Malleable polyaryletherketone compositions

Abstract

The invention relates to pellets consisting of a composition C comprising an unstratified polymer mixture M, the mixture M comprising: at least 50% by weight, relative to the total weight of the mixture, of at least one pseudo-amorphous or semi-crystalline polyaryletherketone, said polyaryletherketone having a melting temperature lower than or equal to 340 DEG C; and 5% to 40% by weight, relative to the total weight of the mixture, of a poly (etherimide-siloxane) copolymer, it should be understood that if mixture M contains 5% to 7.5% by weight of a poly (etherimide-siloxane) copolymer, then mixture M does not contain polysiloxane. The invention also relates to the use of the composition C for producing articles, parts or coatings at a maximum production temperature of no more than 350 DEG C.

Description

TECHNICAL FIELD

[0001] The present patent application relates to a polymeric composition based on one or more polyaryletherketones, which has improved impact strength, elongation at break and flexibility. The invention also relates to a process for manufacturing such composition in the form of pellets, and also to its use. BACKGROUND

[0002] Polyaryletherketones (PAEKs) are well-known high-performance engineering polymers. They can be used in applications that are limited in terms of temperature and / or mechanical constraints or even chemical constraints. They can also be used in applications requiring excellent fire resistance and low emission of smoke or toxic gases. They can also be used because of their low gas permeability. Finally, they have good biocompatibility.

[0003] These polymers are present in various fields such as aerospace, offshore drilling, automotive, rail, marine, wind, sports, construction, electronics or medical implants, etc.

[0004] Despite these advantageous properties, it is sometimes necessary to formulate polyaryletherketones to meet specific specifications. Thus, greater flexibility can be sought to adapt to new uses and modes of insertion of parts with greater bending capacity. In particular, more ductile polyaryletherketone formulations can be sought, i.e. formulations having greater strain at break and / or lower tensile / flexural modulus of elasticity and / or higher impact strength relative to unformulated PAEKs.

[0005] EP 3749714 A1 discloses compositions consisting of a mixture of polyetherketone ketone (PEKK), 3.75% to 7.5% by weight of a polysiloxane / polyetherimide block copolymer and 3.5% to 7% by weight of a polydimethylsiloxane. Although these compositions effectively provide greater strain at break, have a lower tensile modulus of elasticity and higher impact strength compared to unformulated PEKK, the introduction of polydimethylsiloxane in high proportions is sometimes proven to be complex, due to the fact that polydimethylsiloxane can take the form of a highly viscous liquid, which is difficult to handle and difficult to introduce in a well-controlled proportion. Moreover, the addition of polydimethylsiloxane to the composition tends to reduce its barrier properties, notably its low permeability to gases such as CO2.

[0006] US 2009 / 0234060 A1 also discloses compositions consisting of a mixture of polyether ether ketone (PEEK) and polysiloxane / polyetherimide block copolymer, which have a higher impact resistance. More specifically, non-layered mixtures of PEEK have been manufactured and contain 10 to 25 wt% of polysiloxane / polyetherimide block copolymer, including 20 to 30 wt% of polysiloxane (see in particular Table 2 of the patent document). On the other hand, it has been shown that it is not possible to manufacture non-layered PEEK mixtures containing 10 wt% of polysiloxane / polyetherimide block copolymer, which itself contains 40 wt% of siloxane (comparative example CE-4).

[0007] Furthermore, the inventors of the present invention have realized that the use of PEEK as PAEK in the composition means that the composition is heated to a temperature at which the polysiloxane / polyetherimide block copolymer is thermally degradable, which is undesirable, in particular in a process in which the composition is kept molten at a temperature higher than the melting temperature of the PAEK for a sufficiently long time, in particular from 1 to 25 minutes and in particular from 5 to 20 minutes.

[0008] Therefore, there is currently a need to provide a PAEK-based composition having improved impact strength, higher elongation at break and / or lower modulus of elasticity, which allows overcoming one or more drawbacks of the prior art compositions. For many applications, it is furthermore preferred that the PAEK composition retains the advantageous properties of the unformulated PAEK, notably the crystalline unformulated PAEK. These advantageous properties include good chemical resistance, heat resistance and / or low gas permeability. SUMMARY

[0009] It is an object of the present invention to propose a polyaryletherketone-based composition having improved impact resistance and / or higher elongation at break and / or lower modulus of elasticity with respect to the unformulated polyaryletherketone.

[0010] It is another object of the present invention to propose such a composition which is thermally stable in the molten state, even for long residence times in the molten state.

[0011] It is a further object, at least according to certain embodiments, to propose such a composition which is suitable for the manufacture of thick parts, articles or coatings.

[0012] It is a further object, at least according to certain embodiments, of the present invention to propose such a composition which is suitable for the manufacture of thin parts, articles or coatings.

[0013] It is a further object, at least according to certain embodiments, of the present invention to propose a composition having good chemical resistance, good heat resistance and / or low gas permeability.

[0014] The present invention relates to pellets formed from a composition C comprising a non-stratified polymer mixture M,

[0015] Mixture M comprises:

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

[0017] 5% to 40% by weight of poly(etherimide-siloxane) copolymer relative to the total weight of the mixture, it being understood that if the mixture M contains 5% to 7.5% by weight of poly(etherimide-siloxane) copolymer, the mixture M does not contain any polysiloxane.

[0018] According to certain embodiments, the mixture M comprises greater than 7.5% by weight, preferably greater than 8% by weight, of poly(etherimide-siloxane) copolymer relative to the total weight of the mixture.

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

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

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

[0022] According to certain embodiments, the polyaryletherketone having a melting point less than or equal to 340°C is a polyetherketoneketone consisting essentially of, and preferably consisting of:

[0023] Terephthalic acid units and isophthalic acid units, terephthalic acid units have the chemical formula:

[0024] [Chemistry 1]

[0025] (I)

[0026] The isophthalic acid unit has the formula:

[0027] [Chemistry 2]

[0028] (II)

[0029] The repeating unit of formula (III) and the repeating unit of formula (IV), the repeating unit (III) having the following formula:

[0030] [Chemistry 3]

[0031] (III)

[0032] and a repeating unit (IV) having the formula:

[0033] [Chemistry 4]

[0034] (IV)

[0035] A repeating unit of formula (III) and a repeating unit of formula (V), wherein the repeating unit (V) has the following formula:

[0036] [Chemistry 5]

[0037] (V)

[0038] A repeating unit of formula (III) and a repeating unit of formula (VI), wherein the repeating unit (VI) has the following formula:

[0039] [Chemistry 6]

[0040] (VI)

[0041] According to certain embodiments, the polyaryletherketone having a melting point less than or equal to 340°C is a polyetherketoneketone consisting essentially of, and preferably consisting of:

[0042] Terephthalic acid units and isophthalic acid units, terephthalic acid units have the chemical formula:

[0043] [Chemistry 7]

[0044] (I)

[0045] The isophthalic acid unit has the following chemical formula:

[0046] [Chemistry 8]

[0047] (II)

[0048] The molar percentage of terephthalic acid units relative to the sum of terephthalic acid and isophthalic acid units is less than or equal to 74%, preferably 0% to 5% or 45% to 73%, and more preferably 58% to 72%.

[0049] According to certain embodiments, the polyaryletherketone having a melting point less than or equal to 340°C has a melting point less than or equal to 335°C, or less than or equal to 330°C, or less than or equal to 325°C, or less than or equal to 320°C.

[0050] According to certain embodiments, the polyaryletherketone having a melting point less than or equal to 340°C has a melting point greater than or equal to 275°C, or greater than or equal to 285°C, or greater than or equal to 295°C.

[0051] According to certain embodiments, the poly(etherimide-siloxane) copolymer has the formula:

[0052] [Chemistry 9]

[0053]

[0054] (XV)

[0055] wherein n is an integer from 5 to 100, R represents a phenylene group, Z represents a bisphenol A residue, and R 4 represents an n-propylene group, E represents an integer from 2 to 50, and each siloxane R' is a methyl group.

[0056] According to certain embodiments, the mixture M consists of the polyaryletherketone having a melting point less than or equal to 340° C., the poly(etherimide-siloxane) copolymer and 0% to 40% by weight, relative to the total weight of the mixture, of a thermoplastic polymer different from the polyaryletherketone and the poly(etherimide-siloxane) copolymer.

[0057] According to certain embodiments, the mixture M comprises, as different thermoplastic polymer, from 0.1% to 3% by weight and preferably from 0.5% to 2% by weight of polysiloxane, relative to the total weight of the mixture M.

[0058] According to certain embodiments, the mixture M comprises, as different thermoplastic polymer, less than 1% by weight of polysiloxane, relative to the total weight of the mixture M.

[0059] According to some embodiments, relative to the gross weight of composition, composition C comprises the mixture M of at least 70 % by weight and comprises one or more additives of 0 % by weight to 40 % by weight.Composition C can be notably made up of mixture M and 0 % by weight to 40 % by weight, preferably one or more additives of 0 % by weight to 30 % by weight, relative to the gross weight of composition.Composition C can notably comprise the nucleation filler (type of additive) of 0.1 % by weight to 5 % by weight, as mineral filler (notably talc), filler based on carbon (notably carbon nanotube or carbon black), ceramic filler (notably boron nitride (BN)) or metal oxide (notably ZnO or MgO).

[0060] According to certain embodiments, the mixture M comprises a polyaryletherketone consisting essentially of, and preferably consisting of, terephthalic acid units and isophthalic acid units, the molar percentage of terephthalic acid units relative to the sum of terephthalic acid and isophthalic acid units being from 0% to 5% or from 45% to 67%.

