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WO1999060057A1 - Nanocomposites thermoplastiques - Google Patents

Nanocomposites thermoplastiques Download PDF

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Publication number
WO1999060057A1
WO1999060057A1 PCT/EP1999/003004 EP9903004W WO9960057A1 WO 1999060057 A1 WO1999060057 A1 WO 1999060057A1 EP 9903004 W EP9903004 W EP 9903004W WO 9960057 A1 WO9960057 A1 WO 9960057A1
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WIPO (PCT)
Prior art keywords
weight
carbon monoxide
layered silicate
thermoplastic nanocomposites
bis
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PCT/EP1999/003004
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German (de)
English (en)
Inventor
Alexander Glück
Stefan Grutke
Joachim Queisser
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Basf Aktiengesellschaft
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Application filed by Basf Aktiengesellschaft filed Critical Basf Aktiengesellschaft
Priority to EP99924868A priority Critical patent/EP1086173A1/fr
Priority to AU41376/99A priority patent/AU4137699A/en
Publication of WO1999060057A1 publication Critical patent/WO1999060057A1/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
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L59/00—Compositions of polyacetals; Compositions of derivatives of polyacetals

Definitions

  • the present invention relates to thermoplastic nanocomposites containing
  • the present invention relates to a method for producing the aforementioned thermoplastic nanocomposites, their use for the production of films, fibers, moldings or coatings, and such films, fibers, moldings or coatings.
  • thermoplastic nanocomposites based on polyamides, polyesters or polystyrenes are known. These thermoplastic materials are characterized by with good rigidity and good toughness.
  • clay minerals were used early on as a reinforcing material (cf. HKG Theng in "Formation and Properties of Clay-Polymer Complexes", Elsevier, Amsterdam, 1979).
  • the clay mineral was radically polymerized for compatibility in the presence of vinyl monomers.
  • Satisfactory results were only obtained in the polycondensation of caprolactam in the presence of clay mineral / aminolauric acid or clay mineral / amino caproic acid intercalates achieved (cf. Fukushima et al., Clay Miner. 1988, 23, p. 27).
  • the disadvantage here is that only those polymer materials can be used which have a softening temperature which is not too high and which are also stable at this temperature for a relatively long period of time, or at least for the duration of the processing.
  • Another disadvantage is that the products obtained are generally characterized by poor flowability.
  • German patent application DE-A 38 08 623 describes polyamides reinforced with layered silicates.
  • the layered clay minerals used there are pretreated with a cation-active species as a so-called swelling agent in order to create a layer spacing that is suitable for the effective incorporation of the polymer chains.
  • Organic compounds which have an onium and a functional group which can be incorporated into the polyamide chain are used as swelling agents. Only the carboxy group is mentioned as a suitable functional group in the aforementioned German patent application.
  • the tensile strength of glass fiber-reinforced carbon monoxide copolymers can be improved with a special isocyanate size.
  • the fiber materials are preferably used in amounts of not less than 10% by weight, based on the reinforced copolymer.
  • the surface available for glass fibers also limits the efficiency of the mechanical property improvement. Although large quantities of glass fiber material are desirable for mechanical reasons, the surface properties of the reinforced polymers (so-called glass fiber effect) regularly deteriorate, especially with high fiber contents.
  • the present invention was therefore based on the object of developing reinforced carbon monoxide copolymers which are not based on inorganic fiber materials and which, irrespective of the size material used - or entirely without it - are improved compared to unreinforced carbon monoxide copolymers show mechanical property profile and improved surface properties.
  • thermoplastic nanocomposites the reinforced carbon oxide copolymers described at the outset, also referred to herein as thermoplastic nanocomposites. Furthermore, a process for the production of the aforementioned thermoplastic nanocomposites, their use for the production of films, fibers, moldings or coatings as well as such films, fibers, moldings or coatings have been found.
  • the molding compositions according to the invention contain 50 to 99.99% by weight, preferably 55 to 99.0% by weight and in particular 65 to 96% by weight of carbon monoxide copolymers.
