WO2018086873A1 - Copolymère de polyaryléthercétone - Google Patents

Copolymère de polyaryléthercétone Download PDF

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Publication number
WO2018086873A1
WO2018086873A1 PCT/EP2017/077131 EP2017077131W WO2018086873A1 WO 2018086873 A1 WO2018086873 A1 WO 2018086873A1 EP 2017077131 W EP2017077131 W EP 2017077131W WO 2018086873 A1 WO2018086873 A1 WO 2018086873A1
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WIPO (PCT)
Prior art keywords
pedek
formula
copolymer
peek
groups
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PCT/EP2017/077131
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English (en)
Inventor
Chantal Louis
David B. Thomas
Mohammad Jamal El-Hibri
Ryan HAMMONDS
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Solvay Specialty Polymers Usa, Llc
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Application filed by Solvay Specialty Polymers Usa, Llc filed Critical Solvay Specialty Polymers Usa, Llc
Priority to KR1020197016166A priority Critical patent/KR102592751B1/ko
Priority to CN201780083170.2A priority patent/CN110177823B/zh
Priority to US16/348,224 priority patent/US11708457B2/en
Priority to EP17788222.2A priority patent/EP3538589B1/fr
Priority to JP2019524371A priority patent/JP7262387B2/ja
Publication of WO2018086873A1 publication Critical patent/WO2018086873A1/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
    • 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
    • C08G65/4012—Other compound (II) containing a ketone group, e.g. X-Ar-C(=O)-Ar-X for polyetherketones
    • 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
    • C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
    • C08G2650/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing oxygen in addition to the ether group
    • C08G2650/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing oxygen in addition to the ether group containing ketone groups, e.g. polyarylethylketones, PEEK or PEK

Definitions

  • This invention pertains to novel polyarylether ketone copolymers having improved thermal and chemical resistance, to a method of making the same, and to the use thereof in oil and gas exploration and extraction.
  • Polyaryl ether ketone materials are known as high performance plastics with high thermal resistance, which are used for a number of industrial applications where resistance to extreme conditions is required.
  • oil&gas exploration requires materials able to resist high temperature and pressure, and capable of maintaining the required performances upon prolonged exposure in the said extreme pressure and temperature conditions to aggressive chemicals present in downhole environment, including notably salt water, hydrocarbons, CO2, H2S, etc.
  • PAEKs polyaryl ether ketones
  • PEK having characterizing recurring unit of formula -O-Ph-CO-Ph-
  • PEKK having characterizing recurring unit of formula -O-Ph-CO-Ph-CO-Ph-
  • PEKEKK having characterizing recurring unit of formula -O-Ph-CO-Ph-O- Ph-CO-Ph-CO-Ph-
  • copolymers comprising a mixture of units -O-Ph-O-Ph-CO-Ph- (I) and -O-Ph-Ph-O-Ph-CO-Ph- (II) have been proposed, as an attempt to provide materials possessing increased Tg over PEEK, but yet similar or even lower crystalline melting point.
  • EP 0184458 A (ICI PLC) 6/1 1/1986 is directed to aromatic
  • a copolymer having molar proportions l:ll of 50/50 was disclosed as a non-working embodiment, failing to perform adequately to the aim pursued therein.
  • EP 0225750 A (ICI PLC) 6/16/1987 pertains to fibrous
  • reinforced compositions including a polyetherketone containing the repeat units: -O-Ph-O-Ph-CO-Ph- (I) and -O-Ph-Ph-O-Ph-CO-Ph- (II) in the relative molar proportions 1 : 11 of 95:5 to 60:40, preferably 95:5 to 70:30; impact properties of composite laminates processed from the melt were shown to be sensitive to the cooling conditions.
  • WO 2016/016643 (VICTREX MANUFACTURING LIMITED) 2/4/2016 discloses a polymeric material possessing mechanical and chemical resistance, notably high fracture toughness and high crystallinity, obtained by blending (A) a polyetherketone containing the repeat units: -O-Ph-O- Ph-CO-Ph- (I) and -O-Ph-Ph-O-Ph-CO-Ph- (II) in the relative molar proportions l:ll of 95:5 to 50:50, preferably 95:5 to 60:40, more preferably 95:5 to 65:35; and possessing a melting point of less than 330°C; with (B) a polyarylether ketone material which can be notably PEEK or PEK.
  • A a polyetherketone containing the repeat units: -O-Ph-O- Ph-CO-Ph- (I) and -O-Ph-Ph-O-Ph-CO-Ph- (II
  • WO 2016/042492 (GHARDA CHEMICALS LIMITED) 3/24/2016 discloses notably certain polyarylether ketones manufactured from 4,4'- difluorobenzophenone and a mixture of biphenol and hydroquinone, in molar ratios 95:5 to 5:95, as well as copolymers of PEK and PEDEK, including units of formula -Ph-CO-Ph-O- and units of formula -Ph-Ph-O- Ph-CO-Ph-O-, in variable molar ratios, as random or block copolymers. Only these latter copolymers are actually exemplified, possessing properties similar to PEK, i.e. affected by an unfavourable ketone/ether molar ratio.
  • copolymers containing a majority of repeat units -O-Ph-O-Ph-CO-Ph- (I) and a minority of units -O-Ph-Ph-O-Ph-CO- Ph- (II) were generally dwelt on, and recommended for use either alone or in admixture with other PAEKs.
  • each of R' and R" equal to or different from each other is independently selected at each occurrence from a C1-C12 group optionally comprising one or more than one heteroatoms; sulfonic acid and sulfonate groups; phosphonic acid and phosphonate groups; amine and quaternary ammonium groups; each of j' and k", equal to or different from each other, is independently selected at each occurrence from 0 and an integer of 1 to 4;
  • (j) comprises an amount of chemically bound chlorine of less than 2.0 ⁇ eq/g, as determined by microcoulometry, and
  • - MV is the melt viscosity measured pursuant to ASTM D3835 standard at 410°C and at a shear rate of 46.3 sec -1 , using a conical die having a diameter of 1.016 mm a length of 20.32 mm and a cone angle of 120°C and expressed in kN/m 2 ;
  • RV is the reduced viscosity measured pursuant to ASTM D2857 standard at 25°C on 1.0 wt/vol % solution in concentrated H 2 SO (96 wt%) and expressed in dl/g.
  • Another object of the present invention is a method of making a copolymer (PEDEK/PEEK), as above detailed, comprising reacting at least one difluoro-derivative of formula (III):
  • each of R, R' and R" equal to or different from each other is independently selected at each occurrence from a C1-C12 group optionally comprising one or more than one
  • heteroatoms sulfonic acid and sulfonate groups; phosphonic acid and phosphonate groups; amine and quaternary ammonium groups; each of r, j' and k", equal to or different from each other, is independently selected at each occurrence from 0 and an integer of 1 to 4,
  • -E- is a sulfone group of formula -SO2- or a ketone group of formula -C(O)-
  • A is selected from CI, F and H, each of R*, equal to or different from each other, is independently selected at each occurrence from a C1-C12 group optionally comprising one or more than one
  • heteroatoms sulfonic acid and sulfonate groups; phosphonic acid and phosphonate groups; amine and quaternary ammonium groups; each of t, equal to or different from each other, is independently selected at each occurrence from 0 and an integer of 1 to 4,
  • the invention further notably pertains to the a method of making parts
  • PEDEK-type units their structural homogeneity and regularity, and absence of chlorinated end groups, possess a suitable molecular structure and crystallization behaviour so as to deliver improved mechanical properties and outstanding chemical resistance.
