Polyaryl ether ketone polymer

Abstract

The present invention relates to novel polyaryletherketone copolymers, methods for their preparation, polymer compositions containing them, and shaped articles made from said polymer compositions.

Description

[Technical Field]

[0001] This application claims priority from U.S. Provisional Patent Application No. 63 / 005534, filed on April 6, 2020, and European Patent Application Publication No. 20183602.0, filed on July 2, 2020, the entire contents of each of these applications being incorporated herein by reference for all purposes.

[0002] The present invention relates to a novel polyaryletherketone polymer, a method for preparing the same, a polymer composition containing the same, and a molded article produced from the polymer composition. [Background technology]

[0003] In fields such as oil and gas exploration, automotive, aerospace, electronics, semiconductor industries, and industrial or consumer applications, polymers are required to exhibit a combination of high-temperature performance, good chemical resistance, low smoke and flammability, good mechanical properties, and excellent fatigue resistance. Among these, oil and gas exploration requires materials that can withstand high temperatures and pressures and maintain the required performance when exposed for extended periods to extreme pressures and temperatures, as well as aggressive chemicals present in downhole environments such as saltwater and hydrocarbons.

[0004] Poly(aryletherketone) polymer (PAEK) is a high-performance plastic with high heat resistance, used in many industrial applications where resistance to extreme conditions is required.

[0005] In particular, poly(etheretherketone) (PEEK) polymers having repeating units of the formula -Ph-O-Ph-C(=O)-Ph-O- (where -Ph- is a 1,4-phenylene group) have found a wide range of applications due to their high-temperature performance and excellent chemical resistance. However, their glass transition temperature (Tg) is approximately 148°C, which somewhat limits their ability to withstand continuous operation at temperatures above 150°C.

[0006] To raise the glass transition temperature, for example, polyaryletherketone (PAEK) polymers such as 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-, and PEKEKK characterized by repeating units of the formula -O-Ph-C(=O)-Ph-O-Ph-C(=O)-Ph-C(=O)-Ph- have been proposed. Although these polymers have an increased Tg, they are known to be more sensitive to chemicals in a harsh environment, for example, they have low steam resistance, and may also have problems with high melting temperatures related to processing obstacles. These polymers also tend to exhibit modest melt stability that limits processability.

[0007] For the purpose of providing a material that has a higher Tg than PEEK but a similar or even lower crystalline melting point, copolymers containing PEEK and PEDEK repeating units have been proposed in the art. For example, in European Patent Application Publication No. 0225750 (ICI PLC), International Publication No. 2016 / 016643 pamphlet (VICTREX MANUFACTURING LIMITED), these copolymers containing a mixture of unit (I) -O-Ph-O-Ph-C(=O)-Ph- and unit (II) -O-Ph-Ph-O-Ph-C(=O)-Ph- (where -Ph- is a 1,4-phenylene unit) have been proposed.

[0008] Recently, International Publication No. 2018 / 086873 pamphlet (SOLVAY SPECIALTY POLYMERS U.S.A., LLC.) disclosed a copolymer that contains the above-mentioned repeating units (I) and (II) in a molar ratio of 45:55 to 15:85 and has a narrow molecular weight distribution, and is useful for manufacturing parts included in devices used for oil and gas recovery.

[0009] Alternatively, copolymers comprising PEEK units or PEDEK units and PEoEK units of the formula -O-orthoPh-O-Ph-C(O)-Ph- (where -orthoPh- is a 1,2-phenylene unit; -Ph- is a 1,4-phenylene unit) have been proposed in the art.

[0010] For example, Japanese Patent Application Laid-Open No. 01-221426 (Idemitsu Kosan Co., Ltd.) describes, in Examples 2, 5, and 6, a copolymer of PEEK or PEDEK and PEoEK produced from 4,4'-biphenol or hydroquinone, pyrocatechol, and difluorobenzophenone, which is said to have an especially increased glass transition temperature and excellent heat resistance at the same time. The PEDEK-PEoEK copolymer disclosed in Example 2 contains PEDEK units and PeoEK units in a molar ratio of 50:50.

Summary of the Invention

[0011] Despite the efforts made in the art, the applicant has recognized that there is still a need for a PEDEK-PEoEK copolymer having a combination of physical and mechanical properties that can be used in the manufacture of devices for use in harsh conditions and environments, particularly in the oil and gas, automotive, aerospace, electronics, semiconductor industry, industrial or consumer applications, etc.

[0012] More specifically, the applicant has faced the problem of providing a PEDEK-PEoEK copolymer characterized by a more rigid main chain structure and an increased glass transition temperature (Tg) compared to polymers known in the art, such that the copolymer of the present invention has both improved mechanical properties and chemical resistance, which are a unique combination of properties desired for industrial applications such as in the oil and gas, automotive, aerospace, electronics, semiconductor industry, industrial or consumer applications, etc.

[0013] The applicant has surprisingly found that by selecting the molar amounts of the repeating units of PEDEK and PEoEK, it is possible to synthesize PEDEK-PEoEK copolymers exhibiting such desired properties.

[0014] Therefore, in the first aspect, the present invention relates to a polymer [polymer (P)], - Based on 100 mol% of the polymer (P), more than 60 mol% to 85 mol%, of formula (I): [ka] (In the formula, Each R1 is independently selected from C1-C12 alkyl groups, sulfonic and sulfonate groups, phosphonic and phosphonate groups, amines, and quaternary ammonium groups, each containing one or more heteroatoms. Each R3 is independently a 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, or quaternary ammonium. Selected from the group consisting of (Each a and each c are independently integers between 0 and 4.) Repeating unit (R PEDEK ); - Formula (II): [ka] (In the formula, Each R1 and each a are as defined above. Each R2 is independently selected from the group consisting of halogens, alkyls, alkenyls, alkynyls, aryls, ethers, thioethers, carboxylic acids, esters, amides, imides, alkali or alkaline earth metal sulfonates, alkyl sulfonates, alkali or alkaline earth metal phosphonates, alkyl phosphonates, amines, and quaternary ammonium compounds. and Each b is independently either 0 or an integer between 1 and 4. Repeating unit (R PEoEK ) This relates to polymers [polymers (P)] that include [polymers (P)].

[0015] In a second aspect, the present invention relates to a method for synthesizing the polymer (P), (a) In the presence of a base [base (B)] and in a polar organic solvent [solvent (S)], formula (III) [ka] (In the formula, each R1 and each a are as defined above.) At least one compound of formulas (IV) and (V): [ka] (In the formula, each R2, each R3, each b, and each c are as defined above.) A reaction mixture is obtained by contacting a mixture of compounds such that the ratio of (IV) to (V) is 85 / 15 to 60 / 40; (b) optionally, terminate the reaction in step (a) by contacting the reaction mixture with an appropriate reagent to obtain a product mixture; and (c) Recovering the polymer (P) from the reaction mixture or the product mixture. Regarding methods including

[0016] In a third aspect, the present invention relates to a composition [composition (C)] comprising the polymer (P) described above and at least one additional component [composition (in)].

[0017] In a further embodiment, the present invention relates to a molded article comprising a polymer (P) and / or composition (C) according to the present invention.

[0018] More preferably, the molded articles are for use in petroleum and gas recovery, the automotive, aerospace, electronics, semiconductor industries, industrial or consumer applications.

