Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
• • 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
• • 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
• • 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
  • C08G2650/56—Polyhydroxyethers, e.g. phenoxy resins
• • 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
  • C08K3/40—Glass
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
  • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
  • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• • 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

• This invention is directed to glass-reinforced aromatic polycondensation polymer compositions exhibiting enhanced strength properties, such as increased tensile and flexural strength, and elongation and impact properties.
• Aromatic polycondensation polymers provide high temperature service, high strength, and chemical resistance.
• Aromatic polycondensation polymers are polymers formed by the condensation reaction of two different compounds, wherein at least one of the compounds comprises at least one aromatic group, to form chains of alternating chemical groups.
• Sulfone polymers are amorphous aromatic polycondensation polymers that are capable of withstanding long-term exposure to elevated temperatures, which offer many attractive features including good strength, heat resistance, and tolerance to a host of chemical environments.
• Sulfone polymers are high performance thermoplastic engineering resins that contain the characteristic diarylsulfone linkage. Sulfone polymers are known for their high mechanical strength, thermal and oxidative resistance, resistance to hydrolysis, and to many acids, bases, and solvents.
• Commercially important sulfone polymers include polyarylethersulfones, such as polysulfone (PSU), polyphenylsulfone (PPSU), and polyethersulfone (PES).
• Polysulfone is a well-known high temperature amorphous engineering thermoplastic resin. It exhibits a high glass transition temperature of about 185 °C, high strength, stiffness and toughness over a temperature range from about -100 to 150 °C. Being completely amorphous, the polymer also exhibits transparency, which adds to its utility in many end uses. Polysulfone was commercially introduced in 1965 by the Union Carbide Corporation. It has the chemical structure:
• Polysulfone is commercially available as UDEL polysulfone from Solvay Advanced Polymers, LLC.
• PSU is probably the most commercially important member of a broad family of aromatic backbone polymers known as polyarylethers.
• polyarylethers aromatic backbone polymers
• These polymers can be produced by a variety of methods. For example U.S. Pat. Nos. 4,108,837 and 4,175,175 describe the preparation of polyarylethers and in particular polyarylethersulfones, which patents are incorporated herein by reference in their entireties.
• PPSU polyphenylsulfone
• Solvay Advanced Polymers, LLC under the trademark of RADEL ® R. It corresponds to the following formula:
• Polyethersulfone is another polyarylethersulfone that is commercially available from several sources, for example, from Solvay Advanced Polymers, LLC, as RADEL ® A, from BASF as ULTRASON ® E, and from Sumitomo Chemical as SUMIKAEXCEL ® . It has the following formula:
• the average number of repeat units, n, per polymer chain of the above polymers is generally greater than 30 and more typically greater than about 40 to ensure sufficiently high molecular weight for robust physical and mechanical integrity of the polymers when fabricated into structural components.
• U.S. Patent No. 4,798,855 disclose thermoplastic molding materials comprising polyarylethersulfone, polyamide, polymer having hydroxyl groups, rubber impact modifier, and reinforcing fillers.
• the aromatic polycondensation polymer compositions of U.S. Patent No. 4,798,855 require at least 2 % by weight of polyamide.
• U.S. Patent No. 4,960,841 disclose block copolymers composed of polyphenylene sulfide and polyphenylene sulf ⁇ de sulfone, reinforcing filler, and an optional additional polymer.
• the compositions of U.S. Patent No. 4,960,841 require a polyphenylene sulfide/polyphenylene sulfide sulfone block copolymer.
• a polymer composition comprising, as the sole polymer components, at least one aromatic polycondensation polymer comprising sulfone, ketone, imide, or carbonate groups, and at least one phenoxy polymer, and glass.
• a polymer composition comprising at least one aromatic polycondensation polymer comprising sulfone, ketone, imide, or carbonate groups, at least one phenoxy polymer, and glass.
• the polymer composition is substantially free of polyamide.
