WO1999045069A1 - Matieres moulables en polyamide-polyphenylenether comportant des charges minerales - Google Patents

Matieres moulables en polyamide-polyphenylenether comportant des charges minerales Download PDF

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Publication number
WO1999045069A1
WO1999045069A1 PCT/EP1998/005056 EP9805056W WO9945069A1 WO 1999045069 A1 WO1999045069 A1 WO 1999045069A1 EP 9805056 W EP9805056 W EP 9805056W WO 9945069 A1 WO9945069 A1 WO 9945069A1
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Prior art keywords
weight
molding compositions
polyamide
polyphenylene ether
acid
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PCT/EP1998/005056
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German (de)
English (en)
Inventor
Walter Götz
Stefan Grutke
Christiaan Henricus Koevoets
Kristof Lode Leo Eersels
Jozef Herman Peter Bastiaens
Axel Gottschalk
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Basf Aktiengesellschaft
General Electric Company
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Priority to AU93408/98A priority Critical patent/AU9340898A/en
Publication of WO1999045069A1 publication Critical patent/WO1999045069A1/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
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides
    • C08L71/123—Polyphenylene oxides not modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides

Definitions

  • the present invention relates to thermoplastic molding compositions containing as essential components
  • thermoplastic polyamide A) 15 to 84.5% by weight of a thermoplastic polyamide
  • G 0 to 30% by weight of glass or carbon fibers, carbon fibers, carbon black, glass balls or cut glass and
  • the invention relates to the use of these molding compositions for the production of moldings, in particular body components.
  • the invention also relates to the moldings obtained.
  • Blends based on polyamides and polyphenylene ethers are known for a wide range of applications.
  • the great application-technical interest in this blend class is based, among other things, on the fact that the individual components complement each other very well in their advantageous properties.
  • thermoplastic polypropylene ether polymers inter alia, have a relatively good heat resistance and dimensional stability, but have poor solvent resistance and a high melt viscosity
  • polyamide thermoplastics have good solvent resistance and good processability.
  • Polyamides on the other hand, have weaknesses in heat resistance and dimensional stability.
  • polyamide / polyphenylene ether blends are usually still insufficient for many applications with regard to dimensional stability, heat resistance and rigidity.
  • Blends with fibrous or mineral fillers are described, for example, in WO 85/5372, EP-A 0 260 123, WO 87/5304, EP-A 0 046 040, WO 86/2086 or DE-A 34 43 154.
  • a polyamide / polyphenylene ether mixture for example talc with a particle size of 5.0 microns or less, which, when heated to 300 ° C over a period of 2 hours, a weight loss of a maximum of 0.2 wt. -% shows added to obtain molding compositions with improved dimensional stability, surface properties and improved solvent resistance.
  • losses in toughness behavior cannot be avoided even with only small amounts of filler.
  • the impact strength decreases rapidly as the filler content increases.
  • Another disadvantage is that although the heat resistance increases with increasing filler content, at the same time the impact strength decreases sharply, although it is known that mineral fillers such as talc influence the impact strength less than fiber fillers. In this context, it is not particularly advantageous that an improved dimensional stability is only recorded with an increasing proportion of filler.
  • the present invention was therefore based on the object of providing thermoplastic molding compositions based on polyamide and polyphenylene ethers which do not have the disadvantages described or only do so to a limited extent and which have good dimensional stability even at low filler contents, without showing any loss in heat resistance or toughness.
  • thermoplastic molding compositions described at the outset. Furthermore, the use of these molding compositions for the production of moldings, in particular of large-area exterior parts of the body, was found. The moldings obtained were also found. Thermoplastic molding compositions which are particularly preferred are
  • thermoplastic polyamide A) 20 to 70% by weight of a thermoplastic polyamide
  • G 0 to 20% by weight of glass or carbon fibers, carbon fibers, carbon black, glass balls or cut glass and
  • the polyamides contained as component A) in the thermoplastic molding compositions are known per se and comprise the semi-crystalline and amorphous resins with molecular weights (weight average values) of at least 5000, which are usually referred to as nylon.