  • Figure 1 schematically depicts a drilling rig equipment.
  • Figure 2 is a plot of storage modulus (G ⁇ in Pa) versus temperature (°C), as determined by DMTA analysis, for copolymers (PEDEK/PEEK) of the present invention (dotted lines), and reference PEEK, PEK and PEKK materials (solid lines).
  • the copolymer comprises recurring units (RPEEK) and (RPEDEK) as above detailed in molar ratio (RPEEK):(RPEDEK) of 45:55 to 15:85, preferably of 44:56 to 16:84, more preferably of 43:57 to 17:83, and even more preferably of 42:58 to 18:82.
  • Copolymers (PEDEK/PEEK) which have been found particularly advantageous are those comprising recurring units (RPEEK) and (RPEDEK) as above detailed in molar ratio of 40:60 to 20:80.
  • the copolymer (PEDEK/PEEK) of the present invention may additionally comprise recurring units (RPAEK) different from recurring units (RPEEK) and (RPEDEK), as above detailed.
  • the amount of recurring units (RPAEK) is generally comprised between 0 and 5 % moles, with respect to the total number of moles of recurring units of copolymer (PEDEK/PEEK), while recurring units (RPEEK) and (RPEDEK) will be present in an amount of at least 95 % moles, with respect to the total number of moles of recurring units of copolymer (PEDEK/PEEK).
  • recurring units (RPAEK) different from recurring units (RPEEK) and (RPEDEK) are present in the copolymer (PEDEK/PEEK) of the present invention
  • these recurring units (RPAEK) generally comply with any of the following formulae (K-A) to (K-M) herein below:
  • each of R' equal to or different from each other, is independently selected at each occurrence from a C1 -C12 group optionally comprising one or more than one heteroatoms; 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.
  • copolymer (PEDEK/PEEK) of the present invention is essentially composed of recurring units (RPEEK) and (RPEDEK), as above detailed.
  • each of j' is zero, or in other words, for each of the phenyl rings not to bear any further substituents in addition to the catenary ethereal or ketone bridging groups.
  • recurring units (RPEEK) comply with formula (la):
  • recurring units (RPEDEK) of formula (II) the connections among phenyl groups are generally in the para positions of each of the phenyl rings. Further, it is generally preferred for each of k" to be zero, or in other words, for each of the phenyl rings not to bear any further substituents in addition to the catenary ethereal or ketone bridging groups. According to these preferred embodiments, recurring units (RPEDEK) comply with formula (I la):
  • copolymer comprises an amount of chemically bound chlorine of less than 2.0 [leq/g, as determined by microcoulometry. In other terms, copolymer (PEDEK/PEEK) is
  • copolymer (PEDEK/PEEK) to comprise spurious chlorinated end groups, e.g. those derived from chlorine-containing monomers or end-capping agents in an amount such to provide for chemically bound chlorine in an amount of less than 2.0 [leq/g, preferably less than 1 .9 ieq/g, preferably less than 1 .8 ieq/g.
  • copolymer comprises a major amount of end groups selected from the group consisting of:
  • Formula (OH-i) Formula (OH-2) wherein in each of formulae (F), (OH-1 ) and (OH-2), R, R', R"", r, j' and k" have the meanings already defined above, and wherein the symbol is intended to denote the polymer chain comprising recurring units (RPEEK) and (RPEDEK), as above detailed.
  • End groups of formulae (F), (OH-1 ) and (OH-2) preferably represent at more than 50 % moles, preferably at least 60 % moles, even more preferably at least 70 % moles, still more preferably at least 80 % moles, with respect to the total moles of end groups of the copolymer
  • the copolymer (PEDEK/PEEK) possesses a narrow molecular weight distribution such that the following inequality is satisfied:
  • - MV is the melt viscosity measured pursuant to ASTM D3835 standard at 410°C and at a shear rate of 46.3 sec -1 , using a conical die having a diameter of 1.016 mm a length of 20.32 mm and a cone angle of 120°C and expressed in kN/m 2 ;
  • PEDEK/PEEK are such that:
  • the copolymers are such to preferably satisfy the following inequality:
  • the copolymer (PEDEK/PEEK) as above detailed possesses a reduced viscosity (RV) measured as above detailed, i.e. pursuant to ASTM D2857 standard at 25°C on 1.0 wt/vol % solution in concentrated H 2 SO (96 wt%) and expressed in dl/g, of at least 0.2, preferably at least 0.7, more preferably at least 0.9 and/or at most 6.0, preferably at most 5.5, more preferably at most 5.0. Particularly good results were obtained with copolymers (PEDEK/PEEK) having RV of 0.9 to 5.0 dl/g.
  • RV reduced viscosity
  • Another object of the invention is a method of making a copolymer
  • each of R, R' and R" equal to or different from each other is independently selected at each occurrence from a C1-C12 group optionally comprising one or more than one
  • heteroatoms sulfonic acid and sulfonate groups; phosphonic acid and phosphonate groups; amine and quaternary ammonium groups; each of r, j' and k", equal to or different from each other, is independently selected at each occurrence from 0 and an integer of 1 to 4,
  • -E- is a sulfone group of formula -SO2- or a ketone group of formula -C(O)-
  • A is selected from CI, F and H, each of R*, equal to or different from each other, is independently selected at each occurrence from a C1-C12 group optionally comprising one or more than one
  • heteroatoms sulfonic acid and sulfonate groups; phosphonic acid and phosphonate groups; amine and quaternary ammonium groups; each of t, equal to or different from each other, is independently selected at each occurrence from 0 and an integer of 1 to 4,
  • each of R * equal to or different from each other, is independently selected at each occurrence from a C1-C12 group optionally comprising one or more than one heteroatoms; sulfonic acid and sulfonate groups; phosphonic acid and phosphonate groups; amine and quaternary ammonium groups; each of t, equal to or different from each other, is independently selected at each occurrence from 0 and an integer of 1 to 4, wherein the said expression "substantial absence” is hereby intended to mean that if the said compound of formula (VII) is present, its amount is of less than 1 % moles, preferably less than 0.8 % moles, more preferably less than 0.5 % moles, with respect to the total moles of monomers of formula (III), (IV) and (V), as above detailed.
  • the method of the invention may include reacting monomers of
  • G is OH or a group of formula: , bound to the phenyl ring of compound (VIII) through the dotted bond, and wherein R * is H or is selected from a C1-C12 group optionally comprising one or more than one heteroatoms; sulfonic acid and sulfonate groups;
  • method may include adding required amount of compound (VIII) at the beginning of the reaction, and/or may include adding a portion or all the required amount of compound (VIII) at a later stage, after monomers of formula (III), (IV) and (V) have reacted for a certain time, and terminate the reaction after this addition.