[0019] In a further embodiment, the present invention relates to a method for manufacturing components included in devices used in oil and gas recovery, automotive, aerospace, electronics, semiconductor industries, industrial or consumer applications, comprising molding and / or extruding and / or coating these components from the polymer (P) and / or the composition (C). [Modes for carrying out the invention]

[0020] According to a preferred embodiment, the polymer (P) defined above is a repeating unit (R) of the formula (I) defined above. PEDEK ) and the repeating unit (R) of formula (II) defined above. PEoEK ) only.

[0021] Preferably, the polymer (P) consists of repeating units (R) of the formula (I) defined above, from 61 mol%, more preferably 62 mol%, and even more preferably 63 mol%, based on 100 mol% of the polymer (P). PEDEK ) includes.

[0022] According to a preferred embodiment, the polymer (P) comprises repeating units (R) of formula (I) from 64 mol% based on 100 mol% of the polymer (P). PEDEK ) includes.

[0023] A preferred embodiment is in which the polymer (P) comprises repeating units (R) of formula (I) from 65 mol%, more preferably 69 mol%, based on 100 mol% of the polymer (P). PEDEK ) includes.

[0024] At least 70 mol%, more preferably at least 75 mol%, of (R) of formula (I) as defined above. PEDEK Favorable results were obtained with polymers (P) containing ).

[0025] Preferably, the polymer (P) contains, based on 100 mol% of the polymer (P), at most 85 mol%, more preferably at most 84 mol%, even more preferably at most 82 mol% of the repeating unit (R PEDEK ) of the above-defined formula (I).

[0026] According to a preferred embodiment, the polymer (P) contains, based on 100 mol% of the polymer (P), at most 81 mol% of the repeating unit (R PEDEK ) of the formula (I).

[0027] Advantageous results were obtained with a polymer (P) containing, based on 100 mol% of the polymer (P), at most 80 mol% of (R PEDEK ) of the above-defined formula (I).

[0028] Preferably, in the repeating unit (R PEDEK ) of the formula (I), a and c are 0.

[0029] Preferably, the polymer (P) contains, based on 100 mol% of the polymer (P), 15 to 40 mol% of the repeating unit (R PEoEK ) of the above-defined formula (II).

[0030] Preferably, the polymer (P) contains, based on 100 mol% of the polymer (P), at most 39 mol%, more preferably at most 38 mol%, even more preferably at most 37 mol% of the repeating unit (R PEoEK ) of the formula (II).

[0031] According to a preferred embodiment, the polymer (P) contains, based on 100 mol% of the polymer (P), at most 36 mol% of the repeating unit (R PEoEK ) of the formula (II).

[0032] A preferred embodiment is that the polymer (P) contains at most 35 mol%, more preferably at most 31 mol% of the repeating unit (RPEoEK ) includes.

[0033] A maximum of 30 mol%, and more preferably a maximum of 25 mol%, of the (R) of formula (II) as defined above. PEoEK Favorable results were obtained with polymers (P) containing ).

[0034] Preferably, the polymer (P) contains repeating units (R) of formula (II) as defined above, ranging from 15 mol%, more preferably 16 mol%, and even more preferably 18 mol%, based on 100 mol% of the polymer (P). PEoEK ) includes.

[0035] According to a preferred embodiment, the polymer (P) comprises repeating units (R) of formula (II) from 19 mol% based on 100 mol% of the polymer (P). PEoEK ) includes.

[0036] From 20 mol%, the repeating unit (R) of formula (II) defined above. PEoEK Favorable results were obtained with polymers (P) containing ).

[0037] Preferably, the repeating unit of formula (II) (R PEoEK In ), a and b are both 0.

[0038] According to another embodiment, the polymer (P) of the present invention comprises the repeating unit (R PEDEK ) and the repeating unit (R PEoEK ) and different repeating units (R PAEK ) may further include.

[0039] In this embodiment, the repeating unit (R PAEK The amount of ) is preferably 0.1 mol% to 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 polymer (P).

[0040] Preferably, the repeating unit (R PAEK ) is expressed by the following formula: [ka] [ka] (In each of the above equations (KA) to (KM), Each R' is either the same as or different from one another, and in each presence, C1-C optionally contains one or more heteroatoms. 12 A group independently selected from sulfonic acid and sulfonate groups, phosphonic acid and phosphonate groups, amines and quaternary ammonium groups; and Each j' is either the same as or different from the others, and in each existence, is independently selected from integers 0 and 1 through 4, preferably j' is zero. Follow one of the following rules.

[0041] Repeating unit (R PAEK Embodiments of the polymer (P) including ) are included in the present invention, however polymer (P) is defined as the repeating unit (R) as defined above. PEDEK ) and repeating units (R PEoEK It is preferable to be essentially derived from ).

[0042] In this specification and in the following claims, "repeating unit (R)" PEDEK ) and repeating units (R PEoEK The expression "essentially derived from the repeating unit (R) defined above" means PEDEK ) and repeating units (R PEoEK It is intended to indicate that any additional repeating units different from those may be present in the polymer (P) in an amount of up to 1 mol%, more preferably up to 0.5 mol%, relative to 100 mol% of the polymer (P).

[0043] Defects, end groups, and monomer impurities can be incorporated into the polymer (P) of the present invention in extremely small amounts, advantageously without adversely affecting its performance.

[0044] Preferably, the repeating unit (R PEDEK ) and the repeating unit (R PEoEK ) contains a molar ratio (R) of 60 / 40 to 85 / 15, more preferably 65 / 35 to 80 / 20 in the polymer (P). PEDEK ) / (R PEoEK ) exists.

[0045] Advantageously, the polymer (P) according to the present invention is (i) Glass transition temperature (Tg) above 153°C [measured at the midpoint by DSC during the second heating scan up to 450°C, heating and cooling rates of 20°C / min, in accordance with ASTM D3418-03]; and (ii) The ratio of the storage modulus measured at 165°C to the storage modulus measured at 140°C, which exceeds 15% [measured by dynamic mechanical analysis in torsional mode with a TA ARES G2 rheometer, 10 radians / sec, 0.05% strain, heating from 30°C to 330°C at 5.0°C / min, in accordance with ADTM D5279-13]. It is characterized by:

[0046] Furthermore, polymer (P) is advantageous, (iii) Heat of fusion (ΔH) exceeding 40 J / g [determined as the area under endothermic fusion in the second heating scan in differential scanning calorimetry (DSC), measured in accordance with ASTM D3418-03, up to 450°C with heating and cooling rates of 20°C / min]; and (iv) 0.20~9.00 kN / m 2 Preferably 0.30 to 5.00 kN / m 2 More preferably 0.40 to 4.50 kN / m 2 Melt viscosity in the range [according to ASTM D3835 at 410°C and 46s] -1 [Measured at] It is characterized by:

[0047] The polymer (P) characterized by the above-described properties exhibits better processability, particularly in molding or extrusion, compared to polymers already known in the art.

[0048] Preferably, in formula (III), a is 0, and the compound is 4,4'-difluorobenzophenone (DFBP).

[0049] Preferably, in formula (IV), c is 0, and the compound is 4,4'-dihydroxybiphenyl, also known as 4,4'-biphenol.

[0050] Preferably, in formula (V), b is 0, and the compound is pyrocatechol (also known as catechol).

