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WO1992014787A1 - Melanges de compositons de moulage thermoplastique contenant des resines epoxy - Google Patents

Melanges de compositons de moulage thermoplastique contenant des resines epoxy Download PDF

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Publication number
WO1992014787A1
WO1992014787A1 PCT/US1992/001546 US9201546W WO9214787A1 WO 1992014787 A1 WO1992014787 A1 WO 1992014787A1 US 9201546 W US9201546 W US 9201546W WO 9214787 A1 WO9214787 A1 WO 9214787A1
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Prior art keywords
composition
carbon atoms
bisphenol
radical
epoxy resin
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PCT/US1992/001546
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English (en)
Inventor
Clive P. Bosnyak
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The Dow Chemical Company
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Publication of WO1992014787A1 publication Critical patent/WO1992014787A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • 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
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates

Definitions

  • This invention relates to epoxy-modified polycarbonate compositions, and relates particularly to polycarbonate compositions which are easily colored and which have, when in the form of a molded article, a desirable balance of high gloss and low notch sensitivity to impact loading.
  • Polycarbonate has found many uses because, in general, it combines a high level of heat resistance and dimensional stability with good insulating and non- corrosive properties, and it is easily molded. It does, however, suffer from a tendency to craze and crack unr -r the effects of environmental stress, especially contact with organic solvents such as gasoline. Polycarbonate which has crazed is, undesirably, more likely to experience brittle rather than ductile failure.
  • Liu, U.S. Pat. No. 4,629,760 discloses compositions containing polycarbonate, polyalkylene terephthalate, an acrylate elastomer, and a phenoxy resin which is the polymeric reaction product of a dihydric phenol and epichlorohydrin where the phenoxy resin has a degree of polymerization ("D.P.") of three or more.
  • a phenoxy resin is used in the compositions of U.S. 4,629.760 in an amount of 3-14 percent by weight. It is not recognized in U.S. 4,629,760, however, ( i ) that a phenoxy resin having a D.P.
  • a phenoxy resin having a D.P. of three or more can be effectively used in an impact-modified polycarbonate/polyester blend at levels less than 3 percent by weight, or (iii) that a phenoxy resin adequately improves the gloss and colorability, and reduces the notch sensitivity to impact loading, of an article molded from a polycarbonate/polyester blend which does not also contain an elastomeric impact modifier.
  • One of the features of this invention therefore lies in the use of an epoxy resin, including but not limited to a phenoxy resin, having a D.P. of less than three, in a polycarbonate/polyester blend.
  • Another feature of this invention is the use of an epoxy resin, including but not limited to a phenoxy resin, in a polycarbonate/polyester blend at levels less than 3 weight percent.
  • the polycarbonate/polyester blend may or may not also contain an elastomeric impact modifier. It will be understood that, in the case where the composition does not contain an elastomeric impact modifier, the content of the composition can be expressed, for example, as including polycarbonate, polyester and an epoxy resin with the proviso that the composition does not contain an elastomeric impact modifier.
  • this invention involves a composition of matter containing, in admixture, (a) a polycarbonate, (b) a polyester, and (c) 0.05 to 15 parts, by weight of the total composition, of an epoxy resin which has a degree of polymerization of less than three and has been prepared from a bisphenol.
  • this invention involves a composition of matter containing, in admixture, (a) a polycarbonate,
  • this invention involves a composition of matter containing, in admixture, (a) a polycarbonate, (b) a polyester, and (c) less than 3 parts, by weight of the total composition, of an epoxy resin which has a degree of polymerization of three or more and has been prepared from a bisphenol.
  • this invention involves a composition of matter containing, in admixture, (a) a polycarbonate, (b) a polyester, and
  • this invention involves a composition of matter containing, in admixture, (a) a polycarbonate, (b) a polyester, and (c) 0.05 to 15 parts, by weight of the total composition, of an epoxy resin, with the proviso that the composition does not contain an elastomeric impact modifier.
  • This invention also involves a method of forming an article from a polycarbonate/polyester blend comprising (a) providing a polycarbonate/polyester blend by admixing a polycarbonate, a polyester, an epoxy resin and an elastomeric impact modifier; (b) softening said polycarbonate/polyester blend by the application of heat; and (c) forming said heat-softened polycarbonate/polyester blend into an article.
