Ductile compositions based on polyaryl ether ketone(s)

Description

1 / 56 DUCTILE COMPOSITIONS BASED ON POLYARYL ETHER KETONE(S) Technical field

[0001] This patent application relates to a polymer composition based on polyaryletherketone(s) exhibiting improved impact resistance, elongation at break and malleability. It also refers to a method for manufacturing such a composition in granular form, as well as its use. State of the art

[0002] Polyaryletherketones (PAEKs) are well-known high-efficiency technical polymers. They can be used for applications that are temperature and / or mechanically and even chemically restrictive. They can even be used for applications requiring excellent fire resistance and low emission of smoke or toxic gases. They can also be used due to their low gas permeability. Finally, they exhibit good biocompatibility.

[0003] These polymers are found in a variety of sectors, such as the aerospace industry, offshore drilling, the automotive, rail, maritime, wind, sports, construction, and electronics industries, and even in medical implants.

[0004] Despite these advantageous properties, it is sometimes necessary to formulate polyaryletherketones to meet particular specifications. Therefore, greater malleability may be sought to accommodate new uses and installation of parts with greater bending potential. In particular, formulations of more ductile polyaryletherketones are needed, i.e., with greater deformation at break and / or a lower tensile / flexural modulus and / or greater impact resistance, compared to an unformulated PAEK. Petition 870250078433, dated 03 / 09 / 2025, page 9 / 89 2 / 56

[0005] Document EP 3 749 714 A1 discloses compositions consisting of a mixture of polyetherketone-ketone (PEKK), 3.75% to 7.5% by weight of a polysiloxane / polyetherimide block copolymer, and 3.5% to 7% by weight of polydimethylsiloxane. Although they effectively provide greater deformation at break, these compositions exhibit a lower tensile modulus and greater impact resistance compared to an unformulated PEKK. The introduction of polydimethylsiloxane in high proportions can often result in a highly viscous liquid that is difficult to handle and introduce in a properly controlled proportion. Furthermore, the addition of polydimethylsiloxane to a composition tends to decrease its barrier properties, especially its low permeability to gases such as CO2.

[0006] US patent 2009 / 0234060 A1 also discloses compositions consisting of a mixture of polyetheretherketone (PEEK) and polysiloxane / polyetherimide block copolymer with increased impact resistance. More precisely, non-delaminating mixtures of PEEK containing 10% to 25% by weight of polysiloxane / polyetherimide block copolymer, containing 20% ​​to 30% by weight of polysiloxane, could be manufactured (see in particular Table 2 of the patent document). On the other hand, it was demonstrated that it was impossible to manufacture a non-delaminating PEEK mixture containing 10% by weight of a polysiloxane / polyetherimide block copolymer, itself containing 40% by weight of siloxane (comparative example CE-4).

[0007] Furthermore, the inventors of the present invention realized that the use of a PEEK such as PAEK in the composition implies heating the composition to a temperature at which polysiloxane / polyetherimide block copolymers can thermally degrade, which is undesirable, especially in methods where the composition Petition 870250078433, dated 03 / 09 / 2025, p. 10 / 89 3 / 56 remains molten for a sufficiently long period, in particular from 1 minute to 25 minutes and particularly from 5 minutes to 20 minutes, at a temperature above the melting temperature of PAEK.

[0008] There is therefore currently a need to provide PAEK(s)-based compositions that exhibit improved impact resistance, higher elongation at break and / or a lower elastic modulus, which would overcome one or more disadvantages of compositions according to the prior art. For numerous applications, it is also preferable that PAEK(s) compositions retain the advantageous properties of unformulated PAEKs, particularly crystalline unformulated PAEKs. These advantageous properties include good chemical resistance, good temperature resistance and / or low gas permeability. Objective of the invention

[0009] One objective of the invention is to propose a composition based on polyaryletherketone(s) exhibiting improved impact resistance and / or greater elongation at break and / or a lower elastic modulus, compared to an unformulated polyaryletherketone.

[0010] Another objective of the invention is to propose such a composition that is thermally stable in the molten state, including for long residence times in the molten state.

[0011] Another objective, at least in certain forms, is to propose such a composition that is capable of manufacturing thick parts, articles or coatings.

[0012] An additional objective of the invention, at least in certain embodiments, is to provide such a composition that is capable of manufacturing thin parts, articles or coatings.

[0013] Another objective of the invention consists, at least in certain embodiments, in providing a composition with good chemical resistance, good temperature resistance and / or a low Petition 870250078433, dated 03 / 09 / 2025, page 11 / 89 4 / 56 permeation to gases. Summary of the invention

[0014] The present invention relates to granules consisting of a composition C comprising a mixture M of non-delaminating polymers,

[0015] wherein mixture M comprises:

[0016] at least 50% by weight of at least one pseudoamorphous or semicrystalline polyaryletherketone, with said polyaryletherketone having a melting point of less than or equal to 340°C, relative to the total weight of the mixture; and,

[0017] from 5% to 40% by weight of a poly(etherimidasiloxane) copolymer, relative to the total weight of the mixture, it being understood that if mixture M comprises from 5% to 7.5% by weight of a poly(etherimidasiloxane) copolymer, then mixture M does not contain polysiloxane.

[0018] According to certain embodiments, mixture M comprises more than 7.5% by weight, and preferably more than 8% by weight, of the poly(etherimidasiloxane) copolymer, relative to the total weight of the mixture.

[0019] According to certain embodiments, the siloxane groups of the poly(etherimide-siloxane) copolymer represent more than 30% of the total weight of the poly(etherimide-siloxane) copolymer.

[0020] According to certain embodiments, the siloxane groups of the poly(etherimide-siloxane) copolymer represent less than 50% of the total weight of the poly(etherimide-siloxane) copolymer.

[0021] According to certain embodiments, mixture M comprises less than 30%, preferably less than 25% by weight of the poly(etherimide-siloxane) copolymer, relative to the total weight of the mixture.

[0022] According to certain embodiments, polyaryletherketone with a melting point less than or equal to 340°C is a polyether Petition 870250078433, dated 03 / 09 / 2025, p. 12 / 89 5 / 56 ketone-ketone essentially composed of, and preferably composed of:

[0023] a terephthalic unit and an isophthalic unit, the terephthalic unit having the following chemical formula:

[0024] Chemical Formula 1 (I)

[0025] the isophthalic unit has the formula:

[0026] Chemical Formula 2

[0027] a repeating formula unit (III) and a repeating formula unit (IV), wherein the repeating unit (III) has the formula:

[0028] Chemical Formula 3

[0029] and the repeating unit (IV) has the formula:

[0030] Chemical Formula 4

[0031] a formula repeating unit (III) and a formula repeating unit (V), wherein the repeating unit (V) has the formula: Petition 870250078433, dated 03 / 09 / 2025, page 13 / 89 6 / 56 a repeating formula unit (III) and a repeating formula unit (VI), wherein the repeating unit (VI) has the formula:

[0033] Chemical Formula 6

[0034] O(VI) According to certain embodiments, the aforementioned polyaryletherketone with a melting point less than or equal to 340°C is a poly-etherketone-ketone essentially composed of, and preferably composed of:

[0035] a terephthalic unit and an isophthalic unit, the terephthalic unit having the following chemical formula:

[0036] Chemical Formula 7 THE (I)

[0037] the isophthalic unit has the chemical formula:

[0038] Chemical Formula 8 OO ★ (II)

[0039] the molar percentage of terephthalic units in relation to the sum of terephthalic and isophthalic units is less than or equal to 74%, preferably from 0% to 5% or from 45% to 73%, and most preferably from 58% to 72%.

[0040] According to certain embodiments, the said polyaryletherketone with a melting point less than or equal to 340°C has a Petition 870250078433, dated 03 / 09 / 2025, p. 14 / 89 7 / 56 melting point less than or equal to 335°C or less than or equal to 330°C or less than or equal to 325°C or less than or equal to 320°C.

[0041] According to certain embodiments, the said polyaryletherketone with a melting point less than or equal to 340°C has a melting point greater than or equal to 275°C or greater than or equal to 285°C or greater than or equal to 295°C.

[0042] According to certain embodiments, the poly(etherimide-siloxane) copolymer has the following chemical formula:

[0043] Chemical Formula 9 (XV) where n is an integer from 5 to 100, R represents a phenylene, Z represents a bisphenol A residue, R4 represents n-propylene, E represents an integer from 2 to 50, and each R' of the siloxane is a methyl.

[0044] According to certain embodiments, mixture M consists of said polyaryletherketone having a melting point of less than or equal to 340°C, said poly(etherimide-siloxane) copolymer and from 0% to 40% by weight of another thermoplastic polymer different from said polyaryletherketone and said poly(etherimide-siloxane) copolymer, relative to the total weight of the mixture.

[0045] According to certain embodiments, mixture M comprises from 0.1% to 3%, and preferably from 0.5% to 2%, by weight of polysiloxane as the other thermoplastic polymer, relative to the total weight of mixture M.

[0046] According to certain embodiments, mixture M comprises less than 1% by weight of polysiloxane as the other thermoplastic polymer, relative to the total weight of mixture M. Petition 870250078433, dated 03 / 09 / 2025, p. 15 / 89 8 / 56

[0047] According to certain embodiments, composition C comprises at least 70% by weight of mixture M and from 0% to 40% by weight of one or more additives, relative to the total weight of the composition. Composition C may specifically consist of mixture M and from 0% to 40% by weight, preferably from 0% to 30% by weight, of one or more additives, relative to the total weight of the composition. Composition C may particularly comprise from 0.1% to 5% by weight of nucleating fillers (type of additive), such as mineral fillers, in particular talc, carbon-based fillers, in particular carbon nanotubes or carbon blacks, ceramic fillers, in particular boron nitride (BNT), or metal oxides, in particular ZnO or MgO.

[0048] According to certain embodiments, mixture M comprises a polyaryletherketone essentially consisting of, and preferably consisting of: a terephthalic unit and an isophthalic unit, wherein the molar percentage of terephthalic units relative to the sum of terephthalic and isophthalic units is from 0% to 5% or from 45% to 67%.

[0049] According to certain embodiments, the mixture M comprises two polyaryletherketones P1 and P2 with a melting temperature less than or equal to 340°C, where P1 is a semicrystalline polymer with a melting temperature T1, and P2 is a semicrystalline polymer with a melting temperature such that T2 <T1 ou P2 é um polímero pseudoamorfo. O polímero P2 pode representar particularmente pelo menos 50% em peso das poliariletercetonas que têm uma temperatura de fusão menor ou igual a 340°C. De acordo com modalidades particulares, P2 pode ser uma poli-éter-cetona-cetona essencialmente constituída de, e preferencialmente constituída de: uma unidade tereftálica e uma unidade isoftálica, sendo que a porcentagem molar de unidades tereftálicas em relação à soma das unidades tereftálicas e isoftálicas é de 0% a 5% ou de 45% a 67%, e, P1 pode ser uma poli-éter-cetona Petition 870250078433, dated 03 / 09 / 2025, p. 16 / 89 9 / 56 ketone essentially consisting of, and preferably consisting of: a terephthalic unit and an isophthalic unit, wherein the molar percentage of terephthalic units in relation to the sum of terephthalic and isophthalic units is 63% to 73%.

[0050] According to certain embodiments, mixture M comprises two polyaryletherketones P3 and P4, wherein P3 is a semicrystalline or pseudoamorphous polyaryletherketone having a melting point less than or equal to 340°C, preferably less than or equal to 320°C, and P4 is a polyaryletherketone having a melting point strictly above 340°C. Polymer P4 may in particular represent 25% by weight or less, 20% by weight or less, 15% by weight or less, or even 10% by weight or less relative to the total weight of mixture M.According to particular embodiments, polymer P3 may be a polyether-ketone-ketone essentially consisting of, and preferably consisting of: a terephthalic unit and an isophthalic unit, and the molar percentage of terephthalic units relative to the total number of moles of terephthalic and isophthalic units of the polyether-ketone is from 0% to 5% or from 45% to 67%, and polymer P4 may be a polyether-ketone-ketone essentially consisting of, and preferably consisting of: a terephthalic unit and an isophthalic unit, and the molar percentage of terephthalic units relative to the total number of moles of terephthalic and isophthalic units of the polyetherketone-ketone is from 78% to 85%.

