Polyaryletherketone polymers

Abstract

The present invention relates to novel polyaryletherketone copolymers, to a process for their preparation, to polymer compositions comprising these copolymers and to shaped articles manufactured from said polymer compositions.

Description

[0001] This application claims priority to U.S. Provisional Patent Application No. 63 / 005,534 filed April 6, 2020 and EP 20183602.0 filed July 2, 2020, the entire contents of each of which are incorporated by reference into this application for all purposes. TECHNICAL FIELD

[0002] The present invention relates to novel polyaryletherketone polymers, methods of making the same, polymer compositions comprising the same, and shaped articles manufactured from the polymer compositions. BACKGROUND

[0003] In the field of oil and gas exploration, automotive, aerospace, electronics, semiconductor industry, industrial or consumer applications, there is a demand for polymers to show a combination of high temperature performance, good chemical resistance, low smoke and flammability, good mechanical properties, good fatigue resistance, etc. Among these, oil and gas exploration demands materials that can withstand high temperatures and pressures, and can maintain the required properties upon prolonged exposure to extreme pressures and temperatures and to the corrosive chemicals present in the downhole environment, such as brine, hydrocarbons, etc.

[0004] Poly(aryletherketone) polymers (PAEKs) are high performance plastics with high heat resistance, which are used in many industrial applications where resistance to extreme conditions is required.

[0005] In particular, poly(ether ether ketone) (PEEK) polymers, which contain repeating units of the formula -Ph-O-Ph-C(=O)-Ph-O- (where -Ph- is 1,4-phenylene), have found widespread use due to their high temperature performance and excellent chemical resistance. However, their glass transition temperature (Tg) of about 148 °C somewhat limits their ability to withstand continuous operation at temperatures of 150 °C or higher.

[0006] To increase the glass transition temperature, polyaryletherketone (PAEK) polymers have been proposed, such as, for example, PEK (characterized by repeating units of the formula -O-Ph-C(=O)-Ph-), PEKK (characterized by repeating units of the formula -O-Ph-C(=O)-Ph-C(=O)-Ph-), PEKEKK (characterized by repeating units of the formula -O-Ph-C(=O)-Ph-O-Ph-C(=O)-Ph-C(=O)-Ph-). These polymers, while having an increased Tg, are however considered more sensitive to chemicals in aggressive environments, for example they have lower resistance to steam and can suffer from high melt temperatures, associated with processing difficulties. These polymers also tend to exhibit moderate melt stability, which limits their processability.

[0007] In order to provide materials having a Tg higher than PEEK but similar or even lower crystalline melting point, copolymers comprising PEEK and PEDEK repeating units have been proposed in the art. These copolymers comprising a mixture of units (I) -0-Ph-O-Ph-C(=0)-Ph- and (II) -0-Ph-Ph-O-Ph-C(=0)-Ph- (wherein -Ph- is a 1,4-phenylene unit), for example in EP 0225750 (ICI PLC), WO 2016 / 016643 (VICTREX MANUFACTURING LIMITED).

[0008] More recently, WO 2018 / 086873 (SOLVAY SPECIALTY POLYMERS U.S.A., LLC.) discloses copolymers comprising repeating units (I) and (II) above in a molar ratio of 45:55 to 15:85 and having a narrow molecular weight distribution, which can be used to manufacture parts included in devices for oil and gas recovery.

[0009] As an alternative, copolymers comprising PEEK or PEDEK units and PEoEK units having the formula -0-orthoPh-O-Ph-C(O)-Ph- (wherein -orthoPh- is a 1,2-phenylene unit; and -Ph- is a 1,4-phenylene unit) have been proposed in the art.

[0010] For example, JPH1221426 (IDEMITSU KOSAN CO., LTD.) notably describes in its examples 2, 5 and 6 copolymers of PEEK or PEDEK and PEoEK made from 4,4'-dihydroxyphenyl or hydroquinone, ortho- hydroquinone and difluorobenzophenone, which are claimed to have an increased glass transition temperature and at the same time an excellent heat resistance. The PEDEK-PEoEK copolymer disclosed in example 2 contains PEDEK and PEoEK units in a molar ratio of 50:50. SUMMARY

[0011] The present applicant believes that, despite the efforts made in the art, there is still a need to provide PEDEK-PEoEK copolymers having a combination of physical and mechanical properties, so that they can be used to manufacture devices used in harsh conditions and environments, such as notably in the oil and gas, automotive, aerospace, electronics, semiconductor industry, industrial or consumer applications.

[0012] More particularly, the Applicant faced the problem of providing PEDEK-PEoEK copolymers characterized by a more rigid backbone structure and an increased glass transition temperature (Tg) compared to the polymers known in the art, so that the copolymers of the present application have an improved mechanical properties and chemical resistance, which is a unique combination of properties desirable for industrial applications, including notably oil and gas, automotive, aerospace, electronics, semiconductor industry, industrial or consumer applications.

[0013] The Applicant surprisingly found that by selecting the molar amounts of its PEDEK and PEoEK repeating units, it is possible to synthesize PEDEK-PEoEK copolymers showing such desirable properties.

[0014] Thus, in a first aspect, the present application relates to a polymer [polymer (P)] comprising:

[0015] - from greater than 60 to 85 mol.%, based on 100 mol.% of said polymer (P), of repeating units (R PEDEK ) of formula (I):

[0016]

[0017] wherein

[0018] each R1is independently selected from the group consisting of C1-C12 alkyl, sulfonic acid and sulfonate groups, phosphonic acid and phosphonate groups, amine and quaternary ammonium groups, optionally comprising one or more heteroatoms,

[0019] each R3is independently halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkyl sulfonate, alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine and quaternary ammonium

[0020] each a and each c is independently 0 or an integer from 1 to 4;

[0021] - from greater than 60 to 85 mol.%, based on 100 mol.% of said polymer (P), of repeating units (R PEoEK ) of formula (II):

[0022]

[0023] wherein

[0024] each R1and each a are as defined above,

[0025] each R2is independently selected from the group consisting of halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkyl sulfonate, alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine and quaternary ammonium, and

[0026] each b is independently 0 or an integer from 1 to 4.

[0027] In a second aspect, the present application relates to a process for the synthesis of said polymer (P), said process comprising:

[0028] (a) contacting at least one compound of formula (III)

[0029]

[0030] wherein

[0031] each R1and each a are as defined above,

[0032] with a mixture of compounds of formulae (IV) and (V):

[0033]

[0034] wherein each R2, each R3, each b and each c are as defined above,

[0035] such that the ratio of (IV) and (V) is from 85 / 15 to 60 / 40;

[0036] in the presence of a base [base (B)], and in a polar organic solvent [solvent (S)], so as to obtain a reaction mixture;

[0037] (b) optionally, stopping the reaction in step (a) by contacting said reaction mixture with a suitable reagent, so as to obtain a product mixture; and

[0038] (c) recovering said polymer (P) from said reaction mixture or from said product mixture.

[0039] In a third aspect, the present application relates to a composition [composition (C)] comprising a polymer (P) as described above, and at least one additional ingredient [ingredient (in)].

[0040] In a further aspect, the present application relates to a shaped article comprising a polymer (P) and / or a composition (C) according to the present application.

[0041] More preferably, said shaped article is an article for oil and gas recovery, automotive, aerospace, electronics, semiconductor industry, industrial or consumer applications.

[0042] In a further aspect, the present application relates to a process of manufacturing parts included in devices for oil and gas recovery, automotive, aerospace, electronics, semiconductor industry, industrial or consumer applications, said process comprising molding and / or extruding and / or coating those parts from said polymer (P) and / or said composition (C). DETAILED DESCRIPTION

[0043] According to a preferred embodiment, the polymer (P) comprises only said recurring unit (R PEDEK ) of formula (I) as defined above and said recurring unit (R PEoEK ) of formula (II) as defined above.