  • 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, automobile body panels and other components for use in the automotive 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) a polycarbonate has been admixed in a blended composition with (b) an aromatic polyester, and (c) an epoxy resin, and, optionally, (d) an elastomeric impact modifier.
  • Suitable ranges of content for components (a), (b), (c) and (d) in the compositions of this invention, expressed in parts by weight, are as follows: (a) polycarbonate from 1 part to 99 parts, and preferably from 25 parts to 95 parts,
  • aromatic polyester from 1 part to 99 parts, and preferably from 5 parts to 75 parts,
  • epoxy resin (_i) from 0.05 part to 15 parts, preferably from 0.1 part to 10 parts, and more preferably from 0.3 part to 2.0 parts when the epoxy resin is a phenoxy resin having a D.P. of less than three or when the epoxy resin is not a phenoxy resin, and ( i__ ) less than 3 parts, preferably from 0.05 part to 2.5 parts, and more preferably from 0.1 part to 2 parts, when the epoxy resin is a phenoxy resin having a D.P. of three or more, and
  • compositions of this invention can be accomplished by any suitable blending means known in the art, which may include dry mixing, melt mixing and/or mixing in solution.
  • compositions of this invention can undergo fabrication and can therein be formed or molded using conventional techniques such as compression, injection molding, calendering, vacuum forming, 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.
  • polycarbonates suitable for use in the present invention as component (a) may be prepared, for example, by reacting an aromatic dihydric phenol with a carbonate precursor, such as phosgene, a haloformate or a carbonate ester.
  • a carbonate precursor such as phosgene, a haloformate or a carbonate ester.
  • a preferred method for preparing suitable polycarbonates involves the use of a carbonyl halide, such as phosgene, as the carbonate precursor.
  • This method involves passing phosgene gas into a reaction mixture containing an activated dihydric phenol, or a nonactivated dihydric phenol and an acid acceptor, such as pyridine, dimethyl aniline, quinoline and the like.
  • the acid acceptor may be used undiluted or diluted with inert organic solvents, such as methylene chloride, chlorobenzene or 1,2-dichloroethane.
  • Tertiary amines are advantageous since they are good solvents as well as acid acceptors during the reaction.
  • the temperature at which the carbonyl halide reaction proceeds may vary from below 0°C to 100°C, preferably from room temperature to 50°C. Since the reaction is exothermic, the rate of phosgene addition may be used to control the temperature of the reaction.
  • the amount of phosgene required will generally depend upon the amount of dihydric phenol present. Generally speaking, one mole of phosgene will react with one mole of dihydric phenol to form the polycarbonate and two moles of HC1. The HC1 is in turn taken up by the acid acceptor.
  • Another method for preparing aromatic polycarbonates involves adding phosgene to an alkaline aqueous suspension of dihydric phenols. This is preferably done in the presence of inert solvents such as methylene chloride, 1 ,2-dichloroethane and the like. Quaternary ammonium compounds may be employed to catalyze the reaction.
  • Yet another method for preparing aromatic polycarbonates involves the phosgenation of an agitated suspension of an anhydrous alkali salt of an aryl diol in a nonaqueous medium such as benzene, chlorobenzene or toluene. The reaction proceeds by the addition of phosgene to a slurry of the sodium salt of, for example, Bisphenol A in an inert polymer solvent such as chlorobenzene.
  • a haloformate such as the bis-haloformate of Bisphenol A may be used in place of phosgene as the carbonate precursor in any of the methods described above.
  • a carbonate ester is used as the carbonate precursor in the polycarbonate-forming reaction, the materials are reacted at temperatures in excess of 100°C for times varying from 1 to 15 hours. Under such conditions, ester interchange occurs between the carbonate ester and the dihydric phenol used.
  • the ester interchange is advantageously consummated at reduced pressures on the order of from 10 to 100 millimeters of mercury, preferably in an inert atmosphere such as nitrogen or argon.
  • the polymer-forming reaction may be conducted in the absence of a catalyst, one may, if desired, employ a typical ester exchange catalyst, such as metallic lithium, potassium, calcium or magnesium.
  • a typical ester exchange catalyst such as metallic lithium, potassium, calcium or magnesium.
