WO1996006135A1 - Compositions de melanges de polymeres de carbonate charges a resistance accrue aux chocs - Google Patents

Compositions de melanges de polymeres de carbonate charges a resistance accrue aux chocs Download PDF

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Publication number
WO1996006135A1
WO1996006135A1 PCT/US1995/009907 US9509907W WO9606135A1 WO 1996006135 A1 WO1996006135 A1 WO 1996006135A1 US 9509907 W US9509907 W US 9509907W WO 9606135 A1 WO9606135 A1 WO 9606135A1
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weight
composition according
percent
wax
components
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PCT/US1995/009907
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English (en)
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Leo R. Novak
Robert C. Miller
Kevin L. Nichols
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The Dow Chemical Company
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Publication of WO1996006135A1 publication Critical patent/WO1996006135A1/fr

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    • 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
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/12—Copolymers of styrene with unsaturated nitriles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
    • C08L91/06—Waxes

Definitions

  • the present invention relates to filled polymer blend compositions comprising a carbonate polymer, a monovinylidene aromatic copolymer and an inorganic filler. It has unexpectedly been found that certain waxy additives provide these blends with improved impact resistance, particularly at lower temperatures. More particularly, the present invention relates to such a blend having improved combinations of linear thermal expansion, impact resistance, modulus (stiffness), melt flow (melt processability) and heat resistance. These compositions are particularly useful in the preparation of molded objects, particularly parts having large surfaces prepared by injection molding techniques and requiring predictable finished dimensions and smooth, surface finishes. Such properties are particularly desired for exterior automotive body panels.
  • CLTE coefficient of linear thermal expansion
  • the CLTE value reflectsthe tendency of a material to undergo dimensional changes due to thermal fluctuations, especially when in the form of larger molded or extruded articles. For example, if a door or fender component of an automobile expands or contracts excessively in extremely hot or cold conditions it would normally result in buckling or misfit in the assembled finished product and/or stress fracturing at the point of fastening. Otherwise, there must be sufficient compensation in the product construction or fastening device for the expansion and contraction of the sheet or part.
  • JP 52-63,954 (1977) there are disclosed blends composed of 20 to 45 weight percent of an ABS resin, 45 to 20 weight percent of a polycarbonate resin and from 5 to 30 weight percent talc.
  • JP 138,550 (1987) polybutylene terephthalate is added to polycarbonate/inorganic filler blends to attempt to improve toughness.
  • Patent 4,763, 133 discloses, as a layer in multilayer laminate antenna structure, blends of certain thermoplastic resins with inorganic fillers, including glass fiber, talc or clay. The filler is added to lower the coefficient of linear thermal expansion while raising the flexural modulus. Carbonate polymer is listed among the numerous thermoplastic resins alleged to be suitable for use in this layer of the laminate.
  • U.S. Patent 3,424,703 discloses that from 0.025 to 0.5 weight percent silica or talc fillers with a particle size up to 10 micrometers can be incorporated into aromatic polycarbonates to provide thin, relatively haze-free films with a low coefficient of linear thermal expansion.
  • silica or talc fillers with a particle size up to 10 micrometers can be incorporated into aromatic polycarbonates to provide thin, relatively haze-free films with a low coefficient of linear thermal expansion.
  • polymer blend compositions comprising (A) carbonate polymer; (B) monovinylidene aromatic copolymer; (C) a wax which improves the low temperature toughness of the blend; (D) an inorganic filler; and optionally, (E) a rubber impact modifier.
  • the present invention is a filled polymer blend composition
  • a filled polymer blend composition comprising (A) carbonate polymer in an amount of from 50 to 95 percent by weight based on weight of components (A), (B) and (E); (B) monovinylidene aromatic copolymer in an amount of from 5 to 50 percent by weight based on weight of components (A) and (B) and (E); (C) a wax in an amount of from 0.1 to 5 percent by weight based on weight of components (A), (B), (C), (D) and (E), which wax improves the low temperature toughness of the filled blend; (D) an inorganic filler in an amount of from 1 to 17 percent by weight based on weight of components (A), (B), (C), (D) and (E), which inorganic filler preferably has an average diameter to thickness ratio (D/T) of from 4 to 24; and optionally, (E) a homopolymer or copolymer of butadiene in amounts up to 20 percent by weight based on
  • the present invention is also an improved, large molded article having a surface area greater than 400 square inches, which article is prepared from a polymer blend according to the invention described above.