[0061] According to certain embodiments, the mixture M comprises two polyaryletherketones P1 and P2 having a melting point less than or equal to 340° C., P1 being a semicrystalline polymer having a melting point of T1 and P2 being a polymer having a melting point such that T2 <T1的半结晶聚合物,或者P2是伪无定形聚合物。聚合物P2可以值得注意地占熔点小于或等于340℃的聚芳醚酮的至少50重量%。根据特定实施方案,P2可以是基本上由对苯二甲酸单元和间苯二甲酸单元组成的聚醚酮酮并且优选地由对苯二甲酸单元和间苯二甲酸单元组成的聚醚酮酮,对苯二甲酸单元相对于对苯二甲酸和间苯二甲酸单元的总和的摩尔百分比为0%至5%或45%至67%,并且P1可以是基本上由对苯二甲酸单元和间苯二甲酸单元组成的聚醚酮酮并且优选地由对苯二甲酸单元和间苯二甲酸单元组成的聚醚酮酮,对苯二甲酸单元相对于对苯二甲酸和间苯二甲酸单元的总和的摩尔百分比为63%至73%。

[0062] According to certain embodiments, the mixture M comprises two polyaryletherketones P3 and P4, P3 being a semicrystalline or pseudo-amorphous polyaryletherketone having a melting point less than or equal to 340° C., preferably less than or equal to 320° C., and P4 being a polyaryletherketone having a melting point strictly greater than 340° C. The polymer P4 may notably represent 25% by weight or less, 20% by weight or less, 15% by weight or less, or even 10% by weight or less, relative to the total weight of the mixture M. According to a particular embodiment, polymer P3 can be a polyetherketoneketone consisting essentially of, and preferably consisting of, terephthalic acid units and isophthalic acid units, the molar percentage of terephthalic acid units relative to the total molar number of terephthalic acid units and isophthalic acid units in the polyetheretherketone is from 0% to 5% or from 45% to 67%, and polymer P4 can be a polyetherketoneketone consisting essentially of, and preferably consisting of, terephthalic acid units and isophthalic acid units, the molar percentage of terephthalic acid units relative to the total molar number of terephthalic acid units and isophthalic acid units in the polyetherketoneketone is from 78% to 85%.

[0063] According to certain embodiments, the mixture M comprises less than 30% by weight, preferably less than 25% by weight and more preferably less than 20% by weight of poly(etherimide-siloxane) copolymer relative to the total weight of the mixture.

[0064] The invention further relates to compositions C for being no more than 350 ℃ maximum manufacturing temperature by molding, notably by injection molding or compression molding, by extruding, notably ground film or sheet extrusion, calendaring extrusion, pipe or pipeline extrusion, extrusion sheath, by filament melt additive manufacturing (FFAM), spinning, rotational molding or thermoforming to manufacture the purposes of goods, parts or coating.It is worth noting that composition C is adjusted so that it can keep the time 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 25 minutes at the maximum manufacturing temperature.This is particularly advantageous for making parts, goods or coatings greater than 2mm, or greater than 3mm, or greater than 4mm, or greater than 5mm, or greater than 6mm in thickness.According to certain embodiments, therefore the composition C that is suitable for use is the form of pellets.

[0065] The manufactured article, component, or coating may notably have at least one of the following advantageous properties, and according to certain embodiments, may have all of the following advantageous properties:

[0066] a tensile modulus of elasticity of less than 4.0 GPa, preferably less than 3.5 GPa, more preferably less than 3.2 GPa and preferably less than 3.0 GPa, measured at 20° C. according to standard ISO 527-2:2019 / 1A,

[0067] a nominal strain at break measured at 20° C. according to standard ISO 527-2:2019 / 1A of greater than 8%, preferably greater than 10%, notably greater than 15%, or greater than 20%,

[0068] - a Charpy impact strength according to standard ISO 179-1:2010 / 1eA of greater than 5 KJ / m², preferably greater than 6 KJ / m², more preferably greater than 7 KJ / m² and even more preferably greater than 8 KJ / m²,

[0069] a yield stress of less than 95 MPa, and preferably less than 85 MPa, measured at 20° C. according to standard ISO 527-2:2019 / 1A:2019,

[0070] -CO2 permeability measured at 60°C is less than 1.1 x10 -8 (cm 3 .cm) / (cm².s.bar).

[0071] 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, wherein for each cycle the polymeric sheath or tube layer undergoes bending strain levels ranging from -2% up to +2% without rupturing the polymeric sheath or tube layer of composition C. BRIEF DESCRIPTION OF THE DRAWINGS

[0072] Figure 1 Figure 5 shows the mass loss of poly(etherimide-siloxane) copolymer samples (Siltem® STM 1500) obtained by thermogravimetric analysis (TGA) after heating at different temperatures for 1 h under nitrogen.

[0073] Figure 2 are photographs of the outer surface (left) or cross-section (right) of a 7 mm thick strip of composition 1c produced in the experimental part.

[0074] Figure 3 are photographs of the outer surface (left) or cross-section (right) of a 7 mm thick strip of composition 4 produced in the experimental part.

[0075] Figure 4 are photographs of the outer surface (left) or cross-section (right) of a 7 mm thick strip of composition 5 produced in the experimental part. Specific implementation plan

[0076] The term "thermoplastic polymer" refers to a polymer that becomes less viscous or more liquid or becomes liquid when heated sufficiently and reversibly retains its thermoplastic properties. Thermoplastic polymers are generally contrasted with thermosetting polymers, which irreversibly convert to an insoluble polymer network that cannot be thermoformed.

[0077] The term "homopolymer" refers to a polymer consisting of only one type of repeating unit.

[0078] The term "copolymer" is understood to mean a polymer resulting from the copolymerization of at least two chemically different types of monomers, known as comonomers. A copolymer is thus 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.

[0079] The copolymers may have a homogeneous structure, notably of statistical, alternating or random type, or a heterogeneous structure, notably of sequential or block copolymer type.

[0080] In particular, the term "block copolymer" refers to a copolymer within the meaning above in which at least two different homopolymer blocks are covalently bonded. The length of the blocks can be variable. The blocks can each consist of 1 to 1000, preferably 1 to 500, more preferably 1 to 100, and in particular 1 to 50 repeating units. The connection between the two homopolymer blocks can be a simple covalent bond or an intermediate non-repeating unit called a linking block.

[0081] The term "essentially consisting of (one or more) units" means that the (one or more) units account for a molar proportion of 95% to 99.9% relative to the total molar number of repeating units in the polymer.

[0082] The term "consisting of (one or more) units" means that the (one or more) units constitute a molar proportion of at least 99.9%, notably 100%, in the polymer relative to the total moles of repeating units in the polymer.

[0083] The term "non-stratified polymer mixture" is intended to denote a macroscopically homogeneous polymer composition. The term notably encompasses such compositions consisting of mutually immiscible phases dispersed on the micrometer or submicrometer scale. The term "non-stratified" means in particular that the composition or the article derived therefrom does not exhibit any visually observable separation into layers, such as desquamation or an onion-skin effect.

[0084] The term "granulation" refers to granules of the composition, which are more or less cylindrical or spherical in shape, notably suitable for extrusion or injection processes. These granules generally have a characteristic size between 0.5 mm and 10 mm, notably between 1 mm and 5 mm.

[0085] The term "glass transition temperature" (denoted as T g ) means the temperature at which an at least partially amorphous polymer transitions from the rubbery state to the glassy state or vice versa, as measured by differential scanning calorimetry (DSC) according to standard NF ISO 11357-2:2020, on the second heating, using a temperature ramp when heating and cooling at 20° C. / min. In the present invention, when referring to the glass transition temperature, this is more particularly the glass transition temperature at half the step height as defined in this standard, unless otherwise indicated.

[0086] The term "melting temperature" (denoted as T m) is intended to indicate the temperature at which a semi-crystalline polymer transitions into a viscous liquid state, as measured by differential scanning calorimetry (DSC) according to standard NF EN ISO 11357-3:2018 using a heating rate of 20° C. / min on the second heating. In the present invention, when reference is made to the melting temperature, unless otherwise indicated (see in particular the measurement method applicable to pseudo-amorphous polymers below), this is more particularly the peak melting temperature as defined in this standard.

[0087] The term "pseudo-amorphous" polymer is intended to mean a polymer that does not have a melting endotherm, as measured by differential scanning calorimetry (DSC) according to standard NF EN ISO 11357-3:2018 using a heating and cooling rate of 20°C / min during the second heating. However, once a temperature above its glass transition temperature is reached, notably a temperature in the range of Tg+40°C to Tg+110°C, for example, Tg+75°C, for a sufficient time, notably 10 to 30 minutes, for example 20 minutes, the pseudo-amorphous polymer is suitable for crystallization. Therefore, this is also how the melting temperature of the pseudo-amorphous polymer in the present invention is measured during the second heating, as follows:

[0088] - a first heating with a ramp of 20°C / min to a plateau temperature in the range of Tg+40°C to Tg+110°C, for example at Tg+75°C, for a sufficient time, notably 10 to 30 minutes, for example 20 minutes, notably 20 minutes at Tg+75°C;

[0089] - Cool to room temperature at a ramp rate of 20°C / min;

[0090] - A second heating was performed with a ramp of 20°C / min.

[0091] The term "tensile modulus of elasticity," or more simply "elastic modulus," means the slope of the stress-strain curve σ(ε) in the interval between two strains ε1 = 0.05% and ε2 = 0.25%, as defined in ISO 527-1:2019. The elastic modulus is expressed in gigapascals (GPa). The slope is preferably measured by a linear regression method.

[0092] Although the elastic modulus is determined here by mechanical tensile loading, it would not exceed the scope of the present invention if the measurement were based on other types of loading, such as bending or compression.

[0093] The term “nominal strain” refers to the strain calculated from the displacement of the grips and the clamping distance of the test device, as defined in standard ISO 527-1:2019.

[0094] The term "nominal strain at break" refers to the strain at the last point recorded before the stress drops to a value less than or equal to 10% of the resistance at break after the yield point, as defined in standard 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 performed in succession. These tests can be performed, for example, using an MTS 810® (an instrument equipped with a mechanical extensometer sold by MTS Systems Corporation).

[0095] The term "Charpy impact strength" or more simply "impact strength" refers to the 80*10*4mm impact strength measured according to standard ISO 179:2010. 3 Impact strength of A-notched bars. The actual measurement corresponds to the average value of 10 consecutive tests. The notch (V-shaped with a notch radius of 0.25 ± 0.05 mm) can be performed using a device designed specifically for this purpose (Automatic Notchvis Plus, sold by Ceast). The bars are then left to rest for 24 hours. The impact strength test can be performed on a Zwick 5102 impact tester.

[0096] Typically, those skilled in the art use the term "gas permeability" for a jacket or layer and "gas permeability" for a material, but both expressions correspond to the same property. In this patent application, the term "gas permeability" is selected. Gas permeability is typically measured using the method for testing fluid permeability in the 2009 API 17J standard.

