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WO1991011487A1 - Compositions de melanges de copolymeres de styrene ayant une stabilite des couleurs amelioree - Google Patents

Compositions de melanges de copolymeres de styrene ayant une stabilite des couleurs amelioree Download PDF

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Publication number
WO1991011487A1
WO1991011487A1 PCT/US1991/000673 US9100673W WO9111487A1 WO 1991011487 A1 WO1991011487 A1 WO 1991011487A1 US 9100673 W US9100673 W US 9100673W WO 9111487 A1 WO9111487 A1 WO 9111487A1
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weight percent
copolymer
polymer
composition
polymer blend
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PCT/US1991/000673
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English (en)
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Antonios Gkogkidis
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The Dow Chemical Company
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Priority to BR919104236A priority Critical patent/BR9104236A/pt
Priority to KR1019910701237A priority patent/KR920701329A/ko
Publication of WO1991011487A1 publication Critical patent/WO1991011487A1/fr

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    • 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
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • 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
    • 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
    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L59/00—Compositions of polyacetals; Compositions of derivatives of polyacetals
    • 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
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • C08L69/005—Polyester-carbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L59/00—Compositions of polyacetals; Compositions of derivatives of polyacetals
    • C08L59/02—Polyacetals containing polyoxymethylene sequences only
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/06—Polyurethanes from polyesters

