WO1994011429A1 - Melanges contenant du polycarbonate et resistant a l'inflammation - Google Patents

Melanges contenant du polycarbonate et resistant a l'inflammation Download PDF

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Publication number
WO1994011429A1
WO1994011429A1 PCT/US1993/011175 US9311175W WO9411429A1 WO 1994011429 A1 WO1994011429 A1 WO 1994011429A1 US 9311175 W US9311175 W US 9311175W WO 9411429 A1 WO9411429 A1 WO 9411429A1
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composition
acid
copolymer
vinyl
polycarbonate
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PCT/US1993/011175
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English (en)
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Samuel A. Ogoe
Brian K. Grosser
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The Dow Chemical Company
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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
    • C08L27/00—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 a halogen; Compositions of derivatives of such polymers
    • C08L27/02—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 a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—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 a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • 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
    • 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
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones

Definitions

  • This invention relates to ignition resistant blends of polycarbonate with polyester, an acrylate polymer and/or a styrenic thermoplastic resin.
  • this invention involves a composition of matter containing, in admixture, polycarbonate; polyester, an acrylate polymer and/or a styrenic thermoplastic resin; fibril-forming poly(tetrafluoroethylene); a halogenated aryl phosphate; and an acid acceptor.
  • this invention involves modifying a composition as described above by the addition of a halogenated aromatic carbonate oligomer.
  • compositions of this invention exhibit a desirable level of resistance to ignition, impact and solvents, and in particular are characterized by a V-0 rating in the U.L.94 burn test.
  • compositions of this invention are useful, for example, in the production of films, fibers, extruded sheets, multi-layer laminates and molded or shaped articles of virtually all varieties, especially appliance and instrument housings, motor vehicle body panels and other parts and components for use in the automotive, electrical and electronics industries.
  • the methods of this invention are useful for preparing compositions and molded articles having applications which are the same as or similar to the foregoing.
  • compositions of this invention are those in which a blend of (a) polycarbonate with (b)(i) polyester, (b)(ii) an acrylate polymer and/or (b)(iii) a styrenic thermoplastic resin has been admixed in a composition with (c) fibril-forming poly(tetrafluoroethylene), (d) a halogenated aryl phosphate, and (e) an acid acceptor.
  • the compositions of this invention may, optionally, contain (f) a halogenated aromatic carbonate oligomer, and (g) an elastomeric impact modifier.
  • Suitable ranges of content for components (a) - (e) in the compositions of this invention, expressed in parts by weight of the total composition, are as follows:
  • polycarbonate from about 5 parts to about 95 parts, preferably from about 10 parts to about 80 parts, and more preferably from about 30 parts to about 75 parts,
  • polyester up to about 80 parts, preferably from about 16 parts to about 70 parts, and more preferably from about 20 parts to about 60 parts,
  • thermoplastic resin up to about 80 parts, preferably from about 10 parts to about 70 parts, and more preferably from about 20 parts to about 60 parts,
  • fibril-formingpoly(tetrafluoroethylene) from about 0.001 partto about 30 parts, preferably from about 0.01 part to about 10 parts, and more preferably from about 0.01 part to about 5 parts,
  • halogenated aryl phosphate from about 0.001 part to about 50 parts, preferably from about 0.01 part to about 30 parts, and more preferably from about 0.01 part to about 10 parts, and
  • compositions of this invention contain optional components (f) a halogenated aromatic carbonate oligomer, and/or (g) an elastomeric impact modifier, suitable ranges of content for them, expressed in parts by weight of the total composition, are as follows:
  • halogenated aromatic carbonate oligomer from about 0.001 part to about 50 parts, preferably from about 0.01 part to about 30 parts, and more preferably from about 0.01 part to about 10 parts, and
  • elastomeric impact modifier up to about 50 parts, preferably from about 1 to about 40 parts, and more preferably from about 3 to about 20 parts.
  • the sum of the weight parts of the various components from which any particular formulation is prepared may, but need not, be 100.
  • compositions of this invention can be accomplished by any suitable mixing means known in the art.
  • the substances to be admixed with the polycarbonate blend are dry blended in paniculate form with sufficient agitation to obtain thorough distribution thereof.
  • the dry-blended formulation can further be melt mixed, for example in an extruder with or without a vacuum, or otherwise compounded with additional substances.
  • Apparatus which can be used in the blending process include, for example, mixing rolls, a dough-mixer, a Ban bury mixer, or a Lightnin blender.
  • compositions of this invention may undergo fabrication and can therein be formed or molded using conventional techniques such as compression, injection molding, gas assisted injection molding, calendering, vacuum forming, thermoforming, extrusion and/or blow molding techniques, alone or in combination.
  • the compositions can also be formed, spun or drawn into films, fibers, multi-layer laminates or extruded sheets, or can be compounded with one or more organic or inorganic substances, on any machine suitable for such purpose.
  • Articles molded from compositions prepared within the ranges of content stated above exhibit a desirable level of resistance to ignition, impact and solvents.
  • Component (a) in the compositions of this invention is a polycarbonate, which can be prepared from a dihydroxy compound such as a bisphenol, and a carbonate precursor such as a disubstituted carbonic acid derivative, a haloformate (such as a bishaloformate of a glycol or dihydroxy benzene) or a carbonate ester.
  • a dihydroxy compound such as a bisphenol
  • a carbonate precursor such as a disubstituted carbonic acid derivative, a haloformate (such as a bishaloformate of a glycol or dihydroxy benzene) or a carbonate ester.
  • the aqueous alkaline solution has a pH of 7.01 or more and can be formed in water from a caustic soda, such as NaOH, or from other bases such as those included in the alkali metal and alkaline earth metal phosphates, bicarbonates, oxides and hydroxides. These components are often reacted by means of a mixture prepared initially from the aromatic dihydroxy compound, water and a non-reactive organic solvent immiscible with water selected from among those in which the carbonate precursor and polycarbonate product are soluble.
  • a caustic soda such as NaOH
  • bases such as those included in the alkali metal and alkaline earth metal phosphates, bicarbonates, oxides and hydroxides.
  • Representative solvents include chlorinated hydrocarbons such as methylene chloride, 1,2-dichloroethane, tetrachloroethane, chlorobenzene, and chloroform, to which tetrahydrofuran, dioxane, nitrobenzene, dimethyl sulfoxide, xylene, cresol or anisole may be added, if desired.
  • Chinated hydrocarbons such as methylene chloride, 1,2-dichloroethane, tetrachloroethane, chlorobenzene, and chloroform
  • tetrahydrofuran, dioxane, nitrobenzene, dimethyl sulfoxide, xylene, cresol or anisole may be added, if desired.
  • Caustic soda or other base is then added to the reaction mixture to adjust the pH of the mixture to a level at which the dihydroxy compound is activated to dianionic form.
