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WO2019215304A1 - Compositions de polymère - Google Patents

Compositions de polymère Download PDF

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Publication number
WO2019215304A1
WO2019215304A1 PCT/EP2019/061987 EP2019061987W WO2019215304A1 WO 2019215304 A1 WO2019215304 A1 WO 2019215304A1 EP 2019061987 W EP2019061987 W EP 2019061987W WO 2019215304 A1 WO2019215304 A1 WO 2019215304A1
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WIPO (PCT)
Prior art keywords
polymer composition
repeat units
pedek
friction
peek
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP2019/061987
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English (en)
Inventor
Chantal Louis
Brian A. Stern
Ryan HAMMONDS
Mohammad Jamal El-Hibri
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Solvay SA
Solvay Specialty Polymers USA LLC
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Solvay SA
Solvay Specialty Polymers USA LLC
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Publication of WO2019215304A1 publication Critical patent/WO2019215304A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
    • C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers

Definitions

  • the present invention relates to a polymer composition including a PEDEK- PEEK copolymer and a friction and wear additive, methods of making the polymer composition, shaped articles comprising the polymer composition, and their use in friction and wear applications.
  • Thermoplastics are increasingly displacing metals as tribological components in, for example, radial and axial bearings, engines, gears, and seal rings, which are used in automotive and industrial applications and which require materials having the strength and wear resistance found in lubricated metals. It is generally desirable to replace metals with polymers in these applications because of their ease of fabrication, higher performance, lower or little dependence on external lubrication, and lower overall cost; however, such thermoplastics must be able to withstand the loads and speeds that are common in such environments while also retaining suitable wear performance.
  • PAEK Poly(aryl ether ketone)
  • PEEK poly(etheretherketone)
  • PEK poly(etherketone)
  • PEKK poly(etherketoneketone)
  • FIG. 1 is a plot illustrating the results of wear resistance testing of the polymer compositions of Comparative Example 6 and Example 7.
  • Exemplary embodiments are generally directed to a polymer composition including at least one PEDEK-PEEK copolymer having a PEDEK/PEEK mole ratio ranging from 55/45 to 80/20, and at least one friction and wear additive, methods of making the polymer composition, and shaped articles including the polymer composition.
  • polymer compositions of the present invention are effective in providing shaped articles having improved wear resistance and retention of mechanical properties at relatively high temperatures.
  • polymer compositions including at least one PEDEK-PEEK copolymer having a PEDEK/PEEK mole ratio ranging from 55/45 to 80/20 and at least one friction and wear additive surprisingly exhibit 1) increased dynamic elastic modulus at high temperatures (e.g. 175 °C) and 2) markedly improved wear performance, as compared with similar PEEK-containing polymer compositions.
  • the polymer composition exhibits a Dynamic Mechanical Analysis (DMT A) shear modulus of at least 1,000 MPa, preferably at least 1,200 MPa, 1,300 MPa, 1,400 MPa, and most preferably at least 1450 MPa, when measured in accordance with D5279, torsional strain mode, at a temperature of 175 °C and a strain frequency of 10 rad/s.
  • DMT A Dynamic Mechanical Analysis
  • the polymer composition exhibits a decrease in average cumulative thickness of at most 90 pm, preferably at most 85 pm, for “Cycle 1;” at most 150 pm, 140 pm, 130 pm, 125 pm for“Cycle 2;” at most 180 pm, 170 pm, 165 pm for“Cycle 3;” or a combination thereof, when tested according to the Wear Protocol described in the Examples below.
  • the polymer composition does not reach 250 °C until at least 16.5 h, preferably at least 17.0 h, when tested according to the Wear Protocol described in the Examples below.
  • the term“wear” generally refers to the amount of the polymer composition removed from a bearing surface as a result of the relative motion of the bearing surface against a surface with which the bearing surface interacts.
  • the polymer composition exhibits a tensile modulus ranging from 1,500 ksi to 3,000 ksi, preferably from 1,700 ksi to 2800 ksi as measured according to ASTM D638.