Definitions

  • the present invention pertains generally to thermoplastic polymer blends which contain a monovinylidene aromatic cox-tolymer in combination with an acetal polymer and which contain a minor proportion of an oxirane-containing ingredient.
  • the indicated polymer blends also contain an elastomeric polymer such as elastomeric thermoplastic polyurethanes or copolyester elastomers and/or one or more non-elastomeric thermoplastic polycarbonate or polyester homopolymer or copolymer resin ingredients.
  • the monovinylidene aromatic copolymer is a rubber-modified monovinylidene aromatic copolymer having from 1 to 40 weight percent of dispersed rubber particles contained therein.
  • a c proportion that is from 5 to 50 parts) by volume of a partially or completely crystalline polymer such as nylon, polyacetal, etc. wherein said crystalline polymer, even though employed in minor volumetric proportion, is nevertheless considered to form a
  • said major proportion (that is from 50 to 95 parts by volume) component consists of one or more crosslin ed, emulsion-
  • polymerized elastomeric polymers such as, for example, butadiene or acrylate rubber-based graft copolymers containing either from 10 to 50 weight percent of a shell having a glass transition temperature of less than
  • thermoplastic molding compositions composed of a mixture of from 50 to 99 weight percent of an acetal polymer and from 1 to 50 weight percent of a butadiene or acrylate rubber-modified, two-phase polymer mixture. Such thermoplastic molding compositions are described as having considerably improved impact strength relative to that of the acetal polymer per se. Preferred embodiments of this reference utilize 80 to 95 weight percent of the acetal polymer component.
  • U.S. Patent 4,639,488 to Schuette et al. discloses impact resistant polyacetal-based molding materials containing from 30 to 95 weight percent of an acetal polymer and from 5 to 70 weight percent of an emulsion polymerized elastomeric graft copolymer composed, on a graft copolymer weight basis, of from 60 to 90 weight percent of a butadiene-based core (or "grafting base") and from 10 to 40 weight percent of a grafted shell of a styrene and/or methylmethacrylate- based polymer or copolymer.
  • Such molding materials are said to have high impact strength at low temperatures, to exhibit good thermal stability and to resist discoloration in the presence of light.
  • U.S. Patent 4,179,479 to Carter discloses thermoplastic polymer blend compositions containing from 40 to 100 weight percent of a thermoplastic polyurethane in combination with up to 60 weight percent of a thermoplastic polymer which can be an ABS resin, an acetal resin, a polycarbonate resin, a polyester resin or mixtures thereof. Such compositions are also required to contain 0.5 to 10 weight percent of an acrylic polymer processing aid to improve the processabuity and molding characteristics thereof.
  • U.S. Patent 4,117,033 to Gale discloses polymer blends containing an acetal resin in combination with from 0.1 to 5 weight percent of a low molecular weight copolyether-ester resin. Said copolyether-ester resin is said to improve the melt processabuity of the indicated acetal resin.
  • U.S. Patent 4,683.267 to Lindner et al. discloses molding compounds consisting of a mixture of from 60 to 99.00 parts by weight of an acetal resin, from 0 to 40 parts by weight of an elastomer softening below the melting point of said acetal resin and from 0.01 to 40 parts by weight of an aliphatic, rubber-like, high molecular weight adipate-carbonate mixed ester. Elastomers said to be useful in the Lindner et al.
  • blends include homopolymers and copolymers of alpha- olefins, homopolymers and copolymers of 1,3-dienes, copolymers and homopolymers of vinyl esters and copolymers and homopolymers of acrylate and methacrylate esters.
  • the polymer blends thereof optionally may contain small amounts of additional polymer ingredients such as a polyurethane resin, an olefinic homopolymer or copolymer resin, acrylate resins, polyamide resin, ABS resins or polyester resins.
  • additional polymer ingredients such as a polyurethane resin, an olefinic homopolymer or copolymer resin, acrylate resins, polyamide resin, ABS resins or polyester resins.
  • TPU elastomers
  • linear polyols linear polyols
  • polyalkylene terephthalate resin polyalkylene terephthalate resin
  • Preferred compositions are from 40-95 percent POM and from 5-60 percent of a mixture consisting of 60-98 percent TPU and 2-40 percent polyalkylene terephthalate.
  • the present invention in one of its aspects, is a polymer blend composition which contains:
  • A a monovinylidene aromatic copolymer ingredient which is either (1) a non-rubber-modified monovinylidene aromatic copolymer containing, in polymerized form and on an aromatic copolymer ingredient weight basis, from 55 to 99 weight percent of one or more monovinylidene aromatic monomers and from 1 to 45 weight percent of one or more relatively polar comonomer ingredients; or (2) a rubber-modified monovinylidene aromatic copolymer containing, on a rubber-modified copolymer weight basis, from 30 to 99 weight percent of one or more monovinylidene aromatic copolymers as described in item (A) (1) above and from 1 to 70 weight percent of dispersed particles of a rubbery polymer having a glass transition temperature of 0°C or lower; and (B) an acetal homopolymer or copolymer ingredient which can be either linear or branched and which can be employed either singly or in combination; said composition being characterized in that it contains, on a total polymer
  • the aforementioned polymer blend composition employs as its monovinylidene aromatic copolymer ingredient a rubber- modified monovinylidene aromatic copolymer containing, on a rubber-modified copolymer weight basis, from 2 to 35 weight percent of dispersed particles of a rubbery polymer such as a homopolymer of a 1 ,3-conjugated alkadiene monomer or a copolymer of from 60 to 99 weight percent of a 1 ,3-conjugated alkadiene monomer with from 1 to 40 weight percent of a monoethylenically unsaturated monomer.
  • a rubber- modified monovinylidene aromatic copolymer containing, on a rubber-modified copolymer weight basis, from 2 to 35 weight percent of dispersed particles of a rubbery polymer such as a homopolymer of a 1 ,3-conjugated alkadiene monomer or a copolymer of from 60 to 99 weight percent of a 1
  • the indicated polymer blend composition further contains one or more elastomeric thermoplastic polyurethane ingredients and/or one or more copolyester elastomer ingredients.
  • Particularly preferred elastomeric polymers for use within such embodiment are ester-containing or ester- based elastomeric materials (such as, for example, ester-based elastomeric thermoplastic polyurethanes and copolyester elastomers) used either alone or in combination with each other or in combination with up to 70 weight on a total elastomer weight basis of a non- ester-based elastomeric material such as, for example, an ether-based thermoplastic polyurethane.
  • the subject polymer blend composition further contains, in addition to the indicated elastomeric copolyester or thermoplastic polyurethane ingredient, one or more non- elastomeric thermoplastic polycarbonate or polyester resin ingredients.
  • the indicated polymer blends can have a highly advantageous and controllable combination of physical, chemical and aesthetic properties and can be beneficially employed in the preparation of molded articles for use in a wide variety of applications including various interior and exterior automotive applications, household appliance applications, housings for electronic and/or business equipment and the like.
  • oxirane-containing materials have been known in the prior art as being thermal stabilizers for glass reinforced polyacetal compositions (see, for example, Published European Application Number 281,148) and as being thermolysis stabilizers for polyurethanes (see, for example, U.S. Patent 4,775,558)
  • thermal stabilizers for glass reinforced polyacetal compositions see, for example, Published European Application Number 281,148
  • thermolysis stabilizers for polyurethanes see, for example, U.S. Patent 4,775,558
