron.

[0116] Sodium carbonate, light ash, was procured from Solvay SA, France and dried before use. Its particle size was determined by its d 90 was 130 μm.

[0117] d 90 Potassium carbonate with a particle size of <45 μm was sourced from Armand products and dried before use.

[0118] Lithium chloride (anhydrous powder) was sourced from Acros.

[0119] NaH2PO4·2H2O and Na2HPO4 were purchased from Sigma-Aldrich.

[0120] 1,4-bis(4'-fluorobenzoyl)benzene (1,4-DFDK) and 1,3 bis(4'-fluorobenzoyl)benzene (1,3-DFDK) were prepared by Friedel-Crafts acylation of fluorobenzene according to Example 1 of U.S. Pat. No. 5,300,693 to Gilb et al., filed Nov. 25, 1992, incorporated herein by reference in its entirety. A portion of the 1,4-DFDK was purified by recrystallization in chlorobenzene as described in U.S. Pat. No. 5,300,693, and a portion of the 1,4-DFDK was purified by recrystallization in DMSO / ethanol. 1,4-DFDK purified by recrystallization in DMSO / ethanol was used as the 1,4-DFDK in the polymerization reaction to produce PEKK described below, and 1,4-DFDK recrystallized in chlorobenzene was used as the precursor to 1,4-bis(4'-hydroxybenzoyl)benzene (1,4-BHBB).

[0121] 1,4-BHBB and 1,3-bis(4'-hydroxybenzoyl)benzene (1,3-BHBB) were prepared by hydrolysis of 1,4-DFDK and 1,3-DFDK, respectively, according to the procedure described in Example 1 of U.S. Patent No. 5,250,738 to Hackenbruch et al., filed February 24, 1992, which is incorporated herein by reference in its entirety. They were purified by recrystallization in DMF / ethanol.

[0122] Determination of Melt Flow Index The melt flow index was determined according to ASTM D1238 at the indicated temperatures (340-380 °C depending on the melting point of the material) using a 3.8 kg load. The final MFI at an 8.4 kg load was obtained by multiplying the obtained value by 2.35.

[0123] Determination of glass transition temperature, melting point and heat of fusion Glass transition temperature T g (midpoint using half-value method) and melting point T mwas determined in the second heating scan in a differential scanning calorimeter (DSC) according to ASTM D3418-03, E1356-03, E793-06, E794-06, and further details below. The details of the procedure used in this invention are given below: A TA Instruments DSC Q20 was used with nitrogen (99.998% purity, 50 mL / min) as the carrier gas. Temperature and heat flow calibration was performed using indium. Sample size was 5-7 mg. Sealed pans were used. Weights were recorded to ±0.01 mg. The heating cycle was as follows: First heating scan: 30.00°C to 400.00°C at 20.00°C / min, isothermal at 400.00°C for 1 minute, First cooling scan: 400.00°C to 30.00°C at 20.00°C / min, isothermal for 1 minute, Second heating scan: 30.00°C to 400.00°C at 20.00°C / min, isothermal at 400.00°C for 1 min.

[0124] Melting point T m was determined as the peak temperature of the melting endotherm in the second heating scan. The melting enthalpy was measured in the second heating scan and T g The crystallization temperature (T c ) was determined as the peak temperature of the crystallization exotherm in the first cooling scan. The possible presence of cold crystallization was determined from the second heating scan: the presence of an exotherm before the onset of the endothermic melting peak was clearly confirmed when an exothermic heat flow of more than 0.5 J / g was observed.

[0125] Determination of elemental impurities such as aluminum in polymer compositions by ICP-OES A clean, dry platinum crucible was placed on an analytical balance and the balance was zeroed. Three grams of half of the polymer sample was weighed into a boat, and the weight was recorded to the nearest 0.0001 g. The crucible with the sample was placed in a muffle furnace (Thermo Scientific Thermolyne F6000 Programmable Furnace). The furnace was gradually heated to 525°C and held at that temperature for 10 hours to dry ash the sample. After ashing, the furnace was cooled to room temperature, the crucible was removed from the furnace, and placed in a fume hood. The ash was dissolved in dilute hydrochloric acid. Using a polyethylene pipette, this solution was transferred to a 25 mL volumetric flask. The crucible was rinsed twice with approximately 5 mL of ultrapure water (R<18 MΩcm), and the rinse was added to the volumetric flask to perform the quantitative transfer. Ultrapure water was added to the flask to bring the total to 25 mL. The flask was capped with a stopper and shaken to ensure the contents were mixed.