[0044] Preferably, the polymer (P) comprises from 61 mol.%, more preferably from 62 mol.% and even more preferably 63 mol.% of said recurring unit (R PEDEK ) of formula (I) as defined above, based on 100 mol.% of the polymer (P).

[0045] According to a preferred embodiment, the polymer (P) comprises from 64 mol.% of said recurring unit (R PEDEK ) of formula (I), based on 100 mol.% of the polymer (P).

[0046] Preferred embodiments are those wherein the polymer (P) comprises from 65 mol.%, more preferably from 69 mol.% of said recurring unit (R PEDEK ) of formula (I), based on 100 mol.% of the polymer (P).

[0047] Advantageous results have been obtained with a polymer (P) comprising at least 70 mol.%, even more preferably at least 75 mol.% of said recurring unit (R PEDEK ) of formula (I) as defined above.

[0048] Preferably, the polymer (P) comprises up to 85 mol.%, more preferably up to 84 mol.%, even more preferably up to 82 mol.% of said recurring unit (R PEDEK ) of formula (I) as defined above, based on 100 mol.% of the polymer (P).

[0049] According to a preferred embodiment, the polymer (P) comprises up to 81 mol.% of said recurring unit (R PEDEK ) of formula (I), based on 100 mol.% of the polymer (P).

[0050] Advantageous results have been obtained with a polymer (P) comprising up to 80 mol.% of said recurring unit (R PEDEK ) of formula (I) as defined above, based on 100 mol.% of the polymer (P).

[0051] Preferably, in the recurring unit (R PEDEK ) of formula (I), a and c are 0.

[0052] Preferably, the polymer (P) comprises from 15 to 40 mol.% of the recurring unit (R PEoEK ) of formula (II) as defined above, based on 100 mol.% of the polymer (P).

[0053] Preferably, the polymer (P) comprises up to 39 mol.%, more preferably up to 38 mol.% and even more preferably up to 37 mol.% of the recurring unit (R PEoEK ) of formula (II), based on 100 mol.% of the polymer (P).

[0054] According to a preferred embodiment, the polymer (P) comprises up to 36 mol.% of the recurring unit (R PEoEK ) of formula (II), based on 100 mol.% of the polymer (P).

[0055] Preferred embodiments are those wherein the polymer (P) comprises up to 35 mol.%, more preferably up to 31 mol.% of the recurring unit (R PEoEK ) of formula (II) as defined above.

[0056] Advantageous results have been obtained with polymers (P) comprising up to 30 mol.%, even more preferably up to 25 mol.% of the recurring unit (R PEoEK ) of formula (II) as defined above.

[0057] Preferably, the polymer (P) comprises from 15 mol.%, more preferably from 16 mol.%, even more preferably from 18 mol.% of the recurring unit (R PEoEK ) of formula (II) as defined above, based on 100 mol.% of the polymer (P).

[0058] According to a preferred embodiment, the polymer (P) comprises from 19 mol.% of the recurring unit (R PEoEK ) of formula (II), based on 100 mol.% of the polymer (P).

[0059] Advantageous results have been obtained with polymers (P) comprising from 20 mol.% of the recurring unit (R PEoEK ) of formula (II) as defined above.

[0060] Preferably, in the recurring unit (R PEoEK ) of formula (II), each of a and b is 0.

[0061] According to another embodiment, the polymer (P) of the application can additionally comprise a repeating unit (R PEDEK ) different from said repeating unit (R PEoEK ) and said repeating unit (R PAEK ).

[0062] In this embodiment, the amount of repeating unit (R PAEK ) is preferably comprised between 0.1 and less than 50 mol.%, more preferably less than 25 mol.%, even more preferably less than 10 mol.% and still more preferably less than 2 mol.%, based on 100 mol.% of the polymer (P).

[0063] Preferably, said repeating unit (R PAEK ) complies with any one of the following formulae:

[0064]

[0065]

[0066] wherein in each of the above formulae (K-A) to (K-M),

[0067] each R', equal to or different from each other, is at each occurrence independently selected from the group consisting of C1-C 12 groups optionally comprising one or more than one heteroatom, sulfonic acid and sulfonate groups, phosphonic acid and phosphonate groups, amine and quaternary ammonium groups; and

[0068] each j', equal to or different from each other, is at each occurrence independently selected from the group consisting of 0 and an integer from 1 to 4, preferably j' is equal to zero.

[0069] Although the present application encompasses embodiments of said polymer (P) comprising the repeating unit (R PAEK ), it is however preferred that the polymer (P) consists essentially of the repeating unit (R PEDEK ) and the repeating unit (R PEoEK ) as defined above.

[0070] In the present specification and in the following claims, the expression "consists essentially of the repeating unit (R PEDEK ) and the repeating unit (R PEoEK ) is intended to indicate that any one or more additional repeating units different from the repeating unit (R PEDEK ) and the repeating unit (R PEoEK ) as defined above can be present in the polymer (P) in an amount of at most 1 mol.%, more preferably at most 0.5 mol.% relative to 100 mol.% of said polymer (P).

[0071] Defects, end groups and impurities of monomers can be incorporated in the polymer (P) of the application in very small amounts, thereby advantageously not negatively affecting the properties of the polymer.

[0072] Preferably, said recurring unit (R PEDEK ) and said recurring unit (R PEoEK ) are present in said polymer (P) in a molar ratio (R PEDEK ) / (R PEoEK ) from 60 / 40 to 85 / 15, more preferably from 65 / 35 to 80 / 20.

[0073] Advantageously, the polymer (P) according to the application is characterized in that:

[0074] (i) a glass transition temperature (Tg) higher than 153°C [measured by DSC at the midpoint according to ASTM D3418-03 with a heating and cooling rate of 20°C / min on the 2nd heating scan up to 450°C]; and

[0075] (ii) a ratio of the storage modulus measured at 165°C to the storage modulus measured at 140°C higher than 15% [measured according to ADTM D5279-13 by dynamic mechanical analysis on a TA ARES G2 rheometer in torsion mode at 10 rad / s, 0.05% strain with a temperature ramp of 5.0°C / min from 30°C to 330°C].

[0076] Furthermore, the polymer (P) is advantageously characterized in that:

[0077] (iii) a heat of fusion (AH) higher than 40 J / g [determined as the area under the melting endotherm on the 2nd heating scan up to 450°C in a differential scanning calorimeter (DSC) measured according to ASTM D3418-03 with a cooling and heating rate of 20°C / min]; and

[0078] (iv) a melt viscosity ranging from 0.20 to 9.00 kN / m 2 , preferably 0.30 to 5.00 kN / m 2 , more preferably 0.40 to 4.50 kN / m 2 [measured according to ASTM D3835 at 410°C and 46 s -1 ].

[0079] The polymer (P) characterized by the above properties shows a notably better processability in terms of molding or extrusion processing compared to the polymers known in the art.

[0080] Preferably, in formula (III), a is 0 and the compound is 4,4’-difluorobenzophenone (DFBP).

[0081] Preferably, in formula (IV), c is 0 and the compound is 4,4’-dihydroxybiphenyl, also known as 4,4’-biphenol.

[0082] Preferably, in formula (V), b is 0 and the compound is pyrocatechol (also known as catechol).

[0083] Preferably, step (a) is performed at a temperature of at least 130 °C, preferably at least 140 °C, more preferably at least 150 °C, for about 0.5 to 15 hours.

[0084] It is also preferred that compounds (III), (IV) and (V) are heated at a first temperature of at least 130 °C, preferably at least 140 °C, more preferably at least 150 °C, prior to contacting with base (B).

