WO2000064978A1 - Thermoplastic polyketone moulding materials - Google Patents

Thermoplastic polyketone moulding materials Download PDF

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Publication number
WO2000064978A1
WO2000064978A1 PCT/EP2000/003215 EP0003215W WO0064978A1 WO 2000064978 A1 WO2000064978 A1 WO 2000064978A1 EP 0003215 W EP0003215 W EP 0003215W WO 0064978 A1 WO0064978 A1 WO 0064978A1
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Prior art keywords
weight
thermoplastic
composition according
graft
molding composition
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PCT/EP2000/003215
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German (de)
French (fr)
Inventor
Matthias Müller
Herbert Eichenauer
Original Assignee
Bayer Aktiengesellschaft
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Priority to AU41172/00A priority Critical patent/AU4117200A/en
Publication of WO2000064978A1 publication Critical patent/WO2000064978A1/en

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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
    • C08L73/00—Compositions of macromolecular compounds obtained by reactions forming a linkage containing oxygen or oxygen and carbon in the main chain, not provided for in groups C08L59/00 - C08L71/00; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
    • C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
    • 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
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers

Definitions

  • the invention relates to thermoplastic molding compositions based on mixtures of thermoplastic polyketones (olefin-carbon monoxide copolymers) and specially produced mixtures of water-moist elastic-thermoplastic graft polymer obtained by emulsion polymerization and thermoplastic vinyl polymer resin present in the melt form, their use for the production of molded articles and the products produced therefrom Molded body.
  • thermoplastic polyketones olefin-carbon monoxide copolymers
  • water-moist elastic-thermoplastic graft polymer obtained by emulsion polymerization and thermoplastic vinyl polymer resin present in the melt form
  • Thermoplastic polyketones are increasingly used as engineering thermoplastics in the automotive sector e.g. for the production of fuel tanks and fuel line systems and in the electrical / electronics sector e.g. for the production of plug connections.
  • Thermoplastic polyketones are particularly good low-temperature toughness compared to other technical thermoplastics
  • thermoplastic polyketones with regard to special properties by blending with other polymer components.
  • thermoplastic polyketones for example, US-A 5,166,252 mixtures of thermoplastic polyketones with reinforcing materials and thermoplastic polyurethanes to achieve improved rigidity and heat resistance.
  • the production of molding compositions from thermoplastic polyketones and polyurethanes is known (US-A 4,851,482, EP-A 339 747). It is described that the molding compositions have good toughness and rigidity as well as solvent resistance and abrasion resistance.
  • the object of the present invention is now to provide inexpensive materials based on polyketones with a good overall property profile, in particular good toughness and toughness behavior under impact and impact stress even at low temperatures, good surface quality, good processing stability, good processing behavior, good barrier properties to fuel and solvents as well as gases such as oxygen, good UV stability of the molded parts made from them and a low content of volatile components.
  • the molding compositions according to the invention are distinguished in particular by good processing, especially avoidance of yellow spots, good flowability and stability in the melt.
  • Such materials can be used in typical areas of application of engineering thermoplastics such as use in the electrical / electronics sector, the automotive sector or the film and packaging sector and are particularly suitable for the production of thin-walled molded parts.
  • thermoplastic molding compositions containing polyketones and specially prepared mixtures of elastomer-thermoplastic graft rubber produced by emulsion polymerization in the form of water-moist powder and separately by solution polymerization or bulk polymerization, in the form of a copolymer or terpolymer prepared in melt form, preferably selected from monomers from styrene, ⁇ -methylstyrene, acrylonitrile, methacrylonitrile. Methyl methacrylate. N-phenylmaleimide can be met. - j -
  • the present invention therefore relates to thermoplastic molding compositions containing
  • thermoplastic molding compositions according to the invention contain component A) in amounts of 99 to 1 part by weight, preferably 98 to 50 parts by weight and particularly preferably 97 to 70 parts by weight, and component B) in amounts of 1 to 99 parts by weight . Parts, preferably 2 to 50 parts by weight and particularly preferably 3 to 30 parts by weight. The sum of all parts by weight of A) and B) is 100.
  • the molding compositions can also contain additives such as Fillers and reinforcing materials such as Glass fibers or mineral fillers. Flame retardant. Processing aids, stabilizers. Flow aids, antistatic agents. Dyes. Contain pigments and other common additives.
  • the polyketone polymers which are used as component A have a linear alternating structure and essentially contain 1 molecule of carbon mono- noxide per molecule of unsaturated hydrocarbon.
  • Suitable ethylenically unsaturated hydrocarbons as monomers for the construction of the polyketone polymer have up to 20 carbon atoms, preferably up to 10 carbon atoms and are aliphatic, such as ethylene and other ⁇ -olefins, for example propylene, 1-butene, 1-isobutylene, 1-hexene, 1- Octene and 1-dodecene, or are arylaliphatic and contain an aryl substituent on a carbon atom of the linear chain.
  • arylaliphatic monomers are styrene, ⁇ -methylstyrene, p-ethylstyrene and m-isopropylstyrene.
  • Preferred polyketone polymers are copolymers of carbon monoxide and ethylene or terpolymers of carbon monoxide, ethylene and a second ethylenically unsaturated hydrocarbon with at least 3 carbon atoms, in particular an ⁇ -olefin such as e.g. and preferably propylene.
  • Terpolymers of at least 2 monomer units are particularly preferred, one of which is ethylene and the other a second hydrocarbon. About 10 to 100 monomer units of the second hydrocarbon are preferably used.
  • the polymer chain of the preferred polyketone polymer is represented by the following formula
  • G is a monomer unit based on an ethylenically unsaturated hydrocarbon with at least 3 carbon atoms, preferably 3 to 10 carbon atoms, which polymerizes due to the ethylenic double bond the ratio y: x is not more than about 0.5.
  • terpolymers are used and the units -CO- (CH 2 CH 2 ) - and -CO- (G) -unit are statistically distributed over the polymer chain.
  • the preferred ratio of y: x is 0.01 to 0.1.
  • Polyketone polymers with a number average molecular weight of approximately 1,000 to 200,000, in particular 20,000 to 90,000, determined by gel permeation chromatography, are preferred.
  • the mixed component B) is obtained by mixing at least one elastic-thermoplastic graft polymer prepared by emulsion polymerization in the form of a water-moist powder with the melt of at least one thermoplastic copolymer or terpolymer prepared by solution or bulk polymerization, composed of vinyl monomers, in particular selected from at least one , preferably two from the group styrene, ⁇ -methylstyrene. Acrylonitrile, methacrylonitrile, methyl methacrylate, N-phenylmaleimide.
  • the rubber content of the mixed component B) (based on the total component B) is 30 to 70% by weight. preferably 35 to 65% by weight and particularly preferably 36 to 50% by weight.
  • Graft polymer is produced by emulsion polymerization, in which Was at least one partially crosslinked rubber latex vinyl monomers were radically polymerized.
  • Diene rubbers i.e. Homopolymers of conjugated dienes with 4 to 8 carbon atoms such as butadiene, isoprene, chloroprene or their copolymers with up to 60% by weight, preferably up to 30% by weight, of a vinyl monomer, e.g. Acrylonitrile, methacrylonitrile, styrene, ⁇ -methylstyrene, halostyrenes, C1-C4-alkylstyrenes, C 1 -Cg-alkyl acrylates, Ci-Cg-alkyl methacrylates, alkylene glycol diacrylates, alkylene glycol dimethacrylates, divinylbenzene;
  • a vinyl monomer e.g. Acrylonitrile, methacrylonitrile, styrene, ⁇ -methylstyrene, halostyrenes, C1-C4-alkylstyrenes, C 1 -
  • Acrylate rubbers i.e. Homopolymers and copolymers of CI -CI Q alkyl acrylates, e.g. Homopolymers of ethyl acrylate, butyl acrylate or copolymers with up to 40% by weight, preferably not more than 10% by weight
  • Mono vinyl monomers e.g. Styrene, acrylonitrile, vinyl butyl ether, acrylic acid (ester), methacrylic acid (ester). Vinyl sulfonic acid.
  • Such acrylate rubber homo- or copolymers are preferably used which contain 0.01 to 8% by weight of divinyl or polyvinyl compounds and or N-methylolacrylamide or N-methylolmethacrylamide or other compounds which act as crosslinkers, e.g. Divinylbenzene. Triallyl cyanurate.
  • Polybutadiene rubbers are preferred. Styrene / butadiene copolymer rubbers with up to 30% by weight of copolymerized styrene and acrylate rubbers. especially those which have a core-shell structure, for example as described in DE-OS 3 006 804. Lances with average particle diameters d 50 of 0.05 to 2.0 ⁇ m, preferably of 0.08 to 1.0 ⁇ m and particularly preferably of 0.1 to 0.5 ⁇ m are suitable for producing the graft polymers suitable according to the invention. The mean particle diameters are determined using an ultracentrifuge (cf. W. Scholtan, H.
  • the so-called seed polymerization technique can also be used, in which e.g. a finely divided butadiene polymer is prepared and then further polymerized to larger particles by further conversion with monomers containing butadiene.
  • rubber polymer latices can also be produced by emulsifying finished rubber polymers in aqueous media (cf. Japanese patent application 55 125 102).
  • R is hydrogen or methyl
  • R2 halogen or alkyl having 1 to 4 carbon atoms
  • q an integer from 1 to 5, preferably 0.1 to 3, particularly preferably 0 or 1,
  • R-3 is hydrogen or methyl
  • X represents a CN, R 4 OOC or R 5 R 6 NOC group, where
  • R4 is hydrogen or alkyl of 1 to 4 carbon atoms
  • R5 and R6 independently represent hydrogen, phenyl or alkyl having 1 to 4 carbon atoms.
  • Exemplary and preferred for compounds of formula (I) are styrene. ⁇ -methyl styrene, p-methyl styrene and vinyl toluene.
  • Exemplary and preferred for compounds of formula (II) are acrylonitrile and methylene methacrylate.
  • Other suitable monomers are, for example, vinyl acetate and N-phenylene malimide.
  • Preferred monomers are mixtures of styrene and acrylonitrile, ⁇ -methylstyrene and acrylonitrile, of styrene, acrylonitrile and methyl methacrylate and combinations of these monomer mixtures with N-phenylmaleimide.
  • Preferred graft polymers according to the invention are those which have been obtained by graft polymerization of the abovementioned.
  • Compounds of the formulas (I) and (II) in a weight ratio of 90:10 to 50:50, preferably 80:20 to 65:35 in the presence of such amounts of rubber, preferably polybutadiene, are obtained in such a way that graft polymers with rubber contents of 40 up to 90% by weight, preferably 50 to 80% by weight and particularly preferably 55 to 75% by weight result.
  • Initiators in the production of the rubber latices and the elastic-thermoplastic graft rubbers are inorganic and organic peroxides, for example H 2 O 2 , di-tert-butyl peroxide, cumene hydroperoxide, dicyclohexyl percarbonate, tert-butyl hydroperoxide, p-menthane hydroperoxide, azo initiators, such as, for example, azobisiso - butyronitrile.
  • inorganic persalts such as ammonium, sodium or potassium persulfate. Potassium perphosphate, sodium perborate and redox systems into consideration.
  • the compounds usually used as molecular weight regulators such as e.g. Mercaptans or dimeric ⁇ -methylstyrene can be used.
  • anionic emulsifiers are suitable as emulsifiers; anionic emulsifiers are preferably used.