  • Carbon monoxide copolymers for the purposes of the present invention include copolymers of carbon monoxide and olefinically unsaturated compounds.
  • this includes linear, strictly alternating carbon monoxide copolymers of carbon monoxide and at least one olefinically unsaturated compound.
  • all monomers of this class of compounds can be considered as olefinically unsaturated compounds.
  • substituted and unsubstituted alkenes can be used as well as cycloolefins or unsaturated aromatic monomers.
  • alkenes preferred are monomers with a terminal double bond.
  • C 3 - to C IG -, in particular C to Cio-alkenes such as propene, 1-butene, 1-pentene, 1-hexene or 1-octene, are therefore also suitable.
  • Ethylene and propene are preferred, and ethylene is particularly preferred. Of course, ethylene can also be used in a mixture with, for example, propene or 1-butene. Ethylene / propene mixtures are preferred.
  • the radical R can furthermore be C 1 -C 4 -aryl-, in particular C 6- to Cio-aryl, for example phenyl.
  • preferred aryl compounds with an olefinic radical are, for example, styrene or ⁇ -methylstyrene, preferably styrene.
  • vinyl halides for example vinyl chloride, vinyl esters such as vinyl acetate or vinyl propionate and vinyl heterocylenes such as N-vinylpyrrolidone.
  • acrylic acid and methacrylic are of interest further understood acrylic acid and derivatives thereof, including in particular, the nitriles, amides and Ci to C alkyl esters ß.
  • cycloolefins are especially C 3 - to name -Cycloolefine 0 to C ⁇ , so for example, cyclopentene, cyclohexene, norbornene or norbornadiene.
  • di- or tri-substituted olefins can also be used.
  • Carbon monoxide copolymers are preferably obtained catalyzed by transition metals, with generally linear, strictly alternating copolymers of carbon monoxide and at least one olefinically unsaturated compound being obtained.
  • a transition metal of Groups IB, II B or VIII B is generally a chelate complex comprising the Periodic Table of the Elements, so as palladium, • *** ⁇ - ⁇ platinum, ruthenium, rhodium or iridium , and a bidentate ligand system, in question.
  • Suitable catalyst systems are, for example, metal complexes of the general type chelated with bidenate ligands
  • R a independently linear or branched Ci to C 20 alkyl, C 3 - to Cio-cycloalkyl, C ⁇ - to Ci 5 ⁇ aryl, with functional groups based on the non-metallic elements of groups IVA, VA, VIA or VIIA des Periodic table substituted C ⁇ to cis aryl, aralkyl with 1 to 10 C atoms in the alkyl part and 6 to 15 C atoms in the aryl part,
  • R b as R a and additionally hydrogen and Si (R c ) 3 ,
  • R c linear or branched C ⁇ ⁇ to C 2o alkyl, C 3 - bis
  • Z is an element from the VA group of the Periodic Table of the Elements
  • M is a metal selected from Groups VIIIB, IB or IIB of the Periodic Table of the Elements,
  • E 1 , E 2 a non-metallic element from group VA of the periodic table of the elements
  • R 1 to R 4 branched C ⁇ to C 2 o ⁇ alkyl, C 3 - to Cirj-cycloalkyl, C ⁇ - to cis-aryl, with functional groups based on the non-metallic elements of groups IVA, VA, VIA or VIIA of the periodic table substituted Ce * - to cis-aryl, aralkyl with 1 to 10 carbon atoms in the alkyl radical and 6 to 15
  • R d , R e , R f , R9 independently of one another for hydrogen, straight-chain or branched Ci to C 6 alkyl or
  • R e and R f together represent a five- or six-membered carbo- or heterocycle
  • Suitable metals of the metal complexes according to the invention are the metals from groups VIIIB, IB and IIB of the Periodic Table of the Elements, that is to say, in addition to copper, silver or zinc, also iron, cobalt and nickel, and the platinum metals such as ruthenium, rhodium, osmium, iridium and platinum, Palladium is very particularly preferred.
  • the elements E 1 and E 2 of the chelating ligands are the non-metallic elements of the 5th main group of the periodic table of the elements, for example nitrogen, phosphorus or arsenic. Nitrogen or phosphorus, in particular phosphorus, are particularly suitable.
  • the chelating ligands can contain different elements E 1 and E 2 , for example nitrogen and phosphorus.
  • the structural unit G in the metal complex (I) is a mono- or multi-atom bridging structural unit.
  • a bridging structural unit is basically understood to mean a grouping which connects the elements E 1 and E 2 in (I) to one another.
  • the mono-atomic structural units are those with a bridging atom from group IVA of the periodic table of the elements such as -C (R b ) 2 - or -Si (R a ) 2 -, wherein R a independently of one another in particular for linear or branched C ⁇ ⁇ to Cio-alkyl, for example methyl, ethyl, i-propyl or t-butyl, C - to C ⁇ - cycloalkyl, such as cyclopropyl or cyclohexyl, C ⁇ - to Cio-aryl, such as phenyl or naphthyl, with functional groups based on non-metallic elements of groups IVA, VA, VIA or VIIA of the periodic table substituted Cg- to Cio-aryl, for example tolyl, (trifluoromethyl) phenyl, dimethylamino-phenyl, p-methoxyphenyl or partially or perhalogenated phenyl,