  • a reducing agent such as sodium sulfite or sodium
  • a carbonate precursor is contacted with an agitated mixture of the aqueous alkaline solution of the dihydroxy compound, and, for such purpose, the carbonate precursor can be bubbled into the reaction mixture in the form of a gas, or can be dissolved and introduced in solution form.
  • the mixture is agitated in a manner which is sufficient to disperse or suspend droplets of the solvent containing the carbonate precursor in the aqueous alkaline solution. Reaction at the interface of the organic and aqueous phases created by such agitation yields the bis(carbonate precu rsor) ester of the dihydroxy com pound.
  • the carbonate precursor is a carbonyl halide such as phosgene
  • the products of this initial phase of the process are monomers or oligomers which are either mono- or dichloroformates, or contain a phenolate ion at each terminus.
  • a coupling catalyst of which the following are representative: a tertiary amine such as triethyl amine or dimethyl amino pyridine; a hindered secondary amine such as diisopropyl amine; a cyclic aza compound such as 2,2,6,6-tetramethyl piperidine or 1 ,2-dimethylimidazole; an amidine or aminoamidine compound such as 1-methyl-2-phenyliminopyrrolidine; an isourea compound such as N,N-dibutyl-N'-phenyl-o-methylisourea; an iminoether or iminocarboxylate compound such as 1-aza-2-methoxy-1-cycloheptene ort-butyl- cyclohexyliminoacetate; or a phosphonium, sulfonium, ar
  • the reaction can be run at a pH of 7.01 to 14, and at a temperature between 0°C-100°C, although usually not in excess of the boiling point (reflux temperature) of the solvent used. Frequently, the reaction is run at a temperature of about 0°C to about 45°C.
  • the organic and aqueous phases are separated to allow purification of the organic phase and recovery of the polycarbonate product therefrom.
  • the organic phase is washed as needed in a centrifuge with dilute base, water and/or dilute acid until free of unreacted monomer, residual process chemicals and/or other electrolytes.
  • Recovery of the polycarbonate product can be effected by spray drying, steam devolatilization, direct devolati I ization in a vented extruder, or precipitation by use of an anti-solvent such as toluene, cyclohexane, heptane, methanol, hexanol, or methyl ethyl ketone.
  • aromatic diesters of carbonic acid are condensed with an aromatic dihydroxy compound in a transesterification reaction in the presence of a basic catalyst such as sodium methylate, sodium bisphenolate, calcium acetate, phenyl benzoate, N-stearoylphenothiazine, quaternary ammonium chloride, an alkaline(hydroxy)fluoroborate, an alkali metal salt of benzoic acid, an iminocarboxylic acid, or basic metal oxides such as zinc, lead or antimony oxide.
  • the reaction is typically run at 250°C-300°C under vacuum at a progressively reduced pressure of 1-100 mm Hg.
  • the reaction is run in the absence of solvent and typically yields lower viscosity grades of polycarbonate.
  • Polycarbonate can also be prepared in a homogeneous solution through a process in which a carbonate precursor, such as phosgene, is contacted with a solution containing an aromatic dihydroxy compound, a chlorinated hydrocarbon solvent and a substance, such as pyridine, dimethyl aniline or CaOH, which acts as both acid acceptor and condensation catalyst. Washing with acidified water removes the pyridine and its hydrochloride, and precipitation and repulping with an antisolvent such as heptane followed by filtration and distillation removes oligomers and unreacted monomer.
  • a carbonate precursor such as phosgene
  • Yet another process for the preparation of polycarbonate is the polymerization of cyclic oligomers having a weight average molecular weight of approximately 1,300 at 200°C-300°C, using a catalyst such as lithium stearate or tetramethylammonium tetraphenylborate.
  • dihydroxy compounds suitable for the preparation of polycarbonate include variously bridged, substituted or unsubstituted aromatic dihydroxy compounds (or mixtures thereof) represented by the formula
  • Z is (A) a divalent radical, of which all or different portions can be (i) linear, branched, cyclic or bicyclic, (ii) aliphatic or aromatic, and/or (iii) unsaturated, said divalent radical being composed of 1-35 carbon atoms together with up to five oxygen, nitrogen, sulfur, phosphorous and/or halogen (such as fluorine, chlorine and/or bromine) atoms; or (B) S, S 2 , SO, SO., O or CO; or (C) a single bond; and (II) each X is independently hydrogen, a halogen (such as fiourine, chlorine and/or bromine), a C.-C linear or cyclic alkyl, alkoxy, aryl or aryloxy radical, such as methyl, ethyl, isopropyl, cyclopentyl, cyclohexyl, methoxy, ethoxy, benzyl, tolyl,
  • the bridging radical represented by Z in the above formula can be a carbon atom to which is bonded one or more groups such as CH., C.H-, C H , n- C 3 H 7 , i-C.H 7 . cyclohexyl, bicyclo[2.2.1]heptyl, benzyl, CF 2 , CF. CCI 3 , CF.CI, CN, (CH-).COOCH 3 , or PO(0CH 3 ).
  • Tetrahalo Bisphenol-A 2,2-bis(3,5-dihalo-4-hydroxyphenyl)propane
  • halogen can be fluorine, chlorine, bromine or iodine, for example 2,2-bis(3,5- dibromo-4-hydroxyphenyl)propane
  • Tetrabromo Bisphenol-A or "TBBA”
  • TBBA 2,2-bis(3,5- dibromo-4-hydroxyphenyl)propane
  • Tetraalkyl Bisphenol-A 2,2-bis(3,5-dialkyl-4-hydroxyphenyl)propane
  • alkyl can be methyl or ethyl, for example 2,2-bis(3,5-dimethyl-4- hydroxyphenyl)propane
  • Tetramethyl Bisphenol-A 2,2-bis(3,5-dimethyl-4- hydroxyphenyl)propane
  • a polycarbonate product can be obtained having a weight average molecular weight, as determined by light scattering or gel permeation chromatography, of 8,000 to 200,000 and preferably 15,000 to 40,000, although values outside these ranges are permitted as well.
  • Molecular weight can be controlled by addition to the reaction mixture of a chain terminator which may be selected from monofunctional substances such as phenols, alcohols, amines, imides, carbonic acid chlorides, sulfonic acid chlorides, benzyltriethyl ammonium chloride, or phenylchlorocarbonates.
  • a chain terminator may be added to the reaction mixture before or after a dihydroxy compound is contacted with a carbonate precursor.
  • a branched rather than linear polycarbonate molecule can be obtained by adding to the reaction mixture a tri- or polyfunctional monomer such as a tri- or tetrafunctional phenol or carboxylic acid (or a derivative such as an acyl halide or anhydride), a bisphenol containing carboxylic acid side groups, or a nitrogen-containing compound such as cyanuric chloride, or compounds containing a mixture of such groups.
  • Preferred branching agents are trimellitic acid or pyromellitic dianhydride.
  • the preferred process of this invention is that in which an aromatic polycarbonate is prepared.