  • Suitable anionic emulsifiers are, for example, sodium, potassium or ammonium salts of long-chain fatty acids with 10 to 20 carbon atoms, for example potassium oleate, salts of disproportionated abietic acid, salts of long-chain benzene sulfonates, salts of long-chain sulfonic acids, for example the sodium salts of Ccj-Ci g-alkylsulfonic acid mixtures and salts of dicarboxylic acids based on cyclic
  • Any desired temperature can be chosen as the reaction temperature at which the initiator compounds used provide sufficient radicals to initiate and maintain the polymerization reaction.
  • Temperature range is approximately between 50 ° C and 120 ° C, preferably between 55 ° C and 75 ° C.
  • the elastic-thermoplastic graft polymers present in emulsion form are converted into water-moist powders by known methods of
  • Latex coagulation e.g. by adding salts (e.g. magnesium sulfate, calcium chloride, sodium sulfate, sodium chloride), acids (e.g. acetic acid, sulfuric acid) or combinations of acid and salt components and subsequent washing (electrolyte-free or neutral) and, if necessary, partially removing the water (e.g. under Using a centrifuge or belt press).
  • salts e.g. magnesium sulfate, calcium chloride, sodium sulfate, sodium chloride
  • acids e.g. acetic acid, sulfuric acid
  • subsequent washing electrolyte-free or neutral
  • partially removing the water e.g. under Using a centrifuge or belt press.
  • the coagulation can take place continuously or partially.
  • thermoplastic resins based on vinyl monomers.
  • Suitable thermoplastic resins of this type are preferably copolymers of styrene and
  • the styrene can be replaced in whole or in part by .alpha.-methylstyrene or methyl methacrylate and where appropriate up to 25% by weight.
  • thermoplastic resin another monomer from the series of maleic anhydride, maleic or fumaric acid bisalkyl esters, maleimide, N- (cyclo) alkyl maleimide.
  • N- (alkyl) phenylmaleimide can also be used.
  • Thermoplastic resins which are particularly suitable according to the invention are styrene / acrylonitrile copolymers, styrene / acrylonitrile / methyl methacrylate terpolymers. ⁇ -methylstyrene / acrylonitrile copolymers, styrene / acrylonitrile / N-phenylmaleinimide terpolymers, styrene / maleic anhydride copolymers, styrene / acrylonitrile / maleic anhydride terpolymers, styrene / maleic anhydride / N-phenylmaleinimide.
  • Such vinyl polymer resins are known; Details of their manufacture are described, for example, in DE-AS 2 420 358, DE-AS 2 724 360 and EP-A 255 889.
  • Mixing component B) is prepared by mixing the water-moist graft powder with the melt of the thermoplastic resin with removal of the water in a known manner.
  • the water content of the water-moist graft powder used is 1 to 50% by weight, preferably 10 to 40% by weight; the mixing ratio of elastic-thermoplastic graft polymer to thermoplastic resin melt is approximately 1: 4 to 4: 1, preferably 1: 3 to 3: 1.
  • Such methods are e.g. in EP-A 867 463 and the literature cited therein.
  • the residual content of volatile constituents in the mixed component B) before mixing with the polymer component A) is ⁇ 1,000 ppm, preferably ⁇ 500 ppm, particularly preferably ⁇ 250 ppm and very particularly preferably ⁇ 100 ppm.
  • Volatile constituents in particular include residual monomers and
  • Glass fibers and glass spheres can be used as fibrous or particulate fillers and reinforcing materials for the molding compositions according to the invention.
  • Preferred reinforcing materials are commercially available glass fibers.
  • the glass fibers which generally have a fiber diameter between 8 and 14 ⁇ m, can be added as continuous fibers or as cut or ground glass fibers, it being possible for the fibers to be equipped with a suitable sizing system and an adhesion promoter or adhesion promoter system, for example based on silane. 5 to 40, in particular 10 to 30 parts by weight of fillers and reinforcing materials can preferably be added to the mixture.
  • conductive molding compounds conductive carbon blacks, carbon fibrils. Graphite, conductive polymers, metal fibers and other conventional additives to increase the conductivity can be added.
  • Halogenated aromatics halogen-containing molding compounds
  • Phosphorus compounds such as Triphenyl phosphate and resorcinol bis (diphenyl phosphate), mineral flame retardants such as Magnesium hydroxide or calcium / magnesium carbonate, calcium / magnesium carbonate hydrate, huntite, dolomite, nitrogen compounds such as e.g. Melamine cyanurate and tetrafluoroethylene polymers are used.
  • the mineral flame retardants can be used with a suitable sizing system, an adhesion promoter or adhesion promotion system e.g. be surface modified on a silane basis.
  • the molding compositions according to the invention can be conventional additives, such as agents against heat decomposition, agents against heat crosslinking. Means against damage from ultraviolet light. Plasticizers, lubricants and mold release agents. Nucleating agent. Contain antistatic agents, stabilizers, stabilizers against decomposition and crosslinking as well as dyes and pigments.
  • Additives such as stabilizers. Dyes. Pigments. Lubricants and mold release agents, Reinforcing substances, nucleating agents and antistatic agents are produced by mixing the respective constituents in a known manner and melt compounding or melt extruding at temperatures of 200 ° C. to 330 ° C. in conventional units such as internal kneaders, extruders, twin-screw screws. In the melt compounding or melt extruding step, further additives such as reinforcing materials, stabilizers, dyes, pigments, lubricants and mold release agents, nucleating agents, compatalizers and other additives can be added.
  • the present invention furthermore relates to a process for the production of thermoplastic molding compositions from components A and B and, if appropriate, other known additives, such as flame retardants.
  • Stabilizers, pigments, lubricants and mold release agents, reinforcing materials, nucleating agents and antistatic agents which are characterized in that, after mixing, the components are melt-compounded or melt-extruded in conventional units at temperatures of from 200 ° C. to 330 ° C.
  • Another object of the invention is the use of the above-mentioned molding compositions for the production of moldings and semi-finished products such as Sheets, foils, fibers or profiles, whereby the molding compounds can be used for the production of moldings and semi-finished products of all kinds, also in combination with other materials.
  • the moldings according to the invention are made by conventional plastics processing methods such as Injection molding, extrusion, thermoforming, deep drawing, pressing, welding, embossing, sintering, blow molding. Gas injection technology or a combination of these techniques. In particular, moldings can be produced by injection molding.
  • moldings that can be produced are all types of housings, for example for household appliances, power strips and lamp bases, cable ties. Parts from the automotive sector such as fuel tanks, fuel lines. Motor vehicle attachments, motor vehicle exterior parts, fenders, bumpers. Back door. Trunk lid, side door trim, bonnet, grille, exterior mirrors, which can be painted using the offline, inline or online method, if necessary.
  • Linear alternating terpolymer made of carbon monoxide, ethylene and propylene (Carylon DP P 1000, Shell International Chemicals Ltd., London, UK).
  • the elastic-thermoplastic graft polymer prepared by emulsion polymerization and described under "Mixing component B" is coagulated with a magnesium sulfate / acetic acid mixture. washed with water and dried at 70 ° C. The resulting powder has a residual volatile content of
  • the components are mixed in a ZSK 32/1 extruder at 230 to 250 ° C.
  • the moldings are produced on an Arburg 320-210-500 injection molding machine at melt temperatures of 230 to 260 ° C and mold temperatures of 40 to 80 ° C.
  • the determination of the filling pressure and the sealing time is carried out as described in the following literature: book, 27th edition, Saechtling, ISBN 3-446-19054-6, pp. 80 - 83.
  • the measurements are carried out on shoulder bar No. 3 according to ISO 294 on injection molding machines of the Arburg 320 type with process data acquisition (mold control) at a melt temperature of 240 ° C and a tool temperature of 40 ° C.
  • the significantly improved flowability of the molding compositions according to the invention having no negative effects on the solidification behavior. as can be seen from the measured hold times.
  • the measured holding times of Examples 1-3 are shorter than those of Comparative Examples 1 and 2.
  • the better flowability means that thin-walled molded parts can be realized and, in combination with the rapid solidification, significant cycle time reductions can be achieved.
  • the MVR values are determined based on DIN ISO 11333 / Ba at 260 ° C and a load of 15 kg.
  • the results demonstrate, on the one hand, the better flowability of Examples 1-3 compared to Comparative Examples 1 and 2. On the other hand, the results show that the molding compositions according to the invention of Examples 1-3 have a higher melt stability (lower viscosity buildup) than Comparative Example 2.
  • the yellowness index is determined in accordance with DIN 6167 (Dataflash 2000, evaluation method CIELAB, illuminant / normal viewer: D65 / 10 0 , with gloss). The measurement is carried out on sprayed test specimens. The yellowness values given are measured in Examples 1 - 3 and Comparative Example 1 at any point on the test specimens and in Comparative Example 2 in the yellowish areas. From the visual Judgment of the test specimens shows that the polyketones modified according to the invention have a significantly better surface quality than polyketones modified with conventional ABS.
  • the barrier properties are assessed on the basis of electron micrographs (transmission, ultra-thin sections, formalin / OsO4 treatment). Electron micrographs show that comparative example 2 and the examples according to the invention show the good barrier properties of polyketone against fuels and solvents. Oxygen and others have.
  • the behavior in the tensile test was determined according to ISO 527.
  • the molding compositions according to the invention of Examples 1 - 3 show, compared to Comparative Example 2, an improved tensile strength and elongation at break and increased tensile modulus values in the tensile test.
  • the polyketone molding compositions modified in accordance with the invention have better processing properties (improved flowability, shorter solidification time) compared to unmodified polyketone.
  • the polyketone molding compounds modified according to the invention show significantly better properties with regard to processing properties (improved flowability), processing stability (slower viscosity build-up in the melt), surface quality (none Stains, lighter basic color) and mechanical properties in tensile tests (strength, elasticity).

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Abstract

The invention relates to thermoplastic moulding materials based on mixtures of thermoplastic polyketones (olefin-carbon-monoxide-copolymers) and on specially produced mixtures consisting of moistened, graft polymers which are elastically thermoplastic by emulsion polymerisation and of thermoplastic vinyl polymer resin which exists in liquified form. The invention also relates to the use thereof for producing shaped bodies and to the shaped bodies produced by said method.

Description

Thermoplastische Polyketon-FormmassenThermoplastic polyketone molding compounds
Die Erfindung betrifft thermoplastische Formmassen auf Basis von Mischungen thermoplastischer Polyketone (Olefin-Kohlenmonoxid-Copolymere) und speziell hergestellter Gemische aus wasserfeuchtem durch Emulsionspolymerisation erhaltenem elastisch-thermoplastischem Pfropfpolymerisat und in der Schmelzeform vorliegendem thermoplastischem Vinylpolymerisatharz, deren Verwendung zur Herstellung von Formkö ern sowie die daraus hergestellten Formkörper.The invention relates to thermoplastic molding compositions based on mixtures of thermoplastic polyketones (olefin-carbon monoxide copolymers) and specially produced mixtures of water-moist elastic-thermoplastic graft polymer obtained by emulsion polymerization and thermoplastic vinyl polymer resin present in the melt form, their use for the production of molded articles and the products produced therefrom Molded body.