  • Such polyamides and processes for their production are e.g. in U.S. Patents US-2, 071,250, US-2, 071,251, US-2, 130, 523, US-2, 130, 948, US-2,241,322, US-2, 312, 606 and US-3, 393,210 .
  • the polyamides can e.g. by condensation of equimolar amounts of a saturated or an aromatic dicarboxylic acid with 4 to 12 carbon atoms, for example adipic acid, sebacic acid, azelaic acid, 1, 12-dodecanedicarboxylic acid, terephthalic and isophthalic acid, with a saturated or aromatic diamine which has up to 14 carbon atoms, for example
  • 1,6-diaminohexane, 1,4-diaminobutane, m-xylene diamine, di- (4-aminophenyDmethane, di- (4-aminocyclohexyl) methane, 2,2-di- (4-aminopheny1) propane or 2 , 2-di- (4-aminocyclohexyl) propane, and suitable polyamides can also be obtained by condensing ⁇ -aminocarboxylic acids or by polyaddition of Lactams with ring opening to, for example, polycaprolactam (for example nylon 6) or polylauryl lactam.
  • polyamides examples include polycaprolactam (nylon 6), polyhexamethylene adipic acid amide (nylon 66), polyhexamethylene azelaic acid amide (nylon 69), polyhexamethylene sebacic acid amide (nylon 610), polyhexamethylene dodecanedioic acid amide (nylon 612), the polyamides obtained by ring opening of lactams, such as polylauric acid amide such as polylaurolamide Poly-11-aminoundecanoic acid and a polyamide made from (di (p-aminocyclohexyl) methane and dodecanedioic acid.
  • polyamides made according to the invention by copolycondensation of two or more of the above-mentioned polymers or their components, e.g. Copolymers of adipic acid, isophthalic acid or terephthalic acid and hexamethylene diamine or copolymers of caprolactam, terephthalic acid and hexamethylene diamine.
  • Linear polyamides with a melting point above 200 ° C. are preferred.
  • Preferred polyamides are polyhexamethylene adipic acid amide, polyhexamethylene sebacic acid amide and polycaprolactam as well as polyamide 6 / 6T and polyamide 66 / T, particularly preferred is polyhexamethylene adipic acid amide.
  • the polyamides generally have a viscosity number in the range from 90 to 350 ml / g, determined according to ISO 307 on a 0.5% strength by weight solution in 96% strength sulfuric acid at 23 ° C. This generally corresponds to a molecular weight of approximately 15,000 to 45,000 g / mol. Polyamides with a viscosity number in the range from 110 to 240 ml / g are preferably used.
  • Polyamides may also be mentioned, e.g. can be obtained by condensing 1,4-diaminobutane with adipic acid at elevated temperature (polyamide-4, 6). Manufacturing processes for polyamides of this structure are e.g. in EP-A 38 094, EP-A 38 582 and EP-A 39 524. Polyamide-4,6 as well as polyamide 6 / 6T and polyamide 66 / T are preferably used with a triamine content of less than 0.5% by weight, based on component A).
  • the proportion of polyamides A) in the molding compositions according to the invention is 15 to 84.5, preferably 20 to 70 and in particular 25 to 60% by weight.
  • polyamides with an amino end group content in the range from 40 to 80, preferably from 40 to 70 and in particular from 45 to 65 ⁇ eq / g are used.
  • the residual moisture content can e.g. Determine according to the vapor pressure method (ISO 960 D) or the electronically controlled Karl Fischer titration (ISO draft 1988).
  • At least one polyphenylene ether (PPE) known per se is used as component B), which may be homo-, co- or graft copolymers.
  • PPE polyphenylene ether
  • these are compounds based on substituted, in particular disubstituted, polyphenylene ethers, the ether oxygen of one unit being bound to the benzene nucleus of the adjacent unit.
  • Polyphenylene ethers substituted in the 2- and / or 6-position relative to the oxygen atom are preferably used.
  • substituents are halogen atoms, such as chlorine or bromine, and alkyl radicals having 1 to 4 carbon atoms, which preferably have no ⁇ -tertiary hydrogen atom, e.g.