[0051] Preferably, step (a) is carried out at a temperature of at least 130°C, preferably at least 140°C, and more preferably at least 150°C for about 0.5 to 15 hours.

[0052] Compounds (III), (IV), and (V) may also be heated to a first temperature of at least 130°C, preferably at least 140°C, and more preferably at least 150°C, before being brought into contact with base (B).

[0053] Preferably, the base (B) is selected from the group consisting of potassium carbonate (K2CO3), potassium bicarbonate, sodium carbonate (Na2CO3), cesium carbonate (Cs2CO3), potassium phosphate, and sodium bicarbonate.

[0054] Most preferably, the base (B) is selected from the group consisting of potassium carbonate (K2CO3), sodium carbonate (Na2CO3), or a mixture of both; more preferably, the base (B) is a mixture of both.

[0055] While not bound by any particular theory, the base functions to deprotonate components (IV) and (V) during the condensation reaction.

[0056] Step (a) is carried out in a solvent (S) containing diphenylsulfone. In some embodiments, the solvent (S) contains at least 50% by weight of diphenylsulfone based on the total weight of the solvent in the reaction mixture, for example, at least 60% by weight, at least 70% by weight, at least 80% by weight, at least 90% by weight, at least 95% by weight, or at least 98% by weight based on the total weight of the solvent (S) in the reaction mixture.

[0057] In some embodiments, the solvent (S) essentially comprises diphenyl sulfone.

[0058] In the method of the present invention, a solvent (S) containing a limited amount of impurities, as detailed in U.S. Patent No. 9,133,111, is typically used.

[0059] The solvent (S) of the present invention may include benzophenone and / or dibenzothiophene dioxide.

[0060] Optionally, a step (a2) is performed to raise the temperature after step (a) and before step (b) or step (c).

[0061] Preferably, step (a2) includes heating the reaction mixture obtained in step (a) to a temperature of at least 300°C, preferably at least 310°C, at an average heating rate of less than 5°C / min, preferably less than 3°C / min and / or greater than 0.1°C / min.

[0062] Preferably, step (a2) is carried out for 20 seconds to 3 hours, depending on the properties of the starting monomer and the selected reaction conditions.

[0063] Preferably, step (b) is performed after step (a) or after step (a2) and before step (c).

[0064] According to this embodiment, step (b) is carried out in a polar organic solvent as defined above in step (a).

[0065] The solvent (S) used in step (b) may be the same solvent as the one used in step (a), or it may be a different solvent (S) than the one used in step (a). Advantageously, steps (a) and (b) are carried out using the same solvent (S) as defined above.

[0066] Preferably, step (b) is performed to stop the polycondensation reaction in step (a). For this purpose, suitable reagents are selected from reagents that can stop chain growth by being incorporated into the polymer backbone via a condensation reaction (also called end-capping agents) and reagents that can stop chain growth without being incorporated into the polymer backbone via a condensation reaction (also called inhibitors).

[0067] The end capping agent is preferably of the following formula (F): [ka] (In the formula, R 6 is F, Cl, or OH, R 7 is -C(O)-Ar-R 10 , -O-Ar-R 10 , -SO2-Ar-R 10 -Ar-R 10 , alkyl (for example, C1~C 10 Alkyl (C1-C5 alkyl) or -H, where Ar is an arylene group containing at least one benzene ring (i.e., one benzene ring or several benzene rings), and R 10 (It is F, Cl, or H) Follow the rules.

[0068] Preferably, R 6 is F or OH. More preferably, R 6 It is F.

[0069] Preferably, R 7 is -C(O)-Ar-R 10 Ar-R 10Or H, where R 10 is F, Cl, or H.

[0070] According to a particular preferred embodiment, R 10 It is F.

[0071] R 7 If it is different from -H, R 6 and R 7 These can be 1,2- ortho substitutions on the phenylene ring of formula (F), or they can be 1,3- or meta substitutions on the phenylene ring.

[0072] Instead, R 6 and R 7 This is preferably a 1,4-, i.e., para-substitution on the phenylene ring of formula (F).

[0073] In some embodiments, the end capping agent is selected from the group consisting of 4,4'-difluorobenzophenone, phenol, 4-phenoxyphenol, 4-phenylphenol, 4-fluorobenzophenone, 3-fluorobenzophenone, 2-fluorobenzophenone, 4,4'-dichlorodiphenylsulfone, 4,4'-difluorodiphenylsulfone, and mixtures thereof.

[0074] 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 monomers. The end-capping agents used in the method of the present invention are preferably 4,4'-difluorobenzophenone, phenol, 4-phenoxyphenol, 4-phenylphenol, or mixtures thereof.

[0075] An example of a suitable compound as a inhibitor is lithium chloride.

[0076] Preferably, step (b) is carried out using at least one end-capping agent and at least one termination agent. More preferably, 4,4'-difluorobenzophenone and lithium chloride are used in step (b).

[0077] Typically, the (poly)condensation reaction is carried out using a slightly excess amount of the difluoro compound of formula (III).

[0078] If used, it is further understood that the end-capping agent may be added to the reaction mixture at the start of the polycondensation. Thus, overall, considering that the excess monomer (III) may be used as the end-capping agent as described above, the molar ratio [(III)+(F)] / [(IV)+(V)] is ≥1.000, preferably ≥1.003, more preferably ≥1.006, and even more preferably ≥1.010.

[0079] Preferably, step (b) is the following step: (b1) Adding the first end capping agent to the reaction mixture; (b2) The step of adding a first inhibitor to the reaction mixture; and (b3) A step of optionally adding a second end-capping agent and / or a second termination agent to the reaction mixture, wherein the second end-capping agent and the second termination agent are preferably the same as the first end-capping agent and the first termination agent, respectively. Includes.

[0080] More preferably, the first end capping agent in step (b1) is 4,4'-difluorobenzophenone (DFBP).

[0081] More preferably, the inhibitor in step (b2) is lithium chloride (LiCl).

[0082] More preferably, the second end-capping agent in step (b3) is 4,4'-difluorobenzophenone (DFBP), and the second termination agent is lithium chloride (LiCl).

[0083] Preferably, the concentrations of monomers and end-capping agents (if used) in the diphenyl sulfone [(III)+(IV)+(V)+(F)] are at least 15% by weight, preferably at least 20% by weight, and more preferably at least 23% by weight.

[0084] Preferably, the concentrations of monomers and end-capping agents (if used) in the diphenyl sulfone [(III)+(IV)+(V)+(F)] are at most 45% by weight, preferably at most 43% by weight, and more preferably at most 40% by weight.

[0085] In step (a), the polymer (P) is finally obtained in solid form at the end of the reaction in steps (a2) and (b).

[0086] Preferably, step (c) is carried out to recover the polymer (P) by removing the solvent (S) and other organic compounds, such as sodium fluoride or potassium fluoride, or excess base (B), by methods known in the art, such as washing, dissolving, or filtering.

[0087] Before step (c) and optionally after step (c), an additional step [step (d)] may be performed on the polymer (P) recovered as a solid phase, which may preferably include at least one of grinding, pulverization, and tritulation, in order to obtain the polymer (P) in the form of small particles.

[0088] Preferably, the composition (C) contains at least 10% by weight, at least 20% by weight, and at least 30% by weight of polymer (P) based on the total weight of composition (C).