[0051] According to certain embodiments, mixture M comprises less than 30%, preferably less than 25% and most preferably less than 20% by weight of the poly(etherimide-siloxane) copolymer, relative to the total weight of the mixture.

[0052] The invention also relates to the use of composition C for the manufacture of an article, part, or coating, at a maximum manufacturing temperature not exceeding 350°C, by molding, in Petition 870250078433, dated 03 / 09 / 2025, p. 17 / 89 Composition C is particularly suitable for manufacturing by injection molding or compression molding, by extrusion, especially film or sheet extrusion, calendering extrusion, tube or pipe extrusion, sheath extrusion, additive manufacturing of fused filaments (FFF), spinning, rotomolding, thermoforming. Composition C is especially suitable for being heated to the maximum manufacturing temperature for a period exceeding 1 minute, 2 minutes, 3 minutes, 4 minutes, 5 minutes, 10 minutes, or 25 minutes. This is particularly advantageous for manufacturing parts, articles, or coatings with a thickness exceeding 2 mm, 3 mm, 4 mm, 5 mm, or 6 mm. In certain embodiments, composition C is then suitable for use in granule form.

[0053] The manufactured article, part or coating may exhibit at least one, and in certain embodiments all, of the advantageous properties indicated below:

[0054] - a tensile modulus of elasticity, as measured by ISO 527-2:2019 / 1A at 20°C, less than 4.0 GPa, preferably less than 3.5 GPa, preferably less than 3.2 GPa, and preferably less than 3.0 GPa,

[0055] - a nominal strain at break as measured by ISO 527-2:2019 / 1A at 20°C greater than 8%, preferably greater than 10%, mainly greater than 15% or greater than 20%,

[0056] - Charpy impact resistance in accordance with the standard ISO 179-1:2010 / 1eA greater than 5 kJ / m2, preferably greater than 6 kJ / m2, preferably even greater than 7 kJ / m2, and most preferably greater than 8 kJ / m2,

[0057] - a yield strength, as measured by ISO 527-2:2019 / 1A:2019 at 20°C, of ​​less than 95 MPa, and preferably less than 85 MPa, Petition 870250078433, dated 03 / 09 / 2025, p. 18 / 89 11 / 56

[0058] - a CO2 permeation measured at 60°C less than 1.1x10-8(cm3.cm) / (cm2.s.bar).

[0059] Furthermore, according to certain embodiments, in the case of a sheath or tube forming a pipe, it is advantageously possible to have a structural flexibility such that the pipe is able to withstand at least 1,000 cycles, wherein, for each cycle, the layer of the polymeric sheath or the C-composition tube undergoes a level of flexural deformation ranging from -2% to +2%, without rupture of the layer of the polymeric sheath or the C-composition tube. Detailed description of the invention Figures

[0060] Figure 1 represents the mass loss of a sample of poly(etherimide-siloxane) copolymer (Siltem® STM 1500) obtained by thermogravimetric analysis (TGA) after heating in a nitrogen atmosphere at different temperatures for 1 hour.

[0061] Figure 2 is a photograph of the outer surface (left) or cross-section (right) of the 7 mm thick strip of composition 1c manufactured in the experimental section.

[0062] Figure 3 is a photograph of the outer surface (left) or cross-section (right) of the 7 mm thick strip of composition 4 manufactured in the experimental section.

[0063] Figure 4 is a photograph of the outer surface (left) or cross-section (right) of the 7 mm thick strip of composition 5 manufactured in the experimental section. Definitions

[0064] The term “thermoplastic polymer” designates a polymer that becomes less viscous, or more liquid, or liquid when heated sufficiently and that reversibly retains its thermoplasticity. Thermoplastic polymers generally differ from thermosetting polymers, as the latter transform irreversibly. Petition 870250078433, dated 03 / 09 / 2025, page 19 / 89 12 / 56 in a network of insoluble and non-formable polymers at high temperatures.

[0065] The term “homopolymer” designates a polymer consisting of a single repeating unit.

[0066] The term “copolymer” designates a polymer derived from the copolymerization of at least two types of chemically different monomers, called comonomers. A copolymer therefore consists of at least two repeating units derived from different monomers. It can also consist of three or more repeating units of different monomers.

[0067] The copolymer may have a homogeneous structure, in particular of the statistical, alternating or random type, or a heterogeneous structure, especially of the sequenced or block type.

[0068] In particular, the term “sequenced copolymer” or “block copolymer” designates copolymers in the sense mentioned above, in which at least two distinct homopolymer blocks are covalently linked. The length of the blocks may vary. The blocks may consist of 1 to 1,000, preferably 1 to 500, preferably 1 to 100, and in particular 1 to 50 repeating units, respectively. The link between the two homopolymer blocks may be: a single covalent bond or an intermediate non-repeating unit called a junction block.

[0069] By “essentially consisting of the unit(s)” it is understood that the unit(s) represent a molar proportion of 95% to 99.9% in relation to the total number of moles of repeating units in the polymer.

[0070] The term “consisting of the unit(s)” means that the unit(s) represent a molar proportion of at least 99.9%, particularly 100%, in the polymer in relation to the total number of moles of repeating units in the polymer.

[0071] It is understood that the term “polymer mixture” does not Petition 870250078433, dated 03 / 09 / 2025, page 20 / 89 13 / 56 “Delaminating” designates a macroscopically homogeneous polymer composition. The term mainly encompasses compositions composed of immiscible phases dispersed on a micrometric or submicrometric scale. The qualifier “non-delaminating” is a specific reference to the property of a composition, or an article derived from the composition, of not exhibiting a visually perceptible separation into multiple layers, such as scaling or an onion skin effect.

[0072] The term “granule” refers to grains of approximately cylindrical or spherical shape, particularly suitable for extrusion or injection molding methods. In general, these grains have a characteristic size between 0.5 mm and 10 mm, especially between 1 mm and 5 mm.

[0073] The term “glass transition temperature”, abbreviated as Tg, is understood to mean the temperature at which a polymer that is at least partially amorphous transitions from the rubbery state to the glassy state, or vice versa, as measured by differential calorimetric analysis (DSC) in accordance with NF ISO 11357-2:2020, on the second heating, using heating and cooling temperature ramps at 20°C / min. In the present invention, when a glass transition temperature is mentioned, it refers more particularly, unless otherwise indicated, to the glass transition temperature at half the plateau height as defined in that standard.

[0074] It is understood that the term “melting temperature”, abbreviated as Tf, designates the temperature at which a semicrystalline polymer transitions to the viscous liquid state, as measured by differential scanning calorimetry (DSC) in accordance with NF EN ISO 113573:2018, on the second heating, using a heating rate of 20°C / min. In the present invention, when a melting temperature is mentioned, it is referred to more specifically, except Petition 870250078433, dated 03 / 09 / 2025, p. 21 / 89 14 / 56 unless otherwise indicated (in particular see below for the appropriate measurement method for a pseudoamorphous polymer), from the peak melting temperature as defined in that standard.

[0075] The term “pseudoamorphous” polymer is understood to designate a polymer that does not exhibit a melting endotherm as measured by differential scanning calorimetry (DSC) in accordance with standard NF EN ISO 11357-3:2018, on the second heating, using heating and cooling rates of 20°C / min. The pseudoamorphous polymer, however, is capable of crystallizing when heated to a temperature above its glass transition temperature, particularly at a temperature in the range Tg+40°C to Tg+110°C, for example at Tg+75°C, for a sufficient period, particularly for 10 to 30 minutes, for example 20 minutes.Similarly, the melting temperature in the second heating can also be measured for the pseudoamorphous polymers in the present invention, proceeding as follows:

[0076] - 1. Heating with a ramp of 20°C / min to a plateau temperature in the range Tg+40°C to Tg+110°C, for example from Tg+75°C, for a sufficient period, particularly for 10 to 30 minutes, for example 20 minutes, particularly at Tg+75°C for 20 minutes;.

[0077] - cooling with a ramp of 20°C / min to ambient temperature;

[0078] - 2nd heating with a ramp at 20°C / min.

[0079] The term “tensile modulus of elasticity”, or simply “elastic modulus”, is understood to mean the slope of the stress-strain curve σ(ε) in the interval between the two strains si = 0.05% and ε2 = 0.25%, as defined by ISO 527-1:2019. The elastic modulus is expressed here in gigapascals (GPa). The slope is preferably measured by a linear regression method.

[0080] Although the elastic modulus is determined here by a Petition 870250078433, dated 03 / 09 / 2025, page 22 / 89 15 / 56 mechanical tensile load, the scope of the invention will still be maintained if the measurement is made from other types of load, for example flexural or compressive.

[0081] “Nominal deformation” means the deformation calculated from the displacement of the grips and the clamping distance of the test apparatus, as defined by ISO 527-1:2019.

[0082] “Nominal strain at rupture” is understood to mean the strain at the last recorded point before reducing the stress to a value less than or equal to 10% of the strength when rupture occurs after the yield strength, as defined by ISO 527-1:2019. It is expressed as a dimensionless ratio or percentage (%). The effective measurement of the elastic modulus and nominal strain at rupture corresponds to the average of five tests performed consecutively. These tests can be performed, for example, with an MTS 810® device, marketed by MTS Systems Corporation, equipped with a mechanical extensometer.

[0083] The term “Charpy impact resistance”, or simply “impact resistance”, refers to the impact resistance of type A notched bars with dimensions of 80*10*4 mm3, as measured according to ISO 179:2010. The effective measurement corresponds to the average of 10 tests performed consecutively. A notch (V-shaped with a notch bottom radius of 0.25 + / - 0.05 mm) can be made in a specially designed device (Automatic Notchvis Plus, marketed by Ceast). The bars then remain at rest for 24 hours. The impact resistance measurement can be performed with a Zwick 5102 impact tester.

[0084] In general, those skilled in the art use the term “gas permeation” for a sheath or layer, and “gas permeability” for a material, but these two expressions correspond to Petition 870250078433, dated 03 / 09 / 2025, p. 23 / 89 16 / 56 same property. In the context of this application, the term “permeability to a gas” was chosen. Permeability to a gas is typically measured according to the fluid permeability test method of the API17J standard of 2009.

[0085] The singular forms “a / an” and “the” applied to the components of the composition, such as polyaryletherketone which has a melting point of less than or equal to 340°C, or the poly(etherimide-siloxane) copolymer, are hereby conventionally used to mean “at least one” and respectively “the aforementioned at least one”. The singular forms include, however, without the need to reiterate each time, the forms where “a” means “a single” and “the” means “the single”.

[0086] In all value ranges specified in this application, the extremes are included, unless otherwise indicated. Polyaryletherketone

[0087] The M mixture of non-delaminating polymers comprises at least 50% by weight of at least one polyaryletherketone with a melting point of less than or equal to 340°C, relative to the total weight of the mixture. The melting point of a semicrystalline polyaryletherketone is measured in accordance with standard NF EN ISO 11357-3:2018 and that of a pseudoamorphous polyaryletherketone by a suitable measurement method, as specified above.

[0088] In particular, the mixture M of non-delaminating polymers may comprise at least 60% by weight or at least 70% by weight or at least 80% by weight or at least 85% by weight of said at least one polyaryletherketone having a melting temperature less than or equal to 340°C, relative to the total weight of the mixture M.

[0089] Optionally, mixture M may also comprise 0% to 40% by weight of a polyaryletherketone that has a temperature Petition 870250078433, dated 03 / 09 / 2025, page 24 / 89 17 / 56 of melting point strictly above 340°C like the other thermoplastic polymer, in relation to the total weight of the mixture M.