[0085] Preferably, the base (B) is preferably selected from the group consisting of potassium carbonate (K2CO3), potassium bicarbonate, sodium carbonate (Na2CO3), cesium carbonate (Cs2CO3), potassium phosphate and sodium bicarbonate.

[0086] Most preferably, the base (B) is selected from the group consisting of potassium carbonate (K2CO3), sodium carbonate (Na2CO3) or a mixture of both; even most preferably, the base (B) is a mixture of both.

[0087] Without being bound by any theory, the base serves to deprotonate components (IV) and (V) during the condensation reaction.

[0088] Step (a) is performed in a solvent (S) comprising diphenyl sulfone. In some embodiments, solvent (S) comprises at least 50 wt.% diphenyl sulfone, based on the total weight of solvent in the reaction mixture, for example at least 60 wt.%, at least 70 wt.%, at least 80 wt.%, at least 90 wt.%, at least 95 wt.% or at least 98 wt.% diphenyl sulfone, based on the total weight of solvent (S) in the reaction mixture.

[0089] In some embodiments, solvent (S) consists essentially of diphenyl sulfone.

[0090] In the process of the present application, typically a solvent (S) comprising limited amounts of impurities is used, as detailed in U.S. 9,133,111.

[0091] The solvent (S) of the present application can comprise benzophenone and / or dibenzothiophene dioxide.

[0092] Optionally, after step (a) and prior to said step (b) or said step (c), a step (a2) of elevated temperature is performed.

[0093] Preferably, said step (a2) comprises heating the reaction mixture obtained in step (a) to a temperature of at least 300°C, preferably at least 310°C, with an average temperature ramp rate of less than 5°C / minute, preferably less than 3°C / minute and / or with a temperature ramp rate of more than 0.1°C / minute.

[0094] Preferably, said step (a2) is carried out for a time comprised between 20 seconds and 3 hours, depending on the nature of the starting monomers and the chosen reaction conditions.

[0095] Preferably, step (b) is carried out after step (a) or after step (a2) and before step (c).

[0096] According to this embodiment, step (b) is carried out in a polar organic solvent as defined above in step (a).

[0097] The solvent (S) used in step (b) can be the same solvent as used in step (a) or can be a solvent (S) different from the solvent used in step (a). Advantageously, steps (a) and (b) are carried out using the same solvent (S) as defined above.

[0098] Preferably, said step (b) is carried out to terminate the polycondensation reaction in step (a). For this purpose, suitable reagents are selected from reagents capable of terminating chain growth by being incorporated in the polymer backbone through a condensation reaction (also called capping agents) and reagents capable of terminating chain growth by not being incorporated in the polymer backbone through a condensation reaction (also called terminating agents).

[0099] The capping agent preferably complies with the following formula (F):

[0100]

[0101] wherein

[0102] R 6 is F, Cl or OH,

[0103] R 7 is -C(O)-Ar-R 10 , -O-Ar-R 10 , -SO2-Ar-R 10 , -Ar-R 10 , alkyl (e.g. C1-C 10 alkyl or C1-C5 alkyl) or -H, wherein Ar is an arylene group comprising at least one phenyl ring (i.e. one phenyl ring or several phenyl rings) and wherein R 10 is F, Cl or H.

[0104] Preferably, R 6 is F or OH. More preferably, R6 is F.

[0105] Preferably, R 7 is -C(O)-Ar-R 10 , Ar-R 10 or H, wherein R 10 is F, Cl or H.

[0106] According to certain preferred embodiments, R 10 is F.

[0107] When R 7 is different from -H, R 6 and R 7 may be 1,2- or ortho-substituted on the phenylene ring of formula (F), or they can be 1,3- or meta-substituted on the phenylene ring.

[0108] Alternatively, R 6 and R 7 may be preferably 1,4- or para-substituted on the phenylene ring of formula (F).

[0109] In some embodiments, the end-capping agent is selected from the group consisting of 4,4’-difluorobenzophenone, phenol, 4-phenoxyphenol, 4-phenylphenol, 4,4’-dichlorodiphenyl sulfone, 4,4’-difluorodiphenyl sulfone, and mixtures thereof.

[0110] Difluoro compounds and monofunctional phenols are preferably used as end-capping agents. In some embodiments, the end-capping agent is an excess of difluoro compound monomer. The end-capping agent used in the process of the present invention is preferably 4,4’-difluorobenzophenone, phenol, 4-phenoxyphenol, 4-phenylphenol, or mixtures thereof.

[0111] An example of a compound suitable as a terminating agent is lithium chloride.

[0112] Preferably, step (b) is performed using at least one end-capping agent and at least one terminating agent. More preferably, 4,4’-difluorobenzophenone and lithium chloride are used in step (b).

[0113] Generally, the (poly)condensation reaction is performed using a slight excess of the difluoro compound having formula (III).

[0114] It is further understood that the end-capping agent, when used, can be added to the reaction mixture at the beginning of the polycondensation; thus, in general, it is considered that an excess of monomer (III) can be used as an end-capping agent as explained above, the molar ratio [(III) + (F)] / [(IV) + (V)] being > 1.000, preferably > 1.003, more preferably > 1.006, even more preferably > 1.010.

[0115] Preferably, step (b) comprises the following steps:

[0116] (b1 ) adding a first end-capping agent in the reaction mixture;

[0117] (b2) adding a first termination agent in the reaction mixture; and

[0118] (b3) optionally adding a second end-capping agent and / or a second termination agent in the reaction mixture, the second end-capping agent and the second termination agent being preferably identical to the first end-capping agent and the first termination agent, respectively.

[0119] More preferably, said first end-capping agent of step (b1 ) is 4,4’- difluorobenzophenone (DFBP).

[0120] More preferably, said termination agent of step (b2) is lithium chloride (LiCI).

[0121] More preferably, said second end-capping agent of step (b3) is 4,4’- difluorobenzophenone (DFBP) and said second termination agent is lithium chloride (LiCI).

[0122] Preferably, the concentration of monomers and end-capping agents (when used) [(III) + (IV) + (V) + (F)] in the diphenyl sulfone is at least 15 wt.%, preferably at least 20 wt.%, more preferably at least 23 wt.%.

[0123] Preferably, the concentration of monomers and end-capping agents (when used) [(III) + (IV) + (V) + (F)] in the diphenyl sulfone is at most 45 wt.%, preferably at most 43 wt.%, more preferably at most 40 wt.%.

[0124] At the end of the reactions of step (a), final step (a2) and step (b), a polymer (P) is obtained in the form of a solid phase.

[0125] Preferably, step (c) is performed to recover said polymer (P) by removing the solvent (S) and other organic compounds (such as, for example, sodium fluoride or potassium fluoride or the excess of base (B)) by means of methods known in the art, such as washing, dissolution and filtration.

[0126] Before and optionally after said step (c), the polymer (P) recovered as a solid phase can advantageously be subjected to a further step [step (d)] comprising at least one of pulverization, milling, trituration, so as to provide said polymer (P) in the form of small particles.

[0127] Preferably, the composition (C) comprises at least 10 wt.%, at least 20 wt.%, at least 30 wt.% of the polymer (P) based on the total weight of this composition (C).

[0128] Preferably, the composition (C) comprises at least 50 wt.%, more preferably at least 60 wt.%, at least 70 wt.%, at least 80 wt.%, at least 90 wt.%, still more preferably at least 95 wt.% and even more preferably at least 99 wt.% of the polymer (P) based on the total weight of this composition (C).