[0089] Preferably, composition (C) contains at least 50% by weight, more preferably at least 60% by weight, at least 70% by weight, at least 80% by weight, at least 90% by weight, even more preferably at least 95% by weight, and even more preferably at least 99% by weight of polymer (P), based on the total weight of composition (C).

[0090] Preferably, at least one component (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, such as UV stabilizers; (v) heat stabilizers; (vi) antioxidants such as organic phosphites and phosphonic acid esters; (vii) acid scavengers; (viii) processing aids; (ix) nucleating agents; (x) internal lubricants and / or external lubricants; (xi) flame retardants; (xii) smoke suppressants; (xiii) antistatic agents; (xiv) antiblocking agents; (xv) conductive additives such as carbon black and carbon nanofibrils; (xvi) plasticizers; (xvii) flow regulators; (xviii) bulking agents; and (xix) metal deactivators.

[0091] Preferably, composition (C) contains at least one component (in) in less than 20%, preferably less than 10%, more preferably less than 5%, and even more preferably less than 2%.

[0092] Preferred reinforcing fillers are selected from fibrous and particulate fillers different from the pigments described below.

[0093] More preferably, the reinforcing filler is selected from mineral fillers (such as talc, mica, kaolin, calcium carbonate, calcium silicate, magnesium carbonate, and boron nitride), glass fibers, carbon fibers, synthetic polymer fibers, aramid fibers, aluminum fibers, titanium fibers, magnesium fibers, boron carbide fibers, boron nitride fibers, rock wool fibers, steel fibers, wollastonite, and the like.

[0094] Nanoscale reinforcing fillers can also be used, such as single-walled and multi-walled carbon nanotubes, carbon nanofibers, graphene, graphene oxide, and nanoclays such as montmorillonite.

[0095] More preferably, the reinforcing filler is selected from mica, kaolin, calcium silicate, magnesium carbonate, glass fiber, carbon fiber, and wollastonite.

[0096] More preferably, the filler is selected from fibrous fillers. A specific classification of fibrous fillers consists of whiskers, i.e., single-crystal fibers manufactured from various raw materials such as Al2O3, SiC, BC, Fe, and Ni.

[0097] In a preferred embodiment of the present invention, the reinforcing filler is selected from wollastonite and glass fiber.

[0098] Among fibrous fillers, glass fibers are preferred; these include Additives for Plastics Handbook, 2 nd This includes chopped strands A-, E-, C-, D-, S-, T-, and R-glass fibers, as described in Chapter 5.2.3, pages 43-48 of John Murphy's edition.

[0099] The glass fibers may have a circular cross-section or a non-circular cross-section (such as an elliptical or rectangular cross-section).

[0100] When the glass fibers used have a circular cross-section, they preferably have an average glass fiber diameter of 3 to 30 μm, and particularly preferably 5 to 12 μm. Different types of glass fibers with a circular cross-section are available on the market depending on the type of glass from which they are manufactured. In particular, glass fibers made from E-glass or S-glass can be mentioned.

[0101] In some embodiments, the glass fibers are standard E-glass material having a non-circular cross-section. In some embodiments, the polymer composition includes S-glass fibers having a round cross-section.

[0102] In some embodiments, composition (C) comprises at least one carbon fiber.

[0103] As used herein, the term “carbon fiber” is intended to include graphitized, partially graphitized, and non-graphitized carbon-reinforced fibers or mixtures thereof. The term “graphite fiber” is intended to refer to carbon fibers obtained by high-temperature thermal decomposition (above 2000°C) of carbon fibers, in which carbon atoms are arranged in a manner similar to that of graphite structures.

[0104] The carbon fibers are preferably selected from the group consisting of PAN-based carbon fibers, pitch-based carbon fibers, graphite fibers, and mixtures thereof.

[0105] The fibers may be in the form of whiskers, short fibers, continuous fibers, sheets, plies, or combinations thereof. Furthermore, continuous fibers may employ any of the following configurations: unidirectional, multidimensional, nonwoven, woven, knitted, stitched, wound, and braided, as well as swirl mats, felt mats, and chopped mats. The fiber toes can be held in place in such configurations by sizing, cross-toe stitches, weft-inserted knitting stitches, or small amounts of resin. As used herein, "continuous fibers" are fibers having a length greater than 10 mm.

[0106] If present, composition (C) contains reinforcing fillers in preferably less than 80% by weight, more preferably less than 75% by weight, and even more preferably less than 70% by weight, based on the total weight of composition (C).

[0107] If present, composition (C) contains at least 10% by weight, preferably at least 20% by weight, preferably at least 25% by weight, and most preferably at least 30% by weight of reinforcing filler, based on the total weight of composition (C).

[0108] Preferably, the composition (C) comprises at least one nucleating agent selected from talc or boron nitride.

[0109] Preferably, the polymer (P) is the sole polymer component in the polymer composition. As used herein, the term “polymer component” means a compound having repeating units and a molecular weight of at least 2,000 g / mol.

[0110] According to another embodiment, composition (C) contains polymer components other than polymer (P) in amounts of less than 3% by weight, less than 2% by weight, less than 1% by weight, and less than 0.5% by weight.

[0111] The polymer component other than polymer (P) is preferably at least one poly(aryl ether sulfone) (PAES) selected from the group consisting of polysulfone (PSU), polyphenylsulfone (PPSU), and poly(ethersulfone) (PES).

[0112] Composition (C) can be prepared by various methods, including, for example, dry blending, suspension or slurry mixing, solution mixing, melt mixing, a combination of dry blending and melt mixing, or fiber impregnation, which involve homogeneously mixing the components of composition (C). As used herein, “components of polymer composition” includes the polymer (P) detailed above and at least one component (in) as defined above.

[0113] Typically, the dry blending of components of a polymer composition is carried out by using a high-strength mixer such as a Henschel mixer, paddle mixer, or ribbon mixer to obtain the polymer composition as a physical mixture.

[0114] Alternatively, homogeneous mixing of the components of the polymer composition is performed by tumble blending based on a uniaxial or multiaxial rotating mechanism to obtain a physical mixture.

[0115] Alternatively, the slurry mixing of the components of the polymer composition is performed, for example, by slurring the components of the polymer composition in a suitable liquid such as methanol using a stirrer, and then filtering off the liquid to obtain a powder mixture of the components of the polymer composition.

[0116] In some embodiments, the method for producing a polymer composition involves melt-kneading a physical mixture. Conventional melt-kneading equipment such as co-rotating and counter-rotating extruders, single-screw extruders, conneeders, disc pack processors, and various other types of extruders can be used. Preferably, an extruder, more preferably a twin-screw extruder, can be used.

[0117] In some embodiments, the physical mixture is kneaded in an extruder and then cut into pellets or granules. The granules or pellets can then be further processed to produce further molded articles.

[0118] As described above, the molded articles according to the present invention can be advantageously manufactured using the polymer (P) alone or the composition (C) described above.

[0119] According to the first embodiment, the polymer (P) is processed into a molded article on its own without the need to add fillers or additional components.

[0120] According to the second embodiment, the composition (C) is processed into a molded article.

[0121] The molded article may comprise one or more parts. If the molded article is a single part, the single part preferably consists of composition (C).

[0122] Alternatively, a molded article may consist of two or more parts, one or more of which preferably consist of a polymer (P) or composition (C). If two or more parts of a molded article contain a polymer (P) or composition (C), each part may contain the same polymer (P) or composition (C), or different polymers (P) or compositions (C).

