Melt Processable Compositions

Abstract

The present invention relates to compositions of fluoroplastics and poly(aryl ether ketones), methods for making the same, and shaped articles therefrom, such as wire coatings, which combine the advantageous properties of both components, can be easily produced by conventional equipment, and provide, among other things, room temperature toughness combined with, among other things, the chemical resistance and dielectric properties of fluoroplastics and the mechanical performance of poly(aryl ether ketones). [Selection diagram] None

Description

[Technical field]

[0001] Cross-reference to related art This application claims priority to U.S. Provisional Patent Application No. 62 / 469,629, filed March 10, 2017, the entire contents of which are incorporated herein by reference for all purposes.

[0002] The present invention relates to compositions of fluoroplastics and poly(aryl ether ketones), to methods for making same, and to shaped articles therefrom, such as, inter alia, wire coatings, and to coatings. [Background technology]

[0003] Polymers with high fluorine content, especially perfluorinated or mostly perfluorinated polymers such as polytetrafluoroethylene (PTFE), modified PTFE, fluorinated ethylene-propylene copolymers (FEP), tetrafluoroethylene / perfluoroalkylvinylether copolymers, are generally advantageous due to their high temperature ratings, their chemical inertness, low friction, weather resistance, as well as good electrical properties, especially very low dielectric properties. Nevertheless, it is generally recognized that their mechanical performance, such as room temperature toughness, tensile strength and stiffness, as well as high heat resistance under load (e.g. expressed by heat deflection temperature), are in any case inadequate for certain highly demanding fields of use.

[0004] On the other hand, poly(aryl ether ketones) are known high-performance plastics that are particularly advantageous due to their high mechanical performance, high heat resistance, as well as especially very high elastic modulus and strength. Nevertheless, although their chemical resistance and permeability, and / or electrical / dielectric properties may generally be sufficient in different fields of use, it is generally recognized that their performance may nevertheless be inadequate to meet certain highly demanding fields of use in view of these.

[0005] At present, it is known per se to use conventional PTFE or other perfluorinated thermoplastic copolymers of TFE in formulations with poly(aryl ether ketones).

[0006] In particular, European Patent Specification No. 0367629A (BICC PUBLIC LIMITED COMPANY) dated May 9, 1990 discloses a polymer composition for high performance cables comprising a small amount (0.5-15%) of a conjugated aromatic polymer (e.g., PEEK) dispersed in a fully fluorinated polymer matrix. The inclusion of PEEK in the FEP is specifically described for the purpose of enabling laser marking for surface labeling.

[0007] U.S. Patent Application Publication No. 6,177,518 (E.U.D.O.P.N. DE NEMOURS AND CIE.), dated Jan. 23, 2001, discloses compositions of melt-flowable fluoroplastics and poly(ether ketone ketone) that combine the advantageous properties of the two components and are provided as a minor dispersed phase in a matrix of the major component, depending on the composition ratio between the components.

[0008] US Patent No. 9,051,462 (ELRINGKLINGER AG) of June 9, 2015 discloses a polymer blend comprising a proportion of a fully fluorinated thermoplastic processable polymeric material and a proportion of at least one additional high performance polymer selected from polyetherketones, polyetheretherketones and polyetherarylketones, where the blend after melt blending shows a homogeneous distribution of the proportion of the at least one additional high performance polymer and the polymeric material. According to this document, the use of said fully fluorinated thermoplastic processable polymeric material comprising melt-processable PTFE in the form of a copolymer of TFE and a single comonomer (whose content is less than 3.5 mole percent) is effective to achieve a homogeneous distribution of the polymeric components, such that separate domains are no longer detectable.

[0009] Thus, achieving a homogeneous mixture of components to maximize the cumulative effect of properties, especially when blending fluoroplastics and poly(aryl ether ketones) in substantially equal parts by weight (e.g., about 50 / 50), is a widely recognized challenge in these compounding domains.

[0010] It is also known that fluoropolymers may cause adhesion defects when intended to be used in coating compositions. It is known in the art to use small amounts of aromatic resins as adhesion promoters. U.S. Patent No. 6,140,410 (EIDUPONT DE NEMOURS AND CIE.) dated October 31, 2000, discloses a melt-processable fluoropolymer composition that includes a small amount of functionalized fluoropolymer resin and a high-temperature resistant thermoplastic resin adhesion promoter and a large amount of non-functionalized fluoropolymer resin. A typical embodiment disclosed therein (see Example 21) provides a formulation made from 93.5 wt% TFE / perfluoropropyl vinyl ether copolymer, 4.0 wt% PEEK, and 2.5 wt% TFE copolymer containing 2 wt% of repeating units derived from sulfonyl fluoride monomer of formula CF2=CF-[OCF2CF(CF3)]-OCF2CF2-SO2F. Nevertheless, this document does not discuss the problem of blending fluoropolymers with poly(aryl ether ketones) and including significant amounts of this latter component to provide blends that exhibit the advantageous mechanical performance typical of poly(aryl ether ketones).

[0011] Thus, there remains a lack in the art of blends of fluoroplastics and poly(aryl ether ketones) that combine the advantageous performance of both components, which can be easily produced by conventional equipment, and which provide, among other things, room temperature toughness combined with, among other things, the chemical resistance and dielectric properties of fluoroplastics and the mechanical performance of poly(aryl ether ketones). [Brief description of the drawings]

[0012] [Figure 1] FIG. 2 is a cross-sectional view of an insulated cable including a primary insulating jacket made from the composition (C) of the present invention. [Diagram 2] FIG. 2 is a partial cutaway side view of a communication cable in which the jacket and / or primary insulation coating may comprise the composition (C) of the present invention. [Diagram 3] FIG. 3 is a schematic cross-sectional view of the communication cable taken along plane A-A' (see FIG. 2).

[0013] Summary of the Invention Applicants have now discovered that certain blends of fluoroplastics and poly(aryl ether ketones) can be produced by standard manufacturing techniques, which provide the performance ranges described above that combine the advantages of both components. In particular, the blends of the present invention provide excellent mechanical performance, such as toughness at room temperature, good dielectric properties, as well as particularly good cut resistance, which are particularly beneficial when using the blends of the present invention for insulating coatings or jackets for insulated wire.

[0014] The present invention therefore comprises: (i) TFE homopolymer (hereinafter, PTFE) and TFE copolymer (hereinafter, modified PTFE) which contains less than 0.5% by weight, preferably less than 0.1% by weight, of repeating units derived from one or more ethylenically unsaturated fluorinated monomers other than TFE, based on the total weight of the TFE copolymer (these PTFE and modified PTFE are melt-melted at 372° C. and 1000 s using a 1 mm×10 mm Hastelloy die). -1 At most 1.5 x 10 when measured according to ASTM D3835 3 having a melt viscosity of Pa×sec, and (ii) at least one tetrafluoroethylene (TFE) polymer [polymer (F)] selected from the group consisting of thermoplastic TFE copolymers (hereinafter, thermoplastic TFE copolymers) containing at least 1% by weight of repeat units derived from one or more ethylenically unsaturated fluorinated monomers other than TFE, based on the total weight of the TFE copolymer (the polymer (F) is present in an amount of 20 to 59% by weight based on the total weight of the polymer (F), the polymer (PAEK) and the polymer (I)); - at least one poly(aryl ether ketone) [polymer (PAEK)] in an amount of 40 to 79% by weight, relative to the sum of the weights of polymer (F), polymer (PAEK) and polymer (I), - (i) -SO2X groups (X is F, Cl); and (ii) groups of the formula -SO2-Ar*-(X*) in an amount of 0.05 to 20% by weight, relative to the sum of the weights of the polymer (F), the polymer (PAEK) and the polymer (I). n at least one fluorinated polymer [polymer (I)] having at least one of the following formulae: (wherein Ar* is a hydrocarbon group, typically an aromatic group; X* is a -COOM* group; M* is H or a cation (e.g. a metal cation or an ammonium cation); and n is zero or an integer from 1 to 3; The present invention relates to a composition [composition (C)] comprising:

[0015] Description of the embodiments Composition (C) The composition (C) is at least one polymer (F) as detailed above, in an amount ranging from 20 to 59% by weight, preferably from 25 to 55% by weight, relative to the sum of the weights of polymer (F), polymer (PAEK) and polymer (I), at least one polymer (PAEK) as detailed above, in an amount ranging from 40 to 79% by weight, preferably from 44 to 73% by weight, relative to the sum of the weights of polymer (F), polymer (PAEK) and polymer (I), and at least one polymer (I) as detailed above, in an amount ranging from 0.05 to 20% by weight, preferably from 0.1 to 5% by weight, relative to the sum of the weights of polymer (F), polymer (PAEK) and polymer (I); Includes.