Thermoplastische Polyketone finden zunehmend Anwendung als technische Thermoplaste im Automobilbereich z.B. zur Herstellung von Kraftstofftanks und Kraftstoffleitungssystemen und im Elektro-/Elektronikbereich z.B. zur Herstellung von Steckverbindungen. Thermoplastische Polyketone zeichnen sich im Vergleich zu anderen technischen Thermoplasten insbesondere durch gute Tieftemperaturzähigkeit, guteThermoplastic polyketones are increasingly used as engineering thermoplastics in the automotive sector e.g. for the production of fuel tanks and fuel line systems and in the electrical / electronics sector e.g. for the production of plug connections. Thermoplastic polyketones are particularly good low-temperature toughness compared to other technical thermoplastics
Wärmeformbeständigkeit und gute Kraftstoffbarriereeigenschaften aus.Heat resistance and good fuel barrier properties.
Die Verbesserung von thermoplastischen Polyketonen im Hinblick auf spezielle Eigenschaften durch Abmischung mit anderen Polymerkomponenten ist bekannt.The improvement of thermoplastic polyketones with regard to special properties by blending with other polymer components is known.
So beschreibt z.B. US-A 5.166.252 Mischungen thermoplastischer Polyketone mit Verstärkungsstoffen und thermoplastischen Polyurethanen zur Erzielung verbesserter Steifigkeit und Hitzebeständigkeit. Die Herstellung von Formmassen aus thermoplastischen Polyketonen und Polyurethanen ist bekannt (US-A 4.851.482, EP-A 339 747). Es wird beschrieben, daß die Formmassen eine gute Zähigkeit und Steifigkeit sowie Lösungsmittelbeständigkeit und Abriebfestigkeit aufweisen.For example, US-A 5,166,252 mixtures of thermoplastic polyketones with reinforcing materials and thermoplastic polyurethanes to achieve improved rigidity and heat resistance. The production of molding compositions from thermoplastic polyketones and polyurethanes is known (US-A 4,851,482, EP-A 339 747). It is described that the molding compositions have good toughness and rigidity as well as solvent resistance and abrasion resistance.
Die Abmischung von Polyketonen mit kautschukhaltigen Polymeren ist ebenfalls bekannt. So beschreibt z.B. US-A 4.900.789 Mischungen aus Polyketonen und kautschukarmem ABS zur Erzielung höherer Modulwerte. Zur Herstellung von Polyketonen mit verbesserter Zähigkeit werden Mischungen mit speziellen aus Acryl- monomeren aufgebauten Kern/Schalen-Modifikatoren (US-A 5.132.360) oder hoch- kautschukhaltigen Copolymeren (EP-A 345 854, EP-A 451 918) empfohlen.The blending of polyketones with rubber-containing polymers is also known. For example, US-A 4,900,789 describes mixtures of polyketones and low-rubber ABS to achieve higher module values. To produce polyketones with improved toughness, mixtures with special acrylic monomeric core / shell modifiers (US Pat. No. 5,132,360) or copolymers containing high rubber (EP-A 345 854, EP-A 451 918) are recommended.
Die Aufgabe der vorliegenden Erfindung ist nun die Bereitstellung von preisgünsti- gen Werkstoffen auf Basis von Polyketonen mit gutem Gesamteigenschaftsprofil, insbesondere guter Zähigkeit und Zähbruchverhalten bei Schlag- und Stoßbeanspruchung auch bei tiefen Temperaturen, guter Oberflächenqualität, guter Verarbeitungsstabilität, gutem Verarbeitungsverhalten, guten Barriereeigenschaften gegenüber Kraftstoff und Lösungsmitteln sowie Gasen wie Sauerstoff, guter UV-Stabilität der daraus hergestellten Formteile sowie einem geringen Gehalt an flüchtigen Anteilen.The object of the present invention is now to provide inexpensive materials based on polyketones with a good overall property profile, in particular good toughness and toughness behavior under impact and impact stress even at low temperatures, good surface quality, good processing stability, good processing behavior, good barrier properties to fuel and solvents as well as gases such as oxygen, good UV stability of the molded parts made from them and a low content of volatile components.
Die erfindungsgemäßen Formmassen zeichnen sich insbesondere durch eine gute Verarbeitung, speziell Vermeidung von gelben Flecken, gute Fließfähigkeit und Sta- bilität in der Schmelze aus.The molding compositions according to the invention are distinguished in particular by good processing, especially avoidance of yellow spots, good flowability and stability in the melt.
Solche Werkstoffe lassen sich in typischen Einsatzgebieten von technischen Thermoplasten wie z.B. dem Elektro-/Elektronikbereich, dem Automobilbereich oder dem Folien- und Verpackungsbereich verwenden und sind insbesondere zur Herstellung von dünnwandigen Formteilen geeignet.Such materials can be used in typical areas of application of engineering thermoplastics such as use in the electrical / electronics sector, the automotive sector or the film and packaging sector and are particularly suitable for the production of thin-walled molded parts.
Es wurde nun gefunden, daß die gewünschte Eigenschaftskombination von thermoplastischen Formmassen enthaltend Polyketone und speziell hergestellten Gemische aus durch Emulsionspolymerisation hergestelltem elastisch-thermoplastischem Pfropfkautschuk in Form von wasserfeuchtem Pulver und separat durch Lösungspolymerisation oder Massepolymerisation hergestelltem in Schmelzeform vorliegendem Co- oder Terpolymerisat vorzugsweise aufgebaut aus Monomeren ausgewählt aus Styrol, α- Methylstyrol, Acrylnitril, Methacrylnitril. Methylmethacrylat. N-Phe- nyimaleinimid erfüllt werden. - j -It has now been found that the desired combination of properties of thermoplastic molding compositions containing polyketones and specially prepared mixtures of elastomer-thermoplastic graft rubber produced by emulsion polymerization in the form of water-moist powder and separately by solution polymerization or bulk polymerization, in the form of a copolymer or terpolymer prepared in melt form, preferably selected from monomers from styrene, α-methylstyrene, acrylonitrile, methacrylonitrile. Methyl methacrylate. N-phenylmaleimide can be met. - j -
Gegenstand der vorliegenden Erfindung sind daher thermoplastische Formmassen enthaltendThe present invention therefore relates to thermoplastic molding compositions containing
A) wenigstens ein linear alternierendes Polymer aus Kohlenmonoxid und wenigstens einem ethylenisch ungesättigten Kohlenwasserstoff ,A) at least one linearly alternating polymer of carbon monoxide and at least one ethylenically unsaturated hydrocarbon,
B) wenigstens ein Gemisch aus durch Emulsionspolymerisation hergestelltem elastisch-thermoplastischem Pfropfpolymerisat und durch Lösungspolymerisation oder Massepolymerisation hergestelltem thermoplastischen Co- oder Terpolymerisat aufgebaut aus Vinylmonomeren, vorzugsweise aus mindestens einem Monomer ausgewählt aus Styrol, α- Methylstyrol. Acryl- nitril, Methacrylnitril, C,-C4-Alkylacrylat, vorzugsweise Methylacrylat. C,- C4-Alkylmethacrylat, vorzugsweise Methylmethacrylat und N-Phenylmalein- imid, erhältlich durch Abmischung des wasserfeuchten Pulvers des elastisch- thermoplastischen Pfropfkautschuks mit der Schmelze des thermoplastischen aus Vinylmonomeren aufgebauten Harzes unter Entfernung des enthaltenen Wassers.B) at least one mixture of elastic-thermoplastic graft polymer prepared by emulsion polymerization and thermoplastic copolymer or terpolymer prepared by solution polymerization or bulk polymerization composed of vinyl monomers, preferably of at least one monomer selected from styrene, α-methylstyrene. Acrylonitrile, methacrylonitrile, C 1 -C 4 alkyl acrylate, preferably methyl acrylate. C, - C 4 alkyl methacrylate, preferably methyl methacrylate and N-phenylmalein imide, obtainable by mixing the water-moist powder of the elastic-thermoplastic graft rubber with the melt of the thermoplastic resin composed of vinyl monomers with removal of the water contained.
Die erfindungsgemäßen thermoplastischen Formmassen enthalten die Komponente A) in Mengen von 99 bis 1 Gew.-Teilen, vorzugsweise 98 bis 50 Gew.-Teilen und insbesondere bevorzugt 97 bis 70 Gew.-Teilen und die Komponente B) in Mengen von 1 bis 99 Gew.-Teilen, vorzugsweise 2 bis 50 Gew.-Teilen und besonders bevorzugt 3 bis 30 Gew.-Teilen. Die Summe aller Gewichtsteile von A) und B) ist 100.The thermoplastic molding compositions according to the invention contain component A) in amounts of 99 to 1 part by weight, preferably 98 to 50 parts by weight and particularly preferably 97 to 70 parts by weight, and component B) in amounts of 1 to 99 parts by weight . Parts, preferably 2 to 50 parts by weight and particularly preferably 3 to 30 parts by weight. The sum of all parts by weight of A) and B) is 100.
Weiterhin können die Formmassen Zusatzstoffe wie z.B. Füll- und Verstärkungsstoffe wie z.B. Glasfasern oder mineralische Füllstoffe. Flammschutzmittel. Verarbeitungshilfsmittel, Stabilisatoren. Fließhilfsmittel, Antistatika. Farbstoffe. Pigmente und andere übliche Additive enthalten.The molding compositions can also contain additives such as Fillers and reinforcing materials such as Glass fibers or mineral fillers. Flame retardant. Processing aids, stabilizers. Flow aids, antistatic agents. Dyes. Contain pigments and other common additives.
Die Polyketonpolymere, welche als Komponente A eingesetzt werden, haben eine lineare alternierende Struktur und enthalten im wesentlichen 1 Molekül Kohlenmo- noxid pro Molekül ungesättigtem Kohlenwasserstoff. Geeignete ethylenisch ungesättigte Kohlenwasserstoffe als Monomere zum Aufbau des Polyketonpolymeren haben bis zu 20 Kohlenstoffatome, vorzugsweise bis zu 10 Kohlenstoffatome und sind aliphatisch wie beispielsweise Ethylen und andere α-Olefine, z.B. Propylen, 1- Buten, 1 -Isobutylen, 1 -Hexen, 1-Octen und 1-Dodecen, oder sind arylaliphatisch und enthalten einen Arylsubstituenten an einem Kohlenstoffatom der linearen Kette. Beispielhaft genannt werden für arylaliphatische Monomere Styrol, α-Methylstyrol, p- Ethylstyrol und m-Isopropylstyrol.The polyketone polymers which are used as component A have a linear alternating structure and essentially contain 1 molecule of carbon mono- noxide per molecule of unsaturated hydrocarbon. Suitable ethylenically unsaturated hydrocarbons as monomers for the construction of the polyketone polymer have up to 20 carbon atoms, preferably up to 10 carbon atoms and are aliphatic, such as ethylene and other α-olefins, for example propylene, 1-butene, 1-isobutylene, 1-hexene, 1- Octene and 1-dodecene, or are arylaliphatic and contain an aryl substituent on a carbon atom of the linear chain. Examples of arylaliphatic monomers are styrene, α-methylstyrene, p-ethylstyrene and m-isopropylstyrene.
Bevorzugte Polyketonpolymere sind Copolymere aus Kohlenmonoxid und Ethylen oder Terpolymere aus Kohlenmonoxid, Ethylen und einem zweiten ethylenisch ungesättigten Kohlenwasserstoff mit wenigstens 3 Kohlenstoffatomen, insbesondere ein α-Olefin wie z.B. und bevorzugt Propylen.Preferred polyketone polymers are copolymers of carbon monoxide and ethylene or terpolymers of carbon monoxide, ethylene and a second ethylenically unsaturated hydrocarbon with at least 3 carbon atoms, in particular an α-olefin such as e.g. and preferably propylene.