• melt fabricated, injection molded, blow molded, thermoformed, and extruded articles formed from a polymer composition comprising, as the sole polymer components, at least one aromatic polycondensation polymer comprising sulfone, ketone, imide, or carbonate groups, and at least one phenoxy polymer, and glass.
• the polymer composition is substantially free of polyamide.
• certain embodiments of the present invention that provide a method of increasing the strength properties of glass- reinforced polymer compositions comprising the step of blending at least one phenoxy polymer with at least one aromatic polycondensation polymer comprising sulfone, ketone, imide, or carbonate groups and glass.
• the phenoxy polymer and the aromatic polycondensation polymer are the sole polymer components of the composition.
• a method of forming a molded article comprising the use of a polymer composition comprising at least one aromatic polycondensation polymer comprising sulfone, ketone, imide, or carbonate groups, at least one phenoxy polymer, and glass.
• the at least one aromatic polycondensation polymer and the at least one phenoxy polymer are the sole polymers in the composition.
• a method of forming a molded article comprising the use of a polymer composition comprising at least one aromatic polycondensation polymer comprising sulfone, ketone, imide, or carbonate groups, at least one phenoxy polymer, and glass.
• the polymer composition is substantially free of polyamide.
• the instant invention addresses the longstanding limitation of insufficient adhesion between the polymer matrix and glass fibers in glass-reinforced amorphous polymer compositions.
• the present invention addresses this deficiency in strength of glass-reinforced polymer compositions. This has been accomplished by the incorporation of at least one phenoxy polymer as a minor component in glass-reinforced polymer compositions.
• the concentration of the at least one phenoxy polymer in the polymer composition is from about 1 weight % to about 30 weight % of the total composition weight.
• the concentration of the at least one phenoxy resin to impart a dramatic enhancement in tensile and flexural strength and in elongation and impact properties is from about 2 weight % to about 15 weight %.
• Mechanical properties are enhanced by the incorporation of from about 1 % to about 30 % by weight phenoxy polymer into a glass fiber- reinforced polyarylethersulfone formulation. In certain embodiments of the present invention, from about 2 % to about 15 % by weight phenoxy polymer is incorporated into polymer composition.
• compositions of the present invention are prepared by conventional reinforced polymer composition melt compounding techniques using an extruder, preferably a twin- screw extruder.
• the phenoxy polymer modified glass-reinforced formulations exhibit higher tensile strengths and elongations, higher flexural strengths and flexural strains to rupture, as well as higher impact properties compared with formulations that are not modified according to this invention.
• the melt viscosities of the formulations from this invention are also lower than those of unmodified materials, thereby allowing greater processing ease and wider latitude in fabrication and part design.
• the phenoxy polymers utilized are high molecular weight thermoplastic polymers that are produced from a bisphenol, such as bisphenol A, or other aromatic dihydroxy compound such as hydroquinone, and epichlorohydrin.
• the basic chemical structure of the phenoxy polymer is similar to that of epoxy polymers. They are, however, a separate and unique polymer class, differing from epoxies in several important characteristics:
• Phenoxy polymers are tough and ductile thermoplastics. Their average molecular weight is greater than conventional epoxies which cross link on polymerization.
• Phenoxy polymers do not have terminal highly reactive epoxy groups and are thermally stable materials with a long shelf life.
• the phenoxy polymers can be used without further chemical conversion. They require no catalysts, curing agents or hardeners to be useful products while epoxy polymers require catalysts, curing agents or hardeners to be useful.
• a phenoxy polymer used in certain embodiments of the present invention comprises the 4,4'-isopropylidenediphenol (bisphenol A) phenoxy repeat structure illustrated below:
• the terminal structure is completed with hydrogen atoms or suitable end capping groups.
• Bisphenol A phenoxy polymer is commercially available as PHENOXY PKFETM from InChem Corporation.
• phenoxy polymers based on bisphenols other than bisphenol A can be used.