[0123] The weight of the polymer (P) or composition (C) relative to the total weight of the molded article is preferably more than 1%, more than 5%, more than 10%, preferably more than 15%, more than 20%, more than 30%, more than 40%, more than 50%, more than 60%, more than 70%, more than 80%, more than 90%, more than 95%, and more than 99%.

[0124] The polymer (P) or composition (C) is useful for manufacturing articles that are useful for a variety of applications.

[0125] For example, due to the remarkable advantageous properties of the polymer (P) described herein, the polymer (P) or composition (C) is used in automotive applications such as magnet wire coatings, seal rings, bushings, bearings, and thrust washers in hybrid and electric vehicles; oil and gas applications such as downhole cable coatings; electrical and electronic applications such as test sockets for surface mount (SMT) type components of integrated circuit chips on circuit boards, components of lithium-ion batteries including barriers between individual cells for short-circuit prevention, and films used in microspeaker membrane components; and aerospace applications such as electrical / electronic connectors for high-temperature environments (e.g., near engines), thermoplastic composite matrices for composite prepregs and laminates, and injection-molded secondary structural components. Applications; particularly suitable for use in semiconductor manufacturing, such as chemical mechanical planarization (CMP) rings, holders, carriers, cassettes, and trays used in various stages of semiconductor and integrated circuit chip manufacturing and assembly; industrial applications such as compressor valve components including sheets and seal elements, oil and gas backup rings and seal rings, and other sealing components for use in downhole applications, pump impellers and pump impellers and other fluid supply components used in chemical processing, coatings for steel or other metal components for corrosion protection, and insulation of wires and cables for electrical insulation and / or wear protection; and consumer applications such as housings or housing components for electronic nicotine delivery systems (ENDS), also known as e-cigarettes or vape pens.

[0126] In particular, composition (C) is well-suited for use as a continuous fiber-reinforced composite material.

[0127] The molded articles described herein may be manufactured from a polymer (P) or composition (C) by injection molding, extrusion molding, compression molding, additive manufacturing (also known as three-dimensional (3D) printing, and the molded articles may also be called 3D objects or 3D parts), continuous fiber impregnation and continuous fiber composite lamination / consolidation or other molding techniques.

[0128] In some embodiments, a method for manufacturing a molded article or a component thereof includes a step of compression molding or injection molding and a subsequent step of solidifying the polymer (P) or composition (C).

[0129] In some embodiments, the method for manufacturing a molded article or a molded article or a part thereof includes a coating step. For example, a polymer (P) or composition (C) can be applied as a coating to a metal surface by any suitable coating method, preferably by electrostatic powder, aqueous suspension coating, or extrusion coating around a wire, to form a coated wire, preferably a coated magnet wire.

[0130] According to the present invention, a molded article may include a polymer-metal joint. The polymer-metal joint includes the aforementioned polymer (P) or a composition (C) containing the same in contact with a metal substrate.

[0131] The metal substrate may include, but is not limited to, any metal composition containing aluminum, copper, gold, iron, nickel, platinum, silver, steel, and blends or alloys thereof (e.g., brass and bronze). The metal substrate is preferably copper, steel, aluminum, or a combination thereof.

[0132] 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 undergone 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.

[0133] In some embodiments, the metal substrate is a nanostructured metal surface. “Nanostructured metal surface” means a metal surface etched to have a nanopitted surface having surface peaks and valleys with average depth, height, and width dimensions in the nanoscale state, in the range of 10 to 1000 nm, preferably 30 to 800 nm, and more preferably 50 to 500 nm. In some embodiments, the metal substrate includes an NMT-treated metal surface. “NMT-treated metal surface” means a nanostructured surface prepared by any etching / priming process described in European Patent No. 1459882B1, European Patent Application Publication No. 1559542A1, or International Publication Brochure 2011123790A1, the disclosures of which are incorporated herein by reference in their entirety.

[0134] In some embodiments, the metal substrate is a wire or cable. In other embodiments, the metal substrate is part of a mobile electronic device.

[0135] In some embodiments, the polymer-metal joint comprises a layer of polymer composition having a thickness ranging from 0.025 mm to 3 mm.

[0136] Polymer-metal joints can be manufactured by contacting a polymer (P) or composition (C) described herein with a metal substrate, preferably a structured metal surface, more preferably a nanostructured metal surface, and most preferably an NMT-treated metal surface. For example, the polymer (P) or composition (C) can be deposited or overmolded onto a metal substrate using any suitable melting and deposition method.

[0137] In particular, polymer-metal joints can be manufactured by injection molding, compression molding, or coating a polymer (P) or composition (C) onto a metal substrate. Polymer-metal joints can also be formed by electrostatic or solvent-based powder coating processes. In some embodiments, polymer-metal joints can be formed by an extrusion process for coating wires or cables. In another embodiment, polymer-metal joints are manufactured by an additive manufacturing process.

[0138] The polymer-metal joints of the present invention may be suitable for the manufacture of articles useful for a variety of applications. For example, due to the properties of polymer(P) described herein, the polymer compositions are particularly suitable for use in automotive applications such as magnet wire coatings for hybrid and electric vehicles, oil and gas applications such as downhole cable coatings, structural components of mobile electronic devices such as metal parts (e.g., frames or housings), and electrostatic powder coating on metal substrates for corrosion protection and wear resistance.

[0139] An additional exemplary embodiment relates to a method for producing a polymer (P) composite material, comprising impregnating the reinforcing fibers described herein with the polymer matrix described herein.

[0140] For example, various methods can be used to impregnate fibers with a polymer matrix in order to form a ply in the form of a sheet or tape of fibers at least partially impregnated with a polymer matrix, the matrix being either in a molten or granular form, such as powder coating, film lamination, extrusion, pultrusion, aqueous slurry, and melt impregnation. In this specification, “tape” means a strip of material having longitudinally extending reinforcing fibers aligned along a single axis of the strip material.

[0141] By arranging matrix-impregnated fiber plies adjacent to one another, unconsolidated composite material laminates such as prepregs can be formed. In the fiber-reinforced layer of the laminate, each fiber reinforcement can be positioned in a selected direction relative to one another.

[0142] The plies can be laminated manually or automatically, for example by automated tape layup using "pick and place" robotics, or by advanced fiber placement, in which a tow of pre-impregnated fibers is heated and compressed in a mold or mandrel, to form composite material laminates with desired physical dimensions and fiber orientation.

[0143] Unconsolidated laminate layers are typically not completely fused together, and unconsolidated composite laminates may exhibit large porosity, such as over 20 volume%, as measured by, for example, X-ray microscopy tomography. For example, heat and / or pressure may be applied, or ultrasonic vibration welding may be used to stabilize the laminates and prevent the layers from moving relative to each other, in order to form a "blank" of the composite material as an intermediate step that allows for handling of the composite laminate before consolidation.

[0144] The composite laminate thus formed is then typically consolidated, for example by exposing the composite laminate to heat and pressure in a mold, to form a molded fiber-reinforced thermoplastic matrix composite article. As used herein, “consolidation” is the process by which the matrix material is softened, the layers of the composite laminate are pressed together, air, moisture, solvents and other volatile substances are pushed out of the laminate, and adjacent plies of the composite laminate fuse together to form a rigid, cohesive article. Ideally, the consolidated composite article exhibits a minimum porosity, for example, less than 5 volume%, more typically less than 2 volume%, as measured by X-ray microscopy tomography.