  • the article has a smooth surface and a coefficient of linear thermal expansion (CLTE) per ASTM D-696 equal to or less than 3.7 x 10- 5 /°F (6.7 X 10" 5 /°C).
  • an article prepared from the blend will have a dart impact strength at -20°F (-29°C) per ASTM D-3029 of at least 200 inch pounds (in/lbs) (22.6 joules), a heat distortion temperature under load (DTUL) per ASTM D-648-82 at 66 psi (455 kPa) of at least 240°F (1 16°C), and a flexural modulus of at least 350,000 pounds per square inch (psi) (2400 MPa).
  • the present invention is a molded automotive exterior body panel prepared from a polymer blend according to the invention described above.
  • a key aspect in the preparation of the improved blends according to the present invention is the use of an appropriate wax additive. While the theory is not completely understood, it is believed that certain wax additives have a desirable interaction with the filler particles and facilitate their dispersion and incorporation into the blend of carbonate and monovinylidene aromatic polymers. The most noticeable effect of the wax is the unexpected improvement in the low temperature toughness of articles molded from the blends while maintaining a desirably low coefficient of linear thermal expansion and good resistance to heat distortion under load. It was also found that the wax additive unexpectedly resulted in less notch sensitivity in the room temperature impact resistance.
  • the preferred waxes for use according to the present invention are those which result in an improvement in the low temperature toughness of a filled carbonate/monovinylidene aromatic polymer blend as measured by the Dart Impact Resistance test method (at -20°F) by at least 20 percent as compared to the blend not containing the wax while the CLTE of the blend is maintained within 10 percent of the CLTE measured without the wax when the filled blend contains 14 weight percent of the filler and 2 weight percent of the wax.
  • Waxes suitable for use according to this invention are known organic compounds or mixtures of such compounds which are solids at room temperature but which have a relatively low melting point as compared to most thermoplastic molding resins.
  • a non-basic wax is desired since basic waxes, such as the known amide-containing (bis)stearamide waxes, exhibit reactivity with the carbonate polymer and cause degradation of the carbonate polymer molecular weight.
  • suitable waxes include and can be selected from the group consisting of the ester waxes and acid waxes; preferably the Montan derivative ester waxes and the acid waxes; the polyethylene (PE) waxes, both polar and non-polar; and mixtures of two or more of these waxes.
  • the Montan ester waxes and the polyethylene waxes are especially preferred. Avoiding the amide-containing (bis)stearamide waxes is essential to optimized properties of the resin blend compositions.
  • the suitable waxes have molecular weights of at least 100, preferably at least 200 and more preferably at least 400.
  • the main types of suitable waxes (montan ester and acid waxes) generally have molecular weights up to 5,000, preferably up to 2,000, more preferably up to 1 ,000.
  • the typical molecular weights are generally up to 10,000, preferably up to 9,000.
  • ester-type waxes and in particular the Montan ester-type waxes, are known in the literature and are produced by the esterif ication of Montanic acid or extraction from
  • Montanic ester-type waxes are commercially available products such as, for example, Hoechst-Wachs E, commercially available from Hoechst-Celanese. These waxes preferably have a molecular weight in the range of 500 to 1000. These waxes typically have an acid number of at least 6, preferably at least 10 and most preferably at least 15, the acid number units being milligrams KOH required to neutralize one gram wax (mg KOH/g) by titration. Desirably, the
  • ester waxes 15 acid number is less than or equal to 30, preferably 25 and most preferably 20 mg KOH/g wax.
  • the ester waxes also are characterized by their saponif ication number, with saponification numbers for desirable ester waxes being at least 80, preferably at least 100, most preferably at least 130 and typically not more than 200, preferably not more than 180 and more preferably not more than 160.