  • the beneficial U.V. stabilization and impact strength improvements which are achieved by incorporating such ingredients within the subject polymer blends is believed to constitute a totally unexpected and surprising technical result.
  • the polymer blend compositions hereof contain a monovinylidene aromatic copolymer ingredient which can either be rubber-modified or non-rubber-modified.
  • suitable monovinylidene aromatic monomer constituents include styrene, alkyl substituted styrenes.such as alpha-alkyl- styrene (for example alpha-methylstyrene, alpha- ethylstyrene etc.), various ring-substituted styrenes such as para-methylstyrene, ortho-ethylstyrene, 2,4- dimethylstyrene, etc., ring-substituted halo-styrenes such as chloro-styrene, 2,4-dichloro-styrene, etc.
  • Such monovinylidene aromatic monomer typically constitutes from 55 to 99 weight percent of said monovinylidene aromatic copolymer and preferably constitutes from 60 to 95 (more preferably from 65 to 90) weight percent thereof.
  • Such monovinylidene aromatic copolymers are typically normally solid, hard (that is non-elastomeric) materials having a glass transition temperature in excess of 25°C.
  • Suitable relatively polar comonomer ingredients for use as the minor constituent in (that is constituting from 1 to 45 weight percent of) the indicated monovinylidene aromatic copolymers include ethylenically unsaturated nitriles such as acrylonitrile, methacrylonitrile, ethacrylonitrile, etc.; ethylenically unsaturated anhydrides such as maleic anhydride; ethylenically unsaturated amides such as acryla ide, methacrylamide, etc.; esters (especially lower, for example C 1 -C 6 , alkyl esters) of ethylenically unsaturated carboxylic acids such as methyl methacrylate, ethylacrylate, hydroxyethylacrylate, n- butyl acrylate or methacrylate, 2-ethyl-hexylacrylate, etc.; ethylenically unsaturated dicarboxylic acid i ides such as N-
  • the relative polar comonomer ingredient herein are the aforementioned ethylenically unsaturated nitriles.
  • said relatively polar comonomers or mixtures thereof constitute from 5 to 40 (more preferably from 10 to 35) weight percent of the indicated monovinylidene aromatic copolymer.
  • Especially preferred polymer blend compositions hereof are those wherein the monovinylidene aromatic copolymer is rubber modified and comprises on a total rubber odified-copolymer weight basis from 1 to 70 (preferably from 1 to 40, more preferably from 2 to 35, and most preferably from 3 or 5 to 20, 25 or 30) weight percent of dispersed particles of a rubbery polymer having a glass transition temperature of 0°C or lower.
  • Especially preferred rubbery polymers for use herein are those having a glass transition temperature of -20°C or lower.
  • suitable such rubbery polymers include homopolymers of 1,3-conjugated alkadiene monomers; copolymers of from 60 to 99 weight percent of said 1,3-conjugated alkadienes with from 1 to 40 weight percent of a monoethylenically unsaturated monomer such as, for example, monovinylidene aromatic monomers (for example styrene, etc.) and ethylenically unsaturated nitriles such as acrylo-nitrile, methacrylonitrile etc.; ethylene/propylene copolymer rubbers and rubbery ethylene/propylene/non-conjugated diene copolymers.
  • Especially preferred rubbery polymers for use herein include polymers composed of from 60 to 100 weight percent of 1,3-butadiene and from 0 to 40 weight percent of styrene or acrylonitrile.
  • One particular class of rubber-modified monovinylidene aromatic copolymer ingredients of interest for use herein are graft copolymer compositions wherein the above-discussed rubbery polymer particles serve as substrates having grafted thereto a portion of -1 1-
  • the above-described monovinylidene aromatic copolymer as a grafted superstrate and wherein the remainder of said monovinylidene aromatic copolymer constitutes a continuous matrix phase in which the indicated grafted rubbery particles are dispersed.
  • the matrix phase typically constitutes from 40 to 95 (preferably from 60 to 95) percent of the overall weight of the indicated rubber-modified compositions and the grafted copolymer constituents constitutes the remainder thereof.
  • the grafted copolymer constituent will have a grafted superstrate to graftable rubber substrate ratio (that is a graft to rubber or "G/R" ratio) of from 0.1:1 to 1:1 (preferably from 0.35:1 to 0.45:1).
  • the above-described rubber-modified monovinylidene aromatic copolymer ingredient will have a melt flow rate (MFR) of from 0.5 to 12 (preferably from 1 to 10) grams per 10 minutes as determined pursuant to ASTM D-1238 at 230°C and 3.8 kg.
  • MFR melt flow rate
  • the dispersed rubbery polymer particles are of a sort which have a bimodal particle size distribution.
  • substantially higher impact strength is obtained within the polymer blend compositions of interest when the indicated rubbery particles are predominantly composed (for examplefrom 50 to 90, preferably from 65 to 75, weight percent on a total rubbery particle weight basis) of particles having a volume average particle size of less than one micron (preferably from 0.05 to 0.8 micron) and wherein the remainder of said rubbery particles (for example from 10 to 50, preferably from 25 to 35, weight percent thereof) have a volume average particle size of one micron or greater (preferably from 1 to 3 micron) .
  • the use of such bimodal rubber polymer particle has been found to give notably higher impact strength relative to comparable polymer blend compositions wherein the dispersed rubbery polymer particles are composed completely of rubber particles having sizes (that is diameters) of one micron or greater.
  • the aforementioned rubber-modified monovinylidene aromatic graft copolymer hereof can suitably be prepared in any known manner by free radical polymerization of the selected comonomer materials in the presence of the modifying rubber material. Suitable techniques thus include conventional mass, solution, suspension or emulsion polymerization processes. If emulsion polymerized graft copolymers are to be employed, care should be taken to remove or neutralize residual acid moieties. Otherwise decomposition of the acetal polymer component can result. Especially preferred for use herein are rubber-modified monovinylidene aromatic graft copolymers prepared via mass, solution, mass/suspension or mass/solution polymerization techniques.
  • mass polymerization involves polymerizing a solution of the rubber and monomer(s) at conditions sufficient to form discrete rubber particles of the desired particle size dispersed throughout the polymerized monomer.
  • the polymerization is advantageously conducted in one or more substantially linear stratified flow or so-called plug-flow reactors such as described in U.S. Patent No. 2,727,884 which may or may not comprise recirculation of a portion of the partially polymerized product or in a stirred tank reactor wherein the contents of the reactor are essentially uniform throughout.
  • the polymerization is advantageously conducted in an organic liquid reaction diluent or solvent such as aromatic or inertly substituted aromatic hydrocarbons (for example benzene or toluene) and in the presence of a free-radical initiator such as the peroxide initiators, (for example dibenzoyl peroxide or 1,1- bistertiary buty ⁇ peroxycyclohexane) .
  • a free-radical initiator such as the peroxide initiators, (for example dibenzoyl peroxide or 1,1- bistertiary buty ⁇ peroxycyclohexane) .
  • the initiator will be employed in an amount from 100 to 5000 weight parts per million weight parts of the monomers employed.
  • the organic liquid reaction diluent is generally employed to control , the viscosity of the polymerization mixture and is generally employed in an amount from 2 to 20 weight percent based on the total weight of the rubber, monomer and diluent.
  • the polymerization mixture can further contain other adducts such as a plasticizer or lubricant (for example mineral oil); and antioxidant (for example an alkylated phenol such as di-tert-butyl-p-cresol); a polymerization aid (for example a chain transfer agent such as an alkyl • mercaptan) or a mold release agent, (for example zinc stearate).