Besonders bevorzugt sind Terpolymere von wenigstens 2 Monomereinheiten, wovon eine Ethylen und die andere ein zweiter Kohlenwasserstoff ist. Vorzugsweise werden von dem zweiten Kohlenwasserstoff ungefähr 10 bis 100 Monomereinheiten eingesetzt.Terpolymers of at least 2 monomer units are particularly preferred, one of which is ethylene and the other a second hydrocarbon. About 10 to 100 monomer units of the second hydrocarbon are preferably used.
Die Polymerkette des bevorzugten Polyketonpolymers wird durch die folgende Formel dargestelltThe polymer chain of the preferred polyketone polymer is represented by the following formula
CO(CH.CH?) CO(G) (I)CO (CH.CH ? ) CO (G) (I)
wobeiin which
G eine Monomereinheit auf Basis eines ethylenisch ungesättigten Kohlenwasserstoffs mit wenigstens 3 Kohlenstoffatomen, vorzugsweise 3 bis 10 C-Atomen, welche aufgrund der ethylenischen Doppelbindung polymerisiert
Figure imgf000006_0001
das Verhältnis y:x nicht mehr als ungefähr 0,5 ist.G is a monomer unit based on an ethylenically unsaturated hydrocarbon with at least 3 carbon atoms, preferably 3 to 10 carbon atoms, which polymerizes due to the ethylenic double bond
Figure imgf000006_0001
the ratio y: x is not more than about 0.5.
y = 0 für Copolymere aus Kohlenmonoxid und Ethylen.y = 0 for copolymers of carbon monoxide and ethylene.
Falls y von 0 verschieden ist, werden Terpolymere eingesetzt und die Einheit -CO-(CH2CH2)- und -CO-(G)-Einheit sind statistisch über die Polymerkette verteilt.If y is different from 0, terpolymers are used and the units -CO- (CH 2 CH 2 ) - and -CO- (G) -unit are statistically distributed over the polymer chain.
Das bevorzugte Verhältnis von y:x ist 0,01 bis 0,1.The preferred ratio of y: x is 0.01 to 0.1.
Polyketonpolymere mit einem mittleren Molekulargewicht (Zahlenmittel) von ungefähr 1.000 bis 200.000, insbesondere 20.000 bis 90.000, bestimmt durch Gelpermea- tionschromatographie, sind bevorzugt.Polyketone polymers with a number average molecular weight of approximately 1,000 to 200,000, in particular 20,000 to 90,000, determined by gel permeation chromatography, are preferred.
Zur weiteren Charakterisierung und zur Herstellung der Polyketon-Polymere wird auf US-A 5.166.252 verwiesen.For further characterization and for the production of the polyketone polymers, reference is made to US Pat. No. 5,166,252.
Die Mischkomponente B) wird erhalten durch Abmischung von mindestens einem durch Emulsionspolymerisation hergestellten elastisch-thermoplastischen Pfropf- polymerisat in Form eines wasserfeuchten Pulvers mit der Schmelze mindestens eines durch Lösungs- oder Massepolymerisation hergestellten thermoplastischen Co- oder Terpolymerisats aufgebaut aus Vinylmonomeren, insbesondere ausgewählt aus mindestens einem, vorzugsweise zwei aus der Gruppe Styrol, α-Methylstyrol. Acryl- nitril, Methacrylnitril, Methylmethacrylat, N-Phenylmaleinimid.The mixed component B) is obtained by mixing at least one elastic-thermoplastic graft polymer prepared by emulsion polymerization in the form of a water-moist powder with the melt of at least one thermoplastic copolymer or terpolymer prepared by solution or bulk polymerization, composed of vinyl monomers, in particular selected from at least one , preferably two from the group styrene, α-methylstyrene. Acrylonitrile, methacrylonitrile, methyl methacrylate, N-phenylmaleimide.
Der Kautschukgehalt der Mischkomponente B) (bezogen auf die Gesamtkomponente B) beträgt 30 bis 70 Gew.-%. vorzugsweise 35 bis 65 Ge\v.-% und besonders bevorzugt 36 bis 50 Gew.-%.The rubber content of the mixed component B) (based on the total component B) is 30 to 70% by weight. preferably 35 to 65% by weight and particularly preferably 36 to 50% by weight.
Das zur Herstellung der Mischkomponente B) verwendete elastisch-thermoplastischeThe elastic-thermoplastic used to produce the mixed component B)
Pfropfpolymerisat wird hergestellt durch Emulsionspolymerisation, indem in Gegen- wart mindestens eines teilvernetzten Kautschuklatex Vinylmonomere radikalisch polymerisiert werden.Graft polymer is produced by emulsion polymerization, in which Was at least one partially crosslinked rubber latex vinyl monomers were radically polymerized.
Als Kautschuk zur Herstellung des in Mischkomponente B) erfindungsgemäß einzu- setzenden elastisch-thermoplastischen Pfropfpolymerisats eignen sich im Prinzip alle in Emulsionsform vorliegenden kautschukartigen Polymerisate mit einer Glasübergangstemperatur unter 0°C.In principle, all rubber-like polymers with a glass transition temperature below 0 ° C. are suitable as rubber for the production of the elastic-thermoplastic graft polymer to be used according to the invention in mixed component B).
Verwendet werden können z.B.Can be used e.g.
Dienkautschuke, d.h. Homopolymerisate von konjugierten Dienen mit 4 bis 8 C-Atomen wie Butadien, Isopren, Chloropren oder deren Copolymerisate mit bis zu 60 Gew.-%, bevorzugt bis zu 30 Gew.-% eines Vinylmonomeren, z.B. Acrylnitril, Methacrylnitril, Styrol, α- Methylstyrol, Halogenstyrole, C1 -C4- Alkylstyrole, C 1 -Cg-Alkylacrylate, Ci -Cg- Alkylmethacrylate, Alkylengly- koldiacrylate, Alkylenglykoldimethacrylate, Divinylbenzol;Diene rubbers, i.e. Homopolymers of conjugated dienes with 4 to 8 carbon atoms such as butadiene, isoprene, chloroprene or their copolymers with up to 60% by weight, preferably up to 30% by weight, of a vinyl monomer, e.g. Acrylonitrile, methacrylonitrile, styrene, α-methylstyrene, halostyrenes, C1-C4-alkylstyrenes, C 1 -Cg-alkyl acrylates, Ci-Cg-alkyl methacrylates, alkylene glycol diacrylates, alkylene glycol dimethacrylates, divinylbenzene;
Acrylatkautschuke, d.h. Homo- und Copolymerisate von CI -CI Q- Alkyl- acrylaten, z.B. Homopolymerisate von Ethylacrylat, Butylacrylat oder Copo- lymerisate mit bis zu 40 Gew.-%, bevorzugt nicht mehr als 10 Gew.-%Acrylate rubbers, i.e. Homopolymers and copolymers of CI -CI Q alkyl acrylates, e.g. Homopolymers of ethyl acrylate, butyl acrylate or copolymers with up to 40% by weight, preferably not more than 10% by weight
Mono- Vinylmonomeren, z.B. Styrol, Acrylnitril, Vinylbutylether, Acryl- säure(ester), Methacrylsäure(ester). Vinylsulfonsäure. Bevorzugt werden solche Acrylatkautschukhomo- bzw. - copolymerisate eingesetzt, die 0,01 bis 8 Gew.-% Divinyl- oder Polyvinylverbindungen und oder N-Methylolacryl- amid bzw. N-Methylolmethacrylamid oder sonstige Verbindungen enthalten, die als Vernetzer wirken, z.B. Divinylbenzol. Triallylcyanurat.Mono vinyl monomers, e.g. Styrene, acrylonitrile, vinyl butyl ether, acrylic acid (ester), methacrylic acid (ester). Vinyl sulfonic acid. Such acrylate rubber homo- or copolymers are preferably used which contain 0.01 to 8% by weight of divinyl or polyvinyl compounds and or N-methylolacrylamide or N-methylolmethacrylamide or other compounds which act as crosslinkers, e.g. Divinylbenzene. Triallyl cyanurate.
Bevorzugt sind Polybutadienkautschuke. Styrol/Butadien-Copolymer-Kautschuke mit bis zu 30 Gew.-% einpolymerisiertem Styrol und Acrylatkautschuke. besonders solche, die eine Kern-Schalen-Struktur aufweisen, z.B. wie in DE-OS 3 006 804 beschrieben. Zur Herstellung der erfindungsgemäß geeigneten Pfropfpolymerisate kommen Lances mit mittleren Teilchendurchmessern d50 von 0,05 bis 2,0 μm, vorzugsweise von 0,08 bis 1,0 μm und besonders bevorzugt von 0,1 bis 0,5 μm, in Betracht. Die mittle- ren Teilchendurchmesser werden mittels Ultrazentrifuge (vgl. W. Scholtan, H.Polybutadiene rubbers are preferred. Styrene / butadiene copolymer rubbers with up to 30% by weight of copolymerized styrene and acrylate rubbers. especially those which have a core-shell structure, for example as described in DE-OS 3 006 804. Lances with average particle diameters d 50 of 0.05 to 2.0 μm, preferably of 0.08 to 1.0 μm and particularly preferably of 0.1 to 0.5 μm are suitable for producing the graft polymers suitable according to the invention. The mean particle diameters are determined using an ultracentrifuge (cf. W. Scholtan, H.
Lange: Kolloid-Z. u Z. Polymere 250, S. 782-796 (1972) bestimmt. Gemische mehrerer Latices können ebenfalls verwendet werden (vergl. DE-OS 1 813 719). Die Herstellung dieser Latices erfolgt in der Regel durch Emulsionspolymerisation, die erforderlichen Reaktionsbedingungen. Hilfsstoffe und Arbeitstechniken sind grund- sätzlich bekannt.Lange: Colloid-Z. u Z. Polymer 250, pp. 782-796 (1972). Mixtures of several latices can also be used (see DE-OS 1 813 719). These latices are usually produced by emulsion polymerization, the required reaction conditions. Auxiliaries and working techniques are generally known.
Es ist auch möglich, nach bekannten Methoden zunächst ein feinteiliges Kautschukpolymerisat herzustellen und es anschließend in bekannter Weise zur Einstellung der erforderlichen Teilchengröße zu agglomerieren. Einschlägige Techniken sind be- schrieben (vgl. EP-PS 0 029 613; EP-PS 0 007 810; DD-PS 144 415; DE- AS 12 33It is also possible to first produce a finely divided rubber polymer by known methods and then to agglomerate it in a known manner to adjust the required particle size. Relevant techniques are described (cf. EP-PS 0 029 613; EP-PS 0 007 810; DD-PS 144 415; DE-AS 12 33
131; DE-AS 12 58 076; DE-OS 21 01 650; US-PS 1 379 391).131; DE-AS 12 58 076; DE-OS 21 01 650; U.S. Patent 1,379,391).
Ebenfalls kann nach der sogenannten Saatpolymerisationstechnik gearbeitet werden, bei der zunächst z.B. ein feinteiliges Butadienpolymerisat hergestellt und dann durch Weiterumsatz mit Butadien enthaltenden Monomeren zu größeren Teilchen weiter- polymerisiert wird.The so-called seed polymerization technique can also be used, in which e.g. a finely divided butadiene polymer is prepared and then further polymerized to larger particles by further conversion with monomers containing butadiene.