[0016] Depending on the performance required, composition (C) may comprise substantially similar weight amounts of polymer (F) and polymer (PAEK). According to these embodiments, composition (C) comprises: at least one polymer (F) as detailed above, in an amount ranging from 44 to 55% by weight, preferably from 46 to 53% by weight, relative to the sum of the weights of polymer (F), polymer (PAEK) and polymer (I), at least one polymer (PAEK) as detailed above, in an amount ranging from 44 to 55% by weight, preferably from 46 to 53% by weight, relative to the sum of the weights of polymer (F), polymer (PAEK) and polymer (I), and at least one polymer (I) as detailed above, in an amount ranging from 1 to 4% by weight, preferably from 1 to 3% by weight, relative to the sum of the weights of polymer (F), polymer (PAEK) and polymer (I); Includes.

[0017] Alternatively, a composition (C) may also be included in which the polymer (PAEK) predominates in the blend; according to these embodiments, composition (C) comprises: at least one polymer (F) as detailed above, in an amount ranging from 27 to 35% by weight relative to the sum of the weights of polymer (F), polymer (PAEK) and polymer (I), - at least one polymer (PAEK) as detailed above, in an amount ranging from 64 to 72% by weight relative to the sum of the weights of polymer (F), polymer (PAEK) and polymer (I), and at least one polymer (I) as detailed above, in an amount ranging from 1 to 3% by weight relative to the sum of the weights of polymer (F), polymer (PAEK) and polymer (I); Includes.

[0018] Generally, for both of the above described embodiments, the total weight of polymer (F), polymer (PAEK) and polymer (I) represents at least 40% by weight, preferably at least 50% by weight, more preferably at least 70% by weight of the total weight of composition (C). The upper limit is not particularly important, since it is understood that composition (C) essentially composed of polymer (F), polymer (PAEK) and polymer (I) as detailed above is an advantageous embodiment of the present invention, and that small amounts (e.g. amounts less than 1% by weight) of impurities, suspect components can be tolerated in composition (C) essentially composed of the above three described components.

[0019] Such other components may be present in limited or significant amounts and may be, for example, polymers other than polymer (F), polymer (PAEK) and polymer (I), and may be fillers, pigments, stabilizers, additives, and the like.

[0020] Nevertheless, it is relatively generally understood that composition (C) may contain other components other than polymer (F), polymer (PAEK) and polymer (I) within a range that does not substantially impair the aforementioned advantageous properties of the blend of these three components described above.

[0021] Such polymers, in addition to those listed above, include, for example, polycarbonate, polyethylene terephthalate, polbutylene terephthalate, polyarylates, polycaprolactone, phenoxy resins, polysulfone, polyethersulfone, polyamide 6, polyamide 66, polyamide 11, polyamide 12, polyphenylene oxide, polyphenylene sulfide, acrylonitrile / butadiene / styrene copolymer (ABS), polymethyl methacrylate (PMMA), polypropylene, polyethylene, polybutylene, butadiene / styrene copolymer, ethylene / propylene copolymer, ethylene / propylene / diene rubber (EPDM), styrene / butadiene block copolymer, butadiene / acrylonitrile copolymer, acrylic rubber, styrene / maleic anhydride copolymer, styrene / phenylmaleimide copolymer, and the like.

[0022] The fillers are preferably inorganic fillers, including, for example, fibrous fillers (e.g. glass fibers, carbon fibers, boron fibers, stainless steel microfibers, whiskers, ...), powdered fillers (e.g. talc, mica, graphite, molybdenum disulfide, calcium carbonate, silica, silica alumina, alumina, titanium dioxide, magnesium oxide, ...).

[0023] The filler may also be a color pigment, such as an organic or inorganic pigment. Specific examples of color pigments include, for example, carbon black, iron oxide, aluminum cobalt oxide, copper phthalocyanine, perylene, bismuth vanadate, and the like.

[0024] Polymer (I) The polymer (I) comprises (i) -SO2X groups (wherein X is F, Cl); and (ii) groups of the formula -SO2-Ar*-(X*) n wherein Ar* is a hydrocarbon group, typically an aromatic group; X* is a -COOM* group; M* is H or a cation (e.g., a metal cation or an ammonium cation), preferably H; and n is zero or an integer from 1 to 3.

[0025] -SO2X and / or -SO2-Ar*-(X*) in polymer (I) n The amount of -SO2X groups and / or -SO2-Ar*-(X*) groups contained in the polymer (I) is generally at least 0.01, preferably at least 0.05, more preferably at least 0.1 meq / g. n There is no practical limit to the maximum amount of the -SO2X and / or -SO2-Ar*-(X*) groups. n It is generally understood that the groups are generally present in an amount of at most 1 meq / g, preferably at most 0.8 meq / g, more preferably at most 0.5 meq / g.

[0026] Formula -SO2-Ar*-(X*) n is preferably a group in which Ar* is a phenyl group, preferably a group of formula -SO2-Φ-COOM*, where M* is H or a cation (e.g. a metal cation or an ammonium cation), preferably M* is H.

[0027] Generally, the polymer (I) is formed from a -SO2X functional monomer (hereinafter monomer (X)) (which may be optionally functionalized to -SO2-Ar*-(X*) as detailed above). n The -SO2X group and / or -SO2-Ar*-(X*) are covalently bonded to the repeating unit derived from n Includes.

[0028] According to a first embodiment of the present invention, the polymer (I) is a polymer comprising at least one -SO2X group as detailed above, i.e. the polymer (I SO2X ).

[0029] Polymer (I SO2X ) may consist essentially of repeat units derived from one or more monomers (X), as detailed above, or may be a copolymer comprising repeat units derived from one or more monomers (X) and one or more additional monomers different from monomer (X).

[0030] Generally, polymers (I SO2X ) the -SO2X group is a group of formula -SO2F.

[0031] Suitable polymers containing at least one -SO2X group (I SO2X ) are those polymers comprising repeat units derived from at least one ethylenically unsaturated fluorinated monomer containing at least one -SO2X group (where X is F or Cl), hereinafter monomer (A), and repeat units derived from at least one ethylenically unsaturated fluorinated monomer not containing a -SO2X group (where X is F or Cl), hereinafter monomer (B).

[0032] The phrase "at least one monomer" is used herein with respect to both monomers of type (A) and (B) to indicate that one or more of each type of monomer can be present in the polymer. Hereinafter, the term "monomer" will be used to mean both one and more than one monomer of a given type.

[0033] Non-limiting examples of suitable monomers (A) are: - Formula: CF2 = CF(CF2) p Halogenated sulfonyl fluoroolefins of the formula SO2X, where X is F or Cl, preferably F, and where p is an integer between 0 and 10, preferably between 1 and 6, more preferably p is equal to 2 or 3; - Formula: CF2 = CF-O-(CF2) m halogenated sulfonyl fluorovinyl ethers of the formula SO2X, where X is F or Cl, preferably F, and where m is an integer from 1 to 10, preferably from 1 to 6, more preferably from 2 to 4, and even more preferably m is equal to 2; - Formula: CF2 = CF-(OCF2CF(R F1 )) w -O-CF2(CF(R F2 )) ySO2X (wherein X is F or Cl, preferably F; In the formula, w is an integer of 0 to 2, and R F1 and R F2 are independently C1-C optionally substituted with F, Cl, or one or more ether oxygens; 10 is a fluoroalkyl group, y is an integer from 0 to 6; preferably, w is 1, and R F1 is -CF3, y is 1, and R F2 is F) sulfonyl fluoride fluoroalkoxy vinyl ether; - of the formula CF2=CF-Ar-SO2X, where X is F or Cl, preferably F, and Ar is a C5-C 15 wherein the aromatic or heteroaromatic group is It is.

[0034] Preferably, the monomer (A) has the formula CF2=CF-O-(CF2) m The sulfonyl fluoride fluorovinyl ether is selected from the group of sulfonyl fluoride fluorovinyl ethers of the formula -SO2F (wherein m is an integer of 1 to 6, preferably 2 to 4).

[0035] More preferably, monomer (A) is CF2=CFOCF2CF2-SO2F (perfluoro-5-sulfonylfluoride-3-oxa-1-pentene).

[0036] Non-limiting examples of suitable ethylenically unsaturated fluorinated monomers of type (B) are: - C2-C8 perfluoroolefins such as tetrafluoroethylene (TFE), hexafluoropropylene (HFP); - C2-C8 hydrogen-containing fluoroolefins such as trifluoroethylene (TrFE), vinylidene fluoride (VDF), vinyl fluoride (VF), pentafluoropropylene and hexafluoroisobutylene; - C2-C8 chloro- and / or bromo- and / or iodo-containing fluoroolefins such as chlorotrifluoroethylene (CTFE) and bromotrifluoroethylene; - Formula CF2=CFOR f1 (In the formula, R f1 is C1-C6 fluoroalkyl, for example, -CF3, -C2F5, -C3F7) fluoroalkyl vinyl ether; - Formula CF2=CFOX0 (wherein X0 is a C1-C aryl group containing one or more ether oxygen atoms) 12 perfluorooxyalkyl vinyl ethers of the formula CF2=CFOCF2OR f2 (where R f2 is a C1-C3 fluoro(oxy)alkyl group such as CF2CF3, -CF2CF2-O-CF3, and -CF3), - Formula: TIFF0007676110000001.tif35161 (in the formula, R f3 , R f4 , R f5 , R f6 are equal to or different from each other and are independently a fluorine atom or a C1-C6 fluoro(halo)fluoroalkyl optionally containing one or more oxygen atoms, such as -CF3, -C2F5, -C3F7, -OCF3, -OCF2CF2OCF3) fluorodioxol. It is.