  • a plasticizer or lubricant for example mineral oil
  • antioxidant for example an alkylated phenol such as di-tert-butyl-p-cresol
  • a polymerization aid for example a chain transfer agent such as an alkyl • mercaptan
  • a mold release agent for example zinc stearate
  • Mass/suspension polymerization involves initially mass polymerizing the monomer/rubber mixture and, following phase inversion (that is the conversion of the polymer from a discontinuous phase dispersed in a continuous phase of the rubber solution through the point where there is no distinct continuous or discontinuous phase in the polymerization mixture and to the point where there is a continuous polymer phase having the rubber dispersed therethrough) and subsequent size stabilization of the rubber particles, suspending the partially polymerized product, with or without additional monomer(s), in an aqueous medium which generally contains a polymerization initiator. Subsequently, polymerization is completed using suspension polymerization techniques.
  • the above- described mass or mass/suspension-polymerized rubber- modified monovinylidene aromatic graft copolymer ingredient is employed in combination with a finely divided, emulsion polymerized particulate elastomeric material.
  • a finely divided, emulsion polymerized particulate elastomeric material typically have a volume average particle size in the range of from 0.05 to 0.5 (especially from 0.15 to 0.2) micron and, when employed, constitute from 1 to 15 percent by weight of the overall blend composition.
  • Such emulsion polymerized particulate elastomeric materials may be suitably prepared by emulsion polymerizing suitable monomers such as butadiene, isoprene or higher alkyl esters of acrylic acid or methacrylic acid, optionally in the presence of not more than 30 percent by weight of monomers, such as styrene, acrylonitrile, methyl acrylate, methyl methacrylate or any other monomer and polar comonomer described above.
  • suitable monomers such as butadiene, isoprene or higher alkyl esters of acrylic acid or methacrylic acid, optionally in the presence of not more than 30 percent by weight of monomers, such as styrene, acrylonitrile, methyl acrylate, methyl methacrylate or any other monomer and polar comonomer described above.
  • such elastomeric materials contain adhesion promoting groups such as carboxyl, carboxamido, carboxylic anhydride or epoxide groups.
  • adhesion promoting groups such as carboxyl, carboxamido, carboxylic anhydride or epoxide groups.
  • acrylic or methacrylic acid, an amide of one of these, glycidyl acrylate or, instead of the free acid, tert.-butyl acrylate is used as a comonomer, in an amount of from 0.1 to 10 percent by weight.
  • a shell which has a glass transition temperature of less than -10°C and which contains su h an adhesion promoting monomeric building block is grafted onto the indicated emulsion-polymerized elastomeric polymer.
  • Graft monomers which have proven particularly useful are esters of acrylic acid, such as n-butyl acrylate, preferably in combination with multifunctional crosslinking agents and/or with comonomers containing the stated adhesion promoting groups.
  • the shell amounts to 10-50 percent by weight of the total elastomeric polymer.
  • the above-described monovinylidene aromatic copolymer ingredient will generally constitute from 5 to 90 weight percent of the polymer blend compositions hereof.
  • said monovinylidene aromatic copolymer is employed in amounts corresponding to from 10 to 90 (more preferably from 15 to 85, especially from 20 to 65) parts by weight per 100 parts of the combined or total weight of the overall polymer blend composition.
  • the blends hereof are binary in character and are composed of the monovinylidene aromatic copolymer and the acetal polymer only, said blends will preferably contain from 50 to 80 (more preferably from 55 to 75) parts by weight of the monovinylidene aromatic copolymer per 100 parts by weight of the polymer blend composition.
  • the aromatic copolymer will preferably be employed in amounts ranging from 10 to 65(more preferably from 15 to 60) parts by weight per 100 parts by weight of the polymer blend composition.
  • the monovinylidene aromatic copolymer will preferably be employed in amounts ranging from 5 to 65 (more preferably from 10 to 40 and most preferably from 15 to 30 or 35) parts by weight per 100 parts by weight of the overall polymer blend composition.
  • the acetal (sometimes termed polyoxymethylene) resin can be any of those commonly known in the art or commerically available.
  • the acetal resin either can be linear or branched and can be a copolymer or a homopolymer or mixtures of these.
  • Copolymers can contain one or more co onomers such as those generally used in preparing acetal resins.
  • Comonomers more commonly used include alkylene oxides of 2 to 12 carbon atoms, in a less than 20 wt. percent amount.
  • Polyoxymethylenes which contain from 0.5 to 10 percent, in particular from 1 to 5 percent of ethylene oxide are particularly important commercially and are especially preferred for use herein.
  • the available acetal resins have thermally stable terminal groups, such as ester or ether groups, for example acetate or methoxy groups.
  • the polyoxymethylenes have, in general, a molecular weight of from 10,000 to 100,000.
  • melt flow rate MFR
  • Preferred acetal resins for use in the compositions of the present ' invention have MFRs of from 0.1 to 60 (preferably from 0.5 to 30 and most preferably from 0.5 to 5 or 10) grams/10 minutes, as measured pursuant to ASTM D-1238 at 190°C and 2.16Kg.
  • the melt viscosity of the acetal will be too low and it will be difficult to achieve sufficient intimate mixing of components at appropriate shear rates. If the MFR is too low, the temperature for the compounding operation may become too high and degradation can result. As will be e.vident in the examples, and assuming all other parameters are equal, the lower the MFR, the higher the toughness of the compositions of the present invention.
  • the acetal polymer ingredient of the subject polymer blend compositions can generally constitute from 5 to 90 weight percent) of said polymer blend compositions.
  • said acetal polymer is utilized in an amount corresponding to from 10 to 90 (more preferably from 15 to 85, and especially from 15 to 55) parts by weight per 100 parts by weight of the total or combined weight of the indicated polymer blend composition.
  • acetal polymer ingredient in relatively larger proportions such as for example at levels ranging (on a per 100 parts by weight total polymer blend composition basis) from 40 to 90 (more preferably from 45 to 80 and most preferably from 50 to 75) parts by weight.
  • levels ranging on a per 100 parts by weight total polymer blend composition basis
  • 40 to 90 more preferably from 45 to 80 and most preferably from 50 to 75 parts by weight.
  • acetal polymer in smaller proportions such as, for example, at levels ranging from 20 to 50 (especially from 25 to 35 or 40) parts by weight per 100 parts by weight of the polymer blend composition in question.
  • the polymer blend compositions hereof also contain a minor proportion (for example, from 0.01 to 15 parts by weight per 100 parts by weight of the subject polymer blend compositions) of one or more oxirane-containing stabilizer ingredients.
  • the inclusion of the indicated oxirane- containing ingredients within the polymer blend compositions hereof has been observed to substantially improve the thermal color stability of the subject polymer blends during the melt processing (for example, melt blending and/or injection molding) thereof and to thereby widen the processabuity window of such blends by allowing the use of increased processing temperatures without encountering severe thermally induced discoloration problems. Additionally, it has been surprisingly found that the indicated oxirane-containing additives or ingredients can also impart notably improved impact strength to the subject polymer blends