[0129] Preferably, the at least one ingredient (in) is selected from the group consisting of (i) reinforcing fillers; (ii) colorants such as dyes; (iii) pigments such as titanium dioxide, zinc sulfide and zinc oxide; (iv) light stabilizers, for example UV stabilizers; (v) heat stabilizers; (vi) antioxidants such as organic phosphites and phosphonites; (vii) acid scavengers; (viii) processing aids; (ix) Nucleating agent (x) internal and / or external lubricants; (xi) flame retardants; (xii) smoke suppressants; (xiii) antistatic agents; (xiv) anti-blocking agents; (xv) electrically conductive additives such as carbon black and carbon nanofibrils; (xvi) plasticizers; (xvii) flow modifiers; (xviii) extenders; and (xix) metal deactivators.

[0130] Preferably, the composition (C) comprises less than 20%, preferably less than 10%, more preferably less than 5% and even more preferably less than 2% of the at least one ingredient (in).

[0131] Preferred reinforcing fillers are selected from fibrous and particulate fillers different from pigments as described below.

[0132] More preferably, the reinforcing fillers are selected from mineral fillers (such as talc, mica, kaolin, calcium carbonate, calcium silicate, magnesium carbonate, boron nitride), glass fibers, carbon fibers, synthetic polymeric fibers, aramid fibers, aluminum fibers, titanium fibers, magnesium fibers, boron carbide fibers, boron nitride fibers, rock wool fibers, steel fibers, wollastonite, and the like.

[0133] Nanoscale reinforcing fillers such as those selected from single- and multi- walled carbon nanotubes, carbon nanofibers, graphene, graphene oxide and nanoclays such as montmorillonite can also be used.

[0134] Still more preferably, the reinforcing fillers are selected from mica, kaolin, calcium silicate, magnesium carbonate, glass fibers, carbon fibers and wollastonite.

[0135] More preferably, the filler is selected from fibrous fillers. A particular class of fibrous fillers consists of whiskers, i.e. monocrystalline fibers made from different raw materials such as AI2O3, SiC, BC, Fe and Ni.

[0136] In a preferred embodiment of the application, the reinforcing filler is selected from wollastonite and glass fibers.

[0137] Among the fibrous fillers, glass fibers are preferred; they include chopped strands A-, E-, C-, D-, S-, T- and R-glass fibers as described in John Murphy, Additives for Plastics Handbook, 2ndEdition, Chapter 5.2.3, pages 43-48.

[0138] The glass fibers can have a circular cross-section or a non-circular cross-section (such as an elliptical or rectangular cross-section).

[0139] When the glass fibers used have a circular cross-section, they preferably have an average glass fiber diameter of 3 to 30 pm and particularly preferably of 5 to 12 pm. Depending on the type of glass from which they are made, different kinds of glass fibers having a circular cross-section are available on the market. Notably, glass fibers made from E- or S-glass can be cited.

[0140] In some embodiments, the glass fibers are standard E-glass material having a non-circular cross-section. In some aspects, the polymer composition comprises S-glass fibers having a circular cross-section.

[0141] In some embodiments, the composition (C) comprises at least one carbon fiber.

[0142] As used herein, the term "carbon fiber" is intended to include graphitized, partially graphitized, and non-graphitized carbon reinforcing fibers or mixtures thereof. The term "graphite fiber" is intended to mean carbon fibers obtained by high temperature pyrolysis (higher than 2000 °C) of carbon fibers, in which carbon atoms are arranged in a similar manner to graphite structure.

[0143] The carbon fibers are preferably selected from the group consisting of PAN-based carbon fibers, pitch-based carbon fibers, graphite fibers, and mixtures thereof.

[0144] The fibers can be in the form of whiskers, short fibers, continuous fibers, sheets, layers, and combinations thereof. The continuous fibers can further be in any of a unidirectional, multidirectional, nonwoven, woven, knitted, stitched, wrapped, and braided construction, as well as crimped mat, felt mat, and chopped mat structures. The fiber tows can be held in place by cross-tow needling, weft-insertion knitting needles, or a small amount of resin such as a sizing agent. As used herein, "continuous fiber" is a fiber having a length greater than 10 mm.

[0145] When present, the composition (C) preferably comprises less than 80 wt.%, more preferably less than 75 wt.%, even more preferably less than 70 wt.% of reinforcing filler, based on the total weight of the composition (C).

[0146] When present, the composition (C) preferably comprises at least 10 wt.%, preferably at least 20 wt.%, preferably at least 25%, most preferably at least 30 wt.% of reinforcing filler, based on the total weight of the composition (C).

[0147] Preferably, the composition (C) comprises at least one nucleating agent selected from talc or boron nitride.

[0148] Preferably, the polymer (P) is the only polymer component in the polymer composition. As used herein, the expression "polymer component" means a compound having repeating units and a molecular weight of at least 2,000 g / mol.

[0149] According to another embodiment, the composition (C) comprises less than 3 wt.%, 2 wt.%, 1 wt.%, 0.5 wt.% of a polymer component other than the polymer (P).

[0150] The polymer component other than the polymer (P) is preferably at least one poly(aryl ether sulfone) (PAES) selected from the group consisting of polysulfone (PSU), polyphenylsulfone (PPSU) and poly(ether sulfone) (PES).

[0151] The composition (C) can be prepared by various methods involving intimate mixing of the components of the composition (C), for example by dry mixing, suspension or slurry mixing, solution mixing, melt mixing, a combination of dry mixing and melt mixing, or fiber impregnation. As used herein, "components of the polymer composition" include the polymer (P) and at least one ingredient (in) as defined above, as detailed above.

[0152] Typically, dry mixing of the components of the polymer composition is carried out by using a high intensity mixer, such as a Henschel mixer, a paddle mixer or a ribbon blender, to obtain the polymer composition as a physical mixture.

[0153] Alternatively, intimate mixing of the components of the polymer composition is carried out by tumble blending based on single- or multi-axial rotating mechanisms to obtain a physical mixture.

[0154] Alternatively, intimate mixing of the components of the polymer composition is carried out by slurry mixing of the components of the polymer composition using a stirrer in a suitable liquid, such as, for example, methanol, followed by filtering off the liquid to obtain a powder mixture of the components of the polymer composition.

[0155] In some embodiments, the method of manufacturing the polymer composition comprises melt compounding the physical mixture. Conventional melt compounding devices can be used, such as co-rotating and counter-rotating extruders, single-screw extruders, co-kneaders, disc-pack processors, and various other types of extrusion equipment. Preferably, an extruder, more preferably a twin-screw extruder, can be used.

[0156] In some embodiments, the physical mixture is compounded in an extruder and then chopped into pellets or granules. The pellets or granules can then be further processed to manufacture additional shaped articles.

[0157] As mentioned above, the shaped article according to the present application can advantageously be manufactured using the individual polymer (P) or the composition (C) as described above.

[0158] According to a first embodiment, the polymer (P) is processed as such into the shaped article without the need to add any fillers or additional ingredients.

[0159] According to a second embodiment, the composition (C) is processed into the shaped article.

[0160] The shaped article can comprise one or more parts. When the shaped article is a single part, the single part is preferably composed of the composition (C).

[0161] Alternatively, the shaped article can be composed of more than one part, one or more of the parts being preferably composed of the polymer (P) or the composition (C). When the more than one part of the shaped article comprises the polymer (P) or the composition (C), each part can comprise the same polymer (P) or composition (C) or different polymers (P) or compositions (C).

[0162] The weight of the polymer (P) or the composition (C) is preferably greater than 1 %, greater than 5 %, greater than 10 %, preferably greater than 15 %, greater than 20 %, greater than 30 %, greater than 40 %, greater than 50 %, greater than 60 %, greater than 70 %, greater than 80 %, greater than 90 %, greater than 95 %, greater than 99 % based on the total weight of the shaped article.

[0163] The polymer (P) or the composition (C) can be used to manufacture articles useful in a wide variety of applications.