[0037] Preferably, the monomer (B) is - C2-C8 perfluoroolefins, preferably tetrafluoroethylene (TFE) and / or hexafluoropropylene (HFP); - chloro- and / or bromo- and / or iodo-containing C2-C6 fluoroolefins, such as chlorotrifluoroethylene (CTFE) and / or bromotrifluoroethylene; - Formula CF2=CFOR f1 (In the formula, R f1is C1-C6 fluoroalkyl, for example, -CF3, -C2F5, -C3F7) fluoroalkyl vinyl ether; - Formula CF2=CFOR O1 (In the formula, R O1 is a C1-C aryl group having one or more ether groups 12 fluorooxyalkyl vinyl ethers, such as perfluoro-2-propoxy-propyl; - their mixture; is selected from among.

[0038] More preferably, the at least one monomer (B) is TFE.

[0039] Preferably, the polymer (I SO2X ) is a fluorinated polymer comprising at least one -SOF functional group and consisting essentially of repeat units derived from at least one ethylenically unsaturated fluorinated monomer (A) containing at least one sulfonyl fluoride functional group and at least one ethylenically unsaturated fluorinated monomer (B).

[0040] End groups, impurities, defects and other pseudo units in limited amounts (less than 1 mole % based on the total moles of repeat units) may be present in the preferred polymers in addition to the repeat units mentioned above without substantially affecting the properties of the polymer.

[0041] Preferred polymers (I SO2X )teeth, (1) Repeating units derived from tetrafluoroethylene (TFE), generally in an amount of 25 to 99.9 mol %, preferably 40 to 99.5 mol %, based on the total moles of polymer (I); (2) (j) Formula: CF2 = CF-O-(CF2) mhalogenated sulfonyl fluorovinyl ethers of the formula SO2X, where X is F or Cl, preferably F, and where m is an integer from 1 to 10, preferably from 1 to 6, more preferably from 2 to 4, and even more preferably m is equal to 2; (jj) Formula: CF2 = CF-(OCF2CF(R F1 )) w -O-CF2(CF(R F2 )) y SO2X (wherein X is F or Cl, preferably F; In the formula, w is an integer of 0 to 2, and R F1 and R F2 are independently C1-C optionally substituted with F, Cl, or one or more ether oxygens; 10 is a fluoroalkyl group, y is an integer from 0 to 6; preferably, w is 1, and R F1 is -CF3, y is 1, and R F2 is F) sulfonyl fluoride fluoroalkoxy vinyl ether; (jjj) A mixture of these A repeating unit derived from at least one monomer selected from the group consisting of the polymer (I SO2X ), generally in an amount of 0.1 to 30 mol %, preferably 0.5 to 20 mol %, based on the total moles of (3) optionally, repeat units derived from at least one fluorinated monomer different from TFE, preferably a perfluorinated monomer, generally represented by hexafluoropropylene, formula CF2=CFOR' f1 (In the formula, R' f1 is C1-C6 perfluoroalkyl, for example -CF3, -C2F5, -C3F7; perfluoroalkyl vinyl ether of the formula CF2=CFOR' O1 (In the formula, R' O1 is a C2-C aryl group having one or more ether groups 12 perfluoro-oxyalkyl vinyl ethers of the formula CF2=CFOCF2OR' f2 (In the formula, R'f2 is a repeating unit derived from a perfluorinated monomer selected from the group consisting of perfluoroalkyl-methoxy-vinyl ethers of C1-C6 perfluoroalkyl, e.g., -CF3, -C2F5, -C3F7, or C1-C6 perfluorooxyalkyl having one or more ether groups, such as -C2F5-O-CF3, SO2X The repeating unit is generally in an amount of 0 to 45 mol %, preferably 0 to 40 mol %, based on the total moles of The fluorinated polymer is selected from the group consisting essentially of:

[0042] According to a particular embodiment, the preferred polymer (I SO2X ) is generally (1) 45 to 79.9 mol %, preferably 55 to 69.5 mol %, of repeating units derived from TFE; (2) 0.1 to 10 mol %, preferably 0.5 to 5 mol %, of repeating units derived from the -SO2X group-containing monomer (2) as described above; (3) 20 to 45 mol %, preferably 30 to 40 mol %, of repeating units derived from the above-mentioned fluorinated monomer (3) other than TFE. It essentially consists of:

[0043] According to certain other embodiments, the most preferred polymer (I SO2X ) is generally (1) 55 to 95 mol %, preferably 70 to 92 mol %, of repeating units derived from TFE; (2) 5 to 30 mol %, preferably 8 to 20 mol %, of repeating units derived from the -SO2X group-containing monomer (2) as described above; (3) 0 to 15 mol %, preferably 0 to 10 mol %, of repeating units derived from a fluorinated monomer (3) other than TFE as described above. It essentially consists of:

[0044] The fluorinated polymer containing at least one -SO2X functional group can be prepared by any polymerization method known in the art.Suitable methods for preparing such polymers are, for example, those described in U.S. Pat. No. 4,940,525 (THE DOW CHEMICAL COMPANY) dated July 10, 1990, EP-A-1323751A (SOLVAY SOLEXIS SPA) dated July 02, 2003, and EP-A-1172382A (SOLVAY SOLEXIS SPA) dated November 16, 2002.

[0045] Polymers containing at least one -SO2X, in particular -SO2F group (I SO2X ) may be optionally treated, for example with elemental fluorine, to remove polar chain end-groups to provide fully fluorinated structures.

[0046] According to a second embodiment of the invention, the polymer (I) contains at least one -SO2-Ar*-(X*) as described above. n Polymer (I SO2ArY )].

[0047] According to this embodiment, the polymer (I SO2ArY ) is the same as the -SO2-Ar*-(X*) n In addition to the -SO2X and / or -SO3M groups, M may simultaneously contain one or more -SO2X and / or -SO3M groups, where M is H or a cation (e.g., a metal cation or an ammonium cation). According to these embodiments, the polymer (I SO2ArY ) is a polymer (I SO2ArY ) in -SO3M, -SO2-Ar*-(X*) n and -SO2-Ar*-(X*) in an amount of at least 20%, preferably at least 25%, more preferably at least 30%, and / or generally at most 99%, preferably at most 70%, more preferably at most 60%, relative to the total number of -SO2X groups. n It is generally understood that the term "alkyl" refers to a group.

[0048] Nevertheless, the polymer (I SO2ArY ) is -SO2-Ar*-(X*) n Groups, but are substantially free of -SO2X and / or -SO3M groups as detailed above, are also encompassed by the present invention.

[0049] Generally, polymers (I SO2ArY )teeth, -SO2X functional monomer (monomer (X) as detailed above) (which may be optionally functionalized to -SO2-Ar*-(X*) as detailed above) n As a side group covalently bonded to the repeating unit derived from SO2-Ar*-(X*) n groups and, optionally, -SO2X and / or -SO3M groups.

[0050] Therefore, the polymer (I SO2ArY ) can be reacted with the above-mentioned polymer (I) in the presence of a Lewis acid. SO2X ) with aromatic (poly)carboxylic acids.

[0051] The choice of Lewis acid is not particularly limited. Aluminum trihalides, especially AlCl3, iron trihalides, especially FeCl3, and boron trihalides, especially BF3, are typical Lewis acids that may be used.

[0052] Any aromatic (poly)carboxylic acid can be used, including mono- and polynuclear acids containing one or more carboxylic acid groups, in particular benzoic acid.

[0053] Without being bound by this theory, the polymer (I SO2X The precursor (I) is formed via electrophilic substitution of the aromatic groups of the (poly)carboxylic acid by at least a portion of the -SO2X groups of the (I) SO2X ) in place of the -SO2X group of the formula -SO2-Ar*-(X*) n The applicant believes that this will generate a portion of the

[0054] As electrophilic substitution proceeds, the group -SO2X is converted to the group -SO2-Ar*-(X*) n Generally, a hydrolysis step and optionally a neutralization step are carried out to terminate the reaction, and -SO2-Ar*-(X*) n Change the -COOM* group of the moiety to a -COOH group.

[0055] Generally, hydrolysis as detailed above is also effective to convert residual -SO2X groups to groups of formula -SO3M, where M is H or a cation (e.g. a metal cation or an ammonium cation), as detailed above, depending on how the neutralization is carried out.

[0056] In particular, when a phosphate buffer solution, i.e. a mixture of NaH2PO4 / Na2HPO4, is used as the neutralizing agent (resulting in a pH in water of about 7), the residual -SO2X groups are hydrolyzed to groups of the formula -SO3Na, as detailed above.

