Ductile polyaryletherketone compositions

Abstract

The invention relates to granules consisting of a composition C comprising a non-delaminating polymer mixture M, the mixture M comprising: at least 50% by weight of at least one pseudo-amorphous or semi-crystalline polyaryletherketone, said polyaryletherketone having a melting temperature below or equal to 340°C, relative to the total weight of the mixture; and from 5% to 40% by weight of a poly(etherimide-siloxane) 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(etherimide-siloxane) copolymer, then the mixture M does not comprise a polysiloxane. The invention also relates to the use of the composition C for the manufacture of an article, of a part, or of a coating, at a maximum manufacturing temperature not exceeding 350°C.

Description

[0001] Ductile compositions based on polyaryletherketone(s)

[0002] Technical field

[0003] The present patent application relates to a polymer composition based on polyaryletherketone(s) having improved impact resistance, elongation at break and flexibility. It also relates to a method for manufacturing such a composition in the form of granules, as well as its use.

[0004] Prior art

[0005] Polyaryletherketones (PAEKs) are well-known high-performance engineering polymers. They can be used for applications requiring high temperatures and / or mechanical or even chemical stresses. They can also be used for applications requiring excellent fire resistance and low smoke or toxic gas emissions. They can also be used for their low gas permeability. Finally, they exhibit good biocompatibility.

[0006] These polymers are found in fields as varied as aeronautics and space, offshore drilling, automotive, railways, marine, wind power, sports, construction, electronics and even medical implants.

[0007] Notwithstanding these advantageous properties, it is sometimes necessary to formulate polyaryletherketones to meet specific specifications. Thus, greater flexibility may be sought to accommodate new modes of use and part placement, with greater bending potential. In particular, more ductile polyaryletherketone formulations may be sought, i.e., those with greater deformation at break and / or with a lower tensile / flexural elastic modulus and / or higher impact strength, compared to unformulated PAEK.

[0008] It is known from EP 3 749 714 A1, compositions consisting of a mixture of polyether-ketone-ketone (PEKK), from 3.75% to 7.5% by weight of a polysiloxane / polyetherimide block copolymer, and from 3.5% to 7% by weight of polydimethylsiloxane. Although these compositions do indeed provide greater deformation at break, have a lower elastic modulus in tension and a higher impact strength, compared to a non-formulated PEKK, the introduction of polydimethylsiloxane in high proportion has sometimes proved complicated to implement because the polydimethylsiloxane can be in the form of a very viscous liquid which is difficult to handle and to introduce in a well-controlled proportion. Furthermore, the addition of polydimethylsiloxane to a composition tends to reduce its barrier properties, including in particular its low permeation to gases, such as CO2.

[0009] Also known from US 2009 / 0234060 A1 are compositions consisting of a mixture of polyether-ether-ketone (PEEK) and polysiloxane / polyetherimide block copolymer having a higher impact resistance. More specifically, non-delaminating mixtures of PEEK and comprising from 10% to 25% by weight of polysiloxane / polyetherimide block copolymer, comprising from 20% to 30% by weight of polysiloxane, have been able to be manufactured (see in particular Table 2 of the patent document). Conversely, it has been shown that it is not possible to manufacture a non-delaminating mixture of PEEK and comprising 10% by weight of a polysiloxane / polyetherimide block copolymer, itself comprising 40% by weight of siloxane (comparative example CE-4).

[0010] Furthermore, the inventors of the present invention have realized that the use of a PEEK as PAEK in the composition implies that the composition is heated to a temperature at which the polysiloxane / polyetherimide block copolymers can thermally degrade, which is not desirable, particularly in processes where the composition remains molten for a sufficiently long time, particularly from 1 minute to 25 minutes and particularly from 5 minutes to 20 minutes, at a temperature above the melting temperature of the PAEK.

[0011] There is therefore currently a need to provide compositions based on PAEK(s) having better impact resistance, higher elongation at break and / or lower elastic modulus, making it possible to overcome one or more of the disadvantages of the compositions according to the prior art. For many applications, it is also preferable for the PAEK(s) compositions to retain the advantageous properties of unformulated PAEKs, in particular crystallized unformulated PAEKs. Among these advantageous properties are good chemical resistance, good temperature resistance and / or low gas permeation.

[0012] Objective of the invention

[0013] An objective of the invention is to provide a composition based on polyaryletherketone(s) having better impact resistance and / or higher elongation at break and / or lower elastic modulus, compared to a non-formulated polyaryletherketone.

[0014] Another objective of the invention is to provide such a composition which is thermally stable in the molten state, including for long residence times in the molten state. Another objective, at least according to certain embodiments, is to provide such a composition suitable for the manufacture of parts, articles, or thick coatings.

[0015] Another objective of the invention, at least according to certain embodiments, is to provide such a composition suitable for the manufacture of parts, articles, or thin coatings.

[0016] Another objective of the invention is, at least according to certain embodiments, to provide a composition having good chemical resistance, good temperature resistance and / or low gas permeation.

[0017] Summary of the invention

[0018] The present invention relates to granules consisting of a composition C comprising a non-delaminating mixture M of polymers, the mixture M comprising: at least 50% by weight of at least one polyaryletherketone, pseudo-amorphous or semi-crystalline, said polyaryletherketone having a melting temperature 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(etherimide-siloxane) 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(etherimide-siloxane) copolymer, then the mixture M does not comprise polysiloxane.

[0019] According to certain embodiments, the 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.

[0020] According to certain embodiments, the siloxane groups of the poly(etherimide-siloxane) copolymer represent more than 30%, by total weight of the poly(etherimide-siloxane) copolymer.

[0021] According to certain embodiments, the siloxane groups of the poly(etherimide-siloxane) copolymer represent less than 50% by total weight of the poly(etherimide-siloxane) copolymer.

[0022] According to certain embodiments, the 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.

[0023] According to certain embodiments, the polyaryletherketone having a melting temperature of less than or equal to 340°C is a poly-ether-ketone-ketone essentially consisting of, and preferably consisting of: a terephthalic unit and an isophthalic unit, the terephthalic unit having the chemical formula:

[0024] [Chem 1] the isophthalic unit having the formula:

[0025] [Chem 2] a repeating unit of formula (III) and a repeating unit of formula (IV), the repeating unit (III) having the formula:

[0026] [Chem 3] and the repeating motif (IV) having the formula: [Chem 4] a repeating unit of formula (III) and a repeating unit of formula (V), the repeating unit (V) having the formula:

[0027] [Chem 5] a repeating unit of formula (III) and a repeating unit of formula (VI), the repeating unit (VI) having the formula:

[0028] [Chem 6]

[0029] According to certain embodiments, said polyaryletherketone having a melting temperature of less than or equal to 340°C is a poly-ether-ketone-ketone essentially consisting of, and preferably consisting of: a terephthalic unit and an isophthalic unit, the terephthalic unit having the chemical formula:

[0030] [Chem 7] the isophthalic unit having the chemical formula:

[0031] [Chem 8] the molar percentage of terephthalic units relative to the sum of the terephthalic and isophthalic units being less than or equal to 74%, preferably from 0% to 5% or from 45% to 73%, and more preferably from 58% to 72%.

[0032] According to certain embodiments, said polyaryletherketone having a melting temperature less than or equal to 340°C, has a melting temperature 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.

[0033] According to certain embodiments, said polyaryletherketone having a melting temperature less than or equal to 340°C, has a melting temperature greater than or equal to 275°C, or greater than or equal to 285°C, or greater than or equal to 295°C.

[0034] According to certain embodiments, the poly(etherimide-siloxane) copolymer has the chemical formula: [Chem 9]

[0035] (XV) in which n is an integer from 5 to 100, R represents a phenylene, Z represents a residue of bisphenol A, R 4 represents n-propylene, E represents an integer from 2 to 50, and each R' of the siloxane is a methyl.

[0036] According to certain embodiments, the mixture M consists of said polyaryletherketone having a melting temperature less than or equal to 340°C, said poly(etherimide-siloxane) copolymer, and from 0% to 40% by weight of another thermoplastic polymer than said polyaryletherketone and said poly(etherimide-siloxane) copolymer, relative to the total weight of the mixture.

[0037] According to certain embodiments, the mixture M comprises from 0.1% to 3%, and preferably from 0.5% to 2%, by weight of polysiloxane as other thermoplastic polymer, relative to the total weight of the mixture M.

[0038] According to certain embodiments, the mixture M comprises less than 1% by weight of polysiloxane as another thermoplastic polymer, relative to the total weight of the mixture M.

[0039] According to certain embodiments, composition C comprises at least 70% by weight of mixture M and comprises from 0% to 40% by weight of one or more additives, relative to the total weight of the composition. Composition C may in particular 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 in particular comprise from 0.1% to 5% by weight of nucleating fillers (type of additive), such as mineral fillers, in particular talc, carbon fillers, in particular carbon nanotubes or carbon blacks, ceramic fillers, in particular boron nitride (NB), or metal oxides, in particular ZnO or MgO.