Prinzipiell kann man Kautschukpolymerisatlatices auch durch Emulgieren von fertigen Kautschukpolymerisaten in wäßrigen Medien (vgl. japanische Patentanmeldung 55 125 102) herstellen.In principle, rubber polymer latices can also be produced by emulsifying finished rubber polymers in aqueous media (cf. Japanese patent application 55 125 102).
Als Pfropfmonomere, die in Gegenwart der in Emulsionsform vorliegenden kautschukartigen Polymerisate polymerisiert werden, sind praktisch alle Verbindungen geeignet, die in Emulsion zu thermoplastischen Harzen polymerisiert werden können. z.B. Vinylaromaten der Formel (I) oder Verbindungen der Formel (11) bzw. derenPractically all compounds which can be polymerized in emulsion to thermoplastic resins are suitable as graft monomers which are polymerized in the presence of the rubbery polymers present in emulsion form. e.g. Vinylaromatics of formula (I) or compounds of formula (11) or their
Gemische,
Figure imgf000010_0001
(i) (ii) wobeiMixtures,
Figure imgf000010_0001
(i) (ii) where
R Wasserstoff oder Methyl,R is hydrogen or methyl,
R2 Halogen oder Alkyl mit 1 bis 4 Kohlenstoffatomen,R2 halogen or alkyl having 1 to 4 carbon atoms,
q 0, eine ganze Zahl von 1 bis 5, vorzugsweise 0,1 bis 3, besonders bevorzugt 0 oder 1,q 0, an integer from 1 to 5, preferably 0.1 to 3, particularly preferably 0 or 1,
R-3 Wasserstoff oder Methyl bedeuten undR-3 is hydrogen or methyl and
X eine CN, R4OOC- oder R5R6NOC- Gruppe darstellt, wobeiX represents a CN, R 4 OOC or R 5 R 6 NOC group, where
R4 Wasserstoff oder Alkyl mit 1 bis 4 Kohlenstoffatomen undR4 is hydrogen or alkyl of 1 to 4 carbon atoms and
R5 und R6 unabhängig Wasserstoff, Phenyl oder Alkyl mit 1 bis 4 Kohlenstoffatomen bedeuten.R5 and R6 independently represent hydrogen, phenyl or alkyl having 1 to 4 carbon atoms.
Beispielhaft und bevorzugt für Verbindungen der Formel (I) sind Styrol. α- Methylstyrol, p- Methylstyrol und Vinyltoluol. Beispielhaft und bevorzugt für Verbindungen der Formel (II) sind Acrylnitril und Methvlmethacrylat. Weitere geeignete Monomere sind z.B. Vinvlacetat und N-Phenvlmaleinimid. Bevorzugte Monomere sind Mischungen aus Styrol und Acrylnitril, α- Methylstyrol und Acrylnitril, aus Styrol, Acrylnitril und Methylmethacrylat sowie Kombinationen dieser Monomerengemische mit N-Phenylmaleinimid.Exemplary and preferred for compounds of formula (I) are styrene. α-methyl styrene, p-methyl styrene and vinyl toluene. Exemplary and preferred for compounds of formula (II) are acrylonitrile and methylene methacrylate. Other suitable monomers are, for example, vinyl acetate and N-phenylene malimide. Preferred monomers are mixtures of styrene and acrylonitrile, α-methylstyrene and acrylonitrile, of styrene, acrylonitrile and methyl methacrylate and combinations of these monomer mixtures with N-phenylmaleimide.
Bevorzugte erfmdungsgemäße Pfropfpolymerisate sind solche, die durch Pfropfpolymerisation der o.g. Verbindungen der Formel (I) und (II) im Gew.-Verhältnis 90:10 bis 50:50, vorzugsweise 80:20 bis 65:35 in Gegenwart von solchen Mengen Kautschuk, vorzugsweise Polybutadien, erhalten werden, daß Pfropfpolymerisate mit Kautschukgehalten von 40 bis 90 Gew.-%, vorzugsweise 50 bis 80 Gew.-% und be- sonders bevorzugt 55 bis 75 Gew.-% resultieren. Es werden im allgemeinen 10 bisPreferred graft polymers according to the invention are those which have been obtained by graft polymerization of the abovementioned. Compounds of the formulas (I) and (II) in a weight ratio of 90:10 to 50:50, preferably 80:20 to 65:35 in the presence of such amounts of rubber, preferably polybutadiene, are obtained in such a way that graft polymers with rubber contents of 40 up to 90% by weight, preferably 50 to 80% by weight and particularly preferably 55 to 75% by weight result. There are generally 10 to
60 Gew.-%, vorzugsweise 20 bis 50 Gew.-%, insbesondere 45 bis 25 Gew.-% Monomermischung und 90 bis 40 Gew.-%, insbesondere 55 bis 75 Gew.-% Kautschuk eingesetzt.60% by weight, preferably 20 to 50% by weight, in particular 45 to 25% by weight, of monomer mixture and 90 to 40% by weight, in particular 55 to 75% by weight of rubber.
Als Initiatoren bei der Herstellung der Kautschuklatices und der elastisch-thermoplastischen Pfropfkautschuke kommen anorganische und organische Peroxide, z.B. H2O2, Di-tert.-butylperoxid, Cumolhydroperoxid, Dicyclohexylpercarbonat, tert.- Butylhydroperoxid, p-Menthanhydroperoxid, Azoinitiatoren, wie z.B. Azobisiso- butyronitril. anorganische Persalze wie Ammonium-, Natrium- oder Kaliumpersulfat. Kaliumperphosphat, Natriumperborat sowie Redox-Systeme in Betracht.Initiators in the production of the rubber latices and the elastic-thermoplastic graft rubbers are inorganic and organic peroxides, for example H 2 O 2 , di-tert-butyl peroxide, cumene hydroperoxide, dicyclohexyl percarbonate, tert-butyl hydroperoxide, p-menthane hydroperoxide, azo initiators, such as, for example, azobisiso - butyronitrile. inorganic persalts such as ammonium, sodium or potassium persulfate. Potassium perphosphate, sodium perborate and redox systems into consideration.
Bei der Herstellung der erfindungsgemäß geeigneten elastisch-thermoplastischen Pfropfpolymerisate können die üblicherweise als Molekulargewichtsregler eingesetzten Verbindungen wie z.B. Mercaptane oder dimeres α- Methylstyrol verwendet werden.In the preparation of the elastic-thermoplastic graft polymers suitable according to the invention, the compounds usually used as molecular weight regulators, such as e.g. Mercaptans or dimeric α-methylstyrene can be used.
Als Emulgatoren sind praktisch alle Emulgatortypen (anionische, kationische und nichtionische Emulgatoren) geeignet, bevorzugt werden anionische Emulgatoren eingesetzt. Geeignete anionische Emulgatoren sind beispielsweise Natrium-, Kalium- oder Ammoniumsalze langkettiger Fettsäuren mit 10 bis 20 Kohlenstoffatomen, z.B. Kaliumoleat, Salze der disproportionierten Abietinsäure, Salze langkettiger Benzol- sulfonate, Salze langkettiger Sulfonsäuren, z.B. die Natriumsalze von Ccj-Ci g- Alkylsulfonsäure-Gemischen und Salze von Dicarbonsäuren auf Basis cyclischerPractically all types of emulsifiers (anionic, cationic and nonionic emulsifiers) are suitable as emulsifiers; anionic emulsifiers are preferably used. Suitable anionic emulsifiers are, for example, sodium, potassium or ammonium salts of long-chain fatty acids with 10 to 20 carbon atoms, for example potassium oleate, salts of disproportionated abietic acid, salts of long-chain benzene sulfonates, salts of long-chain sulfonic acids, for example the sodium salts of Ccj-Ci g-alkylsulfonic acid mixtures and salts of dicarboxylic acids based on cyclic
Kohlenwasserstoffgerüste gemäß DE-OS 3 639 904 und DE-OS 3 913 509.Hydrocarbon skeletons according to DE-OS 3 639 904 and DE-OS 3 913 509.
Als Reaktionstemperaturen können beliebig solche Temperaturen gewählt werden, bei denen die eingesetzten Initiatorverbindungen in ausreichendem Maße Radikale zur Auslösung und Aufrechterhaltung der Polymerisationsreaktion liefern. DieserAny desired temperature can be chosen as the reaction temperature at which the initiator compounds used provide sufficient radicals to initiate and maintain the polymerization reaction. This
Temperaturbereich liegt etwa zwischen 50°C und 120°C, vorzugsweise zwischen 55°C und 75°C.Temperature range is approximately between 50 ° C and 120 ° C, preferably between 55 ° C and 75 ° C.
Die Überführung der in Emulsionsform vorliegenden elastisch-thermoplastischen Pfropfpolymerisate in wasserfeuchte Pulver erfolgt durch bekannte Verfahren derThe elastic-thermoplastic graft polymers present in emulsion form are converted into water-moist powders by known methods of
Latexkoagulation, beispielsweise durch Zusatz von Salzen (z.B. Magnesiumsulfat, Calciumchlorid, Natriumsulfat, Natriumchlorid), Säuren (z.B. Essigsäure, Schwefelsäure) oder Kombinationen aus Säure- und Salzkomponente und anschließendes Waschen (elektrolytfrei bzw. neutral) und gegebenenfalls teilweises Entfernen des Wassers (z.B. unter Verwendung einer Zentrifuge oder einer Bandpresse). Dabei kann die Koagulation kontinuierlich oder ansatzweise erfolgen.Latex coagulation, e.g. by adding salts (e.g. magnesium sulfate, calcium chloride, sodium sulfate, sodium chloride), acids (e.g. acetic acid, sulfuric acid) or combinations of acid and salt components and subsequent washing (electrolyte-free or neutral) and, if necessary, partially removing the water (e.g. under Using a centrifuge or belt press). The coagulation can take place continuously or partially.
Als Thermoplastharze auf Basis von Vinylmonomeren sind vorzugsweise durch Lösungs- oder Massepolymerisation hergestellte Polymerisate geeignet. Geeignete derartige Thermoplastharze sind vorzugsweise Copolymerisate des Styrols undPolymers produced by solution or bulk polymerization are preferably suitable as thermoplastic resins based on vinyl monomers. Suitable thermoplastic resins of this type are preferably copolymers of styrene and
Acrylnitrils im Gewichtsverhältnis 90:10 bis 50:50. wobei das Styrol ganz oder teilweise durch α-Methylstyrol oder Methvlmethacrylat ersetzt werden kann und wobei gegebenenfalls anteilmäßig bis zu 25 Gew.-%. bezogen auf Thermoplastharz, ein weiteres Monomeres aus der Reihe Maleinsäureanhydrid, Malein- oder Fumarsäure- bisalkylester, Maleinsäureimid, N-(Cyclo)-alkylmaleinimid. N-(Alkyl)-phenylma- leinimid mitverwendet werden kann. Erfindungsgemäß besonders geeignete Thermoplastharze sind Styrol/Acrylnitril- Copolymerisate, Styrol/ Acrylnitril/Methylmethacrylat-Terpolymerisate. α-Methylsty- rol/Acrylnitril-Copolymerisate, Styrol/ Acrylnitril/N-Phenylmaleinimid-Terpolymeri- säte, Styrol/Maleinsäureanhydrid-Copolymerisate, Styrol/Acrylnitril/Maleinsäure- anhydrid-Terpolymerisate, Styrol/Maleinsäureanhydrid/N-Phenylmaleinimid- Ter- polymerisate.Acrylonitrile in a weight ratio of 90:10 to 50:50. where the styrene can be replaced in whole or in part by .alpha.-methylstyrene or methyl methacrylate and where appropriate up to 25% by weight. based on thermoplastic resin, another monomer from the series of maleic anhydride, maleic or fumaric acid bisalkyl esters, maleimide, N- (cyclo) alkyl maleimide. N- (alkyl) phenylmaleimide can also be used. Thermoplastic resins which are particularly suitable according to the invention are styrene / acrylonitrile copolymers, styrene / acrylonitrile / methyl methacrylate terpolymers. α-methylstyrene / acrylonitrile copolymers, styrene / acrylonitrile / N-phenylmaleinimide terpolymers, styrene / maleic anhydride copolymers, styrene / acrylonitrile / maleic anhydride terpolymers, styrene / maleic anhydride / N-phenylmaleinimide.