[0164] For example, the surprising and advantageous properties of the polymers (P) described herein make the polymers (P) or compositions (C) particularly suitable for use in automotive applications (such as magnet wire coatings in hybrid and electric vehicles, seal rings, bushings, bearings, thrust washers), oil and gas applications (such as downhole cable coatings), in electrical and electronic applications (such as test sockets for surface mount technology (SMT) type components on circuit boards, lithium ion battery components including separators between individual cells for short circuit protection, membranes for micro speaker membrane components), aerospace applications (such as electrical / electronic connectors for high temperature environments (e.g. near engines), thermoplastic composite matrix for composite prepreg and laminate, injection molded secondary structure parts), in semiconductor manufacturing (such as chemical mechanical planarization (CMP) rings, fixtures, carriers, boxes and trays used at various stages of semiconductor and integrated circuit chip fabrication and manufacturing), in industrial applications (such as compressor valve parts (including valve seats and sealing elements), oil and gas support and seal rings and other sealing components for downhole applications, pump impellers and other fluid delivery components for chemical processing, coatings on steel or other metal components for corrosion protection, electrical wire and cable insulation for electrical insulation and / or abrasion resistance), in consumer applications (such as housings or housing components for electronic nicotine delivery systems (ENDS) (also known as e-cigarettes or vapes)).

[0165] In particular, the compositions (C) are very suitable for use as continuous fiber-reinforced composites.

[0166] The shaped articles described herein can be manufactured from the polymers (P) or compositions (C) by injection molding, extrusion molding, compression molding, additive manufacturing (also known as three-dimensional (3D) printing, which for shaped articles can also be referred to as 3D objects or 3D parts), continuous fiber impregnation, and continuous fiber composite lamination / consolidation or other shaping techniques.

[0167] In some embodiments, the method for manufacturing a shaped article or a part thereof comprises compression molding or injection molding, and subsequently a step of curing the polymer (P) or composition (C).

[0168] In some embodiments, the method for manufacturing a shaped article or a part thereof comprises a coating step. For example, the polymer (P) or composition (C) can be applied to a metal surface as a coating, preferably by electrostatic powder, aqueous suspension coating or extrusion coating around an electrical wire, preferably a coated magnet wire, by any suitable coating method.

[0169] According to the present application, the shaped article can comprise a polymer-metal joint. The polymer-metal joint comprises the polymer (P) or the composition (C) comprising the same as described above in contact with a metal substrate.

[0170] The metal substrate can comprise any metal composition, including but not limited to aluminum, copper, gold, iron, nickel, platinum, silver, steel, and blends or alloys thereof (e.g., brass and bronze). Preferably, the metal substrate is copper, steel, aluminum, or a combination thereof.

[0171] In some embodiments, the metal substrate (e.g., an aluminum substrate) has a structured metal surface. As used herein, “structured metal surface” means a metal surface that has been subjected to any etching process to roughen the metal surface by removing at least a portion of the metal. Examples of structured metal surfaces include laser-etched metal surfaces and chemically-etched metal surfaces. In some embodiments, the metal surface is an unetched metal surface.

[0172] In some aspects, the metal substrate is a nanostructured metal surface. “Nanostructured metal surface” means a metal surface that has been etched to have a nano-indentation surface having surface peaks and valleys having average depth, height, and width dimensions ranging from 10 to 1000 nm, preferably from 30 to 800 nm, and more preferably from 50 to 500 nm on a nanometer scale regime. In some embodiments, the metal substrate comprises an NMT-treated metal surface. “NMT-treated metal surface” means a nanostructured surface prepared by any etching / primer process described in EP 1459882 B1, EP 1559542 A1, or WO 2011123790 A1, the disclosures of which are incorporated by reference in their entirety in the present application.

[0173] In some embodiments, the metal substrate is an electrical wire or cable. In alternative embodiments, the metal substrate is a part of a mobile electronic device.

[0174] In some embodiments, the polymer-metal joint comprises a layer of the polymer composition having a thickness ranging from 0.025 mm to 3 mm.

[0175] The polymer-metal joint can be manufactured by contacting the polymer (P) or composition (C) as described herein with a metal substrate, preferably a structured metal surface, more preferably a nanostructured metal surface, most preferably an NMT-treated metal surface. For example, the polymer (P) or composition (C) can be deposited on or overmolded onto the metal substrate using any suitable melt processing and deposition method.

[0176] In particular, the polymer-metal bonds can be made by injection or compression molding, or coating of the polymer (P) or composition (C) onto a metal substrate. The polymer-metal bonds can also be formed by electrostatic or solvent-borne powder coating methods. In some aspects, the polymer-metal bonds can be formed by an extrusion process for coating electrical wires or cables. In alternative embodiments, the polymer-metal bonds are made by additive manufacturing processes.

[0177] The polymer-metal bonds of the present invention can be well suited for making articles useful in a wide variety of applications. For example, the properties of the polymers (P) described herein make the polymer compositions particularly suitable for use in automotive applications such as magnet wire coatings in hybrid and electric vehicles, oil and gas applications such as downhole cable coatings, structural parts for mobile electronic devices (e.g., frames or housings), including metal parts, electrostatic powder coatings on metal substrates for corrosion protection and wear resistance.

[0178] Further exemplary embodiments relate to methods of making a polymer (P) composite material, the method comprising impregnating the reinforcing fibers described above with a polymer matrix described herein.

[0179] Various methods can be employed to impregnate the fibers with the polymer matrix, where the matrix is in a molten or particulate form, including, for example, powder coating, film lamination, extrusion, pultrusion, aqueous slurry, and melt impregnation, to form a ply, for example, in the form of a sheet or tape of fibers at least partially impregnated with the polymer matrix. As used herein, “tape” means a strip of material having reinforcing fibers extending lengthwise, the reinforcing fibers being aligned along a single axis of the strip material.

[0180] Plies of matrix-impregnated fibers can be placed adjacent to one another to form an uncured composite laminate, such as a prepreg. The fiber reinforcement plies of the laminate can be positioned in their respective fiber reinforcements in selected orientations relative to one another.

[0181] The plies can be stacked manually or automatically, for example, by automated tape laying using “pick and place” robots, or advanced fiber placement, in which pre-impregnated fiber tows are heated and compacted in a mold or on a mandrel to form a composite laminate having the desired physical dimensions and fiber orientation.

[0182] The uncured laminate plies are typically not fully fused together, and the uncured composite laminate can exhibit a significant void content, for example, greater than 20% by volume as measured by x-ray microtomography. Heat and / or pressure can be applied, or ultrasonic vibration welding can be used, to stabilize the laminate and prevent the plies from moving relative to one another, for example, to form a composite “blank” as an intermediate step to allow handling of the composite laminate prior to consolidating the composite laminate.

[0183] The so-formed composite layup is then typically consolidated, e.g., by subjecting the composite layup to heat and pressure in a mold, to form a shaped fiber-reinforced thermoplastic matrix composite article. As used herein, "consolidation" is the process by which the matrix material is softened, the plies of the composite layup are pressed together, air, moisture, solvent and other volatiles are pressed out of the layup, and the adjacent plies of the composite layup are fused together to form a solid, coherent article. Ideally, the consolidated composite article exhibits minimal void content, e.g., less than 5% by volume, more typically less than 2% by volume, as measured by x-ray microtomography.

[0184] The composite material preferably comprises from 20 to 80 wt.% of reinforcing fibers and from 80 to 20 wt.% of a polymer matrix, based on the weight of the composite material.

[0185] Exemplary embodiments will now be described in the following non-limiting examples.

[0186] To the extent the disclosure of any patent, patent application, and publication incorporated herein by reference conflicts with the description of the application provided herein, the description provided herein controls.