[0090] In particular, mixture M may comprise more than 5% by weight of a polyaryletherketone that has a melting temperature strictly above 340°C like the other thermoplastic polymer, relative to the total weight of mixture M.

[0091] In particular, mixture M may comprise less than 30% by weight or less than 25% by weight or less than 20% by weight or less than 15% by weight or less than 10% by weight of a polyaryletherketone having a melting temperature strictly above 340°C like the other thermoplastic polymer, relative to the total weight of mixture M.

[0092] According to certain embodiments, mixture M comprises no other polyaryletherketone besides the aforementioned at least one polyaryletherketone with a melting point less than or equal to 340°C.

[0093] A polyaryletherketone (PAEK) includes the units of the formulas below: (-Ar-X-) and (-Ar1-Y-), where:

[0094] - Ar and A1 each designate a divalent aromatic radical;

[0095] - Ar and Ai may preferably be chosen from 1,3-phenylene, 1,4-phenylene, 1,1'-divalent biphenylene at positions 3,3', 1,1'-divalent biphenyl at positions 3,4', 1,4-naphthalene, 1,5-naphthalene and 2,6-naphthalene;

[0096] - X designates an electron-withdrawing group; it may preferably be chosen from the carbonyl group and the sulfonyl group,

[0097] - Y designates a group chosen from among an oxygen atom, a sulfur atom, an alkylene group, such as -(CH)2-, and isopropylidene.

[0098] In these units X and Y, at least 50%, preferably Petition 870250078433, dated 03 / 09 / 2025, p. 25 / 89 18 / 56 at least 70% and more particularly at least 80% of the X groups are a carbonyl group, and at least 50%, preferably at least 70% and more particularly at least 80% of the Y groups represent an oxygen atom.

[0099] According to a preferred embodiment, 100% of the X groups designate a carbonyl group and 100% of the Y groups represent an oxygen atom.

[0100] Advantageously, the PAEK(s) can / can be chosen from:

[0101] - a poly-ether-ketone-ketone, also called PEKK; A PEKK contains one (or more) formula unit(s): -Ph-O-PhC(O)-Ph-C(O)-;

[0102] - a polyether-ether-ether-ketone, also called PEEK; A PEEK contains one (or more) formula unit(s): -Ph-O-Ph-OPh-C(O)-;

[0103] - a polyether-ketone, also called PEK; a PEK contains one (or more) unit(s) of formula: -Ph-O-Ph-C(O)-;

[0104] - a poly-ether-ether-ketone-ketone, also called A PEEKK contains one (or more) formula unit(s): -PhO-Ph-O-Ph-C(O)- Ph-C(O)-;

[0105] - a poly-ether-ether-ether-ketone, also called PEEEK; a PEEEK contains one (or more) unit(s) of formula: -Ph-OPh-O-Ph-O- Ph-C(O)-;

[0106] - a poly-ether-diphenyl-ether-ketone also called PEDEK; a PEDEK contains one (or more) formula unit(s): a PEDEK contains one (or more) formula unit(s) -Ph-O-Ph-Ph-OPh-C(O)-;

[0107] - their mixtures; and,

[0108] - copolymers containing at least two of the units mentioned above, Petition 870250078433, dated 03 / 09 / 2025, p. 26 / 89 19 / 56

[0109] where: Ph represents a phenylene group and -C(O)- a carbonyl group, and each of the phenylenes can independently be of the ortho (1-2), meta (1-3) or para (1-4) type, preferably of the meta or para type.

[0110] In addition, defects, end groups and / or monomers may be incorporated in very small quantities into the polymers as described in the list above, without affecting their performance.

[0111] According to certain embodiments, PAEK is a poly-etherketone-ketone (PEKK) essentially consisting of, and preferably consisting of: a terephthalic repeating unit and, if applicable, an isophthalic repeating unit, wherein the terephthalic repeating unit (“T unit”) has the formula:

[0112] Chemical Formula 10 -O OR} (I)

[0113] the isophthalic unit (“unit I”) has the formula:

[0114] Chemical Formula 11 OO ★ (II)

[0115] The weight ratio of T units relative to the sum of T and I units can vary from 0% to 100%.

[0116] The choice of the molar ratio of T units relative to the sum of T and I units is one of the factors that allows adjusting the melting temperature and crystallization rate properties of polyetherketone-ketones. A specific molar ratio of T units relative to the sum of T and I units can be obtained by adjusting the respective concentrations of the reagents during polymerization. Petition 870250078433, dated 03 / 09 / 2025, p. 27 / 89 20 / 56 in an intrinsically known way.

[0117] Preferably, the poly-ether-ketone-ketone has a homogeneous structure, and particularly it can be of the statistical type.

[0118] Poly-ether-ketone-ketones with a weight ratio of T units relative to the sum of T and I units less than or equal to 74% have a melting point less than or equal to 340°C.

[0119] Preferably, a polyetherketone-ketone with a melting point less than or equal to 340°C is chosen from among polyetherketone-ketones that have a weight ratio of T units relative to the sum of T and I units of 0% to 5% or 45% to 73%. The weight ratio of T units relative to the sum of T and I units may be particularly 0% to 5% or 45% to 50% or 50% to 55% or 55% to 58% or 58% to 62% or 62% to 68% or 68% to 72%.

[0120] More preferably, a polyether-ketone-ketone with a melting point of less than or equal to 340°C is chosen from among polyether-ketone-ketones that have a weight ratio of T units relative to the sum of T and I units of 58% to 72%.

[0121] The molar ratio of T units relative to the sum of T and I units may be particularly about 60% or about 70%. A polyether-ketone-ketone with a T:I ratio of about 60% is a pseudoamorphous polymer within the meaning of the present invention. A polyether-ketone-ketone with a ratio of about 70% is a semicrystalline polymer.

[0122] These poly-ether-ketone-ketones are commercially available under the name Kepstan® from the company Arkema.

[0123] According to certain embodiments, PAEK may be a PEEK-PEDEK copolymer essentially consisting of, or even consisting of, a repeating unit having the formula:

[0124] Chemical Formula 12 Petition 870250078433, dated 03 / 09 / 2025, p. 28 / 89 21 / 56

[0125] and a repeating unit has the formula:

[0126] Chemical Formula 13

[0127] Copolymers consisting of repeating units of formula (III) and (IV) with a molar ratio of (III) units relative to the sum of (III) and (IV) units ranging from 5% to 45% have a melting temperature less than or equal to 340°C.

[0128] According to certain embodiments, PAEK may be a copolymer consisting essentially of, or even consisting of, a repeating unit having formula (III) and a repeating unit having formula:

[0129] Chemical Formula 14

[0130] Copolymers consisting of repeating units of formula (III) and (V) that have a molar ratio of (III) units relative to the sum of (III) and (V) units ranging from 5% to 100% have a melting temperature less than or equal to 340°C.

[0131] According to certain embodiments, PAEK may be a copolymer consisting essentially of, or even consisting of, a repeating unit having formula (III) and a repeating unit having formula:

[0132] Chemical Formula 15 Petition 870250078433, dated 03 / 09 / 2025, p. 29 / 89 22 / 56 (VI)

[0133] Copolymers consisting of repeating units of formula (III) and (VI) that have a molar ratio of (III) units relative to the sum of (III) and (VI) units ranging from 5% to 100% have a melting temperature less than or equal to 340°C.

[0134] According to certain embodiments, PAEK with a melting temperature less than or equal to 340°C has a melting temperature less than or equal to 335°C or a melting temperature less than or equal to 330°C or a melting temperature less than or equal to 325°C or a melting temperature less than or equal to 320°C. This is advantageous because it limits the thermal degradation of the poly(etherimide-siloxane) copolymer when the granule according to the invention is melted at a maximum temperature of 5°C to 40°C above the melting temperature of PAEK having a melting temperature less than or equal to 340°C, including for a prolonged residence time in the molten state.

[0135] According to certain embodiments, PAEK has a melting temperature greater than 275°C or greater than or equal to 285°C or greater than or equal to 295°C. This is advantageous so that the article, part and / or coating obtained by extrusion or injection from the granules according to the invention has sufficient thermal resistance properties.

[0136] According to certain embodiments, the mixture M of non-delaminating polymers comprises two polyaryletherketones having a melting point less than or equal to 340°C. The mixture M comprises a first polyaryletherketone P1 which is a polymer Petition 870250078433, dated 03 / 09 / 2025, p. 30 / 89 23 / 56 is a semicrystalline polymer with a melting temperature T1, and a second polyaryletherketone P2 is a semicrystalline polymer with a melting temperature such that T2 <Ti, ou um polímero pseudoamorfo.

[0137] According to certain embodiments, polymer P1 may represent at least 50% by weight of polyaryletherketones that have a melting temperature less than or equal to 340°C.

[0138] According to other embodiments, polymer P2 may represent at least 50% by weight of polyaryletherketones that have a melting temperature less than or equal to 340°C.

[0139] According to certain embodiments, P2 is a poly-ether-ketone-ketone essentially consisting of, and preferably consisting of: a terephthalic unit and an isophthalic unit, and the molar percentage of terephthalic units relative to the sum of terephthalic and isophthalic units is from 0% to 5% or from 45% to 67%, and, P1 is a poly-ether-ketone-ketone essentially consisting of, and preferably consisting of: a terephthalic unit and an isophthalic unit, and the molar percentage of terephthalic units relative to the sum of terephthalic and isophthalic units is from 63% to 73%.

[0140] According to certain embodiments, P2 is a poly-ether-ketone-ketone essentially consisting of, and preferably consisting of: a terephthalic unit and an isophthalic unit, and the molar percentage of terephthalic units relative to the sum of terephthalic and isophthalic units is 58% to 67%, and P1 is a poly-ether-ketone-ketone essentially consisting of, and preferably consisting of: a terephthalic unit and an isophthalic unit, and the molar percentage of terephthalic units relative to the sum of terephthalic and isophthalic units is 63% to 73%. Advantageously, P2 represents at least 50% by weight of polyaryletherketones having a melting point less than or equal to 340°C.

[0141] In the embodiments in which mixture M comprises Petition 870250078433, dated 03 / 09 / 2025, p. 31 / 89 24 / 56 additionally a polyaryletherketone with a melting temperature strictly above 340°C, the latter may be a PEEK homopolymer consisting of repeating unit (III); a PEEK-PEDEK copolymer, essentially consisting of, or consisting of, repeating units of formula (III) and formula (IV), and the molar ratio of units of formula (III) in relation to the total number of moles of units (III) and (IV) is strictly above 45%, particularly greater than or equal to 50%; or a PEKK, essentially consisting of, or consisting of, terephthalic (T) and isophthalic (I) repeating units, and the molar ratio of terephthalic repeating unit in relation to the total number of moles of terephthalic and isophthalic repeating units is strictly above 74%, particularly greater than or equal to 75% or greater than or equal to 76% or greater than or equal to 77% or greater than or equal to 78%.

[0142] According to certain embodiments, mixture M comprises two polyaryletherketones P3 and P4, wherein P3 is a semicrystalline or pseudoamorphous polyaryletherketone with a melting point less than or equal to 340°C, preferably less than or equal to 320°C, and P4 is a polyaryletherketone with a melting point strictly above 340°C. Polymer P4 may represent in particular 25% by weight or less, 20% by weight or less, 15% by weight or less, or even 10% by weight or less in relation to the total weight of mixture M.According to particular embodiments, polymer P3 may be a polyether-ketone-ketone essentially consisting of, and preferably consisting of: a terephthalic unit and an isophthalic unit, and the molar percentage of terephthalic units relative to the total number of moles of terephthalic and isophthalic units of the polyether-ketone is from 0% to 5% or from 45% to 67%, and polymer P4 may be a polyether-ketone-ketone essentially consisting of, and preferably consisting of: a terephthalic unit and an isophthalic unit, and the molar percentage of terephthalic units is... Petition 870250078433, dated 03 / 09 / 2025, p. 32 / 89 25 / 56 in relation to the total number of moles of terephthalic and isophthalic units of polyetherketoneacetone is 78% to 85%.

