EP0973828A1 - Matieres de moulage thermoplastiques - Google Patents

Matieres de moulage thermoplastiques

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Publication number
EP0973828A1
EP0973828A1 EP98913736A EP98913736A EP0973828A1 EP 0973828 A1 EP0973828 A1 EP 0973828A1 EP 98913736 A EP98913736 A EP 98913736A EP 98913736 A EP98913736 A EP 98913736A EP 0973828 A1 EP0973828 A1 EP 0973828A1
Authority
EP
European Patent Office
Prior art keywords
molding compositions
thermoplastic molding
compositions according
layered silicate
weight
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP98913736A
Other languages
German (de)
English (en)
Inventor
Josef WÜNSCH
Michael GEPRÄGS
Volker Warzelhan
Stefan Grutke
Martin Weber
Martin Klatt
Peter Wolf
Thomas Heitz
Thomas Plesnivy
Michael Fischer
Volker Rauschenberger
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
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Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP0973828A1 publication Critical patent/EP0973828A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F12/02—Monomers containing only one unsaturated aliphatic radical
    • C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/0366—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement reinforced, e.g. by fibres, fabrics

Definitions

  • the invention relates to thermoplastic molding compositions containing
  • the invention relates to processes for the production of these molding compositions, their use for the production of fibers, films and moldings of any kind, and the moldings obtainable here. 5
  • polymers of vinyl aromatic compounds are used in many areas, for example as packaging materials or as insulating coatings for metals or plastics, especially in electrical applications.
  • isotactic polystyrene A process for the production of isotactic polystyrene is described in GB-A 826 021. However, isotactic polystyrene crystallizes so slowly that it cannot be processed by injection molding.
  • Syndiotactic polystyrene by reacting styrene in the presence of a metallocene complex and a cocatalyst are described, for example, in EP-A 535 582 and 0 of EP-A 584 646.
  • Syndiotactic polystyrene has high chemical resistance, high rigidity, good dimensional stability and good dielectric properties.
  • stiffness is often not sufficient for technical applications - even in the case of syndiotactic polystyrene. Therefore, an increase in stiffness is usually carried out by assembly with glass fibers.
  • the disadvantage is that the surface properties of injection molded articles and the flow properties of the polymer melt deteriorate. At the same time, the density of the materials increases.
  • Atactic polystyrene which contains a delaminated layered silicate, is from A. Akelah, A. Moet, J. Mat. 1996, 31, 3589-3596.
  • the heat resistance and the flowability of such molding compositions or moldings are not sufficient for many applications.
  • the object of the present invention was therefore to provide vinyl aromatic polymers which have a balanced range of properties in the presence of fillers.
  • the molding compositions according to the invention contain 10 to 99, preferably 30 to 99 and in particular 50 to 98% by weight of a vinylaromatic polymer with a content of at least 30 30 mol%, preferably at least 50 and in particular at least 90 mol%, of syndiotactic Pentads.
  • the proportion of syndiotactic pentads is usually determined using
  • Component A) is preferably composed of vinylaromatic monomers of the general formula I.
  • R 1 is hydrogen or C 1 to C 4 alkyl
  • R 2 to R 6 independently of one another hydrogen, Ci to C 2 alkyl, C 6 to C 8 aryl, halogen or two adjacent
  • Residues together represent groups of 4 to 15 carbon atoms.
  • Vinylaromatic monomers of the formula I are preferably used in which
  • R 1 means hydrogen
  • R 2 to R 6 are hydrogen, Ci to C 4 alkyl, chlorine, phenyl,
  • Naphthalene derivatives or anthracene derivatives result.
  • Styrene p-methylstyrene, p-chlorostyrene, 2, 4-dimethylstyrene, -vinylbiphenyl, vinylnaphthalene or vinylanthracene.
  • Mixtures of different vinyl aromatic compounds can also be used, but preferably only one vinyl aromatic compound is used.
  • vinyl aromatic compounds are styrene and p-methylstyrene.
  • the preparation of vinylaromatic compounds of the general formula I is known per se and is described, for example, in Beilstein 5, 367, 474, 485.
  • Vinylaromatic polymers A) are also understood to mean star polymers which can be obtained by polymerizing the above vinylaromatic monomers with a branched monomer building block which contains at least two vinylaromatic functional radicals in the presence of a catalyst, a cation-forming agent and, if appropriate, an aluminum compound .
  • the end group functionality is above 0.5 mol%, particularly preferably above 0.8 mol%