[0097] The singular forms "a" and "the" as applied to a composition component (e.g., a poly(aryletherketone) or a poly(etherimide-siloxane) copolymer having a melting point of less than or equal to 340° C.) automatically mean "at least one" and "the at least one," respectively. However, the singular forms include (without requiring each reminder) those embodiments in which "a" means "only one" and "the" means "only."

[0098] Throughout the range of values ​​listed in this patent application, the limits are included unless otherwise stated.

[0099] polyaryletherketone

[0100] The undelaminated polymer mixture M comprises at least 50% by weight, relative to the total weight of the mixture, of at least one polyaryletherketone having a melting point of less than or equal to 340° C. The melting point of the semicrystalline polyaryletherketone is measured according to standard NF EN ISO 11357-3:2018 and the melting point of the pseudo-amorphous polyaryletherketone is measured according to a suitable measurement method as described above.

[0101] In particular, the unstratified polymer mixture M may comprise at least 60% by weight, or at least 70% by weight, or at least 80% by weight, or at least 85% by weight of said at least one polyaryletherketone having a melting point less than or equal to 340° C., relative to the total weight of the mixture M.

[0102] Optionally, the mixture M may also contain, as a different thermoplastic polymer, from 0 to 40% by weight, relative to the total weight of the mixture M, of a polyaryletherketone having a melting point strictly above 340° C.

[0103] In particular, the mixture M may comprise, as a different thermoplastic polymer, more than 5% by weight, relative to the total weight of the mixture M, of a polyaryletherketone having a melting point strictly above 340° C.

[0104] In particular, the mixture M may comprise, as a different thermoplastic polymer, less than 30%, or less than 25%, or less than 20%, or less than 15%, or less than 10% by weight of polyaryletherketones having a melting point strictly above 340° C., relative to the total weight of the mixture M.

[0105] According to certain embodiments, the mixture M does not comprise a polyaryletherketone different from the at least one polyaryletherketone having a melting point less than or equal to 340°C.

[0106] Polyaryletherketone (PAEK) comprises units having the formula:

[0107] (-Ar-X-) and (-Ar1-Y-),

[0108] in:

[0109] -Ar and Ar1 each represent a divalent aromatic group;

[0110] - Ar and Ar1 may preferably be selected from 1,3-phenylene, 1,4-phenylene, divalent 1,1'-biphenylene at the 3,3' position, divalent 1,1'-biphenylene at the 3,4' position, 1,4-naphthylene, 1,5-naphthylene and 2,6-naphthylene;

[0111] -X represents an electron-withdrawing group; it may preferably be selected from a carbonyl group and a sulfonyl group;

[0112] -Y represents a group selected from an oxygen atom, a sulfur atom, an alkylene group such as -(CH)2-, and an isopropylidene group.

[0113] Of these X and Y units, at least 50%, preferably at least 70% and more particularly at least 80% of the groups X are carbonyl groups and at least 50%, preferably at least 70% and more particularly at least 80% of the groups Y represent oxygen atoms.

[0114] According to a preferred embodiment, 100% of the groups X represent carbonyl groups and 100% of the groups Y represent oxygen atoms.

[0115] Advantageously, the one or more PAEKs may be selected from:

[0116] - Polyetherketoneketone, also known as PEKK; PEKK comprises one or more units of the following formula: -Ph-O-Ph-C(O)-Ph-C(O)-;

[0117] -polyetheretherketone, also known as PEEK; PEEK comprises one or more units of the formula: -Ph-O-Ph-O-Ph-C(O)-;

[0118] -Polyetherketone, also known as PEK; PEK comprises one or more units of the formula: -Ph-O-Ph-C(O)-;

[0119] -polyetheretherketoneketone, also known as PEEKK; PEEKK comprises one or more units of the following formula: -Ph-O-Ph-O-Ph-C(O)-Ph-C(O)-;

[0120] -Polyetheretherketone, also known as PEEEK; PEEEK comprises one or more units of the following formula: -Ph-O-Ph-O-Ph-O-Ph-C(O)-;

[0121] - Polyether diphenyl ether ketone, also known as PEDEK; PEDEK comprises one or more units of the following formula: -Ph-O-Ph-Ph-O-Ph-C(O)-;

[0122] - mixtures thereof; and

[0123] - copolymers comprising at least two of the above-mentioned units,

[0124] wherein: Ph represents a phenylene group and -C(O)- represents a carbonyl group, each phenylene group may independently be of the ortho (1,2), meta (1,3) or para (1,4) type, preferably the meta or para type.

[0125] Furthermore, defects, end groups and / or monomers may be incorporated in very small amounts into the polymers described in the above list without, however, having an impact on their properties.

[0126] According to certain embodiments, the PAEK is a polyetherketoneketone (PEKK) consisting essentially of, and preferably consisting of, terephthalic acid repeating units and, where appropriate, isophthalic acid repeating units, the terephthalic acid repeating units ("T units") having the formula:

[0127] [Chemistry 10]

[0128] (I)

[0129] The isophthalic acid unit ("I unit") has the formula:

[0130] [Chemistry 11]

[0131] (II)

[0132] The weight proportion of T units relative to the sum of T and I units can vary between 0% and 100%.

[0133] The choice of the molar ratio of T units relative to the sum of T and I units is one of the factors that allows the melting temperature and the crystallization rate of the polyetherketoneketone to be adjusted. A given molar ratio of T units relative to the sum of T and I units can be achieved by adjusting the corresponding concentrations of the reactants during the polymerization in a manner known per se.

[0134] Preferably, the polyetherketoneketone has a homogeneous structure and may notably be of statistical type.

[0135] The polyetherketoneketone having a mass ratio of T units to the sum of T and I units of less than or equal to 74% has a melting point of less than or equal to 340°C.

[0136] Preferably, the polyetherketoneketone having a melting point of less than or equal to 340° C. is selected from polyetherketoneketones having a mass proportion of T units relative to the sum of T and I units of 0% to 5% or 45% to 73%. The mass proportion of T units relative to the sum of T and I units may be notably 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%.

[0137] More preferably, the polyetherketoneketone having a melting point of 340° C. or lower is selected from polyetherketoneketones having a mass ratio of T units relative to the sum of T and I units of 58% to 72%.

[0138] The molar proportion of T units relative to the sum of T and I units can notably be about 60% or about 70%. A polyetherketoneketone with a T:I ratio of about 60% is a pseudo-amorphous polymer within the meaning of the present invention. A polyetherketoneketone with a ratio of about 70% is a semi-crystalline polymer.

[0139] Such polyetherketoneketones are commercially available from Arkema under the trade name Kepstan®.

[0140] According to certain embodiments, the PAEK may be a PEEK-PEDEK copolymer consisting essentially of, or even consisting of, repeating units having the formula:

[0141] [Chemistry 12]

[0142] (III)

[0143] and recurring units of formula:

[0144] [Chem. 13]

[0145] (IV)

[0146] Copolymers consisting of recurring units of formula (III) and (IV) wherein the molar proportion of units (III) relative to the total of units (III) and (IV) ranges from 5% to 45% have a melting point less than or equal to 340°C.

[0147] According to certain embodiments, the PAEK can be a copolymer consisting essentially of or even consisting of recurring units of formula (III) and recurring units of formula:

[0148] [Chem. 14]

[0149] (V)

[0150] Copolymers consisting of recurring units of formula (III) and (V) wherein the molar proportion of units (III) relative to the total of units (III) and (V) ranges from 5% to 100% have a melting point less than or equal to 340°C.

[0151] According to certain embodiments, the PAEK can be a copolymer consisting essentially of or even consisting of recurring units of formula (III) and recurring units of formula:

[0152] [Chem. 15]

[0153] (VI)

[0154] Copolymers consisting of recurring units of formula (III) and (VI) wherein the molar proportion of units (III) relative to the total of units (III) and (VI) ranges from 5% to 100% have a melting point less than or equal to 340°C.

[0155] According to certain embodiments, the PAEK having a melting point less than or equal to 340°C notably has a melting point less than or equal to 335°C, or a melting point less than or equal to 330°C, or a melting point less than or equal to 325°C, or a melting point less than or equal to 320°C. When the pellets according to the application are melted at a maximum temperature of from 5°C to 40°C above the melting temperature of the PAEK having a melting point less than or equal to 340°C, this has the advantage of limiting the thermal degradation of the poly(etherimide-siloxane) copolymer even for prolonged (melt) residence times.

[0156] According to certain embodiments, the PAEK has a melting point 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 articles, parts and / or coatings obtained from the pellets according to the present invention by extrusion or injection molding have sufficient heat resistance.

[0157] According to certain embodiments, the non-stratified polymer mixture M comprises two polyaryletherketones having a melting point of less than or equal to 340° C. The mixture M comprises a first polyaryletherketone P1 and a second polyaryletherketone P2, wherein the first polyaryletherketone P1 is a semi-crystalline polymer having a melting point T1 and the second polyaryletherketone P2 is a semi-crystalline polymer having a melting point T2. <T1的熔点的半结晶聚合物或伪无定形聚合物。

[0158] According to certain embodiments, polymer P1 may represent at least 50% by weight of the polyaryletherketone having a melting point less than or equal to 340°C.

[0159] According to other embodiments, polymer P2 may represent at least 50% by weight of the polyaryletherketone having a melting point less than or equal to 340°C.

[0160] According to certain embodiments, P2 is a polyetherketoneketone consisting essentially of terephthalic acid units and isophthalic acid units, preferably consisting of terephthalic acid units and isophthalic acid units, the molar percentage of terephthalic acid units relative to the sum of terephthalic acid units and isophthalic acid units being from 0% to 5% or from 45% to 67%, and P1 is a polyetherketoneketone consisting essentially of terephthalic acid units and isophthalic acid units, preferably consisting of terephthalic acid units and isophthalic acid units, the molar percentage of terephthalic acid units relative to the sum of terephthalic acid units and isophthalic acid units being from 63% to 73%.