[0126] ICP-OES analysis was performed using a Perkin-Elmer Optima 8300 Dual View inductively coupled plasma optical emission spectrometer. The spectrometer was calibrated using a set of NIST-traceable multi-element mixed standards with analyte concentrations ranging from 0.0 to 10.0 mg / L. Linear calibration curves were obtained for each of the 48 analytes over the concentration range with correlation coefficients better than 0.9999. Standards were run before and after every 10 samples to ensure instrument stability. Results were reported as the average of triplicate experiments. The concentrations of elemental impurities in the samples were calculated using the following formula: A = (B * C) / (D). (where: A = concentration of the element in the sample, mg / kg (= ppm by weight), B = element in solution analyzed by ICP-OES, mg / L; C = volume of solution analyzed by ICP-OES, mL; D = sample weight in grams used in this procedure).

[0127] Determination of fluorine concentration in polymers by combustion ion chromatography For combustion ion chromatography (IC) analysis, a clean, pre-fired, dry ceramic sample boat was placed on an analytical balance and the balance was zeroed. Approximately 20 mg of polymer sample was weighed into the boat and the weight was recorded to the nearest 0.0001 g. The sample boat was then placed in a combustion furnace set at an inlet temperature of 900 °C and an outlet temperature of 1000 °C. The combusted sample and argon carrier gas were passed through 18.2 MΩ ultrapure water and automatically injected into an IC system equipped with a conductivity detector.

[0128] 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 4 mm suppressor set at 50 mA, and a GA-210 gas absorption unit, HF-210 furnace, and ABC-210 boat controller (all manufactured by Mitsubishi Analytech).

[0129] The elution gradient for this method is as follows: 0–10 min: 10 mM KOH 10-15 min: Steady and constant increase to 20 mM KOH 15-30 min: 20 mM KOH

[0130] The equipment is F - The instruments were calibrated using a three-point calibration from a NIST-traceable seven-anion mixture supplied by AllTech, with analyte concentrations ranging from 0.1 to 3.0 mg / L. Linear calibration curves were obtained over the entire range of concentrations with correlation coefficients better than 0.9999 for each analyte. Prior to analyzing samples, control samples were analyzed to ensure the instrument was operating accurately. The concentrations of anions in the samples were calculated using the following formula: A=(B*C) / (D): A = concentration of the element in the sample, mg / kg B = anions in the solution analyzed by IC, mg / L; C = volume of solution analyzed by IC, mL; D = sample weight used in this procedure, mg

[0131] Comparative Preparation Example 1 Preparation of electrophilic PEKK (e-PEKK) with T / I=72 / 28 A 2000 mL four-neck reaction flask equipped with a stirrer, a dry N2 inlet tube, a thermocouple inserted into the reaction medium, and a condenser was charged with 1000 g of 1,2-dichlorobenzene and 40.63 g of 1,4-bis(4-phenoxybenzoyl)benzene. Then, under a dry nitrogen sweep, 7.539 g of terephthaloyl chloride, 9.716 g of isophthaloyl chloride, and 0.238 g of benzoyl chloride were added to the reaction mixture. The reactor was then cooled to -5°C, and 71.88 g of aluminum chloride (AlCl3) was slowly added while maintaining the temperature below 5°C. The reaction was held at 5°C for 10 minutes, and then the temperature of the mixture was increased to 90°C at 5°C / min. The reaction mixture was held at 90°C for 30 minutes and then cooled to 30°C. At 30°C, 250 g of methanol was slowly added to maintain the temperature below 60°C. After the addition was complete, the reaction mixture was allowed to continue stirring for 2 hours and 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 an additional 188 g of methanol. The wet cake was then reslurried in a beaker with 440 g of methanol for 2 hours. The polymer solids were again filtered 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 (3.5 wt%) aqueous hydrochloric acid for 2 hours. The solids were then removed by filtration on a Buchner funnel. The wet cake was rinsed on the filter with an additional 280 g of water. The wet cake was then reslurried in a beaker with 250 g of 0.5 N aqueous sodium hydroxide for 2 hours. The wet cake was then reslurried in a beaker with 475 g of water and filtered on a Buchner funnel. The final water wash step was repeated three more times. The polymer is then slurried with 0.75 g of an aqueous solution containing 6.6 wt % NaH2PO4.2H2O and 3.3 wt % Na2HPO4, and then 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.