Derartige Vinylpolymerisatharze sind bekannt; Einzelheiten zu ihrer Herstellung sind beispielsweise in der DE-AS 2 420 358, der DE-AS 2 724 360 und der EP-A 255 889 beschrieben.Such vinyl polymer resins are known; Details of their manufacture are described, for example, in DE-AS 2 420 358, DE-AS 2 724 360 and EP-A 255 889.
Die Herstellung der Mischkomponente B) erfolgt durch Abmischen des wasserfeuchten Pfropfpulvers mit der Schmelze des Thermoplastharzes unter Entfernung des Wassers in bekannter Weise. Dabei beträgt der Wassergehalt des eingesetzten wasserfeuchten Pfropfpulvers 1 bis 50 Gew.-%, vorzugsweise 10 bis 40 Gew.-%; das Mischungsverhältnis von elastisch-thermoplastischem Pfropfpolymerisat zu Thermoplastharzschmelze beträgt ca. 1 :4 bis 4:1, vorzugsweise 1 :3 bis 3:1. Derartige Verfahren sind z.B. in EP-A 867 463 und der dort zitierten Literatur beschrieben.Mixing component B) is prepared by mixing the water-moist graft powder with the melt of the thermoplastic resin with removal of the water in a known manner. The water content of the water-moist graft powder used is 1 to 50% by weight, preferably 10 to 40% by weight; the mixing ratio of elastic-thermoplastic graft polymer to thermoplastic resin melt is approximately 1: 4 to 4: 1, preferably 1: 3 to 3: 1. Such methods are e.g. in EP-A 867 463 and the literature cited therein.
Der Restgehalt an flüchtigen Bestandteilen in der Mischkomponente B) beträgt vor Abmischung mit der Polymerkomponente A) <1 000 ppm, vorzugsweise <500 ppm, besonders bevorzugt <250 ppm und ganz besonders bevorzugt <100 ppm.The residual content of volatile constituents in the mixed component B) before mixing with the polymer component A) is <1,000 ppm, preferably <500 ppm, particularly preferably <250 ppm and very particularly preferably <100 ppm.
Unter flüchtigen Bestandteilen werden hierbei insbsondere Restmonomere sowieVolatile constituents in particular include residual monomers and
Reste von bei der Herstellung der Polymerkomponenten eingesetzten Lösungsmitteln verstanden.Understood residues of solvents used in the production of the polymer components.
Als faser- oder teilchenförmige Füllstoffe und Verstärkungsstoffe für die erf Indungs- gemäßen Formmassen können Glasfasern, Glaskugeln. Glasgewebe. Glasmatten.Glass fibers and glass spheres can be used as fibrous or particulate fillers and reinforcing materials for the molding compositions according to the invention. Glass fabric. Glass mats.
Kohlenstofffasern, Aramidfasern. Kaliumtitanat-Fasern, Naturfasern, amorphe Kieselsäue, Magnesiumcarbonat, Bariumsulfat, Feldspat, Glimmer, Silikate, Quarz. Talkum, Kaolin, Titandioxid, Wollastonit, u.a. zugesetzt werden, die auch oberflächenbehandelt sein können. Bevorzugte Verstärkungsstoffe sind handelsübliche Glasfasern. Die Glasfasern, die im allgemeinen einen Faserdurchmesser zwischen 8 und 14 μm haben, können als Endlosfasern oder als geschnittene oder gemahlenen Glasfasern zugesetzt werden, wobei die Fasern mit einem geeigneten Schlichtesystem und einem Haftvermittler bzw. Haftvermittlersystem z.B. auf Silanbasis ausgerüstet sein können. Vorzugsweise können der Mischung 5 bis 40, insbesondere 10 bis 30 Gew. -Teile Füll- und Verstärkungsstoffe zugesetzt werden.Carbon fibers, aramid fibers. Potassium titanate fibers, natural fibers, amorphous Silica, magnesium carbonate, barium sulfate, feldspar, mica, silicates, quartz. Talc, kaolin, titanium dioxide, wollastonite, etc. can be added, which can also be surface-treated. Preferred reinforcing materials are commercially available glass fibers. The glass fibers, which generally have a fiber diameter between 8 and 14 μm, can be added as continuous fibers or as cut or ground glass fibers, it being possible for the fibers to be equipped with a suitable sizing system and an adhesion promoter or adhesion promoter system, for example based on silane. 5 to 40, in particular 10 to 30 parts by weight of fillers and reinforcing materials can preferably be added to the mixture.
Um leitfähige Formmassen zu erhalten, können leitfähige Ruße, Carbonfibrillen. Graphit, leitfähige Polymere, Metallfasern sowie andere übliche Additive zur Erhöhung der Leitfähigkeit zugesetzt werden.To obtain conductive molding compounds, conductive carbon blacks, carbon fibrils. Graphite, conductive polymers, metal fibers and other conventional additives to increase the conductivity can be added.
Als Flammschutzmittel können halogenierte Aromaten, halogenhaltige Formmassen,Halogenated aromatics, halogen-containing molding compounds,
Phosphorverbindungen wie z.B. Triphenylphosphat und Resorcinol-bis-(diphenyl- phosphat), mineralische Flammschutzadditive wie z.B. Magnesiumhydroxid oder Calcium-/Magnsiumcarbonat, Calcium-/Magnesiumcarbonathydrat, Huntit, Dolomit, Stickstoffverbindungen wie z.B. Melamincyanurat und Tetrafluoroethylenpolymeri- säte eingesetzt werden. Die mineralischen Flammschutzmittel können mit einem geeigneten Schlichtesystem, einen Haftvermittler bzw. Haftvermittlungssystem z.B. auf Silanbasis oberflächenmodifiziert sein.Phosphorus compounds such as Triphenyl phosphate and resorcinol bis (diphenyl phosphate), mineral flame retardants such as Magnesium hydroxide or calcium / magnesium carbonate, calcium / magnesium carbonate hydrate, huntite, dolomite, nitrogen compounds such as e.g. Melamine cyanurate and tetrafluoroethylene polymers are used. The mineral flame retardants can be used with a suitable sizing system, an adhesion promoter or adhesion promotion system e.g. be surface modified on a silane basis.
Die erfindungsgemäßen Formmassen können übliche Additive, wie Mittel gegen Wärmezersetzung, Mittel gegen Wärmevernetzung. Mittel gegen Beschädigung durch ultraviolettes Licht. Weichmacher, Gleit- und Entformungsmittel. Nukle- ierungsmittel. Antistatika, Stabilisatoren, Stabilisatoren gegen Zersetzung und Vernetzung sowie Farbstoffe und Pigmente enthalten.The molding compositions according to the invention can be conventional additives, such as agents against heat decomposition, agents against heat crosslinking. Means against damage from ultraviolet light. Plasticizers, lubricants and mold release agents. Nucleating agent. Contain antistatic agents, stabilizers, stabilizers against decomposition and crosslinking as well as dyes and pigments.
Die erfindungsgemäßen Formmassen enthaltend gegebenenfalls weitere bekannteThe molding compositions according to the invention optionally containing other known
Zusätze wie Stabilisatoren. Farbstoffe. Pigmente. Gleit- und Entformungsmittel, Ver- stärkungsstoffe, Nukleierungsmittel sowie Antistatika werden hergestellt, indem man die jeweiligen Bestandteile in bekannter Weise vermischt und bei Temperaturen von 200°C bis 330°C in übliche Aggregaten wie z.B. Innenknetern, Extrudern, Doppelwellenschnecken schmelzcompoundiert oder schmelzextrudiert. Bei dem Schmelz- compoundier- oder Schmelzextrudierschritt lassen sich weitere Zusätze wie z.B. Verstärkungsstoffe, Stabilisatoren, Farbstoffe, Pigmente, Gleit- und Entformungsmittel, Nukleierungsmittel, Compatalizer und andere Additive zusetzten.Additives such as stabilizers. Dyes. Pigments. Lubricants and mold release agents, Reinforcing substances, nucleating agents and antistatic agents are produced by mixing the respective constituents in a known manner and melt compounding or melt extruding at temperatures of 200 ° C. to 330 ° C. in conventional units such as internal kneaders, extruders, twin-screw screws. In the melt compounding or melt extruding step, further additives such as reinforcing materials, stabilizers, dyes, pigments, lubricants and mold release agents, nucleating agents, compatalizers and other additives can be added.
Gegenstand der vorliegenden Erfindung ist weiterhin ein Verfahren zur Herstellung von thermoplastischen Formmassen, aus den Komponenten A und B und gegebenenfalls weiteren bekannten Zusätzen wie Flammschutzmitteln. Stabilisatoren, Pigmenten, Gleit- und Entformungsmitteln, Verstärkungsstoffen, Nukleierungsmitteln, sowie Antistatika, das dadurch gekennzeichnet ist, daß man die Komponenten nach erfolgter Vermischung bei Temperaturen von 200°C bis 330°C in gebräuchlichen Aggre- gaten schmelzcompoundiert oder schmelzextrudiert.The present invention furthermore relates to a process for the production of thermoplastic molding compositions from components A and B and, if appropriate, other known additives, such as flame retardants. Stabilizers, pigments, lubricants and mold release agents, reinforcing materials, nucleating agents and antistatic agents, which are characterized in that, after mixing, the components are melt-compounded or melt-extruded in conventional units at temperatures of from 200 ° C. to 330 ° C.
Ein weiterer Gegenstand der Erfindung ist die Verwendung der obengenannten Formmassen zur Herstellung von Formkörpern und Halbzeugen wie z.B. Platten, Folien, Fasern oder Profilen, wobei die Formmassen zur Herstellung von Formkör- pern und Halbzeugen jeder Art, auch im Verbund mit anderen Materalien verwendet werden können. Die erfindungsgemäßen Formkörper werden durch übliche Kunststoffverarbeitungsverfahren wie z.B. Spritzguß, Extrusion, Thermo formen, Tiefziehen, Pressen, Schweißen, Prägen, Sintern, Blasformen. Gasinjektionstechnik oder einer Kombination dieser Techniken hergestellt. Insbesondere können Formkörper durch Spritzguß hergestellt werden.Another object of the invention is the use of the above-mentioned molding compositions for the production of moldings and semi-finished products such as Sheets, foils, fibers or profiles, whereby the molding compounds can be used for the production of moldings and semi-finished products of all kinds, also in combination with other materials. The moldings according to the invention are made by conventional plastics processing methods such as Injection molding, extrusion, thermoforming, deep drawing, pressing, welding, embossing, sintering, blow molding. Gas injection technology or a combination of these techniques. In particular, moldings can be produced by injection molding.