  • R d, R e, R f, R 9 independently of one another represent hydrogen, straight-chain or branched Ci- to C ß alkyl such as methyl, ethyl or i - propyl, or
  • R e and R f together represent a five- or six-membered carbo- or heterocycle
  • Chelate ligands such as 1, 10-phenanthroline, 2, 2 '-bipyridine or 4,4'-dimethylbipyridine or their substituted derivatives can be traced back to diatomically bridged structural units.
  • Suitable three-atom bridged structural units are generally based on a chain of carbon atoms, that is to say
  • Example propylene (-CH 2 CH 2 CH-), or on a bridge unit with a hetero atom from group IVA, VA or VIA of the periodic table of the elements, such as silicon, nitrogen, phosphorus or oxygen in the chain structure.
  • the free valences can be substituted by C * to C ⁇ alkyl, such as methyl, ethyl or t-butyl, C ⁇ to Cio aryl, such as phenyl, or by functional groups such as triorganosilyl, dialkylamino or halogen. be acted upon.
  • Suitable substituted propylene bridges are for Example those with a methyl, phenyl or methoxy group in the 2-position.
  • the radical R 5 in Z may particularly represent: hydrogen, linear or branched C ⁇ ⁇ to C o alkyl, such as methyl, ethyl, i-propyl or t-butyl, C 3 - to C ß cycloalkyl, such as cyclopropyl or cyclohexyl, C 6 - to Cio-aryl, for example phenyl, substituted by functional groups based on the non-metallic elements of groups IVA, VA, VIA or VIIA of the periodic table, C 1 to C 10 -alkyl or C 6 - to Cio-aryl, such as trifluoromethyl, 2, 2,2-trifluoroethyl, nitromethyl, 2-nitroethyl and tolyl, mesityl or 2, 4-difluorophenyl, aralkyl with 1 to 6
  • R a independently of one another hydrogen, linear or branched C 1 to C 10 alkyl, such as methyl, ethyl, i-propyl or t-butyl, C 3 to C 6 cycloalkyl, for example cyclo- hexyl, C 6 ⁇ to Cio-aryl, for example phenyl, C 6 - to Cio-aryl, such as tolyl, trifluoromethylphenyl, aminophenyl, substituted with functional groups based on the non-metallic elements of groups IVA, VA, VIA or VIIA of the periodic table, Hydroxyphenyl, anisyl or mono- or dichlorophenyl, aralkyl with 1 to 6 carbon atoms in the alkyl part and 6 to 10 carbon atoms in the aryl part, for example benzyl,
  • R b as R a and additionally hydrogen and Si (R c ) 3 with
  • Cio-alkyl such as methyl or ethyl, C 3 - to C ⁇ -cycloalkyl, for example cyclohexyl, C 6 - to Cio-aryl, for example phenyl or aralkyl with 1 to 6 carbon atoms in Alkyl part and 6 to 10 carbon atoms in the aryl part, for example benzyl, with which, for example, trimethyl, triethyl, triphenyl or t-butyldiphenylsilyl fall under the formula Si (R c ) 3 .
  • Metal complexes (I) are preferred, for example, in which M is present as divalent positively charged palladium, the elements E 1 and E 2 are phosphorus and the bridging structural unit G is methylene, ethylidene, 2-propylidene, dimethylsilylene or diphenylsilylene, in particular methylene.
  • the monatomically bridged metal complexes advantageously have radicals R 1 to R 4 , at least one of which is a non-aromatic radical.
  • aromatic radicals phenyl and tolyl are particularly noteworthy, among the aliphatic radicals these are those with bulky groups, for example t-butyl, i-propyl, s-butyl, cyclohexyl or menthyl.
  • Metal complexes (I) which have a three-atom bridge are particularly preferred. This includes, for example, compounds in which the elements E 1 and E 2 are connected by a propylene unit (-CH 2 CHCH -).
  • the aforementioned metal complexes (I) can also be used in the form of the corresponding palladium-bis-acetate or palladium dichloride compounds, ie without new tralligands such as acetonitrile or tetrahydrofuran.
  • Examples include bis (diphenylphosphinomethyl) phenylamine-palladium-bis -palladium dichloride and
  • the palladium (II) acetate complexes (I) are preferably used.
  • the transition metal catalysts can be added to the reaction mixture in a defined form or as individual components - in a mixture or successively. They can also be used in supported form, it being possible for the catalyst to be applied to the support in a defined form or in the form of its individual components.
  • transition metal-catalyzed copolymerization processes for the production of carbon monoxide copolymers can be carried out batchwise or continuously.
  • Suitable reaction parameters for the production of copolymers from carbon monoxide and olefinically unsaturated compounds are pressures of 100 to 500,000 kPa, preferably 500 to 350,000 kPa and in particular 1000 to 10,000 kPa, temperatures of -50 to 400 ° C, preferably 10 to 250 ° C and in particular 20 to 150 ° C proved to be suitable.