  • An aromatic polycarbonate is defined herein with reference to the oxygen atoms, of the one or more dihydroxy compounds present in the polycarbonate chain, which are bonded to a carbonyl carbon. In an aromatic polycarbonate, all such oxygen atoms are bridged by a dihydroxy compound residue some portion of which is an aromatic ring.
  • polycarbonate also included within the term “polycarbonate”, as used herein, are various copolycarbonates, certain of which can be prepared by incorporating one or more different dihydroxy compounds into the reaction mixture. This can be accomplished by charging the dihydroxy compounds themselves to the reaction mixture either simultaneously or sequentially. If the dihydroxy compounds are added sequentially or added together but have different reactivities toward the carbonate precursor, a segmented or block copolycarbonate will typically result. Different dihydroxy compounds with the same reactivity typically yield a random copolycarbonate when reacted together. Alternatively, if oligocarbonates are formed separately from one or more different dihydroxy compounds, the oligocarbonates can then be coupled in a condensation reaction to yield a segmented or block copolycarbonate.
  • a poly(ester/carbonate) is obtained.
  • the polycarbonate used in this invention excludes a pol y(ester/carbonate) .
  • Copolycarbonates can also be prepared, for example, by reaction of one or more dihydroxy compounds with a carbonate precursor in the presence of a chlorine- or amino-terminated polysiloxane, with a hydroxy-terminated poly(phenylene oxide) or poly(methyl methacrylate), or with phosphonyl dichioride or an aromatic ester of a phosphonic acid.
  • Siloxane/carbonate block copolymers are discussed in greater detail in Paul, U.S. Pat. No.4,596,970 and poly(ester/carbonate)s are discussed in greater detail in Swart, U.S. Pat. No. 4,105,533, each of which is incorporated herein.
  • Optional component (f) in the compositions of this invention is a halogenated aromatic carbonate oligomer, which may be made, in general, by the methods set forth above for the preparation of polycarbonate.
  • component (f) is halogenated, it may be prepared using, for example, an aromatic dihydroxy compound as described by structure above wherein at least one X is halogen; as it is aromatic, the carbonyl carbons in its polymer chain are bridged by a dihydroxy compound residue some portion of which is an aromatic ring; and as it is an oligomer, it has a degree of polymerization of about 2 to about 30.
  • a suitable halogenated aromatic carbonate oligomer is a carbonate oligomer prepared from Tetrabromo Bisphenol-A, which is available from Great Lakes Chemicals as BC-52 or BC-58.
  • Component (b)(i) in the compositions of this invention is a polyester
  • ester-forming derivatives of a dicarboxylic acid can be heated with a diol to obtain polyesters in an ester interchange reaction.
  • Suitable acid derivatives for such purpose are esters, halides, salts or anhydrides of the acid.
  • the ester interchange reaction istypically run in the presence of a diluent, for example, an inert organic solvent such as chloroform or tetrachloroethane, and in the presence of a base, for example a tertiary organic base such as pyridine.
  • Typical catalysts used when ester interchange involves alcoholysis are weak bases such as carbonates or alkoxides of sodium, lithium, zinc, calcium, magnesium or aluminum, whereas catalysts such as antimony oxide, titanium butoxide or sodium acetate are often used when acidolysis occurs in the interchange reaction.
  • Diol derivatives such as an acetate can be used effectively when it is desired to conduct acidolysis.
  • polyester product of intermediate weight can be heated in a vacuum or stream of inert gas, first to a temperature where it crystallizes and then to a temperature close to its melting point.
  • a chain coupling agent such as diphenyl carbonate
  • Polyesters can also be produced by a ring-opening reaction of cyclic esters or lactones, for which organic tertiary bases and alkali and alkaline earth metals, hydrides and alkoxides can be used as initiators. Whether a polyester is crystalline or amorphous is typically a function of the symmetry of the starting materials from which it is made. When one or more hydrogens on the diol and/or the diacid (or derivative) which are reacted to form a polyester are replaced by larger radicals such as alkyl or halogen, the intermolecular spacing of the resulting molecules may be disrupted if the presence of the substituent creates asymmetric or irregularly shaped molecules.
  • the component containing the substituent may also be combined into the polyester molecule in random orientation, resulting in structural irregularity in the polymer chain.
  • Factors which can influence crystallization of ring-containing polyesters are the directionality of the ester groups, the stereochemistry of the rings and variations in symmetry where the rings are bridged.
  • a poly(alkylene isophthalate) crystallizes only with difficulty, and a polyester prepared from phthalic acid typically does not crystallize at all.
  • the portion of the resulting polyester molecule which suffers from structural irregularity will also be small, and crystallization will typically not be impeded.
  • a crystalline material may be identified by the endotherm it displays on a differential scanning calorimeter.
  • a preferred polyester for use in this invention is a crystalline polyester having a melting point of 254-260°C.
  • Suitable reactants for making the polyester used in this invention, in addition to hydroxycarboxylic acids, are diols and dicarboxylic acids either or both of which can be aliphatic or aromatic.
  • a polyester which is a poly(alkylene alkanedicarboxylate), a poly(alkylene phenylenedicarboxylate), a poly(phenylene alkanedicarboxylate), or a poly(phenylene phenylenedicarboxylate) is therefore appropriate for use herein.
  • Alkyl portions of the polymer chain can be substituted with, for example, halogens, alkoxy groups or alkyl side chains and can contain divalent heteroatomic groups (such as -0-, -S- or -SO.-) in the paraffinic segment of the chain.
  • the chain can also contain unsaturation and non-aromatic rings.
  • Aromatic rings can contain substituents such as halogens, alkoxy or alkyl groups, and can be joined to the polymer backbone in any ring position and directly to the alcohol or acid functionality or to intervening atoms.
  • Typical alkylene diols used in ester formation are the C -C glycols, such as ethylene-, propylene-, and butylene glycol.
  • Alkanedicarboxylic acids frequently used are oxalic acid, adipic acid and sebacic acid.
  • Diols which contain rings can be, for example, a 1 ,4-cyclohexylenyl glycol or a 1,4-cyclohexane-dimethylene glycol, resorcinol, hydroquinone, 4,4'-thiodiphenol, bis-(4-hydroxyphenyl)sulfone, a dihydroxynaphthalene, a xylylene diol, or can be one of the many bisphenols such as 2,2-bis-(4-hydroxyphenyl)propane.
  • Aromatic diacids include, for example, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyletherdicarboxylic acid, diphenyldicarboxylic acid, diphenylsulfonedicarboxylic acid, diphenoxyethanedicarboxylic acid.
  • polyester in addition to polyesters formed from one diol and one diacid only, the term "polyester” as used herein includes random, patterned or block copolyesters, for example those formed from two or more different diols and/or two or more different diacids, and/or from other divalent heteroatomic groups. Mixtures of such copolyesters, mixtures of polyesters derived from one diol and diacid only, and mixtures of members from both of such groups, are also all suitable for use in this invention, and are all included in the term "polyester”.