  • Na2CO3 and K2CO3 are used in an amount such that the ratio between the total amount in moles of said Na2CO3 and K2CO3 and the total amount in moles of hydroxyl-monomers of formulae (IV) and (V), as above detailed, i.e. the molar ratio:
  • the Na2CO3 used in the method of the invention meets the particle size distribution requirements as detailed in US 9175136
  • Preferred monomer (III) is 4,4'-difluorobenzophenone (DFBP). It is
  • Preferred monomer (IV) is hydroquinone and preferred monomer (V) is 4,4'-dihydroxybiphenyl, otherwise known as 4,4'-biphenol.
  • the monomers (III), (IV) and (V) are heated in the method of the invention at a first temperature of at least 120°C, preferably at least 130°C, more preferably at least 140°C before being contacted with the mixture of Na2CO3 and K2CO3.
  • a first temperature of at least 120°C, preferably at least 130°C, more preferably at least 140°C before being contacted with the mixture of Na2CO3 and K2CO3.
  • the addition of the mixture of Na2CO3 and K2CO3 is done stepwise (i.e.
  • the addition rate is of less than 40% of total amount/minute, preferably of less than 30% of total amount/minute, more preferably of less than 20% of total amount/minute, and/or is of more than 3 % of total amount/minute, preferably of more than 5 % of total amount/minute.
  • reaction is generally pursued by heating the resulting mixture at a temperature of at least 300°C, preferably at least 320°C, at a temperature ramp rate of less than 5°C/minute, preferably less than 3°C/minute and/or at a temperature ramp rate of more than 0.5°C/minute.
  • the polycondensation reaction is advantageously terminated by adding an additional amount of monomer (III), such that the molar ratio
  • composition comprising the copolymer (PEDEK/PEEK)
  • the invention further pertains to a composition (C) comprising at least one copolymer (PEDEK PEEK).
  • composition (C) may comprise copolymer (PEDEK/PEEK), as above detailed, in a weight amount of at least 10 %, at least 30 %, at least 40 % or at least 50 %, based on the total weight of the of the said
  • composition (C) According to certain preferred embodiment's,
  • the composition (C) comprises copolymer (PEDEK/PEEK), as above detailed, in a weight amount of at least 70 %, based on the total weight of the said composition (C). According to other embodiment's, the copolymer (PEDEK/PEEK), as above detailed, in a weight amount of at least 70 %, based on the total weight of the said composition (C). According to other embodiment's, the copolymer (PEDEK/PEEK), as above detailed, in a weight amount of at least 70 %, based on the total weight of the said composition (C). According to other embodiment's, the
  • composition (C) comprises the copolymer (PEDEK/PEEK), as above detailed, in a weight amount of at least 90 %, if not at least 95 %, based on the total weight of the said composition (C). Yet, embodiment's are provided wherein the composition (C) consists essentially of the copolymer (PEDEK/PEEK), as above detailed.
  • the expression “consisting essentially of is to be understood to mean that any additional component different from the copolymer
  • PEDEK/PEEK is present in an amount of at most 1 % by weight, based on the total weight of the composition (C), so as not to substantially alter advantageous properties of the composition.
  • composition (C) may further comprise at least one reinforcing filler.
  • Reinforcing fillers are well known by the skilled in the art. They are preferably selected from fibrous and particulate fillers different from the pigment as defined above. More preferably, the reinforcing filler is selected from mineral fillers (such as talc, mica, kaolin, calcium carbonate, calcium silicate, magnesium carbonate), glass fiber, carbon fibers, synthetic polymeric fiber, aramid fiber, aluminum fiber, titanium fiber, magnesium fiber, boron carbide fibers, rock wool fiber, steel fiber, wollastonite etc. Still more preferably, it is selected from mica, kaolin, calcium silicate, magnesium carbonate, glass fiber, carbon fibers and wollastonite etc.
  • the filler is chosen from fibrous fillers.
  • a particular class of fibrous fillers consists of whiskers, i.e. single crystal fibers made from various raw materials, such as AI2O3, SiC, BC, Fe and Ni.
  • the reinforcing filler is chosen from wollastonite and glass fiber.
  • glass fibers are preferred ; they include chopped strand A-, E-, C-, D-, S-, T- and R-glass fibers, as described in chapter 5.2.3, p. 43-48 of Additives for Plastics Handbook, 2 nd edition, John Murphy.
  • Glass fibers optionally comprised in polymer composition (C) may have a circular cross-section or a non-circular cross-section (such as an oval or rectangular cross-section).
  • the glass fibers used have a circular cross-section, they preferably have an average glass fiber diameter of 3 to 30 ⁇ and particularly preferred of 5 to 12 ⁇ .
  • Different sorts of glass fibers with a circular cross- section are available on the market depending on the type of the glass they are made of.
  • the reinforcing filler is a carbon fiber.
  • carbon fiber is intended to include graphitized, partially graphitized and ungraphitized carbon reinforcing fibers or a mixture thereof.
  • Carbon fibers useful for the present invention can advantageously be obtained by heat treatment and pyrolysis of different polymer precursors such as, for example, rayon, polyacrylonitrile (PAN), aromatic polyamide or phenolic resin ; carbon fibers useful for the present invention may also be obtained from pitchy materials.
  • the term “graphite fiber” intends to denote carbon fibers obtained by high temperature pyrolysis (over 2000°C) of carbon fibers, wherein the carbon atoms place in a way similar to the graphite structure.
  • Carbon fibers useful for the present invention are preferably chosen from the group composed of PAN- based carbon fibers, pitch based carbon fibers, graphite fibers, and mixtures thereof.
  • the weight of said reinforcing filler is advantageously preferably
  • the reinforcing filler is present in an amount ranging from 10 to 60 % wt, preferably from 20 to 50 % wt, preferably from 25 to 45 % wt, most preferably from 25 to 35 % wt., based on the total weight of the composition (C).
  • composition (C) may further optionally comprise one or more than one additional ingredient (I) different from the reinforcing filler and from the copolymer (PEDEK/PEEK), as above detailed, generally selected from the group consisting of (i) colorants such as notably a dye (ii) pigments such as notably titanium dioxide, zinc sulfide and zinc oxide (iii) light stabilizers, e.g.
  • UV stabilizers heat stabilizers
  • antioxidants such as notably organic phosphites and phosphonites
  • acid scavengers processing aids
  • nucleating agents ix) internal lubricants and/or external lubricants
  • flame retardants xi) smoke-suppressing agents
  • antistatic agents xi) anti-blocking agents
  • conductivity additives such as notably carbon black and carbon nanofibrils
  • plasticizers xiv) flow modifiers
  • extenders xvi) metal deactivators and combinations comprising one or more of the foregoing additives.
  • composition (C) comprises the
  • polystyrene resin polystyrene resin
  • PEEK/PEEK polystyrene resin
  • sulfone polymers polyaryl sulphides, and the like.
  • the copolymer (PEDEK/PEEK), as
  • polymeric components' is to be understood according to its usual meaning, i.e. encompassing compounds characterized by repeated linked units, having typically a molecular weight of 2 000 or more.
  • composition (C) comprises more than 80 wt. % of the
  • copolymer (PEDEK/PEEK), as above detailed, optionally with the proviso that the copolymer (PEDEK/PEEK), as above detailed, is the only polymeric component in the composition (C), and comprises one or more than one reinforcing filler and/or additional ingredient (I) might be present therein.