[0040] According to certain embodiments, 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%. According to certain embodiments, the mixture M comprises two polyaryletherketones P1 and P2 having a melting temperature less than or equal to 340°C, P1 being a semi-crystalline polymer having a melting temperature T1, and P2 being a semi-crystalline polymer having a melting temperature such that T2 <T 1 ou P2 étant un polymère pseudo-amorphe. Le polymère P2 peut notamment représenter au moins 50% en poids des polyaryléthercétones ayant une température de fusion inférieure ou égale à 340°C.According to particular embodiments, P2 may be a poly-ether-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 the terephthalic and isophthalic units being from 0% to 5% or from 45% to 67%, and, P1 may be a poly-ether-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 the terephthalic and isophthalic units being from 63% to 73%.

[0041] According to certain embodiments, the mixture M comprises two polyaryletherketones P3 and P4, P3 being a semi-crystalline or pseudo-amorphous polyaryletherketone having a melting temperature less than or equal to 340°C, preferably less than or equal to 320°C, and P4 being a polyaryletherketone having a melting temperature strictly greater than 340°C. The 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 by weight relative to the total weight of mixture M.According to particular embodiments, the polymer P3 may be a poly-ether-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 total number of moles of terephthalic and isophthalic units of the poly-ether-ether-ketone being from 0% to 5% or from 45% to 67%, and, the polymer P4 may be a poly-ether-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 total number of moles of terephthalic and isophthalic units of the poly-ether-ketone-ketone being from 78% to 85%.

[0042] According to certain embodiments, the mixture M comprises less than 30%, preferably less than 25%, and more preferably less than 20% by weight of the poly(etherimide-siloxane) copolymer, relative to the total weight of the mixture. The invention also relates to the use of the composition C for the manufacture of an article, a part, or a coating, at a maximum manufacturing temperature not exceeding 350°C, by molding, in particular by injection molding or by compression molding, by extrusion, in particular extrusion of films or sheets, calendering extrusion, extrusion of tubes or pipes, extrusion sheathing, by additive manufacturing by filament fusion (FFF), spinning, rotational molding, thermoforming.Composition C is in particular adapted so as to be brought to the maximum manufacturing temperature for a duration greater than 1 minute, or greater than 2, or greater than 3 minutes, or greater than 4 minutes, or greater than 5 minutes, or greater than 10 minutes, or greater than 25 minutes. This is in particular advantageous for the manufacture of a part, article, or coating having a thickness greater than 2 mm, or greater than 3 mm, or greater than 4 mm, or greater than 5 mm, or greater than 6 mm. According to certain embodiments, composition C thus capable of being used is in the form of granules.

[0043] The article, part, or coating manufactured may in particular have at least one, and according to certain embodiments all, of the following advantageous properties:

[0044] - 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,

[0045] - a nominal strain at break as measured according to ISO 527-2:2019 / 1A at 20°C greater than 8%, preferably greater than 10%, in particular greater than 15%, or greater than 20%,

[0046] - a Charpy impact strength according to ISO 179-1:2010 / 1eA greater than 5 KJ / m 2 , preferably greater than 6 KJ / m 2 , preferably still greater than 7 KJ / m 2 , and more preferably greater than 8 KJ / m 2 ,

[0047] - a yield stress, as measured according to ISO 527-2:2019 / 1A:2019 at 20°C, of ​​less than 95 MPa, and preferably less than 85 MPa,

[0048] - CO2 permeation measured at 60°C less than 1.1x10 -8 (cm 3 .cm) / (cm 2 .s.bar).

[0049] Furthermore, according to certain embodiments, in the case of a sheath or a tube forming a conduit, it is advantageous to have a structural flexibility such that the conduit is capable of undergoing at least 1000 cycles, where for each cycle, the layer of the polymer sheath or of the tube of composition C undergoes a level of flexural deformation varying from -2% to +2%, without rupture of the layer of the polymer sheath or of the tube of composition C. Detailed description of the invention

[0050] Figures

[0051] [Figure 1] represents the mass loss of a poly(etherimide-siloxane) copolymer sample (Siltem® STM 1500) obtained by thermogravimetric analysis (TGA) after heating under nitrogen at different temperatures for 1 hour.

[0052] [Figure 2] is a photograph of the external surface (left) or cross-section (right) of the 7mm thick strip of composition 1c manufactured in the experimental part.

[0053] [Figure 3] is a photograph of the external surface (left) or section (right) of the 7mm thick strip of composition 4 manufactured in the experimental part.

[0054] [Figure 4] is a photograph of the external surface (left) or section (right) of the 7mm thick strip of composition 5 manufactured in the experimental part.

[0055] Definitions

[0056] The term "thermoplastic polymer" refers to a polymer that becomes less viscous, or more liquid, or liquid when heated sufficiently and that reversibly retains its thermoplasticity. Thermoplastic polymers are generally contrasted with thermosetting polymers, which irreversibly transform into an insoluble, non-formable polymer network when heated.

[0057] The term "homopolymer" means a polymer consisting of a single repeating unit.

[0058] The term "copolymer" refers to a polymer resulting from the copolymerization of at least two types of chemically different monomers, called comonomers. A copolymer is therefore formed from at least two repeating units derived from different monomers. It can also be formed from three or more repeating units derived from different monomers.

[0059] The copolymer may have a homogeneous structure, in particular of the statistical, alternating or random type, or a heterogeneous structure, in particular of the sequenced or block type.

[0060] In particular, the term "block copolymer" or "block copolymer" is understood to mean copolymers in the aforementioned sense, in which at least two distinct homopolymer blocks are covalently linked. The length of the blocks may be variable. The blocks may be composed of 1 to 1000, preferably 1 to 500, more preferably 1 to 100, and in particular 1 to 50 repeating units, respectively. The link between the two homopolymer blocks may be: a simple covalent bond or, an intermediate non-repeating unit called a junction block. "Consisting essentially of unit(s)" is understood to mean that the unit(s) represent(s) a molar proportion of 95% to 99.9% relative to the total number of moles of repeating units in the polymer.

[0061] “Consisting of unit(s)” means that the unit(s) represent(s) a molar proportion of at least 99.9%, in particular 100%, in the polymer relative to the total number of moles of repeating units in the polymer.

[0062] The term "non-delaminating polymer blend" is understood to mean a macroscopically homogeneous polymer composition. The term includes in particular such compositions composed of phases immiscible with each other and dispersed on a micrometric or submicron scale. The term "non-delaminating" refers in particular to the property of a composition or an article derived from the composition, of not exhibiting a visually observable separation into several layers, such as flaking or onion skin effect.

[0063] The term "granule" refers to grains of composition, more or less cylindrical or spherical in shape, particularly suitable for extrusion or injection processes. These grains generally have a characteristic size of between 0.5 mm and 10 mm, particularly between 1 mm and 5 mm.

[0064] The term "glass transition temperature", denoted T, is understood to mean g, designate the temperature at which an at least partially amorphous polymer passes from a rubbery state to a glassy state, or vice versa, as measured by differential scanning calorimetry (DSC) according to standard NF ISO 11357-2:2020, in second heating, using temperature ramps in heating and cooling at 20°C / min. In the present invention, when reference is made to a glass transition temperature, it is more particularly, unless otherwise indicated, the glass transition temperature at half-step height as defined in this standard.

[0065] The term "melting temperature", denoted Tf, is understood to mean the temperature at which a semi-crystalline polymer passes into the viscous liquid state, as measured by differential scanning calorimetry (DSC) according to standard NF EN ISO 11357-3:2018, in the second heating, using a heating rate of 20°C / min. In the present invention, when reference is made to a melting temperature, it is more particularly, unless otherwise indicated (see in particular the adapted measurement method below for a pseudo-amorphous polymer), the peak melting temperature as defined in this standard.

[0066] The term “pseudo-amorphous” polymer is understood to mean a polymer that does not exhibit a melting endotherm as measured by differential scanning calorimetry (DSC) according to standard NF EN ISO 11357-3:2018, in the second heating, using heating and cooling rates of 20°C / min. The pseudo-amorphous polymer is nevertheless capable of crystallizing once brought to a temperature above its glass transition temperature, in particular to a temperature in the range Tg+40°C to Tg+110°C, for example at Tg+75°C, for a sufficient time, in particular for 10 to 30 minutes, for example 20 minutes. Thus, a melting temperature in the second heating can also be measured for the pseudo-amorphous polymers in the present invention, by proceeding as follows:

[0067] 1 èreheating according to a ramp of 20°C / min up to a plateau temperature in the range Tg+40°C to Tg+110°C, for example at Tg+75°C, for a sufficient time, in particular for 10 to 30 minutes, for example 20 minutes, in particular at Tg+75°C for 20 minutes;

[0068] Cooling at a 20°C / min ramp to room temperature;

[0069] - 2 ème heating according to a ramp at 20°C / min.

[0070] The term "tensile modulus of elasticity", or more simply "elastic modulus", is understood to mean the slope of the stress-strain curve O(E) in the interval between the two strains £i= 0.05% and £2= 0.25%, as defined in ISO 527-1:2019. The elastic modulus is expressed here in gigapascals (GPa). The slope is preferably measured by a linear regression method.

[0071] Although the elastic modulus is here determined by a mechanical tensile stress, it would not be outside the scope of the invention if the measurement were made using other types of stress, for example bending or compression.

[0072] Nominal deformation means the deformation calculated from the displacement of the jaws and the clamping distance of the test device, as defined in ISO 527-1:2019.