  • Methyl, ethyl, propyl or butyl radicals to name.
  • the alkyl radicals can in turn be substituted by halogen atoms, such as chlorine or bromine, or by a hydroxyl group.
  • Further examples of possible substituents are alkoxy radicals, preferably having up to 4 carbon atoms, such as methoxy, ethoxy, n-propoxy and n-butoxy, or phenyl radicals optionally substituted by halogen atoms and / or alkyl groups.
  • Copolymers of various phenols are also suitable, for example copolymers of 2,6-dimethylphenol and 2,3,6-trimethylphenol. Mixtures of different polyphenylene ethers can of course also be used.
  • the polyphenylene ethers B) are present in the molding compositions according to the invention in an amount of 15 to 84.5, preferably 20 to 70 and in particular 25 to 60% by weight.
  • Suitable polyphenylene ethers and processes for their preparation are described, for example, in US Pat. Nos. 3,306,874, 3,306,875, 3,257,357 and 3,257,358.
  • polyphenylene ethers examples include poly (2,6-dilauryl-1,4-phenylene ether),
  • Polyphenylene ethers in which the substituents are alkyl radicals having 1 to 4 carbon atoms are preferably used; poly (2,6-dialkyl-1,4-phenylene ether), such as poly (2,6-dimethyl-1,4-phenylene ether), poly (2,6-diethyl-1,4-phenylene ether), have proven to be particularly suitable ), Poly (2-methyl-6-ethyl-1,4-phenylene ether), poly (2-methyl-6-propyl-1,4-phenylene ether), poly (2,6-dipropyl-1,4-phenylene ether or Poly (2-ethyl-6-propyl-1,4-phenylene ether) Poly (2,6-dimethyl-1,4-phenylene ether) is particularly preferably used, in particular those with an intrinsic viscosity in the range of 0.30 up to 0.60 dl / g (measured in toluene at 25 ° C and a concentration of 0.6 g /
  • polyphenylene ethers are also to be understood as meaning those which have been modified with monomers such as fumaric acid, citric acid, maleic acid or maleic anhydride.
  • the polyphenylene ether is incorporated by incorporation of at least one carbonyl, carboxylic acid, acid anhydride, acid amide, acid imide, carboxylic ester, carboxylate, amino, hydroxyl, epoxy, oxazoline, urethane, urea, lactam or modified halogenobenzyl group, so that a sufficient compatibility with the second polymer of the mixture, the polyamide, is ensured.
  • Such polyphenylene ethers include in WO-A 86/02086, WO-A-87/00540, EP-A-0 222 246, EP-A-0 223 116 and EP-A-0 254 048.
  • the modification is generally carried out by reacting a polyphenylene ether with a modifier which contains at least one of the abovementioned groups in solution (WO-A 86/2086), in aqueous dispersion, in a gas phase process (EP-A-25 200) or preferred carried out in the melt, if appropriate in the presence of suitable vinylaromatic polymers or impact modifiers, with radical initiators optionally being present.
  • a modifier which contains at least one of the abovementioned groups in solution (WO-A 86/2086), in aqueous dispersion, in a gas phase process (EP-A-25 200) or preferred carried out in the melt, if appropriate in the presence of suitable vinylaromatic polymers or impact modifiers, with radical initiators optionally being present.
  • Particularly suitable modifying agents are maleic acid, methyl maleic acid, itaconic acid, tetrahydrophthalic acid, their anhydrides and imides, fumaric acid, the mono- and diesters of these acids, for example with Ci to Cs alkanols, the mono- or diamides of these acids such as N-phenylmaleimide, Maleic hydrazide, the acid chloride of trimelitic acid anhydride, benzene - 1, 2-dicarboxylic acid anhydride-4-carbon acid-acetic anhydride, chloroethanoylsuccinaaldehyde, chloroformylsuccinaldehyde, citric acid and hydroxysuccinic acid.
  • Preferred modifiers are fumaric acid and citric acid, particularly citric acid is preferred, especially anhydrous citric acid.
  • Component B) can consist exclusively of unmodified polyphenylene ether, exclusively of modified polyphenylene ether or of any mixture of unmodified and modified polyphenylene ether.