  • composition (C) can be prepared by a variety of methods involving intimate admixing of the at least one copolymer (PEDEK/PEEK), as above detailed, optionally the reinforcing filler and optionally additional ingredient (I) desired in the polymeric material, for example by dry blending, suspension or slurry mixing, solution mixing, melt mixing or a combination of dry blending and melt mixing.
  • optionally the reinforcing filler and optionally additional ingredient (I) is carried out by using high intensity mixers, such as notably Henschel-type mixers and ribbon mixers so as to obtain a physical mixture, in particular a powder mixture of the at least one copolymer (PEDEK/PEEK), optionally the reinforcing filler and optionally additional ingredient (I).
  • high intensity mixers such as notably Henschel-type mixers and ribbon mixers so as to obtain a physical mixture, in particular a powder mixture of the at least one copolymer (PEDEK/PEEK), optionally the reinforcing filler and optionally additional ingredient (I).
  • PEDEK/PEEK optionally the reinforcing filler and optionally additional ingredient (I) desired in the composition (C), is carried out by tumble blending based on a single axis or multi-axis rotating mechanism so as to obtain a physical mixture.
  • the slurry mixing of the copolymer (PEDEK/PEEK), optionally the reinforcing filler and optionally additional ingredient (I) is carried out by first slurrying said copolymer (PEDEK/PEEK), as above detailed, in powder form, optionally the reinforcing filler and optionally additional ingredient (I) using an agitator in an appropriate liquid such as for example methanol, followed by filtering the liquid away, so as to obtain a powder mixture of the at least one copolymer (PEDEK/PEEK), optionally the reinforcing filler and optionally additional ingredient (I).
  • an appropriate liquid such as for example methanol
  • the physical mixture, in particular the obtained powder mixture, of the at least one copolymer (PEDEK/PEEK), optionally the reinforcing filler and optionally additional ingredient (I) is typically melt fabricated by known methods in the art including notably melt fabrication processes such as compression molding, injection molding, extrusion and the like, to provide shaped articles, including notably part(s) of an oil and gas recovery article or a finished oil and gas recovery article, as explained below in more detail.
  • the obtained powder mixture can comprise the copolymer (PEDEK/PEEK), the reinforcing filler, as detailed above, and optionally, other ingredients (I) in the weight ratios as above detailed, or can be a concentrated mixture to be used as
  • the obtained physical mixture can be extruded into a stock shape like a slab or rod from which a final part can be machined.
  • the physical mixture can be compression or injection molded into a finished part of the oil and gas recovery article or into a stock shape from which a finished part of the oil and gas recovery article can be machined.
  • melt compounding can be effected on the powder mixture as above detailed, or directly on the copolymer (PEDEK/PEEK), as above detailed, the reinforcing filler, as detailed above, and optionally, other ingredients (I).
  • melt compounding devices such as co-rotating and counter- rotating extruders, single screw extruders, co-kneaders, disc-pack processors and various other types of extrusion equipment can be used.
  • extruders more preferably twin screw extruders can be used.
  • the design of the compounding screw e.g.
  • composition (C) of the invention can be obtained by means e.g. of a rotating cutting knife after some cooling time on a conveyer with water spray.
  • composition (C) which may be present in the form of pellets or beads can then be further used for the manufacture of shaped articles, notably of different shape and size.
  • the copolymer (PEDEK/PEEK) and/or composition (C), as above detailed, can be processed by usual melt processing techniques, including notably extrusion molding, injection molding, compression molding, so as to provide shaped articles.
  • shaped articles are under the form of substantially bidimensional articles, e.g. parts wherein one dimension (thickness or height) is significantly less than the other two characterizing dimensions (width and length), such as notably films and sheets.
  • shaped articles are provided as three- dimensional parts, e.g. substantially extending in the three dimensions of space in similar manner, including under the form of complex geometries parts, e.g. with concave or convex sections, possibly including undercuts, inserts, and the like.
  • copolymer PEDEK/PEEK
  • composition (C) are provided as part(s) of oil and gas recovery article(s).
  • the invention further pertains to a method of making parts included in
  • devices used for oil & gas recovery including shaping those parts from the copolymers (PEDEK/PEEK) or from any composition comprising the same. Shaping can be achieved through any melt processing technique, including notably extrusion molding, injection molding, compression molding, and the like.
  • An oil and gas recovery article including at least one part made from a copolymer (PEDEK/PEEK), as above detailed, or from a composition comprising the same is still another object of the present invention.
  • oil and gas recovery article is intended to denote any article that is designed to conveniently be used in oil and gas recovery applications, in particular in HP/HT conditions.
  • part of an oil and gas recovery article is intended to denote a piece or portion which is combined with others to make up the whole oil and gas recovery article.
  • the external coating of an oil and gas recovery article falls thus within this scope.
  • the at least one part of the oil and gas recovery article according to the present invention can be a coating.
  • Representative examples of oil and gas recovery applications include (i) drilling and completion of deep, higher temperature, higher pressure oil and gas wells, as notably described in U.S. Pat.
  • oil and gas recovery articles useful in the present invention are drilling systems; drilling rigs; compressor systems, as notably described in published U.S. Pat. Appl. US 2010239441 , the entire disclosure of which is incorporated herein by reference; pumping systems; motor systems, sensors, such as reservoir sensors; control systems, such as temperature and/or pressure; stimulation and flow control systems; liner hanger systems, as notably described in U.S. Pat. No. US 6655456 , the entire disclosure of which is incorporated herein by reference; packer systems, as notably described in U.S. Pat.
  • drilling rig a structural housing equipment that is used to drill oil wells, or natural gas extraction wells, and may comprise a single article or comprise two or more components.
  • components of said drilling rig include, but not limited to, mud tanks, shale shakers, mud pumps, drill pipes, drill bits, drilling lines, electric cable trays.
  • jet pump systems submersible pumping systems, in particular electric submersible pumps, as notably described in U.S. Pat. No. US 6863124 the entire disclosure of which is incorporated herein by reference, beam pumps.
  • pipes including rigid pipes and flexible pipes, flexible risers, pipe-in-pipe, pipe liners, subsea jumpers, spools, umbilicals.
  • Such flexible pipes can notably be used for the transport of fluids where very high or very different water pressure prevails over the length of the pipe, and for example can take the form of flexible risers which run from the ocean floor up to equipment at or in the vicinity of the ocean surface, and they can also generally be used as pipes for the transport of liquids or gases between various items of equipment, or as pipes laid at great depth on the ocean floor, or as pipes between items of equipment close to the ocean surface, and the like.
  • Preferred pipe systems are pipes, flexible risers and pipe liners.
  • valves any device for halting or controlling the flow of a liquid, gas, or any other material through a passage, pipe, inlet, outlet, and the like.
  • valve systems useful in the present invention, mention can especially be made of choke valves, thermal expansion valves, check valves, ball valve, butterfly valve, diaphragm valve, gate valve, globe valve, knife valve, needle valve, pinch valve, piston valve, plug valve, poppet valve, spool valve, pressure reducing valve, sampling valves, safety valve.