  • the polyethylene waxes are known in the literature and are commercially available, for example from Hoechst in various grades identified under the tradename Hoechst- Wachs PE 190 and PED 191.
  • the polyethylene waxes are produced by polymerization or oligomerization of olefin monomer or monomer mixture up to molecular weights of 10,000, preferably up to 9,000.
  • Polar versions are available and have acid values in the range of 10 to
  • Noa-polar polyethylene waxes are commercially available products such as, Hoechst Wachs PE 190 while polar polyethylene waxes are commercially available as Hoechst Wachs PED 191 , both from Hoechst-Celanese.
  • the Montan acid-type waxes are known in the literature and are commercially.
  • waxes available, for example, from Hoechst-Celanese as Hoechst Wachs S. These waxes are typically obtained by extraction from lignite. These waxes preferably have a molecular weight in the range of from 400 to 700, and an acid number of at least 100, preferably at least 130 and less than or equal to 180, preferably less than or equal to 150.
  • the suitable wax (including a mixture of waxes), is generally added in amounts
  • the wax is added in amounts of at least 0.1 weight percent wax, based on weights of wax, filler, carbonate and monovinylidene aromatic polymers, and optional impact modifier, more preferably at least 0.5, and most preferably at least 1 weight percent.
  • the carbonate polymer resins usefully employed according to the present invention are those previously known and described in the prior art.
  • such resins include the carbonate resins obtained by the interracial, melt or solution polymerization of a dihydroxy monomer compound, preferably a dihydroxyaryl compound, especially a bis- dihydroxyarylalkane with a polycarbonate precursor such as phosgene, a bischloroformate or a dicarbonate such as diphenyl carbonate or dimethyl carbonate.
  • a dihydroxy monomer compound preferably a dihydroxyaryl compound, especially a bis- dihydroxyarylalkane with a polycarbonate precursor such as phosgene, a bischloroformate or a dicarbonate such as diphenyl carbonate or dimethyl carbonate.
  • the carbonate polymer is an aromatic carbonate polymer, more preferably it is prepared from an aromatic diol such as bisphenol A, tetrabromo-bisphenol A, tetramethyl bisphenol A, 1 ,1-bis(4- hydroxyphenyl)-1 phenylethane, bishydroxyphenylfluorene or mixtures of two or more of these.
  • aromatic diol such as bisphenol A, tetrabromo-bisphenol A, tetramethyl bisphenol A, 1 ,1-bis(4- hydroxyphenyl)-1 phenylethane, bishydroxyphenylfluorene or mixtures of two or more of these.
  • carbonate polymers suitable for use according to the claimed invention could be prepared in the presence of an amount of a diacid or diacid chloride to produce the known poly(ester-carbonates).
  • carbonate polymers are employed in the blends according to the invention in amounts sufficient to provide the desired levels of toughness and resistance to heat.
  • the carbonate polymer is employed in an amount of at least 50, preferably at least 55 and more preferably at least 60 percent by weight based on weight of carbonate and monovinylidene aromatic polymers.
  • the carbonate polymer is employed in an amount of up to and including 95, preferably up to and including 90 and more preferably up to and including 70 percent by weight based on weight carbonate and monovinylidene aromatic polymers.
  • the carbonate polymers suitable for use in the present invention include a broad range of the known carbonate polymers in terms of molecular weight or melt flow rate (which is an indirect indication of resin molecular weight).
  • the carbonate polymer molecular weight should provide a resin melt flow rate (MFR) of at least 3 grams per 10 minutes (as measured by ASTM 1238-35, condition O), preferably at least 3.5, more preferably at least 5, more preferably at least 7, and most preferably at least 10.
  • the carbonate polymer molecular weight should be high enough to provide a resin melt flow rate (MFR) of less than or equal to 80 grams per 10 minutes, preferably 40, more preferably 20, and most preferably 12.