  • the amount of such catalyst, if used, is usually small, ranging from 0.001 percent to 0.1 percent, based on the weight of the dihydric phenols employed.
  • the aromatic polycarbonate emerges from the reaction in either a true or pseudo solution depending on whether an aqueous base or pyridine is used as an acid acceptor.
  • the copolymer may be precipitated from the solution by adding a polymer nonsolvent, such as heptane or isopropanol.
  • the polymer solution may be heated, typically under reduced pressure, to evaporate the solvent.
  • a preferred aromatic polycarbonate is characterized by repeated units corresponding to the general formula:
  • X is a divalent, linear or branched C 1 -C 20 hydrocarbon radical (optionally containing hetero atoms such as 0, S, N or halogen atoms), a single bond, -0-, - S-, -S 2 -, -SO-, -SO2-, or -CO-.
  • Each aromatic ring may additionally contain, instead of hydrogen, up to four substituents such as C.-C 4 alkyl hydrocarbon or alkoxy radicals, aryl or aryloxy radicals, or halo radicals such as chloro or bromo.
  • the polycarbonates mentioned above such as those derived from 2,2-bis(4- hydroxyphenyl)propane (“Bisphenol-A” or “Bis-A”), from 1 , 1-bis(4-hydroxyphenyl)-1-phenyl ethane (“Bisphenol-AP” or “Bis-AP”), or from 2,2-bis(3,5-dibromo, 4- hydroxyphenyl)propane (“Tetrabromobisphenol-A” or "TBBA”)
  • the carbonate polymers used herein can also be derived from two or more bisphenols, or two or more acid- or hydroxy-terminated reactants such as dicarboxylic acids or alkylene glycols, or from two or more different dihydroxy compounds, or mixtures of any of the foregoing, in the event a carbonate copolymer or interpolymer, such as a copolyester/carbonate is desired, rather than a homopolymer.
  • Copolymers can be formed, for example, when a bisphenol is reacted with a carbonic acid derivative and a polydiorganosiloxane containing ⁇ , ⁇ -bishydroxyaryloxy terminal groups to yield a siloxane/carbonate block copolymer (as are discussed in greater detail in Paul, USP 4,569,970).
  • a bisphenol is reacted with a bis(ar-haloformylaryl) carbonate, which is formed by reacting a hydroxycarboxylic acid with a carbonic acid derivative under carbonate forming conditions, an alternating copolyestercarbonate is obtained, same being discussed in greater detail in Swart, USP 4,105,533.
  • polycarbonate as used herein, and in the claims appended hereto, should therefore be understood to include carbonate homopolymers, carbonate copolymers (as described above), and/or blends of carbonate homopolymers and/or carbonate copolymers.
  • the polyester useful as component (b) herein may be made by the self-esteri ication of hydroxycarboxylic acids, or direct esterification, which involves the reaction of a diol with a dicarboxylic acid with the resulting elimination of water, giving an -[- AABB-]- polyester. Temperatures applied exceed the melting points of the reactants and typically approach the boiling point of the diol being used, and usually range from about 150°C to about 280°C. An excess of the diol is typically used, and once all of the acid has reacted with diol, the excess diol is removed by distillation with the application of additional heat under reduced pressure.
  • 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 is typically 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.
  • 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.
  • Typical alkylene diols used in ester formation are the C 2 -C 10 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, -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 aci , diphenoxyethanedicarboxylic acid.
  • polyester in addition to polyesters formed from one diol and one diacid only, the term "polyester” as used herein includes random, pa erned 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'-dihydroxybiphenyl.
  • 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.
  • the epoxy resin utilized in this invention as component (c) is typically prepared from an epihalohydrin such as epichlorohydrin, which is reacted in the presence of a base with a compound containing at least two active hydrogen atoms.
  • Representative materials used as a base for such purpose include caustics such as the alkali metal and alkaline earth oxides and hydroxides.
  • An active hydrogen atom is one which can be abstracted by such a base to form an anion
  • each anion formed thereon by the deprotonating or catalytic action of the base opens the epoxide ring at the alpha carbon on an epichlorohydrin molecule to create a hydroxyl group on the beta carbon.
  • the dichlorohydrin of the active-hydrogen-containing compound results. Dehydrohalogenation then occurs at each such location to regenerate an epoxide ring at the beta and gamma carbons. If, in the active-hydrogen- containing compound, hydrogen was abstracted from oxygen, the product at this point may for practical purposes be represented as the diglycidyl ether of the active-hydrogen-containing compound.