  • PETG clear, amorphous copolyester
  • PCTG liquid crystalline polyesters derived from mixtures of 4-hydroxybenzoic acid and 2-hydroxy-6- naphthoic acid; or mixtures of terephthalic acid, 4-hydroxybenzoic acid and ethylene glycol; or mixtures of terephthalic acid, 4-hydroxybenzoic acid and 4,4'- d i hyd roxybi phenyl .
  • Aromatic polyesters those prepared from an aromatic diacid, such as the poly(alkylene phenylenedicarboxylates) polyethylene terephthalate and polybutylene terephthalate, or mixtures thereof, are particularly useful in this invention.
  • Component (b)(ii) in the compositions of this invention is an acrylate polymer, which is defined as a polymer prepared by homopolymerization of an alkyl acrylate or an alkyl methacrylate or by copolymerization of a mixture of the two; and includes a mixture of any such homopolymers or copolymers.
  • An alkyl acrylate or methacrylate can be prepared, for example, by reaction of an alkyl alcohol or diazoalkane with acrylic or methacrylic acid.
  • Acrylic acid is prepared by the vapor phase oxidation of propylene.
  • the acrylic acid/alcohol esterification reaction can be run at about 80°C using an acid catalyst such as H.S0 4 .
  • Methacrylic acid may be prepared by the oxidation of isobutylene or t-butyl alcohol.
  • a methacrylate may also be prepared by reacting acetone cyanohydrin with an excess of concentrated sulfuric acid to form methacrylamide sulfate, which, when then reacted with an alcohol, yields a methacrylate.
  • a C l - C acrylate or methacrylate may be used for polymer preparation herein, with C. - C. acrylate or methacrylate being preferred, and C ⁇ - C 4 being more preferred.
  • the acrylate polymer used in the compositions of this invention can be prepared in a polymerization reaction initiated by free radical initiators such as azo compounds or peroxides, preferably in the absence of oxygen.
  • Methacrylate monomers are most often polymerized in bulk, but this method has little application for acrylate monomers.
  • Acrylate and methacrylate monomers may be polymerized in an organic solution, using, for example, an aromatic hydrocarbon, ester, ketone or chlorohydrocarbon (such as toluene, chlorobenzene or 3-pentanone) as the solvent.
  • a chain transfer agent such as a thiol may be used to control molecular weight.
  • Polymerization can also occur in an aqueous emulsion in which an anionic surfactant, such as an alkylarene sulfate or phosphate, a nonionic surfactant, such as an alkyl or aryl polyoxyethylene, or a cationic surfactant is used.
  • Suspension polymerization is used primarily for methacrylates and involves suspending in water 0.1-5 mm droplets of monomer which are stabilized by a protective colloid such as cellulose, poly(vinyl alcohol), gelatin or talc. The initiator should be soluble in the monomer but not in water.
  • Acrylates and methacrylates can also be polymerized in a non-aqueous dispersion using an organic diluent such as hexane or methanol.
  • the acrylate When an acrylate and a methacrylate are copolymerized, the acrylate, each can be used in the mix of reactants from which the copolymer results in an amount of up to about 99.0 parts by weight, based on the total weight of the copolymer.
  • the acrylate polymer of component (b) (ii) takes the form of a copolymer, the copolymer may be a random, alternate, block or grafted copolymer.
  • Component (b)(iii) in the compositions of this invention is a styrenic thermoplastic resin, which includes polymers prepared by the emulsion, suspension or bulk polymerization methods which contain at least 25 percent by weight structural units derived from a vinyl aronatic monomer described generally by the formula
  • L is hydrogen, a ⁇ C. alkyl radical or a halogen atom (such as fluorine, chlorine, bromine or iodine)
  • D is a vinyl group, a C ⁇ C. alkyl radical or a halogen atom (such as fluorine, chlorine, bromine or iodine)
  • p is from 0 to 5.
  • These resins include homopolymers of styrene, chlorostyrene and vinyltoluene; and random copolymers of a vinyl aromatic compound with one or more monomers such as vinyl compounds (especially when they bear a polar, electronegative group or functionality) such as vinyl toluene, ethylvinyl benzene, divinylbenzene, alphamethyl styrene, halogenated styrene, a vinyl nitrile compound having lower alkyl or halogen substituents such as acrylonitrile, methacrylonitrile or alpha-halogenated acrylonitrile; a C ⁇ C.
  • vinyl compounds especially when they bear a polar, electronegative group or functionality
  • alkyl acrylate such as ethyl acrylate, hexyl acrylate or hydroxy ethyl acrylate; a C ⁇ C. alkyl methacrylate such as hexyl methacrylate; an acrylic or methacrylic acid; the vinylidene monomers, especially when they bear a polar, electronegative group or functionality such as a halogen group, or an organic group having a double or triple bond such as phenyl, carboxy, cyano or the like; vinyl chloride, vinyl acetate, vinylidene chloride; maleimides; alkyl or aryl esters of olefinically unsaturated carboxylic acids; vinyl esters; vinyl ethers; alpha-olefins; vinyl xylenes; glycidyl methacrylate; an alkyl or aryl maleate or fumarate; maleic anhydride; alkyl or aryl maleimide compounds include the reaction product of a C t -
  • each J is independently hydrogen, halogen, a C.-C. 0 alkyl radical or a C.-C M aryl radical; and the like; or mixtures of two or more of any of the foregoing. If a diene, ethylene/propylene/diene copolymer, or other rubbery comonomer is used, it is typically present is an amount of less than forty percent, and preferably less than thirty percent, of the copolymer by weight.
  • the preferred styrenic thermoplastic resins are a vinyl aromatic/vinyl nitrile copolymer such as styrene/acrylonitrile copolymer ("SAN"), a rubber-modified SAN such as acrylonitrile/butadiene/styrene copolymer.
  • SAN vinyl aromatic/vinyl nitrile copolymer
  • rubber-modified SAN such as acrylonitrile/butadiene/styrene copolymer.
  • a reaction mixture of water, monomer, an emulsifying agent and a suitable polymerization catalyst are charged to the reaction vessel, for example a stirred autoclave.
  • the reaction can be run in the range of 100°F to 200°F, usually between 175°F and 200°F.
  • emulsifying agents can be used, including soaps such as those based on the salt of a fatty acid or an alkyl aromatic sulfonic acid; a rosin acid soap; or non-ionic emulsifying agents are used.
  • Catalysts may be persulfates or of the peroxide type, the azo type or the redox type.
  • a styrenic thermoplastic resin made by the emulsion process, as described above, is discussed in greater detail in Childers, USP 2,820,773 (U.S. Rubber), Calvert, USP 3,238,275 (Borg-Wamer), Murray, USP 3,547,857 (Uniroyal) and Kohlpoth, USP 3,772,257 (Knapsack AG), each of which is hereby incorporated as a part hereof.