[0073] Nominal strain at break is defined as the strain at the last recorded point before the stress is reduced to a value less than or equal to 10% of the strength when failure occurs after the yield point, as defined in ISO 527-1:2019. It is expressed as a dimensionless ratio or as a percentage (%). The actual measurement of the elastic modulus and the nominal strain at break corresponds to the average of five tests carried out consecutively. These tests can, for example, be carried out using an MTS 810® device, marketed by MTS Systems Corporation, equipped with a mechanical extensometer. The term "Charpy impact strength", or more simply "impact strength", is understood to refer to the impact strength of bars of dimension 80*10*4 mm 3notched type A, as measured according to ISO 179:2010. The actual measurement corresponds to the average of 10 tests carried out consecutively. A notch (V-shaped with a notch bottom radius of 0.25 + / - 0.05 mm) can be implemented on a device specially designed for this purpose (Automatic Notchvis Plus, marketed by Ceast). The bars are then left to rest for 24 hours. The impact resistance measurement can be carried out on a Zwick 5102 impact testing machine.

[0074] Generally, 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 the same property. For the purposes of the present application, the term "gas permeation" has been chosen. Gas permeability is typically measured by following the fluid permeability test method of API17J 2009.

[0075] The singular forms “a” and “the” applied to composition constituents, such as polyaryletherketone having a melting temperature of less than or equal to 340°C, or poly(etherimide-siloxane) copolymer, mean by default “at least one” and respectively “said at least one”. The singular forms nevertheless include, without it being necessary to recall it each time, the embodiments where “a” means “a single one” and “the” means “the only one”.

[0076] In all value ranges stated in this application, the terminals are included unless otherwise stated.

[0077] The non-delaminating polymer blend M comprises at least 50% by weight of at least one polyaryletherketone having a melting temperature less than or equal to

[0078] 340°C, relative to the total weight of the mixture. The melting temperature of a semi-crystalline polyaryletherketone is measured according to standard NF EN ISO 11357-

[0079] 3:2018 and that of a pseudo-amorphous polyaryletherketone according to a suitable measurement method, as specified above.

[0080] The non-delaminating mixture M of polymers may in particular 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 of less than or equal to 340°C, relative to the total weight of mixture M. Optionally, the mixture M may also comprise from 0% to 40% by weight of a polyaryletherketone having a melting temperature strictly greater than 340°C as other thermoplastic polymer, relative to the total weight of mixture M.

[0081] The mixture M may in particular comprise more than 5% by weight of a polyaryletherketone having a melting temperature strictly greater than 340°C as other thermoplastic polymer, relative to the total weight of mixture M.

[0082] The mixture M may in particular 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 greater than 340°C as other thermoplastic polymer, relative to the total weight of mixture M.

[0083] According to certain embodiments, the mixture M does not comprise any other polyaryletherketone than said at least one polyaryletherketone having a melting temperature less than or equal to 340°C.

[0084] A polyaryletherketone (PAEK) has the following formula units: (-Ar-X-) and (-Ari-Y-), in which:

[0085] - Ar and An each denote a divalent aromatic radical;

[0086] - Ar and An may preferably be chosen from 1,3-phenylene, 1,4-phenylene, 1,1'-biphenylene divalent in positions 3,3', 1,1'-biphenyl divalent in positions 3,4', 1,4-naphthylene, 1,5-naphthylene and 2,6-naphthylene;

[0087] - X denotes an electron-withdrawing group; it may preferably be chosen from the carbonyl group and the sulfonyl group,

[0088] - Y denotes a group selected from an oxygen atom, a sulfur atom, an alkylene group, such as -(CH)2- and isopropylidene.

[0089] In these X and Y units, at least 50%, preferably 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.

[0090] According to a preferred embodiment, 100% of the X groups denote a carbonyl group and 100% of the Y groups represent an oxygen atom.

[0091] Advantageously, the PAEK(s) can be chosen from:

[0092] - a poly-ether-ketone-ketone, also called PEKK; a PEKK comprises one or more units of formula: -Ph-O-Ph-C(O)-Ph-C(O)-; - a poly-ether-ether-ketone, also called PEEK; a PEEK comprises one or more units of formula: -Ph-O-Ph-O-Ph-C(O)-;

[0093] - a polyether ketone, also called PEK; a PEK comprises one or more units of formula: -Ph-O-Ph-C(O)-;

[0094] - a polyether-ether-ketone-ketone, also called PEEKK; a PEEKK comprises one or more units of formula: -Ph-O-Ph-O-Ph-C(O)- Ph-C(O)-;

[0095] - a polyether-ether-ether-ketone, also called PEEEK; a PEEEK comprises one or more units of formula: -Ph-O-Ph-O-Ph-O- Ph-C(O)-;

[0096] - a poly-ether-diphenyl-ether-ketone also called PEDEK; a PEDEK comprises one or more units of formula: a PEDEK comprises one or more units of formula -Ph-O-Ph-Ph-O-Ph-C(O)-;

[0097] - their mixtures; and,

[0098] - copolymers comprising at least two of the aforementioned units, in which: Ph represents a phenylene group and -C(O)- a carbonyl group, each of the phenylenes being able independently to be of the ortho (1-2), meta (1-3) or para (1-4) type, preferentially being of the meta or para type.

[0099] In addition, defects, end groups and / or monomers may be incorporated in very small amounts into the polymers as described in the list above, without affecting their performance.

[0100] According to certain embodiments, the PAEK is a poly-ether-ketone-ketone (PEKK) consisting essentially of, and preferably consisting of: a terephthalic repeating unit and, where appropriate, an isophthalic repeating unit, the terephthalic repeating unit (“T unit”) having the formula: [Chem 10] the isophthalic unit (“I unit”) having the formula:

[0101] [Chem 11]

[0102] The mass proportion of T units to the sum of T and I units can vary from 0% to 100%. The choice of the molar proportion of T units to the sum of T and I units is one of the factors that allows adjustment of the melting temperature as well as the crystallization rate properties of polyether-ketone-ketones. A given molar proportion of T units to the sum of T and I units can be obtained by adjusting the respective concentrations of the reactants during polymerization, in a manner known per se.

[0103] Preferably, the polyether-ketone-ketone has a homogeneous structure, and can in particular be of the statistical type.

[0104] Polyether-ketone-ketones having a mass proportion of T units relative to the sum of T and I units less than or equal to 74% have a melting temperature less than or equal to 340°C.

[0105] Preferably, a polyetherketoneketone having a melting temperature of less than or equal to 340°C is chosen from polyetherketoneketones having a mass proportion of T units relative to the sum of the T and I units of 0% to 5% or 45% to 73%. The mass proportion of T units relative to the sum of the T and I units may in particular be 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%.

[0106] More preferably, a polyetherketoneketone having a melting temperature of less than or equal to 340°C is chosen from polyetherketoneketones having a mass proportion of T units relative to the sum of T and I units of 58% to 72%.

[0107] The molar proportion of T units relative to the sum of the T and I units may in particular be approximately 60% or approximately 70%. A polyether-ketone-ketone having a T:I ratio of approximately 60% is a pseudo-amorphous polymer within the meaning of the present invention. A polyether-ketone-ketone having a ratio of approximately 70% is a semi-crystalline polymer.

[0108] Such polyether ketone ketones are commercially available under the name Kepstan® from Arkema.

[0109] In some embodiments, the PAEK may be a PEEK-PEDEK copolymer consisting essentially of, or even consisting of, a repeating unit having the formula: [Chem 12] and a repeating unit having the formula: [Chem 13]

[0110] Copolymers consisting of repeating units of formula (III) and (IV) having a molar proportion of units (III) relative to the sum of units (III) and (IV) ranging from 5% to 45% have a melting temperature less than or equal to 340°C.

[0111] According to certain embodiments, the PAEK may be a copolymer essentially consisting of, or even consisting of, a repeating unit having the formula (III) and a repeating unit having the formula:

[0112] [Chem 14]

[0113] Copolymers consisting of repeating units of formula (III) and (V) having a molar proportion of units (III) relative to the sum of units (III) and (V) ranging from 5% to 100% have a melting temperature less than or equal to 340°C.

[0114] According to certain embodiments, the PAEK may be a copolymer essentially consisting of, or even consisting of, a repeating unit having the formula (III) and a repeating unit having the formula:

[0115] [Chem 15]

[0116] Copolymers consisting of repeating units of formula (III) and (VI) having a molar proportion of units (III) relative to the sum of units (III) and (VI) ranging from 5% to 100% have a melting temperature less than or equal to 340°C.

[0117] According to certain embodiments, the PAEK having a melting temperature of less than or equal to 340°C has in particular a melting temperature of less than or equal to 335°C, or a melting temperature of less than or equal to 330°C, or a melting temperature of less than or equal to 325°C, or a melting temperature of less than or equal to 320°C. This has the advantage of limiting 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 the PAEK having a melting temperature of less than or equal to 340°C, including for prolonged residence times in the melt.

[0118] According to certain embodiments, the 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 has the advantage that the article, part, and / or coating obtained by extrusion or injection from the granules according to the invention has sufficient heat resistance properties.