  • a polymer can be formed which (assuming, again, an oxyanion) is a poly(hydroxy ether) containing epoxide rings at its termini. It is possible that one terminus of such polymer could be occupied by an unabstracted hydrogen atom rather than an epoxide ring.
  • Such a polymer can be generally represented by one or the other of the following structures:
  • the diglycidyl ether of the active-hydrogen-containing compound (assuming, again, an oxyanion) is reacted with an additional charge of the active-hydrogen-containing compound.
  • Caustic or other proton acceptor such as triethanolamine, a substitiuted imidazole or Na 9 C0 3
  • the reaction in only a catalytic amount as the oxyanion regenerates itself each time an epoxide ring is opened and secondary hydroxyl group is formed.
  • Reaching high molecular weight is dependent on employment of agitation, and of higher temperature (up to 150°C) and pressure than used in the direct method, because of the viscosity of the reaction mass.
  • Epoxy resins with a degree of polymerization of 30 or more can be prepared by the fusion process.
  • Epoxy resins prepared as desribed above, can be esterified with saturated or unsaturated fatty acids at either the terminal epoxide ring or at a pendant hydroxyl site along the polymer backbone. Such an esterification reaction is typically conducted in an inert atmosphere at 225-260°C, with the removal of water as a by-product.
  • the terminal epoxide rings of epoxy resins prepared as described above can be fully or partially hydrolyzed with water. However, even when the terminal epoxide rings are not hydrolyzed, the highest weight epoxy resins have negligible relative epoxide content and are (when prepared from an oxyanion) essentially polyethers with pendant hydroxyl groups.
  • R 1 and R 2 are the same or different and are alkyl of one to four carbon atoms, inclusive, preferably one to three, and halogen, preferably chloro or bromo; a and b are the same or different and are an integer of 0, 1, 2, 3 or 4, preferably 0, 1 or 2; X 1 is selected from an alkylene radical of 2-15 carbon atoms, an alkylidene radical of 1-15 carbon atoms, a cycloalkylene radical of 4-12 carbon atoms, or a cycloalkylidene radical of 4-12 carbon atoms, S, S 2 , CO, SO, 0 or S0 2 ; and c is 0 or 1.
  • Use of oxyamons such as those prepared from the above described bisphenols yields an epoxy resin of the type which is frequently referred to as a phenoxy resin.
  • oxyanions can also be prepared from bis p-hydroxy phenyl fluorene, from any of the above described bisphenols where the aromatic rings are hydrogenated, or from a diol of the general formula
  • each R 3 is independently hydrogen, an alkyl radical of 1-10 carbon atoms such as ethyl, t-butyl or cyclohexyl, or a halo radical such as chloro or bromo
  • each R 4 is independently an alkyl radical of 1-10 carbon atoms, an alkylene radical of 2-10 carbon atoms, an alkylidene radical of 1-10 carbon atoms such as isopropylidene, a cycloalkylene radical of 4-12 carbon atoms, or a cycloalkylidene radical of 4-12 carbon atoms.
  • diols suitable for such purpose include glycols such as 1 ,2-ethanediol, 1,2- propanediol, 1 ,3-propanediol, 1 ,2-butanediol, 1,3- butanediol, 1 ,4-butanediol, 2,3-butanediol, 2,2'oxydiethanol, cis-2-buten-1 ,4-diol, trans-2-buten- 1,4-diol, 2-butyn-1 ,4-diol, 2,4-pentanediol, 1,5- pentanediol, 1 ,6-hexanediol, 2,5-hexanediol, 2- methyl-1 ,3-pentanediol, 2-methyl-2,4-pentanediol, 2,3- dimethyl-2,3-butanediol, 2,2'-(ethylenedioxy
  • Aminoanions can be prepared from aromatic diamines which include, but are not limited to, dianiline, or phenylenediamines (benzenediamines) such as toluene-2,4-diamine, toluene-2,6-diamine, 2,3,5,6- tetra-methyl-p-phenylenediamine, iV,_V-diethyl-p- phenylenediamine, _V,iV'-di-sec-butyl-p-phenylenediamine, N,N'-bis ( 1-methyl-heptyl)-p-phenylenediamine, N,N'-di- sec-butyl--Y,_V'-dimethyl-p-phenylenediamine, N,N'- diphenyl-p-phenylenediamine, -V,_V'-di-2-naphthyl-p- phenylenediamine, ⁇ T-iso
  • Aminoanions can also be prepared from aliphatic diamines such as ethylenediamine, piperazine, propylenediamine, 1,3-diaminopropane, iminobispropylamine, menthanediamine, hexamethylenediamine, imidazolidine, or from heterocyclic compounds such as p-aminophenol, 2- imidazolidinone (ethyleneurea), triazine or hydantoin.