Beispiele für herstellbare Formkörper sind Gehäuse jeder Art z.B. für Haushaltsgeräte, Steckerleisten und Leuchtensockel, Kabelbinder. Teile aus dem Kraftfahrzeugsektor wie z.B. Kraftstofftanks, Kraftstoffleitungen. Kraftfahrzeuganbauteile, Kraft- fahrzeugaußenteile, Kotflügel, Stoßfänger. Rückwandtür. Kofferraumdeckel, Seiten- türverkleidung, Motorhaube, Kühlergrill, Außenspiegel, die gegebenenfalls nach dem offline- inline- oder online- Verfahren lackierbar sind. Examples of moldings that can be produced are all types of housings, for example for household appliances, power strips and lamp bases, cable ties. Parts from the automotive sector such as fuel tanks, fuel lines. Motor vehicle attachments, motor vehicle exterior parts, fenders, bumpers. Back door. Trunk lid, side door trim, bonnet, grille, exterior mirrors, which can be painted using the offline, inline or online method, if necessary.
Beispiele:Examples:
Die folgenden Komponenten werden in den Beispielen verwendet:The following components are used in the examples:
Polvketon:Polvketon:
Linear alternierendes Terpolymer aus Kohlenmonoxid, Ethylen und Propylen (Cari- lon DP P 1000, Shell International Chemicals Ltd., London, UK).Linear alternating terpolymer made of carbon monoxide, ethylene and propylene (Carylon DP P 1000, Shell International Chemicals Ltd., London, UK).
Mischkomponente B):Mixed component B):
Gemisch aus a) 64 Gew.-% eines elastisch-thermoplastischen Pfropfpolymerisats erhalten durch Emulsionspolymerisation von 40 Gew.-Teilen eines Gemisches aus Styrol und Acrylnitril (Gew.-Verhältnis 73:27) in Gegenwart von 60 Gew.-Teilen eines Polybutadienlatex mit einem mittleren Teilchendurchmesser (d50) von ca. 300 nm und b) 36 Gew.-% eines durch Lösungspolymerisation hergestellten Styrol/ Acrylnitril - Copolymeren (Gew.-Verhältnis 72 : 28) mit einem Mw von ca. 85 000 und einer molekularen Uneinheitlichkeit U = Mw/Mn-1< 2, hergestellt durch Abmischung des nach Koagulation mit einem Magnesiumsulfat/Essigsäure-Gemisch, Waschen mit Wasser und Zentrifugieren erhaltenen wasserfeuchten PfropfpolymerpulversMixture of a) 64% by weight of an elastic-thermoplastic graft polymer obtained by emulsion polymerization of 40 parts by weight of a mixture of styrene and acrylonitrile (weight ratio 73:27) in the presence of 60 parts by weight of a polybutadiene latex with a average particle diameter (d 50 ) of about 300 nm and b) 36% by weight of a styrene / acrylonitrile copolymer (weight ratio 72:28) prepared by solution polymerization with an M w of about 85,000 and a molecular inconsistency U = M w / M n -1 <2, produced by mixing the water-moist graft polymer powder obtained after coagulation with a magnesium sulfate / acetic acid mixture, washing with water and centrifuging
(Wassergehalt 31 Gew.-% ) mit der Schmelze des Styrol/Acrylnitril-Copolymeren bei ca. 230°C unter Entfernung des Wassers. Der Restgehalt an flüchtigen Bestandteilen in Mischkomponente B) beträgt 83 ppm.(Water content 31% by weight) with the melt of the styrene / acrylonitrile copolymer at approx. 230 ° C. with removal of the water. The residual volatile content in mixed component B) is 83 ppm.
Vergleichspfropfpolymerisat:Comparative graft polymer:
Das unter "Mischkomponente B" beschriebene durch Emulsionspolymerisation hergestellte elastisch-thermoplastische Pfropfpolymerisat wird mit einem Magnesiumsulfat/Essigsäure-Gemisch koaguliert. mit Wasser gewaschen und bei 70°C getrock- net. Das resultierende Pulver hat einen Restgehalt an flüchtigen Bestandteilen vonThe elastic-thermoplastic graft polymer prepared by emulsion polymerization and described under "Mixing component B" is coagulated with a magnesium sulfate / acetic acid mixture. washed with water and dried at 70 ° C. The resulting powder has a residual volatile content of
1250 ppm. Das Mischen der Komponenten erfolgt auf einem Extruder des Typs ZSK 32/1 bei 230 bis 250°C. Die Formkörper werden auf einer Spritzgußmaschine des Typs Arburg 320-210-500 bei Massetemperaturen von 230 bis 260°C und Werkzeugtemperaturen von 40 bis 80°C hergestellt.1250 ppm. The components are mixed in a ZSK 32/1 extruder at 230 to 250 ° C. The moldings are produced on an Arburg 320-210-500 injection molding machine at melt temperatures of 230 to 260 ° C and mold temperatures of 40 to 80 ° C.
Zusammensetzung, Eigenschaften und Erläuterungen gehen aus Tabelle 1 und den Bemerkungen zu Tabelle 1 hervor. Composition, properties and explanations are shown in Table 1 and the comments on Table 1.
Tabelle 1 : Zusammensetzung und Eigenschaften der FormmassenTable 1: Composition and properties of the molding compounds
Figure imgf000019_0001
Figure imgf000019_0001
Visuelle Beurteilung der Oberfläche der Probekörper:Visual assessment of the surface of the test specimen:
viele Flecken (gelbe Flecken) 0 fleckenfrei, heller Grundtonmany spots (yellow spots) 0 spot-free, light basic tone
+ völlig fleckenfrei, sehr heller Grundton+ completely stain-free, very light basic tone
1. Die Bestimmung des Fülldruck und der Siegelzeit (Maß für das Erstarrungsverhalten) erfolgt wie in folgender Literatur beschrieben: Kunststoff Taschen- buch, 27. Ausgabe, Saechtling, ISBN 3-446-19054-6, S. 80 - 83. Die Messungen werden an Schulterstab Nr. 3 nach ISO 294 auf Spritzgießmaschinen des Typs Arburg 320 mit Prozessdatenerfassung (Mold Control) bei einer Massetemperatur von 240°C und einer Werkzeugtemperatur von 40°C durchgeführt.1. The determination of the filling pressure and the sealing time (measure of the solidification behavior) is carried out as described in the following literature: book, 27th edition, Saechtling, ISBN 3-446-19054-6, pp. 80 - 83. The measurements are carried out on shoulder bar No. 3 according to ISO 294 on injection molding machines of the Arburg 320 type with process data acquisition (mold control) at a melt temperature of 240 ° C and a tool temperature of 40 ° C.
Die Fülldruckbestimmung beim Spritzgießen stellt eine praxisnahe Beurteilung des Fließverhaltens von Thermoplastschmelzen dar. Die niedrigeren Fülldrücke der Beispiele 1 - 3 zeigen eine deutlich bessere Fließfähigkeit der erfindungsgemäßen Formmassen gegenüber den Vergleichsbeispielen 1 undThe determination of the filling pressure during injection molding represents a practical assessment of the flow behavior of thermoplastic melts. The lower filling pressures of Examples 1-3 show a significantly better flowability of the molding compositions compared to Comparative Examples 1 and
2, wobei die deutlich verbesserte Fließfähigkeit der erfindungsgemäßen Formmassen keine negativen Auswirkungen auf das Erstarrungsverhalten hat. wie aus den gemessenen Nachdruckzeiten hervorgeht. Die gemessenen Nachdruckzeiten der Beispiele 1- 3 sind kürzer als bei den Vergleichsbeispielen 1 und 2. Durch die bessere Fließfähigkeit lassen sich dünnwandige Formteile realisieren und in Kombination mit der schnellen Erstarrung deutliche Zykluszeitverkürzungen erzielen.2, the significantly improved flowability of the molding compositions according to the invention having no negative effects on the solidification behavior. as can be seen from the measured hold times. The measured holding times of Examples 1-3 are shorter than those of Comparative Examples 1 and 2. The better flowability means that thin-walled molded parts can be realized and, in combination with the rapid solidification, significant cycle time reductions can be achieved.
2. Die Bestimmung der MVR-Werte erfolgt in Anlehnung an DIN ISO 11333/Ba bei 260°C und einer Belastung von 15 kg. Die Ergebnisse belegen zum einen die bessere Fließfähigkeit der Beispiele 1 - 3 gegenüber den Vergleichsbeispielen 1 und 2. Zum anderen zeigen die Ergebnisse, daß die erfindungsgemäßen Formmassen der Beispiele 1 - 3 eine höhere Stabilität (geringerer Viskositätsaufbau) in der Schmelze aufweisen als Vergleichsbeispiel 2.2. The MVR values are determined based on DIN ISO 11333 / Ba at 260 ° C and a load of 15 kg. The results demonstrate, on the one hand, the better flowability of Examples 1-3 compared to Comparative Examples 1 and 2. On the other hand, the results show that the molding compositions according to the invention of Examples 1-3 have a higher melt stability (lower viscosity buildup) than Comparative Example 2.
3. Die Bestimmung des Gelbwertes erfolgt in Anlehnung an DIN 6167 (Dataflash 2000, Auswerteverfahren CIELAB, Lichtart/Normalbetrachter: D65/100, mit Glanz). Die Messung wird an verspritzten Prüfkörpern vorgenommen. Die angegebenen Gelbwerte werden bei Beispiel 1 - 3 und Ver- gleichsbeispiel 1 an beliebiger Stelle der Prüfkörper und bei Vergleichsbeispiel 2 in den gelblich verfärbten Bereichen gemessen. Aus der visuellen Be- urteilung der Prüfkörper geht hervor, daß die erfindungsgemäß modifizierten Polyketone eine deutlich bessere Oberflächenqualität haben als Polyketone, die mit üblichem ABS modifiziert sind.3. The yellowness index is determined in accordance with DIN 6167 (Dataflash 2000, evaluation method CIELAB, illuminant / normal viewer: D65 / 10 0 , with gloss). The measurement is carried out on sprayed test specimens. The yellowness values given are measured in Examples 1 - 3 and Comparative Example 1 at any point on the test specimens and in Comparative Example 2 in the yellowish areas. From the visual Judgment of the test specimens shows that the polyketones modified according to the invention have a significantly better surface quality than polyketones modified with conventional ABS.
4. Die Beurteilung der Barriereeigenschaften erfolgt anhand elektronenmikroskopischer Aufnahmen (Transmission, Ultra-Dünnschnitte, Formalin/OsO4- Behandlung). Elektronenmikroskopische Aufnahmen zeigen, daß das Vergleichsbeispiel 2 als auch die erfindungsgemäßen Beispiele die guten Barriereeigenschaften von Polyketon gegen Treibstoffe, Lösungsmittel. Sau- erstoff u.a. besitzen.4. The barrier properties are assessed on the basis of electron micrographs (transmission, ultra-thin sections, formalin / OsO4 treatment). Electron micrographs show that comparative example 2 and the examples according to the invention show the good barrier properties of polyketone against fuels and solvents. Oxygen and others have.