  • MFR resin melt flow rate
  • the monovinylidene aromatic copolymers suitably employed according to the present invention include copolymers of one or more monovinylidene aromatic monomer, such as styrene, alpha methyl styrene and/or ring substituted styrenes, with one or more additional unsatu rated, copolymerizable monomers, particularly the ethylenically unsaturated nitrile monomers (such as acrylonitrile, methacrylonitrile and/or fumaronitrile), maleic acid derivatives such as maleic anhydride, alkyl (meth)acrylates such as methylmethacrylate, N- substituted maleimides such as N-phenylmaleimide or other polymerizable comonomers.
  • monovinylidene aromatic monomer such as styrene, alpha methyl styrene and/or ring substituted styrenes
  • additional unsatu rated, copolymerizable monomers
  • Such monovinylidene aromatic copolymers typically contain at least 40, preferably at least 50, more preferably at least 70 weight percent monovinylidene aromatic monomer and up to 90 preferably up to 85, weight percent monovinylidene aromatic monomer based on weight monovinylidene aromatic copolymer. Highly preferred copolymers contain from 70 to 85 percent styrene monomer and 15 to 30 percent acrylonitrile monomer.
  • the suitable monovinylidene aromatic monomers include the lower alky l-substituted (from 1 to 4 carbon atoms) and halogen-substituted styrenes, where the substitution can be on the aromatic ring or the vinyl moiety.
  • Monovinylidene aromatic copolymers with one or more additional unsaturated, copolymerizable monomer are preferred versus homopolymers of the monovinylidene aromatic monomers due to their better compatibility with the carbonate polymer.
  • the monovinylidene aromatic copolymer is employed in amounts to improve the processability of the blend composition and maintain the desired physical properties.
  • the monovinylidene aromatic copolymer is typically incorporated into the blend of the present invention in amounts of at least 5 weight percent, preferably at least 10 weight percent and more preferably at least 25 weight percent, said weight percentage being based on weight of carbonate polymer and monovinylidene aromatic copolymer components.
  • the monovinylidene aromatic copolymer is typically incorporated into the blend of the present invention in amounts of less than or equal to 50 weight percent, preferably less than or equal to 45 weight percent, and most preferably less than or equal to 40 weight percent based on total weight of the carbonate polymer and monovinylidene aromatic copolymer components.
  • optional rubber impact modifier materials suitable for use in compositions according to the invention can be incorporated in several different fashions.
  • the optional rubber materials are commonly incorporated in the blends according to the invention in order to improve the toughness and impact resistance.
  • Grafting or other compatibilization techniques are desirably used to improve compatibility and miscibiiity with the carbonate and/or monovinylidene aromatic polymer components.
  • a rubber-modified monovinylidene aromatic copolymer can be prepared and used to provide both the monovinylidene aromatic copolymer and rubber components.
  • a separately prepared grafted impact modifier having a higher rubber content and little or no free or ung rafted polymer can be incorporated as a separate component.
  • the optional rubber materials have elastic properties and have glass transition temperatures (Tg's) less than 0°C, generally less than -10°C, preferably less than -20°C and more preferably less than -30°C.
  • Tg's glass transition temperatures
  • Suitable rubbers include the well known homopolymers and copolymers of conjugated dienes, particularly butadiene; as well as other rubbery
  • polymers such as olefin polymers, particularly copolymers of ethylene, propylene and optionally a nonconjugated diene.
  • olefin polymers particularly copolymers of ethylene, propylene and optionally a nonconjugated diene.
  • mixtures of the foregoing rubbery polymers may be employed if desired.
  • Preferred rubbers are homopolymers of butadiene and copolymers thereof with up to 30 percent by weight styrene.
  • Such copolymers may be random or block copolymers and in addition may be hydrogenated to remove residual unsaturation.
  • the rubbers are optionally grafted with an amount of a graft polymer, such as a monovinylidene aromatic copolymer, including polymers of styrene and either acrylonitrile or methyl methacrylate, that compatibilizes the rubber component with the carbonate and/or monovinylidene aromatic polymers.
  • a graft polymer such as a monovinylidene aromatic copolymer, including polymers of styrene and either acrylonitrile or methyl methacrylate, that compatibilizes the rubber component with the carbonate and/or monovinylidene aromatic polymers.