  • Oxirane-containing ingredients suitable for use herein include the various known epoxidized organic materials which have sufficiently high boiling points and decomposition temperatures (for example, preferably at least 180°C, more preferably at least about 200°C and most preferably at least about 220°C) so as to be melt processable within the subject polymer blend compositions without undergoing substantial decomposition or evaporative loss thereof.
  • Suitable oxirane-containing materials for use herein include epoxide derivatives of unsaturated triglycerides such as epoxidized soybean oil, epoxidized linseed oil, epoxidized palm oil, epoxidized tung oil, epoxidized coconut oil, epoxidized peanut oil, epoxidized olive oil, epoxidized rapeseed oil, etc.; epoxy phenol novolac resins; epoxy cresol novolac resins, diglycidyl ethers of bisphenol A; diglycidyl ethers of poly (oxypropylene) glycol; glycidyl ethers of polyethylene glycols; glycidyl ethers of polyhydroxy aliphatic alcohols such as 1,4-butanediol, 1,4-butenediol, glycerin, trimethylol propane, pentaerythritol, etc.; and glycidyl esters of polyvalent aromatic,
  • epoxidized unsaturated triglycerides especially epoxidized soybean oil and epoxidized linseed oil
  • epoxy resins derived from the reaction of epichlorohydrin with aromatic or aliphatic polyols such as bisphenol A, polyethylene glycol, polypropylene glycol, etc.
  • the aforementioned oxirane-containing stabilizer ingredients can be employed within the polymer blend compositions hereof in an amount ranging from 0.01 to 15 weight percent based upon the total weight of said compositions.
  • said stabilizer ingredient will more typically be employed in an amount ranging from 0.1 to 10 (more preferably from 0.2 to 5 and most preferably from 0.5 to 2 or 3) parts by weight per 100 parts by weight of the subject polymer blend composition.
  • Polycarbonate resins suitable for use herein include aromatic polycarbonates which contain the repetitive carbonate group,
  • the polycarbonate can be characterized as possessing recurring structural units of the following formula and structural isomers thereof:
  • A is a single bond or is a divalent aliphatic radical such as an alkylene or an alkylidene radical usually with 1-7 carbon atoms, or a cycloalkylene or cycloalkylidene radical usually with 5-15 carbon atoms, with all including their aromatically and aliphatically substituted derivatives.
  • polycarbonate resin A can also represent -0-, -S-, - CO-, -SO- or - SO 2 -.
  • R' and R 1 ' are substituents other than hydrogen such as, for example, halogen or a saturated or unsaturated monovalent aliphatic radical having usually
  • n 1-7 carbon atoms, and n equals 0 to 4.
  • Typical of the above-mentioned structural unit are those which result from the reaction of phosgene (or other carbonyl-providing species) with bis-
  • the carbonate polymer may be derived from two or more different hydric phenols or a copolymer of a hydric phenol with a glycol if a copolymer carbonate rather than a carbonate homopolymer is desired. Also suitable for the practice of this invention are blends of any of the above carbonate polymers.
  • polycarbonate polymer also included in the term "polycarbonate polymer" are the ester carbonate copolymers of types described in U.S. Patent Numbers 3,169,121; 4,330,662 and 4,105,633.
  • Typical comonomers are dicarboxylic acid, for example, terephthalic acid.
  • branched polycarbonates which are made by using the above-described polyhydric monomers in combination with a suitable branching agent, normally tri- or higher polyfunctional molecules.
  • the polycarbonate resins employed herein preferably have a melt flow rate, measured according ASTM D-1238 (condition 0 : 300°C, 1.2 kg load), of from 0.5 to 200 g/10 min, preferably from 2.5 to 100 g/10 min, more preferably from 5 to 90 g/10 min, and especially preferred from 8 to 75 g/10 min.
  • Thermoplastic polyester resin components suitable for use herein are those which are obtained by reaction of glycol and dicarboxylic acid such as, for example, as are described in U.S. Patent Number 2,465,319.
  • the glycol preferably has the general formula:
  • n is an integer from 2 to 12, such as for example ethylene glycol, 1,2- or 1,3-propane diol, 1,2-, 1,3- or 1,4- butane diol, 1,5- or 1,4-pentane diol, 1,6- hexane diol, 1,7- heptane diol or 1,8-octane diol.
  • cycloaliphatic diols typically containing up to 21 carbon atoms, are employed, such as, for example, cyclohexane-l,4-dimethanol, 2,2-bis-(4- hydroxycyclohexyl) propane, 2,4-dihydroxy-l,l,3,3- tetramethyl cyclobutane and 2,2-bis-(3- ⁇ -hydroxy- ethoxyphenyl)-propane.
  • Dicarboxylic acid components suitably employed to prepare said polyester resins include those having the general formula
  • R" ' and R n " each representing the -(CH 2 ) ⁇ -group, with m being zero or an integer from 1 to 4.
  • B is a divalent aromatic radical represented by the following formulas or structural isomers thereof:
  • D may be: O
  • D m a*y also be:
  • Typical dicarboxylic acids include phthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, 4,4'-diphenyl dicarboxylic acid, succinic acid, adipic acid, sebacic acid, azelaic acid and cyclohexane diacetic acid.
  • the polyester resin obtained from reaction of the indicated dicarboxylic acid and a glycol may be branched by incorporation of relatively small quantities of tri-or tetrahydric alcohols or tri- or tetrabasic polycarboxylic acids of the type described, for example, in German Offenlegungsschrift No. 1,900,270 and in U.S. Patent Number 3,692,744.
  • copolymer resins are often preferred, polymerized from a combination of one or more dicarboxylic acids and a combination of one or more glycols.
  • Such a product, made from terephthalic acid, and a combination of cyclohexane dimethanol and ethylene glycol is commerically available from Eastman Laboratories under the tradename KODAR PETG (TM) Copolyester.
  • the homo- and copolyesters derived from dicarboxylic acid and glycol have preferably a molecular weight ranging from 5,000 to 200,000, more preferably from 10,000 to 60,000-
  • thermoplastic polyester and/or polycarbonate resins can suitably be employed if and as desired such as, for example, polycarbonate and polyethylene glycol terephthalate or polybutylene glycol terephthalate or any other combination of the various polyester and polycarbonate resins mentioned above.
  • thermoplastic polyester or polycarbonate resin ingredient when employed within the compositions hereof, can typically be employed in amounts ranging from 5 to 90 parts by weight thereof per 100 parts by weight of the subject polymer blend compositions.
  • said ingredient is employed in an amount corresponding to from 10 to 75 (more preferably from 15 to 55, especially from 20 to 45 or 50) parts of the combined weight of the polymers contained within the subject polymer blend composition.
  • Elastomeric materials suitable for use herein include, as noted above, thermoplastic polyurethanes and elastomeric copolyester materials.
  • Thermoplastic polyurethanes suitable for use herein include any of those generally known in the art and thus include those prepared from a diisocyanate, a polyester, poly- caprolactone or polyether and a chain extender. Such thermoplastic polyurethanes are substantially linear and maintain thermoplastic processing characteristics.
  • a preferred group of polyether-based polyurethanes used in the polymer blend composition of the present invention are the reaction products of: (i) 4,4'-methylene bis(phenyl isocyanate), (ii) a polyether polyol (such as for example, a poly (oxy-1,2 propylene) glycol or a polyoxytetramethylene glycol) having a number average molecular weight within the range of 600 to 3000 (preferably from 1000 to 2500) and (iii) chain extending agent such as diol extenders selected from the group consisting of aliphatic straight chain diols having from 2 to 6 carbon atoms, bis(2-hydroxy-ethyl) ether of hydroquinone, bis(2-hydroxy-ethyl) ether of resorcinol, and mixtures of any two or more of such diol extenders and/or other difunctional chain extending agents containing 2 active hydrogen-containing groups which are reactive with isocyanate groups.
  • a polyether polyol such as