• other bisphenol compounds that can be used to form phenoxy polymers included within the scope of this invention include: dihydroxydiphenyl, bis- (hydroxyphenyl)alkanes, bis-(hydroxyphenyl)cycloalkanes, bis-(hydroxyphenyl)sulfide, bis- (hydroxyphenyl)ketone, bis-(hydroxyphenyl)ether, bis-(hydroxyphenyl)sulfoxide, bis- (hydroxyphenyl)sulfone and ⁇ , ⁇ '-bis-(hydroxyphenyl)diisopropylbenzene, and derivatives thereof resulting from substitution of alkyl or halogen at the ring.
• suitable bisphenols include 4,4'-dihydroxydiphenylether, 4,4'-dihydroxyphenylsulfone, and 4,4'-dihydroxybenzophenone, 2,4-bis-(4-hydroxyphenyl)-2-methylbutane, 1 , 1 -bis-(4- hydroxyphenyl)cyclohexane, ⁇ , ⁇ '-bis-(4-hydroxyphenyl)-p-diisopropylbenzene, 2,2-bis-(3- methyl-4-hydroxyphenyl)propane, 2,2-bis-(3-chloro-4-hydroxyphenyl)propane, bis-(3,5- dimethyl-4-hydroxyphenyl)methane, 2,2-bis-(3,5-dimethyl-4-hydroxyphenyl)propane, bis- (3,5-dimethyl-4-hydroxyphenyl)sulfone, 2,4-bis-(3,5-dimethyl-4-hydroxyphenyl)-2- mercaptan, l
• Certain embodiments of the present invention comprise 4,4'-isopropylidenediphenol phenoxy polymer, 4,4'-dihydroxydiphenylether phenoxy polymer, 4,4'- dihydroxyphenylsulfone phenoxy polymer, and 4,4'-dihydroxybenzophenone phenoxy polymer.
• the aromatic polycondensation polymer can be a sulfone polymer, copolymer, or blend of sulfone polymers according to certain embodiments of this invention.
• the sulfone polymers used in certain embodiments of this invention are polyarylethersulfones, defined as a polyarylene compound in which arylene units exist irregularly or regularly together with ether and sulfone linkages.
• Examples of polyarylethersulfones within the scope of the present invention are polymers comprising the following structural formulae (1) to (16) where n is an integer of at least 10:
• the polyarylethersulfone may preferably comprise polysulfone, polyphenylsulfone, polyethersulfone, polyetherethersulfone, or copolymers and mixtures thereof.
• the polyarylethersulfone is polysulfone.
• the structural repeat units of polysulfone, polyphenylsulfone, polyethersulfone, and polyetherethersulfone are listed below: polysulfone (PSU)
• PEES polyetherethersulfone
• copolymers suitable for use in this invention include a polyethersulfone/polyetherethersulfone copolymer formed by the polycondensation of 4,4'- dihalodiphenylsulfone (typically 4,4'-dichlorodiphenylsulfone), 4,4'- dihydroxydiphenylsulfone and hydroquinone.
• 4,4'- dihalodiphenylsulfone typically 4,4'-dichlorodiphenylsulfone
• 4,4'- dihydroxydiphenylsulfone 4,4'- dihydroxydiphenylsulfone and hydroquinone.
• PEEK polyetheretherketone
• VI PEEK is commercially available as VICTREX ® from Victrex, LTD.
• Certain other embodiments of the present invention may include a polymer " composition comprising a polyetherimide or a polycarbonate.
• the polyetherimide may be obtained by reacting an aromatic bis(ether acid anhydride) with an organic diamine as described in U.S. Patents No. 4,960,841; 4,017,511; 3,887,588; and 3,833,544; which are incorporated herein by reference in their entireties.
• the polyetherimides include polymers produced from the polycondensation of 4,4'-isopropylidenediphenol dianhydride with meta- or para-phenylene diamine.
• polyetherimides include polycondensation products of 4,4'-isopropylidenediphenol dianhydride and aromatic diamines other than meta- or para- phenylene diamine.
• Polyetherimides are commercially available as ULTEM ® resins from General Electric.
• Certain embodiments of the present invention comprise polycarbonates based on the aforesaid bisphenols.