[0145] The composite material preferably comprises 20-80% by weight of reinforcing fibers and 80-20% by weight of a polymer matrix, based on the weight of the composite material.

[0146] Herein, an exemplary embodiment is described in the following non-limiting examples.

[0147] If any disclosure of a patent, patent application, or publication incorporated herein by reference conflicts with the description of this application to such an extent that it could obscure the terminology, the description herein shall prevail. [Examples]

[0148] raw materials: KETASPIRE® KT-820P, an aromatic polyether ether ketone (PEEK) polymer available from Solvay Specialty Polymers USA, LLC. - Comparative Polymer C Aromatic polyether ketone polymer (PEKK) obtained from Cypek® HT and Solvay SA - Comparative Polymer D Aromatic polyether ketone (PEK) - Comparative polymer A, available from Arlon® 2000, Greene, Tweede & Company, USA. PEKEKK ST-45P, an aromatic polyetherketone etherketone ketone available from Victrex - Comparative Polymer B 4,4'-biphenol, polymer grade, was sourced from SI, USA. Pyrocatechol, in flake form, was sourced from Solvay, USA. Its purity was 99.85% by GC. It contained 680 ppm of moisture, which was used to adjust the additive weight. All weights shown include moisture. 4,4'-Difluorobenzophenone, polymer grade (99.8%+), was sourced from Malwa, India. Diphenyl sulfone (polymer grade) (99.8% purity) was sourced from Proviron. The light soda ash, sodium carbonate, was sourced from Solvay SA, France. d 90 Potassium carbonate particles <45μm were sourced from Armand Products. The lithium chloride (anhydrous grade) was sourced from Acros. Hydroquinone, photo grade, was sourced from Eastman, USA. It contains 0.38% by weight of water, which was used to adjust the added weight. All weights shown include water.

[0149] method Determination of melting temperature (Tm) and heat of fusion The melting temperature (Tm) was determined as the peak temperature of the endothermic melting during the second heating scan using a differential scanning calorimeter (DSC) according to ASTM D3418-03, E1356-03, E793-06, and E794-06. Details of the procedure used in this invention are as follows: A TA Instruments DSC Q20 was used with nitrogen (99.998% purity, 50 mL / min) as the carrier gas. Temperature and heat flow calibration was performed using indium. Sample size was 5–7 mg. Weight was recorded to ±0.01 mg. The thermal cycle was as follows: First heating cycle: 20.00°C / min to 30.00°C to 450.00°C, then isothermal at 450.00°C for 1 minute; First cooling cycle: 400.00°C to 30.00°C at 20.00°C / min, isothermal for 1 minute; Second heating cycle: Heat at 20.00°C / min from 30.00°C to 450.00°C, then isothermally at 450.00°C for 1 minute.

[0150] The melting temperature (Tm) was determined as the peak temperature of the endothermic melting during the second heating scan. The enthalpy of melting was measured during the second heating scan. Melting of the composition was obtained as the area over a linear baseline drawn from 220°C to a temperature exceeding the final endothermic melt.

[0151] The glass transition temperature (Tg) (midpoint) was determined by a second heating scan according to ASTM D3418-03, E1356-03, E793-06, and E794-06.

[0152] Determination of melt viscosity and melt stability (VR40) Melt viscosity was measured using a capillary rheometer according to ASTM D3835. The following characteristics were observed: a die with a diameter of 1.016 mm, a length of 20.32 mm, and a cone angle of 120° was used, and readings were taken after residence times of 10 minutes and 40 minutes at 410°C and a shear rate of 46.3 s⁻¹. Melt stability VR40 was measured as the ratio of viscosity at 40 minutes to viscosity at 10 minutes. The melt viscosity values ​​shown in the table below were recorded for a 10-minute residence time.

[0153] Determination of tensile properties Plaques measuring 102 mm x 102 mm x 3.2 mm were manufactured from polymer by compression molding under conditions matched to the melting temperature of the composition.

[0154] The molding conditions for Examples 0-2 were as follows: Preheat to 420℃. 420℃ / 15 min, 2000kgf 420℃ / 2 min, 2700kgf Cooling to 320°C over 20 minutes, 2000 kgf Hold at 320°C for 50 minutes, 2000 kgf Cool to 30°C for 25 minutes, 2000 kgf.

[0155] Unless otherwise stated in the table below, the plaques were annealed in air at 275°C for 3 hours. The molding and annealing conditions were determined by the melting temperature of the material and the need to achieve the maximum level of crystallinity.

[0156] The temperatures for steps 2, 3, and 5 were changed as follows:

[0157] [Table 1]

[0158] The crystallization level of the plaque was determined by DSC (one heating cycle, 20°C / min, up to 450°C), assuming 130 J / g for 100% crystalline material.

[0159] Compression-molded plaques were machined into V-type ASTM tensile test specimens, and three of these specimens representing various polymer compositions were subjected to tensile testing according to ASTM method D638 at room temperature (i.e., 23°C) at 0.05 inches / min. The average of the three specimens is shown.

[0160] Rectangular test specimens (1.2 cm × 5.1 cm × 0.32 cm) were also prepared from these molded plaques and dried under vacuum at 120°C for 12 hours. The test specimens were then analyzed by dynamic mechanical analysis (DMA) according to ASTM D 5279-13 using a TA ARES G2 rheometer under a torsional mode (10 radians / sec, 0.05% strain) from 30°C to 330°C at 5.0°C / min to measure the storage modulus (G', Pa) at different temperatures in the range of approximately 50°C to 310°C.

[0161] The data shown in the table below indicates that PEDEK-PEoEK with a PEDEK / PEoEK ratio of 60 / 40 to 85 / 15 exhibits higher temperature capabilities than PEEK or PEDEK-PEoEK with a PEDEK / PEoEK unit ratio of less than 60 / 40.

[0162] Method for evaluating the chemical resistance of compression-molded samples Compression-molded plaques of all polymer compositions measuring 102 mm × 102 mm × 3.2 mm (prepared according to the methods detailed above and the compositions shown in Table 2) were machined into Type V ASTM tensile test specimens. Three of these specimens were subjected to tensile testing at room temperature (i.e., 23°C) at 0.05 inches / min according to ASTM method D638.

[0163] Three V-shaped tensile test rods 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% KCl aqueous solution) at 300°C under nitrogen for 7 days.

[0164] At the end of the exposure test, the rod was wiped clean and its weight before and after exposure was compared. Table 3 summarizes the weight gain, appearance, and mechanical properties of the rod measured before and after exposure.

[0165] The strength retention rate was calculated as follows:

number

[0166] Comparative Example 1: Preparation of PEDEK-PEEK copolymer 60 / 40 127.70 g of diphenylsulfone, 9.894 g of hydroquinone, 25.103 g of 4,4'-biphenol, and 50.130 g of 4,4'-difluorobenzophenone were introduced into a 500 mL four-necked reaction flask equipped with a stirrer, an N2 injection tube, a Claisen adapter with a thermocouple inserted into the reaction medium, and a Dean-Stark trap with a condenser and dry eye strap. The flask contents were evacuated under vacuum and then filled with high-purity nitrogen (containing less than 10 ppm of O2). The reaction mixture was then subjected to a constant nitrogen purge (60 mL / min).