  • graft copolymers are prepared by a graft generating process such as by a bulk or solution polymerization or an
  • ABS-type resins typically have a glass transition temperature (Tg) of greater
  • ABS-type resins typically comprise at least 3 percent by weight rubber, preferably at least 5 percent by weight rubber, more preferably at least 8 percent by weight rubber, most preferably at least 10 percent by weight rubber, based on the weight of rubber
  • the ABS-type rubber modified monovinylidene aromatic copolymers can comprise up to 50 percent by weight rubber, preferably up to 40 percent by weight rubber, more preferably up to 25 percent by weight rubber and most preferably up to
  • ABS-type resins the monovinylidene aromatic copolymers are prepared simultaneously with the grafting of the rubber component to prepare the optional grafted rubber impact modifier.
  • Preferred ABS-type rubber modified monovinylidene aromatic copolymer resins are those prepared by the solution or bulk polymerization of styrene and acrylonitrile comonomers in the presence of butadiene polymer rubber and an optional solvent or diluent.
  • ABS resins may be prepared by mixing together previously prepared components comprising the monovinylidene aromatic copolymer and grafted rubbery polymer.
  • Suitable monovinylidene aromatic copolymer grafted rubber components include the rubber modified polymers of styrene or ⁇ -methylstyrene with other polymerizable monomers including methylmethacrylate, methacrylonitrile, fumaronitrile and/or an N-aryl- maleimide such as N-phenylmaleimide.
  • Some of the preferred rubber-containing materials of this type are the known MBS-type core/shell grafted copolymers having a Tg less than 0°C and a rubber content greater than 40 percent, preferably greater than 50 percent.
  • styrene and methylmethacrylate and/or equivalent monomers producing a small amount of a mostly grafted monovinylidene aromatic polymer component
  • a conjugated diene polymer rubber core preferably a butadiene homo- or co-polymer.
  • the grafting monomers may be added to the reaction mixture simultaneously or in sequence, and, when added in sequence, layers, shells or wart-like appendages can be built up around the substrate latex, or core.
  • the monomers can be added in various ratios to each other.
  • an optional rubber component to use the optional grafted rubber in amounts to provide at least 0.5 percent by weight rubber based on weight monovinylidene aromatic, carbonate and rubber polymer components, preferably at least 1 percent and more preferably at least 2 percent. It has correspondingly been found desirable to maintain levels of the optional rubber less than or equal to 20 weight percent rubber, preferably less than or equal to 15, more preferably less than or equal to 10 weight percent based on weight monovinylidene aromatic, carbonate and rubber polymer components.
  • the blends according to the present invention can incorporate talc, clay or a similar type of filler which provides the desired levels of physical and other property requirements such as toughness, modulus (stiffness) and resistance to linear thermal expansion.
  • talc a similar type of filler which provides the desired levels of physical and other property requirements such as toughness, modulus (stiffness) and resistance to linear thermal expansion.
  • talc and clay filler materials Several varieties of talc and clay filler materials have been found to be especially suitable.
  • compositions incorporating fillers having an average diameter/thickness ratio as measured according to the below-described technique of at least 4, preferably at least 6, more preferably at least 7.
  • D/T ratio it has been found desirable to have a value up to and including 30, preferably up to and including 24, preferably up to and including 18, more preferably up to and including 13, and most preferably up to and including 10.
  • the diameter (or longest dimension) of the fillers as well as their thickness (shortest dimension of the 2 dimensions measurable) can be measured by preparing a filler modified polymeric resin sample and measuring the particle dimensions of the dispersed particles on electron photomicrographs of thin sections of the polymers.
  • the electron photomicrograph should have a magnification of from 3000X to 15000X, preferably 7500X.
  • the inorganic fillers preferably employed according to the present invention are the known mineral talcs and clays.
  • talcs and clays having very low free metal oxide content.
  • Talcs and clays are generally known fillers for various polymeric resins. See for example U.S. Patents 5,091,461 and 3,424,703 and EP 391,413, where these materials and their suitability as filler for polymeric resins are generally described.