  • the polymer composition exhibits a tensile strength ranging from 20 ksi to 25 ksi as measured according to ASTM D638.
  • the polymer composition exhibits a flexural modulus of 1500 ksi to 2400 ksi as measured according to ASTM D790.
  • the polymer composition comprises at least one PEDEK-PEEK copolymer, as detailed below, at least one friction and wear additive, as detailed below, and optionally, one or more additional ingredients, as detailed below.
  • the at least one PEDEK-PEEK copolymer, the at least one friction and wear additive, and the optional one or more additional ingredients collectively represent greater than 50 wt.%, preferably greater than 70 wt. %, 80 wt. %, 90 wt. %, 95 wt. % of the polymer composition, based on the total weight of the polymer composition.
  • the polymer composition preferably consists essentially of the at least one
  • PEDEK-PEEK copolymer as detailed below, the at least one friction and wear additive, as detailed below, and the optional one or more additional ingredients, as detailed below.
  • the expression“consisting essentially of’ is to be understood to mean that any additional component different from the recited components is present in an amount of at most 1 % by weight, based on the total weight of the polymer composition, so as not to substantially alter the advantageous properties of the composition.
  • a“PEDEK-PEEK copolymer” denotes a polymer comprising greater than 50 mol %, collectively, of repeat units (RPEDEK) and repeat units (RPEEK), relative to the total number of moles of repeat units in the PEDEK-PEEK copolymer.
  • the total number of repeat units (RPEDEK) and (RPEEK) in the PEDEK-PEEK copolymer is at least 60 mol %, 70 mol %, 80 mol %, 90 mol %, 95 mol %, and most preferably at least 99 mol %, relative to the total number of repeat units in the PEDEK-PEEK copolymer.
  • re icat units are represented by formula : (B), where each R 1 and R 2 , equal to or different from each other, is independently at each occurrence selected from the group consisting of halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkyl sulfonate, alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine and quaternary ammonium; and
  • each a and b is independently selected from the group consisting of integers ranging from 0 to 4.
  • repeat units are selected from units of formula :
  • repeat units are selected from units of formula:
  • each of R 1 , R 2 , a’, and b’ is independently selected from the groups described above for R 1 , R 2 , a, and b, respectively.
  • repeat units are repeat units of formula (A-l)
  • repeat units (RPEEK) are repeat units of formula (B-l).
  • each a’ is zero, such that the repeat units (RPEDEK) are re )eat units of formula:
  • each b’ is zero, such that the repeat units (RPEEK) are repeat units of formula : (B-2).
  • repeat units are repeat units of formula (A-2), and repeat units (RPEEK) are repeat units of formula (B-2).
  • the PEDEK-PEEK copolymer of the present invention may additionally comprise repeat units (RPAEK) different from repeat units (RPEDEK) and (RPEEK), as above detailed.
  • RPAEK repeat units
  • the amount of repeat units (RPAEK) is generally comprised between 0 and 5 mol %, with respect to the total number of moles of repeat units of PEDEK-PEEK copolymer.
  • the PEDEK-PEEK copolymer includes repeat units (RPAEK) different from repeat units (RPEEK) and (RPEDEK).
  • Repeat units (RPAEK) are selected from the group consisting of units of formulae:
  • each of R’ equal to or different from each other, is independently selected at each occurrence from a Ci-Ci 2 group optionally comprising one or more than one heteroatom; sulfonic acid and sulfonate groups; phosphonic acid and phosphonate groups; amine and quaternary ammonium groups; and each of j’, equal to or different from each other, is independently selected at each occurrence from 0 and an integer of 1 to 4, preferably j’ being equal to zero.
  • the PEDEK-PEEK copolymer of the present invention is essentially comprised of repeat units (RPEDEK) and (RPEEK), as above detailed.
  • the PEDEK-PEEK copolymer consists essentially of repeat units RPEDEK and RPEEK- AS used herein, the expression“consists essentially of repeat units RPEDEK and RPEEK” means that any additional repeat unit different from repeat units RPEDEK and RPEEK, as above detailed, may be present in the PEDEK-PEEK copolymer in amount of at most 1 mol %, relative to the total number of moles of repeat units in the PEDEK-PEEK copolymer, and so as not to substantially alter the advantageous properties of the PEDEK-PEEK copolymer.