[0132] [Table 1]

[0133] Comparative Preparation Examples 2-4: e-PEKK of different molecular weights, T / I=60 / 40 and 82 / 18 The same procedure as in Example 1 was followed, but with the amounts of reagents shown in the table below.

[0134] Table 1: Comparative Preparation Examples 2-4

[0135] Preparation Example 5: Synthesis of nucleophilic PEKK (n-PEKK) 71 / 29 low MV A 500 mL four-neck reaction flask equipped with a stirrer, a N2 inlet tube, a Claisen adapter with a thermocouple immersed in the reaction medium, and a Dean-Stark trap with a condenser and dry ice trap was charged with 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. The flask contents were evacuated under vacuum and then filled with high-purity nitrogen (containing less than 10 ppm O2). The reaction mixture was then placed under a constant nitrogen purge (60 mL / min). The reaction mixture was slowly heated to 270 °C. At 270 °C, 13.725 g of Na2CO3 and 0.078 g of K2CO3 were added to the reaction mixture from a powder dispenser over 60 minutes. At the end of the addition, the reaction mixture was heated to 310 °C at 1 °C / min. After 2 minutes at 310°C, 1.107g of 1,4-DFDK was added to the reaction mixture while maintaining a nitrogen purge in the reactor. After 5 minutes, 0.741g of lithium chloride was added to the reaction mixture. After 10 minutes, another 0.402g of 1,4-DFDK was added to the reactor, and the reaction mixture was held at temperature for 15 minutes. An additional 15g of diphenyl sulfone was charged to the reaction mixture, which was held under stirring for 15 minutes.

[0136] The reactor contents were then poured from the reactor into a stainless steel pan and allowed to cool. The solids were crushed and ground in an attrition mill through a 2 mm screen. Diphenyl sulfone and salts were extracted from a mixture of acetone and water at pH 1-12. For the final wash, 0.67 g of NaH2PO4·2H2O and 0.62 g of Na2HPO4 were dissolved in 1200 mL of DI water. The powder was then removed from the reactor and dried under vacuum at 120 °C for 12 hours, yielding 72 g of a yellow powder.

[0137] Preparative Examples 6-13: Synthesis of Nucleophilic PEKK (n-PEKK) with Variable T / I and / or Different Melt Viscosities (MV) The same procedure as in Example 5 was followed, but with the amounts of reagents shown in the table below.

[0138] [Table 2]

[0139] [Table 3]

[0140] Basic Procedure for Solution Blending Various PEKKs A 500 mL, four-neck reaction flask equipped with a stirrer, a N2 inlet tube, a Claisen adapter with a thermocouple immersed in the reaction medium, and a condenser was charged with 235.00 g of diphenyl sulfone (DPS) and optional boron nitride (see Table 3). The contents of the flask were slowly heated to 330°C. At 330°C, 100 g of a blend of polymer powders in the proportions shown in Table 3 was slowly added via a flex tube to the molten DPS. At the end of the addition, the stirring speed was increased to ensure good mixing, and the mixture was held at 330°C for an additional hour.