  • a styrenic thermoplastic resin can be prepared by the suspension process.
  • An aqueous mixture of monomers, initiator and suspending agent is reacted in a pressure vessel at a temperature between 100°C and 200°C, and between 6.9 and 690 kPa, after which the residual monomers are removed by steam stripping.
  • Suspending agents which can be used are materials such as polyvinyl pyrrolidone, carboxymethyl cellulose, lecithin or calcium phosphate.
  • thermoplastic resin made by the suspension process is discussed in greater detail in Aliberti, USP 3,444,270 (Monsanto), Carrock, USP 3,515,692 (Dart) and Ackerman, USP 4, 151 ,128 (Mobil), each being hereby incorporated as a part hereof.
  • a styrenic thermoplastic resin can also be prepared by the bulk or mass process wherein polymerization occurs because of the direct contact between the monomers in the presence of heat, but without need for any sort of suspending or emulsifying agent.
  • a solvent such as benzene, toluene or xylene is frequently added to the reaction mixture to facilitate machine processing.
  • the process can be run in either a continuous tube or a stirred vessel.
  • a styrenic thermoplastic resin made by the bulk or mass process, as described above, is discussed in greater detail in Hanson, USP 2,989,517 (Dow), Latinen, USP 3,813,369 (Monsanto), Simon, USP 4,252,911 (Monsanto) and Weber, USP 4,526,926 (Dow), each being hereby incorporated as a part hereof.
  • Component (c) in the compositions of this invention is fibril-forming poly(tetrafluoroethylene) ("PTFE").
  • PTFE can be made by the granular polymerization process wherein tetrafluoroethylene (“TFE”) is pressured into an agitated aqueous solution of free radical initiator at pressures of 5-80 kg/cm 2 and at temperatures of 50- 150°C.
  • Initiators can be redox systems, azo initiators, peroxides or inorganic persulfates. The polymer particles coagulate as they are formed.
  • Fine-powder PTFE can be made by a process similar to the foregoing except that sufficient dispersing agent is used to maintain a stable dispersion throughout polymerization and avoid premature coagulation.
  • the dispersing agent is anionic and substantially non-telogenic, such as a fluorinated carboxylate containing 7-20 carbons.
  • TFE is prepared by reacting hydrogen fluoride and chloroform to give chlorodifluoromethane, which is then pyrolyzed in a noncatalytic gas-phase reaction at atmospheric or reduced pressure, usually at about 590-900°C, to obtain tetrafluoroethylene.
  • the processes for making PTFE described above are discussed in greaterdetail in U.S. Patents 2,393,967, 3,855,191 and 4,186,121 , each of which is incorporated herein.
  • Fibril-forming PTFE is typically considered to be that which has a structure wherein PTFE particles having an average size of 0.1-0.2 microns are held together by fibrils having diameters from a fourth to a tenth or less of the diameters of the particles. PTFE which loses or does not form such structure, as a result of mechanical shearing, is typically considered to be non-fibril-forming. Fibril-forming PTFE is disclosed, in general, by U.S. Patents 3,005,795, 3,671,487 and 4,463,130, each of which is incorporated herein.
  • the PTFE employed in the compositions of this invention has a high elastic memory such that, when incorporated into the polymeric blend and molded into a molded object, such molded object will have a heat shrinkage equal to or greater than 15 percent when tested, for example, at a level of 0.5 weight percent in a composition of this invention in an injection-molded bar measuring 127 mm x 27 mm x 1.6 mm which is heated at 160°C for 1 hour.
  • Representative examples of PTFE which have high elastic memory are various members of the TeflonTM PTFE series available from E.I. du Pont de Nemours & Co., to-wit: 6C, 6CN, 60, 64, 65 and 67.
  • Component (d) in the compositions of this invention is a halogenated aryl phosphate which may be described by formula as follows:
  • R 1 and R 2 are each independently a C ⁇ C. alkyl radical, a C--C._ alkaryl radical, or a C,-C_ 0 halogenated aryl radical containing 1-5 halogen (such as fluorine, chlorine, bromine and/or iodine) atoms, and R 3 is a C -C 20 aryl radical containing 1-5 bromine atoms.
  • Exemplary halogenated aryl phosphates which are suitable according to this invention are tris (4-bromophenyl) phosphate, dicresyl 4-bromophenyl phosphate, 2,4-dibromophenyl 2-ethylcresyl phosphate, 2,4-dibromophenyl methyl phosphate and diethyl 4-bromophenyl phosphate.
  • the preparation of these halogenated aryl phosphates is well known from U.S. patents 3,557,053, 4,033,927 and 4,710,530, which are incorporated herein by reference.
  • a preferred halogenated aryl phosphate is PB- 460 bromoaryl phosphate, tris (2,4-dibromophenyl) phosphate, from FMC Corporation.
  • Component (e) in the compositions of this invention is an acid acceptor or scavenger which will neutralize acidic species contained therein, particularly those resulting from residual phenol in the halogenated aryl phosphate remaining from the manufacturing process.
  • an acid acceptor include metal oxides such as red lead oxide, magnesium oxide and calcium oxide; lead salts such as lead carbonate, lead phthalate and lead phosphite; metal stearates such as calcium stearate and zinc stearate; basic carbonates such as barium carbonate and calcium carbonate; calcium hydroxide; and synthetic hydrocalcite.
  • metal oxides such as red lead oxide, magnesium oxide and calcium oxide
  • lead salts such as lead carbonate, lead phthalate and lead phosphite
  • metal stearates such as calcium stearate and zinc stearate
  • basic carbonates such as barium carbonate and calcium carbonate
  • calcium hydroxide calcium hydroxide
  • synthetic hydrocalcite synthetic hydrocalcite
  • Optional component (g) in the compositions of this invention is an elastomeric impact modifier, several different varieties of which, or a mixture thereof, are suitable for use herein.
  • thermoplastic elastomer which is characterized, for example, in that it can be melted and recooled, or dissolved and reformed upon removal of the solvent, without undergoing any significant change in properties.
  • Thermoplastic elastomers are also characterized by the randomness of the shape and size they take on when mixed by shearing forces with the other components making up the compositions of this invention, especially when heat is applied during such mixing. Because thermoplastic elastomer is typically a long chain molecule, segments of a thermoplastic elastomer in the polymer composition matrix are generally elongated, linear ribbons or bands. The molecules tend to fuse and flow together in a continuous structure.
  • thermoplastic elastomer is a block copolymer which can be either linear, branched, radial orteleblock, and can be either a di-biock ("A-B") copolymer, tri-block (“A-B-A”) copolymer, or radial teleblock copolymer with or without tapered sections, i.e. portions of the polymer where the monomers alternate or are in random order close to the point of transition between the A and B blocks.