  • R a is hydrogen, halogen, or an inert organic radical having up to 20 C atoms, where R a can be the same or different in the case of p> 2 and two radicals R a together with the metal atom bonded to them form a 3 to 8 can form a membered ring and R a can also be a common complex ligand when M is a transition metal,
  • R is hydrogen, -CC 4 alkyl or phenyl;
  • R c is hydrogen, C 1 -C 4 alkyl, phenyl, chlorine or an unsaturated hydrocarbon radical with 2 to 6 C atoms;
  • MC Si, Ge, Sn, B, AI, Ga, N, P, Sb, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Zn, Cd,
  • These monomers can e.g. via the Grignard compounds of chloro (alkyl) styrenes with the corresponding carbon, metal or transition metal compounds, e.g. the halogen compounds obtained.
  • Such reactions are, for example, in the case where M is silicon, germanium or tin in K. Nankishi, J. Chem. Soc. Perkin Trans I, 1990, page 3362.
  • Branching monomer units are particularly preferred
  • M means carbon, silicon, germanium, tin or titanium because they are easily accessible.
  • the index m is preferably 0 to 8, particularly preferably 0 to 4.
  • the molding compositions according to the invention contain 0.1 to 20, preferably 1 to 10 and in particular 2 to 9% by weight of a delaminated layered silicate (phyllosilicate).
  • Layered silicate is generally understood to be silicates in which the SiO 4 tetrahedra are connected in two-dimensional infinite networks. (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.
  • the layer thicknesses of such silicates before delamination are usually from 5 to 100 ⁇ , preferably 5 to 50 ⁇ and in particular 8 to 20 ⁇ .
  • synthetic and natural layered silicates are montmorillonite, smectite, illite, sepiolite, palygorskite, muscovite, allevardite, amesite, hectorite, fluororectite, saponite, beidellite, talc, nontronite, stevensite, vermiculite, glendonite, glitonite, glitonite , Halloysite and fluorine-containing synthetic mica types.
  • a delaminated layered silicate in the sense of the invention is to be understood as meaning layered silicates in which the layer spacings are initially increased by setting with so-called hydrophobizing agents and subsequent addition of monomers (so-called swelling, for example with styrene).
  • hydrophobizing agents which are often also referred to as onium ions or onium salts.
  • the cations of the layered silicates are replaced by organic hydrophobizing agents, it being possible for the type of organic residue to set the desired layer spacings, which depend on the type of the particular monomer or polymer into 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 of layered silicate and 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 III and / or IV:
  • R 7 , R 8 , R 9 , R 10 independently of one another are hydrogen, a straight-chain branched, saturated or unsaturated hydrocarbon radical having 1 to 40, preferably 1 to 20, carbon atoms, which can optionally carry at least one functional group or 2 of the radicals are linked to one another, in particular to form a heterocyclic radical having 5 to 10 carbon atoms,
  • u for an integer from 1 to 5, preferably 1 to 3 and
  • Suitable anions G are derived from proton-providing acids, in particular mineral acids, with halogens such as chlorine, bromine, fluorine, iodine, sulfate, sulfonate, phosphate, phosphonate, phosphite and carboxylate, in particular acetate, being preferred.
  • 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, in particular 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.
  • suspending agents are ketones and hydrocarbons.
  • a water-miscible solvent is usually preferred.
  • An ion exchange occurs with the layered silicate, which usually makes the layered silicate more hydrophobic and precipitates out of the solution.
  • the metal salt formed as a by-product of the ion exchange is preferably water-soluble so that the hydrophobic layered silicate can be separated off as a crystalline solid by, for example, filtering off.
  • 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 40 and 80 ° C.
  • hydrophobizing agents for syndiotactic vinyl aromatic polymers, preference is given to using hydrophobizing agents in which R 7 , R 8 , R 9 and, if appropriate, R 10 independently of one another for the methyl, ethyl, propyl, isopropyl, chloromethyl, benzyl, p-methylbenzyl - And very particularly preferably stand for the p-vinylbenzyl radical.
  • vinyl aromatic radicals R 7 , R 8 , R 9 are alkoxystyrene, alkylstyrenes containing silyl groups, aminostyrene, vinylbenzyldimethoxyphosphide, ethylvinylbenzylsulfonate, amino-substituted alkylstyrenes and alkylstyrenes containing ether groups, carboxyl groups and carboxylate groups.
  • Hydrophobing agents of the formula purple and / or IVa are particularly preferred:
  • R 11 to R 14 independently of one another represent hydrogen, a Ci to C 0 alkyl radical, a C 6 to Ci ⁇ aryl radical, halogens or two adjacent radicals together represent groups having 4 to 15 C atoms.
  • trimethylbenzylvinylammonium ions being particularly preferred.
  • the preferred sulfonium ion is (p-, m-, o-) vinyl-dimethylmethylbenzylsulfonium.
  • the preparation can be carried out according to processes known per se (e.g. Stirling, the chemistry of the Sulfonium Group, Part 1, pp. 267-312 and pp. 313 - 385, Verlag Wiley New York 1981; Deady et al, Austr. J. Chem. 32 (1979), p. 1735; Meerwein et al., Arch. Pharm. 291/63 (1958), p. 541 ff.
  • processes known per se e.g. Stirling, the chemistry of the Sulfonium Group, Part 1, pp. 267-312 and pp. 313 - 385, Verlag Wiley New York 1981; Deady et al, Austr. J. Chem. 32 (1979), p. 1735; Meerwein et al., Arch. Pharm. 291/63 (1958), p. 541 ff.
  • the layered silicates After the hydrophobization, the layered silicates have a layer spacing of 10 to 40 ⁇ , preferably of 13 to 20 ⁇ .
  • 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 which has been rendered hydrophobic in the above manner can then be mixed in suspension or as a solid with the vinyl aromatic monomers and the polymerization can be carried out in the customary manner. It is possible to further increase the layer spacing by using the layered silicate with the vinyl aromatic monomers at temperatures from 0 to 300, preferably from 25 to 120 and in particular from 40 to 100 ° C. over a residence time of 5 to 5 180 minutes, preferably from 10 to 120 minutes (so-called swelling). Depending on the duration of the residence time and the type of monomer chosen, the layer spacing is additionally increased by 10 to 150, preferably by 20 to 50 ⁇ .
  • the polymerization is then carried out in the presence of a metallocene catalyst, an agent which forms cations and, if appropriate, an aluminum compound in the customary manner.
  • the polymerization is carried out particularly advantageously with simultaneous shear, preferably with shear stresses in accordance with DIN 11 443 of 10 to 10 5 Pa, in particular 10 2 to 10 4 Pa. 5
  • Metallocene complexes of the general formula V are suitable for the preparation of the vinylaromatic polymer in the presence of the hydrophobized and optionally swollen sheet silicate
  • R 15 to R 19 hydrogen, C ⁇ ⁇ to C ⁇ 0 alkyl, 5- to 7-membered 0 cycloalkyl, which in turn C ⁇ ⁇ to C ⁇ -alkyl groups as
  • C ß - to cis-aryl or aryl - alkyl and where optionally two adjacent radicals together can represent cyclic groups having 4 to 15 C atoms, or Si (R 20 ) 3 , 5 with R 20 Ci to -C 0 alkyl, C 6 to C 5 aryl or C 3 to Cio-cycloalkyl,
  • Z 1 to Z 5 are hydrogen, halogen, C ⁇ ⁇ to Cio-alkyl, C 6 - bis
  • Particularly preferred metallocene complexes of the general formula V are those in which
  • M stands for a metal of subgroup IV of the Periodic Table of the Elements, in particular for titanium
  • Z 1 to Z 5 are C 1 to C 10 alkyl, C 1 to C 0 alkoxy or halogen.
  • Metallocene complexes such as those described in EP-A 584 646 can also be used.
  • Mixtures of two different metallocene complexes have proven to be particularly suitable, but mixtures of up to 5 different metallocene complexes can also be used.
  • a mixture of pentamethylcyclopentadienyltrimethyl and pentamethylcyclopentadienyltrimethylate is preferably used.
  • Such complex compounds can be synthesized by methods known per se, the reaction of the appropriately substituted cyclic hydrocarbon anions with
  • Halides of titanium, zirconium, hafnium, vanadium, niobium or tantalum are preferred.
  • Suitable as metallocenium ion-forming compounds are, for example, open-chain or cyclic alumoxane compounds of the general formula VI or VII R1 ⁇
  • R 21 is a -C ⁇ to C 4 alkyl group, preferably methyl or ethyl group and m is an integer from 5 to 30, preferably 10 to 25.
  • oligomeric alumoxane compounds are usually prepared by reacting a solution of trialkylaluminum with water and are, inter alia, in EP-A 284 708 and US-A 4,794,096.
  • the oligomeric alumoxane compounds obtained are generally present as mixtures of both linear and cyclic chain molecules of different lengths, so that m is to be regarded as the mean.
  • the alumoxane compounds can also be present in a mixture with other metal alkyls, preferably with aluminum alkyls.
  • metallocenium ions are in particular strong, neutral Lewis acids, ionic compounds with Lewis acid cations and ionic compounds with Bronsted acids as the cation.
  • M 1 is an element of III.
  • Main group of the periodic table means, in particular B, Al or Ga, preferably B, XX X 2 and X 3 for hydrogen, Ci to Cio alkyl, C 6 to Cis aryl, alkylaryl, arylalkyl, haloalkyl or haloaryl, each with 1 to 10 C atoms in the alkyl radical and 6 to 20 C atoms in the aryl radical or fluorine, chlorine, bromine or iodine, in particular for haloaryls, preferably for pentafluorophenyl.