[0141] The reactor contents were then poured from the reactor into a stainless steel pan and allowed to cool. The solids were crushed and ground in an attrition mill through a 2 mm screen. Diphenyl sulfone was extracted from the mixture using acetone and water. For the final wash, 0.67 g of NaH2PO4·2H2O and 0.62 g of Na2HPO4 were dissolved in 1200 mL of DI water. The powder was then removed from the reactor and dried under vacuum at 120 °C for 12 hours, yielding 90–95 g of a yellow powder.

[0142] [Table 4]

[0143] The thermal properties (DSC at 20°C / min up to 400°C) of copolymers (Examples 7-13) and solution blends of n-PEKK (Examples 17-21) with different T / I ratios are shown in Table 4. In the table, T g is the glass transition temperature, Tm is the melting point, and T c is the crystallization temperature, and Equation 1 is the inequality: T c ≧1.3716*T m -190°C; T in Eq. c *min is the theoretical minimum T corresponding to the measured Tm so as to satisfy the above inequality. c and T c * min =1.3716*T m -190°C. In Table 4, the measured T c ≧T c * min When, or measured T c ≧1.3716*T m At -190°C, the test is marked as Y (pass) as it meets the criteria of Equation 1. In the low-temperature crystallization test, if an exotherm of more than 0.5 J / g is measured, the test result is marked as "Y (fail)" and if no detectable exotherm is measured, the test result is marked as "N (pass)."

[0144] [Table 5]

[0145] As shown by the data collected above, the copolymer PEKK itself, which has a lower melting point, is generally less crystalline and exhibits low-temperature crystallization behavior, with T as an indicator of slow crystallization rates. c and T m The copolymer PEKK itself, which has a higher melting point, has inherently poor processability and, although it has adequate crystallinity, also has a slow crystallization rate, indicating a T c and T m In contrast, the above data, also shown in Figure 1, shows that the blends according to the present invention have a large gap between the T m higher T than copolymers with c and the heat of fusion ΔH f This clearly demonstrates that the blends of the present invention have a higher crystallization rate (higher T c ) and the appropriate final crystal fraction (ΔH f Improved processing (its low T kept below 330°C) combined with m Overall, the blends according to the invention exhibit: T m <330℃ Heat of fusion ΔH f >25J / g No low-temperature crystallization peak in the second heating scan ·T that satisfies the following formula c T c ≧1.3716*T m -190℃ [Formula 1] (T m and T c has the meaning given above).

[0146] The data presented in Table 5 below further demonstrates that while nucleophilic PEKK is used, these beneficial effects are only achieved with the blend. Table 5 compares the performance obtained with Example 14 (a blend of nPEKK from Example 6 and nPEKK from Example 5) against the poor results obtained with the ePEKK blend.

[0147] [Table 6]

[0148] The data presented in Table 5 below further demonstrate that while nucleophilic PEKK is used, these beneficial effects are only achieved through blending. Table 5 compares the performance obtained with closely related ePEKK blends, particularly Example 14 (a blend of nPEKK T / I=58 / 42 from Example 6 and nPEKK T / I=71 / 29 from Example 5), to the poor results obtained with Example 16C (a blend of 85% ePEKK T / I=60 / 40 from Example 2CP and 15% ePEKK T / I=71 / 28 from Example 1CP). Example 16C achieves too low a crystallinity (19 J / g), resulting in cold crystallization, an indicator of a slow crystallization rate. Example 15C also has some shortcomings, due to a gap between the melting point and crystallization temperature that is too wide to allow for effective crystallization, providing clear evidence that the nature of the nucleophilic form of PEKK used is key to achieving an optimized property compromise.

[0149] General Procedure for Preparing the Compositions of the Invention by Melt Blending The compositions in the following series of examples were prepared by melt blending in a twin-screw extruder, the details of which are described in detail below. The PEKK starting material was an n-PEKK polymer, the preparation of which is described above.

