Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
  • C08K3/22—Oxides; Hydroxides of metals
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
  • C08K5/098—Metal salts of carboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
  • C08L81/06—Polysulfones; Polyethersulfones

Definitions

• sulfone polymers are such that a certain amount of extractable sulfate is irremediably present aside the polymers.
• aromatic high glass transition temperature polymers such as polysulfone, polyethersulfone, and polyphenylsulfone , suitable to be used in applications where extractable ionics must be minimized, like in sensitive electronics applications such as the semiconductor industry. It has been already attempted to develop additive packages for the purpose of lowering the level of extracted sulfate.
• aromatic high glass transition temperature sulfone polymer composition comprising :
• the combination of the oxide and the carboxylate advantageously provides an exceptional efficiency in sequestering the sulfate ion. It is preferred that these additives provide this benefit, and, in addition, they retain the transparent appearance of the aromatic sulfone polymer.
• polymer is intended to denote any material consisting essentially of recurring units, and having a molecular weight above 2000.
• aromatic sulfone polymer (P) are intended to denote any polymer, at least 5 % wt of the recurring units thereof comprise at least one group of formula 1 :
• the aromatic sulfone polymer (P) has a glass transition temperature of advantageously at least 150°C, preferably at least 160°C, more preferably at least 175°C.
• the aromatic sulfone polymer (P) comprises at least 5 % wt, preferably at least 20 % wt, more preferably at least 30 % wt, still more preferably at least 50 % wt, even more preferably at least 75 % wt of recurring units comprising at least one group of formula 1 here above. Most preferably, the aromatic sulfone polymer (P) contains no recurring unit other than recurring units comprising at least one group of formula 1 here above.
• the Applicant has found that a percentage of at least 5 wt % of recurring units comprising at least one group of formula 1 here above in the aromatic sulfone polymer (P) is enough to impart to the inventive composition the high temperature behavior sought for sensitive electronics applications.
• composition of the invention comprises advantageously less than 10 % by weight, based on the total weight of the composition, of aromatic polycarbonate (PC).
• PC aromatic polycarbonate
• aromatic polycarbonate PC
• PC aromatic polycarbonate
• Ar"' is a bivalent group comprising at least one aromatic ring, preferably comprising at least two aromatic rings.
• PC aromatic polycarbonates
• Ra and Rb are independently a hydrogen atom, a halogen or a C 1 -C 6 hydrocarbon group;
• - E is a divalent bridging group chosen among the following structures :
• Aromatic polycarbonates are notably commercially available under the trade names LEXAN ® (from GE), MAKROLON ® (from Bayer), CALIBER* 8 (from Dow), PANLITE ® (from Teijin), and IUPILON ® (from Mitsubishi).
• Aromatic polycarbonates can be prepared commercially by two different processes : Schotten-Baumann reaction of phosgene and an aromatic diol in an amine-catalyzed interfacial condensation reaction, or via base- catalyzed transesterification of a bisphenol with a monomeric carbonate such as diphenyl carbonate. - A -
• composition of the invention comprises preferably less than 8 %, more preferably less than 7 %, even more preferably less than 5 % by weight, based on the total weight of the composition, of aromatic polycarbonate (PC).
• PC aromatic polycarbonate
• the composition of the invention is free from aromatic polycarbonate (PC).
• composition of the invention comprises advantageously more than 90 %, preferably more than 92 %, more preferably more than 95 %, still more preferably more than 97.5 % by weight of aromatic sulfone polymer (P), based on the total weight of the composition.
• composition comprises more than 90 % by weight of aromatic sulfone polymer (P), based on the total weight of the composition, then it possesses the outstanding mechanical properties and thermal resistance appreciated in sensitive electronics applications, such as the semiconductor industry.
• P aromatic sulfone polymer
• At least 5 % wt of the recurring units of aromatic sulfone polymer (P) are recurring units (Rl), in their imide form (Rl-A) and/or amic acid forms [(Rl-B) and (Rl-C)] :
• linking groups being in ortho, meta or para position and R' being a hydrogen atom or an alkyl radical comprising from 1 to 6 carbon
• R being an aliphatic divalent group of up to 6 carbon atoms, such as methylene, ethylene, isopropylene and the like, and mixtures thereof.