[0119] According to certain embodiments, the non-delaminating mixture M of polymers comprises two polyaryletherketones having a melting temperature less than or equal to 340°C. The mixture M comprises a first polyaryletherketone P1 being a semi-crystalline polymer having a melting temperature T1, and a second polyaryletherketone P2 being either a semi-crystalline polymer having a melting temperature such that Ï2 <TI, soit un polymère pseudo-amorphe.

[0120] According to certain embodiments, the polymer P1 may represent at least 50% by weight of the polyaryletherketones having a melting temperature less than or equal to 340°C.

[0121] According to other embodiments, the polymer P2 may represent at least 50% by weight of the polyaryletherketones having a melting temperature less than or equal to 340°C.

[0122] 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, 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%, and, P1 is a poly-ether-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 the terephthalic and isophthalic units being from 63% to 73%.

[0123] 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, the molar percentage of terephthalic units relative to the sum of the terephthalic and isophthalic units being from 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, the molar percentage of terephthalic units relative to the sum of the terephthalic and isophthalic units being from 63% to 73%. Advantageously, P2 represents at least 50% by weight of the polyaryletherketones having a melting temperature of less than or equal to 340°C.

[0124] In the embodiments where the mixture M further comprises a polyaryletherketone having a melting temperature strictly greater than 340°C, the latter may be a PEEK homopolymer consisting of the repeating unit (III); a PEEK-PEDEK copolymer, essentially consisting of, or consisting of, the repeating units of formula (III) and of formula (IV), the molar proportion of units of formula (III) relative to the total number of moles of units (III) and (IV) being strictly greater than 45%, in particular greater than or equal to 50%; or a PEKK, essentially consisting of, or consisting of, terephthalic (T) and isophthalic (I) repeating units, the molar proportion of terephthalic repeating units relative to the total number of moles of terephthalic and isophthalic repeating units being strictly greater than 74%, in particular 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%.

[0125] According to certain embodiments, the mixture M comprises two polyaryletherketones P3 and P4, P3 being a semi-crystalline or pseudo-amorphous polyaryletherketone having a melting temperature less than or equal to 340°C, preferably less than or equal to 320°C, and P4 being a polyaryletherketone having a melting temperature strictly greater than 340°C. The 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 by weight relative to the total weight of mixture M.According to particular embodiments, the polymer P3 may be a poly-ether-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 total number of moles of terephthalic and isophthalic units of the poly-ether-ether-ketone being from 0% to 5% or from 45% to 67%, and, the polymer P4 may be a poly-ether-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 total number of moles of terephthalic and isophthalic units of the poly-ether-ketone-ketone being from 78% to 85%.

[0126] According to certain embodiments, the mixture M comprises a poly-ether-ketone-ketone having a mass proportion of T units relative to the sum of the T and I units of 78% to 85%. The molar proportion of T units relative to the sum of the T and I units may in particular be approximately 80%. Such a poly-ether-ketone-ketone is commercially available under the name Kepstan® from the company Arkema.

[0127] According to certain embodiments, the mixture M comprises a poly-ether-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 total number of moles of terephthalic and isophthalic units of the poly-ether-ketone-ketone being from 0% to 5% or from 45% to 67%, and, a poly-ether-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 total number of moles of terephthalic and isophthalic units of the poly-ether-ketone-ketone being from 78% to 85%.

[0128] Advantageously, the mixture M comprises 25% by weight or less, 20% by weight or less, 15% by weight or less, or 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.

[0129] Polyfetherimide-siloxane copolymer)

[0130] The poly(etherimide-siloxane) copolymer makes it possible in particular to improve the toughness, flexibility, elongation at break and resistance to crack propagation of composition C.

[0131] The polymer blend M comprises from 5% to 40% by weight of a poly(etherimide-siloxane) copolymer, relative to the total weight of the blend.

[0132] Preferably, the 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.

[0133] According to certain embodiments, the 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.

[0134] Preferably, the mixture M comprises more than 7.5% by weight of the poly(etherimide-siloxane) copolymer, relative to the total weight of the mixture. The mixture M may in particular comprise more than 8.0% by weight of the poly(etherimide-siloxane) copolymer, relative to the total weight of the mixture.

[0135] According to certain embodiments, the mixture M comprises from 5% to 8% by weight of the poly(etherimide-siloxane) copolymer, relative to the total weight of the mixture. According to certain embodiments, the mixture M comprises from 8% to 15% by weight of the poly(etherimide-siloxane) copolymer, relative to the total weight of the mixture.

[0136] According to certain embodiments, the mixture M comprises from 15% to 25% by weight of the poly(etherimide-siloxane) copolymer, relative to the total weight of the mixture.

[0137] Poly(etherimide-siloxane) copolymers comprise polyetherimide units and polysiloxane units, for example 5 to 1000, or 10 to 500 etherimide units and siloxane units.

[0138] Polyetherimide units include structural units of formula (VII): [Chem 16] wherein 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 chain 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):

[0139] [Chem 17] in which Q 1 represents — O — , — S — , — C(O) — , — SO2 — , — SO — , — C y H2 y— , where y represents an integer from 1 to 5 or a halogenated derivative thereof (which includes perfluoroalkylene groups) or — (CeHio)z — , where z represents an integer from 1 to 4. In one embodiment, R is m-phenylene, p-phenylene or diaryl sulfone.

[0140] Further, in formula (VI), T represents — O — or a group of formula — O — Z — O — , where the divalent bonds of the — O — group or the — O — Z — O — group are 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 moiety optionally substituted with 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):

[0141] [Chem 18] in which R a and R b may be the same or different and represent, for example, a halogen atom or a monovalent C1-6 alkyl group; p and q each independently represent integers from 0 to 4; c represents 0 to 4; and X arepresents a bridging group connecting the hydroxy-substituted aromatic groups, the bridging group and the hydroxy substituent of each C6 arylene group being arranged in the ortho, meta or para (more precisely para) position 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 C1-18 organic bridging group may be cyclic or acyclic, aromatic or non-aromatic, and may further comprise heteroatoms such as halogens, oxygen, nitrogen, sulfur, silicon or phosphorus. The C1-18 organic group may be arranged so that the C6 arylene groups attached thereto are each attached to a common alkylidene carbon or to different carbons of the C1-18 organic bridging group.

[0142] A particular example of a Z group is a divalent group of formula (X): [Chem 19] wherein Q represents — O — , — S — , — C(O) — , — SO2 — , — SO — or — CyhLy — , wherein y represents an integer from 1 to 5 or a halogenated derivative thereof (including a perfluoroalkylene group). In a particular embodiment, Z represents a bisphenol A derivative, such that Q, in formula (X), is 2,2-isopropylidene. In one embodiment in formula (VII), R represents m-phenylene or p-phenylene and T represents — O — Z — O — , where Z represents a divalent group of formula (X). Alternatively, R represents m-phenylene or p-phenylene and T represents — O — Z — O — , where Z represents a divalent group of formula (X) and Q represents 2,2-isopropylidene.

[0143] The polyetherimide blocks may be prepared by any of the methods well known to those skilled in the art, including the reaction of an aromatic bis(ether anhydride) of formula (XI):

[0144] [Chem 20] with an organic diamine of formula (XII):

[0145] H2N— R— NH2(XII) in which T and R are defined as described above. Copolymers of polyetherimides may be made by using a combination of an aromatic bis(ether anhydride) of formula (XI) and a different bis(anhydride), e.g., a bis(anhydride), where T does not contain ether functionality, and e.g., T represents a sulfone.

[0146] Illustrative examples of bis(anhydrides) include 3,3-bis[4-] dianhydride

[0147] (3,4-dicarboxyphenoxy)phenyl]propane; 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)diphenylsulfone dianhydride; 2,2-bis[4-(2,3-dicarboxyphenoxy)phenyl]propane dianhydride; 4,4'-bis(2,3-dicarboxyphenoxy)diphenyl ether dianhydride; 4,4'-bis(2,3-dicarboxyphenoxy)diphenyl sulfide dianhydride; 4,4'-bis(2,3-dicarboxyphenoxy)benzophenone dianhydride; 4,4'-bis(2,3-dicarboxyphenoxy)diphenylsulfone dianhydride; 4-(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)diphenyl-2,2-propane dianhydride; 4-(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)diphenyl ether dianhydride; 4-(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride;4-(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)benzophenone dianhydride; and 4-(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)diphenylsulfone dianhydride, as well as various combinations thereof.;

[0148] Examples of organic diamines include ethylenediamine, propylenediamine, trimethylenediamine, diethylenetriamine, triethylenetetramine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, 1,12-dodecanediamine, 1,18-octadecanediamine, 3-methylheptamethylenediamine, 4,4-dimethylheptamethylenediamine, 4-methylnonamethylenediamine, 5-methylnonamethylenediamine, 2,5-dimethylhexamethylenediamine, 2,5-dimethylheptamethylenediamine, 2,2-dimethylpropylenediamine, N-methyl-bis(3-aminopropyl)amine, 3-methoxyhexamethylenediamine, 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-1,3-phenylenediamine, 5-methyl-4,6-diethyl-1,3-phenylenediamine, 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 these compounds may also be used. In some embodiments, the organic diamine is m-phenylenediamine, p-phenylenediamine, sulfonyldianiline, or a combination comprising one or more thereof.