  • Suitable chain extending agents for use herein may include any difunctional compounds containing two active hydrogen-containing groups which are reactive with isocyanate groups.
  • suitable chain extending agents thus include diols including ethylene glycol, propylene glycol, butylene glycol, 1,4- butanediol, butenediol, butynediol, xylylene glycols, amylene glycols, 1,4-phenylene-bis- ⁇ -hydroxyethyl ether, 1,3-phenylene-bis- ⁇ -hydroxy ethyl ether, bis-(hydroxy- methyl-cyclohexane) , hexanediol, thiodiglycol and the like; diamines including ethylene diamine, propylene diamine, butylene diamine, hexamethylene diamine, cyclohexalene diamine, phenylene diamine, toluylene diamine, xylylene diamine, 3,3'-dichlorobenz
  • polyfunctional material may be utilized.
  • This polyfunctional chain extender should not be present in an amount greater than about 1 percent by weight.
  • Any suitable polyfunctional compound may be used for such purpose such as, for example, glycerine, trimethylolpropane, hexanetriol, pentaerythritol and the like.
  • aliphatic straight chain diols having from 2 to 6 carbon atoms means diols of the formula HO(CH 2 )n OH wherein n is 2 to 6 and there is no branching in the aliphatic chain separating the OH groups.
  • the term is inclusive or ethylene glycol, 1,3- propanediol, 1,4-butanediol, 1,5-pentanediol and 1,6- hexanediol.
  • Preferred diol extenders for use herein include 1,4-butanediol, 1,6-hexanediol and the bis(2- hydroxy-ethyl) ether of hydroquinone; an especially preferred diol extender being 1,4-butanediol.
  • diisocyanates which may be used in place of or in combination with the preferred species mentioned above [that is 4,4'-methylene bis (phenyl isocyanate)] include ethylene diisocyanate, ethylidene diisocyanate, propylene diisocyanate, butylene diisocyanate, cyclopentylene-1,3-diisocyanate , cyclohexylene-1,4-diisocyanate, 2,6-tolylene diisocyanate, 2,2-diphenylpropane-4,4'-diisocyanate, P- phenylene diisocyanate, m-phenylene diisocyanate, xylylene diisocyanate, 1,4-naphtylene diisocyanate, 1,5- naphthylene diisocyanate, diphenyl-4,4'-diisocyanate, azobenzene-4,4'diisocyanate, diphenyl sulf
  • the polyether polyol and chain extending agent are typically used in the polyurethane reaction medium in a ratio of 0.5 to 2.5 equivalents (for example mole equivalents) of the chain extender per equivalent of the polyol.
  • the equivalents ratio is from 1 to 2.
  • the ratio is from 1.2 to 1.6 equivalents of extender per equivalent of the polyol when said polyol has a molecular weight of 2000, and especially when the extender is an aliphatic straight chain diol.
  • the equivalents ratio may be lower than the above-mentioned preferred ranges, for example, as low as 0.5 equivalents of the extender per equivalent of the polyol.
  • the polyether polyol and the chain extender and the diisocyanate are typically used in relative proportions to each other such that the overall ratio of isocyanate equivalents or groups to total hydroxyl equivalents or groups or other active hydrogen- containing groups (that is polyol plus extender) is within the range of 1:1 to 1.08:1.0 and preferably is within the range of 1.02:1.0 to 1.07:1.0.
  • the most preferred ratio of isocyanate (NCO) groups to total hydroxyl (OH) groups (or combined hydroxyl plus other active hydrogen groups) is within the range of from 1.03:1.0 to 1.06:1.0.
  • polyether-based thermoplastic polyurethanes employed in the practice of the present invention are typically characterized by a ClashBerg modulus (Tf) which is less than -10°C
  • Tf glass j - transition temperature
  • the polyether-based polyurethanes may suitably have, for example a Shore A Hardness of 95A or less, and a weight average molecular weight in excess of 100,000. 0
  • thermoplastic polyester- based polyurethanes for use in the present invention are the reaction products of: (i) 4,4'methylenebis(phenyl isocyanate; (ii) a polyester of adipic acid and a glycol having at least one primary hydroxyl group; and (iii) a difunctional chain extender of the sort described above having 2 active hydrogen-containing groups which are reactive with isocyanate groups.
  • the adipic acid is condensed with a suitable glycol or mixture of glycols which have at least one primary hydroxyl group.
  • the condensation is stopped when an acid number of from 0.5 to 2.0 is reached.
  • the water formed during the reaction is removed simultaneously therewith or subsequently thereto such that the final water content is from 0.01 to 0.02 percent preferably from 0.01 to 0.05 percent.
  • Any suitable glycol may be used in reaction with the adipic acid such as, for example, ethylene glycol, propylene glycol, butylene glycol, hexanediol, bis-(hydroxymethylcyclohexane) , 1,4-butanediol, diethylene glycol, 2,2-dimethyl propylene glycol, 1,3- propylene glycol and the like.
  • a small amount of trihydric alcohol up to 1 percent may be used along with the glycols such as, for example, trimethylolpropane, glycerine, hexanetriol and the like.
  • the resulting hydroxyl polyester has a molecular weight of at least 600, a hydroxyl number of 25 to 190 and preferably between 40 and 60, and an acid number of between 0.5 and 2 and a water content of 0.01 to 0.2 percent.
  • any suitable chain extending agent including those described above for the polyether-based thermoplastic polyurethanes) having active hydrogen containing groups reactive with isocyanate groups may be used in preparing the subject polyester-based materials.
  • extenders thus include diols such as ethylene glycol, propylene glycol, butylene glycol, 1,4- butanediol, butenediol, butynediol, xylylene glycols, amylene glycols, 1,4-phenylene-bis- ⁇ -hydroxyethyl ether, 1,3-phenylene-bis- ⁇ -hydroxy ethyl ether, bis-(hydroxy- methyl-cyclohexane) , hexanediol, thiodiglycol and the like.
  • polyether polyols may also be employed as the chain extending agent (or as a portion thereof) with the result being a copolyester/polyether based thermoplastic polyurethane which ,is also suitable for
  • thermoplastic polyurethanes based upon adipate polyesters are generally preferred for use herein, other polyester-based thermoplastics
  • polyurethanes can also be suitably employed within the present invention such as, for example, those in which there is employed (in place of the adipic acid) succinic acid, suberic acid, sebacL.c acid, oxalic acid, methyl adipic acid, glutaric aci ⁇ d, pimelic acid, azelaic acid,
  • phthalic acid terephthalic acid, isophthalic acid and the like as well as those prepared using hydroxycarboxylic acids, lactones, and cyclic carbonates such as ⁇ -caprolactone and 3-hydroxy-butyric acid in place of the adipic acid component.
  • polyester-based thermoplastic polyurethanes prepared using the above-described alternative diisocyanates in place of 4,4'-methylene bis (phenyl isocyanate) can also be suitably employed in the practice of. the present
  • polyester-based thermoplastic polyurethanes are generally known materials. Suitable methodology for the preparation thereof is disclosed within Column 7 of U.S. Patent 4,665,126.
  • thermoplastic polyurethanes for use herein include those having a Shore hardness (ASTM D2240) between 70 on the "A” scale and 60 on the “D” scale.
  • thermoplastic polyurethane employed in the practice of the present invention can have incorporated in it additives such as pigments, fillers, lubricants, stabilizers, antioxidants, coloring agents, fire retardants, and the like, which are commonly used in conjunction with polyurethane elastomers.
  • Elastomeric polymer ingredients suitable for use herein also include polyester-based elastomers other than the ester-based polyurethane materials which have been discussed above.
  • examples of such other elastomers include elastomeric copolyether-ester resin material and elastomeric adipate-carbonate mixed ester resin materials.
  • Suitable copolyether-ester elastomer ingredients can be generally described as comprising a multiplicity of recurring intralinear long-chain and short-chain ester units connected head-to-tail through ester linkages, said long chain ester units generally constituting from 25 to 85 weight percent of said copolyether-ester elastomer and corresponding to the formula: 00