  • the mineral talcs best suited are hydrated magnesium silicates as generally represented by the theoretical formula:
  • compositions of talcs may vary somewhat with locality in which they are mined. Montana talcs, for example, closely approach this theoretical composition. Suitable mineral talcs of this type are commercially available as Microtalc MP 25-38 and Microtalc MP 10-52 from Pfizer.
  • hydrous alumino silicate-type compounds generally represented by the formula:
  • Suitable clay materials are commercially available as Tex 10R brand clay from Anglo American Clay Co.
  • the carbonate polymer compositions included within the scope of this invention generally utilize such inorganic fillers with a number average particle size as measured by Coulter Counter of less than or equal to 10 micrometers ( ⁇ m) preferably less than or equal to 3 ⁇ m, more preferably less than or equal to 2 ⁇ m, more preferably less than or equal to 1.5 ⁇ m and most preferably less than or equal to 1.0 ⁇ m.
  • such fillers can have number average particle sizes of at least 0.05 ⁇ m, preferably at least 0.1 ⁇ m, and more preferably at least 0.5 ⁇ m.
  • the smaller average particle sizes, if available, could very suitably be employed but it has been found difficult to commercially obtain fillers of this type having an average particle size less than 1.5 ⁇ m.
  • Suitable fillers generally have a maximum particle size less than or equal to 50 ⁇ m, preferably less than or equal to 30 ⁇ m, more preferably less than or equal to 25 ⁇ m, more preferably less than or equal to 20 ⁇ m and most preferably less than or equal to 15 ⁇ m.
  • Another way of specifying the desired uniform small particle size and particle size distribution of the fillers preferably used in the practice of the present invention is to specify that at least 98 weight percent, preferably at least 99 weight percent, of the particles thereof in final blend have an equivalent spherical volume diameter less than 44 ⁇ m, preferably less than 20 ⁇ m.
  • the weight percentage of the filler particles having such diameters can similarly be measured by particle size analysis with a Coulter Counter.
  • the inorganic filler(s) in an amount of at least 1, preferably at least 5 and more preferably at least 7 percent by weight based on weight of wax, filler, carbonate polymer, monovinylidene aromatic polymer and optional rubber.
  • the coefficient of linear thermal expansion is less than 3.9 x 10" 5 /°F (7 x 10- 5 /°C), preferably less than 3.5 x 10-->/°F (6.3 x 10" 5 /°C), and more preferably less than 3.3 x 10- 5 /°F (5.6 x 10-5/°C), over the temperature range of 70 to 120°F (21 to 49°C), preferably over the range of -22 to 185°F (-30 to 85°C).
  • injection molded components prepared from the resin blends of the present invention generally have an exceptionally smooth, defect-free, paintable surface finish.
  • compositions according to the present invention are prepared by blending the foregoing components according to known blending and mixing techniques. Desirably the components may be first mixed or dry blended prior to melt blending in an appropriate extruder or other melt blending device. The components may be combined and blended in any order.
  • additional additives may be included in the blend as long as they do not substantially deleteriously affect the other physical properties of the composition.
  • additional additives may include, for example, pigments; light stabilizers such as U.V. absorbers; antioxidants; other processing aids such as lubricants and mold release agents; flame and dripping retardants; filler coupling agents, for example the polyfunctional organosilicon compounds disclosed in U.S. Patent 4,528,303 and other additives.
  • a, series of filled polycarbonate/monovinylidene aromatic polymer blends were prepared varying the wax type, filler type, filler amount, carbonate polymer, monovinylidene aromatic polymer and rubber polymer component ratios.
  • the blends also contained standard antioxidants and used epoxidized soybean oil to tackify the resin pellets to facilitate the combination of powdery additives such as the filler.
  • the carbonate polymer resins are commercially available grades of CALIBRE (TM) brand, bisphenol A-based polycarbonate (PC) produced by The Dow Chemical Company.
  • the melt flow rates (MFR) are measured in grams per 10 minutes (g/ 10 min) according to ASTM D-1238, condition O while the weight average molecular weight values (Mw) are measured by gel permeation chromatography using a polystyrene standard. Table 1
  • the monovinylidene aromatic polymer resins are butadiene rubber modified copolymers of styrene (“STY”) and acrylonitrile (“AN”) commercially available as grades of
  • ABS poly(stryrene-acrylonitrile)
  • (E) which butadiene rubber level does not include grafted SAN.