[0150] raw materials: n-PEKK Example 6P: T / I=58 / 42 High MV n-PEKK Example 7P: T / I=58 / 42 Low MV n-PEKK Example 9P: T / I=61 / 39 n-PEKK Example 5P: T / I=71 / 29 PEEK: KT-880UFP, a low-viscosity grade PEEK polymer commercially available from Solvay Specialty Polymers, has a melt viscosity in the range of 0.12 to 0.18 kPa-s when measured according to ASTM D3835 at a temperature of 400°C and a shear rate of 10,000 l / s using a capillary die with a length of 3.175 mm, a length of 0.5 mm, and an entrance angle of 120°. Boron nitride: Boronid® S1-SF, a hexagonal boron nitride grade commercially available from 3M Corporation

[0151] Blend Preparation 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 (L / D) ratio of 30. The components, all in either powder or pellet form, were first tumble blended in each case according to the compositional ratios shown in the tables of the following examples. Tumble blending was performed for approximately 20 minutes, followed by melt compounding using the extruder described above. The extruder had six barrel sections, with barrel sections 2 through 6 being heated. During compounding, barrel section 5 was vacuum vented at a vacuum level exceeding 25 in Hg to strip the compound of moisture and any possible residual volatiles. The extrudate, in each case, was stranded on a conveyor belt, air-cooled, and fed to a pelletizer, where it was cut into pellets approximately 3 mm in diameter and approximately 3 mm in length. Other compounding conditions were as follows: barrel sections 2 through 6 and the die section were heated to 360°C. The extruder was operated at a screw speed of about 200 rpm, with a throughput rate of about 6 lb / hr.

[0152] Table 6: Examples showing blends of PEKK (Example 9P) T / I=61 / 39 with the addition of PEKK from Example 5P compared to the addition of another polyaryletherketone polymer.

[0153] [Table 7]

[0154] Table 7: Examples showing the addition of boron nitride to a blend of PEKK (Example 6P) T / I=58 / 42 with PEKK (Example 5P) according to the invention and to a single PEKK as a comparison

[0155] [Table 8]

[0156] Table 8: Examples according to the invention showing modification of PEKK (Example 7P) T / I=58 / 42 with PEKK (Example 5P) with and without boron nitride

[0157] [Table 9]

[0158] Table 9: Examples showing blends of PEKK (Example 7P) T / I=58 / 42 with PEKK (Example 5P) according to the invention

[0159] [Table 10]

[0160] [Table 11]

Claims

1. A composition [composition (C)] comprising: - repeating unit (R Ｔ ) and repeating units (R Ｉ ) and the unit (R Ｔ ) first molar content [(T ｌｏｗ )] and units (R Ｉ ) first molar content [(I ｌｏｗ a major amount of a first PEKK polymer [polymer (PEKK )]; ｌｏｗ ) ], [Equation 1] and [Equation 2] and First T / I ratio [(T / I) ｌｏｗ ]but [Equation 3] is defined as Repeating unit (R Ｔ ) is represented by the formula (T): 【number】 is expressed as Repeating unit (R Ｉ ) is a compound of formula (I): 【number】 is expressed as During the ceremony: - Each R １ and R ２ is independently selected at each occurrence from the group consisting of alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali metal or alkaline earth metal sulfonate, alkyl sulfonate, alkali metal or alkaline earth metal phosphonate, alkyl phosphonate, amine, and quaternary ammonium; and each i and j, at each occurrence, is an independently selected integer ranging from 0 to 4; The first PEKK polymer [polymer (PEKK ｌｏｗ )];and - the repeating unit (R Ｉ ) and the repeating unit (R Ｔ ) and the unit (R Ｔ ) the second molar content [(T ｈｉｇｈ )] and units (R Ｉ ) the second molar content [(I ｈｉｇｈ a minor component amount of a second PEKK polymer [polymer (PEKK ｈｉｇｈ ) ], [Equation 4] and [Equation 5] and The second T / I ratio [(T / I) ｈｉｇｈ ]but [Equation 6] a second PEKK polymer [polymer (PEKK ｈｉｇｈ ) ]; A composition [composition (C)] comprising: Polymer (PEKK ｌｏｗ ) is a nucleophilic PEKK; PEKK ｌｏｗ (T / I) ｌｏｗ PEKK ｈｉｇｈ (T / I) ｈｉｇｈ Less than The following inequality: T ｈｉｇｈ -T ｌｏｗ ≦17 mol% Fulfilling - said polymer (PEKK low ) has a (T / I) low of at most 64 / 36; and said polymer (PEKK high ) has a (T / I) high of at least 65 / 35; Composition [Composition (C)].