  • the polymerization reactions can be carried out in the gas phase in a fluidized bed or stirred, in suspension, in liquid and in supercritical monomers and in solvents which are inert under the polymerization conditions.
  • Particularly suitable solvents or suspending agents for the processes according to the invention are those which are protic or which contain a protic component in portions.
  • low molecular weight alcohols such as methanol, ethanol, i-, n-propanol or water come into question; methanol is preferably used as the solvent / suspending agent or as the solvent / suspending agent component.
  • the polymerization reactions can also be carried out in a virtually alcohol-free or water-free polymerization medium. This means that the reaction mixture of monomers, catalyst and possibly inert solvent or suspending agent, except optionally the ligand L 1 or L 2 , contains no further alcohol or water components.
  • Suitable inert solvents and suspending agents are those which do not contain any hydroxyl group in the molecule, i.e. ethers such as diethyl ether, tetrahydrofuran, aromatic solvents such as benzene, toluene, ethylbenzene, chlorobenzene, aliphatic hydrocarbons such as i-butane or chlorinated aliphatic hydrocarbons such as dichloromethane, 1, 1 , 1-trichloromethane or mixtures of the compounds mentioned.
  • ethers such as diethyl ether, tetrahydrofuran
  • aromatic solvents such as benzene, toluene, ethylbenzene, chlorobenzene
  • aliphatic hydrocarbons such as i-butane or chlorinated aliphatic hydrocarbons such as dichloromethane, 1, 1 , 1-trichloromethane or mixtures of the compounds mentioned.
  • One method for producing the carbon monoxide copolymers is to initially charge the catalyst in an inert solvent and, after the monomers have been added, to carry out the polymerization at a temperature in the range from 20 to 150 ° C. and a pressure in the range from 1000 to 10,000 kPa.
  • copolymerization processes described can also be carried out in the presence of an oxidizing agent such as benzoquinone or naphthoquinone and / or with the addition of hydrogen.
  • an oxidizing agent such as benzoquinone or naphthoquinone
  • binary linear alternating carbon monoxide / ethene copolymers or ternary carbon monoxide / ethene / propene or carbon monoxide / ethene / 1-butene copolymers can be produced.
  • the molecular weights of the linearly alternating copolymers are generally in the range from 5000 to 500,000 g / mol.
  • Suitable carbon monoxide copolymers are also to be understood in the present case as copolymers obtained by free radical means, it being possible to use the starting monomers already described in the transition metal-catalyzed copolymerization.
  • the polymerization can be started either by means of radical initiators such as peroxides, hydroperoxides or oxygen or with the aid of high-energy radiation, for example ⁇ -radiation.
  • radical initiators such as peroxides, hydroperoxides or oxygen
  • high-energy radiation for example ⁇ -radiation.
  • temperatures in the range from 120 to 165 ° C. and pressures up to approximately 1000 bar are required in order to obtain suitable carbon monoxide copolymers.
  • the radical copolymerization of carbon monoxide and olefinically unsaturated compounds can be found, for example, in US Pat. No. 2,495,286.
  • the molding compositions according to the invention contain 0.01 to 50, preferably 0.5 to 15 and in particular 2 to 10% by weight of a
  • silicates Under a layer silicate is generally understood silicates, in which the Si0 4 tetrahedra are connected etzwerken in two-dimensional infinite N. (The empirical formula for the anion is (Si 2 ⁇ 5 2 ") n ). The individual layers are connected to each other by the cations between them, mostly as cations Na, K, Mg, Al or / and Ca in the natural occurring layered silicates.
  • P hyllosilikate examples include montmorillonite, smectite, illite, sepiolite, palygorskite, muscovite, allevardite, amesite, hectorite, fluorine hectorite, saponite, beidellite, talc, nontronite, stevensite, bentonite, mica, vermiculite, Fluoromiculite, halloysite and fluorine-containing synthetic mica types called.
  • a delaminated layered silicate within the meaning of the invention is to be understood as meaning layered silicates in which the layer spacings are initially increased and a similar polarity is achieved by reaction with so-called hydrophobizing agents (before the molding compositions according to the invention are produced).
  • the hydrophobicized swollen layered silicate is made up with carbon monoxide copolymers, and the layers are widened again, before the shaped body preferably leads to a layer spacing of at least 30 ⁇ , preferably at least 40 ⁇ .