  • REDEK and (RPEEK) are present in the PEDEK-PEEK copolymer in a (RPEDEK)/(RPEEK) molar ratio ranging from 55/45 to 80/20, preferably 60/40 to 80/20, more preferably from 60/40 to 75/25.
  • PEDEK/PEEK mole ratio is used interchangeably herein with the
  • MV melt viscosity
  • the PEDEK-PEEK copolymer is present in the polymer composition in an amount of at most 99.5 wt.%, preferably at most 99 wt.%, 98 wt.%, 95 wt.%,
  • the PEDEK-PEEK copolymer is present in the polymer composition in an amount of at least 50 wt.%, preferably at least 60 wt.%, 70 wt.%, 80 wt.%, 90 wt.%, 95 wt.%, based on the total weight of the polymer composition.
  • the amount of PEDEK-PEEK copolymer ranges from 40 wt.% to 95 wt.%, preferably from 50 wt.% to 90 wt.%, more preferably from
  • the polymer composition includes at least one friction and wear additive.
  • a“friction and wear additive” denotes a component that provides the polymer composition with a decreased coefficient of friction as compared to a comparable polymer composition not including the friction reducing component.
  • the friction and wear additive causes the resultant polymer composition and articles comprising the polymer composition to have a more slippery, silky, or slick feel, with reduced friction between the polymer composition (or articles comprising the polymer composition) and materials that come into contact with the polymer composition.
  • the polymer composition preferably includes the at least one friction and wear additive in an amount of at least 0.5 wt.%, preferably at least 1 wt.%, 2 wt.%,
  • the polymer composition includes the at least one friction and wear additive in an amount of at most 50 wt.%, preferably at most 40 wt.%, based on the total weight of the polymer composition.
  • the polymer composition includes the at least one friction and wear additive in an amount ranging from 1 wt.% to 50 wt.%, preferably from 10 wt.% to 45 wt.%, 15 wt.% to 40 wt.%, 20 wt.% to 35 wt.%, 25 wt.% to 35 wt.%, based on the total weight of the polymer composition. Most preferably, the polymer composition includes about 30 wt.% of the at least one friction and wear additive, based on the total weight of the polymer composition. Any of the friction and wear additives known to those of skill in the art can be used in the polymer composition. In addition, the friction and wear additive can be present in the polymer composition in a variety of forms such as, for example, powders, fibers, beads, and oils.
  • the friction and wear additive is selected from the group consisting of fluoropolymers, siloxane polymers, silicone oils, silicon carbide, silicon dioxide, mica, aluminum oxide, zirconium oxide, molybdenum disulfide, certain nitrides (as described below), carbon fiber, and graphite.
  • fluoropolymers, siloxane polymers, silicone oils, silicon carbide, silicon dioxide, mica, aluminum oxide, zirconium oxide, molybdenum disulfide, certain nitrides (as described below), carbon fiber, and graphite are most preferred.
  • Fluoropolymers suitable for use in the invention may be any of the
  • fluoropolymers known in the art for use as lubricants including, for example, polytetrafluoroethylene (PTFE) and perfluoroalkoxy polymers (PFA, MFA).
  • PTFE polytetrafluoroethylene
  • PFA perfluoroalkoxy polymers
  • Fluoropolymer resins are readily available from a variety of commercial sources.
  • PTFE is most preferred.
  • the PTFE polymers suitable for use in the polymer composition are generally polymers of
  • the PTFE may also comprise minor amounts of one or more co-monomers such as hexafluoropropylene, perfluoro(methyl vinyl ether), perfluoro(propyl vinyl ether), perfluoro-(2, 2-dimethyl- l,3-dioxole), and the like, provided, however that the latter do not significantly adversely affect the unique properties, such as thermal and chemical stability of the tetrafluoroethylene homopolymer.
  • the amount of such co-monomer is less than 3 mol%, preferably less than 1 mol %, more preferably less than 0.5 mol %. Most preferred are PTFE homopolymers.