[0161] According to certain embodiments, P2 is a polyetherketoneketone consisting essentially of terephthalic acid units and isophthalic acid units, preferably consisting of terephthalic acid units and isophthalic acid units, the molar percentage of terephthalic acid units relative to the sum of terephthalic acid units and isophthalic acid units being 58% to 67%, and P1 is a polyetherketoneketone consisting essentially of terephthalic acid units and isophthalic acid units, preferably consisting of terephthalic acid units and isophthalic acid units, the molar percentage of terephthalic acid units relative to the sum of terephthalic acid units and isophthalic acid units being 63% to 73%. Advantageously, P2 represents at least 50% by weight of the polyaryletherketone having a melting point of less than or equal to 340°C.

[0162] In certain embodiments in which the mixture M also comprises a polyaryletherketone having a melting point strictly above 340° C., the latter may be a PEEK homopolymer consisting of recurring units (III); a PEEK-PEDEK copolymer consisting essentially of or consisting of recurring units of formula (III) and formula (IV), the molar proportion of units of formula (III) relative to the total molar number of units (III) and (IV) being strictly greater than 45%, notably greater than or equal to 50%; or even a PEKK consisting essentially of or consisting of recurring units of terephthalic acid (T) and isophthalic acid (I), the molar proportion of terephthalic acid recurring units relative to the total molar number of terephthalic acid and isophthalic acid recurring units being strictly greater than 74%, notably 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%.

[0163] According to certain embodiments, the mixture M comprises two polyaryletherketones P3 and P4, P3 being a semicrystalline or pseudo-amorphous polyaryletherketone having a melting point less than or equal to 340° C., preferably less than or equal to 320° C., and P4 being a polyaryletherketone having a melting point strictly greater than 340° C. The polymer P4 may notably represent 25% by weight or less, 20% by weight or less, 15% by weight or less, or even 10% by weight or less, relative to the total weight of the mixture M. According to a specific embodiment, polymer P3 can be a polyetherketoneketone consisting essentially of, and preferably consisting of, terephthalic acid units and isophthalic acid units, the molar percentage of terephthalic acid units in the polyetheretherketone relative to the total molar number of terephthalic acid and isophthalic acid units being from 0% to 5% or from 45% to 67%, and polymer P4 can be a polyetherketoneketone consisting essentially of, and preferably consisting of, terephthalic acid units and isophthalic acid units, the molar percentage of terephthalic acid units in the polyetherketoneketone relative to the total molar number of terephthalic acid and isophthalic acid units being from 78% to 85%.

[0164] According to certain embodiments, the mixture M comprises a polyetherketoneketone having a mass ratio of 78% to 85% of T units to the sum of T and I units. The molar ratio of T units relative to the sum of T and I units may notably be about 80%. Such polyetherketoneketone is commercially available from Arkema under the trade name Kepstan®.

[0165] According to certain embodiments, the mixture M comprises a polyetherketoneketone consisting essentially of terephthalic acid units and isophthalic acid units, the molar percentage of terephthalic acid units of the polyetherketoneketone being from 0% to 5% or from 45% to 67% relative to the total moles of terephthalic acid and isophthalic acid units, and,

[0166] The polyetherketoneketone is essentially composed of terephthalic acid units and isophthalic acid units, wherein the mole percentage of the terephthalic acid units of the polyetherketoneketone is 78% to 85% relative to the total moles of the terephthalic acid units and the isophthalic acid units.

[0167] Advantageously, the mixture M comprises 25% by weight or less, 20% by weight or less, 15% by weight or less, or even 10% by weight or less of said polyetherketoneketone in a molar ratio T / (T+1) ranging from 78% to 85% relative to the total weight of the mixture M.

[0168] Poly(etherimide-siloxane) copolymer

[0169] The poly(etherimide-siloxane) copolymer notably allows improving the toughness, flexibility, elongation at break and crack growth resistance of composition C.

[0170] The polymer mixture M comprises from 5% to 40% by weight of poly(etherimide-siloxane) copolymer, relative to the total weight of the mixture.

[0171] Preferably, the mixture M comprises less than 30% by weight and more preferably less than 25% by weight of poly(etherimide-siloxane) copolymer relative to the total weight of the mixture.

[0172] 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 poly(etherimide-siloxane) copolymer relative to the total weight of the mixture.

[0173] Preferably, the mixture M comprises more than 7.5% by weight of poly(etherimide-siloxane) copolymer relative to the total weight of the mixture. The mixture M may notably comprise more than 8.0% by weight of poly(etherimide-siloxane) copolymer relative to the total weight of the mixture.

[0174] According to certain embodiments, the mixture M comprises from 5% to 8% by weight of poly(etherimide-siloxane) copolymer relative to the total weight of the mixture.

[0175] According to certain embodiments, the mixture M comprises from 8% to 15% by weight of poly(etherimide-siloxane) copolymer relative to the total weight of the mixture.

[0176] According to certain embodiments, the mixture M comprises from 15% to 25% by weight of poly(etherimide-siloxane) copolymer relative to the total weight of the mixture.

[0177] The poly(etherimide-siloxane) copolymer comprises polyetherimide units and polysiloxane units, for example, 5 to 1000, or 10 to 500, etherimide units and siloxane units.

[0178] The polyetherimide unit comprises a structural unit of formula (VII):

[0179] [Chemistry 16]

[0180] (VII)

[0181] wherein each R is the same or different and represents a substituted or unsubstituted divalent organic group, such as a C6-20 aromatic hydrocarbon-based group or a halogenated derivative thereof, a linear or branched C2-20 alkylene group or a halogenated derivative thereof, a C3-8 cycloalkylene group or a halogenated derivative thereof, in particular a divalent group of formula (VIII):

[0182] [Chemistry 17]

[0183]

[0184]

[0185]

[0186]

[0187] or

[0188] (VIII)

[0189] where Q 1 Indicates -O-, -S-, -C(O)-, -SO2-, -SO-, -C y H 2y -, wherein y represents an integer from 1 to 5, or a halogenated derivative thereof (including a perfluoroalkylene group) or -(C6H 10 )z-, wherein z represents an integer from 1 to 4. In one embodiment, R is m-phenylene, p-phenylene or diaryl sulfone.

[0190] In addition, in formula (VI), T represents -O- or a group of the formula -OZO-, wherein the divalent bond of the -O- or -OZO- group is at the 3,3', 3,4', 4,3' or 4,4' position. The group Z of -OZO- can be a divalent substituted or unsubstituted organic group, and can be a C6-24 aromatic monocyclic or polycyclic fragment 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 the group Z include groups derived from dihydroxy compounds of formula (IX):

[0191] [Chemistry 18]

[0192] (IX)

[0193] where 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 an integer from 0 to 4; c represents 0-4; and X a represents a bridging group connecting 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 relative to each other on the C6 arylene group. a "C" 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 also contain heteroatoms such as halogen, oxygen, nitrogen, sulfur, silicon, or phosphorus. The C1-18 organic group may be arranged such that each of the C6 arylene groups connected thereto is connected to a common alkylidene carbon or to different carbons of the C1-18 organic bridging group.

[0194] Specific examples of the group Z are divalent groups of formula (X):

[0195] [Chemistry 19]

[0196] (X)

[0197] Wherein Q represents -O-, -S-, -C(O)-, -SO2-, -SO- or -C y H 2y -, wherein y represents an integer from 1 to 5 or a halogenated derivative thereof (including perfluoroalkylene). In a particular embodiment, Z represents a bisphenol A derivative, such that Q in formula (X) is 2,2-isopropylidene.

[0198] In one embodiment, in formula (VII), R represents m-phenylene or p-phenylene and T represents -OZO-, wherein Z represents a divalent group of formula (X). Alternatively, R represents m-phenylene or p-phenylene and T represents -OZO-, wherein Z represents a divalent group of formula (X) and Q represents 2,2-isopropylidene.

[0199] The polyetherimide blocks can be prepared by any method known to those skilled in the art, including aromatic bis(ether anhydrides) of formula (XI):

[0200] [Chemistry 20]

[0201] (XI)

[0202] Reaction with an organic diamine of formula (XII):

[0203] H2N-R-NH2(XII)

[0204] wherein T and R are as defined above. The polyetherimide copolymers can be made using a combination of an aromatic bis(ether anhydride) of formula (XI) and a different bis(anhydride), such as a bis(anhydride) wherein T does not contain any ether functionality and, for example, T represents a sulfone.

[0205] Illustrative examples of bis(anhydrides) include 3,3-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride; 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl ether dianhydride; 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride; 4,4'-bis(3,4-dicarboxyphenoxy)benzophenone dianhydride; 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfone dianhydride; 2,2-bis[4-(2,3-dicarboxyphenoxy)phenyl]propane dianhydride; 4,4'-bis(2,3-dicarboxyphenoxy)diphenyl ether dianhydride; 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, and various combinations thereof.

[0206] Examples of the 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-methylbis(3-aminopropyl)amine, 3-methoxyhexamethylenediamine, 1,2-bis(3-aminopropyloxy)ethane sulfide, bis(3-aminopropyl)sulfide, 1,4-cyclohexanediamine, bis(4-aminocyclohexyl)methane, m-phenylenediamine, p-phenylenediamine, Combinations of these compounds may also be used. In certain embodiments, the organic diamine is m-phenylenediamine, p-phenylenediamine, sulfonyl dianiline, or a combination comprising one or more thereof.

[0207] The siloxane blocks comprise units of formula (XIII):

[0208] [Chemistry 21]

[0209] (XIII)

[0210] Wherein each R ' independently represents C1-13 monovalent hydrocarbon group, and E is 1 to 100, notably 2 to 50 integer.For example, each R ' can independently represent C1-13 alkyl, C1-13 alkoxy, C2-13 alkenyl, C2-13 alkenyloxy, C3-6 cycloalkyl, C3-6 cycloalkyloxy, C6-14 aryl, C6-10 aryloxy, C7-13 arylalkyl, C7-13 arylalkoxy, C7-13 alkylaryl or C7-13 alkylaryloxy.The above-mentioned groups can be halogenated completely or partially by fluorine, chlorine, bromine or iodine or the combination comprising at least one of these.In one embodiment, there is no bromine or chlorine, and in other embodiments, there is no halogen.The combination of the above-mentioned groups R ' can be used in identical copolymer.In one embodiment, the polysiloxane block comprises group R ', and it has the hydrocarbon-based group of minimum content.In a specific embodiment, the group R ' of the hydrocarbon-based compound with minimum content is methyl.