  • M average molecular weight
  • M weight average
  • This corresponds to an intrinsic viscosity of approximately 0.18 to 0.9, preferably 0.25 to 0.7 and in particular 0.39 to 0.6 dl / g, measured in chloroform at 25 ° C. according to DIN 53 726.
  • the molecular weight distribution is generally determined by means of gel permeation chromatography (Shodex separation column 0.8 ⁇ 50 cm of the types A 803, A 804 and A 805 with tetrahydrofuran (THF) as eluent at room temperature).
  • the solution of the PPE samples in THF is carried out under pressure at 110 ° C., 0.16 ml of a 0.25 wt. -% solution to be injected.
  • the detection is generally carried out with a UV detector.
  • the columns are calibrated with PPE samples whose absolute molecular weight distributions can be determined using a GPC laser light scattering combination.
  • the disclosure of the present invention also includes mixtures of polyamide and polyphenylene ethers to which an unsaturated organic compound with at least one carboxylic acid, anhydride, amide, imide, ester, amine or hydroxy functionality has been added.
  • Organic compounds with at least one carboxylic acid, ester or amide functionality are preferred.
  • the organic compounds mentioned also have at least one unsaturated functional unit. This includes both carbon / carbon triple bonds and double bonds, the latter being able to be substituted at the end, two, three or four times.
  • Suitable compounds include, for example, citric acid, malic acid or agaricinic acid in anhydrous and hydrated forms, acetyl citrate, mono- and / or distearyl citrate, N, N '-diethyl citric acid amide, N, N' -dipropyl citric acid amide, N-phenyl citric acid amide Dodecyl citric acid amide, N, N'-didodecyl citric acid amide or N-dodecyl malic acid amide. Under Saturated organic compounds with carboxylic acid functionality in particular also fall in their salts. Examples include the ammonium salts and preferably the alkali and alkaline earth metal salts, such as calcium citrate or potassium citrate, and the calcium and potassium salts of malic acid.
  • the aforementioned functionalized unsaturated organic compound is preferably used in amounts in the range from 0.05 to 4% by weight, based on the total weight of the thermoplastic molding compositions according to the invention.
  • the molding compositions according to the invention contain, as component C), 0.5 to 10, preferably 1 to 8, particularly preferably 1.5 to 6.5 and in particular 2 to 6% by weight of kaolinite, dickite, nacrite, halloysite, wollastonite, especially ß-wollastonite, entatite, diopsite or spodumene.
  • Kaolinite and wollastonite are particularly preferred.
  • kaolinite is also to be understood as meaning kaolin with a total proportion of mica, feldspar and / or quartz not greater than 10% by weight, based on the amount of kaolin used.
  • the minerals kaolinite, dickite, nacrite and halloysite are preferably used in calcined form, i.e. these substances are subjected to an annealing process, for example at about 800 ° C., over a period of several hours before they are used for the production of the molding composition according to the invention.
  • Any mixtures of the aforementioned minerals can also be used, e.g. Kaolinite and ß-wollastonite or kaolinite and enstatite.
  • the compounds falling under component C) are particularly preferably used in coated form (“coated”).
  • size materials known from glass fiber technology can be used for the coating.
  • Suitable sizing materials are, for example, aqueous starch emulsions, lubricating oils, aqueous dispersions of surface-active substances and silicon-containing compounds such as vinylsilanes, alkyltrimethoxysilanes, aminosilanes or trimethoxysilanes.
  • Aminosilanes have proven to be particularly advantageous. Like the silane sizes mentioned above, these can also have urethane, acrylate or epoxy functionalities.
  • the silane sizes can likewise be present in a mixture with compounds containing urethane, acrylate or epoxy functionalities.
  • Mineral compounds of component C) treated with aminosilane sizes are commercially available. Wollastonite or kaolinite treated with these sizes can be obtained, for example, from Quarzwerke or ECC (English China Clay). Very good results with regard to dimensional stability and heat resistance are achieved in particular if the particle or grain size of the filling materials used does not assume too high values. As a rule, the compounds of component C) with an upper particle or grain size d 95%
  • ⁇ 30 ⁇ m preferably ⁇ 20 ⁇ m and in particular ⁇ 15 ⁇ m.