[0143] According to certain embodiments, mixture M comprises a polyether-ketone-ketone having a weight ratio of T units to the sum of T and I units of 78% to 85%. The molar ratio of T units to the sum of T and I units may be particularly around 80%. Such polyether-ketone-ketone is commercially available under the name Kepstan® from the company Arkema.

[0144] According to certain embodiments, mixture M comprises a polyetherketone-ketone essentially consisting of, and preferably consisting of: a terephthalic unit and an isophthalic unit, and the molar percentage of terephthalic units relative to the total number of moles of terephthalic and isophthalic units of the polyetherketone-ketone is from 0% to 5% or from 45% to 67%, and,

[0145] a poly-ether-ketone-ketone essentially consisting of, and preferably consisting of: a terephthalic unit and an isophthalic unit, and the molar percentage of terephthalic units in relation to the total number of moles of terephthalic and isophthalic units of the polyetherketone-ketone is 78% to 85%.

[0146] Advantageously, mixture M comprises 25% by weight or less, 20% by weight or less, 15% by weight or less, or even 10% by weight or less of said polyether-ketone-ketone having a molar ratio T / (T+I) of 78% to 85%, relative to the total weight of mixture M. (Polyetherimide-siloxane copolymer)

[0147] The poly(etherimide-siloxane) copolymer allows for particularly improved toughness, flexibility, elongation at break and crack propagation resistance of composition C.

[0148] The M mixture of polymers comprises from 5% to 40% in Petition 870250078433, dated 03 / 09 / 2025, p. 33 / 89 26 / 56 weight of a poly(etherimide-siloxane) copolymer, relative to the total weight of the mixture.

[0149] Preferably, mixture M comprises less than 30%, and even more preferably less than 25% by weight of the poly(etherimide-siloxane) copolymer, relative to the total weight of the mixture.

[0150] According to certain embodiments, mixture M may comprise less than 20% by weight or less than 17.5% by weight or less than 15% by weight of the poly(etherimide-siloxane) copolymer, relative to the total weight of the mixture.

[0151] Preferably, mixture M comprises more than 7.5% by weight of the poly(etherimide-siloxane) copolymer, relative to the total weight of the mixture. Mixture M may particularly comprise more than 8.0% by weight of the poly(etherimide-siloxane) copolymer, relative to the total weight of the mixture.

[0152] According to certain embodiments, mixture M comprises from 5% to 8% by weight of the poly(etherimide-siloxane) copolymer, relative to the total weight of the mixture.

[0153] According to certain embodiments, mixture M comprises from 8% to 15% by weight of the poly(etherimide-siloxane) copolymer, relative to the total weight of the mixture.

[0154] According to certain embodiments, mixture M comprises from 15% to 25% by weight of the poly(etherimide-siloxane) copolymer, relative to the total weight of the mixture.

[0155] Poly(etherimide-siloxane) copolymers contain polyetherimide units and contain polysiloxane units, for example 5 to 1,000, or 10 to 500 etherimide units and siloxane units.

[0156] The polyetherimide units comprise the structural units of formula (VII):

[0157] Chemical Formula 16 Petition 870250078433, dated 03 / 09 / 2025, page 34 / 89 27 / 56 where each R is the same or different and represents a substituted or unsubstituted divalent organic group, such as a C6-20 aromatic hydrocarbon group or a halogenated derivative thereof, a straight or branched C2-20 alkylene group or a halogenated derivative thereof, a C3-8 cycloalkylene group or a halogenated derivative thereof, in particular a divalent group of formula (VIII):

[0158] Chemical Formula 17 Petition 870250078433, dated 03 / 09 / 2025, p. 35 / 89 28 / 56 or where Q1 represents — O —, — S —, — C(O) —, — SO2 —, — SO —, — Cyhhy —, wherein y represents an integer from 1 to 5 or a halogenated derivative thereof (encompassing perfluoroalkylene groups) or — (CeHio)z — and z represents an integer from 1 to 4. In one embodiment, Ré is an m-phenylene, a p-phenylene, or a diaryl sulfone.

[0159] Furthermore, in formula (VI), T represents — O — or a group of formula — O — Z — O —, the divalent bonds of the — O — group or the — O — Z — O — group are located in the 3,3', 3,4', 4,3' or 4,4' positions. The Z group of — O — Z — O — may be a substituted or unsubstituted divalent organic group and may be a C6-24 aromatic monocyclic or polycyclic fragment optionally substituted by 1 to 6 C1-8 alkyl groups, 1 to 8 halogen atoms or a combination thereof, provided that the valence of Z is not exceeded. Examples of Z groups include groups derived from a dihydroxy compound of formula (IX):

[0160] Chemical Formula 18 Petition 870250078433, dated 03 / 09 / 2025, p. 36 / 89 29 / 56 OH (IX) where Rae Rb may be the same or different and represent, for example, a halogen atom or a monovalent C1-6 alkyl group; peq each independently represent integers from 0 to 4; c represents 0 to 4; and Xa represents a bridging group linking the aromatic groups to the hydroxyl substitution, with the bridging group and the hydroxyl substituent of each C6 arylene group being arranged in the ortho, meta, or para (more precisely para) position relative to each other on the C6 arylene group. The bridging group Xa may represent a single bond, — O —, — S —, — S(O) —, — S(O)2 —, — C(O) — or a C1-18 organic bridging group. The organic C1-18 bridging group can be cyclic or acyclic, aromatic or non-aromatic, and may additionally contain heteroatoms such as halogens, oxygen, nitrogen, sulfur, silicon, or phosphorus.The C1-18 organic group can be arranged so that the C6 arylene groups attached to it are attached to a common alkylidene carbon or to carbons other than the C1-18 organic bridging group.

[0161] A particular example of a Z group is a divalent group with formula (X):

[0162] Chemical Formula 19 (X) where Q represents — O —, — S —, — C(O) —, — SO2 —, — SO — or — CyH2y — where y represents an integer from 1 to 5 or a halogenated derivative thereof (including a perfluoroalkylene group). In a particular embodiment, Z represents a derivative of bisphenol A, Petition 870250078433, dated 03 / 09 / 2025, p. 37 / 89 30 / 56 so that Q, in formula (X), is a 2,2-isopropylidene.

[0163] In one embodiment of formula (VII), R represents an m-phenylene or a p-phenylene and T represents — O — Z — O —, where Z represents a divalent group of formula (X). Alternatively, R represents an m-phenylene or a p-phenylene and T represents — O — Z — O —, where Z represents a divalent group of formula (X) and Q represents a 2,2-isopropylidene.

[0164] Polyetherimide blocks may be prepared by any method familiar to those skilled in the art, including by the reaction of an aromatic bis(ether anhydride) of formula (XI):

[0165] Chemical Formula 20 with an organic diamine of formula (XII)

[0166] H2N— R— NH2(XII)

[0167] where T and R are defined as described above. Polyetherimide copolymers can be manufactured using a combination of an aromatic bis(ether anhydride) of formula (XI) and a different bis(anhydride), for example a bis(anhydride), where T does not have the ether functionality and, for example, T represents a sulfone.

[0168] Illustrative examples of bis(anhydrides) include 3,3-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride; 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl ether dianhydride; 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride; 4,4'-bis(3,4-dicarboxyphenoxy)benzophenone dianhydride; 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfone dianhydride; 2,2-bis[4-(2,3-dicarboxyphenoxy)phenyl]propane dianhydride; 4,4'-bis(2,3-dicarboxyphenoxy)diphenyl ether dianhydride; the dianhydride of 4,4'-bis(2,3-dicarboxyphenoxy)diphenyl sulfide; the dianhydride of 4,4'-bis(2,3 Petition 870250078433, dated 03 / 09 / 2025, p. 38 / 89 31 / 56 dicarboxyphenoxy)benzophenone; the dianhydride of 4,4'-bis(2,3-dicarboxyphenoxy)diphenylsulfone; the dianhydride of 4-(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)diphenyl-2,2-propane; the dianhydride of 4-(2,3-dicarboxyphenoxy)4'-(3,4-dicarboxyphenoxy)diphenyl ether; the dianhydride of 4-(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)diphenyl sulfide; the dianhydride of 4-(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)benzophenone; and the dianhydride of 4(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)diphenylsulfone, as well as different combinations thereof.

[0169] Examples of organic diamines include ethylenediamine, propylenediamine, trimethylenediamine, diethylenetriamine, triethylenetetramine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, 1,12-dodecanediamine, 1,18-octadecanediamine, 3-methyl-heptamethylenediamine, 4,4-dimethyl-heptamethylenediamine, 4-methylnonamethylenediamine, 5-methylnonamethylenediamine, 2,5-dimethyl-hexamethylenediamine, 2,5-dimethyl-heptamethylenediamine, 2,2-dimethylpropylenediamine, N-methyl-bis(3-aminopropyl)amine, 3-methoxyhexamethylenediamine, the 1,2-bis(3-aminopropoxy)ethane, bis(3-aminopropyl sulfide), 1,4-cyclohexanediamine, bis-(4-aminocyclohexyl)methane, m-phenylenediamine, p-phenylenediamine, 2,4-diaminotoluene, 2,6-diaminotoluene, m-xylylenediamine, p-xylylenediamine, 2-methyl-4,6-diethyl-1,3phenylene-diamine, 5-methyl-4,6-diethyl-1,3-phenylene-diamine, benzidine, 3,3'-dimethylbenzidine, 3,3'-dimethoxybenzidine, 1,5-diaminonaphthalene, bis-(4-aminophenyl)methane, bis(2-chloro-4-amino-3,5-diethylphenyl)methane, bis(4-aminophenyl)propane, 2,4-bis(p-amino-t-butyl)toluene, bis(p-amino-t-butylphenyl)ether, bis(p-methyl-o-aminophenyl)benzene, bis(p-methyl-o-aminopentyl)benzene, 1,3-diamino-4-isopropylbenzene, bis(4-aminophenyl) sulfide, bis-(4-aminophenyl)sulfone, and bis(4-aminophenyl)ether. Combinations of such compounds may also be used. In certain embodiments, the organic diamine is am, Petition 870250078433, dated 03 / 09 / 2025, p. 39 / 89 32 / 56 phenylenediamine, p-phenylenediamine, sulfonyldianiline, or a combination including one or more of the aforementioned.

[0170] Siloxane blocks contain units of formula (XIII):

[0171] Chemical Formula 21 R' R' SiO (XIII) where each R' independently represents a C1-13 monovalent hydrocarbyl group and E is an integer from 1 to 100, in particular from 2 to 50. For example, each R' may independently represent an 01-13 alkyl group, a C1-13 alkoxy group, a C2-13 alkenyl group, a C2-13 alkenyloxy group, a C3-6 cycloalkyl group, a C3-6 cycloalkoxy group, an 06-14 aryl group, an 06-10 aryloxy group, an 07-13 arylalkyl group, an 07-13 arylalkoxy group, an 07-13 alkylaryl group or an 07-13 alkylaryloxy group. The above groups may be wholly or partially halogenated with fluorine, chlorine, bromine or iodine, or a combination including at least one of the aforementioned. In one embodiment, no bromine and no chlorine are present, and in other embodiments, no halogen is present. Combinations of the above R' groups can be used in the same copolymer. In one embodiment, the polysiloxane blocks comprise the R' groups with a minimum proportion of hydrocarbon radicals.In one particular embodiment, an R' group with a minimum proportion of hydrocarbon compounds is a methyl group.