  • the A portion is made by polymerizing one or more vinyl aromatic hydrocarbon monomers, and has an average molecular weight of about 4,000 to about 1 15,000, and a weight preferably of about 8,000 to about 60,000.
  • the B portion of the block copolymer results from polymerizing a diene and has a molecular weight of about 20,000 to about 450,000, and a weight preferably of about 50,000 to about 300,000.
  • each block, A or B can vary from 10-90% of the total weight of the copolymer.
  • the A end groups typically constitute about 2 wt% to about 55 wt% of the whole block copolymer, and preferably are between 5 wt% and 45 wt% of the whole block copolymer.
  • the A block of the block copolymer has properties characteristic of thermoplastic substances in that it has the stability necessary for processing at elevated temperatures and yet possesses good strength below the temperature at which it softens.
  • the A block is polymerized predominantly from vinyl aromatic hydrocarbons, and substituted derivatives thereof wherein the aromatic moiety can be either mono- or polycyclic.
  • Monomers from which the thermoplastic end blocks can be formed are, for example, styrene and substituted derivatives thereof such as ⁇ -methyl styrene, vinyl xylene, vinyl naphthalene, and the like, and mixtures of two or more thereof.
  • vinyl monomers such as methyl acrylate, methyl methacrylate, phenyl maleimide, acrylonitrile or vinyl pyridine may be used in the formation of the A block together with the aromatic monomers.
  • the polymerization can be initiated by lithium metal, or alkyl- or aryl lithium compounds such as butyl lithium or isoamyl lithium. Polymerization is normally conducted at temperatures ranging from about -20°C to about 100°C.
  • the B block of the copolymer can be formed, for example, simply by injecting suitable monomer into the reaction vessel and displacing the lithium radical from the just-polymerized A block, which then acts as an initiator because it is still charged.
  • the B block is formed predominantly from substituted or unsubstituted C.-C dienes, particularly conjugated dienes such as butadiene or isoprene.
  • Other diene, vinyl or olefinic monomers such as chloroprene, 1 ,4-pentadiene, isobutylene, ethylene or vinyl chloride may be used in the formation of the B block provided that they are present at a level low enough to not alter the fundamental olef i nic character of the B block.
  • the B block will be characterized by elastomeric properties which allow it to to absorb and dissipate an applied stress and then regain its shape.
  • the second end block A can be formed in a manner similar to the first, by injecting appropriate vinyl aromatic monomer into the reaction vessel.
  • a bivalent lithium initiator can be used, which, when brought together with the diene monomer under the same conditions described above, will form an elastomeric mid block B which carries a charge at each end. Then, upon addition of vinyl aromatic monomer to the reaction mixture, a thermoplastic end block A will form on both ends of the mid block B, yielding a thermoplastic elastomeric A-B-A copolymer.
  • the block copolymers used herein can also desirably be hydrogenated to reduce the degree of unsaturation on the polymer chain and on the pendant aromatic rings.
  • the block copolymer may be selectively hydrogenated by hydrogenating only the elastomeric block B.
  • Typical hydrogenation catalysts utilized are Raney nickel, molybdenum sulfide, finely divided palladium and platinum oxide. The hydrogenation reaction is typically run at 75-450°F and at 100-1 ,000 psig for 10-25 hours.
  • the most preferred block copolymers are vinyl aromatic/conjugated diene block copolymers formed from styrene and butadiene or styrene and isoprene.
  • styrene/butadiene copolymers When the styrene/butadiene copolymers are hydrogenated, they are frequently represented as styrene/(ethylene/butylene) copolymer in the di-block form, or as styrene/(ethylene/butylene)/styrene copolymer in the tri-block form.
  • styrene/isoprene copolymers When the styrene/isoprene copolymers are hydrogenated, they are frequently represented as styrene/(ethylene/propylene) copolymer in the di-block form, or as styrene/(ethylene/propylene)/styrene copolymer in the tri-block form.
  • the vinyl aromatic/diene block copolymers described above are discussed in greater detail in Holden, USP 3,265,766; Haefele, USP 3,333,024; Wald, USP 3,595,942; and Witsiepe, USP 3,651,014, each of which is incorporated herein.
  • Linear, branched, radial or teleblock A-B-A or A-B block copolymer thermoplastic elastomers can also be prepared from materials other then vinyl aromatic systems. These other copolymers also have a rigid block "A" having a T g above room temperature (approximately 23-25°C) and a rubbery block "B” having a T g below room temperature. Examples of typical pairings of the various materials used to form the respective A and B blocks of such other block copolymer thermoplastic elastomers are shown below in Table I.
  • Block copolymer thermoplastic elastomers can be prepared, for example, by anionic polymerization using an alkyl-lithium initiator.
  • Thermoplastic elastomers based on urethane are discussed in greater detail in Schollenberger, USP 3,015,650 and Saunders, USP 3,214,41 1 ; and those based on copolyester-ether are discussed in Witsiepe, USP 3,651,014, each of which is incorporated herein.
  • thermoplastic elastomers useful as an impact modifier in the compositions of this invention include olefinic elastomers, which are based generally on a long-chain, hydrocarbon backbone, which may or may not be grafted with one or more vinyl monomers.
  • olefinic elastomers which illustrate the variation in the known substances which would suffice for such purpose are as follows: butyl rubber; chlorinated polyethylene rubber; chlorosulfonated polyethylene rubber; ethylene/propylene copolymer and ethylene/propylene/diene copolymer, which may be grafted with one or more vinyl monomers; neoprene rubber; nitrile rubber; polybutadiene and polyisoprene.
  • elastomeric impact modifiers useful in the compositions of this invention are emulsion-type, core-shell graft copolymer elastomers containing greater than forty percent rubber by weight.
  • the random shape and size assumed in the polymer composition matrix by a thermoplastic elastomer, as described above, is to be distinguished from the shape and size assumed by a core-shell graft copolymer.
  • a core- shell graft copolymer is typically present in the polymer matrix in a bead shape both before and after mixing by application of shearing forces, whether heat is used or not, and is usually present in a rather narrow size range, for example 0.05-0.8 microns.
  • this core-shell, or spherical, shape by the graft polymer results from the fact that the outer layers, which surround the core, are formed by grafting appropriate monomers onto the core.
  • a core-shell graft copolymer typically cannot be melted and recooled without a significant change in properties because the graft polymer will tend to decompose or crosslink, and the bead-shaped segments of graft polymer will tend to agglomerate upon melting, making dispersion of them by mixing difficult.
  • core-shell graft copolymer elastomers suitable for use herein are those which can be based on either a diene rubber, an acrylate rubber or on mixtures thereof.
  • a diene rubber contains a substrate latex, or core, which is made by polymerizing a diene, preferably a conjugated diene, or by copolymerizing a diene with a mono-olefin or polar vinyl compound, such as styrene, acrylonitrile, or an alkyl ester of an unsaturated carboxylic acid such as methyl methacrylate.