  • the copolymerization of carbon monoxide and olefinically unsaturated compounds can be carried out in the presence of hydrophobic layered silicate.
  • Suitable as water repellents are e.g. Onium ions or onium salts.
  • the cations of the layered silicates are replaced by these organic hydrophobizing agents, it being possible for the nature of the organic residue to set the desired layer spacings, which depend on the type of the particular monomer or polymer in which the layered silicate is to be incorporated.
  • the metal ions can be exchanged completely or partially. A complete exchange of the metal ions is preferred.
  • the amount of exchangeable metal ions is usually given in milliequivalents (meq) per 100 g layered silicate and is referred to as the ion exchange capacity.
  • Layered silicates with a cation exchange capacity of at least 50, preferably 80 to 130 meq / 100 g are preferred.
  • Suitable organic water repellents are derived from
  • Oxonium, ammonium, phosphonium and sulfonium ions which can carry one or more organic radicals.
  • Suitable hydrophobicizing agents are those of the general formula IV and / or IV:
  • R 6 , R 7 , R 8 , R 9, independently of one another, are hydrogen, a straight-chain or branched, saturated or unsaturated hydrocarbon radical having 1 to 40, preferably 1 to 20, carbon atoms or 2 of the radicals, in particular to form a heterocyclic radical Radical having 5 to 10 carbon atoms, preferably at least one radical R 6 to R 9 having a terminal unsubstituted olefinic double bond,
  • Suitable anions (V) are derived from proton-providing acids, in particular mineral acids, halides such as chloride, bromide, fluoride or iodide and sulfate, sulfonate, phosphate, phosphonate, phosphite and carboxylate and in particular acetate being preferred as anions.
  • alkylammonium ions for example laurylammonium, myristylammonium, palmitylammonium, stearylammonium, pyridinium, octadecylammonium, monomethyloctadecylammonium and dimethyloctadecylammonium ions are preferred.
  • W hen appropriate phosphonium include for example thylphosphonium Dicosyltrime-, Hexatriacontyltricyclohexylphosphonium, octadecyl cyltriethylphosphonium, Dicosyltriisobutylphosphonium, nonylphosphonium methyltri-, Ethyltrihexadecylphosphonium, Dimethyldidecyl - phosphonium, Diethyldioctadecylphosphonium, lylphosphonium Octadecyldiethylal-, Trioctylvinylbenzylphosphonium, hydroxyethylphosphonium Dioctadecylethyl-, Docosyldiethyldichlorbenzylphosphoniu, Octylnonyldecylpropargylphosphonium, Triisobutylperfluordecyl - phosphonium,
  • Suitable water repellents include in WO 93/4118, WO 93/4117, EP-A 398 551 and DE-A 36 32 865.
  • alkylammonium ions with vinyl functionality.
  • Preferred alkylammonium ions are obtained by reacting suitable amino-1-lenes, e.g. of ⁇ -amino-1-alkenes, such as ⁇ -amino-1-dodecene, ⁇ -amino-1-undecene or ⁇ -amino-1-hexene, or of allylamines such as allyl-n-hexylamine with conventional mineral acids, for example
  • the amino group can be a primary, secondary or tertiary amino group.
  • the amino group can be both in the allylic position to the terminal double bond and in a more distant position to this, such as in the 5-amino-1-octene.
  • the layered silicates used as starting materials are generally implemented in the form of a suspension.
  • the preferred suspending agent is water, optionally in a mixture with alcohols, especially lower alcohols with 1 to 3 carbon atoms. It can be advantageous to use a hydrocarbon, for example heptane, together with the aqueous medium, since the hydrophobized phyllosilicates are usually more compatible with hydrocarbons than with water.
  • Other suitable examples of suspending agents are ketones and hydrocarbons.
  • a water-miscible solvent is usually preferred.
  • the ion exchange is largely independent of the reaction temperature.
  • the temperature is preferably above the crystallization point of the medium and below its boiling point. In aqueous systems, the temperature is between 0 and 100 ° C, preferably between room temperature (about 20 ° C) and 80 ° C.
  • the layered silicates After the hydrophobization, the layered silicates have a layer spacing of 5 to 100 ⁇ , preferably 5 to 50 ⁇ and in particular 8 to 40 ⁇ .
  • the layer spacing usually means the distance from the lower layer edge of the upper layer to the upper layer edge of the lower layer.
  • the length of the leaflets is usually up to 2000 ⁇ , preferably up to 1500 ⁇ .
  • the layered silicate hydrophobicized in the above manner can then be mixed in suspension or as a solid with the monomers or prepolymers and the polymerization can be carried out in the customary manner as described above for the carbon monoxide copolymerization.
  • the hydrophobization step is possible not to introduce the hydrophobization step separately from the carbon monoxide copolymerization, but rather to carry it out in a reaction container simultaneously or almost simultaneously with the copolymerization.