  • Qi to Q z for single negatively charged radicals such as C 1 to C 28 alkyl, C 6 to Cis aryl, alkylaryl, arylalkyl,
  • a represents integers from 1 to 6
  • d corresponds to the difference a - z, but d is greater than or equal to 1.
  • Carbonium cations, oxonium cations and sulfonium cations as well as cationic transition metal complexes are particularly suitable.
  • the triphenylmethyl cation, the silver cation and the 1,1 '-dimethylferrocenyl cation should be mentioned in particular. They preferably have non-coordinating counterions, in particular boron compounds, as they are also mentioned in WO 91/09882, preferably tetrakis (pentafluorophenyDborat.
  • Ionic compounds with Bronsted acids as cations and preferably also non-coordinating counterions are mentioned in WO 93/3067, the preferred cation is N, N-dimethylanilinium.
  • the vinyl aromatic compounds can be polymerized in solution, in bulk, in suspension or in the gas phase. It is preferred to work in solution, using, for example, aromatic hydrocarbons such as benzene, toluene, ethylbenzene or xylenes, and ethers such as diethyl ether, dibutyl ether, ethylene glycol dimethyl ether or tetrahydrofuran, or aliphatic hydrocarbons such as propane, n-butane, isobutane or pentanes , and mixtures of the various solvents can be used, or in bulk.
  • aromatic hydrocarbons such as benzene, toluene, ethylbenzene or xylenes
  • ethers such as diethyl ether, dibutyl ether, ethylene glycol dimethyl ether or tetrahydrofuran, or aliphatic hydrocarbons such as propane, n-butane, isobutane or pentanes
  • the polymerization conditions are not critical per se, temperatures in the range from 0 to 150 ° C., preferably from 10 to 100 ° C., pressures from 0.1 to 100 bar, preferably from 1 to 5 bar and polymerization times from 0.1 to 24 are suitable Hours, preferably from 0.5 to 6 hours.
  • the metallocene complexes are preferably used unsupported, but they can also be used supported.
  • Suitable carrier materials are, for example, silica gels, preferably those of the formula Si0 • aAl 2 0 3 , in which a stands for a number in the range from 0 to 2, preferably 0 to 0.5; essentially aluminum silicates or silicon dioxide.
  • the carriers preferably have a particle diameter in the range from 1 to 200 ⁇ m, in particular 30 to 80 ⁇ m. Products of this type are commercially available, for example as Silica Gel 332 from Grace.
  • Other carriers include finely divided polyolefins, for example finely divided polypropylene or polyethylene, but also polyethylene glycol, polybutylene terephthalate, polyethylene terephthalate, polyvinyl alcohol, polystyrene, polybutadiene, polycarbonates or their copolymers.
  • aluminum alkyls can also be used in the polymerization.
  • trimethyl aluminum, triethyl aluminum, tri-iso-propyl aluminum, tri-n-propyl aluminum, tri- Isobutyl aluminum and tri-n-butyl aluminum are particularly suitable, but especially triisobutyl aluminum.
  • aluminum alkyls is particularly suitable when using strong neutral Lewis acids, ionic compounds with Lewis acid cations and ionic compounds with Bronsted acids as cations, as compounds forming metallocenium ions.
  • the molar ratio of the vinyl aromatic compound to the compound forming metallocenium ions is in the range from 10 2 : 1 to 10: 1, preferably in the range from 10 3 : 1 to 10 6 : 1.
  • the molar ratio of metallocenium ion-forming compound to the total molar amount of metallocene complexes is preferably in the range from 10 ⁇ 2 : 1 to 10 7 : 1, in particular in the range from 10 2 : 1 to 10 5 : 1.
  • the molar ratio of one metallocene complex to the other metallocene complex preferably being in the range from 10 _3 : 1 to 10 3 : 1, in particular in the range from 10 _2 : 1 to 10 2 : 1 lies. If three or more metallocene complexes are used, the composition can vary so much that a metallocene complex is present up to a 1000-fold molar excess compared to the next most common metallocene complex. However, at most a 100-fold molar excess is preferred.
  • a molar ratio of aluminum alkyl to the total amount of metallocene complexes from 10,000: 1 to 10: 1, preferably from 1000: 1 to 100: 1, has thus proven to be particularly suitable.
  • the polymerization is preferably carried out under a pressure of 0.5 to 30 bar, preferably from 1 to 20 bar.
  • the reaction temperature is generally from -78 ° C to 150 ° C, preferably from 0 ° C to 120 ° C. But it is also possible that a temperature gradient of 0 ° C to 120 ° C is applied in the course of the reaction.
  • the polymerization is preferably carried out in the vinyl aromatic monomer as the reaction medium, ie in bulk.
  • the alkylalumoxane and the trialkylaluminium can be brought into contact with the vinylaromatic monomer before the polymerization and metered into the reactor via a metering pump.