  • a value ⁇ 10 and in particular ⁇ 5 ⁇ m is advantageously chosen as the average grain size dso % .
  • Impact modifiers are used as impact modifiers for the polyphenylene ether phase (component D) in proportions of 0 to 20, preferably 2.5 to 20 and preferably in proportions of 4 to 15% by weight, based on the total weight of the molding composition.
  • Natural and / or synthetic rubbers can be used as component D).
  • impact modifiers are e.g. Polybutadiene, polyisoprene or copolymers of butadiene and / or isoprene with styrene and other comonomers, which have a glass transition temperature, determined according to KHIllers and H. Breuer, Kolloidzeitschrift 190 (1), 16-34 (1963), of -100 ° C up to + 25 ° C, preferably below 0 ° C, suitable.
  • Correspondingly hydrogenated products can also be used.
  • Preferred impact modifiers D are block polymers, in particular two- or three-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. The disclosure of the above publications is hereby expressly made
  • SEBS hydrogenated styrene-butadiene-block copolymers
  • SEP hydrogenated styrene isoprene-two - block copolymers
  • Kraton ® 1701 examples of products Shell
  • impact-modifying polymers are, for example, copolymers of ethylene with propylene (EP rubbers) and optionally with a conjugated diene (EPDM rubbers), the ethylene content preferably 45 and is particularly 50% by weight (based on component E).
  • EP rubbers propylene
  • EPDM rubbers conjugated diene
  • Such impact modifiers are generally known, for which reason reference is made here to the publication by Carta-segna in Kautschuk, Kunststoffe 39, 1186-91 (1986).
  • the rubbers which improve the toughness of polyamides generally have an elastomeric component with a glass transition temperature of less than -10 ° C., preferably less than -30 ° C., and contain at least one functional group which can react with the polyamide. Suitable functional groups are, for example, carboxylic acid, carboxylic anhydride, carboxylic acid ester, carboxylic acid amide, carboximide, amino, hydroxyl, epoxy, urethane and oxazoline groups.
  • EP or EPDM rubbers which have been grafted with the above functional groups.
  • Suitable grafting reagents are, for example, maleic anhydride, itaconic acid, acrylic acid, glycidyl acrylate and glycidyl methacrylate. These monomers can be grafted onto the polymer in the melt or in solution, if appropriate in the presence of a radical initiator such as cumene hydroperoxide. Copolymers of ⁇ -olefins with (meth) acrylates and / or vinyl esters may also be mentioned.
  • the ⁇ -olefins are usually monomers with 2 to 8 carbon atoms, preferably ethylene and propylene.
  • Suitable comonomers are alkyl acrylates or alkyl methacrylates which are derived from alcohols having 1 to 8 carbon atoms, preferably from ethanol, butanol or ethylhexanol, and reactive comonomers such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride or glycidyl (meth) acrylate and also vinyl esters, especially vinyl acetate, proved to be suitable. Mixtures of different comonomers can also be used. Copolymers of ethylene with ethyl or butyl acrylate and acrylic acid and / or maleic anhydride have proven to be particularly suitable.
  • the copolymers can be produced in a high pressure process at a pressure of 400 to 4500 bar or by grafting the comonomers onto the poly- ⁇ -olefin.
  • the proportion of the ⁇ -olefin in the copolymer is generally in the range from 99.95 to 55% by weight.
  • Core-shell graft rubbers are another group of suitable elastomers. These are graft rubbers produced in emulsion, which consist of at least one hard and one soft component.
  • a hard component is usually understood to mean a polymer with a glass transition temperature of at least 25 ° C.
  • a soft component is a polymer with a glass transition temperature of at most 0 ° C.
  • These products have a structure of a core and at least a shell, the structure resulting from the order of the monomer addition.
  • the soft constituents are derived, inter alia, from butadiene, isoprene, alkyl acrylates or alkyl methacrylates and, if appropriate, further comonomers.