  • the at least one part of the oil and gas recovery articles according to the present invention may be selected from a large list of articles such as fitting parts; such as seals, in particular sealing rings, preferably backup seal rings, fasteners and the like; snap fit parts; mutually moveable parts; functional elements, operating elements; tracking elements; adjustment elements; carrier elements; frame elements; films; switches; connectors; wires, cables; bearings, housings, compressor components such as compressor valves and compressor plates, any other structural part other than housings as used in an oil and gas recovery articles, such as for example shafts, shells, pistons.
  • fitting parts such as seals, in particular sealing rings, preferably backup seal rings, fasteners and the like
  • snap fit parts mutually moveable parts
  • functional elements operating elements
  • tracking elements adjustment elements
  • carrier elements carrier elements
  • frame elements film
  • switches connectors
  • wires, cables bearings, housings, compressor components such as compressor valves and compressor plates, any other structural part other than housings as used in an oil and gas recovery articles, such as for example shafts
  • the copolymer (PEDEK/PEEK) is very well suited for the
  • the at least one part of the oil and gas is selected from the at least one part of the oil and gas
  • recovery article is advantageously an oil and gas recovery housing, a seal, an electrical connector or a cable.
  • a cable can be notably wires electrically connecting the different parts within an oil and gas recovery article, for example connecting different electrical connectors, connecting tools to connectors, instruments or other tools, connecting instruments to connectors, other instruments or tools, connecting a power source to connectors, instruments or tools.
  • a cable can also advantageously be used for carrying a signal to computer systems.
  • the cable is a coated wire.
  • oil and gas recovery housing is meant one or more of the back cover, front cover, frame and/or backbone of an oil and gas recovery article.
  • the housing may be a single article or comprise two or more components.
  • backbone is meant a structural component onto which other components of the oil and gas recovery article, are mounted.
  • the backbone may be an interior component that is not visible or only partially visible from the exterior of the oil and gas recovery article.
  • threaded fasteners such as bolts, nuts, screws, headless set screws, scrivets, threaded studs and threaded bushings, and unthreaded fastener, such as notably pins, retaining rings, rivets, brackets and fastening washers and the like.
  • seals are used in all types of oil and gas recovery articles, as well as those used in parts of oil and gas recovery articles which remains in the well after completion, testing and production of the well.
  • seals need to resist to these extreme conditions, as mentioned above, in substantially indefinite time. It is worthwhile mentioning that seals besides electronics can be considered as the most vulnerable parts of oil and gas recovery articles.
  • the at least part of an oil and gas recovery article is a seal system, wherein said seal system is selected from a group consisting of a metal seal, an elastomeric seal, a metal-to- metal seal and an elastomeric and metal-to-metal seal.
  • Seal systems are typically used in drill bits, motor systems, in particular mud motors, reservoir sensors, stimulation and flow control systems, pump systems, in particular electric submersible pumps, packers, liner hangers, tubing's, casings and the like.
  • Representative examples of seal systems are, without limitation, seal rings such as notably C-rings, E-rings, O-rings, U-rings, spring energized C-rings, backup rings and the like; fastener seals; piston seals, gask-O- seals; integral seals, labyrinth seals.
  • the at least one part of the oil and gas recovery article according to the present invention is a seal ring, preferably a backup seal ring.
  • the weight of the copolymer (PEDEK/PEEK), based on the total weight of oil and gas recovery article, is usually above 1 %, above 5 %, above 10 %, preferably above 15 %, above 20 %, above 30 %, above 40 %, above 50 %, above 60 %, above 70 %, above 80 %, above 90 %, above 95 %, above 99 %.
  • the oil and gas recovery article may consist of one part, i.e. it is a single- component article. Then, the single part preferably consists of the copolymer (PEDEK/PEEK) or of any composition thereof.
  • the oil and gas recovery article may consist of several parts.
  • either one part or several parts of the oil and gas recovery article may consist of the copolymer (PEDEK/PEEK) or of any composition thereof.
  • the oil and gas recovery article consist of copolymer (PEDEK/PEEK) or of any composition thereof, each of them may consist of the very same copolymer (PEDEK/PEEK) or of any composition thereof; alternatively, at least two of them may consist of different copolymer (PEDEK/PEEK) or of any composition thereof.
  • Another objective of the present invention is to provide a method for the manufacture of the above described part of the oil and gas recovery article. Such method is not specifically limited.
  • the copolymer is not specifically limited.
  • PEDEK/PEEK or a composition comprising the same, as above detailed, may be generally processed by injection molding, extrusion molding, compression molding, or other shaping technologies.
  • manufacture of the above described part of the oil and gas recovery article or oil and gas recovery article includes the step of compression molding or injection molding and subsequent solidification of the copolymer
  • oil and gas recovery article or oil and gas recovery article includes the step of coating.
  • the copolymer (PEDEK/PEEK) or the composition
  • manufacture of the above described part of the oil and gas recovery article or the oil and gas recovery article, as described above includes the machining of a standard shaped structural part in a part having any type of size and shape.
  • a standard shaped structural part include notably a plate, a rod, a slab and the like.
  • Said standard shaped structural parts can be obtained by extrusion molding,
  • the method of the invention is advantageously a method for recovering oil and/or gas from a subterranean formation including using said oil and gas recovery article.
  • the subterranean formations can be advantageously deeply buried
  • the method of the invention may advantageously comprises at least one of the operations selected from the group consisting of :
  • the operation of drilling boreholes for exploring or exploiting oil and/or natural gas reservoirs generally includes the use of drilling rig equipment, which is an embodiment of the oil and gas recovery article as defined above.
  • FIG. 1 schematically depicts drilling rig equipment.
  • a drill pipe or string (#5) acts as a conduit for a drilling fluid; it is generally made of joints of hollow tubing connected together and stood in the derrick vertically.
  • a drill bit (#7) device is attached to the end of the drill string; this bit breaks apart the rock being drilled. It also contains jets through which the drilling fluid exits.
  • the rotary table (#6) or a top drive (not shown) rotates the drill string along with the attached tools and bit.
  • a mechanical section or draw-works section (#13) contains the spool, whose main function is to reel in/out the drill line to raise/lower the travelling block.
  • a mud pump (#1 1) is used to circulate drilling fluid through the system; the mud is suctioned from the mud tank or mud pit (#9) which provides a reserve store of drilling fluid.
  • the mud flows through the conduit #14 and through the drill pipe (#5) down to the bit (#7). Loaded with drill cuttings it flows upwards in the borehole and is extracted through the conduit (#12) back to the mud pit.
  • a shale shaker (#10) separates drill cuttings from the drilling fluid before it is pumped back down the borehole.
  • the equipment can further comprise devices installed at the wellhead to prevent fluids and gases from unintentionally escaping from the borehole (not shown).
  • Any of the components of the drilling rig as above detailed maybe an oil and gas recovery article, as above detailed, i.e. may comprise at least a part comprising the copolymer (PEDEK/PEEK) or any composition thereof, as above defined.
  • the operation b) of completing a well is the operation comprehensive of all the preparation or outfitting operations required for bringing in operations a geologic formation from the wellbore. This principally involves preparing the bottom of the hole to the required specifications, running in the production tubing and its associated down hole tools and controlling devices as well as perforating and stimulating as required. Sometimes, the process of running in and cementing the casing is also included. In all these single operations, articles comprising at least one part comprising the copolymer (PEDEK/PEEK) or any composition thereof, as above detailed, can be used.