  • the PTFE has a mean particle size of at most 75 pm, preferably at most 60 pm, more preferably at most 50 pm.
  • the mean particle size of the PTFE is preferably at least 1 pm, more preferably at least 2 pm, most preferably at least 3 pm.
  • the fluoropolymer (preferably PTFE) may be present in a concentration of 1 wt.% to 20 wt.%, or preferably 2 wt.% to 15 wt.%, preferably 7 wt.% to 12 wt.%, most preferably about 10 wt.%, based on the total weight of the polymer composition.
  • Carbon fibers useful for the present invention can be obtained by heat treatment and pyrolysis of different polymer precursors such as, for example, rayon, polyacrylonitrile (PAN), aromatic polyamide or phenolic resin; suitable carbon fibers may also be obtained from pitchy materials.
  • PAN polyacrylonitrile
  • suitable carbon fibers may also be obtained from pitchy materials.
  • a variety of carbon fibers known to those of skill in the art are available from commercial sources.
  • the carbon fiber may be present in a concentration of 1 wt.% to 40 wt.%, preferably 2 wt.% to 20 wt.%, preferably 5 wt.% to 15 wt.%, most preferably about 10 wt.% based on the total weight of the polymer composition.
  • Nitrides suitable for use as the at least one friction and wear additive are selected from the group consisting of aluminum nitride, antimony nitride, beryllium nitride, boron nitride, chromium nitride, copper nitride, gallium nitride,
  • trigermanium dinitride trigermanium tetranitride, hafnium nitride, iron nitrides, mercury nitride, niobium nitride, silicon nitride, tantalum nitride, titanium nitride, tungsten dinitride, vanadium nitride, zinc nitride, and zirconium nitride.
  • silicon nitride and boron nitride are preferred. Boron nitride is most preferred.
  • the polymer composition includes one or more of the above nitrides (preferably boron nitride) in an amount of 1 wt.% to 20 wt.%, preferably 2 wt.% to 15 wt.%, preferably 3 wt.% to 10 wt.%, preferably 3 wt.% to 6 wt.%, most preferably about 5 wt.%, based on the total weight of the polymer composition.
  • the above nitrides preferably boron nitride
  • the graphite may be present in a concentration of 1 wt.% to 55 wt.%, preferably 2 wt.% to 20 wt.%, preferably 5 wt.% to 15 wt.%, most preferably about 10 wt.% based on the total weight of the polymer composition.
  • the polymer composition may include any combination of the friction and wear additives described herein, and, in some embodiments, may comprise two, three, or more friction and wear additives.
  • the polymer composition includes at least one of a fluoropolymer (preferably PTFE), graphite, carbon fiber, and a nitride as described above (preferably boron nitride).
  • a fluoropolymer preferably PTFE
  • graphite preferably graphite
  • carbon fiber preferably carbon fiber
  • a nitride as described above (preferably boron nitride).
  • the polymer composition includes as friction and wear additives:
  • PTFE preferably in an amount of 5 to 15 wt.%, preferably about 10 wt.%;
  • the polymer composition includes as friction and wear additives:
  • carbon fiber preferably in an amount of 10 to 20 wt.%, preferably about
  • boron nitride preferably in an amount of 1 to 10 wt.%, preferably about 5 wt.%, where the weight percents are based on the total weight of the polymer composition.
  • ingredients other than the PEDEK-PEEK copolymer and friction and wear additives may be incorporated in the polymer composition.
  • These ingredients may be polymeric or non-polymeric in nature.
  • reinforcing or filling additives may be incorporated into the polymeric composition to improve certain of properties of the polymer composition such as: short-term mechanical capabilities (e.g. mechanical strength, toughness, hardness, stiffness), thermal conductivity, creep strength, fracture resistance, high temperature dimensional stability, and fatigue resistance.
  • Additives other than friction and wear additives may include, for example, glass fibers; asbestos fibers ; boron fibers, metal fibers; calcium silicate fibers; metal borides fibers (e.g. TiB 2 ) and mixtures thereof.