  • Suitable comonomers are, for example, styrene, acrylonitrile and crosslinking or graft-active monomers with more than one polymerizable double bond such as diallyl phthalate, divinylbenzene, butanediol diacrylate or triallyl (iso) cyanurate.
  • the hard constituents are derived, inter alia, from styrene, ⁇ -methylstyrene and their copolymers, the preferred comonomers here being acrylonitrile, methacrylonitrile and methyl methacrylate.
  • Preferred core-shell graft rubbers contain a soft core and a hard shell or a hard core, a first soft shell and at least one further hard shell.
  • Functional groups such as carbonyl, carboxylic acid, acid anhydride, acid amide, acid imide, carboxylic ester, amino, hydroxyl, epoxy, oxazoline, urethane, urea, lactam or halobenzyl groups are incorporated here preferably by adding suitable functionalized monomers in the polymerization of the last shell.
  • Suitable functionalized monomers are, for example, maleic acid, maleic anhydride, mono- or diesters of maleic acid, tert-butyl (meth) acrylate, acrylic acid, glycidyl (meth) acrylate and vinyloxazoline.
  • the proportion of monomers with functional groups is generally 0.1 to 25% by weight, preferably 0.25 to 15% by weight, based on the total weight of the core-shell graft rubber.
  • the weight ratio of soft to hard components is generally 1: 9 to 9: 1, preferably 3: 7 to 8: 2.
  • Rubbers of this type which increase the toughness of polyamides are known per se and are described, for example, in EP-A-0 208 187.
  • polyester elastomers are understood to mean segmented copolyether esters which contain long-chain segments which are generally derived from poly (alkylene) ether glycols and short-chain segments which are derived from low molecular weight diols and dicarboxylic acids. Products of this type are known per se and are described in the literature, for example in US Pat. No. 3,651,015. Corresponding products are also commercially available under the names Hytrel® (Du Pont), Arnitel® (Akzo) and Pelprene®. Mixtures of different rubbers can of course also be used.
  • the molding compositions according to the invention can furthermore contain flame retardants F) in amounts of 0 to 20% by weight, preferably 1 to 15% by weight, based on the total weight of the molding composition according to the invention.
  • All known flame retardants can be used, e.g. Polyhalodiphenyl, polyhalodiphenyl ether, polyhalophthalic acid and its derivatives, polyhalo oligo- and polycarbonates, the corresponding bromine compounds being particularly effective.
  • Examples of these are polymers of 2, 6, 2 ', 6' tetrabromobisphenol A of tetrabromophthalic acid, 2, 6-dibromophenol and 2,4, 6-tribromophenol and their derivatives.
  • a preferred flame retardant F is elemental phosphorus.
  • the elementary phosphorus can e.g. Polyurethanes or other aminoplasts are phlegmatized or coated.
  • concentrates of red phosphorus are e.g. in a polyamide, elastomer or polyolefin.
  • 1,2,3,4,7, 8,9, 10, 13, 13, 14, 14 -dodecachloro- 1, 4, 4a, 5, 6, 6a, 7, 10, 10a, 11 is particularly preferred , 12, 12a-dodecahy- DRO 1,4: 7, 10-dimethanodibenzo (a, e) cyclooctane (Dechlorane plus ®, Occidental Chemical Corp.), optionally together with a synergist such as antimony trioxide.
  • a synergist such as antimony trioxide.
  • phosphorus compounds such as organic phosphoric acid, phosphonates, phosphinites, phosphine oxides, phosphines, phosphites or phosphates are also preferred.
  • An example is triphenylphosphine oxide. This can be used alone or mixed with hexabromobenzene or a chlorinated biphenyl or red phosphorus and, optionally, antimony trioxide.
  • Typical preferred phosphorus compounds are those of the following general formula
  • Hydrocarbon radicals or halogenated hydrocarbon radicals such as alkyl, cycloalkyl, aryl, alkyl-substituted aryl and aryl substituted alkyl is provided that at least one of the radicals Q is an aryl radical.