  • the carbon monoxide copolymerization can be started by adding the monomers and the catalyst under the process conditions already described.
  • the hydrophobicizing agents used suitably have an olefinically unsaturated group capable of being incorporated into the copolymer chain.
  • thermoplastic nanocomposites according to the invention can be obtained by carbon monoxide copolymers with delaminated layered silicate by generally known methods, for example by means of extrusion, at a temperature assemblies in the range of 160 to 260 ° C, preferably from 180 to 250 ° C.
  • thermoplastic nanocomposites according to the invention may also contain, as component C), 0 to 40, preferably 0.5 to 30 and in particular 2 to 25% by weight of a fibrous or particulate filler.
  • Carbon fibers, aramid fibers and potassium titanate fibers may be mentioned as preferred fibrous fillers, with glass fibers, in particular E-glass, being particularly preferred. These can be used as rovings or cut glass in the commercially available forms.
  • the fibrous fillers can be pretreated with a size for better compatibility with the thermoplastic. Suitable sizes are based, for example, on organic compounds with a silane, (poly) urethane or epoxy functionality. Among the silane sizes, aminosilane sizes are preferred. Mixtures of silane, (poly) urethane and / or epoxy compounds can also be used as the sizing material. It is also possible for suitable sizing materials to be based on polyfunctional compounds, for example on aminosilanes with (poly) urethane or epoxy functionality.
  • Preferred silane sizes are aminopropyltrimethoxysilane, aminobutyltrimethoxysilane, aminopropyltriethoxysilane, aminobutyltriethoxysilane and the corresponding silanes which contain a glycidyl group as a substituent.
  • the silane compounds are generally used in amounts of
  • the molding compositions of the invention contain, as component D), from 0 to 30% by weight, preferably from 0 to 15% by weight, of further additives.
  • additives include, for example, heat and light stabilizers, antioxidants, lubricants and mold release agents, colorants such as dyes and pigments.
  • Preferred antioxidants are phenols shielded with sterically demanding groups, in particular those with substituents in the ortho-position to the OH group. These antioxidants are described, for example, in DE-A 27 02 661 (US 4,360,617). Examples include 4-methyl -2, 6-di-tert-butylphenol and octadecyl -3 - (3, 5-di-butyl-4-hydroxyphenyl) propanoate.
  • alkaline earth metal carbonates in particular calcium carbonate, or calcium phosphate (Ca 3 (P0 4 ) 2
  • additives are reinforcing agents such as gypsum fibers, synthetic calcium silicates, kaolin, calcined kaolin, wollastonite, talc and chalk.
  • polyethylene waxes can be considered as lubricants.
  • Carbon blacks or titanium oxide can be used as pigments, for example.
  • the average particle size is generally in the range from 50 to 400 nm, in particular from 150 to 240 nm.
  • Industrial uses include rutile and anatase, which are optionally coated with metal oxides, for example aluminum oxides, silicon oxides, oxides of zinc, or siloxanes are. Under soot, micro-
  • thermoplastic nanocomposites according to the invention contain 0 to 30, preferably 0 to 25 and particularly 25 preferably 0 to 20% by weight of a rubber-elastic polymer (often also referred to as an elastomer or impact modifier).
  • a rubber-elastic polymer often also referred to as an elastomer or impact modifier
  • Natural or synthetic rubbers can be used as component E). In addition to natural rubber,
  • modifiers e.g. polybutadiene, polyisoprene, polyisobutylene or
  • Copolymers of butadiene and / or isoprene with styrene and other comonomers are suitable which have a glass transition temperature, determined according to K.H. Illers and H. Breuer, Kolloidzeitschrift 190 (1), pp. 16-34 (1963), from about -100 to 25 ° C, preferably below
  • Suitable rubber-elastic polymers are based, for example, on graft rubbers with a crosslinked elastomer
  • 40 core which is preferably derived from butadiene, isoprene or alkyl acrylates, and a graft shell made of polystyrene.
  • copolymers of ethene and acrylates or methacrylates are also suitable, as well as the so-called ethylene-propylene (EP) and ethylene-propylene-diene (EPDM) rubbers, as well as those grafted with styrene.
  • EP ethylene-propylene
  • EPDM ethylene-propylene-diene
  • EP or EPDM rubbers 45th EP or EPDM rubbers.