[0211] Poly(etherimide-siloxane)s can be formed by polymerizing an aromatic bisanhydride (XI) and a diamine component comprising an organic diamine (XII) or a mixture of diamines as described above, and a polysiloxane diamine of formula (XIV):

[0212] [Chemistry 22]

[0213] (XIV)

[0214] wherein R' and E are as described in formula (XIII), and each R 4 R4 independently represents a C2-C20 hydrocarbon-based fragment, in particular a C2-C20 arylene, alkylene or arylenealkylene. According to certain embodiments, R4 represents a C2-C20 alkylene, more particularly a C2-C10 alkylene 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. The procedures for preparing the polysiloxane diamines of formula (XIV) are well known in the art.

[0215] In certain poly(etherimide-siloxane) copolymers, the diamine component used to prepare the copolymer may contain 10 mol% to 90 mol% or 20 mol% to 50 mol% or 25 mol% to 40 mol% of a polysiloxane diamine (XIV) and 10 mol% to 90 mol% or 50 mol% to 80 mol% or 60 mol% to 75 mol% of a diamine (XII), as described, for example, in U.S. Pat. No. 4,404,350. The diamine components may be physically mixed prior to reaction with one or more dianhydrides to form a substantially statistical copolymer. Alternatively, block or alternating copolymers may be formed by selective reaction of (XII) and (XIV) with an aromatic bis(ether anhydride) (XI) to produce polyimide blocks, which are subsequently reacted together. Thus, the poly(etherimide-siloxane) copolymer may be a statistical or grafted block copolymer. The poly(etherimide-siloxane) block copolymer comprises etherimide blocks and siloxane blocks in its polymer backbone. The etherimide blocks and siloxane blocks can be present in a statistical order, in blocks (i.e., AABB), alternating blocks (i.e., ABAB), or a combination thereof. Poly(etherimide-siloxane) graft copolymers are non-linear copolymers comprising siloxane blocks attached to a linear or branched polymer backbone comprising etherimide blocks.

[0216] Examples of specific poly(etherimide-siloxanes) are described in US Pat. Nos. 4,404,350, 4,808,686 and 4,690,997.

[0217] According to a preferred embodiment, the poly(etherimide-siloxane) consists essentially of or consists of units of formula (XV):

[0218] [Chemistry 23]

[0219] (XV)

[0220] wherein R' and E of the siloxane are as in formula (XIII), R and Z of the imide are as in formula (VII), R 4 and R in formula (XIV) 4 are the same, and n is an integer from 5 to 100. In a particular embodiment, R represents a phenylene group, Z represents a bisphenol A residue, and R 4 represents an n-propylene group, E represents an integer of 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 group.

[0221] The relative amounts of polysiloxane units and etherimide units in the poly(etherimide-siloxane) are determined by the desired properties and are selected using the guidance provided herein. 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 ensure the desired weight percent (wt%) of siloxane units in the thermoplastic composition. In certain embodiments, the polysiloxane block of the copolymer has a number average molecular weight (Mn) of 300 to 3000 g / mole (Daltons).

[0222] According to certain embodiments, the poly(etherimide-siloxane) copolymer comprises greater than 30 weight percent siloxane groups relative to the total weight of the poly(etherimide-siloxane) copolymer.

[0223] According to certain embodiments, the poly(etherimide-siloxane) copolymer comprises greater than 35 weight percent siloxane groups relative to the total weight of the poly(etherimide-siloxane) copolymer.

[0224] According to certain embodiments, the poly(etherimide-siloxane) copolymer comprises less than 50 weight percent siloxane groups relative to the total weight of the poly(etherimide-siloxane) copolymer.

[0225] According to certain embodiments, the poly(etherimide-siloxane) copolymer comprises less than 45 weight percent siloxane groups relative to the total weight of the poly(etherimide-siloxane) copolymer.

[0226] Poly(etherimide-siloxane) copolymers are commercially available from Sabic Corporation under the trade name SILTEM®.

[0227] Different thermoplastic polymers

[0228] According to certain embodiments, the mixture M may comprise from 0% to 40% by weight, relative to the total weight of the mixture M, of a thermoplastic polymer other than polyaryletherketone and poly(etherimide-siloxane) copolymer having a melting point less than or equal to 340° C.

[0229] According to certain embodiments, the mixture M does not comprise thermoplastic polymers other than polyaryletherketone and poly(etherimide-siloxane) copolymers having a melting point less than or equal to 340°C.

[0230] The different thermoplastic polymers may notably include polyaryletherketones, polysiloxanes, fluoropolymers, polyetherimides (PEI), polyphenylenesulfone (PPSU), polysulfone (PSU), polycarbonate (PC), polyphenylene ether (PPE), polyphenylene sulfide (PPS), polyethylene terephthalate (PET), polyamide (PA), polybenzimidazole (PBI), polyamideimide (PAI), polyethersulfone (PES), polyarylsulfone, polyetherimidesulfone, polyphenylene, polybenzoxazole, polybenzothiazole, or mixtures thereof, having a melting point strictly above 340°C.

[0231] According to certain embodiments, the different thermoplastic polymer may notably be a polyaryletherketone having a melting point strictly above 340° C., as described above.

[0232] According to certain embodiments, the different thermoplastic polymer may notably be a polysiloxane.According to these embodiments, the mixture M thus comprises greater than 7.5% by weight of poly(etherimide-siloxane) copolymer relative to its total weight.

[0233] The polysiloxane may be mono- or disubstituted by C1 to C12, preferably C1 to C6 and most particularly C1 to C4 alkyl and / or phenyl groups. Preferably, the alkyl group is methyl. The alkyl or phenyl groups of the polysiloxane may be substituted by one or more functional groups, such as epoxy, alkoxy (notably 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 with a view to reacting them during blending (reactive siloxanes).

[0234] However, preferably, the polysiloxane does not include any functional groups.In addition, the alkyl or phenyl groups of the polysiloxane may be substituted with one or more carbocyclic, aryl, heteroaryl, alkyl, alkenyl, bicyclic or tricyclic groups.

[0235] Preferably, the polysiloxane present as the different thermoplastic polymer in the mixture M is poly(dimethylsiloxane) (PDMS).

[0236] To facilitate handling, the polysiloxanes may be combined with a solid support such as silica, notably fumed silica.

[0237] According to certain embodiments, the mixture M comprises, as different thermoplastic polymer, from 0.1% to 3% by weight and preferably from 0.5% to 2% by weight of polysiloxane, relative to the total weight of the mixture M.

[0238] According to certain embodiments, the mixture M comprises less than 1% by weight of polysiloxane relative to the total weight of the mixture M.

[0239] According to certain embodiments, the mixture M does not comprise any polysiloxane. In particular, in embodiments in which the mixture M comprises 5% to 7.5% by weight of poly(etherimide-siloxane) copolymer, then the mixture M does not comprise any polysiloxane.

[0240] additive

[0241] 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.

[0242] Advantageously, composition C comprises from 0% to 30% by weight, or from 0% to 25% by weight, or from 1% to 20% by weight, or even from 2% to 10% by weight of additives relative to the total weight of the composition.

[0243] Among the additives, one or more fillers may be mentioned. Among the conceivable fillers, mention may be made of silica and alumina, nucleating fillers such as mineral fillers, notably talc, carbon-based fillers, notably carbon nanotubes or carbon black, ceramic fillers, notably boron nitride (NB), or metal oxides, notably ZnO or MgO, and reinforcing fillers, such as glass fibers or carbon fibers.

[0244] According to a particular embodiment, composition C may contain 0.1% to 5% by weight, notably 0.25% to 2.5% by weight, of nucleating filler relative to the total weight of the composition. This makes it possible to modify the crystallization behavior of one or more polyaryletherketones and, notably, to increase the final crystallinity in conventional processes for forming slower-crystallizing polyaryletherketones without substantially changing the implementation conditions. These slower-crystallizing polyaryletherketones can achieve a sufficient degree of crystallinity without, for example, requiring an additional annealing step.

[0245] According to certain embodiments, the polyaryletherketone of composition C may be a polyetherketoneketone having a mass ratio of T units relative to the sum of T and I units of less than or equal to 74%, and preferably 0% to 5% or 45% to 67%, and the nucleating filler may be a carbon-based filler. The polyaryletherketone of composition C may, for example, be a polyetherketoneketone having a mass ratio of T units to the sum of T and I units in the range of 55% to 65%, notably about 60%, and the carbon-based filler may be a carbon nanotube.

[0246] Among the additives, mention can also be made of plasticizers. The plasticizers can allow the glass transition temperature of the composition C to be lowered. The plasticizers can for example be chosen from the compounds defined in the Handbook of Plasticizers edited by Georges Wypych. The composition C can notably comprise from 0 to 20% by weight of plasticizer(s) relative to the total weight of the composition C.

[0247] Furthermore, the composition C can optionally comprise small amounts of functional additives, notably less than 1% by weight relative to the total weight of the composition. Examples of such additives that can be mentioned include antistatic agents, antioxidants, melt stabilizers, electrically conductive agents, flame retardants, colorants and reactive agents such as basic carbonates.

[0248] Composition C

[0249] The composition C constituting the pellets comprises a non-layered polymer mixture M, said mixture M comprising:

[0250] - at least 50% by weight relative to the total weight of the mixture of at least one pseudo-amorphous or semi-crystalline polyaryletherketone having a melting point less than or equal to 340°C; and,

[0251] - from 5 to 40% by weight relative to the total weight of the mixture of poly(etherimide-siloxane) copolymer, it being understood that if the mixture M comprises from 5 to 7.5% by weight of poly(etherimide-siloxane) copolymer, the mixture M does not comprise any polysiloxane.

[0252] According to certain embodiments, the mixture M consists of:

[0253] said at least one polyaryletherketone having a melting point less than or equal to 340°C, said poly(etherimide-siloxane) copolymer, and

[0254] from 0 to 40% by weight relative to the total weight of the mixture of a thermoplastic polymer different from said polyaryletherketone and said poly(etherimide-siloxane) copolymer.

[0255] According to certain embodiments, the mixture M consists of said at least one polyaryletherketone and said poly(etherimide-siloxane) copolymer.