[0167] The reaction mixture was slowly heated to 150°C. At 150°C, a mixture of 25.097 g of Na2CO3 and 0.155 g of K2CO3 was added to the reaction mixture from a powder dispenser over 30 minutes. At the end of the addition, the reaction mixture was heated to 320°C at a rate of 1°C / min. After 2 minutes at 320°C, 5.892 g of 4,4'-difluorobenzophenone was added to the reaction mixture while maintaining a nitrogen purge in the reactor. After 5 minutes, 0.384 g of lithium chloride was added to the reaction mixture. After 10 minutes, another 1.964 g of 4,4'-difluorobenzophenone was added to the reactor, and the temperature of the reaction mixture was maintained for 15 minutes.

[0168] Next, the contents of the reactor were poured from the reactor into an SS receiving dish and cooled. The solid material was crushed and ground through a 2 mm screen using an attrition mill. Diphenyl sulfone and salts were extracted from a mixture of acetone and water at pH 1-12. The powder was then removed from the reactor and dried under vacuum at 120°C for 12 hours to obtain 74 g of white powder. The repeating units of the polymer are, [ka] That was the case.

[0169] 410℃, 46s -1 The melt viscosity, measured by capillary rheology, was 0.18 kN-s / m 2 That was the case.

[0170] This embodiment corresponds to Example 1 in International Publication No. 2018 / 086873.

[0171] Comparative Example 2: Preparation of PEDEK-PEEK copolymer 75 / 25 The same procedure as described in Comparative Example 1 above was followed, but the following reagents and reaction conditions were used.

[0172] 212.00 g of diphenylsulfone, 4.226 g of hydroquinone, 21.442 g of 4,4'-biphenol, and 33.853 g of 4,4'-difluorobenzophenone.

[0173] A mixture of 16.812 g of Na2CO3 and 0.106 g of K2CO3 was added at 150°C.

[0174] At the end of the addition, the reaction mixture was heated to 340°C at a rate of 1°C / min. After 7 minutes at 340°C, 3.928 g of 4,4'-difluorobenzophenone was added to the reaction mixture while maintaining a nitrogen purge in the reactor.

[0175] After 5 minutes, 0.651 g of lithium chloride was added to the reaction mixture. After 10 minutes, another 1.309 g of 4,4'-difluorobenzophenone was added to the reactor, and the temperature of the reaction mixture was maintained for 15 minutes.

[0176] 53 g of white powder was obtained.

[0177] The repeating units of polymers are, [ka] That was the case.

[0178] The melt viscosity, measured by capillary rheology at 410°C and 46 s⁻¹, was 8.75 kN-s / m².

[0179] This polymer showed a chlorine content of 0.7 μequivalents / g = 25 ppm (Cl) by microcoulometric titration.

[0180] This embodiment corresponds to Example 5 in International Publication No. 2018 / 086873.

[0181] Example 3: Preparation of PEDEK-PEoEK copolymer 80 / 20 445.22 g of diphenylsulfone, 9.365 g of pyrocatechol, 63.321 g of 4,4'-biphenol, and 93.384 g of 4,4'-difluorobenzophenone were placed in a 1000 mL four-necked reaction flask equipped with a stirrer, an N2 injection tube, a Claisen adapter with a thermocouple placed in the reaction medium, and a Dean-Stark trap with a condenser and dry eye strap. The contents of the flask were degassed under vacuum and then filled with high-purity nitrogen (containing less than 10 ppm of O2). The reaction mixture was then subjected to a constant nitrogen purge (60 mL / min).

[0182] The reaction mixture was slowly heated to 150°C. At 150°C, a mixture of 46.487 g of Na2CO3 and 0.294 g of K2CO3 was added to the reaction mixture from a powder dispenser over 30 minutes. At the end of the addition, the reaction mixture was heated to 340°C at a rate of 1°C / min. After 22 minutes at 340°C, 11.128 g of 4,4'-difluorobenzophenone (first stop) was added to the reaction mixture while maintaining a nitrogen purge in the reactor. After 5 minutes, 1.812 g of lithium chloride (second stop) was added to the reaction mixture. After 10 minutes, another 1.855 g of 4,4'-difluorobenzophenone (third stop) was added to the reactor, and the reaction mixture was maintained at that temperature for 15 minutes.

[0183] Next, the contents of the reactor were poured from the reactor into an SS receiving dish and cooled. The solid was crushed and ground through a 2 mm screen using an attrition mill. The diphenyl sulfone and salt were extracted from the mixture by successively washing the solid at room temperature with acetone (4 times with 3600 mL), demineralized water (8 times with 3600 mL, with 30.00 g of 37% HCl in the 3rd wash, and 0.90 g of NaH2PO4.2H2O and 0.90 g of Na2HPO4 in the 8th wash), and acetone (2 times with 3600 mL at room temperature). The powder was then removed from the reactor and dried under vacuum at 120°C for 12 hours to obtain 139 g of white powder.

[0184] The repeating units of polymers are, [ka] That was the case.

[0185] The properties of the polymer are summarized below.

[0186] Examples 4-7: Preparation of PEDEK-PEoEK copolymers 80 / 20, 75 / 25, 70 / 30, and 65 / 35 Comparative Examples 8 and 9: Preparation of PEDEK-PEoEK copolymers 55 / 45 and 50 / 50 The polymers of Examples 4-7 and Comparative Examples 8 and 9 were prepared according to the procedure detailed for Example 3, but using the reagents, quantities, and final polymerization temperatures detailed in Table 2 below.

[0187] [Table 2]

[0188] Comparative Example 10: Preparation of PEDEK-PEoEK copolymer 50 / 50 according to Japanese Patent Publication No. 01-221426 The procedure described in Japanese Patent Publication No. 01-221426 was reproduced.

[0189] A 1000 mL four-necked reaction flask equipped with a stirrer, an N2 injection tube, a Claisen adapter with a thermocouple placed in the reaction medium, and a Dean-Stark trap with a condenser and dry eye strap contained 462.60 g of N-methylpyrrolidinone, 34.449 g of 4,4'-biphenol, 20.370 g of pyrocatechol, 81.549 g of 4,4'-difluorobenzophenone, 45.556 g of Na2CO3, and 15 mL of toluene. The contents of the flask were degassed under vacuum and then filled with high-purity nitrogen (containing less than 10 ppm of O2). The reaction mixture was then subjected to a constant nitrogen purge (60 mL / min).

[0190] The reaction mixture was slowly heated to 200°C over 50 minutes. The reaction mixture was maintained at 200°C for 4 hours while refluxing toluene into the reaction mixture. The reaction mixture was then cooled to room temperature and solidified in 1 L of acetone in a Waring blender. The solid was filtered through a Buchner funnel and washed three more times with 1 L of acetone at room temperature for 30 minutes per cycle, followed by three washes with 1000 mL of deionized water at room temperature (30 minutes per cycle).

[0191] Next, the powder was dried under vacuum at 120°C for 12 hours to obtain 115 g of white powder.

[0192] The properties of the obtained polymer are reported below.

[0193] The table below in this specification summarizes a comparison of the properties of the polymer according to the present invention with polymers having similar Tg, i.e., similar performance.