  • Suitable phosphates are, for example, the following: phenylbisdodecyl phosphate, phenylbisneopentyl phosphate, phenylethylene hydrogen phosphate, phenyl bis (3,5,5 '- trimethylhexyl phosphate), ethyl diphenyl phosphate, 2-ethylhexyl di (p-tolyl) phosphate, diphenyl phosphate hydrogen phosphate, bis (2-ethylhexyl) phenyl phosphate, tri (nonyl phenyl) phosphate, phenyl methyl hydrogen phosphate, di (dodecyl) p-tolyl phosphate, tricresyl phosphate, triphenyl phosphate, dibutyl phenyl phosphate and diphenyl hydrogen phosphate.
  • phenylbisdodecyl phosphate phenylbisneopentyl
  • Phosphates are those in which each Q is aryl.
  • the most preferred phosphate is triphenyl phosphate.
  • the combination of triphenyl phosphate with red phosphorus is also preferred.
  • hydroquinone or resorcinol diphenyl diphosphates and compounds which are obtained by reaction of bisphenol A or S with triphenyl phosphate with base catalysis.
  • phosphine oxides with phosphates are also suitable. Mixtures of triphenylphosphine oxide triphenylphosphate or trixylylphosphate, tricyclohexylphosphine oxide and triphenylphosphate, tris (cyanoethyl) phosphine oxide and triphenylphosphate, tris (n-octyl) phosphine oxide and triphenylphosphate may be mentioned as examples.
  • those compounds which contain phosphorus-nitrogen bonds such as phosphonitrile chloride, phosphoric acid ester amides, phosphoric acid ester amines, phosphoric acid amides, phosphonic acid amides, phosphinic acid amides, tris (aziridinyl) phosphine oxide or tetrakis (hydroxymethylphosphonium chloride), are also suitable as flame retardants are mostly commercially available.
  • halogen-containing flame retardants are tetrabromobenzene, hexachlorobenzene and hexabromobenzene as well as halogenated polystyrenes and polyphenylene ethers.
  • halogenated phthalimides described in DE-A 19 46 924 can also be used. Of these, N, N'-ethylene bistetrabromophthalimide in particular has become important.
  • Polymeric siloxane compounds or boron compounds as described in EP-A 0 714 951 can also be used as flame retardants.
  • the silicon-containing flame retardants are those from the group of the siloxane copolymers, for example poly phenylene ether / - or polyetherimide / siloxane copolymers in question. Such polysiloxanes are commercially available.
  • Suitable boron compounds include both inorganic and organic boron compounds, for example boric acid, metal borates, phosphates of boric acid or perborates, in particular metal borates or perborates, such as alkali metal borates (for example sodium or potassium), alkaline earth metal borates (for example calcium, barium or magnesium) or transition metal borates like zinc borate.
  • the metal borates and perborates are preferably used in anhydrous form.
  • the proportion of boron compounds in the molding compositions according to the invention is preferably, based on the amount of boron, in the range from 0.02 to 5, preferably from 0.2 to 1,% by weight.
  • the molding compositions according to the invention contain 0 to 30, preferably 0 to 25 and in particular 0 to 20% by weight of glass or carbon fibers, carbon fibers, carbon black, glass balls or cut glass or mixtures thereof.
  • the average fiber length I 5 0 in the granules or in the molded body, since these molded articles have a very good mechanical Eigenschaftspro il, if the average fiber length I 50 150 .mu.m to 400, preferably 170 is up to 300 ⁇ m and in particular 180 to 280 ⁇ m.
  • the mean fiber length I 50 is generally the value at which 50% of the fibers have a shorter length and 50% of the fibers have a longer length than the 1 50 value. In general, the fibers used have a diameter in the range from 6 to 20 ⁇ m.
  • the glass fibers can contain alkali metals as well as be free of alkali metals. If glass fibers are used, they can be coated with a size, e.g. Polyurethane or epoxy and an adhesion promoter, e.g. Aminotrialkoxisilanen be equipped. Otherwise, the size materials listed under component C) can also be used.
  • a size e.g. Polyurethane or epoxy and an adhesion promoter, e.g. Aminotrialkoxisilanen be equipped. Otherwise, the size materials listed under component C) can also be used.