  • the substrate latex is typically made up of about 40-85% diene, preferably a conjugated diene, and about 15- 60% of the mono-olefin or polar vinyl compound.
  • the elastomeric core phase should have a glass transition temperature ("T g ") of less than about 10°C, and preferably less than about -20°C.
  • a mixture of ethylenically unsaturated monomers is then graft polymerized to the substrate latex.
  • monomers may be used for this grafting purpose, of which the following are exemplary: vinyl compounds such as vinyl toluene or vinyl chloride; vinyl aromatics such as styrene, alpha-methyl styrene or halogenated styrene; acrylonitrile, methacrylonitrile or alpha-halogenated acrylonitrile; a C -C alkyl acrylate such as ethyl acrylate or hexyl acrylate; a C ⁇ C.
  • alkyl methacrylate such as methyl methacrylate or hexyl methacrylate; glycidyl methacrylate; acrylic or methacrylic acid; and the like or a mixture of two or more thereof.
  • the preferred grafting monomers include one or more of styrene, acrylonitrile and methyl methacrylate.
  • 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 although, when just two are used, they are frequently utilized in equal amounts.
  • a typical weight ratio for methyl methacrylate/butadiene/styrene copolymer (“MBS" rubber) is about 60-80 parts by weight substrate latex, about 10-20 parts by weight of each of the first and second monomer shells.
  • a preferred formulation for an MBS rubber is one having a core built up from about 71 parts of butadiene, about 3 parts of styrene, about 4 parts of methyl methacrylate and about 1 part of divinyl benzene; a second phase of about 1 1 parts of styrene; and a shell phase of about 11 parts of methyl methacrylate and about 0.1 part of 1 ,3-butylene glycol dimethacrylate, where the parts are by weight of the total composition.
  • a diene-based, core-shell graft copolymer elastomer and methods for making same, as described above, are discussed in greater detail in Saito, USP 3,287,443, Curfman, USP 3,657,391, and Fromuth, USP 4,180,494.
  • An acrylate rubber has a first phase forming an elastomeric core and a second phase forming a rigid thermoplastic phase about said elastomeric core.
  • the elastomeric core is formed by emulsion or suspension polymerization of monomers which consist of at least about 50 weight percent alkyl and/or aralkyl acrylates having up to fifteen carbon atoms, and, although longer chains may be used, the alkyls are preferably C.-C., most preferably butyl acrylate.
  • the elastomeric core phase should have a T g of less than about 10°C, and preferably less than about -20°C.
  • the rigid thermoplastic phase of the acrylate rubber is formed on the surface of the elastomeric core using suspension or emulsion polymerization techniques.
  • the monomers necessary to create this phase together with necessary initiators are added directly to the reaction mixture in which the elastomeric core is formed, and polymerization proceeds until the supply of monomers is substantially exhausted.
  • Ethylenically unsaturated monomers such as glycidyl methacrylate, or an alkyl ester of an unsaturated carboxylic acid, for example a C ⁇ C, alkyl acrylate like methyl acrylate, hydroxy ethyl acrylate or hexyl acrylate, or a C ⁇ C.
  • alkyl methacrylate such as methyl methacrylate or hexyl methacrylate, or mixtures of any of the foregoing, are some of the vinyl monomers which can be used for this purpose. Either thermal or redox initiator systems can be used. Because of the presence of the graft linking agents on the surface of the elastomeric core, a portion of the chains which make up the rigid thermoplastic phase are chemically bonded to the elastomeric core. It is preferred that there be at least about 20% bonding of the rigid thermoplastic phase to the elastomeric core.
  • a preferred acrylate rubber is made up of more than about 40% to about 95% by weight of an elastomeric core and about 60% to about 5% of a rigid thermoplastic phase.
  • the elastomeric core can be polymerized from about 75% to about 99.8% by weight C.-C. acrylate, preferably n-butyl acrylate.
  • the rigid thermoplastic phase can be polymerized from at least 50% by weight of C ⁇ C. alkyl methacrylate, preferably methyl methacrylate. Acrylate rubbers and methods for making same, as described above, are discussed in greater detail in Owens, USP 3,808, 180 and Witman, USP 4,299,928.
  • thermo and oxidative stabilizers which can be advantageously utilized are hindered phenols, hydroquinones, phosphites, including substituted members of those groups and/or mixtures of more than one thereof.
  • a preferred phenolic anti-oxidant is Irganox 1 " 1076 anti-oxidant, available from Ciba-Geigy Corp.
  • Ultra-violet stabilizers such as various substituted resorcinols, salicylates, benzotriazoles, benzophines, hindered amines and hindered phenols can also be usefully included in the compositions hereof, as can be lubricants, colorants, fillers such as talc, clay, phosphate, metal, inorganic or graphite fibers, or mica, dyes, pigments, mold release agents, and reinforcement agents such as fiberglass or phosphate, metal, inorganic or graphite fibers. Additives and stabilizers of the same or a similar kind as the foregoing are known, and the use and selection thereof is within the skill in the art.
  • additives typically do not exceed 15 percent by weight of the total composition, except fillers or reinforcing agents, which may constitute up to 40 percent of the composition.
  • Ignition resistant metal salts may be added, however, their presence, therefore, may not be desirable in the compositions of this invention.
  • the polycarbonate compositions prepared in Controls A-B and Examples 1- 4 are made by dry blending the ingredients thereof in a Lightnin blender for thirty seconds without agitation and then for thirty seconds with agitation. The dry blended formulations are then melt mixed in a vented 30mm Werner-Pfleiderer co-rotating, twin screw extruder using a set temperature of 250°C for all barrel zones. Each extruded composition is passed through a water bath, chopped into granules and collected for molding. Granules are thoroughly dried in an air draft oven at 100°C for at least 4 hours prior to molding. All testing samples are prepared by injection molding on a 55 ton Negri Bossi molding machine, usinga 250°C temperature for the barrel.
  • Polycarbonate is a Bisphenol-A polycarbonate having a melt flow rate of 14, as determined according to ASTM Designation D 1238-89, Condition 300/1.2, available from The Dow Chemical Company;
  • Poly(ethylene terephthalate) having an 0.95 intrinsic viscosity, available from Goodyear Tire and Rubber Company
  • “Elastomer” is ParaloidTM 8967 elastomeric copolymer, a methacryiate/butadiene/styrene core-shell elastomer available from Rohm & Haas Company;
  • PTFE is TeflonTM 6C polymer, fibril-forming poly(tetrafluoroethylene), available from E.I. du Pont de Nemours & Co.;
  • PB-460 is tris(2,4-dibromophenyl) phosphate from F.M.C. Corporation;
  • Calcium Stearate is calcium stearate from Witco.
  • “1 1076” is phenolic anti-oxidant stabilizer, available from Ciba-Geigy Corporation.