[0194] [Table 3]

[0195] [Table 4]

[0196] [Table 5]

[0197] The above data demonstrates that polymer (P) of the present invention exhibits higher temperature capabilities (Tg > 153°C and G' retention > 15% at temperatures above 140°C and above 165°C) than PEDEK-PEoEK (representative of the prior art) produced with PEEK or DPS and NMP, having a PEDEK / PEoEK unit ratio of less than 60 / 40, particularly a PEDEK-PEoEK unit ratio of 50 / 50. Therefore, as a result, polymer (P) of the present invention is well-suited for high-temperature applications.

[0198] The above data shows that polymer (P) of the present invention retains excellent crystallinity, as indicated by a heat of fusion value of >40 J / g, and exhibits superior melt stability compared to comparative polymers B(*) and D(*), which indicates that they have improved processability.

[0199] The above data shows that the polymer (P) of the present invention exhibits improved chemical resistance (higher % strength retention and elongation at break) at high temperatures and improved tensile strength compared to the comparative polymer.

[0200] Overall, the polymer (P) of the present invention, characterized by the unit ratios of 60 / 40 to 85 / 15 as described in the claims, was found to exhibit a unique combination of high-temperature capability, excellent chemical resistance, and high melt stability.

Claims

1. A polymer [polymer (P)], - Formula (I) in an amount of more than 60 mol% to 85 mol% based on 100 mol% of the polymer (P): 【Chemistry 1】 (In the formula, Each R1 independently contains one or more heteroatoms in a C １ ~C １２ Selected from alkyl groups, sulfonic and sulfonate groups, phosphonic and phosphonate groups, amines and quaternary ammonium groups, Each R3 is independently selected from the group consisting of halogens, alkyls, alkenyls, alkynyls, aryls, ethers, thioethers, carboxylic acids, esters, amides, imides, alkali or alkaline earth metal sulfonates, alkyl sulfonates, alkali or alkaline earth metal phosphonates, alkyl phosphonates, amines, and quaternary ammonium compounds, and each a and each c is independently 0 or an integer from 1 to 4. Repeating unit (R ＰＥＤＥＫ ); - Formula (II): 【Chemistry 2】 (In the formula, Each R1 and each a are as defined above. Each R2 is independently selected from the group consisting of halogens, alkyls, alkenyls, alkynyls, aryls, ethers, thioethers, carboxylic acids, esters, amides, imides, alkali or alkaline earth metal sulfonates, alkyl sulfonates, alkali or alkaline earth metal phosphonates, alkyl phosphonates, amines, and quaternary ammonium compounds, and each b is independently 0 or an integer from 1 to 4. Repeating unit (R ＰＥｏＥＫ ) Includes, In accordance with ASTM D3418-03, the heat of fusion (ΔH) greater than 40 J / g was determined as the area under endothermic fusion during the second heating scan in differential scanning calorimetry (DSC), measured up to 450°C with heating and cooling rates of 20°C / min; and 410°C and 46s according to ASTM D3835 －１ The measured values ​​were 0.20–9.00 kN / m ２ melt viscosity in the range A polymer [polymer (P)] characterized by...

2. - A repeating unit (R) of formula (I) according to claim 1, starting from 61 mol% based on 100 mol% of the polymer (P). ＰＥＤＥＫ ) and / or a maximum of 85 mol% of the repeating unit (R) of formula (I) according to claim 1, based on 100 mol% of the polymer (P). ＰＥＤＥＫ ) The polymer (P) according to claim 1, comprising:

3. - 15 to 40 mol% based on 100 mol% of the polymer (P) of the repeating unit (R) of the formula (II) according to claim 1 ＰＥｏＥＫ and / or up to 39 mol% based on 100 mol% of the polymer (P) of the repeating unit (R) of the formula (II) according to claim 1 ＰＥｏＥＫ ) The polymer (P) according to claim 1, comprising:

4. - Repeating unit (R) of the above formula (I) ＰＥＤＥＫ In ), a and c are 0; and / or - Repeating unit of formula (II) above (R ＰＥｏＥＫ The polymer (P) according to claim 1, wherein a and b are 0.

5. A method for synthesizing a polymer (P) according to any one of claims 1 to 4, (a) In the presence of a base [base (B)] and in a polar organic solvent [solvent (S)], formula (III) 【Transformation 3】 (In the formula, each R1 and each a are as defined above.) At least one compound of formulas (IV) and (V): 【Chemistry 4】 (In the formula, each R2, each R3, each b, and each c are as defined above.) A step of obtaining a reaction mixture by contacting a mixture of compounds such that the ratio of (IV) to (V) is 85 / 15 to 60 / 40; (b) A step of bringing the reaction mixture into contact with a suitable reagent to complete the reaction in step (a) and obtain a product mixture; and (c) A step of recovering the polymer (P) from the product mixture. A method that includes this.

6. The above step (a) is, - Na ２ CO ３ _K ２ CO ３ or in the presence of a base (B) selected from these combinations; and / or - In a solvent (S) containing diphenyl sulfone; and / or - The method according to claim 5, wherein the process is carried out at a temperature of at least 130°C for about 0.5 to 15 hours.

7. - 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'-dihydroxybiphenyl; The method according to claim 5, wherein in formula (V), b is 0, and the compound is catechol.

8. The above step (b) is given by the following equation (F): 【Transformation 5】 (In the formula, R ６ is F, Cl, or OH, R ７ is -C(O)-Ar-R １０ ,-O-Ar-R １０ , -SO ２ -Ar-R １０ , -Ar-R １０ , alkyl or -H, where Ar is an arylene group containing at least one benzene ring, and R １０ (This is F, Cl, or H) The method according to any one of claims 5 to 7, carried out in the presence of at least one end capping agent conforming to the following.

9. The above step (b) is, (b1) Adding a first end capping agent to the reaction mixture; (b2) A step of adding a first inhibitor to the reaction mixture; and (b3) Optionally adding a second end-capping agent and / or a second termination agent to the reaction mixture. The method according to claim 5, including the method described in claim 5.

10. A composition [composition (C)] comprising a polymer (P) according to any one of claims 1 to 4 and at least one additional component [component (in)].

11. The composition (C) according to claim 10, wherein component (in) is selected from the group consisting of (i) reinforcing fillers; (ii) colorants; (iii) pigments; (iv) light stabilizers; (v) heat stabilizers; (vi) antioxidants; (vii) acid scavengers; (viiii) processing aids; (ix) nucleating agents; (x) internal and / or external lubricants; (xi) flame retardants; (xii) smoke suppressants; (xiiii) antistatic agents; (xiv) antiblocking agents; (xv) conductive additives; (xvi) plasticizers; (xvii) flow regulators; (xviiii) bulking agents; and (xix) metal deactivators.

12. The composition (C) according to claim 11, comprising less than 80% by weight and at least 10% by weight of the reinforcing filler based on the total weight of the composition (C).

13. The composition (C) according to claim 11, wherein at least one of the nucleating agents is selected from talc or boron nitride.

14. A molded article comprising a polymer (P) according to any one of claims 1 to 4 or a composition (C) according to any one of claims 10 to 13.

15. A molded article according to claim 14, which is an article for use in the oil and gas recovery, automotive, aerospace, electronics, semiconductor industries, or for industrial or consumer applications.

16. A method for producing at least one component included in a molded article according to claim 14 or 15, comprising at least one step of molding, extruding or coating a polymer (P) according to any one of claims 1 to 4 or a composition (C) according to any one of claims 10 to 13 to produce the at least one component.

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