[0256] The mixture M can 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.

[0257] According to certain embodiments, composition C comprises at least 60% by weight, and preferably at least 70% by weight, of mixture M and 0% to 40% by weight, and preferably 0% to 30% by weight, of one or more additives, relative to the total weight of the composition. Composition C may notably consist of at least 70% by weight of mixture M and 0% to 30% by weight of one or more additives.

[0258] According to certain embodiments, the composition C consists of the mixture M and from 0% to 30% by weight of additives relative to the total weight of the composition C.

[0259] According to certain embodiments, the composition C consists of the mixture M and from 0% to 30% by weight of additives relative to the total weight of the composition C.

[0260] 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 plasticizers, 0% to 5% by weight of nucleating fillers and less than 1% by weight of functional additives, relative to the total weight of composition C.

[0261] According to certain embodiments, composition C consists of mixture M, 0.1% to 5% by weight of nucleating filler and less than 1% by weight of functional additives, relative to the total weight of composition C.

[0262] Uses of pellets

[0263] The process for preparing the composition C in pellet form can be carried out in a melt-blending apparatus. Any melt-blending apparatus known to those skilled in the art for preparing polymer compositions by melt-blending can be used.

[0264] Suitable melt blending equipment includes, for example, kneaders, Banbury mixers, single screw extruders, and twin screw extruders.

[0265] Preferably, an extruder is used which is equipped with means for metering all required components into the extruder, into the main hopper of the extruder and / or by side feeds.

[0266] For pellet production, the melt residence time in the melt blending equipment is typically very short, notably less than 1 minute.

[0267] According to certain embodiments, the maximum temperature for melt blending is above 350°C. This may be necessary, notably, when the polymer mixture M comprises a semicrystalline polyaryletherketone with a melting point strictly above 340°C. However, these embodiments are not preferred. In these cases, the melt residence time for pelletizing should be kept low, notably less than or significantly less than 1 minute.

[0268] According to certain embodiments, the maximum temperature for carrying out the melt blending is kept lower than or equal to 350° C., or lower than or equal to 340° C., or lower than or equal to 335° C. This is notably possible when the polyaryletherketone having a melting point of less than or equal to 340° C. of the polymer mixture M is the polymer of the mixture having the highest melting point among the polymers of the mixture.

[0269] The various components of the composition can be fed simultaneously in the form of a mixture of powders or granules or a mixture of powders and granules (also known as a dry blend). They can also be fed separately.

[0270] The order of combining the components during melt blending is not particularly limited.

[0271] The compositions according to the present invention generally have a multiphasic appearance, but are not stratified. Specifically, the poly(etherimide-siloxane) copolymer is generally not very miscible with the poly(aryletherketone). The dispersed phase is then observed by electron microscopy in the form of nodules within the continuous phase. Preferably, the nodules have an average diameter of less than 20 μm, advantageously less than 10 μm, and most particularly less than 5 μm.

[0272] Preferably, the poly(aryletherketone) forms the continuous phase (also referred to as the matrix) of the composition and the poly(etherimide-siloxane) copolymer forms the dispersed phase.

[0273] Use according to the invention

[0274] The composition C according to the invention can be used for producing parts, articles or coatings via one of the customary forming methods at a maximum production temperature not exceeding 350° C.

[0275] According to certain embodiments, the maximum temperature during the manufacturing method does not exceed 345°C, or does not exceed 340°C, or does not exceed 335°C.

[0276] Typically, the maximum temperature during the production process is set 5 to 40°C higher than the melting temperature of the polyaryletherketone having a melting point of 340°C or less.

[0277] According to certain embodiments, the maximum temperature during the manufacturing method is set to 10 to 30°C or 15 to 25°C higher than the melting temperature of the polyaryletherketone having a melting point of 340°C or less.

[0278] A sufficiently low maximum temperature allows the part, article, or coating to be manufactured for use even with long residence times at or near the maximum manufacturing temperature. This residence time can be notably 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.

[0279] Thus, composition C can be formed by, for example, molding (notably injection molding or compression molding), extrusion (notably film or sheet extrusion), calendering extrusion, tube or pipe extrusion, sheathing extrusion, filament fusion additive manufacturing (FFAM), spinning, rotational molding or thermoforming.

[0280] According to certain embodiments, thick parts, articles or coatings can be manufactured. They typically have a thickness of 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 manufacture of such components typically involves an average residence time at or near the maximum manufacturing temperature of 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.

[0281] As examples of thick parts or articles, mention may be made of plates, rods, jackets or tubes.

[0282] In addition, thin parts, products or coatings can also be manufactured. They usually have a thickness of less than or equal to 2 mm, or less than or equal to 1 mm, or less than or equal to 0.5 mm, or less than or equal to 0.25 mm. The manufacture of such elements usually involves an average residence time shorter than that of thick elements. However, locally, particularly in the stagnant zone, the residence time of composition C at or near the maximum manufacturing temperature can 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.

[0283] As examples of thin parts or articles, films, coatings or sheaths may be mentioned.

[0284] The term "thickness" generally refers to one of the dimensions of an article, component, or coating, measured by the distance between its two major sides. For coatings where the thickness is generally uniform along the length of the coating, the thickness refers to the average thickness of the coating over the entire coating. Typically, at any point in the coating, the coating thickness is the same within ±5%, often within ±2%. The thickness can be measured, for example, using a caliper.

[0285] According to certain embodiments, composition C can be used as a thin or thick coating or jacketing layer of an electrical cable.

[0286] Composition C is particularly advantageous for producing articles, parts or coatings having improved impact strength and / or higher elongation at break and / or lower elastic modulus relative to unformulated polyaryletherketone pellets. This creates the possibility of producing durable parts because they exhibit lower crack growth.

[0287] The pellets notably allow for imparting one or more, and according to certain embodiments, all of the following properties to the manufactured article, component, or coating:

[0288] - a tensile modulus of elasticity measured at 20° C. according to standard ISO 527-2:2019 / 1A of less than 4.0 GPa, preferably less than 3.5 GPa, more preferably less than 3.2 GPa and preferably less than 3.0 GPa, and / or

[0289] a nominal strain at break measured at 20° C. according to standard ISO 527-2:2019 / 1A of greater than 8%, preferably greater than 10%, notably greater than 15%, or greater than 20%,

[0290] - a Charpy impact strength according to standard ISO 179-1:2010 / 1eA of greater than 5 KJ / m², preferably greater than 6 KJ / m², more preferably greater than 7 KJ / m² and even more preferably greater than 8 KJ / m²,

[0291] - a yield point stress of less than 95 MPa and preferably less than 85 MPa, measured at 20°C according to standard ISO 527-2:2019 / 1A:2019,

[0292] -CO2 permeability measured at 60°C is less than 1.1 × 10 -8 (cm 3 .cm) / (cm².s.bar),

[0293] - In the case where the sheath or tube forms a conduit, the structural flexibility is such that the conduit is capable of undergoing at least 1000 cycles, wherein for each cycle the polymeric sheath or tube layer of composition C undergoes bending strain levels ranging from -2% up to +2% without the polymeric sheath or tube layer of composition C rupturing, as shown in Example 2.

[0294] The increase in flexibility and elongation at break allows for higher strains and thus new designs, in particular for installation or winding. The composition according to the invention is therefore particularly advantageous for the manufacture of pipes, cables, components in the aeronautical, automotive, electronics, electrical, composite, additive manufacturing and medical device sectors.

[0295] The manufactured parts, articles or coatings can achieve different levels of crystallinity, which can notably be controlled by the crystallization kinetics of composition C.

[0296] As described above in specific embodiments, and as notably illustrated in Example 1, control of the crystallization kinetics of Composition C can be achieved in various ways: i) by selecting a single polyaryletherketone having a melting point less than or equal to 340°C, ii) mixing two different polyaryletherketones having melting points less than 340°C, iii) mixing two polyaryletherketones having different melting points, one less than or equal to 340°C and the other strictly greater than 340°C, and iv) mixing a polyaryletherketone having a melting point less than or equal to 340°C and a nucleating filler.

[0297] The crystallinity level can be determined by DSC at 20 °C / min for the first heating by calculating ΔH f1 -ΔH CC To evaluate. The term "Δ H CC ” corresponds to the enthalpy of cold crystallization, and the term “Δ H f1 " corresponds to the enthalpy of melting on first heating at a heating rate of 20°C / min. These enthalpies are expressed in joules per gram of composition.

[0298] Expression Δ H f1 -ΔH CC It may have a value generally ranging from 0 to 50 J / g of composition C. It may notably have a value from 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.

[0299] Crystallinity levels of 0 to 10 J / gram of composition are considered low to medium levels of crystallinity. Therefore, parts, articles, or coatings having this level of crystallinity have the advantage of being easier to implement due to a lower transition temperature and good subsequent thermoformability.

[0300] A crystallinity level strictly greater than 10 J / gram of composition is considered to be a medium to high level of crystallinity. Parts, articles, or coatings having this level of crystallinity have the following advantages: generally having better chemical resistance, better temperature resistance, and / or lower gas permeability, but are generally less pliable and / or less amenable to thermoforming than parts, articles, or coatings having lower levels of crystallinity.

[0301] According to certain uses of the present invention, composition C may be in the form of pellets. These pellets may be used as described above.

[0302] Alternatively, according to other uses of the present invention, the constituent elements of composition C can be added by melt blending during a conventional forming process. For example, it is conceivable that all the constituent elements of composition C are added by melt blending during a conventional forming process. It is also conceivable that mixture M is in pelletized form and the other components of composition C, notably additives, are added by melt blending during a conventional forming process.

[0303] Example

[0304] Starting materials

[0305] The following commercial polymers were used:

[0306] Kepstan® PEKK, grades in the 6000, 7000, and 8000 series suitable for extrusion, are sold by Arkema. These polymers are PEKK copolymers with T / I ratios of approximately 60 / 40 (pseudo-amorphous, melting point equal to 303°C), 70 / 30 (semi-crystalline, melting point equal to 331°C), and 80 / 20 (semi-crystalline, melting point equal to 355°C), respectively.

[0307] Siltem® STM1500, sold by Sabic, is a poly(etherimide-dimethylsiloxane) (PEI-PDMS) copolymer containing 40% polydimethylsiloxane by weight relative to the total weight of the polymer.