[0057] Generally, depending on the reaction conditions, the number of groups -SO2-Ar*-(X*) relative to the total number of groups -SO2X and / or -SO3M as detailed above is n The portions can be adjusted.

[0058] Polymer (PAEK) As used herein, the expression "poly(aryl ether ketone)" or polymer (PAEK)" is hereby defined to mean a polymer having more than 50 mole % repeat units (R ) that contain -O-Ar'-C(=O)-Ar* groups, where Ar' and Ar* are equal to or different from each other and are aromatic groups. PAEK ), and the mole % is based on the total moles in the polymer (PAEK). PAEK ) generally comprises units of the following formulae (KA) to (KO) and mixtures of two or more of the same units: TIFF0007676110000002.tif122161TIFF0007676110000003.tif221161TIFF0007676110000004.tif70161[In each of the above formulas (KA) to (KO), each of R' which is equal to or different from each other is independently, for each occurrence, C1 to C5 optionally containing one or more heteroatoms. 12 groups; sulfonic acid and sulfonate groups; phosphonic acid and phosphonate groups; amine and quaternary ammonium groups; and each j', equal to or different from each other, is independently, at each occurrence, selected from 0 and integers from 1 to 4, preferably j' is equal to zero.

[0059] Repeating unit (R PAEK Each phenylene moiety of the repeating unit (R ) may, independently of one another, have 1,2-, 1,3- or 1,4-bonds to other phenylene moieties. PAEK Each phenylene moiety of the repeating unit (R) independently of the other phenylene moieties has a 1,3- or 1,4-bond to the other phenylene moieties. PAEK Each phenylene moiety in has 1,4-bonds to the other phenylene moieties.

[0060] According to a preferred embodiment, j' is zero for each R' of formulae (KA) to (KO) detailed above.

[0061] According to a preferred embodiment, the repeating unit (R PAEK ) is represented by the formulas (J'-A) to (J'-D): TIFF0007676110000005.tif120161 units.

[0062] In some embodiments, the polymer (PAEK) is poly(ether ether ketone) [polymer (PEEK)]. As used herein, "poly(ether ether ketone)" or "polymer (PEEK)" refers to its repeating units (R PAEK) are of the formula K'-A: TIFF0007676110000006.tif21161 repeat units, and mole % is based on the total moles of repeat units in the polymer (PEEK).

[0063] According to these embodiments, at least 60 mol%, at least 70 mol%, at least 80 mol%, at least 90 mol%, at least 95 mol%, at least 99 mol%, or even substantially all of the repeat units (R PAEK ) are repeat units (K'-A) as detailed above. The preferred polymer (PEEK) is a polymer in which substantially all repeat units are units of formula (K'-A), it being understood that end groups, defects and small amounts of impurities may be present.

[0064] In another embodiment, the polymer (PAEK) is poly(ether ketone ketone) [polymer (PEKK)]. As used herein, the terms "poly(ether ketone ketone)" or "polymer (PEKK)" refer to the repeating unit (R PAEK ) are more than 50 mol % of repeating units of the formula (K'-B) and / or repeating units of the formula (K''-B): TIFF0007676110000007.tif54161, and the mole % is based on the total moles of repeat units in the polymer (PEKK).

[0065] According to these embodiments, the repeat unit (R PAEK At least 60 mol%, at least 70 mol%, at least 80 mol%, at least 90 mol%, at least 95 mol%, at least 99 mol%, or even substantially all of the repeat units are of the formula (K'-B) or (K"-B), or preferably combinations thereof. Preferred polymers (PEKK) are polymers in which substantially all of the repeat units are units of the formula (K'-B) and / or (K"-B), it being understood that end groups, defects and small amounts of impurities may be present.

[0066] In yet another embodiment, the polymer (PAEK) is a poly(ether ketone) [polymer (PEK)]. As used herein, "poly(ether ketone)" and "polymer (PEK)" refer to the repeating units (R PAEK ) are of formula (K″-C): TIFF0007676110000008.tif24161 repeat units, and mole % is based on the total moles of repeat units in the polymer (PEK).

[0067] According to these embodiments, the repeat unit (R PAEK At least 60 mol%, at least 70 mol%, at least 80 mol%, at least 90 mol%, at least 95 mol%, at least 99 mol%, or even substantially all of the repeat units are of the formula (K'-C). Preferred polymers (PEK) are polymers in which substantially all of the repeat units are units of the formula (K'-C), it being understood that end groups, defects and small amounts of impurities may be present.

[0068] In some embodiments, the polymer (PAEK) is poly(ether diphenyl ether ketone) [polymer (PEDEK)]. As used herein, the terms "poly(ether diphenyl ether ketone)" or "polymer (PEDEK)" refer to the repeating unit (R K ) are more than 50 mol % of repeat units of the formula (K'-D): TIFF0007676110000009.tif18161(K'-D), where mole % is based on the total moles of repeat units in the polymer (PEDEK).

[0069] According to these embodiments, at least 60 mol%, at least 70 mol%, at least 80 mol%, at least 90 mol%, at least 95 mol%, at least 99 mol%, or even substantially all of the repeat units (R K) is a repeating unit (K’-D) as detailed above. Preferred polymers (PEDEK) are polymers in which substantially all repeating units are units of formula (K’-D), and it is understood that end groups, defects, and minor impurities may be present.

[0070] In some other embodiments, the polymer (PAEK) is a poly(ether diphenyl ether ketone)-poly(ether ether ketone) copolymer [polymer (PEEK-PEDEK)]. As used herein, the expression “poly(ether diphenyl ether ketone)-poly(ether ether ketone) copolymer” or “polymer (PEEK-PEDEK)” means any polymer in which more than 50 mol% of the repeating units (R K ) is a mixture of repeating units of formula (K’-A) and (K’-D) with a relative molar ratio (K’-A):(K’-D) of 95:5 to 5:95, preferably 80:20 to 20:80.

[0071] Preferably, the polymer (PAEK) has a melt viscosity of at least 0.07 kPa·s, more preferably at least 0.09 Pa·s, most preferably at least 0.12 kPa·s, and / or at most 0.65 kPa·s, more preferably at most 0.55 kPa·s, more preferably at most 0.50 kPa·s, most preferably at most 0.45 kPa·s, as measured according to ASTM D3835 using a 0.5×3.175 mm tungsten carbide die at 400 °C and 1000 s -1 when measured.

[0072] According to a preferred embodiment, PAEK is PEEK. PEEK is in particular commercially available as KetaSpire® PEEK from Solvay Specialty Polymers USA, LLC.

[0073] Polymer (F) Polymer (F) is (i) TFE homopolymer (hereinafter, PTFE) and TFE copolymer (hereinafter, modified PTFE) containing less than 0.5% by weight, preferably less than 0.1% by weight, of repeat units derived from one or more ethylenically unsaturated fluorinated monomers other than TFE, based on the total weight of the TFE copolymer (these PTFE and modified PTFE are melt-melted at 372° C. and 1000 s using a 0.5×3.175 mm tungsten carbide die). -1 At most 1.5 x 10 when measured according to ASTM D3835 3 having a melt viscosity of Pa×sec, and (ii) At least one tetrafluoroethylene (TFE) polymer selected from the group consisting of thermoplastic TFE copolymers, which contain at least 1% by weight, based on the total weight of the TFE copolymer, of repeat units derived from one or more ethylenically unsaturated fluorinated monomers other than TFE (hereinafter thermoplastic TFE copolymers).

[0074] Non-limiting examples of suitable ethylenically unsaturated fluorinated monomers different from the TFE of the modified PTFE and / or thermoplastic TFE copolymers are: - C3-C8 perfluoroolefins such as hexafluoropropene (HFP) and perfluoroisobutylene; - C2-C8 hydrogen-containing fluoroolefins such as trifluoroethylene (TrFE), vinylidene fluoride (VDF), vinyl fluoride (VF), pentafluoropropylene and hexafluoroisobutylene; - C2-C8 chloro- and / or bromo- and / or iodo-containing fluoroolefins such as chlorotrifluoroethylene (CTFE) and bromotrifluoroethylene; - Formula CF2=CFOR f1 (In the formula, R f1 is C1-C6 fluoroalkyl, for example, -CF3, -C2F5, -C3F7) fluoroalkyl vinyl ether; - Formula CF2=CFOX0 (wherein X0 is a C1-C aryl group containing one or more ether oxygen atoms) 12fluorooxyalkyl vinyl ethers of the formula CF2=CFOCF2OR f2 (where R f2 is a C1-C3 fluoro(oxy)alkyl group such as -CF2CF3, -CF2CF2-O-CF3, and -CF3; - Formula: TIFF0007676110000010.tif28161 (in the formula, R f3 , R f4 , R f5 , R f6 are equal to or different from each other and are independently a fluorine atom or a C1-C6 fluoro(halo)fluoroalkyl optionally containing one or more oxygen atoms, such as -CF3, -C2F5, -C3F7, -OCF3, -OCF2CF2OCF3) fluorodioxole.