  • Pigments, such as titanium dioxide and/or ultramarine blue, may also be incorporated into the polymeric composition.
  • the polymer composition may also optionally include additional additives such as zinc sulfide, zinc oxide, ultraviolet light stabilizers, heat stabilizers, antioxidants such as organic phosphites and phosphonites, acid scavengers, processing aids, nucleating agents, flame retardants, smoke-suppressing agents, anti-static agents, anti-blocking agents, and conductivity additives such as carbon black.
  • additional additives such as zinc sulfide, zinc oxide, ultraviolet light stabilizers, heat stabilizers, antioxidants such as organic phosphites and phosphonites, acid scavengers, processing aids, nucleating agents, flame retardants, smoke-suppressing agents, anti-static agents, anti-blocking agents, and conductivity additives such as carbon black.
  • their total concentration is preferably less than 10 wt. %, more preferably less than 5 wt. %, and most preferably less than 2 wt. %, based on the total weight of polymer composition.
  • the polymer composition can be prepared by melt-mixing the at least one
  • PEDEK-PEEK copolymer the at least one friction and wear additive, and, optionally, the one or more additional ingredients to provide a molten mixture, followed by extrusion and cooling of the molten mixture.
  • polymer compositions described herein are advantageously provided in the form of pellets, which may be used in injection molding, compression molding, or extrusion processes known in the art.
  • the preparation of the polymer composition can be carried out by any known melt-mixing process that is suitable for preparing thermoplastic molding
  • Such a process is typically carried out by heating the thermoplastic polymer above the melting temperature of the thermoplastic polymer thereby forming a melt of the thermoplastic polymer.
  • the process for the preparation of the polymer composition can be carried out in a melt-mixing apparatus as known to those of skill in the art. Suitable melt-mixing apparatus include, for example, kneaders, Banbury mixers, single-screw extruders, and twin-screw extruders.
  • the components of the polymer composition can be fed to the melt-mixing apparatus and melt-mixed in the apparatus.
  • the components may be fed simultaneously as a powder mixture or granule mixture, also known as a dry-blend, or may be fed separately.
  • the invention concerns a method for making the polymer compositions as described herein, comprising melt mixing the at least one PEDEK-PEEK copolymer, the at least one friction and wear additive, and, optionally, the one or more additional ingredients.
  • the polymer composition can be further processed following standard methods for injection moulding, extrusion, blow moulding, foam processing, compression molding, casting, coating and the like to form shaped articles comprising the polymer composition.
  • Exemplary embodiments are also directed to shaped articles including the polymer composition described above and methods of making the shaped articles.
  • the total weight of the polymer composition in the shaped article is preferably at least 50 wt.%, 80 wt.% , 90 wt.% , 95 wt.%, and most preferably at least 99 wt.%, based on the total weight of the shaped article.
  • the shaped article is an injection moulded article, an extrusion moulded article, a machined article, a coated article, or a casted article.
  • the shaped article is a single part formed from the polymer composition.
  • the shaped article includes two or more parts, at least one of which includes the polymer composition.
  • the shaped article is a friction and wear article.
  • a “friction and wear article” means an article including at least one surface (“bearing surface”) adapted to interact with another surface in relative motion, for example, by sliding, pivoting, oscillating, reciprocating, rotating, or the like.
  • the bearing surface of the friction and wear article may be subjected to relatively high loads, relatively high speed motion, or both, which may result in the generation of heat through friction.
  • Examples of such articles include, but are not limited to, thrust bearings, sleeve bearings, journal bearings, thrust washers, rub strips, bearing pads, needle bearings, ball bearings, including the balls, valve seats, piston rings, valve guides, compressor vanes, and seals, both stationary and dynamic.
  • the friction and wear article is an article for use in automotive or oil and gas applications, for example: seal rings for hydraulically actuated clutch components, axial thrust bearings, gears, labyrinth seals for turbo compressors, compressor plates for oil/gas compressors, compressor poppets and discharge valves for reciprocating and linear AC compressors, CMP rings for semiconductor manufacturing, vanes or vane tips for vacuum assist brakes, bearing cages for needle and ball bearings, and turbo compressor vanes for turbocharging
  • the friction and wear article can be used with a lubricant.