[0308] Siltem® STM1500 is amorphous and therefore has a glass transition temperature, Tg, of 168°C.

[0309] PEEK 450G TM , sold by the company Victrex, suitable for extrusion (semi-crystalline, melting point 343°C).

[0310] Carbon nanotubes (CNTs), GraphiStrength® C100, sold by Arkema.

[0311] Preparation of pellets

[0312] Several formulations containing PAEK, poly(etherimide-siloxane) copolymer and optional nucleating agent were produced by compounding on a Coperion ZSK MC26 twin-screw extruder with L / D=40 and 10 barrels.

[0313] After drying, the starting materials were introduced in varying proportions (see Table 1) via one or two feeders on the first barrel, with a third feeder allowing for side-feeding of the poly(etherimide-siloxane) copolymer prior to the melting zone on the fourth barrel. The screw speed for all tests was set at approximately 200 rpm and the flow rate at 20 kg / h. The residence time of the composition while in molten form was estimated to be much less than 1 minute.

[0314] To make pellets of compositions 2, 3, 4 and 8, a temperature profile was used having a maximum nominal temperature of 320°C and a die temperature of 320°C.

[0315] For the production of pellets of composition 5, the profile used had a maximum nominal temperature of 340° C. and a die temperature of 340° C. This profile notably allowed a better appearance of the rods compared to the previous temperature profiles.

[0316] To produce pellets of composition 1c, a profile with a nominal maximum temperature of 370°C and a die temperature of 370°C was used. Specifically, the first two profiles were unsuitable, and unmelted material remained in the rods. It should be noted that the appearance of the rods improved as the profile temperature increased to 370°C, but the rods easily broke when stretched.

[0317] To make pellets of composition 7c, the curve had a maximum nominal temperature of 370°C and a die temperature of 370°C.

[0318] [Table 1]

[0319]

[0320] Example 1 - Extrusion of 7 mm thick strips

[0321] After drying overnight at 150°C, pellets of various formulations were used to prepare extruded tapes.

[0322] A Collin single-screw extruder with a 30 mm screw diameter and an L / D ratio of 25 was used. The extruder was connected to a flat die with a width of 50 mm and a gap of 8 mm. At the die exit, the melt was conveyed on a three-roll calendaring system. The gap between the rollers was adjusted to just above the desired thickness to produce a 7 mm thick strip. The strip was then cut to the desired length at the end of the line.

[0323] The temperature conditions of the extruder are as follows:

[0324] To produce composition strips 2, 3 and 4, a temperature profile with a temperature ramp up to the last zone and a die at 320°C was used.

[0325] To make composition strip 5, a bell-shaped temperature profile was used to have uniform material and stable extrusion with a maximum nominal temperature of 335°C and the last zone and die at 325°C.

[0326] To produce composition strip 1 c , a bell curve was used in order to have sufficiently homogeneous material and sufficiently stable extrusion, with a maximum nominal temperature of 370° C. and the last zone and die at 350° C.

[0327] To produce the composition strip 6c, a bell-shaped temperature profile was used in order to have a sufficiently homogeneous material and a sufficiently stable extrusion, with a maximum nominal temperature equal to 350°C and a die temperature equal to 330°C.

[0328] For all strips, the screw speed was set to 30 rpm and the overall line speed was set to about 0.2 m / min. The residence time of the material in the extruder to form a 7 mm thick strip was estimated to be about 3-4 minutes.

[0329] Appearance of the stripes

[0330] refer to Figure 2 , the strips of composition 1c were delaminated (sheets were visible in cross section) and had many pores (many bubbles were visible on the surface or in cross section).

[0331] In contrast to the strips of composition 1c, the strips of compositions 2-5; 6c had no visible delamination (smooth appearance in cross section) and no porosity (no visible bubbles on the surface or in cross section). Figure 3 and 4 A cross-sectional view and a surface view of composition strip 4 and composition strip 5 are shown, respectively.

[0332] Preparation of Type 1A test specimens, Type 1 bars, and Type A notches

[0333] For mechanical testing, Type 1A test coupons and Type 1A bars were subtractively manufactured by machining / milling, retaining only the core of the strip.

[0334] Due to the inhomogeneous and layered nature of the composition strip 1c, it was not possible to produce a correct test specimen / rod. Consequently, the latter could not be subjected to mechanical testing.

[0335] The dimensions and shape of type 1A test specimens are described in standard ISO 527-2:2012 (Section 11 and Table 1, page 5). These test specimens are referred to hereinafter as "ISO 527-2 / 1A test specimens".

[0336] Type 1 rod has 80.0 × 10.0 × 4.0 mm 3of 1 mm / min. The dimensions of the notched bars are as described in standard ISO 179-1 :2010 (section 6.3, table 1). The notch tip radius is equal to 0.25 ± 0.05 mm of a “V” notch (type A notch). These bars are hereinafter referred to as “ISO 179-1 / 1 eA bars”.

[0337] The test specimens and notched bars are then left to rest for 24 hours at 23 °C and 50% relative humidity.

[0338] Mechanical characterization

[0339] ISO 527-2 / 1A test specimens are used to determine the elastic modulus and the nominal strain at break of compositions 2-5, 6c and 8 at 23 °C and 50% RH according to standard ISO 527-1 :2019.

[0340] To determine the elastic modulus, a crosshead speed equal to 1 mm / min is used.

[0341] To determine the nominal strain at break, a crosshead speed equal to 50 mm / min is used.

[0342] The Charpy impact strength of compositions 2-5, 6c and 8 is determined using ISO 179-1 / 1 eA bars according to standard ISO 179-1 :2010.

[0343] The mechanical characterization of composition 1c is not possible due to the presence of many porosities in the core of the extruded strip.

[0344] Crystallinity characterization

[0345] The crystallinity of the samples is evaluated by calculating the AH f1 - AH CC at the first heating at 20 °C / min by DSC.

[0346] The results of the various characterizations are reported in the following table 2.

[0347] [Table 2]

[0348]

[0349] These examples demonstrate the benefits of using different compositions containing PAEKs having a melting point less than or equal to 340 °C and poly(etherimide-siloxane) copolymers, allowing to be formed in the shape of objects such as:

[0350] even in the case of a relatively long residence time at the processing temperature, they are not delaminated and homogeneous;

[0351] It is ductile, i.e., has a relatively low elastic modulus, a high nominal strain at break, and a high notched Charpy impact strength;

[0352] It can optionally be very thick without losing the advantageous properties mentioned above.

[0353] The modification of the crystallization behavior provided by i) compounding the polyaryletherketone and / or ii) adding additives results in objects that can have good crystallinity while maintaining good ductility. These higher crystallinity levels can be sought for improved chemical resistance, high barrier properties, or even to allow the mechanical properties of the composition to be maintained when used above the glass transition temperature of the polyaryletherketone.

[0354] Example 2 - Preparation of Sheaths by Extrusion and Evaluation of Certain Properties

[0355] Three types of pellets were used, with formulations 4, 5 and 7c. They were first dried at 180° C. for 48 hours in a drying apparatus (Piovan) with a dew point of −40° C. After drying, the moisture level was checked with a moisture meter (Aquatrac) and was below 50 ppm.

[0356] The pellets were then fed into a single screw extruder (manufactured by Maillefer, 45 mm in diameter, equipped with a three-zone screw) at a temperature of 100° C. and the temperature profile as described in Example 1 .

[0357] The residence time of the polymer composition in the molten state is directly dependent on the extruder screw speed and can be calculated.

[0358] Several screw speeds were used and a significant effect of the speed (and hence the melt residence time) on the surface appearance of the produced sheath was observed.

[0359] Table 3 shows that the temperatures of the extrudates obtained differ as a function of the composition used. Composition 4, which has the lowest melting point, has the best surface appearance, due to the fact that the poly(etherimide-siloxane) copolymer has not degraded during extrusion.

[0360] [Table 3]

[0361]

[0362] A 7 mm thick sheath could be extruded onto the metal skeleton, demonstrating the possibility of extruding thick layers.

[0363] Microscopic observation of the sheath

[0364] Microscopic observations were performed on the sheaths produced from compositions 4, 5, and 7c. Thin 15 μm sections were obtained using a microtome (Leica 2065) and observed using a digital microscope (Keyence VHX 700F). The region of the weld line where the residence time of the known polymer compositions in the molten state was the longest was studied.

[0365] Composition 5 has a distinct weld line without debonding, but may have some microstructural anomalies and potentially minor degradation. Composition 4, on the other hand, has virtually no anomalies in this area. Composition 7c shows clear signs of degradation around the entire circumference of the jacket, with bubbles in the first 0.2 mm below the jacket's outer surface and additional localized bubbles at the weld line, indicating degradation related to dwell time.

[0366] Mechanical properties

[0367] Tensile test specimens were prepared and tensile tested at room temperature from extruded sheathing according to standard ISO 527-1A.

[0368] Table 4 presents the results of this test for the extruded sheathing of compositions 4 and 5 from Table 3.

[0369] [Table 4]

[0370]

[0371] No mechanical characterization of composition 7c is given here due to the presence of numerous voids in the core of the extruded strip, and due to the presence of defects and numerous surface scratches throughout the sheath (see Table 3).

[0372] Flexibility

[0373] A 4-meter-long prototype flexible pipe, consisting of a metal skeleton surrounded by an extruded polymer sheath, was subjected to bending tests. To perform the tests, the prototype flexible pipe was mounted in a fixed position, attached at one end and free to deform at the other, allowing it to be set in motion by means of a test bench's jacks.

[0374] Bending and reverse bending stresses were applied sequentially, with the pipe returning to its natural, unbent shape at the end of the cycle. Thus, for each cycle, the pipe was subjected to stress levels ranging from -2% to +2%, which was performed for 1,000 cycles without any observed damage to the polymer sheath.

[0375] Penetration resistance (penetration resistance)

[0376] The parts of the sheath produced from composition 4 were prepared by mechanical processing so as to obtain a film 1.5 mm thick from the area situated at the core of the cross section of the sheath.