[0075] Preferably, polymer (F) is selected from TFE homopolymers, modified PTFE and thermoplastic TFE copolymers as detailed above, said modified PTFE and thermoplastic TFE copolymers comprising (preferably consisting essentially of) repeat units derived from TFE and from at least one perfluorinated monomer other than TFE.

[0076] The expression "consisting essentially of," when used in conjunction with modified PTFE and thermoplastic TFE copolymers, is intended to indicate that end chains, impurities, defects may be present in the polymer as long as they do not impair / substantially alter the properties of said modified PTFE and thermoplastic TFE copolymers.

[0077] The aforementioned perfluorinated monomers [monomers (PFM)] other than TFE are advantageously (a) a C3 to C8 perfluoroolefin, preferably selected from the group consisting of hexafluoropropylene (HFP) and perfluoroisobutylene (PFIB); (b) Formula CF2=CFOR f1 (In the formula, Rf1 is a C1 to C6 perfluoroalkyl group such as CF3 (PMVE), C2F5 or C3F7), and (c) Formula CF2=CFOX0 (wherein X0 is a C1-C alkyl group containing one or more ether oxygen atoms) 12 perfluorooxyalkyl vinyl ethers of the formula CF2=CFOCF2OR f2 (where R f2 is a C1 to C3 perfluoro(oxy)alkyl group such as -CF2CF3, -CF2CF2-O-CF3, and -CF3), (d) Formula: TIFF0007676110000011.tif27161 (in the formula, R f3 , R f4 , R f5 , and R f6 are each equal to or different from one another and are independently selected from the group consisting of a (per)fluorodioxole, which is a fluorine atom or a C1-C6 perfluoro(oxy)alkyl group optionally containing one or more oxygen atoms, such as -CF3, -C2F5, -C3F7, -OCF3, or -OCF2CF2OCF3.

[0078] According to a particular embodiment, the polymer (F) is a PTFE or modified PTFE as detailed above, comprising less than 0.5% by weight, preferably less than 0.1% by weight, of repeating units derived from said monomer (PFM) relative to the total moles of repeating units. Preferably, the modified PTFE according to this embodiment consists essentially of repeating units derived from TFE and 0.0001-0.5% by weight, preferably 0.001-0.1% by weight, of repeating units derived from said monomer (PFM) relative to the total weight of the modified PTFE.

[0079] As explained above, the polymer (F) according to this embodiment is a low melt viscosity, optionally modified PTFE. The PTFE and modified PTFE suitable for use according to this embodiment are generally provided by ultrafine powders, which can be obtained by irradiation of standard high molecular weight PTFE / modified PTFE, and are generally known to have a molecular weight significantly lower than the typical molecular weight of standard high molecular weight / high melt viscosity PTFE / modified PTFE, whereby the ultrafine powders of PTFE and / or modified PTFE can be melt-flowable by themselves.

[0080] Preferably, the polymer (F) according to this embodiment is resistant to oxidation at 372° C. and 1000 s according to ASTM D3835, as detailed above. -1 at least 1 Pa×sec, preferably at least 10 Pa×sec, more preferably at least 50 Pa×sec, and / or at most 1.2×10 3 Pa×sec, preferably at most 1.0×10 3 and optionally modified PTFE ultrafine powders having a melt viscosity of at most 800 Pa×sec, and even more preferably at most 500 Pa×sec.

[0081] Ultrafine powders of PTFE or modified PTFE suitable for use in the composition (C) of the present invention advantageously have an average particle size d of at most 25.0 μm, preferably at most 22.0 μm, more preferably at most 20.0 μm, as determined by laser light diffraction according to ISO 13320. 50 It is characterized by: 50 The lower boundary of is not particularly limited. Nevertheless, for convenience of handling, the d of ultrafine powder of PTFE or modified PTFE is 50 is generally understood to be at least 0.5 μm, preferably at least 1.0 μm.

[0082] Average size d between 2.0 μm and 15.0 μm, preferably between 2.5 μm and 12.0 μm 50Particularly good results have been obtained with ultrafine powders of PTFE or modified PTFE having the formula:

[0083] The average size d of ultrafine powder of PTFE or modified PTFE 50 is determined according to ISO 13320 by laser light diffraction, for example using a laser diffraction particle sizer LS™ 13320MW-Beckman Coulter instrument.

[0084] The ultrafine powders of PTFE or modified PTFE suitable for use in the composition (C) of the invention are advantageously characterized by a quantity of end groups of carboxylic acid chains (in particular -COOH and -COF groups) of at least 13 mmol / kg, preferably at least 14 mmol / kg, more preferably at least 15 mmol / kg and / or advantageously at most 50 mmol / kg, preferably at most 40 mmol / kg, more preferably at most 30 mmol / kg.

[0085] The amount of carboxylic acid chain end groups (-COOH and -COF) was determined according to the method described in PIANCA, M. et al., End groups in fluoropolymers. Journal of Fluorine Chemistry. 1999, vol. 95, p. 71-84. The concentration of the chain ends is expressed as mmol of groups per kg of polymer (F).

[0086] A micronized PTFE powder that has been found to be particularly useful in the compositions of the present invention is POLYMIST® micronized PTFE powder, available from Solvay Specialty Polymers USA, LLC.

[0087] According to another embodiment, polymer (F) is selected from thermoplastic TFE copolymers (hereinafter thermoplastic TFE copolymers) that contain at least 1% by weight of repeat units derived from one or more ethylenically unsaturated fluorinated monomers other than TFE, based on the total weight of said TFE copolymer.Due to the presence of such a significant amount of repeat units derived from fluorinated monomers other than TFE, the TFE copolymers of this embodiment have melt processability.

[0088] The thermoplastic TFE copolymers of this embodiment generally comprise repeat units derived from one or more monomers (PFM) as detailed above.

[0089] The TFE copolymers of these embodiments advantageously contain at most 30% by weight, preferably at most 25% by weight, of repeat units derived from monomer (PFM) relative to all repeat units of said TFE copolymer.

[0090] Good results have been obtained with a TFE copolymer as detailed above, which contains at least 1% by weight and at most 25% by weight of repeat units derived from monomer (PFM) relative to all repeat units of said TFE copolymer.

[0091] According to a particular alternative of these embodiments, the polymer (F) comprises repeating units derived from hexafluoropropylene (HFP) and, optionally, a repeating unit of the general formula CF2=CFOR f1’ (In the formula, R f1’ is a C1-C6 perfluoroalkyl) TFE copolymer comprising a repeating unit derived from at least one perfluoroalkyl vinyl ether according to the formula:

[0092] Preferred polymers (F) according to this alternative are chosen from among tetrafluoroethylene (TFE) and hexafluoropropylene (HFP) in an amount ranging from 3 to 15% by weight, and optionally comprising (preferably consisting essentially of) repeat units derived from 0.5 to 3% by weight of at least one perfluoroalkylvinyl ether, as defined above.

[0093] The expression "consisting essentially of" is used in the context of the present invention to define the constituent elements of a polymer such that it takes into account end chains, defects, irregularities and monomer rearrangements that may be present in small amounts in said polymer without modifying the essential properties of the polymer.

[0094] Descriptions of such polymers (F) can be found, inter alia, in U.S. Pat. No. 4,029,868 (DUPONT) of June 14, 1977, U.S. Pat. No. 5,677,404 (DUPONT) of October 14, 1997, U.S. Pat. No. 5,703,185 (DUPONT) of December 30, 1997 and U.S. Pat. No. 5,688,885 (DUPONT) of November 18, 1997.

[0095] Polymers (F) according to this alternative are commercially available under the trademarks TEFLON® FEP 9494, 6100 and 5100 from EI DuPont de Nemours, or from Daikin (e.g. FEP NP-101 material), or from Dyneon LLC (FEP 6322).

[0096] Best results within this embodiment have been obtained with TFE copolymers comprising (preferably consisting essentially of) repeat units derived from tetrafluoroethylene (TFE) and hexafluoropropylene (HFP) in an amount ranging from 4 to 12 weight percent, and repeat units derived from either perfluoro(ethyl vinyl ether) or perfluoro(propyl vinyl ether) in an amount ranging from 0.5 to 3 weight percent.

[0097] According to another alternative of these embodiments, the polymer (F) is selected from the group consisting of TFE copolymers comprising repeat units derived from at least one perfluoroalkyl vinyl ether, as defined above, and optionally further comprising repeat units derived from at least one C3-C8 perfluoroolefin.

[0098] Good results within this second alternative have been obtained with TFE copolymers containing repeat units derived from one or more perfluoroalkyl vinyl ethers as specified above; particularly good results have been achieved with TFE copolymers in which the perfluoroalkyl vinyl ethers are perfluoromethyl vinyl ether (of formula CF2=CFOCF3), perfluoroethyl vinyl ether (of formula CF2=CFOC2F5), perfluoropropyl vinyl ether (of formula CF2=CFOC3F7) and mixtures thereof.