[0187] Experimental part

[0188] Raw materials:

[0189] KT-820P, an aromatic polyether ether ketone (PEEK) polymer available from Solvay Specialty Polymers USA, LLC. - Comparative Polymer C

[0190] HT, an aromatic polyether ketone ketone (PEKK) available from Solvay S.A. - Comparative Polymer D

[0191] 2000, an aromatic polyether ketone (PEK) available from Greene, Tweede & Company. - Comparative Polymer A

[0192] PEKEKK ST-45P, an aromatic polyether ketone ether ketone ketone available from Victrex. - Comparative Polymer B

[0193] 4,4'-Biphenol, polymer grade, obtained from SI, USA.

[0194] Catechol, flake, was obtained from Solvay USA. Its purity was 99.85% by GC. It contained 680 ppm moisture, which amount was used to adjust the charge weight. All indicated weights include moisture.

[0195] 4,4'-difluorobenzophenone, polymer grade (99.8+%), was obtained from Malwa, India.

[0196] Diphenyl sulfone (polymer grade) was obtained from Proviron (99.8% pure).

[0197] Sodium carbonate, light soda ash, was obtained from Solvay S.A., France.

[0198] Potassium carbonate, where d 90 <45 μm, was obtained from Armand products.

[0199] Lithium chloride (anhydrous grade) was obtained from Acros.

[0200] Hydroquinone, optical grade, was obtained from Eastman, USA. It contained 0.38 wt% moisture, which amount was used to adjust the charge weight. All indicated weights include moisture.

[0201] Method

[0202] Determination of melting temperature (Tm) and heat of fusion

[0203] The melting temperature (Tm) was determined as the peak temperature of the melting endotherm upon the 2nd heating scan in a differential scanning calorimeter (DSC) according to ASTM D3418-03, E1356-03, E793-06, E794-06. Details of the procedure as used in the present application are as follows: a TA Instruments DSC Q20 was used, with nitrogen as carrier gas (99.998% purity, 50 mL / min). Temperature and heat flow calibration was done using indium. The sample mass was 5 to 7 mg. The weight was recorded to ± 0.01 mg. The heating cycle was:

[0204] 1st heating cycle: 30.00 to 450.00 °C at 20.00 °C / min,

[0205] isothermal at 450.00 °C for 1 min;

[0206] 1st cooling cycle: 400.00 to 30.00 °C at 20.00 °C / min,

[0207] Isotherm for 1 min;

[0208] 2nd heating cycle: 30.00°C to 450.00°C at 20.00°C / min,

[0209] Isotherm at 450.00°C for 1 min.

[0210] Melting temperature (Tm) was determined as the peak temperature of the melting endotherm on the 2nd heating scan. The enthalpy of fusion was determined on the 2nd heating scan. The melting of the composition was taken as the area above a line drawn from 220°C to above the temperature of the last endotherm.

[0211] Glass transition temperature (Tg) (midpoint) was determined according to ASTM D3418-03, E1356-03, E793-06, E794-06 on the 2nd heating scan.

[0212] Determination of melt viscosity and melt stability (VR40)

[0213] Melt viscosity was measured according to ASTM D3835 using a capillary rheometer. Readings were taken after 10 and 40 minute dwell times at 410°C and a shear rate of 46.3 s"1using a die with the following characteristics: diameter = 1.016 mm, length = 20.32 mm, cone angle = 120°. Melt stability VR40 was measured by the ratio of the viscosity at 40 minutes to the viscosity at 10 minutes. The melt viscosity values shown in the table below were recorded at 10 minute dwell time.

[0214] Determination of tensile properties

[0215] A 102 mm x 102 mm x 3.2 mm plaque was prepared from the polymer by compression molding under conditions matching the melting temperature of the composition:

[0216] For Examples 0 to 2, the molding conditions were:

[0217] Pre-heat at 420°C,

[0218] 420°C / 15 min, 2000 kgf

[0219] 420°C / 2 min, 2700 kgf

[0220] Cool to 320°C in 20 min, 2000 kgf

[0221] Hold at 320°C for 50 min, 2000 kgf

[0222] 25 min - cool to 30°C, 2000 kgf.

[0223] Unless otherwise noted in the tables below, the substrates were annealed in air at 275°C for 3 hours. The molding and annealing conditions depend on the melting temperature of the material and the need to form a maximum crystallinity level.

[0224] The temperatures of steps 2, 3 and 5 were modified as follows:

[0225] Table 1 - Compression molding conditions

[0226]

[0227] (*) Comparative

[0228] The crystallinity level of the substrates was determined by DSC (one heating cycle, 20°C / min to 450°C) assuming 130 J / g for a 100% crystalline material.

[0229] Compression molded substrates of 102 mm x 102 mm x 3.2 mm were machined into Type V ASTM tensile specimens. The specimens of the different polymer compositions were subjected to tensile testing according to ASTM method D638 on 3 specimens at room temperature (i.e. 23°C) at 0.05 inch / minute. The average of 3 specimens is presented.

[0230] In addition, oblong test samples (1.2 cm x 5.1 cm x 0.32 cm) were prepared from the molded substrates and dried under vacuum at 120°C for 12 hours. The test samples were then analyzed by dynamic mechanical analysis (DMA) according to ASTM D 5279-13 on a TA ARES G2 rheometer in torsion mode (10 rad / s, 0.05% stress) at 5.0°C / min from 30°C to 330°C in order to measure the storage modulus (G', Pa) at different temperatures ranging from about 50°C to 310°C.

[0231] The data presented in the table below show that PEDEK-PEoEK having a PEDEK / PEoEK ratio of 60 / 40 to 85 / 15 exhibit a higher temperature resistance than PEEK or PEDEK-PEoEK having a PEDEK / PEoEK unit ratio lower than 60 / 40.

[0232] Method for evaluating the chemical resistance of compression molded samples

[0233] Compression molded substrates of 102 mm x 102 mm x 3.2 mm of all polymer compositions (prepared following the methods detailed above and having the composition in Table 2) were machined into Type V ASTM tensile specimens. The specimens were subjected to tensile testing according to ASTM method D638 on 3 specimens at room temperature (i.e. 23°C) at 0.05 inch / minute.

[0234] Three Type V tensile bars of each composition were exposed to a mixture of sweet brine and hydrocarbons in a 600 mL Inconel pressure vessel (154 mL heptane + 44 mL cyclohexane + 22 mL toluene + 36 mL 15 wt% aqueous KCl) at 300°C under nitrogen for 7 days.

[0235] At the end of the exposure test, the bars were wiped and the weight after exposure compared to before. Table 3 summarizes the weight gain measured before and after exposure, the appearance of the bars, and the mechanical properties.

[0236] Strength retention was calculated as follows:

[0237]

[0238] Comparative Example 1 : Preparation of PEDEK-PEEK copolymer 60 / 40

[0239] In a 500 mL 4 neck reaction flask (fitted with stirrer, N2inlet tube, claisen adapter with thermocouple inserted into the reaction medium, and Dean-Stark trap with condenser and dry ice trap), 127.70 g of diphenyl sulfone, 9.894 g of hydroquinone, 25.103 g of 4,4'-biphenol, and 50.130 g of 4,4'-difluorobenzophenone were introduced. The contents of the flask were evacuated under vacuum and then filled with high purity nitrogen (containing less than 10 ppm of O2). The reaction mixture was then placed under constant nitrogen purge (60 mL / min).

[0240] The reaction mixture was slowly heated to 150°C. At 150°C, a mixture of 25.097 g of Na2CO3and 0.155 g of K2CO3was added to the reaction mixture over 30 minutes via a powder dispenser. At the end of the addition, the reaction mixture was heated to 320°C at 1 °C / minute. After 2 minutes at 320°C, 5.892 g of 4,4'-difluorobenzophenone was added to the reaction mixture while maintaining the nitrogen purge on the reactor. After 5 minutes, 0.384 g of lithium chloride was added to the reaction mixture. After 10 minutes, an additional 1.964 g of 4,4'-difluorobenzophenone was added to the reactor and the reaction mixture was held at temperature for 15 minutes.