  • G is a divalent radical remaining after removal of terminal hydroxyl groups from a poly-(alkylene oxide) glycol having a carbon-to-oxygen mole ratio of 2-4.3 and a molecular weight of 400-6000;
  • R is a divalent radical remaining after removal of carboxyl groups from a dicarboxylic acid having a molecular weight less than 300; and said short chain ester units generally constituting from 15 to 75 weight percent of said elastomer and corresponding to the formula:
  • D is a divalent radical remaining after removal of hydroxyl groups from a low molecular weight diol having a molecular weight less than 250;
  • the indicated polyether-ester elastomers have a relatively low molecular weight as evidenced by their exhibiting an inherent viscosity of 0.05-0.95 (preferably from 0.1 to o.8 and most preferably from 0.1 to 0.5) when measured in m-cresol at a O.lg/dl concentration at 30°C.
  • Suitable elastomeric adipate-carbonate mixed ester materials for use herein include those described within U.S. Patent 4,683,267 to Lindner et al. for use as property modifiers for polyoxymethylene resin-based molding compositions. Such materials are rubber-like high molecular weight compounds corresponding to the formula
  • X and X' represent residues of the reaction product of a polyhydric alcohol and adipic acid having a molecular weight of from 800 to 3,500;
  • k represents an integer of from 0 to 10;
  • n represents an integer greater than 20, preferably from 22 to 100; which compounds have a limiting viscosity number [ ⁇ ] (Sta ⁇ dinger Index) in tetrahydrofuran of from 0.8 to 2.5 dl/g.
  • polyhydric alcohols which may be used, optionally as mixtures, for the polyesters from which the residues X and X' are derived: ethylene glycol, propylene glycol-(l,2) and - (1,3), butylene glycol-(1,4) and -(2,3), hexane diol- (1,6), octane diol-(1,8), neopentyl glycol, cyclohexane dimethanol, l,4-bis-(hydroxymethyl cyclohexane), 2- methyl-l,3-propane diol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol and dibutylene glycol.
  • the reaction products obtained from adipic acid and the alcohols are polyesters having hydroxyl end groups.
  • the molecular weights thereof range from 800 to 3,500.
  • the adipate-carbonate mixed esters are prepared from these polyesters by a reaction with difunctional carbonic acid aryl esters. These correspond in particular to the following general formula:
  • Ar represents a substituted or unsubstituted aryl group having from 6 to 18 carbon atoms, preferably 6 carbon atoms;
  • k and X' are as defined above.
  • elastomeric polymer - c * ingredients When the above-described elastomeric polymer - c * ingredients are employed within the subject polymer blends hereof, they are typically utilized in an amount ranging from 1 to 80 (preferably from 3 to 70 and most preferably from 10 to 65) parts by weight per 100 parts of the combined weight of the stated polymer 20 ingredients. In certain preferred embodiments, said elastomeric ingredient is employed in amounts ranging from 3 to 40 (especially from 5 to 30 and most preferably from 10 to 25) parts by weight per 100 parts by weight of the total polymer ingredients.
  • the elastomeric ingredient be employed at relatively lower levels such as, for example, in amounts of from 3 to 25 (especially from 5 or 10 to 20 or 25) parts by weight on
  • the indicated elastomeric ingredient be employed in amounts ranging -37-
  • the polymer blend compositions hereof are conveniently prepared by dry blending the individual polymer ingredients to be employed in particulate (for example pelletized) form along with the oxirane- containing stabilizer ingredient in the quantitative proportions desired in a given instance and thereafter melt compounding the particulate polymer mixture in accordance with known extrusion compounding techniques.
  • additives may also be included in the polymer blend compositions hereof for different purposes as well known in the art, including bisphenol- type, ester-type or hindered phenol-type additives and anti-oxidants as disclosed, for example, in U.S. Patent Nos. 3,103,499 and 3,240,753, amine and amidine as disclosed, for example, in U.S. Patent Nos. 3,313,767 and 3,314,918, nucleants, UV screens and absorbers, metal soaps, glass fibers, glass beads, talc, polymeric substances other than those critical to this invention such as additives commonly known as mold release agents, plasticizers, antistatic agents, etc. which are compatible with the blends and color pigments which are compatible with acetal polymers.
  • additives commonly known as mold release agents, plasticizers, antistatic agents, etc. which are compatible with the blends and color pigments which are compatible with acetal polymers.
  • the use of the mentioned additives is not considered to be necessary for the operability of present invention.
  • the inclusion of the aforementioned oxirane-containing ingredients has been found to substantially improve the thermal stability, U.V. light resistance and impact strength of the subjeci polymer blends and can thereby serve to enhance the recycling capability of such blends which may of necessity entail additional melt processing (that is more thermal exposure) and/or prolonged U.V. exposure.
  • the inclusion of the indicated oxirane- containing ingredients can also serve to offset or minimize the adverse thermal and/or chemical destabilizing effect and/or reduced impact strength that can otherwise be imparted to the subject acetal- containing polymer blends by virtue of the inclusion therein of various additives such as mold release agents, plasitcizers, antistatic agents, colorants, and the like.
  • compositions can be formulated so as to be particularly useful in such applications wherein good thermal/dimensional stability, creep resistance and chemical resistance properties and/or paintability is required.
  • Suitable exemplary end-use applications thus include automotive interior and exterior parts, tool casings, appliance housings and the like.
  • thermoplastic resins and oxirane- containing additives employed within such examples are identified and described in Tables A and B respectively.
  • a 4 component POM/ABS/PC/TPU blend was prepared containing the indicated polymer components, respectively, in a 30/23/30/17 weight ratio and also containing 5 weight percent of ESO-1.
  • thermoplastic polymer components in pelletized form, were weighed out and combined in the desired proportions, tumble blended for 15 minutes, melt compounded with the epoxidized soybean oil ingredient using a BUSS Ko-Kneader operated at approximately 220- 240°C, 20 kg throughput and pelletized for subsequent drying and injection molding (at 180-240C) into appropriate testing specimens.
  • the corresponding polymer blend was prepared without the epoxidized soybean oil component (that is, ESO-1) being included.
  • the degree of discoloration exhibited by the resulting molded samples was determined using a DATACOLOUR DC 3890 photospectrometer using a sample of the same resin composition molded at a temperature of 180°C and a 300 second residence time as the color standard.
  • Each of the resulting blends were then injection molded under two different sets of molding conditions, namely at 210°C for a medium residence time (that is, 210 seconds) and at 240°C for a long residence time (that is, 475 seconds).
  • the color difference or discoloration encountered under the more severe molding conditions (that is, relative to that of the samples molded at 210°C and a medium residence time) is set forth in Table II below.
  • Comparative compositions were prepared and tested in each instance which did not contain the requisite oxirane containing additive.
  • Example 11 2 component ABS/POM compositions of Example 11 and comparative experiment C- 11 above were molded into test specimens and were subjected to room temperature (that is, 23°C) Notched Izod Impact Strength Testing pursuant to ISO 180.
  • the C-11 composition had a room temperature Notched Izod impact strength of 15 kJ/ ⁇ _2 whereas the ESO-2-containing Example 11 composition had a corresponding value of 20 kJ/ ⁇ _2.
  • compositions of the present invention that is, containing the oxirane ingredient