[0099] In particular, the polymer (F) of this second alternative form is advantageously (a) 3 to 35% by weight, preferably 5 to 12% by weight, of repeating units derived from perfluoromethyl vinyl ether; (b) different from perfluoromethyl vinyl ether and having the general formula CF2=CFOR f1’ (In the formula, R f1’ is C1-C6 perfluoroalkyl) and perfluoroalkyl vinyl ethers according to the general formula CF2=CFOX 01’ (In the formula, X 01’ is a C1-C aryl group having one or more ether groups 12 0-6 wt. % of repeat units derived from one or more fluorinated comonomers selected from the group consisting of perfluoro-oxyalkyl vinyl ethers according to the formula (I) above, preferably perfluoroethyl vinyl ether and / or perfluoropropyl vinyl ether; (c) repeating units derived from tetrafluoroethylene in an amount such that the sum of the percentages of repeating units (a), (b) and (c) is equal to 100% by weight. A TFE copolymer consisting essentially of

[0100] MFA and PFA suitable for use in the compositions of the present invention are commercially available under the trade names HYFLON® PFA P and M series and HYFLON® MFA from Solvay Specialty Polymers Italy SpA.

[0101] According to another alternative form of the invention, the polymer (F) is advantageously (a) 0.5 to 5% by weight of repeat units derived from perfluoromethyl vinyl ether; (b) 0.4 to 4.5 wt. % of repeat units derived from one or more fluorinated comonomers other than perfluoromethyl vinyl ether and selected from the group consisting of perfluoroalkyl vinyl ethers, as detailed above, and / or perfluoro-oxyalkyl vinyl ethers, as detailed above; preferably repeat units derived from perfluoroethyl vinyl ether and / or perfluoropropyl vinyl ether; (c) 0.5 to 6 wt. % of repeat units derived from at least one C3 to C8 perfluoroolefin, preferably hexafluoropropylene; and (d) repeating units derived from tetrafluoroethylene in an amount such that the sum of the percentages of repeating units (a), (b), (c) and (d) is equal to 100% by weight. A TFE copolymer consisting essentially of

[0102] The present invention further relates to a method for producing a composition (C) as detailed above, said method advantageously comprising a step of mixing polymer (F), polymer (PAEK) and polymer (I) as detailed above.

[0103] The mixing of polymer (F), polymer (PAEK) and polymer (I) can be achieved by dry blending. Nevertheless, the manufacturing method preferably includes a step of melt blending polymer (F), polymer (PAEK) and polymer (I), although a step of dry blending may be carried out prior to the melt blending step.

[0104] From the viewpoint of operational efficiency, the method of the present invention advantageously comprises a step of melt-kneading the polymer (F), the polymer (PAEK) and the polymer (I) by means of an extruder, typically a twin-screw extruder.

[0105] The melt-kneading temperature is preferably 280°C to 420°C.

[0106] The compositions (C) of the invention can be processed into shaped articles by standard techniques applicable to thermoplastic materials.

[0107] Therefore, yet another object of the invention is a process for the manufacture of a shaped product comprising a step of processing composition (C) in the molten state.

[0108] The process of processing in a molten state may include at least one of extrusion, wire extrusion, compression molding, injection molding, melt calendaring, rotational molding, thermoforming, and the like.

[0109] The products shaped thereby may be of different types, in particular wire jackets and coatings, but the combined properties of polymer (PAEK) and polymer (F) are particularly advantageous.

[0110] More specifically, composition (C) can be used to provide a wire coating around a conductor, either as a primary insulation or as a cable jacket.

[0111] In this case, the preferred manufacturing technique is wire extrusion, ie the composition (C) in the molten state is extruded by means of an extruder onto a core made of a wire or an assembly of two or more wires.

[0112] The invention further relates to a cable comprising a component comprising the composition (C) as detailed above.

[0113] The components made from composition (C) may include jackets, primary insulation coatings, and various subcomponents, such as shielding tapes, strength members, crosswebs, films, buffers, separators, withdrawal cords, subjackets, all known in the industry, any one or more of which may be made from or otherwise include the composition (C) of the present invention.

[0114] Preferably, the cable of the present invention comprises at least one component selected from the group consisting of the primary insulating coating and the jacket made from the composition (C) as detailed above.

[0115] Preferred cables according to the present invention are insulated wires, communication cables, and optical cables.

[0116] Figure 1 is a cross-sectional view of an insulated cable with a primary insulating jacket made from composition (C) according to a first embodiment of the invention. The insulated wire (3) in Figure 1 consists of an optical fiber (1) or a metal conductor wire (1), typically of aluminum or copper, preferably copper, surrounded by a primary insulating jacket (2) made from composition (C) of the invention. A preferred cable of this embodiment is an insulated wire consisting of a metal conductor wire.

[0117] The primary insulating coating (2) can be advantageously obtained by extruding composition (C) using a tube (including semi-tube) technique that includes a crosshead assembly and a tip and die configuration that contains flow passages designed to maximize the uniformity of the coating on the central conductor wire or optical fiber. A tube of the composition (C) of the present invention is advantageously extruded around and spaced from the conductor wire or optical fiber, said tube being advantageously extruded such that the thickness of composition (C) is reduced or drawn down before it comes into contact with the conductor wire or optical fiber. Advantageously, a vacuum is applied between the conductor wire or optical fiber and the composition (C) extruded under the form of a tube, thereby allowing atmospheric pressure to progressively pressurize said extruded tube of composition (C) into contact with the conductor wire or optical fiber.

[0118] Alternatively, application of composition (C) by pressure extrusion techniques may also be suitable. In pressure extrusion, composition (C) can be fed into an extruder, where the conductor wire is contacted with the molten composition (C), advantageously in a crosshead die, to form a coating directly on the conductor wire or optical fiber. According to this embodiment, a preformed tube of composition (C) is not extruded.

[0119] Figure 2 is a partial cutaway side view of a communications cable (7) according to a second embodiment of the present invention. The electrical cable embodiment of the present invention shown in Figure 2 generally includes a plurality of single electrical conductors, each of which includes a conductor wire (1) and a primary insulating jacket (2) such that they are electrically insulated from one another. Pairs of said wires are generally twisted into bundles (5), with some bundles held together by a jacket (4). Both the jacket (4) and the primary insulating jacket (2) may include composition (C) as detailed above.

[0120] The jacket (4) may similarly be formed by extrusion, either by tube extrusion or pressure extrusion techniques, as described above for the primary insulating coating, it being understood that in this embodiment the conductor wires or optical fibers are replaced with insulated conductors or insulating fibers or assemblies thereof.

[0121] In a communications cable, four pairs of insulated wires are generally twisted together, and the twisted pairs (5) are typically held together by a jacket (4).

[0122] Any one or more of the jacket (4) and the primary insulation coating (2) may be made from the composition (C) as detailed above.

[0123] 3 is a cross-sectional view along the A-A' plane (see FIG. 2) of a communication cable (7) according to a second embodiment of the present invention. A rip cord (6) may be present.

[0124] According to another embodiment of the invention, the cable is an optical cable. In the optical cable according to the invention, the conductor wires are replaced by glass optical fiber strands. Thus, a typical structure of an optical cable according to the invention comprises a number of groups of glass fiber optic strands wrapped around another glass strand or a coated steel wire or core, each of said groups being surrounded by a primary coating material, and said groups being surrounded by a jacket. Again, the primary coating material and / or the jacket can be made of composition (C) as detailed above.

[0125] To the extent that the disclosures of any patents, patent applications, and publications incorporated herein by reference conflict with the statements of this application to the extent that the term may be unclear, this statement shall control. EXAMPLES

[0126] The present invention will now be described in more detail with reference to the following examples, whose purposes are merely illustrative and are not intended to limit the scope of the present invention.

[0127] raw materials Polymer (PAEK): KETASPIRE® KT-880P and KT-820P are aromatic polyetheretherketone (PEEK) polymers available from Solvay Specialty Polymers USA, LLC.

[0128] Polymer (F): Polymist® F5A and XPP-511 are ultrafine PTFE powders available from Solvay Specialty Polymers USA, LLC and are heat-resistant at 372°C and 1000s in accordance with ASTM D3835. -1 melt viscosities of 150 Pa×sec (F5A) and 1880 Pa×sec (XPP-511), respectively, when measured by laser light diffraction, and d 50 and has a quantity of carboxylic acid chain end groups of about 20 mmol / kg (F5A) and about 10 mmol / kg (XPP-511). Hyflon® PFA M620, Hyflon® PFA P 420 are melt processable copolymers of TFE and PAVE available from Solvay Specialty Polymers Italy SPA.