2. 10. The composition of claim 1, wherein the composition comprises: Melting point (T ｍ ); Heat of fusion (ΔH) greater than 25 J / g ｆ ); - No crystallization peak upon heating ("low-temperature crystallization peak") in the second DSC heating scan Melting point (T in °C) determined in the second DSC heating scan ｍ ) and the crystallization temperature (T in °C) determined by the first DSC cooling scan. ｃ ) satisfies the following inequality: T ｃ ≧1.3716×T ｍ -190℃ (In the formula, T ｍ , T ｃ , ΔH ｆ , and the absence of a low-temperature crystallization peak is measured by differential scanning calorimetry (DSC) in accordance with ASTM D3418-03, E1356-03, E793-06, E794-06 standards, applying a heating and cooling rate of 20°C / min in a sweep from 30°C to 400°C.

3. The repeating unit (R Ｔ ) and (R Ｉ 3. The composition (C) according to claim 1 or 2, wherein each of the formulas (T′) and (I′) is represented by the formula (T′): 【Transformation 3】 。

4. The polymer (PEKK ｌｏｗ ) and the polymer (PEKK ｈｉｇｈ ) are collectively called polymer (PEKK), The polymer (PEKK) has a repeating unit (R Ｔ ) and repeating units (R Ｉ ) in a total amount of at least 60 mole %, said mole % being based on the total number of moles in said polymer (PEKK); and / or - The polymer (PEKK) has a repeating unit (R Ｔ ) and repeating units (R Ｉ ), which may contain repeating units different from those of the following formulae (JA) and (JC) to (JO): 【Chemistry 4】 【Transformation 5】 【Transformation 6】 (In the formula, each R', whether equal to or different from one another, is selected from the group consisting of halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkyl sulfonate, alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine, and quaternary ammonium; j' is an integer from 0 to 4. The composition (C) according to any one of claims 1 to 3, selected from the group consisting of:

5. - the polymer (PEKK ｌｏｗ ) contains fluorine in an amount greater than 100 ppm, preferably greater than 200 ppm, more preferably greater than 300 ppm, and / or contains Al in an amount less than 50 ppm, preferably less than 25 ppm, more preferably less than 10 ppm, the Al and F content being determined by elemental analysis such as ICP-OES analysis for Al and combustion ion chromatography for fluorine; and / or - the polymer (PEKK ｌｏｗ ) has a 1 wt. % thermal decomposition temperature T of at least 500°C, preferably at least 505°C, and more preferably at least 510°C, as measured by thermogravimetric analysis according to ASTM D3850, heating from 30°C to 800°C under nitrogen using a heating rate of 10°C / min. ｄ (1%); The composition (C) according to any one of claims 1 to 4.

6. - the polymer (PEKK ｌｏｗ ) is at least 50 / 50, preferably at least 54 / 46, more preferably at least 56 / 44, and most preferably at least 57 / 43 (T / I) ｌｏｗ and / or having a (T / I) of at most 63 / 37, more preferably at most 62 / 38 ｌｏｗ and more preferably, the polymer (PEKK ｌｏｗ ) is 57 / 43 to 62 / 38 (T / I) ｌｏｗ and / or - the polymer (PEKK ｈｉｇｈ ) is at least 66 / 34, more preferably at least 67 / 33 (T / I) ｈｉｇｈ and / or (T / I) of at most 75 / 25, preferably at most 73 / 27, more preferably at most 72 / 28 ｈｉｇｈ and more preferably, the polymer (PEKK ｈｉｇｈ ) is included in 67 / 33 to 72 / 28 (T / I) ｈｉｇｈ and / or - Polymer (PEKK ｌｏｗ ) and polymer (PEKK ｈｉｇｈ ) but T ｈｉｇｈ -T ｌｏｗ ≦16 mol %, more preferably T ｈｉｇｈ -T ｌｏｗ ≦15 mol %, and / or T ｈｉｇｈ -T ｌｏｗ ≧3 mol%, more preferably T ｈｉｇｈ -T ｌｏｗ ≧4 mol%, more preferably T ｈｉｇｈ -T ｌｏｗ ≥ 5 mol%; The composition (C) according to any one of claims 1 to 5.