  • Preferred impact modifiers are block copolymers of vinyl aromatics and dienes. Impact modifiers of this type are known. DE-AS 1 932 234, DE-AS 2 000 118 and DE-OS 2 255 930 describe differently constructed vinyl aromatic and diene blocks comprising elastomeric block copolymers. The use of corresponding hydrogenated block copolymers, optionally in a mixture with the non-hydrogenated precursor as an impact modifier, is described, for example, in DE-OS 2 750 515, DE-OS 2 434 848, DE-OS 3 038 551, EP-A-0 080 666 and WO 83/01254. On the revelation above
  • the vinyl aromatic compounds mentioned are generally styrene, ⁇ -methylstyrene, vinyl toluene, vinyl or isopropenyl naphthalene. Styrene is preferred as the vinyl aromatic. Particularly suitable services are e.g. Butadiene, isoprene, 1, 3 -pentadiene or 2, 3-dimethylbutadiene.
  • Preferred impact modifiers are also block copolymers of vinyl aromatics and dienes, which are distinguished by the fact that instead of a pure diene rubber, a soft block of diene and vinyl aromatics is present, with diene and vinyl aromatics being statistically distributed in the soft block.
  • a soft block of diene and vinyl aromatics is present, with diene and vinyl aromatics being statistically distributed in the soft block.
  • transitions between the blocks can be both sharp and smeared.
  • Mixtures of block copolymers of different structures e.g. Mixtures of two- and three-block copolymers or of hydrogenated and unhydrogenated block copolymers can also be used.
  • Suitable products are also commercially available, such as the ethylene lenmethacryl Acidcopolymer "Nucrel ® 0910" from. DuPont
  • Suitable block copolymers with at least one vinylaromatic and one elastomeric block are commercially available.
  • Examples include the Cariflex ® TR types (Shell), the Kraton ® types (Shell), the Finaprene (Fina) and the
  • thermoplastic nanocomposites according to the invention are expediently produced by mixing the components at temperatures in the range from 220 to 260 ° C. in conventional mixing Devices such as kneaders, Banburyisers and single-screw extruders, preferably twin-screw extruders. Intensive mixing is necessary to obtain the most homogeneous molding compound possible.
  • the order of mixing the components can be varied, two or optionally three components can be premixed or all components can also be mixed together, components A) to E) being able to be homogenized both as solids and in suspension.
  • Components A) and B) of the molding compositions according to the invention are preferably mixed in such a way that, in the course of the copolymerization of carbon monoxide with olefinically unsaturated compounds, the hydrophobizing agent and delaminated or undelaminated layered silicate are added or introduced.
  • the molding compositions according to the invention are notable for very good heat resistance, measured, for example, via the forestry temperature HDT / B according to ISO 75-2, and very good rigidity with high strength at the same time.
  • a lower mold shrinkage in the case of injection molded parts made from the molding compositions according to the invention compared to those made from non-reinforced materials can be determined.
  • an improved surface behavior and comparable mechanical properties are observed with a significantly lower filler content.
  • the thermoplastic nanocomposites according to the invention are distinguished by very good melting behavior, i.e. very good flowability. A melt index greater than 60, measured according to ISO 1133, is generally readily possible.
  • melt index values greater than 70 and also greater than 85 can also be obtained reproducibly. Accordingly, the molding compositions according to the invention are suitable for the production of fibers, foils, moldings or coatings of any kind, applications in the electrical and electronics sector being just as possible as those in the automotive sector.
  • the components obtained according to Ia) and Ib) were processed at a weight ratio of 93: 7 using a twin-screw extruder (ZSK 40) at 240 ° C. to give the molding composition according to the invention.
  • a suspension of montmorillonite (29 g), allyl-n-hexylamine (7.1 g) and p-toluenesulfonic acid (9.3 g) in methanol (4 l) was placed in a 9.0 liter pressure vessel for 6 hours at 75 ° C stirred intensively.
  • propene (440 g) was added, a total pressure of 70 bar was set with a 1: 1 CO / ethene gas mixture and the temperature was brought to 90 ° C. with stirring (500 rpm).
  • the carbon monoxide copolymer produced according to Ia) was made up with glass fibers from PPG (PPG 22517) in a weight ratio of 70:30 on a twin-screw extruder (ZSK 40) at 240 ° C.
  • the glass fibers used had a 1 / d ratio of 20 to 23 in the injection molded part.
  • the carbon monoxide copolymer prepared according to Ia) was made up with talc (2.4 Moh) in a weight ratio of 70:30 on a twin-screw extruder (ZSK 40) at 240 ° C.
  • the production of the reinforced molding compound was carried out in accordance with GB 2217720.
  • the glass fibers used had a 1 / d ratio of 28 to 32.