[0241] The reactor contents were then poured from the reactor into a SS pan and cooled. The solid was broken up and ground in a mill (through a 2 mm screen). The diphenyl sulfone and salts were extracted from the mixture with acetone and water at a pH between 1 and 12. The powder was then removed from the reactor and dried under vacuum at 120°C for 12 hours, yielding 74 g of white powder. The repeat unit of the polymer was:

[0242]

[0243] At 410 °C, 46 s-1, the melt viscosity measured by capillary rheology was 0.18 kN-s / m -1 The melt viscosity measured by capillary rheology at 410 °C, 46 s-1, was 0.18 kN-s / m 2 .

[0244] This example corresponds to Example 1 of WO 2018 / 086873.

[0245] Comparative Example 2: Preparation of PEDEK-PEEK copolymer 75 / 25

[0246] The same procedure as described in Comparative Example 1 was followed except for using the following reagents and reaction conditions.

[0247] 212.00 g of diphenyl sulfone, 4.226 g of hydroquinone, 21.442 g of 4,4’-biphenol and 33.853 g of 4,4’-difluorobenzophenone.

[0248] At 150 °C, a mixture of 16.812 g of Na2C03and 0.106 g of K2C03was added.

[0249] At the end of the addition, the reaction mixture was heated to 340 °C at 1 °C / min. After 7 min at 340 °C, 3.928 g of 4,4’-difluorobenzophenone was added to the reaction mixture while maintaining a nitrogen purge on the reactor.

[0250] After 5 min, 0.651 g of lithium chloride was added to the reaction mixture. After 10 min, another 1.309 g of 4,4’-difluorobenzophenone was added to the reactor and the reaction mixture was kept at this temperature for 15 min.

[0251] 53 g of a white powder was obtained.

[0252] The repeat unit of the polymer is:

[0253]

[0254] The melt viscosity measured by capillary rheology at 410 °C, 46 s-1, was 8.75 kN-s / m2.

[0255] The polymer exhibited a chlorine content of 0.7 peq / g = 25 wtppm Cl (by microcoulometry).

[0256] This example corresponds to Example 5 of WO 2018 / 086873.

[0257] Example 3: Preparation of PEDEK-PEoEK copolymer 80 / 20

[0258] In a 1000 mL 4 necked reaction flask (fitted with stirrer, N2inlet tube, Claisen adapter with thermocouple inserted into the reaction medium, and Dean-Stark trap with condenser and dry ice trap) was introduced 445.22 g of diphenyl sulfone, 9.365 g of catechol, 63.321 g of 4,4'-biphenol, and 93.384 g of 4,4'-difluorobenzophenone. The contents of the flask were evacuated under vacuum and then filled with high purity nitrogen (containing less than 10 ppm of O2). The reaction mixture was then placed under constant nitrogen purge (60 mL / min).

[0259] The reaction mixture was slowly heated to 150 °C. At 150 °C, a mixture of 46.487 g of Na2CO3and 0.294 g of K2CO3was added to the reaction mixture over 30 minutes via a powder dispenser. At the end of the addition, the reaction mixture was heated to 340 °C at 1 °C / min. After 22 minutes at 340 °C, 11.128 g of 4,4'-difluorobenzophenone (1st termination) was added to the reaction mixture while maintaining the nitrogen purge on the reactor. After 5 minutes, 1.812 g of lithium chloride (2nd termination) was added to the reaction mixture. After 10 minutes, an additional 1.855 g of 4,4'-difluorobenzophenone (3rd termination) was added to the reactor and the reaction mixture was held at temperature for 15 minutes.

[0260] The reactor contents were then poured from the reactor into a SS pan and cooled. The solid was broken up and ground in a mortar (through a 2 mm screen). The diphenyl sulfone and salts were extracted from the mixture by washing the solid sequentially with acetone (3600 mL 4 times), demineralized water (with 3600 mL 8 times, the 3rd wash with 30.00 g of 37% HC1, and the 8th wash with 0.90 g of NaH2PO4.2H2O and 0.90 g of Na2HPO4), and acetone (3600 mL 2 times at room temperature). The powder was then removed from the reactor and dried under vacuum at 120 °C for 12 hours to yield 139 g of white powder.

[0261] The repeat unit of the polymer is:

[0262]

[0263] The polymer properties are summarized below.

[0264] Examples 4 to 7: Preparation of PEDEK-PEoEK copolymers 80 / 20, 75 / 25, 70 / 30, 65 / 35

[0265] Comparative Examples 8 and 9: Preparation of PEDEK-PEoEK copolymers 55 / 45 and 50 / 50

[0266] The procedure detailed in Example 3 was followed to prepare the polymers of Examples 4 to 7 and Comparative Examples 8 and 9, except that the reagents and amounts detailed in Table 2 below were used, and the final polymerization temperature.

[0267] Table 2

[0268]

[0269]

[0270] (*) Comparative

[0271] Comparative Example 10: Preparation of PEDEK-PEoEK copolymer 50 / 50 according to JP H1221426

[0272] The procedure described in JP H1221426 was repeated.

[0273] In a 1000 mL 4-necked reaction flask (equipped with a stirrer, N2inlet tube, a Claisen adapter with a thermocouple inserted into the reaction medium, and a Dean-Stark trap with a condenser and a dry-ice trap), 462.60 g of N-methylpyrrolidone, 34.449 g of 4,4'-biphenol, 20.370 g of catechol, 81.549 g of 4,4'-difluorobenzophenone, 45.556 g of Na2C03, and 15 mL of toluene were introduced. The contents of the flask were evacuated under vacuum and then filled with high-purity nitrogen (containing less than 10 ppm of 02). The reaction mixture was then placed under constant nitrogen purge (60 mL / min).

[0274] The reaction mixture was slowly heated to 200°C over 50 minutes. The reaction mixture was held at 200°C for 4 hours while toluene was refluxed into the reaction mixture. The reaction mixture was then cooled to room temperature and coagulated in a Waring blender with 1 L of acetone. The solid was filtered on a Buchner funnel and washed with 1 L of acetone 3 times over 30 minutes per cycle at room temperature, then

[0275] The resulting polymer was washed with 1000 mL of demineralized water 3 times (30 minutes per cycle) at room temperature.

[0276] The powder was then dried under vacuum at 120°C for 12 hours, yielding 115 g of a white powder.

[0277] The properties of the resulting polymers are reported below.

[0278] The tables provided below summarize the properties of the and comparative polymers according to the application, comparing polymers having similar Tg, i.e. similar properties.

[0279] Table 3

[0280]

[0281]

[0282] (*) comparative; np = not performed

[0283] Table 4

[0284]

[0285]

[0286] (*) comparative; np = not performed

[0287] Table 5

[0288]

[0289]

[0290] (*) comparative; np = not performed

[0291] The above data show that the polymers (P) of the application exhibit higher temperature resistance (Tg > 153°C and retention of G' > 15% at 140°C at 165°C) compared to PEEK or PEDEK-PEoEK with a PEDEK / PEoEK unit ratio lower than 60 / 40 (notably PEDEK-PEoEK 50 / 50 manufactured from DPS or NMP (representative of the prior art)). As a consequence, the polymers (P) of the application are thus well suited for high temperature applications.

[0292] The above data show that the polymers (P) of the application maintain a good crystallinity (as shown by the values of heat of fusion > 40 J / g) and exhibit a better melt stability than the comparative polymers B (*) and D (*), which indicates that they have an improved processability.

[0293] The above data show that the polymers (P) of the application exhibit an improved chemical resistance at high temperature (higher % strength retention and % elongation at break retention) compared to the comparative polymers; and an improved tensile strength than the comparative polymers.