[0172] Poly(etherimide-siloxanes) can be formed by the polymerization of an aromatic bisanhydride (XI) and a diamine component containing an organic diamine (XII) as described above or a mixture of diamines, and a polysiloxanediamine formula (XIV):

[0173] Chemical Formula 22 Petition 870250078433, dated 03 / 09 / 2025, p. 40 / 89 33 / 56 Rr Rr Nib--R4--SiO R' Si--R4—Nib R' (xiv) where R' and E are as described in formula (XIII), and each R4 independently represents a C2-C20 hydrocarbon fragment, in particular a C2-C20 arylene, an alkylene or an arylenealkylene group. According to certain embodiments, R4 represents a C2-C20 alkylene group, more precisely a C2-C10 alkylene group such as propene, and E has an average value of 5 to 100, 5 to 75, 5 to 60, 5 to 15 or 15 to 40. The operational methods that allow the preparation of polysiloxane diamines of formula (XIV) are well known in the art.

[0174] In certain poly(etherimide-siloxane) copolymers, the diamine component used for the preparation of the copolymers may contain 10 to 90 mole percent (mol%) or 20 to 50 mol percent or 25 to 40 mol percent of a polysiloxane diamine (XIV) and 10 to 90 mol percent or 50 to 80 mol percent or 60 to 75 mol percent of diamine (XII), for example, as described in US Patent No. 4,404,350. The diamine components may be physically mixed before reaction with one or more bisanhydride(s), thus forming a substantially statistical copolymer. Alternatively, block or alternating copolymers can be formed by the selective reaction of (XII) and (XIV) with aromatic bis(ether anhydrides) (XI) to give polyimide blocks, which are then joined together to react together. Thus, the poly(etherimide-siloxane) copolymer can be a block, statistical or graft copolymer.Poly(etherimide-siloxane) block copolymers comprise eterimide blocks and siloxane blocks in their polymer backbone. The eterimide blocks and siloxane blocks may be present in a statistical order, in the form of blocks (namely, ...). Petition 870250078433, dated 03 / 09 / 2025, p. 41 / 89 34 / 56 Graft poly(etherimide-siloxane) copolymers are nonlinear copolymers containing siloxane blocks attached to a linear or branched polymeric backbone containing etherimide blocks, alternating (namely, ABAB) or in combination.

[0175] Examples of particular poly(etherimide-siloxanes) are described in US Patents Nos. 4,404,350, 4,808,686 and 4,690,997.

[0176] According to preferred embodiments, poly(etherimidasiloxane) is essentially composed of, or is composed of, units of formula (XV):

[0177] Chemical Formula 23 (XV) where R' and E of the siloxane are as in formula (XIII), R and Z of the imide are as in formula (VII), R4 is the same R4 as in formula (XIV), n is an integer from 5 to 100. In a particular embodiment, R represents a phenylene, Z represents a bisphenol A residue, R4 represents n-propylene, E represents an integer from 2 to 50, or 5 to 20, or 6 to 15, n represents 5 to 100 and each R' of the siloxane is a methyl.

[0178] The relative amounts of polysiloxane and etherimide units in poly(etherimide-siloxane) depend on the desired properties and are chosen in accordance with the guidelines set forth in the present invention. In particular, the poly(etherimidesiloxane) copolymer is chosen to have a certain average E value and is selected and used in sufficient quantity to ensure the desired weight percentage (% wt) of siloxane units in the thermoplastic composition. In certain embodiments, the polysiloxane block of the copolymer has a number-average molecular weight (Mn) of 300 to 3,000 grams / mole (Daltons). Petition 870250078433, dated 03 / 09 / 2025, page 42 / 89 35 / 56

[0179] According to certain embodiments, the siloxane groups of the poly(etherimide-siloxane) copolymer represent more than 30% by weight, relative to the total weight of the poly(etherimide-siloxane) copolymer.

[0180] According to certain embodiments, the siloxane groups of the poly(etherimide-siloxane) copolymer represent more than 35% by weight, relative to the total weight of the poly(etherimide-siloxane) copolymer.

[0181] According to certain embodiments, the siloxane groups of the poly(etherimide-siloxane) copolymer represent less than 50% by weight, relative to the total weight of the poly(etherimide-siloxane) copolymer.

[0182] According to certain embodiments, the siloxane groups of the poly(etherimide-siloxane) copolymer represent less than 45% by weight, relative to the total weight of the poly(etherimide-siloxane) copolymer.

[0183] Poly(etherimide-siloxane) copolymers are commercially available under the name SILTEM® from the company Sabic. Another thermoplastic polymer

[0184] According to certain embodiments, mixture M may comprise from 0% to 40% by weight of another thermoplastic polymer other than polyaryletherketone with a melting temperature less than or equal to 340°C and poly(etherimide-siloxane) copolymer, relative to the total weight of mixture M.

[0185] According to certain embodiments, mixture M does not comprise any other thermoplastic polymer other than polyaryletherketone having a melting temperature less than or equal to 340°C and poly(etherimide-siloxane) copolymer.

[0186] Like the other thermoplastic polymer, it is particularly possible to have a polyaryletherketone with a melting temperature Petition 870250078433, dated 03 / 09 / 2025, page 43 / 89 36 / 56 strictly above 340°C, a polysiloxane, a fluorinated polymer, a polyetherimide (PEI), a polyphenylene sulfone (PPS1), a polysulfone (PSU), a polycarbonate (PC), a polyphenyl ether (PPE), a poly(phenylene sulfide) (PPS), a poly(ethylene terephthalate) (PET), a polyamide (PA), a polybenzimidizole (PBI), a poly(amide-imide) (PAI), a poly(ether sulfone) (PES), a poly(aryl sulfone), a poly(ether imide sulfone), a polyphenylene, a polybenzoxazole, a polybenzothiazole or mixtures thereof.

[0187] According to certain embodiments, the other thermoplastic polymer may be particularly a polyaryletherketone that has a melting temperature strictly above 340°C, as described above.

[0188] According to certain embodiments, the other thermoplastic polymer may especially be a polysiloxane. According to these embodiments, mixture M therefore comprises more than 7.5% by weight of the poly(etherimide-siloxane) copolymer, relative to the total weight of mixture M.

[0189] Polysiloxane can be monosubstituted or disubstituted by C1 to C12 alkyl groups, preferably C1 to C6, and very particularly C1 to C4, and / or by phenyl groups. Preferably, the alkyl groups are methyl groups. The alkyl or phenyl groups of the polysiloxane can be substituted by one or more functional groups such as epoxy, alkoxy, in particular methoxy, amine, ketone, thioether, halogen, nitrile, nitro, sulfone, phosphoryl, imino or thioester. These functional groups can also be located at the end of the polysiloxane chain. Such functionalized polysiloxanes can be used for their reaction during mixing (reactive siloxanes).

[0190] However, preferably the polysiloxane does not contain functional groups. In addition, the alkyl or phenyl groups of the polysiloxane can be replaced by one or more aryl groups, Petition 870250078433, dated 03 / 09 / 2025, p. 44 / 89 37 / 56 heteroaryl, alkyl, alkenyl, bicyclic or tricyclic carbocyclics.

[0191] Preferably, the polysiloxane present in mixture M as the other thermoplastic polymer is a poly(dimethylsiloxane) (PDMS).

[0192] To facilitate handling, polysiloxane can be combined with a solid support such as silica, particularly fumed silica.

[0193] According to certain embodiments, mixture M comprises from 0.1% to 3%, and preferably from 0.5% to 2% by weight of polysiloxane as the other thermoplastic polymer relative to the total weight of mixture M.

[0194] According to certain embodiments, mixture M comprises less than 1% by weight of polysiloxane relative to the total weight of mixture M.

[0195] According to certain embodiments, mixture M does not contain polysiloxane. In particular, in embodiments where mixture M comprises from 5% to 7.5% by weight of a poly(etherimidasiloxane) copolymer, mixture M does not contain polysiloxane. Additives

[0196] Composition C may comprise from 0% to 40% by weight of one or more non-polymeric additives, relative to the total weight of the composition.

[0197] Advantageously, composition C comprises 0% to 30% or 0% to 25% or 1% to 20% or 2% to 10% by weight of additives, relative to the total weight of the composition.

[0198] Among the additives, one or more fillers may be mentioned. Among the possible fillers, silica and alumina are mentioned, as well as nucleating fillers such as mineral fillers, especially talc, carbon-based fillers, especially carbon nanotubes or carbon black, ceramic fillers, especially boron nitride (Bn), or metal oxides, especially ZnO or MgO, and fillers of Petition 870250078433, dated 03 / 09 / 2025, page 45 / 89 38 / 56 reinforcement such as fiberglass or carbon fiber.

[0199] According to particular embodiments, composition C may comprise from 0.1% to 5%, particularly from 0.25% to 2.5%, by weight of a nucleating charge relative to the total weight of the composition. This allows for modification of the crystallization behavior of the polyaryletherketone(s), and specifically allows for increasing the final crystallinity in the usual methods of forming slower-crystallizing polyaryletherketones without substantially modifying the implementation conditions. These slower-crystallizing polyaryletherketones can achieve sufficient crystallinity without, for example, requiring a supplementary annealing step.

[0200] According to certain embodiments, the polyaryletherketone of composition C may be a polyetherketone-ketone with a weight ratio of T units relative to the sum of T and I units less than or equal to 74%, and preferably from 0% to 5% or from 45% to 67%, and the nucleating charge may be a carbon-based charge. The polyaryletherketone of composition C may be, for example, a polyetherketone-ketone that has a weight ratio of T units relative to the sum of T and I units ranging from 55% to 65%, particularly from about 60%, and the carbon-based charge may be carbon nanotubes.

[0201] Among the additives, plasticizers can also be mentioned. A plasticizer could lower the glass transition temperature of composition C. The plasticizer(s) can be selected, for example, from the compounds defined in the Handbook of Plasticizers edited by Georges Wypych. Composition C may particularly comprise 0% to 20% by weight of plasticizer(s), relative to the total weight of composition C.

[0202] In addition, composition C may eventually contain smaller amounts, specifically less than 1% by weight in Petition 870250078433, dated 03 / 09 / 2025, page 46 / 89 39 / 56 in relation to the total weight of the composition, of functional additives. Such a qualification may include, for example, antistatic agents, antioxidants, molten state stabilizers, conductive agents, ignitizing agents, colorants and reactive agents such as alkaline carbonates. Compositions C

[0203] Composition C constituting the granules comprises a mixture M of non-delaminating polymers, and this mixture M comprises:

[0204] - at least 50% by weight of at least one pseudoamorphous or semicrystalline polyaryletherketone, wherein said polyaryletherketone has a melting point of less than or equal to 340°C, relative to the total weight of the mixture; and,

[0205] - from 5% to 40% by weight of a poly(etherimidasiloxane) copolymer, relative to the total weight of the mixture, it being understood that if mixture M comprises from 5% to 7.5% by weight of a poly(etherimida-siloxane) copolymer, then mixture M does not contain polysiloxane.

[0206] According to certain embodiments, mixture M consists of: of said polyaryletherketone having a melting point of less than or equal to 340°C, of ​​said poly(etherimide-siloxane) copolymer, and from 0% to 40% by weight of another thermoplastic polymer different from said polyaryletherketone and said poly(etherimide-siloxane) copolymer, relative to the total weight of the mixture.

[0207] According to certain embodiments, mixture M consists of said at least one polyaryletherketone and said poly(etherimide-siloxane) copolymer.

[0208] Mixture M may constitute at least 60% by weight or at least 70% by weight or at least 75% by weight or at least Petition 870250078433, dated 03 / 09 / 2025, p. 47 / 89 40 / 56 80% by weight, or at least 85% by weight, or at least 90% by weight, in relation to the total weight of the composition.

[0209] According to certain embodiments, composition C comprises at least 60% by weight, and preferably at least 70% by weight, of mixture M, and from 0% to 40% by weight, and preferably from 0% to 30% by weight of one or more additives, relative to the total weight of the composition. Composition C may be constituted in particular of at least 70% by weight of mixture M and from 0% to 30% of one or more additives.