[0149] Siloxane blocks contain units of formula (XIII): [Chem 21] wherein each R' independently represents a monovalent C1-13 hydrocarbyl group and E is an integer from 1 to 100, especially from 2 to 50. For example, each R' may independently represent a C1-13 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, a C6-14 aryl group, a C6-10 aryloxy group, a C7-13 arylalkyl group, a C7-13 arylalkoxy group, a C7-13 alkylaryl group or a C7-13 alkylaryloxy group. The above groups may be wholly or partially halogenated with fluorine, chlorine, bromine or iodine, or a combination comprising at least one of these. In one embodiment, no bromine or chlorine is present and, in other embodiments, no halogen is present. Combinations of the above R' groups may be used in the same copolymer.In one embodiment, the polysiloxane blocks comprise R' groups that have a minimal content of hydrocarbon radicals. In a particular embodiment, an R' group having a minimal content of hydrocarbon compounds is a methyl group.

[0150] Poly(etherimide-siloxanes) may be formed by polymerization of an aromatic bisanhydride (XI) and a diamine component comprising an organic diamine (XII) as described above or a mixture of diamines, and a polysiloxanediamine of formula (XIV):

[0151] [Chem 22] wherein R' and E are as described in formula (XIII), and each R 4 independently represents a C2-C20 hydrocarbon moiety, in particular a C2-C20 arylene, an alkylene or an arylenealkylene group. In some embodiments, R 4represents a C2-C20 alkylene group, more specifically a C2-C10 alkylene group such as propylene, and E has an average value of 5 to 100, 5 to 75, 5 to 60, 5 to 15 or 15 to 40. Procedures for preparing the polysiloxane diamines of formula (XIV) are well known in the art.

[0152] In certain poly(etherimide-siloxane) copolymers, the diamine component used for preparing the copolymers may contain 10 to 90 mole percent (mol-%) or 20 to 50 mol-% or 25 to 40 mol-% of a polysiloxane diamine (XIV) and 10 to 90 mol-% or 50 to 80 mol-% or 60 to 75 mol-% of the diamine (XII), for example as described in U.S. Pat. No. 4,404,350. The diamine components may be physically mixed prior to reaction with one or more bisanhydrides, thereby forming a substantially random copolymer. Alternatively, block or alternating copolymers may be formed by selectively reacting (XII) and (XIV) with aromatic bis(ether anhydrides) (XI), to make polyimide blocks which are then reacted together. Thus, the poly(etherimide-siloxane) copolymer can be a block, random or graft copolymer.Poly(etherimide-siloxane) block copolymers comprise etherimide blocks and siloxane blocks in their polymer backbone. The etherimide blocks and siloxane blocks may be present in a random order, as blocks (i.e., AABB), alternating (i.e., ABAB), or in a combination thereof. Poly(etherimide-siloxane) graft copolymers are non-linear copolymers comprising the siloxane blocks connected to a linear or branched polymer backbone comprising etherimide blocks.

[0153] Examples of particular poly(etherimide-siloxanes) are described in U.S. Patent Nos. 4,404,350, 4,808,686 and 4,690,997.

[0154] According to preferred embodiments, the poly(etherimide-siloxane) consists essentially of, or consists of, units of formula (XV):

[0155] [Chem 23]

[0156] (XV) in which R' and E of the siloxane are as in formula (XIII), R and Z of the imide are as in formula (VII), R 4 is the same as R 4 as in formula (XIV), and n is an integer from 5 to 100. In a particular embodiment, R represents a phenylene, Z represents a residue of bisphenol A, R 4 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.

[0157] The relative amount of polysiloxane units and etherimide units in the poly(etherimide-siloxane) depends on the desired properties and is selected using the guidelines given in the present invention. In particular, the poly(etherimide-siloxane) copolymer is selected to have a certain average E value and is selected and used in an amount sufficient to provide the desired weight percentage (wt%) of siloxane units in the thermoplastic composition. In some embodiments, the polysiloxane block of the copolymer has a number average molecular weight (Mn) of 300 to 3,000 grams / mole (Daltons).

[0158] 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.

[0159] 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.

[0160] 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.

[0161] 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.

[0162] Poly(etherimide-siloxane) copolymers are commercially available under the name SILTEM® from Sabic.

[0163] Other thermoplastic polymer

[0164] According to certain embodiments, the mixture M may comprise from 0% to 40% by weight of a thermoplastic polymer other than the polyaryletherketone having a melting temperature less than or equal to 340°C and the poly(etherimide-siloxane) copolymer, relative to the total weight of mixture M.

[0165] According to certain embodiments, the mixture M does not comprise any other thermoplastic polymer than the polyaryletherketone having a melting temperature less than or equal to 340°C and the poly(etherimide-siloxane) copolymer. Other thermoplastic polymers that may include polyaryletherketone having a melting temperature strictly above 340°C, polysiloxane, fluoropolymer, polyetherimide (PEI), polyphenylene sulfone (PPS11), polysulfone (PSU), polycarbonate (PC), polyphenylene ether (PPE), polyphenylene sulfide (PPS), polyethylene terephthalate (PET), polyamide (PA), polybenzimidizole (PBI), polyamide-imide (PAI), polyether sulfone (PES), polyaryl sulfone, polyether imide sulfone), polyphenylene, polybenzoxazole, polybenzothiazole, or a mixture thereof.

[0166] According to certain embodiments, the other thermoplastic polymer may in particular be a polyaryletherketone having a melting temperature strictly greater than 340°C, as described above.

[0167] According to certain embodiments, the other thermoplastic polymer may in particular be a polysiloxane. According to these embodiments, the mixture M then comprises more than 7.5% by weight of the poly(etherimide-siloxane) copolymer, relative to the total weight of mixture M.

[0168] The polysiloxane may be mono- or di-substituted with C1-C12, preferably C1-C6, and especially C1-C4, alkyl groups and / or phenyl groups. Preferably, the alkyl groups are methyl groups. The alkyl or phenyl groups of the polysiloxane may be substituted with one or more functional groups such as epoxy, alkoxy, especially methoxy, amine, ketone, thioether, halogen, nitrile, nitro, sulfone, phosphoryl, imino or thioester. These functional groups may also be located at the end of the polysiloxane chain. Such functionalized polysiloxanes may be used for their reaction during mixing (reactive siloxanes).

[0169] Preferably, however, the polysiloxane does not have functional groups. Furthermore, the alkyl or phenyl groups of the polysiloxane may be substituted with one or more carbocyclic, aryl, heteroaryl, alkyl, alkenyl, bicyclic or tricyclic groups.

[0170] Preferably, the polysiloxane present in the mixture M as another thermoplastic polymer is a poly(dimethylsiloxane) (PDMS).

[0171] To facilitate handling, the polysiloxane can be combined with a solid support such as silica, particularly fumed silica.

[0172] According to certain embodiments, the mixture M comprises from 0.1% to 3%, and preferably from 0.5% to 2% by weight of polysiloxane as other thermoplastic polymer relative to the total weight of mixture M. According to certain embodiments, the mixture M comprises less than 1% by weight of polysiloxane relative to the total weight of mixture M.

[0173] In some embodiments, the mixture M does not comprise polysiloxane. In particular, in embodiments where the mixture M comprises from 5% to 7.5% by weight of a poly(etherimide-siloxane) copolymer, then the mixture M does not comprise polysiloxane.

[0174] Additives

[0175] 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.

[0176] Advantageously, composition C comprises from 0% to 30%, or from 0% to 25%, or from 1% to 20%, or from 2% to 10% by weight of additives, relative to the total weight of the composition.

[0177] Among the additives, one or more fillers may be mentioned. Among the possible fillers, one may mention in particular silica and alumina, nucleating fillers such as mineral fillers, in particular talc, carbon fillers, in particular carbon nanotubes or carbon blacks, ceramic fillers, in particular boron nitride (BN), or metal oxides, in particular ZnO or MgO, and reinforcing fillers, such as glass fibers or carbon fibers.

[0178] According to particular embodiments, composition C may comprise from 0.1% to 5%, in particular from 0.25% to 2.5%, by weight of a nucleating charge relative to the total weight of the composition. This makes it possible to modify the crystallization behavior of the polyaryletherketone(s), and in particular makes it possible to increase the final crystallinity in usual processes for forming polyaryletherketones that are slower to crystallize without significantly modifying the processing conditions. These polyaryletherketones that are slower to crystallize can in particular achieve sufficient crystallinity without, for example, having to consider an additional annealing step.

[0179] According to certain embodiments, the polyaryletherketone of composition C may be a poly-ether-ketone-ketone having a mass proportion of T units relative to the sum of the T and I units of 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 for example be a poly-ether-ketone-ketone having a mass proportion of T units relative to the sum of the T and I units ranging from 55% to 65%, in particular approximately 60%, and the carbon-based charge may be carbon nanotubes. Among the additives, mention may also be made of plasticizers. A plasticizer can lower the glass transition temperature of composition C. The plasticizer(s) can, for example, be chosen from the compounds defined in the Handbook of Plasticizers published by Georges Wypych.Composition C may in particular comprise 0% to 20% by weight of plasticizer(s), relative to the total weight of composition C.

[0180] Furthermore, composition C may optionally comprise minor quantities, in particular less than 1% by weight relative to the total weight of the composition, of functional additives. Examples of such additives include antistatic agents, antioxidants, molten stabilizers, conductive agents, flame retardants, colorants and reactive agents such as alkali carbonates.