[0129] Polymer (I): Aquivion® SO2F PFSP is a TFE copolymer containing repeat units derived from CF2=CF-O-CF2CF2-SO2F (in their -SO2F form) available in the form of a powder with equivalent weight=980 g / eq (PFSP980) or 790 g / eq (PFSP790) from Solvay Specialty Polymers Italy SPA (referred to as "Aquivion® SO2F" in the following paragraphs).

[0130] Diphenylsulfone (polymer grade) (99.8% purity) was sourced from Proviron.

[0131] Benzoic acid (Reagent Plus brand), aluminum chloride (anhydrous powder), and acetone (reagent grade) were obtained from Aldrich.

[0132] Magnesium oxide, Kyowamag MF-150, was sourced from Kyowa Chemical Industry Co., Ltd., Japan.

[0133] Example 1: Preparation of grafted benzoic acid on Aquivion® SO2F Into a 1000 mL 4-neck reaction flask equipped with a stirrer, a N2 inlet tube, a Claisen adapter with a thermocouple submerged in the reaction medium, and a condenser connected to a KOH scrubber, 375.00 g of benzoic acid, 138.75 g of Aquivion® SO2F were introduced. The flask contents were evacuated under vacuum and then filled with high purity nitrogen (containing less than 10 ppm O2). The reaction mixture was then placed under a constant nitrogen purge (60 mL / min).

[0134] The reaction mixture was slowly heated to 180°C. At 180°C, 20.96 g of aluminum chloride was added to the reaction mixture by a powder dispenser over a period of 20 minutes. After the addition, the reaction mixture was maintained at 180°C for 5 hours, and then the reactor contents were drained from the reactor into a SS pan and cooled. The solids were crushed and ground in an attrition mill through a 2 mm screen. Benzoic acid and residual catalyst were extracted from the mixture using acetone and water, and the solids so obtained were neutralized using NaH2PO4 / Na2HPO4 buffer. The powder was then dried at 50°C under vacuum for 12 hours to produce 287 g of white powder. Analysis of the polymer by back titration in NaOH and KHCO3 showed 335 μeq of carboxylic acid-containing groups [-SO2-Φ-COOH] / g polymer, thus corresponding to 496 μeq of sodium sulfonate groups [-SO3Na] / g polymer.

[0135] Use of Grafted Benzoic Acid on Aquivion® SO2F PFSP The compositions of Examples C1 and E1 are set forth in Table 1 and were compounded using a Leistritz 18 mm co-rotating intermeshing twin screw 5 barrel extruder. The extruder barrel was maintained at 284°C in the feed section, after which the barrel temperature was increased to 390°C. The melt temperature of each blend was obtained by handheld probe and ranged between 395-410°C. Vacuum degassing was performed at four barrel sections and maintained at 25 mm Hg to remove residual moisture and volatiles. The molten extrudate was stranded and pelletized for testing or later processed by injection molding.

[0136] Injection molding was performed after drying the material at 150°C under a vacuum of >25mmHg for at least 2 hours. A Miniature Plastic Molding Mini-Jector was used to mold test Type I specimens conforming to the corresponding ASTM test method. Barrel temperatures of 370-380°C and mold temperatures of approximately 190°C were used to process the material.

[0137] The data in Table 1 show the improvement in mechanical performance when Aquivion® SO2F grafted with benzoic acid is utilized in high loading PTFE / PEEK blends. Specifically, the ductility of the blend is improved as shown by a tensile strain at break of 12% compared to 6.5% for the control material. Testing was performed at 2 in / min according to ASTM D638.

[0138] TIFF0007676110000012.tif87170

[0139] Examples C2-E3: Preparation of compositions using the Aquivion® SO2F masterbatch process Examples C2-E3 from Table 2 were combined using the Leistritz 18 mm extruder previously described. Prior to preparing the PEEK / fluoropolymer blends, a masterbatch of PEEK / Aquivion® SO2F (polymer powder with equivalent weight=980 g / eq) was compounded with 0.3 pph of magnesium oxide in an 80 / 20 wt / wt ratio following similar compounding conditions as previously described. The masterbatch was utilized in the listed ratios contained in Table 2, where the weight percent composition of PEEK was held constant. Injection molding and testing were performed as previously described. Additionally, impact testing was performed according to ASTM D256.

[0140] Table 2 shows the improvement when utilizing Aquivion® SO2F via the masterbatch method. The properties shown here show similar tensile properties with the exception of a notable improvement in notched impact.

[0141] TIFF0007676110000013.tif123170

[0142] Examples E6-E7: Improved processability using Aquivion® SO2F The masterbatch method and testing for the work described in Table 3 as previously described was used again here. A similar process to that in the previous section was used here except a larger twin screw extruder, a Coperion ZSK 26 mm co-rotating intermeshing extruder, was used. The barrel was set at a range of 340-360°C with a vacuum of 26 millimeters of mercury before the melt exited the extruder and was pelletized. The PEEK / Aquivion® SO2F 80 / 20 wt / wt masterbatch used in Table 5 contained 0.3 pph magnesium oxide. An attempt was made to simultaneously make a control group of 50% PEEK and 50% Hyflon® PFA M620, but the material could not be collected due to insufficient strand strength exiting the extruder. The ability to collect, mold, and test compositions containing Aquivion® SO2F show improved compatibility with better processing.

[0143] TIFF0007676110000014.tif165170

[0144] Examples C4-C6: Selection of PTFE The following data in Table 5 was collected using a Leistritz 18 mm extruder and Mini-Jector molding machine as previously described. The 80 / 20 wt / wt masterbatch used in Table 5 contained 0.3 pph of magnesium oxide. The data in Table 4 show that optimal properties are obtained by combining PEEK with high flow PTFE (F5A) and Aquivion® SO2F masterbatch as a compatibilizer. The material obtained using the lower flow PTFE (XPP-511) shows lower strength and ductility (elongation at break). The dielectric constant was measured at 10 kHz according to ASTM D150-98 using non-contact electrodes on 3 mm thick samples obtained by injection molding. The data summarized below well demonstrate that while effective in compatibilization, the introduction of an effective amount of Aquivion® SO2F, which contains a polar portion of the formula -SO2F, does not adversely affect the overall advantageous dielectric performance of the formulation.

[0145] TIFF0007676110000015.tif148170

[0146] Examples C7 to E10: Viscosity of PEEK and Blending of PTFE Examples C7-E9 (Table 5) and C8-E10 (Table 6) were prepared using a Leistritz 18 mm twin screw extruder, a Mini-Jector injection molding machine, and test methods as previously described, where the masterbatch contained 52 wt% KT-820, 28 wt% KT-880, 20 wt% Aquivion® SO2F (polymer powder with equivalent weight = 980 g / eq), and 0.3 pph magnesium oxide. Comparative sample C7 shows lower strength, modulus, and break strain from tensile testing than E9, which contains Aquivion® SO2F. Table 6 shows the improved impact performance of the 30 wt% PTFE 70 wt% PEEK composition.

[0147] TIFF0007676110000016.tif118170

[0148] TIFF0007676110000017.tif116170

[0149] Examples C9-E11: Blending of PEEK clay and PTFE Examples C9 and E11 (Table 7) were prepared using a Leistritz 18mm twin screw extruder, a Mini-Jector injection molding machine, and the test method as previously described. In this case, the molded parts were annealed in a forced air oven at 200°C for 2 hours. The masterbatch used contained 80wt% KT-820, 20wt% Aquivion® SO2F (polymer powder with equivalent weight = 980g / eq), and 0.3pph magnesium oxide. Comparative sample C9 shows lower tensile strain at break and notched impact performance compared to E11, which contains Aquivion® SO2F. Furthermore, the annealing step eliminates the possibility of artificially high tensile strain at break or notched impact performance of materials that are not fully crystallized. The retention of high tensile strain at break and notched impact performance after annealing is even more improved by the introduction of Aquivion® SO2F. Also, as already shown before, the inclusion of Aquivion® SO2F polymer did not affect the dielectric constant.

[0150] TIFF0007676110000018.tif102170

Claims

1. - (i) TFE homopolymer (hereinafter, PTFE) and TFE copolymers (hereinafter, modified PTFE) containing less than 0.5% by weight, preferably less than 0.1% by weight, of repeat units derived from one or more ethylenically unsaturated fluorinated monomers other than TFE, based on the total weight of the TFE copolymer (these PTFE and modified PTFE are melt-melted at 372 ° C. and 1000 s using a 1 mm × 10 mm Hastelloy die). －１ At most 1.5 x 10 when measured according to ASTM D3835 ３ having a melt viscosity of 100 Pa×sec; and (ii) A thermoplastic TFE copolymer, which contains at least 1% by weight of repeat units derived from one or more ethylenically unsaturated fluorinated monomers other than TFE, based on the total weight of the TFE copolymer (hereinafter, thermoplastic TFE copolymer). at least one tetrafluoroethylene (TFE) polymer [polymer (F)] selected from the group consisting of: (said polymer (F) is present in an amount of 25 to 55% by weight based on the total weight of polymer (F), polymer (PAEK) and polymer (I)); at least one poly(aryl ether ketone) [polymer (PAEK)] in an amount of 44 to 73% by weight, relative to the sum of the weights of polymer (F), polymer (PAEK) and polymer (I), - (i) -SO in an amount of 0.1 to 5% by weight, based on the sum of the weights of polymer (F), polymer (PAEK) and polymer (I). ２ (ii) a group X, where X is F, Cl; and ２ -Ar ＊ - (X ＊ ) ｎ (In the formula, Ar ＊ is a hydrocarbon group, typically an aromatic group, and X ＊ -COOM ＊ is a group, M ＊ is H or a cation (e.g., a metal cation or an ammonium cation), and n is an integer from 1 to 3; A composition comprising the above [Composition (C)].