7. The polymer (PEKK ｈｉｇｈ 7. Composition (C) according to any one of claims 1 to 6, wherein (C) is a nucleophilic PEKK and has a fluorine content of more than 100 ppm, preferably more than 200 ppm, and more preferably more than 300 ppm, and / or an Al content of less than 50 ppm, preferably less than 25 ppm, and more preferably less than 10 ppm, the Al and F contents being determined by elemental analysis such as ICP-OES analysis for Al and combustion ion chromatography for fluorine.

8. Polymer (PEKK ｌｏｗ ) and polymer (PEKK ｈｉｇｈ 8. Composition (C) according to any one of claims 1 to 7, wherein the weight ratio between the hydroxybenzoates (H2O3) and the hydroxybenzoates (H2O4) is at least 60 / 40, preferably at least 65 / 35, more preferably at least 70 / 30, even more preferably at least 75 / 25, and / or at most 99 / 1, preferably at most 97 / 3, even more preferably at most 96 / 4.

9. - further comprising at least one nitride (NI) of an element with an electronegativity (ε) between 1.3 and 2.5; and / or - further comprising one or more additional components different from nitrides (NI) 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, antiblocking agents, thermally and electrically and magnetically conductive materials (i.e. materials that can be useful for induction heating), reinforcing fibrous additives and reinforcing non-fibrous additives; The composition (C) according to any one of claims 1 to 8.

10. Polymer (PEKK ｌｏｗ ) and polymer (PEKK ｈｉｇｈ ) is 60% by weight or more, preferably 70% by weight or more, more preferably 80% by weight or more, more preferably 85% by weight or more, and most preferably 90% by weight or more, based on the total weight of the composition (C) of the present invention; and / or - composition (C) is a polymer (PEKK ｌｏｗ ) and polymer (PEKK ｈｉｇｈ ) other than the other polyaryletherketone polymer [polymer (PAEK)], and polymer (PAEK) does not include polymer (PEKK) ｌｏｗ ) but polymer (PEKK ｈｉｇｈ ), and more than 50% by mole of the repeating units are Ar ＊ —C(O)—Ar ＊ A repeating unit containing a ' group (R ＊ ＰＡＥＫ ) a polymer (Ar ＊ and Ar ＊ ' are the same or different and are aromatic groups; and / or - composition (C) is a polymer (PEKK ｌｏｗ ) and polymer (PEKK ｈｉｇｈ consisting essentially of composition (C) further comprises at least one nitride (NI) of an element having an electronegativity (ε) of 1.3 to 2.5, the total weight of said nitrides (NI) in said composition (C) being at least about 0.1 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 said composition (C); The composition (C) according to any one of claims 1 to 9.

11. Polymer (PEKK ｌｏｗ ), polymer (PEKK ｈｉｇｈ 11. A method for producing composition (C) according to any one of claims 1 to 10, comprising mixing a mixture of the above-mentioned components, optionally with other ingredients, wherein the mixing can be carried out by dry (or powder) blending, suspension or slurry mixing, solution mixing, melt mixing, or any combination thereof.

12. A shaped article comprising the composition (C) according to any one of claims 1 to 10.

13. 13. A method for producing a shaped article according to claim 12, comprising processing 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 a combination thereof.

14. A method for producing a composite material, comprising impregnating reinforcing fibers with a matrix of the composition (C) according to any one of claims 1 to 10.

15. A method for producing an assembly comprising a first substrate layer and a second substrate layer, the method comprising placing a bonding layer made from composition (C) according to any one of claims 1 to 10 in contact between the first substrate and the second substrate.

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