[0181] Compositions C

[0182] Composition C constituting the granules comprises a non-delaminating mixture M of polymers, said mixture M comprising: at least 50% by weight of at least one polyaryletherketone, pseudo-amorphous or semi-crystalline, said polyaryletherketone having a melting temperature 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(etherimide-siloxane) 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(etherimide-siloxane) copolymer, then the mixture M does not comprise polysiloxane.

[0183] According to certain embodiments, the mixture M consists of: said at least one polyaryletherketone having a melting temperature less than or equal to 340°C, said poly(etherimide-siloxane) copolymer, and from 0% to 40% by weight of another thermoplastic polymer than said polyaryletherketone and said poly(etherimide-siloxane) copolymer, relative to the total weight of the mixture.

[0184] According to certain embodiments, the mixture M consists of said at least one polyaryletherketone and said poly(etherimide-siloxane) copolymer.

[0185] The mixture M may constitute at least 60% by weight, or at least 70% by weight, or at least 75% by weight, or at least 80% by weight, or at least 85% by weight, or at least 90% by weight, relative to the total weight of the composition.

[0186] 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 composition. Composition C may in particular consist of at least 70% by weight of mixture M and from 0% to 30% of one or more additives.

[0187] According to certain embodiments, composition C consists of mixture M and from 0% to 30% by weight of additives, relative to the total weight of composition C

[0188] According to certain embodiments, composition C consists of mixture M and from 0% to 30% by weight of additives, relative to the total weight of composition C.

[0189] According to certain embodiments, composition C consists of mixture M and 0% to 30% by weight of additives, including 0% to 20% by weight of plasticizer(s), 0% 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.

[0190] 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.

[0191] Implementation of pellets

[0192] The process for preparing composition C in the form of granules may be carried out in a melt-mixing apparatus. Any melt-mixing apparatus known to those skilled in the art for preparing polymer compositions by melt-mixing may be used.

[0193] Suitable melt mixing equipment includes, for example, kneaders, Banbury mixers, single-screw extruders and twin-screw extruders.

[0194] Preferably, an extruder is used which is equipped with means for dosing all the desired components into the extruder, in the main hopper of the extruder and / or by side feed.

[0195] For the manufacture of granules, the melt residence time in the melt mixing apparatus is generally very short, in particular less than 1 minute.

[0196] According to certain embodiments, the maximum temperature used to carry out the melt mixing is greater than 350°C. This may in particular be necessary when the polymer mixture M comprises a semi-crystalline polyaryletherketone having a melting temperature strictly greater than 340°C. These embodiments are not, however, preferred. In these cases, the residence time in the melt for the processing of the granules must remain low, in particular less than or much less than 1 minute. According to certain embodiments, the maximum temperature used to carry out 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 in particular possible when said polyaryletherketone having a melting temperature less than or equal to 340°C of the polymer mixture M is the polymer of the mixture having the highest melting temperature among the polymers of the mixture.

[0197] The various components of the composition can be fed simultaneously as a mixture of powders or granules or as a mixture of powder and granules, also called a dry blend. They can also be fed separately.

[0198] The order of combining components during melt mixing is not particularly limited.

[0199] The composition according to the invention generally appears as a heterophasic, but non-delaminating, composition. Indeed, most often, the poly(etherimide-siloxane) copolymer is poorly miscible in the poly(aryletherketone). A dispersed phase in the form of nodules in a continuous phase is then observed under electron microscopy. Preferably, the nodules have an average diameter of less than 20 μm, advantageously less than 10 μm and very particularly less than 5 μm.

[0200] Preferably, the poly(aryletherketone) forms the continuous phase (also called matrix) of the composition and the poly(etherimide-siloxane) copolymer forms the dispersed phase.

[0201] Uses according to the invention

[0202] Composition C according to the invention can be used for the manufacture of parts, articles or coatings, by one of the conventional shaping processes, at a maximum manufacturing temperature not exceeding 350°C.

[0203] In some embodiments, the maximum temperature during the manufacturing process does not exceed 345°C, or does not exceed 340°C, or does not exceed 335°C. Generally, the maximum temperature during the manufacturing process is set at 5°C to 40°C above the melting temperature of the polyaryletherketone having a melting temperature of less than or equal to 340°C.

[0204] According to certain embodiments, the maximum temperature during the manufacturing process is set at: from 10°C to 30°C or from 15°C to 25°C above the melting temperature of the polyaryletherketone having a melting temperature less than or equal to 340°C.

[0205] A sufficiently low maximum temperature allows the manufacture of parts, articles, or coatings to be carried out, even for long residence times at the maximum manufacturing temperature or a nearby temperature. This residence time may in particular 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 greater than 10 minutes, or greater than 20 minutes. Thus, composition C can be shaped for example by molding, in particular by injection molding or by compression molding, by extrusion, in particular extrusion of films or sheets, calendering extrusion, extrusion of tubes or pipes, extrusion sheathing, by additive manufacturing by filament fusion (FFF), spinning, rotational molding, thermoforming.

[0206] In some embodiments, thick parts, articles, or coatings may be manufactured. They generally have a thickness in composition 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 implementation of the manufacture of such elements generally involves an average residence time at the maximum manufacturing temperature or at a temperature thereabout, 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.

[0207] Examples of thick parts or articles include plates, bars, sheathing, or tubes.

[0208] Furthermore, thin parts, articles or coatings can also be manufactured. They generally 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 implementation of the manufacture of such elements generally involves shorter average residence times than for the manufacture of thick elements. However, locally, particularly in stagnation zones, the residence time of composition C at the maximum manufacturing temperature or a nearby 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 greater than 10 minutes, or greater than 20 minutes.

[0209] Examples of thin parts or articles include films, coatings, or sheathing.

[0210] "Thickness" is generally understood to mean one of the dimensions of the article, part, or coating, measured by the distance between its two major faces. For a coating, where the thickness is generally uniform along the coating, thickness refers to the average thickness of the coating over the entire coating. Generally, the coating thickness is the same within ±5%, typically ±2%, at any point along the coating. Thickness can be measured, for example, using a caliper.

[0211] In some embodiments, composition C may be used as a thin or thick layer of coating or sheathing for electrical cables. Composition C is particularly advantageous for the manufacture of articles, parts, or coatings having better impact resistance and / or higher elongation at break and / or lower elastic modulus, compared to unformulated polyaryletherketone granules. This results in the possibility of manufacturing durable parts because they have lower crack propagation.

[0212] The granules make it possible in particular to confer one or more, and according to certain embodiments all, of the following properties to the articles, parts, or coatings manufactured: a tensile modulus of elasticity, as measured by the ISO 527-2:2019 / 1 A standard 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 according to the ISO 527-2:2019 / 1A standard at 20°C of greater than 8%, preferably greater than 10%, in particular greater than 15%, or greater than 20%, a Charpy impact strength according to the ISO 179-1:2010 / 1 eA standard of greater than 5 KJ / m 2 , preferably greater than 6 KJ / m 2 , preferably still greater than 7 KJ / m 2 , and more preferably greater than 8 KJ / m 2, a yield stress, as measured according to 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 1.1x10 -8 (cm 3 .cm) / (cm 2 .s.bar),

[0213] - in the case of a sheath or a tube forming a conduit, a structural flexibility such that the conduit is capable of undergoing at least 1000 cycles, where for each cycle, the layer of the polymer sheath or of the tube of composition C undergoes a level of bending deformation varying from -2% to +2%, without rupture of the layer of the polymer sheath or of the tube of composition C, as presented in example 2.

[0214] The increased flexibility and elongation at break allow higher deformations and consequently access to new designs, in particular for assembly or winding. Thus, the composition according to the invention is particularly interesting for the manufacture of parts in the field of pipes, cables, aeronautics, automobiles, electronics, electrical engineering, composites, additive manufacturing and medical devices.

[0215] The manufactured parts, articles or coatings can achieve different levels of crystallinity, in particular controllable by the crystallization kinetics of composition C. As described above in particular embodiments, and as illustrated in particular in example 1, the control of the crystallization kinetics of composition C can be obtained in various ways: i) by selection of a single polyaryletherketone having a melting temperature less than or equal to 340°C, ii) mixing two polyaryletherketones having a different melting temperature and less than 340°C, iii) mixing two polyaryletherketones having a different melting temperature, one less than or equal to 340°C and the other strictly greater than 340°C and iv) mixing a polyaryletherketone having a melting temperature less than or equal to 340°C and a nucleating charge.

[0216] The level of crystallinity can be evaluated by DSC in first heating at 20°C / min by the calculation: AHH-AHCC. The term "AHcc" corresponds to the cold crystallization enthalpy and the term "AHn" corresponds to the fusion enthalpy in first heating at a heating rate of 20°C / min. These enthalpies are expressed in Joule per gram of composition.

[0217] The expression AHfi-AHcc can have a value generally ranging from 0 to 50 J / gram of composition C. It can notably have a value of 0 to 5 J / g, or from 5 J / g to 10 J / g, or from 10 J / g to 15 J / g, or from 15 J / g to 20 J / g, or from 20 J / g to 25 J / g, or from 25 J / g to 30 J / g, or from 30 J / g to 35 J / g, or from 35 J / g to 40 J / g, or from 40 J / g to 45 J / g, or from 45 J / g to 50 J / g. A crystallinity level of 0 to 10 J / gram of composition is considered a low to moderate level of crystallinity. Parts, articles or coatings with this level of crystallinity have the advantage of allowing easier processing thanks to lower processing temperatures as well as good subsequent thermoformability.