[0210] According to certain embodiments, composition C consists of mixture M and 0% to 30% by weight of additives, relative to the total weight of composition C.

[0211] According to certain embodiments, composition C consists of mixture M and 0% to 30% by weight of additives, relative to the total weight of composition C.

[0212] According to certain embodiments, composition C consists of mixture M and 0% to 30% by weight of additives, of which 0% to 20% by weight is plasticizer(s), 0% to 5% by weight is nucleating filler(s) and less than 1% by weight is functional additives, relative to the total weight of composition C.

[0213] According to certain embodiments, composition C consists of mixture M, from 0.1% to 5% by weight of nucleating filler(s) and less than 1% by weight of functional additives, relative to the total weight of composition C. Granule production

[0214] The method of preparing composition C in granular form can be carried out in a melt mixing apparatus. Any melt mixing apparatus known to those skilled in the art for the preparation of polymeric compositions by melt mixing may be used. Petition 870250078433, dated 03 / 09 / 2025, page 48 / 89 41 / 56

[0215] Suitable equipment for mixing in the molten state includes, for example, kneaders, Banbury mixers, single-screw extruders and twin-screw extruders.

[0216] Preferably, an extruder equipped with means for dosing all desired components into the extruder, into the main extruder hopper and / or by side feeding is used.

[0217] For the manufacture of granules, the residence time in the molten state in the melt mixing apparatus is generally quite short, especially less than 1 minute.

[0218] According to certain embodiments, the maximum temperature used to perform the melt mixing is greater than 350°C. This may be especially necessary when the polymer mixture M includes a semicrystalline polyaryletherketone that has a melting point strictly above 340°C. However, these embodiments are not preferred. In these cases, the residence time in the melt state for the production of the granules must remain low, particularly less than or well below 1 minute. According to certain embodiments, the maximum temperature used to perform the melt mixing remains less than or equal to 350°C or less than or equal to 340°C or less than or equal to 335°C. This is particularly possible when the aforementioned polyaryletherketone with a melting point less than or equal to 340°C of the polymer mixture M is the polymer in the mixture that has the highest melting point among the polymers in the mixture.

[0219] The different components of the composition can be fed simultaneously in the form of a mixture of powders or granules or a mixture of powders and granules, also called a dry blend. They can also be fed separately.

[0220] The order in which the components combine during fusion mixing is not particularly limited. Petition 870250078433, dated 03 / 09 / 2025, page 49 / 89 42 / 56

[0221] The composition according to the invention generally presents itself as a heterophasic, but non-delaminating, composition. In fact, the poly(etherimide-siloxane) copolymer is most often poorly miscible in poly(aryletherketone). By electron microscopy, a dispersed phase in the form of nodules is observed in a continuous phase. Preferably, the nodules have an average diameter of less than 20 µm, advantageously less than 10 µm, and most particularly less than 5 µm.

[0222] Preferably, poly(aryletherketone) forms the continuous phase (also called the matrix) of the composition and the poly(etherimide-siloxane copolymer) forms the dispersed phase. Uses according to the invention

[0223] Composition C according to the invention can be used for the manufacture of parts, articles or coatings, by one of the conventional forming methods, at a maximum manufacturing temperature not exceeding 350°C.

[0224] According to certain embodiments, the maximum temperature during the manufacturing method does not exceed 345°C or does not exceed 340°C or does not exceed 335°C. In general, the maximum temperature throughout the manufacturing method is set at 5°C to 40°C above the melting point of polyaryletherketone which has a melting point less than or equal to 340°C.

[0225] According to certain embodiments, the maximum temperature during the manufacturing method is set at: 10°C to 30°C or 15°C to 25°C above the melting temperature of polyaryletherketone which has a melting temperature less than or equal to 340°C.

[0226] A sufficiently low maximum temperature allows the manufacture of parts, articles, or coatings, even for long residence times at the maximum manufacturing temperature or at an adjacent temperature. This residence time can be particularly Petition 870250078433, dated 03 / 09 / 2025, p. 50 / 89 43 / 56 a period longer than 1 minute or longer than 2 minutes or longer than 3 minutes or longer than 4 minutes or longer than 5 minutes or longer than 10 minutes or longer than 20 minutes.

[0227] Thus, composition C can be shaped, for example, by molding, especially injection molding or compression molding, by extrusion, especially film or sheet extrusion, extrusion calendering, tube or pipe extrusion, sheath extrusion, by additive manufacturing of fused filaments (FFF), spinning, rotomolding, thermoforming.

[0228] According to certain embodiments, thick parts, articles, or coatings can be manufactured. In general, they have a composition thickness C greater than 2 mm or greater than 3 mm or greater than 4 mm or greater than 5 mm or greater than 6 mm. The manufacture of such elements generally implies an average residence time at the maximum manufacturing temperature or at an adjacent temperature greater than 1 minute or greater than 2 minutes or greater than 3 minutes or greater than 4 minutes or greater than 5 minutes or greater than 10 minutes or greater than 20 minutes.

[0229] As examples of thick parts or articles, plates, bars, sheaths or tubes are mentioned.

[0230] In addition, thin parts, articles or coatings can also be manufactured. In general, they have a thickness less than or equal to 2 mm or less than or equal to 1 mm or less than or equal to 0.5 mm or less than or equal to 0.25 mm. The manufacture of such elements generally implies a shorter average residence time than for the manufacture of thick elements. However, locally, specifically at the level of stagnation areas, the residence time of composition C at the maximum manufacturing temperature or at an adjacent temperature may be greater than 1 minute or greater than 2 minutes or greater than 3 minutes or greater than 4 minutes or greater than 5 minutes or Petition 870250078433, dated 03 / 09 / 2025, p. 51 / 89 44 / 56 greater than 10 minutes or greater than 20 minutes.

[0231] Examples of fine parts or articles include films, coatings or sheaths.

[0232] The term “thickness” generally means one of the dimensions of the article, part or coating, measured by the difference between its two principal faces. For a coating in which the thickness is generally homogeneous throughout the coating, the thickness designates the average thickness of the coating across the entire coating. Generally, the coating thickness is the same ±5%, typically ±2%, at any point on the coating. The thickness can be measured, for example, with a caliper.

[0233] According to certain embodiments, composition C can be used as a thin or thick coating or sheath for electrical cables.

[0234] Composition C is particularly interesting for the manufacture of articles, parts or coatings that exhibit better impact resistance and / or greater elongation at break and / or a lower elastic modulus, compared to the granules of unformulated polyaryletherketones. As a result, there is the possibility of manufacturing durable parts, as they exhibit less crack propagation.

[0235] In particular, granules allow manufactured articles, parts or coatings to be given one or more, and depending on certain methods, all of the properties listed below:

[0236] - a tensile modulus of elasticity, as measured by ISO 527-2:2019 / 1 A at 20°C, less than 4.0 GPa, preferably less than 3.5 GPa, preferably less than 3.2 GPa, and preferably less than 3.0 GPa, and / or

[0237] - a nominal strain at break as measured by ISO 527-2:2019 / 1A at 20°C greater than 8%, preferably greater than 10%, mainly greater than 15% or greater than 20%, Petition 870250078433, dated 03 / 09 / 2025, p. 52 / 89 45 / 56

[0238] - Charpy impact resistance in accordance with the standard ISO 179-1:2010 / 1 eA greater than 5 kJ / m2, preferably greater than 6 kJ / m2, more preferably greater than 7 kJ / m2, and most preferably greater than 8 kJ / m2,

[0239] - a yield strength, as measured by ISO 527-2:2019 / 1A:2019 at 20°C, of ​​less than 95 MPa, and preferably less than 85 MPa,

[0240] - a CO2 permeation measured at 60°C less than 1.1x10-8 (cm3.cm) / (cm2.s.bar),

[0241] - in the case of a sheath or tube forming a pipe, a structural flexibility such that the pipe is able to withstand at least 1,000 cycles, wherein, for each cycle, the layer of the polymeric sheath or the tube of composition C undergoes a flexural deformation that varies from -2% to +2%, without rupture of the layer of the polymeric sheath or the tube of composition C, as shown in example 2.

[0242] Increased malleability and elongation at break allow for greater deformations and consequently access to new designs, especially for assembly or winding. Thus, the composition according to the invention is particularly interesting for the manufacture of parts in the pipe, cabling, aeronautical, automotive, electronics, electrical engineering, composites, additive manufacturing and medical device segments.

[0243] The manufactured parts, articles or coatings can achieve different levels of crystallinity, especially controllable by the crystallization kinetics of composition C.

[0244] As previously described in the particular embodiments, and as specifically illustrated in example 1, the crystallization kinetics of composition C can be controlled in several ways: i) by selecting a single polyaryletherketone that has a melting point less than or equal to 340°C, ii) by mixing two Petition 870250078433, dated 03 / 09 / 2025, page 53 / 89 46 / 56 polyaryletherketones that have a different melting point below 340°C, iii) by mixing two polyaryletherketones that have different melting points, one less than or equal to 340°C and the other strictly above 340°C, and iv) by mixing a polyaryletherketone that has a melting point less than or equal to 340°C and a nucleating charge.

[0245] The level of crystallinity can be evaluated by DSC on the first heating at 20°C / min using the calculation: ΔHf1-ΔHcc. The term “ΔHcc” corresponds to the cold enthalpy of crystallization and the term “ΔMη” corresponds to the enthalpy of fusion on the first heating at a heating rate of 20°C / min. These enthalpies are expressed in Joules per gram of composition.

[0246] The expression ΔHf1-ΔHcc can have a value generally ranging from 0 to 50 J / gram of composition C. In particular, it can have a value of 0 to 5 J / g or 5 J / g 10 J / g or 10 J / g 15 J / g or 15 J / g 20 J / g or 20 J / g 25 J / g or 25 J / g 30 J / g or 30 J / g 35 J / g or 35 J / g 40 J / g or 40 J / g 45 J / g or 45 J / g 50 J / g. A crystallinity level of 0 to 10 J / gram of composition is considered a low to moderate crystallinity level. Parts, articles, or coatings with this level of crystallinity have the advantage of being easier to manufacture, given the lower transformation temperatures and subsequent good thermoformability.

[0247] A crystallinity level strictly above 10 J / gram of composition is considered a moderate to high crystallinity level. Parts, articles or coatings with this level of crystallinity generally have the advantage of exhibiting better chemical resistance, better temperature resistance and / or lower gas permeability when compared to those with a lower level of crystallinity, but which are usually more difficult to produce and / or less easily thermoformable. Petition 870250078433, dated 03 / 09 / 2025, page 54 / 89 47 / 56

[0248] According to certain uses of the invention, composition C may be in the form of granules. These granules may have been produced in the manner described above.

[0249] Alternatively, according to other uses of the invention, the elements that make up composition C can be added by mixing in the molten state during conventional formation methods. For example, it can be considered that all the elements that make up composition C are added by mixing in the molten state during conventional formation methods. It can also be considered that mixture M is in the form of granules and that the other elements of composition C, especially the additives, are added by mixing in the molten state during conventional formation methods. Examples Raw materials

[0250] The following commercial polymers were used:

[0251] KEPSTAN® PEKK, 6000, 7000, and 8000 series grades suitable for extrusion, marketed by Arkema. These polymers are PEKK copolymers with T / l ratios of approximately 60 / 40 (pseudoamorphous with a melting point of 303°C), 70 / 30 (semicrystalline with a melting point of 331°C), and 80 / 20 (semicrystalline with a melting point of 355°C), respectively. SILTEM® STM1500, marketed by Sabic. It is a poly(etherimide-dimethylsiloxane) copolymer (PEI-PDMS). It has a weight proportion of 40% polydimethylsiloxane relative to the total weight of the polymer.

[0252] SILTEM® STM1500 is amorphous and its glass transition temperature Tg is 168°C.