  • the metal ocene catalyst is dissolved or suspended, in the case of supported catalysts - in conventional organic solvents, such as cyclic or acyclic hydrocarbons, for example (i-, n-, c-) butane, pentane, hexane, heptane or aromatic solvents, for example in benzene, toluene, ethylbenzene, or in oxygen-containing solvents , such as tetrahydrofuran, in halogenated solvents, such as dichloromethane, in nitrogen-containing solvents, such as N-methylpiperidine etc., metered in by means of a pump.
  • organic solvents such as cyclic or acyclic hydrocarbons, for example (i-, n-, c-) butane, pentane, hexane, heptane or aromatic solvents, for example in benzene, toluene, ethylbenzene, or in oxygen-
  • Suitable reactors are stirred reactor, autoclave, continuous kneader and vertical reactors (see DE-A 196 31 365).
  • the molar masses of the polymers prepared are in the range from 1000 to 10 7 g / mol, preferably 10,000 to 10 6 g / mol and in particular from 50,000 to 500,000 g / mol.
  • Suitable star polymers which, as stated above, are produced in the presence of the layered silicate, can be prepared in accordance with the processes described in DE-A 196 34 375.
  • the molding compositions according to the invention may contain up to 50, preferably up to 30 and in particular up to 8% by weight of further additives and processing aids as component C).
  • Suitable flame retardants which can be used in amounts of up to 15% by weight, are red phosphorus and phosphorus-containing compounds, nitrogen-containing compounds such as melamine and melamine cyanurate. In principle, all known flame retardants are suitable.
  • stabilizers are octadecyl-3 - (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, triethylene glycol -bis -3 (3-tert-butyl-4-hydroxy-5-methylphenyl) - propionate, 1, 1,3-tris (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, dilauryl thiodipropionate and tris (nonylphenyl) phosphite or mixtures thereof.
  • thiobisphenols alkylidene-bisphenols, alkylphenols, substituted dicyclopentadienes, hydroxybenzyl compounds, acylaminophenols, poly-hydroxyphenylpropionates, amines, thioethers, phophites and phophonites and zinc dibutyldithiocarbamate in amounts of up to 2% by weight can be used for stabilization. % are used.
  • Antioxidants such as organic sulfides, phosphites, quinone and its derivatives, aromatic nitro and nitroso compounds, substituted, in particular ortho-disubstituted phenols, sulfonic acids, thiolsulfinates, thiolsulfoxylic acids, dithio- carbamates and dithiophosphates can be used individually or in mixtures in an amount of up to 2% by weight.
  • Low molecular weight fatty acid esters, fatty alcohols, dicarboxylic acid esters, calcium stearate, amide wax, stearic acid and hydroxystearic acid, montan wax, PE waxes and paraffins such as white oil can be used as lubricants.
  • the additives C) can be made using conventional devices such as 10 e.g. Extruders can be mixed into components A) and B). After the extrusion, the extrudate is cooled and crushed.
  • the molding compositions according to the invention are notable for good heat resistance, flowability and low density. 15 They can be easily processed into moldings with a good surface. The moldings have a
  • layer A is the thermoplastic matrix and layer B is the delaminated layered silicate.
  • Components for electrical and electronic applications such as printed circuit boards, plug connectors, chip carriers, capacitor foils and components for automotive applications such as coatings under the hood, surface coatings and microwave dishes and housings for hot water pumps and pipes are mentioned as applications.
  • the montmorillonite had a cation exchange capacity of 40 90 meq / 100 g.
  • Component B) is hereinafter referred to as montmorillonite which has been rendered hydrophobic with vinylbenzyltrimethylammonium.
  • the syndiotactic part, measured on pentads, determined by 13 C-NMR was> 98%. The conversion was 76% based on the styrene monomer used.
  • the polymerization was stopped by adding methanol.
  • the polymer obtained was washed with methanol and dried at 50 ° C. in vacuo.
  • the molar masses and their distribution were determined by high-temperature GPC with 1, 2, 4-trichlorobenzene as solvent at 135 ° C.
  • the calibration was carried out using narrowly distributed polystyrene standards.
  • the syndiotactic fraction, measured on pentads, determined by 13 C-NMR was> 96%.
  • the conversion was 84% based on the monomer styrene used.
  • Standard test specimens were produced on an injection molding machine from the molding compositions of Examples 1, 2 and VI to V5 at a melt temperature of 290 to 310 ° C. and a mold surface temperature of 130 to 150 ° C. The results of the measurements and the test methods can be found in the table.