• the polycarbonate copolymers are copolymers of 4,4'-isopropylidenediphenol and another of the other aforesaid bisphenols.
• the polycarbonates are based only on 4,4'-isopropylidenediphenol or 2,2-bis-(3,5-dimethyl-4- hydroxyphenyl)propane.
• Polycarbonate is commercially available as LEXAN ® from General Electric.
• Polymer compositions according to certain embodiments of the present invention are substantially free of polyamide. Certain embodiments of the present invention do not contain polyamide. Certain embodiments of the present invention are substantially free of block copolymers comprising polyphenylene sulfide. Certain embodiments of the present do not contain block copolymers comprising polyphenylene sulfide blocks. In certain embodiments of the present invention an aromatic polycondensation polymer comprising sulfone, ketone, imide, or carbonate groups and a phenoxy polymer are the sole polymer components of the polymer composition.
• the concentration of glass in certain embodiments of the present invention ranges from about 1 weight % to about 80 weight % based on the total weight of the polymer composition. In certain embodiments of the present invention, the polymer composition comprises from about 10 weight % to about 50 weight % glass.
• the glass is a glass fiber.
• Glass fibers are commercially available in continuous filament, chopped, and milled forms. Any of these forms of glass fiber can be used in the practice of this invention.
• a suitable glass fiber for embodiments of this invention is CERTAINTEED 910 fiberglass, available from Vetrotex CertainTeed Corp.
• compositions of two polysulfone compositions with the phenoxy polymer additive (Examples 1 and 2) and a polysulfone composition without the phenoxy polymer additive (Control 1) are listed in Table 1.
• UDEL ® the polysulfone used in the compositions of the examples, controls, and comparative example in this disclosure has a melt flow of about 30 dg/min as measured per ASTM method D1238 at a temperature of 343 °C and using a weight of 2.16 kg.
• Polysulfone with other melt flow values can be used equally effectively in the practice of this invention. Polysulfone is available commercially from a number of sources in the melt flow range of from about 2 dg/min to about 40 dg/min as measured according the above mentioned method and conditions.
• compositions shown in Table 1 were prepared by dry blending the ingredients except for the chopped fiberglass then feeding these ingredients gravimetrically to the hopper of a ZSK-40 Werner-Pfleiderer twelve barrel twin-screw compounding extruder.
• the fiberglass was side-fed at barrel 7 using a gravimetric feeder and was metered at the appropriate rate to achieve the target fiberglass loading of 34.9 wt.%.
• Compounding was performed using barrel temperature settings of 330-345 °C, a die temperature of 345 °C and a screw speed of 300 RPM. Each of the compounds was produced at a total throughput rate of 225 lb/hr.
• Vacuum venting of the extruder was provided at barrel 6 to allow for removal of moisture and other trace volatiles evolved at the elevated compounding temperatures.
• the extruder was fitted with a four-hole die, each hole being 3 mm in diameter and the formed molten strands were cooled in a water bath then cut in a pelletizer to form good quality pellets.
• the pellets from the Control and each of Examples 1 and 2 were then dried overnight in a desiccated air oven operated at about 150 °C.
• the dried resin pellets of each formulation were then injection molded using a 125-ton Battenfeld injection molding machine using a melt temperature of about 360 °C and a mold temperature of about 125 °C to produce 0.125 inch-thick ASTM test parts.
• the ASTM test parts molded included Type 1 tensile bars, flexural/Izod HDT bars, and 4 inch x 4 inch plaques.
• the test methods employed in elucidating the physical and mechanical characteristics of all the various polymer compositions of this invention are listed in Table 2.
• Example 1 The improvements in impact properties are even more dramatic, with the impact properties of Examples 1 and 2 being two to three times that of Control 1 by the various measures impact resistance techniques employed. Furthermore, marked improvements in impact resistance are surprisingly realized with only 2.5% by weight of the phenoxy polymer additive, as shown by Example 1.