  • KETASPIRE ® KT-820 P (KT-820P herein after) is an aromatic
  • PEEK polyetheretherketone
  • Cypek ® FC (PEKK FC, herein after) and HT (PEKK HT, herein after) are aromatic polyetherketoneketones (PEKK) available from Solvay S.A.
  • Arlon ® 2000 is an aromatic polyetherketone (PEK, herein after) available from Green, Tweede & Company, USA.
  • Lithium chloride was procured from Acros
  • RV Reduced viscosity
  • the glass transition temperature T g was determined by the mid-point
  • T m was determined as the peak temperature of the melting endotherm on the 2 nd heat scan in differential scanning calorimeter (DSC) according to ASTM D3418-03, E1356-03, E793-06, E794-06. Details of the procedure as used in this invention are as follows: a TA Instruments DSC Q20 was used with nitrogen as carrier gas (99.998% purity, 50 mL/min). Temperature and heat flow calibrations were done using indium. Sample size was 5 to 7 mg. The weight was recorded ⁇ 0.01 mg. The heat cycles were:
  • the melting temperature T m was determined as the peak temperature of the melting endotherm on the 2 nd heat scan.
  • the crystallinity level of the molded plaque was determined measuring the enthalpy of fusion, as determined on the 1 st heat scan of the DSC of the plaque and was taken as the area over a linear baseline drawn from above the T g to a temperature above end of the endotherm.
  • Claisen adapter with a thermocouple plunging in the reaction medium, and a Dean-Stark trap with a condenser and a dry ice trap were introduced 288.96 g of diphenyl sulfone, 28.718 g of hydroquinone, 48.415 g of 4,4' biphenol and 1 14.258 g of 4,4'-difluorobenzophenone.
  • the flask content was 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). [0158]
  • the reaction mixture was heated slowly to 150 °C.
  • a mixture of 57.044 g of Na2CO3 and 0.359 g of K2CO3 was added via a powder dispenser to the reaction mixture over 30 minutes.
  • the reaction mixture was heated to 320 °C at 1 °C/minute.
  • 13.616 g of 4,4'-difluorobenzophenone were added to the reaction mixture while keeping a nitrogen purge on the reactor.
  • 0.887 g of lithium chloride were added to the reaction mixture.
  • another 4.539 g of 4,4'-difluorobenzophenone were added to the reactor and the reaction mixture was kept at temperature for
  • 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 150 g of a white powder.
  • the structure of the obtained copolymer can be sketched, in terms of repeat units, as follows:
  • the reduced viscosity of the copolymer measured at 1 wt/vol% in 96% H2SO 4 at 25°C, as above detailed, was found to be 1.25 dL/g.
  • Claisen adapter with a thermocouple plunging in the reaction medium, and a Dean-Stark trap with a condenser and a dry ice trap were introduced 287.65 g of diphenyl sulfone, 35.123 g of hydroquinone, 39.477 g of 4,4' biphenol and 1 16.455 g of 4,4'-difluorobenzophenone.
  • the flask content was 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).
  • the reaction mixture was heated slowly to 150 °C.
  • a mixture of 58.141 g of Na2CO3 and 0.366 g of K2CO3 was added via a powder dispenser to the reaction mixture over 30 minutes.
  • the reaction mixture was heated to 320 °C at 1 °C/minute.
  • 13.878 g of 4,4'-difluorobenzophenone were added to the reaction mixture while keeping a nitrogen purge on the reactor.
  • 0.904 g of lithium chloride were added to the reaction mixture.
  • another 4.626 g of 4,4'-difluorobenzophenone were added to the reactor and the reaction mixture was kept at temperature for
  • 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 160 g of a white powder.
  • the structure of the obtained copolymer can be sketched, in terms of repeat units, as follows:
  • Comparative Example F preparation of PEDEK-PEEK copolymer 75/25 following example 3 of US4766197
  • the reduced viscosity of the copolymer measured at 1 wt/vol% in 96% H2SO 4 at 25°C, as above detailed, was found to be 3.13 dL/g.
  • Comparative example G preparation of PEDEK-PEEK copolymer 30/70
  • Claisen adapter with a thermocouple plunging in the reaction medium, and a Dean-Stark trap with a condenser and a dry ice trap were introduced 129.80 g of diphenyl sulfone, 18.942 g of hydroquinone, 13.686 g of 4,4' biphenol and 54.368 g of 4,4'-difluorobenzophenone.
  • the flask content was evacuated under vacuum and then filled with high purity nitrogen
  • reaction mixture (containing less than 10 ppm O2). The reaction mixture was then placed under a constant nitrogen purge (60 mL/min).
  • the reaction mixture was heated slowly to 150 °C.
  • a mixture of 26.876 g of Na 2 CO 3 and 0.1524 g of K2CO3 was added via a powder dispenser to the reaction mixture over 30 minutes.
  • the reaction mixture was heated to 320 °C at 1 °C/minute.
  • 6.415 g of 4,4'-difluorobenzophenone were added to the reaction mixture while keeping a nitrogen purge on the reactor.
  • 0.418 g of lithium chloride were added to the reaction mixture.
  • another 2.138 g of 4,4'-difluorobenzophenone were added to the reactor and the reaction mixture was kept at temperature for
  • 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 73 g of a white powder.
  • the structure if the obtained copolymer can be sketched, in terms of repeat units, as follows:
  • the melt viscosity measured by capillary rheolology at 410°C, 46 s -1 was found to be 0.16 kN-s/m 2 .
  • Example 1 preparation of PEDEK-PEEK copolymer 60/40
  • Claisen adapter with a thermocouple plunging in the reaction medium, and a Dean-Stark trap with a condenser and a dry ice trap were introduced 127.70 g of diphenyl sulfone, 9.894 g of hydroquinone, 25.103 g of 4,4' biphenol and 50.130 g of 4,4'-difluorobenzophenone.
  • the flask content was evacuated under vacuum and then filled with high purity nitrogen
  • reaction mixture (containing less than 10 ppm O2). The reaction mixture was then placed under a constant nitrogen purge (60 mL/min).
  • the reaction mixture was heated slowly to 150 °C.
  • a mixture of 25.097 g of Na2CO3 and 0.155 g of K2CO3 was added via a powder dispenser to the reaction mixture over 30 minutes.
  • the reaction mixture was heated to 320 °C at 1 °C/minute.
  • 5.892 g of 4,4'-difluorobenzophenone were added to the reaction mixture while keeping a nitrogen purge on the reactor.
  • 0.384 g of lithium chloride were added to the reaction mixture.
  • another 1.964 g of 4,4'-difluorobenzophenone were added to the reactor and the reaction mixture was kept at temperature for
  • 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 structure of the obtained copolymer can be sketched, in terms of repeat units, as follows:
  • the melt viscosity measured by capillary rheolology at 410°C, 46 s -1 was found to be 0.18 kN-s/m 2 .
  • Example 2 preparation of PEDEK-PEEK copolymer 60/40
  • Claisen adapter with a thermocouple plunging in the reaction medium, and a Dean-Stark trap with a condenser and a dry ice trap were introduced 127.95 g of diphenyl sulfone, 9.940 g of hydroquinone, 25.138 g of 4,4' biphenol and 50.273 g of 4,4'-difluorobenzophenone.