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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)
  • Polyethers (AREA)

Abstract

L'invention concerne des nanocomposites thermoplastiques contenant A) 50 à 99,99 % en poids de copolymère de monoxyde de carbone constitué de monoxyde de carbone et d'au moins un composé oléfiniquement insaturé sous forme de motifs monomères, B) 0,01 à 50 % en poids d'un phyllosilicate délamifié, C) 0 à 40 % en poids de charges fibreuses, D) 0 à 30 % en poids d'autres additifs et E) 0 à 30 % en poids d'un polymère caoutchouteux, la somme des pourcentages en poids des constituants A) à E) totalisant respectivement 100 %.
PCT/EP1999/003004 1998-05-14 1999-05-04 Nanocomposites thermoplastiques WO1999060057A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP99924868A EP1086173A1 (fr) 1998-05-14 1999-05-04 Nanocomposites thermoplastiques
AU41376/99A AU4137699A (en) 1998-05-14 1999-05-04 Thermoplastic nanocomposites

Applications Claiming Priority (2)

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DE19821477A DE19821477A1 (de) 1998-05-14 1998-05-14 Thermoplastische Nanocomposite
DE19821477.4 1998-05-14

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WO1999060057A1 true WO1999060057A1 (fr) 1999-11-25

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Publication number Priority date Publication date Assignee Title
DE19943774A1 (de) 1999-09-13 2001-03-15 Basf Ag Biologisch abbaubare, thermoplastische Formmassen
DE10061877A1 (de) * 2000-12-12 2002-06-13 Basf Ag Verfahren zur Herstellung wässriger Copolymerisatdispersionen von Copolymerisaten aus Kohlenmonoxid und wenigstens einer olefinisch ungesättigten Verbindung
US7157517B2 (en) 2003-07-16 2007-01-02 Wayne State University Method of delaminating a graphite structure with a coating agent in a supercritical fluid
US7387749B2 (en) 2004-02-20 2008-06-17 Wayne State University Method of delaminating aggregated particles with a coating agent in a substantially supercritical fluid

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3806548A1 (de) * 1987-03-04 1988-09-15 Toyoda Chuo Kenkyusho Kk Verbundmaterial und verfahren zu dessen herstellung
WO1998010012A1 (fr) * 1996-09-03 1998-03-12 Raychem Corporation Composites de polymere et d'argile organique

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3806548A1 (de) * 1987-03-04 1988-09-15 Toyoda Chuo Kenkyusho Kk Verbundmaterial und verfahren zu dessen herstellung
WO1998010012A1 (fr) * 1996-09-03 1998-03-12 Raychem Corporation Composites de polymere et d'argile organique

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DE19821477A1 (de) 1999-11-18
EP1086173A1 (fr) 2001-03-28

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