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Abstract

Yélanges de polymères thermoplastiques contenant un copolymère aromatique de monovinylidène ainsi qu'un polymère acétal, et pouvant également, facultativement, contenir une matière élastomère telle qu'un polyuréthane thermoplastique élastomère ou un copolyester élastomère et/ou un polycarbonate non élastomère ou une résine polyester. Les mélanges de polymères de l'invention sont caractérisés en ce qu'ils contiennent également un ou plusieurs ingrédients de stabilisation contenant de l'oxiranne, et de ce fait ils présentent une meilleure stabilité thermique, et de manière étonnante, une stabilité aux UV améliorée, ainsi qu'une résistance à l'impact améliorée. Lesdits mélanges de polymères présentent une bonne aptitude aux traitements, et ils sont adaptés à une utilisation dans la préparation d'une variété d'articles utilitaires moulés présentant une combinaison avantageuse de propriétés chimiques et physiques.
PCT/US1991/000673 1990-02-02 1991-01-28 Compositions de melanges de copolymeres de styrene ayant une stabilite des couleurs amelioree WO1991011487A1 (fr)

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BR919104236A BR9104236A (pt) 1990-02-02 1991-01-28 Composicoes de misturas polimericas estirenicas possuindo estabilidade de cor melhorada
KR1019910701237A KR920701329A (ko) 1990-02-02 1991-01-28 색상 안정성이 향상된 스티렌성 공중합체 혼합 조성물

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EP0590420A1 (fr) * 1992-09-28 1994-04-06 BASF Aktiengesellschaft Masses à mouler résistantes aux chocs à base de polyoxyméthylène
WO2006012039A1 (fr) * 2004-06-25 2006-02-02 E.I. Dupont De Nemours And Company Compositions de polyoxymethylene stabilisees a faible viscosite a l'etat fondu

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US3213158A (en) * 1960-03-31 1965-10-19 Teikoku Jinzo Kenshi Kk Thermally stable compositions comprising polyoxymethylene and partially cured epoxy resin
GB1023212A (en) * 1961-10-23 1966-03-23 Celanese Corp Improvements in the treatment of polymers
GB1311305A (en) * 1969-06-20 1973-03-28 Hoechst Ag Thermoplastic moulding compositions on the basis if polyacetals
US4296216A (en) * 1980-03-05 1981-10-20 Sumitomo Naugatuck Co., Ltd. Thermoplastic resin composition
US4639488A (en) * 1984-11-14 1987-01-27 Basf Aktiengesellschaft Impact-resistant polyoxymethylene molding materials and their preparation

Patent Citations (5)

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Publication number Priority date Publication date Assignee Title
US3213158A (en) * 1960-03-31 1965-10-19 Teikoku Jinzo Kenshi Kk Thermally stable compositions comprising polyoxymethylene and partially cured epoxy resin
GB1023212A (en) * 1961-10-23 1966-03-23 Celanese Corp Improvements in the treatment of polymers
GB1311305A (en) * 1969-06-20 1973-03-28 Hoechst Ag Thermoplastic moulding compositions on the basis if polyacetals
US4296216A (en) * 1980-03-05 1981-10-20 Sumitomo Naugatuck Co., Ltd. Thermoplastic resin composition
US4639488A (en) * 1984-11-14 1987-01-27 Basf Aktiengesellschaft Impact-resistant polyoxymethylene molding materials and their preparation

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0590420A1 (fr) * 1992-09-28 1994-04-06 BASF Aktiengesellschaft Masses à mouler résistantes aux chocs à base de polyoxyméthylène
WO2006012039A1 (fr) * 2004-06-25 2006-02-02 E.I. Dupont De Nemours And Company Compositions de polyoxymethylene stabilisees a faible viscosite a l'etat fondu

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EP0466906A1 (fr) 1992-01-22
AU7257191A (en) 1991-08-21

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