  • the flask content was evacuated under vacuum and then filled with high purity nitrogen
  • reaction mixture (containing less than 10 ppm O2). The reaction mixture was then placed under a constant nitrogen purge (60 mL/min).
  • the reaction mixture was heated slowly to 150 °C.
  • 150 °C a mixture of 24.325 g of Na 2 CO 3 and 0.1244 g of K2CO3 was added via a powder dispenser to the reaction mixture over 30 minutes.
  • the reaction mixture was heated to 320 °C at 1 °C/minute.
  • 5.892 g of 4,4'-difluorobenzophenone were added to the reaction mixture while keeping a nitrogen purge on the reactor.
  • 0.384 g of lithium chloride were added to the reaction mixture.
  • another 1.964 g of 4,4'-difluorobenzophenone were added to the reactor and the reaction mixture was kept at temperature for
  • 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 structure of the obtained copolymer can be sketched, in terms of repeat units, as follows:
  • melt viscosity measured by capillary rheolology, as above detailed, at 410 °C, 46 s- 1 was found to be 1.85 kN-s/m 2 .
  • Example 3 preparation of PEDEK-PEEK copolymer 60/40
  • Claisen adapter with a thermocouple plunging in the reaction medium, and a Dean-Stark trap with a condenser and a dry ice trap were introduced 145.87 g of diphenyl sulfone, 9.940 g of hydroquinone, 25.138 g of 4,4' biphenol and 49.831 g of 4,4'-difluorobenzophenone.
  • the flask content was evacuated under vacuum and then filled with high purity nitrogen
  • reaction mixture (containing less than 10 ppm O2). The reaction mixture was then placed under a constant nitrogen purge (60 mL/min).
  • the reaction mixture was heated slowly to 150 °C.
  • a mixture of 24.682 g of Na2CO3 and 0.1555 g of K2CO3 was added via a powder dispenser to the reaction mixture over 30 minutes.
  • the reaction mixture was heated to 340 °C at 1 °C/minute.
  • 5.892 g of 4,4'-difluorobenzophenone were added to the reaction mixture while keeping a nitrogen purge on the reactor.
  • 0.384 g of lithium chloride were added to the reaction mixture.
  • another 1.964 g of 4,4'-difluorobenzophenone were added to the reactor and the reaction mixture was kept at temperature for
  • 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 75 g of a white powder.
  • the structure of the obtained copolymer can be sketched, in terms of repeat units, as follows:
  • melt viscosity measured by capillary rheolology as above detailed, at 410 °C, 46 s- 1 , was found to be 1.89 kN-s/m 2 .
  • Example 4 preparation of PEDEK-PEEK copolymer 70/30
  • Claisen adapter with a thermocouple plunging in the reaction medium, and a Dean-Stark trap with a condenser and a dry ice trap were introduced 145.87 g of diphenyl sulfone, 7.290 g of hydroquinone, 28.676 g of 4,4' biphenol and 48.580 g of 4,4'-difluorobenzophenone.
  • the flask content was evacuated under vacuum and then filled with high purity nitrogen
  • reaction mixture (containing less than 10 ppm O2). The reaction mixture was then placed under a constant nitrogen purge (60 mL/min).
  • the reaction mixture was heated slowly to 150 °C.
  • a mixture of 24.134 g of Na2CO3 and 0.152 g of K2CO3 was added via a powder dispenser to the reaction mixture over 30 minutes.
  • the reaction mixture was heated to 340 °C at 1 °C/minute.
  • 5.761 g of 4,4'-difluorobenzophenone were added to the reaction mixture while keeping a nitrogen purge on the reactor.
  • 0.375 g of lithium chloride were added to the reaction mixture. 10 minutes later, another 1 .920 g of 4,4'-difluorobenzophenone were added to the reactor and the reaction mixture was kept at temperature for
  • 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 75 g of a white powder.
  • the structure of the obtained copolymer can be sketched, in terms of repeat units, as follows:
  • melt viscosity measured by capillary rheology, as above detailed, at 410 °C, 46 s- was found to be 2.04 kN-s/m 2 .
  • Example 5 preparation of PEDEK-PEEK copolymer 75/25
  • Claisen adapter with a thermocouple plunging in the reaction medium, and a Dean-Stark trap with a condenser and a dry ice trap were introduced 212.00 g of diphenyl sulfone, 4.226 g of hydroquinone, 21 .442 g of 4,4' biphenol and 33.853 g of 4,4'-difluorobenzophenone.
  • the flask content was evacuated under vacuum and then filled with high purity nitrogen
  • reaction mixture (containing less than 10 ppm O2). The reaction mixture was then placed under a constant nitrogen purge (60 mL/min).
  • the reaction mixture was heated slowly to 150 °C.
  • a mixture of 16.812 g of Na 2 CO 3 and 0.106 g of K2CO3 was added via a powder dispenser to the reaction mixture over 30 nninutes.
  • the reaction mixture was heated to 340 °C at 1 °C/minute.
  • 3.928 g of 4,4'-difluorobenzophenone were added to the reaction mixture while keeping a nitrogen purge on the reactor.
  • 0.651 g of lithium chloride were added to the reaction mixture.
  • another 1.309 g of 4,4'-difluorobenzophenone were added to the reactor and the reaction mixture was kept at temperature for
  • 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 53 g of a white powder.
  • the structure of the obtained copolymer can be sketched, in terms of repeat units, as follows:
  • the reduced viscosity of the material measured as above detailed was 3.50 dL/g.
  • the melt viscosity measured by capillary rheolology, as above detailed, at 410 °C, 46 s -1 was found to be 8.75 kN-s/m 2 .
  • Example 6 preparation of PEDEK-PEEK copolymer 80/20
  • Claisen adapter with a thermocouple plunging in the reaction medium, and a Dean-Stark trap with a condenser and a dry ice trap were introduced 156.09 g of diphenyl sulfone, 3.291 g of hydroquinone, 22.196 g of 4,4' biphenol and 32.902 g of 4,4'-difluorobenzophenone.
  • the flask content was evacuated under vacuum and then filled with high purity nitrogen
  • reaction mixture (containing less than 10 ppm O2). The reaction mixture was then placed under a constant nitrogen purge (60 mL/min).
  • the reaction mixture was heated slowly to 150 °C.
  • a mixture of 16.345 g of Na2CO3 and 0.103 g of K2CO3 was added via a powder dispenser to the reaction mixture over 30 minutes.
  • the reaction mixture was heated to 340 °C at 1 °C/minute.
  • 3.901 g of 4,4'-difluorobenzophenone were added to the reaction mixture while keeping a nitrogen purge on the reactor.
  • 0.254 g of lithium chloride were added to the reaction mixture. 10 minutes later, another 1.300 g of 4,4'-difluorobenzophenone were added to the reactor and the reaction mixture was kept at temperature for
  • 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 53 g of a white powder.
  • the structure of the obtained copolymer can be sketched, in terms of repeat units, as follows:
  • a 102 mm x 102 mm x 3.2 mm plaque was prepared from each of the
  • the plaques so obtained were annealed under air at 275°C for 3 hours.
  • PEDEK-PEEK was determined by DSC (one heat cycle, 20 °C /min up to 450 °C), assuming 130 J/g for 100% crystalline material.