[0377] Use as Figure 2 The permeation resistance was determined using the device for measuring the permeability coefficient of a sheath sample relative to a gas, shown and described on page 13, line 16, to page 15, line 2, of patent application FR 2987666. The method used was the method described on page 15, line 7, to page 18, line 26 of said application, wherein the gas used was pure CO2, the temperature was 60°C, and the pressure difference between the two sides of the membrane was 40 bar. The permeation resistance was calculated using equation [6] described on page 18, line 12 of said patent application. The value obtained for composition 4 was less than 1.1×10 -8 (cm 3 .cm) / (cm².s.bar).

Claims

1. A pellet consisting of a composition C comprising an unstratified polymer mixture M, The mixture M comprises: at least 50% by weight, relative to the total weight of the mixture, of at least one pseudo-amorphous or semicrystalline polyaryletherketone having a melting point less than or equal to 340° C.; and 5% to 40% by weight of poly(etherimide-siloxane) copolymer relative to the total weight of the mixture, it being understood that if the mixture M comprises 5% to 7.5% by weight of poly(etherimide-siloxane) copolymer, the mixture M does not comprise any polysiloxane. 2 . The pellet according to claim 1 , wherein the mixture M comprises more than 7.5% by weight, and preferably more than 8% by weight, of poly(etherimide-siloxane) copolymer relative to the total weight of the mixture.

3. The pellet of any one of claims 1 and 2, wherein the siloxane groups of the poly(etherimide-siloxane) copolymer comprise greater than 30% of the total weight of the poly(etherimide-siloxane) copolymer.

4. The pellet of any one of claims 1 to 3, wherein the siloxane groups of the poly(etherimide-siloxane) copolymer comprise less than 50% of the total weight of the poly(etherimide-siloxane) copolymer. 5 . The pellet according to claim 1 , wherein the mixture M comprises less than 30% by weight, preferably less than 25% by weight, of poly(etherimide-siloxane) copolymer relative to the total weight of the mixture.

6. The pellet according to any one of claims 1 to 5, wherein the polyaryletherketone having a melting point of less than or equal to 340°C is a polyetherketoneketone, the polyetherketoneketone consisting essentially of, and preferably consisting of: Terephthalic acid units and isophthalic acid units, terephthalic acid units have the chemical formula: [Chemistry 24] (I) The isophthalic acid unit has the formula: [Chemistry 25] (II) The repeating unit of formula (III) and the repeating unit of formula (IV), the repeating unit (III) having the following formula: [Chemistry 26] (III) And the repeating unit (IV) has the following formula: [Chemistry 27] (IV) A repeating unit of formula (III) and a repeating unit of formula (V), wherein the repeating unit (V) has the following formula: [Chemistry 28] (V) A repeating unit of formula (III) and a repeating unit of formula (VI), wherein the repeating unit (VI) has the following formula: [Chemistry 29] (WE).

7. The pellet according to any one of claims 1 to 6, wherein the polyaryletherketone having a melting point of less than or equal to 340°C is a polyetherketoneketone, the polyetherketoneketone consisting essentially of, and preferably consisting of: Terephthalic acid units and isophthalic acid units, terephthalic acid units have the chemical formula: [Chemistry 30] (I) The isophthalic acid unit has the following chemical formula: [Chemistry 31] (II) The molar percentage of terephthalic acid units relative to the sum of terephthalic acid and isophthalic acid units is less than or equal to 74%, preferably 0% to 5% or 45% to 73%, and more preferably 58% to 72%.

8. The pellet according to any one of claims 1 to 7, wherein the polyaryletherketone having a melting point less than or equal to 340 °C has a melting point less than or equal to 335 °C, or less than or equal to 330 °C, or less than or equal to 325 °C, or less than or equal to 320 °C.

9. The pellet according to any one of claims 1 to 8, wherein the polyaryletherketone having a melting point less than or equal to 340 °C has a melting point greater than or equal to 275 °C, or greater than or equal to 285 °C, or greater than or equal to 295 °C.

10. The pellet according to any one of claims 1 to 9, wherein the poly(etherimide-siloxane) copolymer has the chemical formula: [Chemical formula 32] (XV) wherein n is an integer from 5 to 100, R represents a phenylene group, Z represents a bisphenol A residue, and R 4 represents an n-propylene group, E represents an integer from 2 to 50, and each siloxane R' is a methyl group.

11. The pellet according to any one of claims 1 to 10, wherein the mixture M consists of the polyaryletherketone having a melting point less than or equal to 340 °C, the poly(etherimide-siloxane) copolymer, and a thermoplastic polymer different from the polyaryletherketone and the poly(etherimide-siloxane) copolymer in an amount of 0 to 40% by weight based on the total weight of the mixture.

12. The pellet according to any one of claims 1 to 11, wherein the mixture M contains 0.1% to 3% by weight, and preferably 0.5% to 2% by weight of polysiloxane as a different thermoplastic polymer based on the total weight of the mixture M.

13. The pellet according to any one of claims 1 to 12, wherein the mixture M contains less than 1% by weight of polysiloxane as a different thermoplastic polymer based on the total weight of the mixture M.

14. The pellet according to any one of claims 1 to 13, wherein the composition C consists of the mixture M and one or more additives in an amount of 0 to 40% by weight, preferably 0 to 30% by weight based on the total weight of the composition.

15. The pellet according to claim 14, wherein the composition C contains 0.1% to 5% by weight of a nucleating filler, such as a mineral filler, notably talc, a carbon-based filler, notably carbon nanotubes or carbon black, a ceramic filler, notably boron nitride (BN), or a metal oxide, notably ZnO or MgO.

16. The pellets according to claim 15, wherein the mixture M comprises a polyaryletherketone consisting essentially of, and preferably consisting of: The terephthalic acid unit and the isophthalic acid unit, and the molar percentage of the terephthalic acid unit relative to the sum of the terephthalic acid and isophthalic acid units is 0% to 5% or 45% to 67%.

17. The pellet according to any one of claims 1 to 16, wherein the mixture M contains two polyaryletherketones P1 and P2 having a melting point less than or equal to 340 °C, P1 is a semi-crystalline polymer having a melting point of T1, and P2 is a semi-crystalline polymer having a melting point such that T2 < T1, or P2 is a pseudo-amorphous polymer.

18. The pellet according to claim 17, wherein P2 accounts for at least 50% by weight of the polyaryletherketone having a melting point less than or equal to 340 °C.

19. The pellet according to any one of claims 17 and 18, wherein: P2 is polyetherketoneketone, which consists essentially of terephthalic acid units and isophthalic acid units, and preferably consists of terephthalic acid units and isophthalic acid units. The molar percentage of terephthalic acid units relative to the sum of terephthalic acid and isophthalic acid units is 0% to 5% or 45% to 67%, and P1 is a polyetherketoneketone consisting essentially of, and preferably consisting of, terephthalic acid units and isophthalic acid units, The molar percentage of the terephthalic acid units relative to the sum of the terephthalic acid and isophthalic acid units is 63% to 73%.

20. The pellet according to claim 1, wherein the mixture M comprises two polyaryletherketones P3 and P4, P3 is a semicrystalline or pseudo-amorphous polyaryletherketone having a melting point less than or equal to 340°C, preferably less than or equal to 320°C, and P4 is a polyaryletherketone having a melting point strictly greater than 340°C. 21 . The pellet according to claim 20 , wherein the mixture M comprises 25% by weight or less, 20% by weight or less, 15% by weight or less, or even 10% by weight or less of polymer P4 relative to the total weight of the mixture M.

22. The pellet according to any one of claims 20 and 21, wherein: P3 is a polyetherketoneketone consisting essentially of terephthalic acid units and isophthalic acid units, and preferably consisting of terephthalic acid units and isophthalic acid units, the molar percentage of terephthalic acid units of the polyetheretherketone relative to the total moles of terephthalic acid and isophthalic acid units of the polyetheretherketone being 0% to 5% or 45% to 67%, and P4 is a polyetherketoneketone consisting essentially of terephthalic acid units and isophthalic acid units, and preferably consisting of terephthalic acid units and isophthalic acid units, The mole percentage of the terephthalic acid units of the polyetherketoneketone is 78% to 85% relative to the total moles of the terephthalic acid and isophthalic acid units.

23. The pellet according to claim 1, wherein the mixture M comprises less than 30% by weight, preferably less than 25% by weight and more preferably less than 20% by weight of poly(etherimide-siloxane) copolymer relative to the total weight of the mixture.

24. Use of the composition C according to any one of claims 1 to 23 for the manufacture of articles, parts or coatings by molding, notably by injection molding or compression molding, by extrusion, notably film or sheet extrusion, calendering extrusion, tube or pipe extrusion, extruded sheathing, by filament fusion additive manufacturing (FFAM), spinning, rotational molding or thermoforming at a maximum manufacturing temperature not exceeding 350°C.

25. The use according to claim 24, wherein composition C is maintained at the maximum manufacturing temperature for a period of 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 25 minutes.

26. The use according to any one of claims 24 and 25, wherein the article, or the component, or the coating has a thickness of the 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, wherein composition C is in the form of pellets.

28. The use according to any one of claims 24 to 27, wherein the article or the component or the coating has at least one of the following properties: - a tensile modulus of elasticity measured at 20° C. according to standard ISO 527-2:2019 / 1A of less than 4.0 GPa, preferably less than 3.5 GPa, more preferably less than 3.2 GPa and preferably less than 3.0 GPa, and / or a nominal strain at break measured at 20° C. according to standard ISO 527-2:2019 / 1A of greater than 8%, preferably greater than 10%, notably greater than 15%, or greater than 20%, - a Charpy impact strength according to standard ISO 179-1:2010 / 1eA of greater than 5 KJ / m², preferably greater than 6 KJ / m², more preferably greater than 7 KJ / m² and even more preferably greater than 8 KJ / m², - a yield point stress of less than 95 MPa and preferably less than 85 MPa, measured at 20°C according to standard ISO 527-2:2019 / 1A:2019, -CO2 permeability measured at 60°C is less than 1.1×10 -8 (cm 3 .cm) / (cm².s.bar), - in the case where the jacket or tube forms a conduit, the structural flexibility is such that the conduit is capable of undergoing at least 1000 cycles, wherein for each cycle the polymeric jacket or tube layer of composition C is subjected to bending strain levels ranging from -2% up to +2% without the polymeric jacket or tube layer of composition C rupturing.

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