  • aliphatic diamines such as ethylenediamine, piperazine, propylenediamine, 1,3-diaminopropane, iminobispropylamine, menthanediamine, hexamethylenediamine, imidazolidine, or from heterocyclic compounds such as p-aminophenol, 2- imidazolidinone (ethyleneurea), triazine or hydantoin.
  • each R 5 is independently hydrogen, an alkyl radical of 1-10 carbon atoms such as ethyl, t-butyl or cyclohexyl, or a halo radical such as chloro or bromo
  • each R 6 is independently an alkyl radical of 1-10 carbon atoms, an alkylene radical of 2-10 carbon atoms, an alkylidene radical of 1-10 carbon atoms such as isopropylidene, a cycloalkylene radical of 4-12 carbon atoms, a cycloalkylidene radical of 4-12 carbon atoms, or (with or without the adjacent carbon atoms) an aromatic radical of 6-12 carbon atoms such as benzyl or naphthyl.
  • Suitable dithiols include 1,2-ethanedithiol, 2,2-propanedithiol and p-benzenedithiol.
  • the epoxies useful in this invention can also be prepared from the reaction of a novolac and epihalohydrin.
  • Representative novolacs are phenol/formaldehyde condensates in which multiple phenol functionalities are joined by methylene bridges.
  • novolac epoxies multiepoxy functionality can increase with increasing molecular weight because the polymer is formed from the methylene bridges, leaving each phenolic hydroxyl group free to react with epichlorohydrin to form a pendant epoxide ring.
  • the novolac may additionally be prepared from a substituted phenol.
  • Novolac epoxies may be generally represented by a formula such as
  • the elatomeric impact modifier when used as component (d) in this invention, is a rubbery or elastomeric substance, typically with a T ⁇ less than 10°C, which is suitable or effective for the purpose of improving the toughness of a polycarbonate/polyester blend; reducing its notch sensitivity to impact loading; and enabling it to recover from the deformation of applied stress without fracture.
  • the rubber content of the impact modifier used in this invention is greater than 40 percent by weight, and a mixture of two or more elastomeric substances can be used as the impact modifier.
  • ⁇ gj glass transition temperature is the temperature or temperature range at which an amorphous polymeric material shows an abrupt change in its physical properties, including, for example, mechanical strength. T g can be determined by differential scanning calorimetry.
  • 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, 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 -20°C to 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 2 -C 10 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 olefinic character of the B block.
  • the mid 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 alkenyl aromatic monomer (as described above) into the reaction vessel.
  • appropriate alkenyl aromatic monomer as described above
  • 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.
  • a thermoplastic end block A upon addition of alkenyl 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.
  • styrene/isoprene copolymers When the styrene/isoprene copolymers are hydrogenated, they are frequently represented as styrene/ethylene/propylene (or styrene/ethylene/propylene/styrene in the tri-block form) copolymers.
  • the block copolymers described above are discussed in greater detail in Haefele, USP 3,333,024 and Wald, USP 3,595,942.
  • a thermoplastic elastomer similar to those described above is available from Shell Chemical Company as KratonTM G 1651 elastomer.
  • Core-shell graft copolymer elastomers useful in this invention can be based on either a diene rubber, an acrylate rubber or on mixtures thereof.
  • the substrate latex is typically made up of 40-85 percent diene, preferably a conjugated diene, and 15-60 percent of the mono-olefin or polar vinyl compound.
  • 15 elastomeric core phase should have a glass transition temperature ("Tg") of less than 10°C, and preferably less than -20°C.
  • Tg glass transition temperature
  • a mixture of monomers is then graft polymerized to the substrate latex.