• Aromatic sulfone polymer (P) according to the first preferred embodiment of the invention comprises at least 5 % wt, preferably at least 20 % wt, more preferably at least 30 % wt, still more preferably at least 50 % wt, even more preferably at least 75 % wt of recurring units (Rl). Most preferably, it contains no recurring unit other than recurring units (Rl).
• At least 5 % wt of the recurring units of aromatic sulfone polymer (P) are recurring units (R2) and/or recurring units (R3):
• - Q is a group chosen among the following structures
• n integer from 1 to 6, or an aliphatic divalent group, linear or branched, of up to 6 carbon atoms; and mixtures thereof;
• - Ar is a group chosen among the following structures :
• n integer from 1 to 6, or an aliphatic divalent group, linear or branched, of up to 6 carbon atoms; and mixtures thereof;
• - Ar' is a group chosen among the following structures :
• wi ,t,h n i .n t teger ftom 1 to 6, or an aliphatic divalent group, linear or branched, of up to 6 carbon atoms; and mixtures thereof.
• Recurring units (R3) are preferably chosen from
• Aromatic sulfone polymer (P) according to the second preferred embodiment of the invention comprises at least 5 % wt, preferably at least 20 % wt, more preferably at least 30 % wt, still more preferably at least 50 % wt, even more preferably at least 75 % wt of recurring units (R2) and/or (R3). Most preferably, it contains no recurring unit other than recurring units (R2) and/or (R3).
• Polyphenylsulfone is notably available as RADEL® R PPSF from Solvay Advanced Polymers, L.L.C..
• Polysulfone is notably available as UDEL® PSF from Solvay Advanced Polymers, L.L.C..
• Polyethersulfone is notably available as RADEL® A PES from Solvay Advanced Polymers, L.L.C..
• aromatic sulfone polymer (P) is chosen among the group consisting of polybiphenyldisulfone, polysulfone, polyphenylsulfone, polyethersulfone, copolymers and mixtures thereof.
• the oxide of a metal is an oxide of an alkaline-earth metal or of a group 12 transition metal.
• group 12 transition metal we intend designate the group of metals consisting of Zn, Cd, Hg, Uub.
• the oxide is chosen among the group consisting of CaO, MgO, ZnO and mixtures thereof. Still more preferably, the oxide is ZnO.
• the carboxylate of a metal is a carboxylate of an alkaline-earth metal or of a group 12 transition metal.
• the carboxylate is chosen among the group consisting of carboxylates of Ca, Mg, Zn and mixtures thereof. Still more preferably, the carboxylate is a Zn carboxylate.
• the carboxylate is chosen among caprates (C 10 ), laurates (C 12 ), myristates (C 14 ), palmitates (C 16 ), stearates (C 18 ), arachidates (C 20 ), behenates (C 22 ), palmitoleates (C 16 ), oleates (C 18 ), gadoleates (C 20 ), ricinoleates (C 18 ), linoleates (C 18 ), linolenates (C 18 ), and mixtures thereof. More preferably, the carboxylate is a stearate.
• the aromatic high glass transition temperature polymer composition advantageously comprises at least 0.001 % wt, preferably at least 0.005 % wt, more preferably at least 0.01 % wt of the oxide, based on the total weight of the composition.
• the aromatic high glass transition temperature polymer composition advantageously comprises at most 0.7 % wt, preferably at most 0.6 % wt, more preferably at most 0.5 % wt, even more preferably at most 0.3 % wt, most preferably at most 0.2 % wt of the oxide, based on the total weight of the composition.
• the aromatic high glass transition temperature polymer composition advantageously comprises at least 0.005 % wt, preferably at least 0.01 % wt, more preferably at least 0.05 % wt of the carboxylate, based on the total weight of the composition.
• the aromatic high glass transition temperature polymer composition advantageously comprises at most 1.00 % wt, preferably at most 0.75 % wt, more preferably at most 0.50 % wt of the carboxylate, based on the total weight of the composition.
• composition comprised from 0.05 to 0.35 % wt, based on the total weight of the composition, of the carboxylate.
• the weight ratio between the oxide and the carboxylate in the composition of the invention is advantageously at most 1 wt/wt, preferably at most 0.75 wt/wt, more preferably at most 0.5 wt/wt.
• the weight ratio between the oxide and the carboxylate in the composition of the invention is advantageously at least 0.05 wt/wt, preferably at least 0.075 wt/wt, more preferably at least 0.10 wt/wt.