  • lubricant refers to a substance, such as a liquid, that may be disposed between two moving surfaces, one of which may include a surface of the friction and wear article, to reduce friction between the surfaces.
  • the lubricant may include an oil, such as a motor oil or transmission oil.
  • the friction and wear article is adapted to be used without a lubricant.
  • the friction and wear article (or a surface thereof) is adapted to be subjected to temperatures of at least 150 °C, preferably at least 175 °C, 200 °C, 225 °C, 250 °C without, e.g., deformation, or loss of ability to perform its designated function.
  • the invention also includes a method of making the shaped articles (e.g. a friction and wear article) comprising the polymer composition as described above.
  • the method includes at least one step of injection moulding, extrusion moulding, blow moulding, compression moulding, casting, or coating the polymer composition as above detailed.
  • the shape article is milled from a stock shape including the polymer composition.
  • stock shapes include plates, rods, slabs or the like.
  • KetaSpire ® KT-820 P (“KT-820P” herein) is an aromatic compound
  • PEEK polyetheretherketone
  • Kitamura KT-300M is a PTFE micropowder available from Kitamura Limited in Japan.
  • Sigrafil C30 S006 APS is a Carbon fiber available from SGL Group in Germany.
  • Superior Graphite grade 4735FF is a graphite powder available from Superior
  • Boronid Sl-SF Boron Nitride powder is available from ESK Ceramics GmbH and Co, KG in Germany.
  • Hostanox P-EPQ is a thermal stabilizer available from Clariant in
  • Hydroquinone photo-grade was procured from Eastman.
  • KetaSpire® PEEK KT-820P was used as Comparative Example 1.
  • reaction mixture was heated slowly to 150 °C.
  • 150 °C a mixture of 25.097 g of Na 2 C0 3 and 0.155 g of K 2 C0 3 was added via a powder dispenser to the reaction mixture over 30 minutes.
  • the reaction mixture was heated to 320 °C at l°C/minute. After 2 minutes at 320°C, 5.892 g of
  • the reactor content was then poured from the reactor into a SS pan and cooled.
  • the solid was broken up and ground in an attrition mill through a 2 mm screen.
  • Diphenyl sulfone and salts were extracted from the mixture with acetone and water at pH between 1 and 12.
  • the powder was then removed from the reactor and dried at l20°C under vacuum for 12 hours yielding 74 g of a white powder.
  • the structure of the obtained copolymer can be represented by its repeat units as follows:
  • the melt viscosity measured by capillary rheology at 4lO°C, 46 s 1 was found to be 0.18 kN-s/m 2 .
  • reaction mixture was heated slowly to 150 °C.
  • 150 °C a mixture of 22.391 g of Na 2 C0 3 and 0.141 g of K 2 C0 3 was added via a powder dispenser to the reaction mixture over 30 minutes.
  • the reaction mixture was heated to 340 °C at l°C/minute.
  • 3.127 g of 4,4’-difluorobenzophenone were added to the reaction mixture while keeping a nitrogen purge on the reactor.
  • 0.868 g of lithium chloride were added to the reaction mixture. 10 minutes later, another 1.787 g of
  • the reactor content was then poured from the reactor into a SS pan and cooled.
  • the solid was broken up and ground in an attrition mill through a 2 mm screen.
  • Diphenyl sulfone and salts were extracted from the mixture with acetone and water at pH between 1 and 12.
  • the powder was then removed from the reactor and dried at 120 °C under vacuum for 12 hours yielding 62 g of a white powder.
  • the structure of the obtained copolymer can be sketched, in terms of repeat units, as follows:
  • the melt viscosity measured by capillary rheology, at 410 °C, 46 s 1 was found to be 4.2 kN-s/m 2 .
  • the copolymer of Example 3 was prepared following the same procedure as
  • Example 2 but the reaction was held at 340 °C for 2 min before the addition of the termination charge of 4,4’-difluorobenzophenone.
  • the melt viscosity measured by capillary rheology at 410 °C, 46 s 1 was 0.32 kN-s/m 2 .