  • a variety of monomers may be used for this grafting purpose, of which
  • 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 pe - acrylonitrile; a C 1 -C 8 alkyl acrylate such as ethyl acrylate or hexyl acrylate; a C- ⁇ C g alkyl methacrylate such as methyl methacrylate or hexyl methacrylate; acrylic or methacrylic acid; and the like or a mixture of two or more thereof.
  • 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 pe - acrylonitrile
  • 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 60-80 parts by weight substrate latex, 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 71 parts of butadiene, 3 parts of styrene, 4 parts of methyl methacrylate and 1 part of divinyl
  • An acrylate rubber has a first phase forming an
  • the elastomeric core is formed by emulsion or suspension polymerization of monomers which consist of at least 50 pc - 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 2 -C 6 , most preferably butyl acrylate.
  • the elastomeric core phase should have a ⁇ g of less than 10°C, and preferably less
  • 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.
  • Monomers such as an alkyl ester of an unsaturated carboxylic acid, for example a C j -C 8 alkyl acrylate like methyl acrylate, hydroxy ethyl acrylate or hexyl acrylate, or a C j -C 8 alkyl methacrylate such as methyl methacrylate or hexyl methacrylate, or mixtures of any of the foregoing, are some of the 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 20 percent bonding of the rigid thermoplastic phase to the elastomeric core.
  • a preferred acrylate rubber is made up of more than 40 percent to 95 percent by weight of an elastomeric core and 60 percent to 5 percent of a rigid thermoplastic phase.
  • the elastomeric core can be polymerized from 75 percent to 99.8 percent by weight C j -C 8 acrylate, preferably n-butyl acrylate.
  • the rigid thermoplastic phase can be polymerized from at least 50 percent by weight of C,,-C 8 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.
  • additives may be used in the compositions of this invention for purposes such as protection against thermal, oxidative and ultra-violet degradation.
  • Such additives may be included in the composition at any point during the processing, and the choice as to which additive is employed, if any, is not critical to this invention.
  • certain additives such as hindered amines may be used advantageously with epoxy moieties to promote the added performance of the additive or epoxy moiety. As such, there may be some advantage to premixing the components present in minor amount before addition to
  • thermal and oxidative stabilizers which can advantageously be utilized are hindered phenols, hydroquinones, phosphites, including
  • a preferred phenolic anti- oxidant is IrganoxTM 1076 anti-oxidant, available from Ciba-Geigy Corp.
  • Ultra-violet stabilizers such as various substituted resorcinols, salicylates,
  • benzotriazoles can also be usefully included in the compositions of this invention, as can be lubricants, colorants, fillers such as talc, clay or mica, pigments, pe - ignition resistant additives and mold release agents, and reinforcement agents such as fiberglass.
  • Additives and stabilizers such as the foregoing, and many others which have not been mentioned, are known in the art, and the decision as to which, if any, to use is not critical
  • the polycarbonate compositions prepared in Controls A-G and Examples 1-11 are made by dry blending granules of polycarbonate, poly(ethylene terephthalate), and methacrylate/butadiene/styrene copolymer, which were used without drying.
  • the epoxy resin was added to the granules of the desired weight ratio (by syringe when liquid) prior to tumble mixing for five minutes followed by extrusion with a Werner-Pfleiderer 30 mm twin-screw extruder.
  • the feed zone was set at 200°C, all other zones were set at 260°C.
  • the feed-rate was adjusted to give torque values of 50 percent with a screw speed of 300 rpm.
  • MVS is ParaloidTM 3607 grafted core-shell pc - elastomer, a methacrylate/butadiene/styrene copolymer available from Rohm & Haas Chemical Company;
  • Epoxy is an epoxy resin prepared from Bisphenol-A and epichlorohydrin; the epoxy resin used in all formulations except Example 3 and Control G has a
  • Specular gloss is measured according to ASTM Designation D 523-85 using a Hunter Lab reflectometer. The beam axis angle is 20°.
  • Impact resistance is measured at 25°C by the Izod test according to ASTM Designation D 256-84 (Method A).
  • the notch is 10 mils (0.254 mm) in radius.
  • Izod pp indicates that the notch is cut so that the flexural shock caused by the striking nose of the pendulum is propagated parallel to the direction of flow taken by the molten extrudate during formation of the sample.