  • the rubber levels are determined by the relative amounts of rubber and monomers incorporated during production of the ABS resin.
  • MMA methylmethacrylate
  • the monovinylidene aromatic copolymer (MVAC) components are styrene, methyl methacrylate and small amounts of other crosslinking and proprietary comonomers and are substantially completely graft polymerized to the rubber.
  • the fillers used in the experiments were the commercially available mineral talcs identified below. Chemically these materials were h yd rated magnesium silicates as represented by the formula:
  • Type Shape D/T Particle Particle Wt % Name Size Size ⁇ 20 ⁇ m
  • the components to be blended were dried for 4 hours at 210°F (99°C) in a circulated air dryer and then dry blended by tumble blending.
  • the mixtures were then extruded under vacuum through a Werner Pf proprietaryer ZSK-30 twin screw extruder.
  • the heaters were maintained at 518°F (270°C), the screw was run at 400 RPM, and the throughput rate was 30 lbs/hour (13.6 Kg/hr). Strands were cooled in a water bath and chopped.
  • the granules were then dried for 4 hours at 210°F (99°C) in a circulated air oven and molded into test specimens in an Arburg 28 ton injection molding machine at 550°F (288°C) melt temperature and 180°F (82°C) mold temperature.
  • the physical properties of the resulting injection molded samples were then measured and the test results are contained in the Tables below.
  • the CLTE values, as measured by ASTM D-696 are given in units of "x 10 *5 millimeter per millimeter per degree Celsius" (x 10- 5 mm/mm °C) and "x 10- 5 inch per inch per degree Fahrenheit” (x 10- 5 in/in °F).
  • Dart impact strength is measured according to ASTM D-3763-86 and is reported in inch-pounds (In-Lbs) and Joules (J).
  • the Notched Izod values are determined according to ASTM D-256 and reported in foot pounds per inch (ft-lb/in) and Joules per meter (J/m).
  • the selection of the wax additive and the inorganic filler provide the claimed blends with surprising combinations of properties that are not attainable when the proper wax additive or the proper filler type are not employed.
  • compositions were injection molded into plaques and exterior automotive door panels. Both materials had a 10 percent improvement in processability, as measured by injection pressure and capillary rheology, over the same materials without wax.
  • the plaques were painted and subjected to Distinctness of Reflected Image Gloss (ASTM-E-430-83), 20 Degree Specular Gloss (ASTM D-523-85), Tape Adhesion Test for Paint Finishes (General Motors Test GM9071P), Knife Cross-Hatch Adhesion (General Motors Test GM9502P), Humidity Aging (General Motors Test GM4465P), and Chip Resistance of Coating (General Motors Test BM9508P) testing. The material passed all of these tests. The body panels were painted and passed one year durability testing.

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  • Compositions Of Macromolecular Compounds (AREA)

Abstract

On prépare des mélanges chargés composés (A) de polymères de carbonate et (B) de copolymères aromatiques de monovinylidène et présentant des caractéristiques combinées améliorées de résistance à la dilatation thermique linéaire et de ténacité à basse température. Un additif à base de cire (C) est utilisé pour améliorer la ténacité à basse température du mélange polymère chargé. Cet additif se compose de préférence d'une cire ester, d'une cire acide, d'une cire polyéthylène ou d'un mélange d'au moins deux de ces cires, la cire ester étant de préférence utilisée. Des charges de remplissage (D) de forme spécifique et à faible grosseur de particules sont de préférence utilisées afin de conférer la résistance requise à la dilatation thermique linéaire et de maintenir la résistance aux chocs du mélange chargé. Ce mélange contient éventuellement un modificateur de la résistance aux chocs, à base de caoutchouc (E), qui permet d'améliorer la ténacité d'articles moulés produits à partir de ces mélanges chargés. Ces mélanges contiennent généralement de 50 à 95 % en poids de (A) et de 5 à 50 % en poids de (B) par rapport au poids total des constituants (A), (B) et (E); de 0,1 à 5 % en poids de (C) et de 1 à 17 % en poids de (D) par rapport au poids total des constituants (A), (B), (C), (D) et (E); et, éventuellement, de 1 à 20 % en poids de (E) par rapport au poids total des constituants (A), (B) et (E).