2. at least one polymer (F) in an amount of from 44 to 55% by weight, preferably from 46 to 53% by weight, relative to the sum of the weights of polymer (F), polymer (PAEK) and polymer (I); at least one polymer (PAEK) in an amount of 44 to 55% by weight, preferably 46 to 53% by weight, relative to the sum of the weights of polymer (F), polymer (PAEK) and polymer (I); Composition (C) according to claim 1, comprising at least one polymer (I) in an amount of 1 to 4% by weight, preferably 1 to 3% by weight, relative to the sum of the weights of polymer (F), polymer (PAEK) and polymer (I).

3. at least one polymer (F) in an amount of 27 to 35% by weight, relative to the sum of the weights of polymer (F), polymer (PAEK) and polymer (I), at least one polymer (PAEK) in an amount of 64 to 72% by weight, relative to the sum of the weights of polymer (F), polymer (PAEK) and polymer (I), Composition (C) according to claim 1, comprising at least one polymer (I) in an amount of 1 to 3% by weight relative to the sum of the weights of polymer (F), polymer (PAEK) and polymer (I).

4. 4. Composition according to any one of claims 1 to 3, wherein the total weight of polymer (F), polymer (PAEK) and polymer (I) represents at least 40% by weight, preferably at least 50% by weight, more preferably at least 70% by weight of the total weight of composition (C), and / or said composition (C) is essentially constituted by polymer (F), polymer (PAEK) and polymer (I).

5. -SO in polymer (I) ２ X and / or -SO ２ -Ar ＊ - (X ＊ ) ｎ 5. The composition according to any one of claims 1 to 4, wherein the amount of groups is at least 0.01 meq / g, preferably at least 0.05 meq / g, more preferably at least 0.1 meq / g and / or at most 1 meq / g, preferably at most 0.8 meq / g, more preferably at most 0.5 meq / g.

6. The polymer (I) is a compound represented by the formula -SO ２ -Ar ＊ - (X ＊ ) ｎ (In the formula, Ar ＊ is a phenyl group), preferably at least one group of the formula -SO ２ -Φ-COOM ＊ (M ＊ is H or a cation (e.g., a metal cation or an ammonium cation), preferably M ＊ The composition of any one of claims 1 to 5, comprising at least one group of the formula:

7. The polymer (I) is -SO ２ X-functional monomer (which may be optionally functionalized to -SO ２ -Ar ＊ - (X ＊ ) ｎ The repeating unit derived from ２ X group and / or -SO ２ -Ar ＊ - (X ＊ ) ｎ The composition according to any one of claims 1 to 6, comprising:

8. The polymer (PAEK) has a repeating unit (R ＰＡＥＫ ) based on the total number of moles in said polymer (PAEK), which are units of the following formulae (K-A) to (K-O) and mixtures of two or more of the same units: [In each of the above formulas (K-A) to (K-O), each of R', which is equal to or different from each other, independently represents, for each occurrence, a C １ ~C １２ 8. The composition of claim 1, wherein j' is selected from the group consisting of: sulfonic acid and sulfonate groups; phosphonic acid and phosphonate groups; amine and quaternary ammonium groups; and each j', equal to or different from one another, is independently, for each occurrence, selected from 0 and integers from 1 to 4, preferably j' is equal to zero.

9. The repeating unit (R ＰＡＥＫ ) is represented by the formula (J'-A) to (J'-D): The composition (C) of claim 8, wherein the unit is selected from the group consisting of:

10. The polymer (F) is selected from TFE homopolymers, modified PTFE and thermoplastic TFE copolymers, said modified PTFE and thermoplastic TFE copolymers comprising repeat units derived from TFE and repeat units derived from at least one perfluorinated monomer other than TFE, said perfluorinated monomer other than TFE [monomer (PFM)] being (a) preferably selected from the group consisting of hexafluoropropylene (HFP) and perfluoroisobutylene (PFIB); ３ ~C ８ A perfluoroolefin, (b) Formula CF ２ =CFOR ｆ１ (In the formula, R ｆ１ CF ３ (PMVE), C ２ F ５ Or C ３ F ７ Such as C １ ~C ６ perfluoroalkyl vinyl ether (PAVE), (c) Formula CF ２ =CFOX ０ (In the formula, X ０ is a C group containing one or more etheric oxygen atoms １ ~C １２ perfluorooxyalkyl vinyl ethers of the formula CF ２ = CFOCF ２ OR ｆ２ (Here, R ｆ２ is -CF ２ CF ３ , -CF ２ CF ２ -O-CF ３ , and -CF ３ Such as C １ ~C ３ perfluoromethoxyalkyl vinyl ethers, each of which is a perfluoro(oxy)alkyl group; (d) Formula: (In the formula, R ｆ３ , R ｆ４ , R ｆ５ , and R ｆ６ are equal to or different from each other, and are independently a fluorine atom or -CF ３ , -C ２ F ５ , -C ３ F ７ , -OCF ３ , or -OCF ２ CF ２ O.C.F. ３ C optionally containing one or more oxygen atoms, such as １ ~C ６ The composition (C) according to any one of claims 1 to 9, wherein the (per)fluorodioxole is selected from the group consisting of (perfluoro(oxy)alkyl groups).

11. 11. The composition according to claim 10, wherein the polymer (F) is PTFE or modified PTFE, said modified PTFE consisting essentially of repeating units derived from TFE and 0.0001 to 0.5 wt. %, preferably 0.001 to 0.1 wt. %, of repeating units derived from said monomer (PFM) relative to the total weight of the modified PTFE.

12. Polymer (F) is subjected to ASTM D3835 at 372°C and 1000s －１ At least 1 Pa×sec, preferably at least 10 Pa×sec, more preferably at least 50 Pa×sec, and / or at most 1.2×10 ３ Pa×sec, preferably at most 1.0×10 ３ 12. The composition according to claim 11, wherein the composition is selected from the group consisting of optionally modified PTFE ultrafine powders having a melt viscosity of at most 800 Pa x sec, even more preferably at most 800 Pa x sec, and even more preferably at most 500 Pa x sec.

13. The polymer (F) comprises: an average particle size d of at most 25.0 μm, preferably at most 22.0 μm, more preferably at most 20.0 μm, and / or at least 0.5 μm, preferably at least 1.0 μm, as determined by laser light diffraction according to ISO 13320; ５０ and / or A composition according to claim 11 or 12, selected from ultrafine powders of PTFE or modified PTFE having a content of end groups of carboxylic acid chains (-COOH and -COF groups) of at least 13 mmol / kg, preferably at least 14 mmol / kg, more preferably at least 15 mmol / kg and / or advantageously at most 50 mmol / kg, preferably at most 40 mml / kg, more preferably at most 30 mmol / kg.

14. The polymer (F) is a thermoplastic TFE copolymer comprising at least 1% by weight and at most 25% by weight, relative to all repeating units of said TFE copolymer, of repeating units derived from monomer (PFM), which is preferably - Repeating units derived from hexafluoropropylene (HFP) and optionally of the general formula CF ２ =CFOR ｆ１’ (In the formula, R ｆ１’ C １ -C ６ and a repeat unit derived from at least one perfluoroalkyl vinyl ether according to - General formula CF ２ =CFOR ｆ１’ (In the formula, R ｆ１’ C １ -C ６ perfluoroalkyl), and optionally at least one C ３ -C ８ 11. The composition of claim 10, selected from the group consisting of TFE copolymers further comprising repeat units derived from a perfluoroolefin.

15. A method for producing a composition (C) according to any one of claims 1 to 14, advantageously comprising a step of mixing polymer (F), polymer (PAEK) and polymer (I), preferably comprising a step of melt-kneading polymer (F), polymer (PAEK) and polymer (I).

16. A method for producing a shaped product comprising a step of processing a composition (C) according to any one of claims 1 to 14 in the molten state, said step of processing in the molten state may comprise at least one of extrusion, such as wire extrusion, compression moulding, injection moulding, melt calendaring, rotational moulding and thermoforming.

17. A cable comprising components manufactured from the composition (C) according to any one of claims 1 to 14, wherein the components made from the composition (C) may include a jacket, a primary insulating coating, and may include various sub-components, such as shielding tapes, strength members, cross webs, films, buffers, separators, pull cords, and sub-jackets.

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