[0218] A level of crystallinity strictly greater than 10 J / gram of composition is considered a moderate to high level of crystallinity. Parts, articles or coatings with this level of crystallinity have the advantage of generally having better chemical resistance, better temperature resistance and / or lower gas permeation compared to those with a lower level of crystallinity, but are generally less easy to process and / or less easily heat-formable.

[0219] According to certain uses of the invention, composition C may be in the form of granules. These granules may have been implemented as described above. Alternatively, according to other uses of the invention, the constituent elements of composition C may be added by mixing in the molten state during conventional shaping processes. For example, it may be envisaged that all the constituent elements of composition C are added by mixing in the molten state during conventional shaping processes. It may also be envisaged that mixture M is in the form of granules and the other elements of composition C, in particular additives, are added by mixing in the molten state during conventional shaping processes.

[0220] Examples

[0221] Raw materials

[0222] The following commercial polymers were used:

[0223] KEPSTAN® PEKK, grades of the 6000, 7000, 8000 series suitable for extrusion, marketed by Arkema. These polymers are PEKK copolymers with a T / l ratio of approximately 60 / 40 (pseudo-amorphous with a melting temperature of 303°C), 70 / 30 (semi-crystalline with a melting temperature of 331°C) and 80 / 20 (semi-crystalline with a melting temperature of 355°C) respectively. SILTEM® STM1500, marketed by Sabic. It is a poly(etherimide-dimethylsiloxane) (PEI-PDMS) copolymer. It has a mass proportion of 40% polydimethylsiloxane relative to the total weight of the polymer.

[0224] SILTEM® STM1500 is amorphous and has a glass transition temperature Tg of 168°C.

[0225] PEEK 450G™, marketed by Victrex, suitable for extrusion (semi-crystalline with a melting temperature of 343°C).

[0226] Carbon nanotubes (CNTs), GraphiStrength® C100, marketed by Arkema.

[0227] Preparation of granules

[0228] Several formulations including a PAEK, a poly(etherimide-siloxane) copolymer, and optionally a nucleating agent were made by compounding on a COPERION ZSK MC26 L / D =40 Twin-Vis extruder and 10 barrels.

[0229] After drying the raw materials, they were introduced in different proportions (see Table 1) via 1 or 2 feeders on the first barrel and a third feeder allowing lateral feeding before the melting zone on the 4th barrel of the poly(etherimide-siloxane) copolymer. The screw speed for all the tests was set at approximately 200 rpm and the flow rate at 20 kg / h. The residence time where the compositions are in the melt is estimated to be much less than 1 minute. To manufacture the granules of compositions 2, 3, 4 and 8 the temperature profile used has a maximum set temperature at 320°C and a die temperature at 320°C.

[0230] To manufacture composition 5 pellets, the profile used has a maximum set temperature of 340°C and a die temperature of 340°C. This profile allows in particular to give a better appearance to the rod than the previous temperature profile. To manufacture composition 1c pellets, the profile used has a maximum set temperature of 370°C and a die temperature of 370°C. Indeed, the two previous profiles were not suitable and the presence of unmelted particles remained in the rod. It should be noted that the appearance of the rod improves by increasing the profile temperatures up to 370°C, but the rod breaks easily when stretched.

[0231] To manufacture composition 7c pellets, the profile has a maximum set temperature of 370°C, and a die temperature of 370°C.

[0232] [Table 1]

[0233] Example 1 - Extrusion of 7mm thick strips

[0234] After drying overnight at 150°C, the granules of the different formulations were used to prepare extruded strips.

[0235] A Collin single-screw extruder with a screw diameter of 30 mm and an L / D of 25 was used. The extruder is connected to a flat die with a width of 50 mm and an air gap of 8 mm. At the die outlet, the melt is conveyed onto a 3-roll calendering system. The spacing between the rolls was adjusted just above the desired thickness to produce 7 mm thick strips. The strips were then cut to the desired length using a guillotine at the end of the line.

[0236] The extruder temperature conditions were as follows:

[0237] To manufacture the composition 2, 3 and 4 strips, a temperature profile with rising temperatures up to the last zone and die at 320°C was used.

[0238] To manufacture the composition 5 strip, a bell-shaped temperature profile was used to achieve a homogeneous material and stable extrusion, with a maximum set temperature of 335°C and a final zone and die at 325°C.

[0239] To manufacture the composition 1c strip, a bell profile was used to have a sufficiently homogeneous material and a sufficiently stable extrusion, with a maximum set temperature of 370°C and a final zone and die at 350°C.

[0240] 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 set temperature equal to 350°C and a die temperature equal to 330°C.

[0241] For all strips, the screw speed was set at 30 rpm and an overall line speed of approximately 0.2 m / min. The residence time of the material in the extruder to form 7 mm thick strips is estimated to have been approximately 3-4 minutes.

[0242] Appearance of the bands

[0243] Referring to Figure 2, the composition 1c band is delaminated (sheets visible on the section) and has numerous porosities (numerous bubbles visible on the surface or on the section).

[0244] Unlike the composition strip 1c, the composition strips 2-5; 6c do not show any delamination visible to the naked eye (smooth appearance on the section) and do not show any porosity (no bubbles visible on the surface or on the section). Figures 3 and 4 represent respectively sectional and surface views of the composition strip 4 and the composition strip 5.

[0245] Preparation of type 1A specimens and type 1 bars, type A notch

[0246] To carry out mechanical tests, type 1A specimens and type 1A bars were manufactured subtractively by machining / milling, retaining only the core of the strips.

[0247] Due to the heterogeneous and delaminated nature of the 1c composition strip, it was not possible to produce correct specimens / bars. Therefore, it could not be mechanically tested. The dimensions and shape of the type 1A specimens are described in ISO 527-2:2012 (section 11 and Table 1 page 5). These specimens are hereinafter referred to as “ISO 527-2 / 1A specimens”.

[0248] Type 1 bars have a dimension of 80.0x10.0x4.0 mm 3, as described in ISO 179-1:2010 (section 6.3, Table 1). A “V” 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”.

[0249] The specimens and notched bars were then left to stand for 24 hours at 23°C and 50% relative humidity.

[0250] Mechanical characterizations

[0251] ISO 527-2 / 1A specimens were used to determine the modulus of elasticity and nominal strain at break at 23°C and 50% RH of compositions 2-5, 6c and 8 according to ISO 527-1:2019.

[0252] For the determination of the modulus of elasticity, a crosshead speed equal to 1 mm / min was used.

[0253] For the determination of the nominal strain at break, a crosshead speed equal to 50 mm / min was used.

[0254] ISO 179-1 / 1eA bars were used to determine the Charpy impact strength of compositions 2-5, 6c and 8 according to ISO 179-1:2010.

[0255] No mechanical characterization was possible for composition 1c due to the presence of numerous porosities in the core of the extruded strips.

[0256] Crystallinity characterization

[0257] The crystallinity of the samples was evaluated by DSC in first heating at 20°C / min by the calculation: AHH-AHCC.

[0258] The results of the different characterizations are grouped in Table 2 below.

[0259] [Table 2]

[0260] These examples demonstrate the advantage of using different compositions of PAEK having a melting temperature less than or equal to 340°C and poly(etherimide-siloxane) copolymer, allowing the shaping of objects: o non-delaminated and homogeneous, even in the case of relatively long residence times at the transformation temperature; o ductile, i.e. having a relatively low elastic modulus, a high nominal strain at break, and a high Charpy notched impact strength; o possibly being of great thickness without losing the aforementioned advantageous properties.

[0261] The modification of crystallization behavior brought about by i) mixing polyaryletherketones and / or ii) adding an additive leads to objects that can have good crystallinity while maintaining good ductility. These higher levels of crystallization can be sought for better chemical resistance, high barrier properties or to allow the mechanical properties of the composition to be maintained when used above the glass transition temperature of the polyaryletherketones.

[0262] Example 2 - Preparation of a sheath by extrusion and evaluation of certain properties Three types of granules with formulation 4, 5 and 7c were used. They were first dried in a drying apparatus (Piovan) with a dew point of -40°C for 48h at 180°C. The humidity level was checked after drying with a humidity meter (Aquatrac) and was less than 50 ppm.

[0263] The granules were then introduced at a temperature of 100°C into a single-screw extruder (manufactured by Maillefer - 45mm diameter equipped with a three-zone screw), with a temperature profile as described in Example 1. The residence time of the polymer composition in the molten state depends directly on the speed of the extruder screw and can be calculated.

[0264] Several 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 sheath produced was observed.

[0265] Table 3 shows that depending on the composition used, the temperature of the extrudate obtained was different. Composition 4, which is the one with the lowest melting temperature, had the best surface appearance, which is explained by the fact that the poly(etherimide-siloxane) copolymer was not degraded during extrusion.

[0266] [Table 3]

[0267] A 7mm thick sheath could be extruded onto a metal frame, thus demonstrating the possibility of extruding a thick layer.