[0253] PEEK 450G™, marketed by Victrex, suitable for extrusion (semi-crystalline with a melting temperature Petition 870250078433, dated 03 / 09 / 2025, page 55 / 89 48 / 56 of 343°C).

[0254] Carbon nanotubes (CNTs), GraphiStrength® C100, marketed by the company Arkema. Preparation of the granules

[0255] Several formulations containing a PAEK, a poly(etherimide-siloxane) copolymer and optionally a nucleating agent were carried out by combination in a COPERION ZSK MC26 L / D =40 twin-screw extruder and 10 barrels.

[0256] After drying, the raw materials were introduced in different proportions (see Table 1) by means of 1 or 2 feeders in the first barrel and a third feeder allowing a side feed before the melting zone in the 4th barrel of the poly(etherimide-siloxane) copolymer. The screw speed for all tests was set at approximately 200 rpm and the flow rate at 20 kg / h. The residence time during which the compositions are in the molten state is estimated to be less than 1 minute.

[0257] To manufacture the granules of compositions 2, 3, 4 and 8, the temperature profile used has a maximum nominal temperature of 320°C and a die temperature of 320°C.

[0258] To manufacture the composition 5 granules, the profile used has a maximum nominal temperature of 340°C and a die temperature of 340°C. This profile specifically allows for a better appearance of the rods than the preceding temperature profile.

[0259] To manufacture the granules of composition 1 c, the profile used has a maximum nominal temperature of 370°C and a die temperature of 370°C. In reality, the two previous profiles were not suitable and there was the presence of infusions in the rod. It should be noted that the appearance of the rod improves as the profile temperatures are increased up to 370°C, but that the rod breaks easily when stretched. Petition 870250078433, dated 03 / 09 / 2025, p. 56 / 89 49 / 56

[0260] To manufacture the granules of composition 7c, the profile has a maximum nominal temperature of 370°C and a die temperature of 370°C. Table 1 Composition PAEK PEKK (T / I ratio) mass % PAEK mass % PEI / PDMS Additive mass % additives 1c PEEK * 90 10 * 0 2 PEKK 60 / 40 90 10 * 0 3 PEKK 60 / 40 54 10 * 0 PEKK 70 / 30 36 4 PEKK 60 / 40 89.3 10 CNT 0.7 5 PEKK 60 / 40 72 10 * 0 PEKK 80 / 20 18 0 6c PEKK 70 / 30 100 0 * 0 7c PEKK 80 / 20 90 10 * 0 8 PEKK 60 / 40 84.3 15 CNT 0.7 Example 1 - Extrusion of 7 mm thick strips

[0261] After drying overnight at 150°C, the granules from the different formulations were used to prepare extruded strips.

[0262] A Collin single-screw extruder was used, with a 30 mm diameter screw and L / D=25. The extruder is connected to a flat die with a width of 50 mm and an air gap of 8 mm. At the die exit, the molten material is conveyed through a 3-roll calendering system. The spacing between the rolls was adjusted exactly above the desired thickness to produce 7 mm thick strips. The strips were then cut on the “guillotine” to the desired length at the end of the line.

[0263] The temperature conditions of the extruder were as follows:

[0264] To manufacture composition strips 2, 3 and 4, a temperature profile with increasing temperatures up to the last zone and a die at 320°C was used.

[0265] To manufacture the composition strip 5, a profile of Petition 870250078433, dated 03 / 09 / 2025, p. 57 / 89 50 / 56 bell-shaped temperatures to obtain a homogeneous material and stable extrusion, with a maximum nominal temperature of 335°C and a final zone and die at 325°C.

[0266] To manufacture the composition strip 1c, a bell-shaped profile was used to obtain a sufficiently homogeneous material and a sufficiently stable extrusion, with a maximum nominal temperature of 370°C and a final zone and die at 350°C.

[0267] To manufacture the 6c composition strip, a bell-shaped temperature profile was used to obtain a sufficiently homogeneous material and a sufficiently stable extrusion, with a maximum nominal temperature of 350°C and a die temperature of 330°C.

[0268] For all strips, the screw speed was set at 30 revolutions / min and an overall line speed of approximately 0.2 m / min. The residence time of the material in the extruder to form thick 7 mm strips was estimated at approximately 3 to 4 minutes. Aspect of the strips

[0269] Referring to Figure 2, the composition strip 1c is delaminated (visible laminae in cross-section) and exhibits numerous porosities (numerous bubbles visible on the surface or in cross-section).

[0270] Unlike composition strip 1c, composition strips 2-5; 6c do not exhibit delamination visible to the naked eye (smooth appearance in cross-section) and are free of porosity (no visible bubbles on the surface or in cross-section). Figures 3 and 4 represent, respectively, the cross-sectional and surface views of composition strip 4 and composition strip 5. Preparation of type 1A test specimens and type 1 bars, type A notch.

[0271] To carry out mechanical tests, test specimens of the type Petition 870250078433, dated 03 / 09 / 2025, pages 58 / 89 51 / 56 Type 1A bars and bars of type 1A were manufactured subtractively by machining / milling, preserving only the core of the strips.

[0272] Given the heterogeneous and delaminated nature of the composition strip 1c, it was not possible to produce correct test specimens / bars. Therefore, the latter cannot be mechanically tested.

[0273] The dimensions and shape of type 1A test specimens are described in ISO 527-2:2012 (section 11 and Table 1, page 5). These test specimens are hereinafter referred to as “ISO 527-2 / 1A test specimens”.

[0274] The dimensions of type 1 bars are 80.0 x 10.0 x 4.0 mm3, as described in ISO 179-1:2010 (section 6.3, Table 1). A “V” shaped notch (type A notch) with a notch tip radius of 0.25 + / - 0.05 mm. These bars are hereinafter referred to as “ISO 179-1 / 1 eA bars”.

[0275] The test specimens and notched bars are then left to rest for 24 hours at 23°C and 50% relative humidity. Mechanical characterizations

[0276] ISO 527-2 / 1A test specimens were used to determine the modulus of elasticity and nominal strain at break at 23°C and 50% relative humidity of compositions 2 to 5, 6c and 8 in accordance with ISO 527-1:2019.

[0277] To determine the modulus of elasticity, a crosshead speed of 1 mm / min was used.

[0278] To determine the nominal strain at rupture, a crosshead speed of 50 mm / min was used.

[0279] ISO 179-1 / 1eA bars were used to determine the Charpy impact resistance of compositions 2 to 5, 6c and 8 in accordance with ISO 179-1:2010.

[0280] No mechanical characterization was possible for composition 1c due to the presence of numerous porosities in the core of Petition 870250078433, dated 03 / 09 / 2025, p. 59 / 89 52 / 56 extruded strips. Crystallinity characterization

[0281] The crystallinity of the samples was evaluated by DSC on the first heating at 20°C / min by the calculation: ΔHf1-ΔHcc.

[0282] The results of the different characterizations are gathered in Table 2 below. Table 2 Composition E(Gpa) ε (%) Notched Charpy impact resistance (KJ / m2) ΔHf1-ΔHcc (J / g) 2 2.8 37 9 0 3 2.8 >50 10 7 4 2.9 16 11 14 5 3.2 24 9 24 6c 4.2 6 4 37 8 2.5 18 65 Measurement not performed

[0283] These examples demonstrate the interest in using different PAEK compositions with a melting temperature less than or equal to 340°C and the poly(etherimide-siloxane) copolymer, allowing the formation of shaped objects:

[0284] non-delaminated and homogeneous, even in the case of relatively long residence times at the transformation temperature;

[0285] ductile, that is, with a relatively low elastic modulus, a high nominal strain at break and a high notched Charpy impact resistance;

[0286] which may eventually be very thick without losing the advantageous properties already mentioned.

[0287] The modification of crystallization behavior provided i) by mixing polyaryletherketones and / or ii) by adding an additive allows the objects to have good crystallinity and retain good ductility. These higher levels of crystallization can be sought for improved chemical resistance, for Petition 870250078433, dated 03 / 09 / 2025, pp. 60 / 89 53 / 56 high barrier properties or to maintain the mechanical properties of the composition during use above the glass transition temperature of polyaryletherketones. Example 2 - Preparation of a sheath by extrusion and evaluation of certain properties.

[0288] Three types of granules with formulations 4 and 7c were used. First, they were dried in a drying apparatus (Piovan) with a dew point of -40°C for 48 hours at 180°C. The moisture level was checked after drying with a humidimeter (Aquatrac) and was less than 50 ppm.

[0289] The granules were then introduced to a temperature of 100°C in a single-screw extruder (manufactured by Maillefer - 45 mm in diameter, equipped with a three-zone screw), and with a temperature profile as described in Example 1.

[0290] The residence time of the polymeric composition in the molten state depends directly on the speed of the extruder screw, and can be calculated.

[0291] Various screw speeds were used and a significant impact of this speed (and therefore of the residence time in the molten state) on the surface appearance of the resulting sheath was observed.

[0292] Table 3 shows that, depending on the composition used, the temperature of the extrudate obtained was different. Composition 4, which has the lowest melting temperature, showed the best surface appearance, which is explained by the fact that the poly(etherimide-siloxane) copolymer was not degraded during extrusion. Table 3 Extrudate temperature (°C) at 20 rpm Surface appearance at 30 rpm Extrudate temperature (°C) at 40 rpm Surface appearance at 40 rpm Composition 4 315 Smooth 321 Smooth Composition 5 333 Slight signs of 340 Smooth, Petition 870250078433, dated 03 / 09 / 2025, pp. 61 / 89 54 / 56 Extrudate temperature (°C) at 20 rpm Surface appearance at 30 rpm Extrudate temperature (°C) at 40 rpm Surface appearance at 40 rpm Surface scratches Light residual scratches on the weld line Composition 7c 350 Presence of defects and many surface scratches throughout the sheath 358 Presence of defects and many surface scratches throughout the sheath Sheath surface appearance as a function of extruder screw speed.

[0293] A 7 mm thick sheath could be extruded onto a metal casing, thus demonstrating the possibility of extruding a thick layer. Microscopic observations of the sheaths

[0294] Microscopic observations were made on sheaths produced from compositions 4, 5 and 7c. Thin lamellae of 15 µm were obtained by sectioning with a microtome (Leica 2065) and observed under a numerical microscope (Keyence VHX 700F). The weld line zone was studied, where the residence time of the molten polymer composition is known to be the longest.

[0295] Composition 5 exhibited a pronounced weld line without decohesion, but likely with some microstructural peculiarities and potentially slight degradation. Composition 4, on the other hand, shows almost no peculiarities in this region. Composition 7c shows clear signs of degradation around the entire circumference of the sheath, with bubbles in the first 0.2 mm below the outer surface of the sheath, and more bubbles located at the weld line, a sign of degradation related to residence time. Mechanical properties

[0296] Tensile test specimens were prepared, which were Petition 870250078433, dated 03 / 09 / 2025, pp. 62 / 89 55 / 56 tested for tensile strength at ambient temperature according to ISO 527-1A standard from the extruded sheath.

[0297] Table 4 presents the results of this test for the extruded sheaths of composition 4 and 5 from Table 3. Table 4 Elastic modulus (GPa) Nominal deformation at rupture (%) Yield strength (MPa) Composition 4 2.8 35 79 Composition 5 3.3 21 85 Mechanical properties

[0298] No mechanical characterization is presented here for composition 7c due to the presence of numerous porosities in the core of the extruded strips, porosities caused by the presence of defects and various scratches on the surface throughout the sheath (see Table 3). Flexibility

[0299] A prototype flexible pipe, 4 meters long, composed of a metal casing around which a polymer sheath is extruded, was subjected to a bending test. For the test, the prototype flexible pipe is mounted in a fixed position, locked at one end and left free to deform at the other end to allow it to be set in motion by the cylinders of the test bench.