PCT/US1995/009907 1994-08-22 1995-08-04 Compositions de melanges de polymeres de carbonate charges a resistance accrue aux chocs WO1996006135A1 (fr)

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US29416394A 1994-08-22 1994-08-22
US08/294,163 1994-08-22

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WO1996006135A1 true WO1996006135A1 (fr) 1996-02-29

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EP0878506A2 (fr) * 1997-05-14 1998-11-18 Daicel Chemical Industries, Ltd. Composition à base de polycarbonate
EP0979843A2 (fr) * 1998-08-13 2000-02-16 Idemitsu Petrochemical Co., Ltd. Composition de résine thermoplastique et des pièces moulées par injection
WO2001034691A1 (fr) * 1999-11-11 2001-05-17 Bayer Aktiengesellschaft Matieres moulables en polycarbonate
WO2002059203A1 (fr) * 2001-01-25 2002-08-01 Bayer Aktiengesellschaft Compositions polycarbonate a teneur en fer reduite
US7241825B2 (en) 2002-05-08 2007-07-10 Teijin Chemicals, Ltd. Polycarbonate resin composition, pellets thereof and molded article thereof
CN103467958A (zh) * 2013-09-03 2013-12-25 上海锦湖日丽塑料有限公司 无机填料增强无卤阻燃pc/abs合金及其制备方法
WO2021148325A1 (fr) * 2020-01-23 2021-07-29 Covestro Deutschland Ag Compositions de polycarbonate

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Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0878506A3 (fr) * 1997-05-14 1999-10-13 Daicel Chemical Industries, Ltd. Composition à base de polycarbonate
EP0878506A2 (fr) * 1997-05-14 1998-11-18 Daicel Chemical Industries, Ltd. Composition à base de polycarbonate
US6348527B1 (en) 1998-08-13 2002-02-19 Idemitsu Petrochemical Co., Ltd. Thermoplastic resin composition based on a combination of polycarbonate and styrenic resins
EP0979843A2 (fr) * 1998-08-13 2000-02-16 Idemitsu Petrochemical Co., Ltd. Composition de résine thermoplastique et des pièces moulées par injection
EP0979843A3 (fr) * 1998-08-13 2000-05-31 Idemitsu Petrochemical Co., Ltd. Composition de résine thermoplastique et des pièces moulées par injection
KR100693972B1 (ko) * 1999-11-11 2007-03-12 바이엘 악티엔게젤샤프트 폴리카보네이트 성형 화합물
US6740693B1 (en) 1999-11-11 2004-05-25 Bayer Aktiengesellschaft Polycarbonate moulding compounds
WO2001034691A1 (fr) * 1999-11-11 2001-05-17 Bayer Aktiengesellschaft Matieres moulables en polycarbonate
WO2002059203A1 (fr) * 2001-01-25 2002-08-01 Bayer Aktiengesellschaft Compositions polycarbonate a teneur en fer reduite
US7030180B2 (en) 2001-01-25 2006-04-18 Bayer Aktiengesellschaft Polycarbonate compositions with reduced iron content
KR100842134B1 (ko) * 2001-01-25 2008-06-27 바이엘 악티엔게젤샤프트 철의 함량이 감소된 폴리카르보네이트 조성물
US7241825B2 (en) 2002-05-08 2007-07-10 Teijin Chemicals, Ltd. Polycarbonate resin composition, pellets thereof and molded article thereof
CN103467958A (zh) * 2013-09-03 2013-12-25 上海锦湖日丽塑料有限公司 无机填料增强无卤阻燃pc/abs合金及其制备方法
WO2021148325A1 (fr) * 2020-01-23 2021-07-29 Covestro Deutschland Ag Compositions de polycarbonate

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