[0294] Overall, it is found that the polymers (P) of the application, characterized by the claimed unit ratio from 60 / 40 to 85 / 15, exhibit a unique combination of high temperature capability, excellent chemical resistance and high melt stability.

Claims

1. A polymer [polymer (P)] comprising: - from greater than 60 to 85 mol.%, based on 100 mol.% of said polymer (P), of recurring units (R PEDEK ) of formula (I): wherein each R1 is independently selected from the group consisting of C1-C12 alkyl groups, optionally comprising one or more heteroatoms, sulfonic acid and sulfonate groups, phosphonic acid and phosphonate groups, amine and quaternary ammonium groups, each R3 is independently a halogen, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an ether, a thioether, a carboxylic acid, an ester, an amide, an imide, an alkali or alkaline earth metal sulfonate, an alkyl sulfonate, an alkali or alkaline earth metal phosphonate, an alkyl phosphonate, an amine and a quaternary ammonium each a and each c is independently 0 or an integer from 1 to 4; - repeat units (R PEoEK ) of formula (II): wherein each R1 and each a are as defined above, each R2 is independently selected from the group consisting of a halogen, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an ether, a thioether, a carboxylic acid, an ester, an amide, an imide, an alkali or alkaline earth metal sulfonate, an alkyl sulfonate, an alkali or alkaline earth metal phosphonate, an alkyl phosphonate, an amine and a quaternary ammonium, and each b is independently 0 or an integer from 1 to 4.

2. The polymer (P) according to claim 1, wherein the polymer (P) comprises: - from 61 mol.-% of the recurring units of formula (I) as defined in claim 1 PEDEK ) and / or up to 85 mol.-% of the recurring units of formula (I) as defined in claim 1 PEDEK ) based on 100 mol.-% of the polymer (P).

3. The polymer (P) according to claim 2, wherein said polymer (P) comprises from 63 mol. % of said repeating unit (R PEDEK ) of formula (I).

4. The polymer (P) according to claim 1, wherein the polymer (P) comprises: - from 15 to 40 mol.%, based on 100 mol.% of said polymer (P), of said recurring unit of formula (II) (R PEoEK ) as defined in claim 1 and / or up to 39 mol.%, based on 100 mol.% of said polymer (P), of said recurring unit of formula (II) (R PEoEK ) as defined in claim 1.

5. The polymer (P) according to claim 1, wherein: - in the recurring units (R PEDEK ) of formula (I) a and c are 0; and / or - in the recurring units (R PEoEK ) of formula (II) a and b are 0.

6. A process for the synthesis of the polymer (P) according to any one of claims 1 to 5, said process comprising: (a) contacting at least one compound of formula (III) wherein each R1 and each a are as defined above, with a mixture of compounds of formulae (IV) and (V): wherein each R2, each R3, each b and each c are as defined above, such that the ratio of (IV) and (V) is from 85 / 15 to 60 / 40; in the presence of a base [base (B)], and in a polar organic solvent [solvent (S)], so as to obtain a reaction mixture; (b) optionally, stopping the reaction in step (a) by contacting the reaction mixture with a suitable reagent, so as to obtain a product mixture; and (c) recovering the polymer (P) from the reaction mixture or from the product mixture.

7. The method of claim 6, wherein, said step (a) is performed: - in the presence of a base (B) selected from Na2C03, K2C03, or a combination thereof; and / or - in a solvent (S) comprising diphenyl sulfone; and / or - at a temperature of at least 130°C for 0.5 to 15 hours.

8. The process according to claim 6, wherein: - in formula (III), a is 0, and the compound is 4,4’-difluorobenzophenone (DFBP); and / or - in formula (IV), c is 0, and the compound is 4,4’-dihydroxydiphenyl; - in formula (V), b is 0, and the compound is catechol.

9. The method of any one of claims 6-8, wherein, said step (b) is performed in the presence of at least one capping agent.

10. The process according to claim 9, wherein the at least one capping agent complies with the following formula (F): wherein R 6 is F, CI or OH, R 7 is -C(O)-Ar-R 10 , -O-Ar-R 10 , -SO2-Ar-R 10 , -Ar-R 10 , C1-C 10 alkyl or -H, wherein Ar is an arylene group comprising at least one phenyl ring, and wherein R 10 is F, CI or H.

11. A composition [composition (C)] comprising the polymer (P) according to any one of claims 1 to 5, and at least one additional ingredient [ingredient (in)].

12. The composition (C) according to claim 11, wherein The ingredient (in) is selected from the group consisting of (i) reinforcing filler; (ii) colorant; (iii) pigment; (iv) light stabilizer; (v) heat stabilizer; (vi) antioxidant; (vii) acid scavenger; (viii) processing aid; (ix) nucleating agent; (x) internal and / or external lubricant; (xi) flame retardant; (xii) smoke suppressant; (xiii) antistatic agent; (xiv) antiblock agent; (xv) conductivity additive; (xvi) plasticizer; (xvii) flow modifier; (xviii) extender; and (xix) metal deactivator.

13. The composition (C) according to claim 12, wherein The composition (C) comprises less than 80 wt.% and at least 10 wt.% of the reinforcing filler based on the total weight of the composition (C).

14. The composition (C) according to claim 12, wherein The at least one nucleating agent is selected from talc or boron nitride.

15. A shaped article comprising the polymer (P) according to any one of claims 1 to 5 and / or the composition (C) according to any one of claims 11 to 14.

16. The shaped article according to claim 15, which article is an article of industrial or consumer application.

17. The shaped article according to claim 15, which article is an article for oil and gas recovery, automotive, aerospace, electronics or semiconductor industry.

18. A method of manufacturing at least one part included in a shaped article according to any one of claims 15 and 16, the method comprising: At least one step of molding, extruding or coating the polymer (P) according to any one of claims 1 to 5 and / or the composition (C) according to any one of claims 11 to 14 to manufacture the at least one part.

18. The shaped article according to claim 15, which article is a pipe, a valve, a fitting, a connector, a hose, a cable, a wire, a gasket, a seal, a bushing, a bearing, a bushing, a bearing, a bushing, a bearing, a bushing, a bearing, a bushing, a bearing, a bushing, a bearing, a bushing, a bearing, a bushing, a bearing, a bushing, a bearing, a bushing, a bearing, a bushing, a bearing, a bushing, a bearing, a bushing, a bearing, a bushing, a bearing, a bushing, a bearing, a bushing, a bearing, a bushing, a bearing, a bushing, a bearing, a bushing, a bearing, a bushing, a bearing, a bushing, a bearing, a bushing, a bearing, a bushing, a bearing, a bushing, a bearing, a bushing, a bearing, a bushing, a bearing, a bushing, a bearing, a bushing, a bearing, a bushing, a bearing, a bushing, a bearing, a bushing, a bearing, a bushing, a bearing, a bushing, a bearing, a bushing, a bearing, a bushing, a bearing, a bushing, a bearing, a bushing, a bearing, a bushing, a bearing, a bushing, a bearing, a bushing, a bearing, a bushing, a bearing, a bushing, a bearing, a bushing, a bearing, a bushing, a bearing, a bushing, a bearing, a bushing, a bearing, a bushing, a bearing, a bushing, a bearing, a bushing, a bearing, a bushing, a bearing, a bushing, a bearing, a bushing, a bearing, a bushing, a bearing, a bushing, a bearing, a bushing, a bearing, a bushing, a bearing, a bushing, a bearing, a bushing, a bearing, a bushing, a bearing, a bushing, a bearing, a bushing, a bearing, a bushing, a bearing, a bushing, a bearing, a bushing, a bearing, a bushing, a bearing, a bushing, a bearing, a bushing, a bearing, a bushing

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