[0268] Microscopic observations of the sheaths

[0269] Microscopic observations were made on the claddings produced from compositions 4, 5 and 7c. Thin lamellae of 15 μm were obtained with a microtome section (Leica 2065) and observed under a digital microscope (Keyence VHX 700F). The area of ​​the weld line where the residence time of the polymer composition in the molten state is known to be the longest was studied. Composition 5 showed a marked weld line without debonding but probably with some microstructural singularities and potentially slight degradation. Composition 4, on the contrary, shows almost no singularities in this area. Composition 7c shows clear signs of degradation around the entire circumference of the cladding with bubbles in the first 0.2 mm below the outer surface of the cladding, and in addition, bubbles localized at the weld line, indicating degradation related to residence time.

[0270] Mechanical properties

[0271] Tensile specimens were prepared and tested in tension at room temperature according to ISO 527-1A from the extruded sheath.

[0272] Table 4 shows the results of this test for extruded sheaths of composition 4 and 5 of Table 3.

[0273] [Table 4]

[0274] No mechanical characterization is presented here for composition 7c due to the presence of numerous porosities in the core of the extruded strips due to the presence of defects and numerous surface scratches throughout the sheath (see Table 3).

[0275] Flexibility

[0276] A 4-meter-long flexible pipe prototype consisting of a metal frame around which a polymer sheath is extruded was subjected to a bending test. To carry out the test, the flexible pipe prototype is mounted fixed and is blocked at one of its ends and left free to deform at its other end to allow it to be moved by the test bench cylinders.

[0277] Bending and counter-bending stresses were applied sequentially, with the pipe returning to its natural unbent shape at the end of a cycle. The pipe thus experienced a stress level varying from -2% to +2% for each cycle, and this for 1000 cycles, without any damage being observed on the polymer sheath.

[0278] Permeation resistance Portions of the sheath produced from composition 4 were prepared by machining to obtain thin membranes 1.5 mm thick from a localized area in the core of the sheath cross-section.

[0279] The permeation resistance was determined using the device for measuring the permeation coefficient of a sheath sample with respect to a gas as illustrated in Figure 2 and described from page 13, line 16 to page 15 line 2 of application FR 2 987 666. The method used is that described on page 15, line 7 to page 18, line 26 of this application, in which the gas used was pure CO2, the temperature was 60°C and the pressure difference between the two sides of the membrane was 40 bars. The permeation resistance was calculated using equation [6] described on page 18, line 12 of this application. The values ​​obtained for composition 4 are less than 1.1*10 -8 (cm3 .cm) / (cm 2 .s.bar).

Claims

Claims 1. Granules consisting of a composition C comprising a non-delaminating mixture M of polymers, the mixture M comprising: - at least 50% by weight of at least one polyaryletherketone, pseudoamorphous or semi-crystalline, said polyaryletherketone having a melting temperature 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(etherimide-siloxane) 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(etherimide-siloxane) copolymer, then the mixture M does not comprise polysiloxane.

2. Granules according to claim 1, in which the 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 any one of claims 1 and 2, in which 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, in which the siloxane groups of the poly(etherimide-siloxane) copolymer represent less than 50% by total weight of the poly(etherimide-siloxane) copolymer.

5. Granules according to any one of claims 1 to 4, in which the 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 one of claims 1 to 5, in which said polyaryletherketone having a melting temperature less than or equal to 340°C is a poly-ether-ketone-ketone essentially consisting of, and preferably consisting of: a terephthalic unit and an isophthalic unit, the terephthalic unit having the chemical formula: [Chem 24] the isophthalic motif having the formula: [Chem 25] a repeating unit of formula (III) and a repeating unit of formula (IV), the repeating unit (III) having the formula: [Chem 26] and the repeating motif (IV) having the formula: [Chem 27] a repeating unit of formula (III) and a repeating unit of formula (V), the repeating unit (V) having the formula: [Chem 28] a repeating unit of formula (III) and a repeating unit of formula (VI), the repeating unit (VI) having the formula: [Chem 29] 7. Granules according to any one of claims 1 to 6, in which said polyaryletherketone having a melting temperature of less than or equal to 340°C is a poly-ether-ketone-ketone essentially consisting of, and preferably consisting of: a terephthalic unit and an isophthalic unit, the terephthalic unit having the chemical formula: [Chem 30] the isophthalic unit having the chemical formula: [Chem 31] the molar percentage of terephthalic units relative to the sum of the terephthalic and isophthalic units being 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, wherein said polyaryletherketone having a melting temperature less than or equal to 340°C, has a melting temperature 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, wherein said polyaryletherketone having a melting temperature less than or equal to 340°C, has a melting temperature 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, in which the poly(etherimide-siloxane) copolymer has the chemical formula: [Chem 32] (XV) in which n is an integer from 5 to 100, R represents a phenylene, Z represents a residue of bisphenol A, R 4represents n-propylene, E represents an integer from 2 to 50, and each R' of the siloxane is a methyl.

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

12. Granules according to any one of claims 1 to 11, in which the mixture M comprises from 0.1% to 3%, and preferably from 0.5% to 2%, by weight of polysiloxane as other thermoplastic polymer, relative to the total weight of the mixture M.

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

14. Granules according to any one of claims 1 to 13, in which composition C consists of mixture M and from 0% to 40% by weight, of 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, in which composition C comprises from 0.1% to 5% by weight of nucleating fillers, such as mineral fillers, in particular talc, carbon fillers, in particular carbon nanotubes or carbon blacks, ceramic fillers, in particular boron nitride (NB), or metal oxides, in particular ZnO or MgO.

16. Granules according to claim 15, in which 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, in which the mixture M comprises two polyaryletherketones P1 and P2 having a melting temperature less than or equal to 340°C, P1 being a semi-crystalline polymer having a melting temperature T1, and P2 being a semi-crystalline polymer having a melting temperature such that T2 <T1 ou P2 étant un polymère pseudo-amorphe.

18. Granules according to claim 17, in which P2 represents at least 50% by weight of the polyaryletherketones having a melting temperature less than or equal to 340°C.

19. Granules according to any one of claims 17 and 18, in which, P2 is a poly-ether-ketone-ketone essentially consisting of, and preferentially 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%, and, P1 is a poly-ether-ketone-ketone essentially consisting of, and preferentially 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 63% to 73%.

20. Granules according to any one of claims 1 to 16, in which the mixture M comprises two polyaryletherketones P3 and P4, P3 being a semi-crystalline or pseudo-amorphous polyaryletherketone having a melting temperature less than or equal to 340°C, preferably less than or equal to 320°C, and P4 being a polyaryletherketone having a melting temperature strictly greater than 340°C.

21. Granules according to claim 20, in which the mixture M comprises 25% by weight or less, 20% by weight or less, 15% by weight or less, or 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, in which P3 is a poly-ether-ketone-ketone essentially consisting of, and preferentially consisting of: a terephthalic unit and an isophthalic unit, the molar percentage of terephthalic units relative to the total number of moles of terephthalic and isophthalic units of the poly-ether-ether-ketone being from 0% to 5% or from 45% to 67%, and, P4 is a polyether-ketone-ketone essentially consisting of, and preferentially consisting of: a terephthalic unit and an isophthalic unit, the molar percentage of terephthalic units relative to the total number of moles of terephthalic and isophthalic units of the polyether-ketone-ketone being 78% to 85%.

23. Granules according to any one of claims 1 to 22, in which the mixture M comprises less than 30%, preferably less than 25%, and more preferably less than 20% by weight of the poly(etherimide-siloxane) copolymer, relative to the total weight of the mixture.

24. Use of a composition C according to any one of claims 1 to 23 for the manufacture of an article, a part, or a coating, at a maximum manufacturing temperature not exceeding 350°C, by molding, in particular by injection molding or by compression molding, by extrusion, in particular extrusion of films or sheets, calendering extrusion, tube or pipe extrusion, sheathing extrusion, by additive manufacturing by filament fusion (FFF), spinning, rotational molding, thermoforming.

25. Use according to claim 24, in which composition C remains at the maximum manufacturing temperature for a period of time greater than 1 minute, or greater than 2, or greater than 3 minutes, or greater than 4 minutes, or greater than 5 minutes, or greater than 10 minutes, or greater than 25 minutes.

26. Use according to any one of claims 24 and 25, wherein said article, or said part, or said coating has a thickness in said composition 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, in which composition C is in the form of granules.

28. Use according to any one of claims 24 to 27, wherein 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 / 1 A 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 / 1 A at 20°C of greater than 8%, preferably greater than 10%, in particular greater than 15%, or greater than 20%, a Charpy impact strength according to ISO 179-1:2010 / 1eA of greater than 5 KJ / m 2 , preferably greater than 6 KJ / m 2 , preferably still greater than 7 KJ / m 2 , and more preferably greater than 8 KJ / m 2, a yield stress, as measured according to 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 1.1x10' 8 (cm 3 .cm) / (cm 2 .s.bar), in the case of a sheath or a tube forming a conduit, a structural flexibility such that the conduit is capable of undergoing at least 1000 cycles, where for each cycle, the layer of the polymer sheath or of the tube of composition C undergoes a level of flexural deformation varying from -2% to +2%, without rupture of the layer of the polymer sheath or of the tube of composition C.

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