  • Molded samples of the compositions of Control A and Examples 1-3 are evaluated according to the following tests, the results of which are also reported in Table II: (1) the U.L. (Underwriters Laboratory) 94 burn test; and (2) the Izod test according to ASTM Designation D 256-84 (Method A) at 23°C to measure impact resistance. The notch is 10 mils (0.254 mm) in radius. Izod results are reported in ft-lb/in.
  • Examples 1-3 show the effect of small amounts of an acid acceptor in achieving a better balance of several properties when higher loadings of a halogenated aryl phosphate are used.
  • Examples 1-3 are not only ductile, but they had a natural white color and a desirably low decrease after molding in the weight average molecular weight (as determined by gel permeation chromatography) of the polycarbonate in the compostion.
  • Control B has no halogenated aryl phosphate and is rated V-2.
  • I have found that by substituting an aromatic carbonate oligomer for a portion of the halogenated aryl phosphate, as in Example 4, it is possible to use a halogenated aryl phosphate at a level which results in a V-0 burn rating, and also obtain good impact resistance in the composition.
  • Example 4 In a further test of Example 4, a molded sample was held at a 0.7 percent strain in a desicator and was saturated every day for two weeks with Black Flag ® Wasp, Bee and Hornet Killer from Boyle-Midway Household Products, Inc. The sample was visually inspected each day for stress cracks caused by the organic solvent in the insect spray, but in two weeks no such cracks appeared. By contrast, when polycarbonate alone is tested in the same manner, it fails from contact with the spray in less than a day.

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Abstract

Composition constituée d'un mélange de polycarbonate, de polyester, d'un polymère d'acrylate et/ou d'une résine thermoplastique styrémique, de poly(tétrafluoroéthylène), d'un accepteur d'acide, d'un phosphate d'aryle halogéné et facultativement d'un oligomère de carbonate aromatique halogéné. Cette composition présente un bon équilibre de ses propriétés de résistance à l'inflammation, aux chocs et aux solvants.
PCT/US1993/011175 1992-11-18 1993-11-17 Melanges contenant du polycarbonate et resistant a l'inflammation WO1994011429A1 (fr)

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0846729A2 (fr) * 1996-12-03 1998-06-10 General Electric Company Composition modifiée de polycarbonate et de polyester
EP0936244A2 (fr) * 1998-02-13 1999-08-18 General Electric Company Composition de polycarbonate ignifugée
US6838502B1 (en) * 1999-07-28 2005-01-04 Idemitsu Petrochemical Co., Ltd. Polycarbonate resin composition
US7067567B2 (en) 2002-07-29 2006-06-27 Bayer Aktiengesellschaft Impact-modified polycarbonate blends
WO2008105761A1 (fr) * 2007-02-26 2008-09-04 Bayer Materialscience Llc Composition de moulage thermoplastique résistant aux impacts et ignifugée
US7799868B2 (en) 2006-02-22 2010-09-21 Bayer Materialscience Llc Flame retardant, impact resistant thermoplastic molding composition
US8357739B2 (en) * 2006-12-11 2013-01-22 Sabic Innovative Plastics Ip B.V. Low fluoride thermoplastic composition, method of manufacture and product made therefrom
US9856406B2 (en) 2013-03-11 2018-01-02 Covestro Llc Flame retardant polycarbonate
US11339263B2 (en) 2015-03-16 2022-05-24 Shpp Global Technologies B.V. Fibrillated polymer compositions and methods of their manufacture

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3903045A (en) * 1973-12-12 1975-09-02 Allied Chem Stabilized, melt processable 3,3,3-trifluoro-2-trifluoromethyl propene/vinylidene fluoride copolymer compositions
US4491553A (en) * 1979-07-17 1985-01-01 Lion Corporation Method for producing filler-loaded thermoplastic resin composite
US4983677A (en) * 1988-04-15 1991-01-08 Minnesota Mining And Manufacturing Company Extrudable thermoplastic hydrocarbon polymer composition
US5030675A (en) * 1987-08-29 1991-07-09 Bayer Aktiengesellschaft Flame-resistant thermoplastic moulding compounds based on polycarbonate, polyalkylene terephthalate, graft copolymer, fluorinated polyolefine and phosphorus compound

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3903045A (en) * 1973-12-12 1975-09-02 Allied Chem Stabilized, melt processable 3,3,3-trifluoro-2-trifluoromethyl propene/vinylidene fluoride copolymer compositions
US4491553A (en) * 1979-07-17 1985-01-01 Lion Corporation Method for producing filler-loaded thermoplastic resin composite
US5030675A (en) * 1987-08-29 1991-07-09 Bayer Aktiengesellschaft Flame-resistant thermoplastic moulding compounds based on polycarbonate, polyalkylene terephthalate, graft copolymer, fluorinated polyolefine and phosphorus compound
US4983677A (en) * 1988-04-15 1991-01-08 Minnesota Mining And Manufacturing Company Extrudable thermoplastic hydrocarbon polymer composition

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0846729A2 (fr) * 1996-12-03 1998-06-10 General Electric Company Composition modifiée de polycarbonate et de polyester
EP0846729A3 (fr) * 1996-12-03 1998-07-29 General Electric Company Composition modifiée de polycarbonate et de polyester
EP0936244A2 (fr) * 1998-02-13 1999-08-18 General Electric Company Composition de polycarbonate ignifugée
EP0936244A3 (fr) * 1998-02-13 2000-10-04 General Electric Company Composition de polycarbonate ignifugée
KR100431885B1 (ko) * 1998-02-13 2004-05-17 제너럴 일렉트릭 캄파니 가수분해 안정성이 향상된 난연성 카보네이트 중합체 조성물
US6838502B1 (en) * 1999-07-28 2005-01-04 Idemitsu Petrochemical Co., Ltd. Polycarbonate resin composition
US7067567B2 (en) 2002-07-29 2006-06-27 Bayer Aktiengesellschaft Impact-modified polycarbonate blends
US7799868B2 (en) 2006-02-22 2010-09-21 Bayer Materialscience Llc Flame retardant, impact resistant thermoplastic molding composition
US8357739B2 (en) * 2006-12-11 2013-01-22 Sabic Innovative Plastics Ip B.V. Low fluoride thermoplastic composition, method of manufacture and product made therefrom
WO2008105761A1 (fr) * 2007-02-26 2008-09-04 Bayer Materialscience Llc Composition de moulage thermoplastique résistant aux impacts et ignifugée
KR101378234B1 (ko) 2007-02-26 2014-03-27 바이엘 머티리얼싸이언스 엘엘씨 난연성 내충격성 열가소성 성형 조성물
US9856406B2 (en) 2013-03-11 2018-01-02 Covestro Llc Flame retardant polycarbonate
US11339263B2 (en) 2015-03-16 2022-05-24 Shpp Global Technologies B.V. Fibrillated polymer compositions and methods of their manufacture

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