  • Izod par indicates that the notch is cut so that the flexural shock caused by the striking nose of the pendulum is propagated perpendicular to the direction of flow taken by the molten extrudate during formation of the sample. The result is reported first in ft-lb/in and second in J/m.
  • Example 1 has improved gloss and an improved Izod impact value over the associated control, Control A, and a similar trend may be seen with reference to the other examples.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Epoxy Resins (AREA)

Abstract

Mélange polycarbonate permettant de réaliser par moulage des articles présentant un excellent fini brillant et une faible vulnérabilité aux éraflures résultant d'un choc, élaboré en additionnant à un polycarbonate un polyester aromatique, une résine epoxy et, facultativement, un modificateur élastomère pour la résistance aux chocs.
PCT/US1992/001546 1991-02-26 1992-02-26 Melanges de compositons de moulage thermoplastique contenant des resines epoxy WO1992014787A1 (fr)

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US661,922 1984-10-16
US66192291A 1991-02-26 1991-02-26

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0601226A1 (fr) * 1991-06-10 1994-06-15 Kanegafuchi Chemical Industry Co., Ltd. Composition de résine polyester à combustion retardée
WO1994022955A1 (fr) * 1993-04-05 1994-10-13 Alliedsignal Inc. Melange de polyesters et de polycarbonates a haute resistance a l'impact
EP0714934A1 (fr) * 1994-11-22 1996-06-05 Bayer Corporation Séchage à basse température des compositions modifiées au choc de polycarbonate/polyester
EP0945491A3 (fr) * 1998-03-23 2001-02-14 DAICEL CHEMICAL INDUSTRIES, Ltd. Composition de résine et produits formés
WO2001038436A1 (fr) * 1999-11-24 2001-05-31 Basf Aktiengesellschaft Matieres moulables polyesteriques thermostables
WO2007073399A1 (fr) * 2005-12-22 2007-06-28 General Electric Company Articles thermoplastiques a faible brillance
US8084550B2 (en) 2005-05-23 2011-12-27 Sabic Innovative Plastics Ip B.V. Low gloss thermoplastic composition
US8222351B2 (en) 2007-02-12 2012-07-17 Sabic Innovative Plastics Ip B.V. Low gloss polycarbonate compositions
US8222350B2 (en) 2007-02-12 2012-07-17 Sabic Innovative Plastics Ip B.V. Low gloss polycarbonate compositions

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0601226A1 (fr) * 1991-06-10 1994-06-15 Kanegafuchi Chemical Industry Co., Ltd. Composition de résine polyester à combustion retardée
WO1994022955A1 (fr) * 1993-04-05 1994-10-13 Alliedsignal Inc. Melange de polyesters et de polycarbonates a haute resistance a l'impact
EP0714934A1 (fr) * 1994-11-22 1996-06-05 Bayer Corporation Séchage à basse température des compositions modifiées au choc de polycarbonate/polyester
EP0945491A3 (fr) * 1998-03-23 2001-02-14 DAICEL CHEMICAL INDUSTRIES, Ltd. Composition de résine et produits formés
WO2001038436A1 (fr) * 1999-11-24 2001-05-31 Basf Aktiengesellschaft Matieres moulables polyesteriques thermostables
US6894112B1 (en) 1999-11-24 2005-05-17 Basf Aktiengesellschaft Thermally stable polyester molding materials
US8084550B2 (en) 2005-05-23 2011-12-27 Sabic Innovative Plastics Ip B.V. Low gloss thermoplastic composition
US8592523B2 (en) 2005-05-23 2013-11-26 Sabic Innovative Plastics Ip B.V. Low gloss thermoplastic articles
WO2007073399A1 (fr) * 2005-12-22 2007-06-28 General Electric Company Articles thermoplastiques a faible brillance
CN101384663B (zh) * 2005-12-22 2011-11-16 沙伯基础创新塑料知识产权有限公司 低光泽热塑性制品
US8222351B2 (en) 2007-02-12 2012-07-17 Sabic Innovative Plastics Ip B.V. Low gloss polycarbonate compositions
US8222350B2 (en) 2007-02-12 2012-07-17 Sabic Innovative Plastics Ip B.V. Low gloss polycarbonate compositions

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