  • Example 4 The copolymer of Example 4 was prepared following the same procedure as Example 2 but the reaction was not held at 340 °C before the addition of the termination charge of 4,4’-difluorobenzophenone.
  • the melt viscosity measured by capillary rheology at 410 °C, 46 s 1 was 0.18 kN-s/m 2 .
  • the reaction mixture was heated slowly to 150 °C.
  • 150 °C a mixture of 26.626 g of Na 2 C0 3 and 0.167 g of K 2 C0 3 was added via a powder dispenser to the reaction mixture over 30 minutes.
  • the reaction mixture was heated to 320 °C at l°C/minute.
  • 3.697 g of 4,4’- difluorobenzophenone were added to the reaction mixture while keeping a nitrogen purge on the reactor.
  • 1.026 g of lithium chloride were added to the reaction mixture.
  • another 2.112 g of 4,4’-difluorobenzophenone were added to the reactor and the reaction mixture was kept at temperature for 15 minutes.
  • the reactor content was then poured from the reactor into a SS pan and cooled.
  • the solid was broken up and ground in an attrition mill through a 2 mm screen.
  • Diphenyl sulfone and salts were extracted from the mixture with acetone and water at pH between 1 and 12.
  • the powder was then removed from the reactor and dried at 120 °C under vacuum for 12 hours yielding 74 g of a white powder.
  • the reaction mixture was heated slowly to 150 °C.
  • a mixture of 26.626 g of Na 2 C0 3 and 0.167 g of K 2 C0 3 was added via a powder dispenser to the reaction mixture over 30 minutes.
  • the reaction mixture was heated to 320 °C at l°C/minute.
  • 3.697 g of 4,4’- difluorobenzophenone were added to the reaction mixture while keeping a nitrogen purge on the reactor.
  • 1.026 g of lithium chloride were added to the reaction mixture. 10 minutes later, another 2.118 g of 4,4’-difluorobenzophenone were added to the reactor and the reaction mixture was kept at temperature for 15 minutes.
  • the reactor content was then poured from the reactor into a SS pan and cooled.
  • the solid was broken up and ground in an attrition mill through a 2 mm screen.
  • Diphenyl sulfone and salts were extracted from the mixture with acetone and water at pH between 1 and 12.
  • the powder was then removed from the reactor and dried at 120 °C under vacuum for 12 hours yielding 74 g of a white powder.
  • the melt viscosity measured by capillary rheology at 410 °C, 46 s 1 was 0.16 kN-s/m 2 .
  • the carbon fiber was fed further downstream, also with a gravimetric feeder, at a rate of 10 wt.% (C8, E9, E10, C14, C15) or 15 wt.% (Cl l, E12, E13) of the total throughput rate of the overall composition.
  • the total throughput rate for the compounding was 35 lb/hr.
  • the melt extrudate was stranded and pelletized to produce pellets approximately 3 mm long by 3 mm in diameter.
  • the polymer compositions were injection molded to produce standard Type I ASTM tensile specimens and flexural bars with a thickness of 3.2 mm for use in the analysis that follows.
  • test specimens for the following tests were produced from ASTM tensile (Type I) or flexural bars.
  • DMTA Dynamic Mechanical Analysis
  • the inventive polymer compositions of Examples, 9, 10, 12, and 13 exhibited similar tensile modulus, tensile strength, and flexural modulus as did the analogous PEEK compositions of Comparative Examples 8 and 11 and the analogous PEDEK-PEEK compositions of Comparative Examples 14 and 15; however, the PEDEK- PEEK copolymer compositions of the invention shown in Examples 9 and 10 unexpectedly exhibited markedly superior performance at elevated temperature as shown by their significantly higher DMA elastic modulus values at 175 °C. Wear Testing
  • Thrust washer test specimens approximately one inch in diameter, and having an initial wear contact area of 0.02 in 2 , were injection molded from the polymer compositions of Comparative Examples 8, 14 and 15 and Examples 9 and 10 in Tables 1 and 1 A. The test specimens were annealed at 230 °C for 2 hours.