[0300] Bending and counter-bending stresses are applied sequentially, with the barrel returning to its natural unbent shape at the end of a cycle. The barrel thus underwent a stress level that varied from -2% to +2% for each cycle, for 1,000 cycles, without any damage being observed to the polymer sheath. Permeation resistance

[0301] Parts of the sheath produced from composition 4 were prepared by machining to obtain thin membranes with a thickness of 1.5 mm. Petition 870250078433, dated 03 / 09 / 2025, pp. 63 / 89 56 / 56 thickness from a zone located in the core of the sheath's cross-section.

[0302] Permeation resistance was determined using the permeation coefficient measuring device of a sheath sample relative to a gas, as illustrated in Figure 2 and described on page 13, line 16 to page 15, line 2 of patent application FR 2 987 666. The method used is that described on page 15, line 7 to page 18, line 26 of that patent application, in which pure CO2 was used as the gas, the temperature was 60°C and the pressure differential between the two sides of the membrane was 40 bars. Permeation resistance was calculated using equation [6] described on page 18, line 12 of that patent application. The values ​​obtained for composition 4 are less than 1.1x10-8(cm3.cm) / (cm2.s.bar). Petition 870250078433, dated 03 / 09 / 2025, pp. 64 / 89

Claims

1 / 8 CLAIMS 1. Granules characterized in that they consist of a composition C containing a mixture M of non-delaminating polymers, wherein the mixture M comprises: - at least 50% by weight of at least one pseudoamorphous or semicrystalline polyaryletherketone, and said polyaryletherketone has a melting point of less than or equal to 340°C, relative to the total weight of the mixture; and, - from 5% to 40% by weight of a poly(etherimidasiloxane) copolymer, relative to the total weight of the mixture, it being understood that if the mixture M comprises from 5% to 7.5% by weight of a poly(etherimida-siloxane) copolymer, then the mixture M does not contain polysiloxane.

2. Granules according to claim 1, characterized in that mixture M comprises more than 7.5% by weight, and preferably more than 8% by weight, of the poly(etherimide-siloxane) copolymer, relative to the total weight of the mixture.

3. Granules according to either of claims 1 and 2, characterized in that the siloxane groups of the poly(etherimide-siloxane copolymer) represent more than 30% by total weight of the poly(etherimide-siloxane copolymer).

4. Granules, according to any one of claims 1 to 3, characterized in that the siloxane groups of the poly(etherimide-siloxane copolymer) represent less than 50% of the total weight of the poly(etherimide-siloxane copolymer).

5. Granules, according to any one of claims 1 to 4, characterized in that mixture M comprises less than 30%, preferably less than 25% by weight of the poly(etherimide-siloxane) copolymer, relative to the total weight of the mixture.

6. Granules, according to any of the claims Petition 870250078433, dated 03 / 09 / 2025, page. 65 / 89 2 / 8 tions 1 to 5, characterized by the fact that said polyaryletherketone with a melting point less than or equal to 340°C is a poly-etherketone-ketone essentially constituted of, and preferably constituted of: a terephthalic unit and an isophthalic unit, wherein the terephthalic unit has the chemical formula: Chemical Formula 24 the isophthalic unit has the formula: Chemical Formula 25 a repeating unit of formula (III) and a repeating unit of formula (IV), wherein the repeating unit (III) has the formula: Chemical Formula 26 and the repeating unit (IV) has the formula: Chemical Formula 27 a repeating unit of formula (III) and a repeating unit of formula (V), wherein the repeating unit (V) has the formula: Chemical Formula 28 a repeating unit of formula (III) and a repeating unit Petition 870250078433, of 03 / 09 / 2025, p.66 / 89 3 / 8 of formula (VI), wherein the repeating unit (VI) has the formula: Chemical Formula 29 (VI).

7. Granules according to any one of claims 1 to 6, characterized in that said polyaryletherketone with a melting point less than or equal to 340°C is a poly-etherketone-ketone essentially consisting of, and preferably consisting of: a terephthalic unit and an isophthalic unit, the terephthalic unit having the chemical formula: Chemical Formula 30 O L. (I) the isophthalic unit having the chemical formula: Chemical Formula 31 the molar percentage of terephthalic units relative to the sum of the terephthalic and isophthalic units is less than or equal to 74%, preferably from 0% to 5% or from 45% to 73% and more preferably from 58% to 72%.

8. Granules, according to any one of claims 1 to 7, characterized in that said polyaryletherketone with a melting point less than or equal to 340°C, has a melting point less than or equal to 335°C or less than or equal to 330°C or less than or equal to 325°C or less than or equal to 320°C.

9. Granules, according to any one of claims 1 to 8, characterized in that said polyaryletherketone with a melting point less than or equal to 340°C, has a melting point greater than or equal to 275°C or greater than or equal to 285°C or greater than or equal to 295°C.

10. Granules according to any one of claims 1 to 9, characterized in that the poly(etherimide-siloxane) copolymer has the following chemical formula: Chemical Formula 32 (XV) where n is an integer from 5 to 100, R represents a phenylene, Z represents a bisphenol A residue, R4 represents n-propylene, E represents an integer from 2 to 50, and each R' of siloxane is a methyl.

11. Granules, according to any one of claims 1 to 10, characterized in that said mixture M consists of said polyaryletherketone having a melting point of less than or equal to 340°C, said poly(etherimidasiloxane) copolymer and from 0% to 40% by weight of another thermoplastic polymer different from said polyaryletherketone and said poly(etherimida-siloxane) copolymer, relative to the total weight of the mixture.

12. Granules, according to any one of claims 1 to 11, characterized in that mixture M comprises from 0.1% to 3%, and preferably from 0.5% to 2%, by weight of Petition 870250078433, dated 03 / 09 / 2025, page 68 / 89 5 / 8 polysiloxane as another thermoplastic polymer, relative to the total weight of mixture M.

13. Granules, according to any one of claims 1 to 12, characterized in that mixture M comprises less than 1% by weight of polysiloxane as the other thermoplastic polymer, relative to the total weight of mixture M.

14. Granules, according to any one of claims 1 to 13, characterized in that composition C consists of mixture M and 0% to 40% by weight, preferably 0% to 30% by weight, of one or more additives, relative to the total weight of the composition.

15. Granules, according to claim 14, characterized in that composition C comprises from 0.1% to 5% by weight of nucleating fillers, such as mineral fillers, in particular talc, carbon-based fillers, in particular carbon nanotubes or carbon blacks, ceramic fillers, in particular boron nitride (BNT), or metal oxides, in particular ZnO or MgO.

16. Granules, according to claim 15, characterized in that the mixture M comprises a polyaryletherketone essentially consisting of, and preferably consisting of: a terephthalic unit and an isophthalic unit, the molar percentage of terephthalic units relative to the sum of the terephthalic and isophthalic units being from 0% to 5% or from 45% to 67%.

17. Granules, according to any one of claims 1 to 16, characterized in that the mixture M comprises two polyaryletherketones P1 and P2 with a melting temperature less than or equal to 340°C, P1 is a semicrystalline polymer with a melting temperature T1, and P2 is a semicrystalline polymer with a melting temperature such that T2 <T1 ou P2 é um polímero pseudoamorfo.

18. Granules, according to claim 17, characterized by the fact that P2 represents at least 50% by weight of polyaryletherketones that have a melting point less than or equal to 340°C.

19. Granules according to any one of claims 17 and 18, characterized in that P2 is a polyether-ketone-ketone essentially consisting of, and preferably consisting of: a terephthalic unit and an isophthalic unit, the molar percentage of terephthalic units relative to the sum of terephthalic and isophthalic units being from 0% to 5% or from 45% to 67%, and P1 is a polyether-ketone-ketone essentially consisting of, and preferably consisting of: a terephthalic unit and an isophthalic unit, the molar percentage of terephthalic units relative to the sum of terephthalic and isophthalic units being from 63% to 73%.

20. Granules, according to any one of claims 1 to 16, characterized in that the mixture M comprises two polyaryletherketones P3 and P4, wherein P3 is a semicrystalline or pseudoamorphous polyaryletherketone with a melting point less than or equal to 340°C, preferably less than or equal to 320°C, and P4 is a polyaryletherketone with a melting point strictly above 340°C.

21. Granules, according to claim 20, characterized in that mixture M comprises 25% by weight or less, 20% by weight or less, 15% by weight or less, or even 10% by weight or less of polymer P4 relative to the total weight of mixture M.

22. Granules, according to any one of claims 20 and 21, characterized in that P3 is a poly-ether-ketone-ketone essentially consisting of, and preferably consisting of: a terephthalic unit and Petition 870250078433, dated 03 / 09 / 2025, page. 70 / 89 7 / 8 an isophthalic unit, the molar percentage of terephthalic units in relation to the total number of moles of terephthalic and isophthalic units of the polyether-ether-ketone is from 0% to 5% or from 45% to 67%, and, P4 is a polyether-ketone-ketone essentially consisting of, and preferably consisting of: one terephthalic unit and one isophthalic unit, the molar percentage of terephthalic units in relation to the total number of moles of terephthalic and isophthalic units of the polyether-ketone-ketone is from 78% to 85%.

23. Granules, according to any one of claims 1 to 22, characterized in that the mixture M comprises less than 30%, preferably less than 25%, and most preferably less than 20% by weight of the poly(etherimidasiloxane) copolymer, relative to the total weight of the mixture.

24. Use of a composition C as defined in any one of claims 1 to 23, characterized in that it is intended for the manufacture of an article, part or coating, at a maximum manufacturing temperature not exceeding 350°C, by molding, in particular by injection molding or compression molding, by extrusion, in particular by extrusion of films or sheets, extrusion by calendering, extrusion of tubes or pipes, extrusion of sheathing, by additive manufacturing of fused filaments (FFF), spinning, rotomolding, thermoforming.

25. Use according to claim 24, characterized in that composition C remains at the maximum manufacturing temperature for a period exceeding 1 minute or exceeding 2 minutes or exceeding 3 minutes or exceeding 4 minutes or exceeding 5 minutes or exceeding 10 minutes or exceeding 25 minutes.

26. Use, according to any of claims 24 and 25, characterized in that said article or said part or said coating has a thickness in said composition Petition 870250078433, dated 03 / 09 / 2025, p. 71 / 89 8 / 8 C greater than 2 mm or greater than 3 mm or greater than 4 mm or greater than 5 mm or greater than 6 mm.

27. Use, according to any one of claims 24 to 26, characterized in that composition C is in the form of granules.

28. Use, according to any one of claims 24 to 27, characterized in that said article or said part or said coating has at least one of the following properties: - a tensile modulus of elasticity, as measured by ISO 527-2:2019 / 1A at 20°C, of ​​less than 4.0 GPa, preferably less than 3.5 GPa, preferably less than 3.2 GPa, and preferably less than 3.0 GPa, and / or - a nominal strain at break as measured by ISO 527-2:2019 / 1A at 20°C greater than 8%, preferably greater than 10%, mainly greater than 15% or greater than 20%, - a Charpy impact resistance under ISO 179-1:2010 / 1eA greater than 5 kJ / m², preferably greater than 6 kJ / m², still preferably greater than 7 kJ / m². kJ / m2, and more preferably greater than 8 kJ / m2, - a tensile strength at the yield strength, as measured by ISO 527-2:2019 / 1A:2019 at 20°C, of ​​less than 95 MPa,and preferably less than 85 MPa, - a CO2 permeation measured at 60°C of less than 1.1x10⁸ (cm³.cm) / (cm².s.bar), - in the case of a sheath or tube forming a pipe, a structural flexibility such that the pipe is capable of withstanding at least 1,000 cycles, wherein for each cycle, the layer of the polymeric sheath or the composition C tube undergoes a level of flexural deformation ranging from -2% to +2%, without rupture of the layer of the polymeric sheath or the composition C tube. Petition 870250078433, dated 03 / 09 / 2025, pp. 72 / 89.

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