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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)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne des matières de moulage thermoplastiques contenant: A) entre 10 et 99 % en poids d'un polymère vinylaromatique ayant une teneur en pentadène syndiotactique d'au moins 30 % en moles, B) entre 0,1 et 20 % en poids d'un silicate stratifié délaminé (phyllosilicate), C) entre 0 et 50 % en poids d'autres additifs et auxiliaires de traitement, la somme des pourcentages en poids des constituants A) à C) étant égale à 100 %.
EP98913736A 1997-04-09 1998-03-26 Matieres de moulage thermoplastiques Withdrawn EP0973828A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19714548 1997-04-09
DE19714548A DE19714548A1 (de) 1997-04-09 1997-04-09 Thermoplastische Formmassen
PCT/EP1998/001802 WO1998045362A1 (fr) 1997-04-09 1998-03-26 Matieres de moulage thermoplastiques

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EP0973828A1 true EP0973828A1 (fr) 2000-01-26

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EP (1) EP0973828A1 (fr)
JP (1) JP2001518954A (fr)
KR (1) KR20010006140A (fr)
CN (1) CN1246878A (fr)
CA (1) CA2275197A1 (fr)
DE (1) DE19714548A1 (fr)
WO (1) WO1998045362A1 (fr)

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KR100364491B1 (ko) * 2000-07-18 2002-12-12 삼성종합화학주식회사 신디오탁틱 폴리스티렌 나노컴포지트 및 그 제조방법
JP4369134B2 (ja) * 2003-01-31 2009-11-18 株式会社フジクラ 基板及び成形品
JP4335572B2 (ja) * 2003-04-24 2009-09-30 株式会社フジクラ スチレン系樹脂組成物、フィルム、基板及び成形品

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EP0307488B1 (fr) * 1987-09-15 1992-07-22 Idemitsu Kosan Company Limited Composition résineuse à base de polystyrène

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JP2001518954A (ja) 2001-10-16
WO1998045362A1 (fr) 1998-10-15
DE19714548A1 (de) 1998-10-15
CN1246878A (zh) 2000-03-08
CA2275197A1 (fr) 1998-10-15

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