• the material modulus which is a measure of stiffness, is not affected by the addition of the phenoxy polymer, while the heat deflection temperatures are slightly reduced due to the relatively low glass transition temperature, of about 100 °C, for the bisphenol A phenoxy polymer.
• Example 3 and Comparative Example 1 The material modulus, which is a measure of stiffness, is not affected by the addition of the phenoxy polymer, while the heat deflection temperatures are slightly reduced due to the relatively low glass transition temperature, of about 100 °C, for the bisphenol A phenoxy polymer.
• Example 6 The mechanical properties were tested for the compositions of Example 3 and Comparative Example 1 according to the methods outlined in Table 2 and the results for the two compositions are summarized and compared in Table 6. As can be seen in Table 6, the composition with the phenoxy polymer has higher tensile strength, tensile elongation, flexural strength, flexural strain, notched Izod impact, and unnotched Izod impact. Table 6
• Example 7 A composition similar to that of Example 3 was prepared according to another embodiment of the present invention. This composition is shown in Table 7 and it was produced using procedures similar to those used to produce the compositions of Examples 1 and 2.
• Control 2 is a 30% glass reinforced UDEL ® polysulfone resin available commercially from Solvay Advanced Polymers as UDEL ® GF-130 NT and is included herein for reference as another illustration of the improvement in performance for compositions of this invention over the prior art.
• the mechanical properties of the compositions of Example 4 are shown in Table 8 and are contrasted against those for commercially available glass reinforced polysulfone prepared without the use of the phenoxy polymer. Table 7
• Carbon B ack Concentrate s po ysu one nto w c 13.7 % y weig t RAVEN ® 3500 carbon black has been precompounded.
• compositions of the present invention may optionally include reinforcing filler, pigments, additives, and like.
• Representative fibers which may serve as reinforcing media include asbestos, graphitic carbon fibers, amorphous carbon fibers, synthetic polymeric fibers, aluminum fibers, aluminum silicate fibers, oxide of metals such as aluminum fibers, titanium fibers, magnesium fibers, woUastonite, rock wool fibers, steel fibers, tungsten fibers, silicon carbide fibers, alumina fibers, boron fibers, etc.
• Representative filler and other materials include glass, calcium silicate, silica, clays, such as kaolin, talc, chalk, mica, potassium titanate, and other mineral fillers; pigments such as carbon black, titanium dioxide, zinc oxide, such as KADOX ® 911, available from Zinc Corporation of America, iron oxide, cadmium red, iron blue; and other additives such as alumina trihydrate, sodium aluminum carbonate, barium ferrite, etc.
• Suitable polymeric fibers include fibers formed from high temperature engineering polymers such as, for example, poly(benzothiazole), poly(benzimidazole), polyarylates, poly(benzoxazole), polyaryl ethers and the like, and may include mixtures comprising two or more such fibers.
• compositions of this invention may further include additional additives commonly employed in the art, such as thermal stabilizers, ultraviolet light stabilizers, oxidative stabilizers, plasticizers, lubricants, and mold release agents, such as polytetrafluoroethylene (PTFE) powder, and the like.
• PTFE powder is POLYMIST ® 5A, available from Solvay Solexis.
• a suitable carbon black is RAVEN ® 3500 carbon black, available from Columbian Chemicals Company.
• Other commercially available carbon blacks include SHAWINIGAN BLACK ® , available from Chevron Phillips Chemical Company; and BLACK PEARLS ® , MONARCH ® , and REGAL ® carbon blacks, all available from Cabot Corporation.
• the levels of such additives will be determined for the particular use envisioned, with up to about 50 weight %, based on the total weight of the composition, of such additional additives considered to be within the range of ordinary practice in the extrusion art.
• Additional embodiments of the present invention include melt fabricated, injection molded, extruded, thermoformed, or blow-molded articles made from any of the polymer compositions described herein.

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• 2003
  • 2003-08-26 DE DE60317221T patent/DE60317221T2/de not_active Expired - Lifetime
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  • 2003-08-26 AU AU2003260044A patent/AU2003260044A1/en not_active Abandoned
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