• the high glass transition temperature sulfone polymer composition of the invention can further comprise fillers, lubricating agents, heat stabilizer, anti-static agents, extenders, reinforcing agents, organic and/or inorganic pigments like TiO 2 , carbon black, antioxidants, flame retardants, smoke-suppressing agents.
• the composition of the invention advantageously comprises at least one filler chosen from reinforcing fillers, structural fibers and mixtures thereof.
• Structural fibers may include glass fiber, carbon or graphite fibers, and fibers formed of silicon carbide, alumina, titania, boron and the like, and may include mixtures comprising two or more such fibers.
• Reinforcing fillers which can also be used in the composition of the invention include notably pigments, flake, spherical and fibrous particulate filler reinforcements and nucleating agents such as talc, mica, titanium dioxide, potassium titanate, silica, kaolin, chalk, alumina, mineral fillers, and the like.
• the reinforcing fillers and structural fibers can be used alone or in any combination.
• Another aspect of the present invention concerns a process for manufacturing the high glass transition temperature sulfone polymer composition as above described, which comprises mixing :
• the process of the invention comprises mixing by dry blending and/or melt compounding polymer (P), the oxide and the carboxylate.
• polymer (P), the oxide and the carboxylate are mixed by melt compounding.
• polymer (P), the oxide and the carboxylate are melt compounded in continuous or batch devices. Such devices are well-known to those skilled in the art.
• polymer (P), the oxide and the carboxylate and optionally other ingredients are advantageously fed in powder or granular form in an extruder and the composition is extruded into strands and the strands are chopped into pellets.
• fillers may be added to the composition during the compounding step.
• lubricating agents heat stabilizer, anti-static agents, extenders, reinforcing agents, organic and/or inorganic pigments like TiO 2 , carbon black, flame-retardants, smoke-suppressing agents may be added to the composition during the compounding step.
• polymer (P), the oxide and the carboxylate are melt compounded in a twin-screw extruder.
• composition can be further processed following standard methods for injection molding, extrusion, thermoforming, machining, and blow molding. Solution-based processing for coatings and membranes is also possible. Finished articles comprising the composition as above described can undergo standard post-iabrication operations such as ultrasonic welding, adhesive bonding, and laser marking as well as heat staking, threading, and machining.
• Another object of the invention is an article comprising the polymer composition as above described.
• the article is an injection molded article, an extrusion molded article, a shaped article, a coated article or a casted article.
• it is an injection molded article.
• the articles according to the invention can be fabricated by processing the composition as above described following standard methods.
• Zinc Oxide, Zn stearate and Mg stearate were mixed with the RADEL® R 5600 polyphenylsulfone pellets and melt compounded using a 25 mm diameter twin screw double vented Berstorff extruder having an L/D ratio of 33/1. Details of quantities used in the examples are reported in Table 1. Ionics extraction and analytical determinations
• Dionex DX500 Chromatography System Dionex GP50 Standard bore Gradient Pump; Dionex ASRS Ultra 4 mm Suppressor; Dionex CD20 Conductivity Detector; Dionex ASl IA Column, 4 mm; Dionex AGl IA Guard Column, 4 mm; Dionex AS40 Autosampler, Inert Peek Flow Path.
• the eluent used was 18 m ⁇ water, 0.2-0.4 mM KOH by provided by the EG40 Eluent Generator.
• the ion chromatography was quantified using a minimum of 5-points linear calibration curve for each ion. Results are joined in Table 1. Table 1
• UDEL® P3703 polysulfone commercially available from Solvay Advanced Polymers, L.L.C., is a polysulfone obtained from the polycondensation of a 4,4'-dihalodiphenylsulfone and bisphenol A. Compounding :
• Zinc Oxide and Zinc stearate were mixed with the UDEL® P3703 polysulfone pellets and melt compounded using a 25 mm diameter twin screw double vented Berstorff extruder having an L/D ratio of 33/1. Details of quantities used in the examples are reported in Table 2. Ionics extraction and analytical determinations

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• Compositions Of Macromolecular Compounds (AREA)
• Manufacture Of Macromolecular Shaped Articles (AREA)

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• 2005
  • 2005-02-24 DE DE602005014334T patent/DE602005014334D1/de not_active Expired - Lifetime
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  • 2005-02-24 EP EP05101408A patent/EP1695994B1/en not_active Revoked
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