5. Das Verhalten bei Stoßbeanspruchung im Durchstoßversuch (Durchstoßarbeit Wges an 60 mm Rundscheiben mit 3 mm Dicke, ISO 6603-2) wurde untersucht. Die erfindungsgemäßen Formmassen der Beispiele 1 - 3 zeigen gegen- über Vergleichsbeispiel 1 über den gesamten Temperaturbereich ein deutlich verbessertes und gegenüber Vergleichsbeispiel 2 bei tiefen Temperaturen ein verbessertes Zähigkeitsverhalten.5. The behavior under impact stress in the puncture test (puncture work Wges on 60 mm round disks with 3 mm thickness, ISO 6603-2) was investigated. The molding compositions according to the invention of Examples 1-3 have a significantly improved toughness behavior over Comparative Example 1 over the entire temperature range and compared with Comparative Example 2 at low temperatures.
6. Das Verhalten im Zugversuch wurde nach ISO 527 ermittelt. Die erfindungs- gemäßen Formmassen der Beispiele 1 - 3 zeigen gegenüber Vergleichsbeispiel 2 im Zugversuch eine verbesserte Bruchspannung und Bruchdehnung und erhöhte Zugmodul werte.6. The behavior in the tensile test was determined according to ISO 527. The molding compositions according to the invention of Examples 1 - 3 show, compared to Comparative Example 2, an improved tensile strength and elongation at break and increased tensile modulus values in the tensile test.
Es zeigt sich, daß die erfindungsgemäß modifizierten Polyketon-Formmassen im Vergleich zu unmodifiziertem Polyketon bessere Eigenschaften hinsichtlich Verarbeitungseigenschaften (verbesserte Fließfähigkeit, kürzere Erstarrunngszeit). Farbeigenschaften (hellerer Grundfarbton) und Tieftemperaturzähigkeit im Durchstoßversuch haben unter Beibehaltung der guten Eigenschaften des unmodifizierten Polyketons bezüglich Zähigkeit im Durchstoßversuch bei Raumtemperatur, mecha- nische Eigenschaften im Zugversuch und Barriereeigenschaften. Im Vergleich zu der nächsthegenden modifizierten Polyketon-Formmasse (Vergleichsbeispiel 2) zeigen die erfindungsgemäß modifizierten Polyketon-Formmassen (Beispiele 1 - 3) deutlich bessere Eigenschaften hinsichtlich Verarbeitungseigenschaften (verbesserte Fließfähigkeit), Verarbeitungsstabilität (langsamerer Viskosi- tätsaufbau in der Schmelze), Oberflächenqualität (keine Flecken, hellerer Grundfarbton) und mechanische Eigenschaften im Zugversuch (Festigkeit, Dehnbarkeit). It can be seen that the polyketone molding compositions modified in accordance with the invention have better processing properties (improved flowability, shorter solidification time) compared to unmodified polyketone. Color properties (lighter base color) and low-temperature toughness in the puncture test, while maintaining the good properties of the unmodified polyketone with regard to toughness in the puncture test at room temperature, have mechanical properties in the tensile test and barrier properties. Compared to the next modified polyketone molding compound (comparative example 2), the polyketone molding compounds modified according to the invention (examples 1-3) show significantly better properties with regard to processing properties (improved flowability), processing stability (slower viscosity build-up in the melt), surface quality (none Stains, lighter basic color) and mechanical properties in tensile tests (strength, elasticity).

Claims

Patentansprüche claims
1. Thermoplastische Formmassen enthaltend1. Containing thermoplastic molding compositions
A) wenigstens ein linear alternierendes Polymer aus Kohlenmonoxid und wenigstens einem ethylenisch ungesättigten Kohlenwasserstoff,A) at least one linearly alternating polymer of carbon monoxide and at least one ethylenically unsaturated hydrocarbon,
B) wenigstens ein Gemisch aus durch Emulsionspolymerisation hergestelltem elastisch-thermoplastischem Pfropfpolymerisat und durch Lösungspolymerisation oder Massepolymerisation hergestelltem thermoplastischen Co- oder Terpolymerisat aufgebaut aus Vinylmonomeren, wobei das Gemisch erhältlich ist durch Abmischung des wasserfeuchten Pulvers des elastisch-thermoplastischen Pfropfkautschuks mit der Schmelze des thermoplastischen aus Vinylmonomeren aufgebauten Harzes unter Entfernung des enthaltenen Wassers.B) at least one mixture of elastic-thermoplastic graft polymer produced by emulsion polymerization and thermoplastic copolymer or terpolymer prepared by solution polymerization or bulk polymerization, built up from vinyl monomers, the mixture being obtainable by mixing the water-moist powder of the elastic-thermoplastic graft rubber with the melt of the thermoplastic from vinyl monomers built up resin with removal of the contained water.
2. Formmasse gemäß Anspruch 1 enthaltend 99 bis 1 Gew.-Teile A) und 1 bis 99 Gew.-Teile B).2. Molding composition according to claim 1 containing 99 to 1 part by weight of A) and 1 to 99 parts by weight of B).
3. Formmasse gemäß Anspruch 1 enthaltend 98 bis 50 Gew.-Teile A) und 2 bis3. Molding composition according to claim 1 containing 98 to 50 parts by weight of A) and 2 to
50 Gew.-Teile B).50 parts by weight B).
4. Formmasse gemäß Anspruch 1 enthaltend 97 bis 70 Gew.-Teile A) und 3 bis 30 Gew.-Teile B).4. Molding composition according to claim 1 containing 97 to 70 parts by weight of A) and 3 to 30 parts by weight of B).
5. Formmasse nach einem der vorhergehenden Ansprüche enthaltend ein oder mehrere Pfropfpolymerisate enthaltend als Pfropfbasis einen Dienkautschuk oder Acrylatkautschuk oder Mischungen davon, wobei der Kautschuk ein Homo- oder Copolymerisat sein kann und als Pfropfmonomere Vinylmono- mere der Verbindungen der Formel (1) oder (II) oder Gemische davon
Figure imgf000024_0001
5. Molding composition according to one of the preceding claims containing one or more graft polymers containing a diene rubber or acrylate rubber or mixtures thereof as the graft base, wherein the rubber can be a homo- or copolymer and vinyl monomers of the compounds of the formula (1) or (II.) As graft monomers ) or mixtures thereof
Figure imgf000024_0001
(I) (II) wobei(I) (II) where
R1 Wasserstoff oder Methyl,R 1 is hydrogen or methyl,
R , ?~ Halogen oder Alkyl mit 1 bis 4 Kohlenstoffatomen,R,? ~ Halogen or alkyl having 1 to 4 carbon atoms,
0 oder eine ganze Zahl von 1 bis 5 bedeuten,0 or an integer from 1 to 5,
R^ Wasserstoff oder Methyl undR ^ is hydrogen or methyl and
X -CN, -COOR4, -CONR5R6 bedeuten, wobeiX is -CN, -COOR 4 , -CONR 5 R 6 , where
R4 Wasserstoff oder C, C4-Alkyl undR 4 is hydrogen or C, C 4 alkyl and
R^ und R6 unabhängig Wasserstoff. Phenyi oder C,-C4- Alkyl bedeuten.R ^ and R6 are independently hydrogen. Phenyi or C, -C 4 - alkyl mean.
6. Formmasse gemäß Anspruch 5, wobei die Pfropfbasis Polybutadien oder ein6. Molding composition according to claim 5, wherein the graft base is polybutadiene or
Styrol/Butadien-Copolymer ist.Is styrene / butadiene copolymer.
7. Formmasse gemäß einem oder mehreren der vorhergehenden Ansprüche, wobei die Pfropfmonomere ausgewählt sind aus mindestens einer Verbindung der Gruppe bestehend aus Styrol. α-Methylstyrol. p-Methylstyrol. Vinyltoluol. Vinylacetat. N-Phenylmaleinimid, Acrylnitril und Methylmethacrylat. 7. Molding composition according to one or more of the preceding claims, wherein the graft monomers are selected from at least one compound from the group consisting of styrene. α-methyl styrene. p-methylstyrene. Vinyl toluene. Vinyl acetate. N-phenylmaleimide, acrylonitrile and methyl methacrylate.
8. Formmasse gemäß einem oder mehreren der vorhergehenden Ansprüche, wobei der Kautschukgehalt des Pfropfpolymerisats 40 bis 90 Gew.-% beträgt.8. Molding composition according to one or more of the preceding claims, wherein the rubber content of the graft polymer is 40 to 90% by weight.
9. Formmasse gemäß einem oder mehreren der vorhergehenden Ansprüche, ent- haltend Co- bzw. Terpolymerisate aus Styrol, Acrylnitril, wobei Styrol ganz oder teilweise durch α-Methylstyrol oder Methylmethacrylat ersetzt sein kann und wobei bis zu 25 Gew.-%, bezogen auf Co- bzw. Terpolymerisat, ein weiteres Monomer aus der Gruppe Maleinsäureanhydrid, Malein- oder Fumarsäurebisalkylester, Maleinsäureimid, N-(Cyclo)-alkylmaleinimid und N-(Alkyl)-phenylmaleinimid mitverwendet werden kann.9. Molding composition according to one or more of the preceding claims, containing copolymers or terpolymers of styrene or acrylonitrile, it being possible for styrene to be replaced in whole or in part by α-methylstyrene or methyl methacrylate and with up to 25% by weight, based on Co- or terpolymer, another monomer from the group of maleic anhydride, maleic or fumaric acid bisalkyl esters, maleimide, N- (cyclo) -alkylmaleinimide and N- (alkyl) -phenylmaleimide can also be used.
10. Formmasse gemäß einem oder mehreren der vorhergehenden Ansprüche, wobei das Mischungsverhältnis von Pfropfpolymerisat zu Co- bzw. Terpolymerisat 1:4 bis 4:1 beträgt.10. Molding composition according to one or more of the preceding claims, wherein the mixing ratio of graft polymer to copolymer or terpolymer is 1: 4 to 4: 1.
1 1. Formmassen gemäß einem oder mehreren der vorhergehenden Ansprüche, wobei der Wassergehalt des eingesetzten wasserfeuchten Pfropfpolymerisat- Pulvers 1 bis 50 Gew.-% beträgt.1 1. Molding compositions according to one or more of the preceding claims, wherein the water content of the water-moist graft polymer powder used is 1 to 50 wt .-%.
12. Formmasse gemäß einem oder mehreren der vorhergehenden Ansprüche, wobei der Restgehalt an flüchtigen Bestandteilen in der Komponente B) <1 000 ppm ist.12. Molding composition according to one or more of the preceding claims, wherein the residual volatile content in component B) is <1,000 ppm.
13. Formmassen gemäß einem oder mehreren der vorhergehenden Ansprüche. enthaltend übliche Additive. Füll- und Verstärkungsstoffe. Additive zur Erhöhung der Leitfähigkeit und Flammschutzmittel.13. Molding compositions according to one or more of the preceding claims. containing common additives. Fillers and reinforcing materials. Additives to increase conductivity and flame retardants.
14. Verwendung der Formmassen gemäß einem oder mehreren der vorhergehenden Ansprüche, zur Herstellung von Formkörpern und/oder Halbzeugen. 14. Use of the molding compositions according to one or more of the preceding claims, for the production of moldings and / or semi-finished products.
5. Formkörper bzw. Halbzeuge, erhältlich aus Formmassen gemäß einem oder mehreren der vorhergehenden Ansprüche. 5. Moldings or semi-finished products, obtainable from molding compositions according to one or more of the preceding claims.
PCT/EP2000/003215 1999-04-24 2000-04-11 Thermoplastic polyketone moulding materials WO2000064978A1 (en)

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US8969476B2 (en) 2002-06-21 2015-03-03 Sabic Global Technologies B.V. Impact-modified compositions

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