  • Rectangular test samples (1.2 cm x 5.1 cm) were prepared from these molded plaques and were dried at 120°C under vacuum for 12 hours. Said test specimens were then analyzed by Dynamic Mechanical Analysis (DMTA) on a TA ARES G2 rheometer under torsion mode (10 rad/s; 0.05% strain) from 50 to 350°C at 5.0°C/min, in order to measure the storage modulus (G' in Pa) at different temperatures, ranging from 50 up to 310°C, as shown in the following Table and presented in the graph of Figure 2.
  • DMTA Dynamic Mechanical Analysis
  • copolymers (PEDEK-PEEK) of the invention present a better retention of properties at 165°C, as shown by higher percentage values of ratio G'(165°C)/G'(140°C) than PEEK and PEKK or copolymers PEEK-PEDEK with less than 60% moles of PEDEK- type units (Comp. ex D and E).
  • Compositions are endowed with mechanical performances retention with temperature similar to PEK or even superior to PEK (ex. 3-5).
  • the higher retention of properties at higher temperature is unexpected based on the T g alone (compare Ex. 0 vs Comp. D): while copolymer (PEDEK-PEEK) of Ex. 0, having
  • PEDEK/PEEK molar ratio of 60/40 has substantially similar T g to copolymer of comparative Ex. D, having PEDEK/PEEK molar ratio of 50/50, this latter copolymer has a much inferior retention of mechanical properties with temperature, showing a G'(165°C)/G'(140°C) percent ratio of only 15 %, which is significantly worse than the outstanding value of 41 % demonstrated by the copolymer of the present invention.
  • 3 Type V tensile bars of each polymer were exposed to a sweet salt water and hydrocarbon mixture in a 600 ml_ Inconel pressure vessel (154 ml_ heptanes + 44 ml_ cyclohexane + 22 ml_ toluene + 36 ml_ aq 15 wt% KCI solution) at 300 °C for 7 days under nitrogen. At the end of this exposure time, the specimens were wiped and the weight after and before exposure were compared. Tables below summarize the weight gain, appearance of the bars and mechanical properties measured before and after exposure.
  • EB is the elongation at break
  • TS y is the tensile strength at yield and TSb is the tensile strength at break
  • EY is the elongation at yield
  • TM is the tensile modulus.
  • copolymers with a ratio of PEDEK/PEEK units higher than 55/45 exhibit a better chemical resistance than the ones with a ratio of 50/50 or lower (Comp. Ex. D and E and G).
  • the copolymers according to the invention possessing low amount of organic chlorine and possessing ordered structure and narrow molecular weight distribution exhibits a higher flow than the copolymers described in US 4766197 and a better retention of properties after exposure to chemicals (see ex. 4 vs Comp. Ex. F).

Abstract

L'invention concerne certains copolymères (PEDEK/PEEK), comprenant une majorité de motifs récurrents de type « PEDEK », qui, grâce à la prédominance des motifs de type PEDEK, à leur homogénéité structurale et à leur régularité, et à l'absence de groupes terminaux chlorés, possèdent une structure moléculaire et un comportement de cristallisation appropriés pour leur permettre de présenter des propriétés mécaniques améliorées et une exceptionnelle résistance chimique, et qui sont utiles dans de nombreux secteurs, y compris notamment dans l'industrie pétrolière et gazière, et plus particulièrement pour la fabrication de pièces utilisées dans des systèmes d'extraction de pétrole et de gaz.
PCT/EP2017/077131 2016-11-11 2017-10-24 Copolymère de polyaryléthercétone WO2018086873A1 (fr)

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KR1020197016166A KR102592751B1 (ko) 2016-11-11 2017-10-24 폴리아릴에테르 케톤 공중합체
CN201780083170.2A CN110177823B (zh) 2016-11-11 2017-10-24 聚芳醚酮共聚物
US16/348,224 US11708457B2 (en) 2016-11-11 2017-10-24 Polyarylether ketone copolymer
EP17788222.2A EP3538589B1 (fr) 2016-11-11 2017-10-24 Copolymère de polyaryléther cétone
JP2019524371A JP7262387B2 (ja) 2016-11-11 2017-10-24 ポリアリールエーテルケトンコポリマー

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WO2020254096A1 (fr) * 2019-06-20 2020-12-24 Solvay Specialty Polymers Usa, Llc Copolymère de peek-peodek et procédé de fabrication du copolymère
EP3783047A1 (fr) * 2019-08-20 2021-02-24 Solvay Specialty Polymers USA, LLC. Copolymère peek-peodek et son procédé de fabrication
WO2021089746A1 (fr) 2019-11-08 2021-05-14 Solvay Specialty Polymers Usa, Llc Mélange de copolymère de polyaryléthercétone
WO2021089747A1 (fr) 2019-11-08 2021-05-14 Solvay Specialty Polymers Usa, Llc Mélange de copolymère de polyaryléthercétone
EP3854834A1 (fr) 2020-01-21 2021-07-28 Solvay Specialty Polymers USA, LLC. Mélange de copolymère de cétone polyaryléther
WO2021204718A1 (fr) 2020-04-06 2021-10-14 Solvay Specialty Polymers Usa, Llc Polymères de polyaryléthercétone
WO2022013520A1 (fr) * 2020-07-15 2022-01-20 Victrex Manufacturing Limited Copolymères, leur préparation et leur utilisation
WO2022096373A1 (fr) 2020-11-04 2022-05-12 Solvay Specialty Polymers Usa, Llc Articles microporeux et procédés de formation correspondants
GB2608794A (en) * 2021-02-26 2023-01-18 Victrex Mfg Ltd Copolymers and related methods, uses and components

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WO2020254096A1 (fr) * 2019-06-20 2020-12-24 Solvay Specialty Polymers Usa, Llc Copolymère de peek-peodek et procédé de fabrication du copolymère
CN113924329A (zh) * 2019-06-20 2022-01-11 索尔维特殊聚合物美国有限责任公司 PEEK-PEoDEK共聚物以及制造该共聚物的方法
EP3783047A1 (fr) * 2019-08-20 2021-02-24 Solvay Specialty Polymers USA, LLC. Copolymère peek-peodek et son procédé de fabrication
WO2021089746A1 (fr) 2019-11-08 2021-05-14 Solvay Specialty Polymers Usa, Llc Mélange de copolymère de polyaryléthercétone
WO2021089747A1 (fr) 2019-11-08 2021-05-14 Solvay Specialty Polymers Usa, Llc Mélange de copolymère de polyaryléthercétone
EP3854834A1 (fr) 2020-01-21 2021-07-28 Solvay Specialty Polymers USA, LLC. Mélange de copolymère de cétone polyaryléther
WO2021204718A1 (fr) 2020-04-06 2021-10-14 Solvay Specialty Polymers Usa, Llc Polymères de polyaryléthercétone
WO2022013520A1 (fr) * 2020-07-15 2022-01-20 Victrex Manufacturing Limited Copolymères, leur préparation et leur utilisation
WO2022096373A1 (fr) 2020-11-04 2022-05-12 Solvay Specialty Polymers Usa, Llc Articles microporeux et procédés de formation correspondants
GB2608794A (en) * 2021-02-26 2023-01-18 Victrex Mfg Ltd Copolymers and related methods, uses and components

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