  • thermocouple was used to measure the specimen temperature throughout the test, and the final cycle was stopped when the specimen temperature reached 250 °C.
  • Results for the average cumulative change in the thickness of the washer after each wear step are shown in the bar graph of Fig. 1.
  • the data shows that the thrust washer molded from the polymer composition of Example 9, according to the invention, surprisingly both exhibited significantly less wear and remained below the cut-off temperature of 250 °C for a longer time than did the washer molded from the polymer composition of Comparative Example 8.
  • E9 and E10 had significantly reduced wear rates relative to C 8 , C 14 , and C 15.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Une composition polymère comprend au moins un copolymère PEDEK-PEEK ayant un rapport molaire PEDEK/PEEK allant de 55/45 à 80/20, et au moins un additif de frottement et d'usure. L'invention concerne également des procédés de production de la composition polymère et des articles façonnés comprenant la composition polymère.
PCT/EP2019/061987 2018-05-11 2019-05-09 Compositions de polymère Ceased WO2019215304A1 (fr)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2608369A (en) * 2021-06-28 2023-01-04 Victrex Mfg Ltd Copolymers and related methods, uses and components
GB2608794A (en) * 2021-02-26 2023-01-18 Victrex Mfg Ltd Copolymers and related methods, uses and components
WO2024047337A1 (fr) * 2022-09-02 2024-03-07 Victrex Manufacturing Limited Ensemble de manipulation, de transport et de stockage d'hydrogène, l'ensemble comprenant un composant comprenant un polymère de polyaryléthercétone, utilisation d'un tel matériau et procédé utilisant un tel matériau
WO2024047336A1 (fr) * 2022-09-02 2024-03-07 Victrex Manufacturing Limited Matériaux polymères

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015189567A1 (fr) * 2014-06-09 2015-12-17 Victrex Manufacturing Limited Matériaux polymères
GB2540679A (en) * 2015-07-24 2017-01-25 Victrex Mfg Ltd Polymeric materials
WO2017153290A1 (fr) * 2016-03-09 2017-09-14 Solvay Specialty Polymers Usa, Llc Compositions de polyaryléthercétone et procédé de revêtement d'une surface métallique
WO2018024744A1 (fr) * 2016-08-02 2018-02-08 Solvay Specialty Polymers Usa, Llc Compositions de poly(aryléthercétone) (paec) comprenant un composé aromatique de bas poids moléculaire
WO2019053164A1 (fr) * 2017-09-14 2019-03-21 Solvay Specialty Polymers Usa, Llc Jonction polymère-métal

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015189567A1 (fr) * 2014-06-09 2015-12-17 Victrex Manufacturing Limited Matériaux polymères
GB2540679A (en) * 2015-07-24 2017-01-25 Victrex Mfg Ltd Polymeric materials
WO2017153290A1 (fr) * 2016-03-09 2017-09-14 Solvay Specialty Polymers Usa, Llc Compositions de polyaryléthercétone et procédé de revêtement d'une surface métallique
WO2018024744A1 (fr) * 2016-08-02 2018-02-08 Solvay Specialty Polymers Usa, Llc Compositions de poly(aryléthercétone) (paec) comprenant un composé aromatique de bas poids moléculaire
WO2019053164A1 (fr) * 2017-09-14 2019-03-21 Solvay Specialty Polymers Usa, Llc Jonction polymère-métal

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2608794A (en) * 2021-02-26 2023-01-18 Victrex Mfg Ltd Copolymers and related methods, uses and components
GB2608369A (en) * 2021-06-28 2023-01-04 Victrex Mfg Ltd Copolymers and related methods, uses and components
WO2024047337A1 (fr) * 2022-09-02 2024-03-07 Victrex Manufacturing Limited Ensemble de manipulation, de transport et de stockage d'hydrogène, l'ensemble comprenant un composant comprenant un polymère de polyaryléthercétone, utilisation d'un tel matériau et procédé utilisant un tel matériau
WO2024047336A1 (fr) * 2022-09-02 2024-03-07 Victrex Manufacturing Limited Matériaux polymères

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