  • These glass fibers can be incorporated both in the form of short glass fibers and in the form of endless strands (rovings).
  • carbon fibers or hollow fibers and carbon black can be used as component G).
  • Electrically conductive carbon blacks are preferred among the carbon blacks, in particular also when the molding composition or the shaped body is to be subjected to an electrostatic painting or coloring process.
  • the conductive carbon black is advantageously added at a temperature of at least 300 ° C as described in EP-A 0 685 527 for the blend of polyphenylene ether and polyamide.
  • the amount of carbon black is preferably in the range from 1 to 7% by weight, particularly preferably from 2 to 5% by weight.
  • the polymer mixtures according to the invention with conductive carbon black as a constituent have, in particular, a volume resistance of less than 10 6 ohm ⁇ cm, determined according to ISO 3167.
  • glass spheres or microspheres or cut glass can be incorporated as component G) into the molding compositions according to the invention.
  • Such materials as additives for polymer mixtures are well known to the person skilled in the art and are commercially available.
  • Possible additives and processing aids H) are oxidation retardants, heat and light stabilizers, lubricants and mold release agents and colorants such as dyes or pigments and plasticizers in amounts of 0 to 10, preferably 0 to 5,% by weight.
  • Low molecular weight or high molecular weight polymers are also suitable as additives, polyethylene wax being particularly preferred as a lubricant.
  • Oxidation retarders and heat or heat stabilizers that can be added to the thermoplastic molding compositions according to the invention are e.g. Group I metals of the Periodic Table, e.g. Sodium, potassium, lithium halides, optionally in combination with copper (I) halides, e.g. Chlorides, bromides or iodides.
  • Zinc fluoride and zinc chloride can also be used.
  • Sterically hindered phenols, hydroquinones, substituted representatives of this group and mixtures of these compounds, preferably in concentrations of up to 1% by weight, based on the weight of the mixture, can be used.
  • light and UV stabilizers are various substituted resorcinols, salicylates, benzotriazoles and benzophenones, which are generally used in amounts of up to 2% by weight.
  • Materials for increasing the shield against electromagnetic waves such as metal flakes, powders, fibers, metal-coated fillers and conductive polymers can also be used.
  • Lubricants and mold release agents which are generally added in amounts of up to 1% by weight of the thermoplastic composition, are, for example, stearic acid, stearyl alcohol, alkyl stearates and amides and esters of pentaerythritol with long-chain fatty acids.
  • Additives also include stabilizers which prevent the decomposition of the red phosphorus as flame retardant F) in the presence of moisture and atmospheric oxygen.
  • stabilizers which prevent the decomposition of the red phosphorus as flame retardant F) in the presence of moisture and atmospheric oxygen.
  • Compounds of cadmium, zinc, aluminum, silver, iron, copper, antimony, tin, magnesium, manganese, vanadium, boron, aluminum and titanium may be mentioned as examples.
  • Particularly suitable compounds include oxides of the metals mentioned, carbonates or oxicarbonates, hydroxides and salts of organic or inorganic acids such as acetates or phosphates or hydrogen phosphates and sulf
  • the molding compositions according to the invention are expediently produced by mixing the components at temperatures in the range from 250 to 320 ° C. in conventional mixing devices, such as kneaders, Banbury mixers or single- or twin-screw extruders. A twin-screw extruder is preferably used. Intensive mixing is necessary to obtain the most homogeneous molding compound possible.
  • the order of mixing the components can be varied, two or optionally more components can be premixed, or all components can also be mixed together. It has proven to be advantageous to mix the filler (component C) together with the polyamide (component A), e.g. by extrusion, and in the form of a polyamide / filler masterbatch with the other components, as described.
  • molding compositions according to the invention e.g. by injection molding or extrusion to produce moldings which are notable for particularly good dimensional stability and, at the same time, good toughness and heat resistance properties.
  • the molding compositions according to the invention are very suitable for the production of moldings of all kinds, e.g. by injection molding or extrusion.
  • the molding compositions according to the invention are suitable, for example, in automobile construction for the production of body parts or else electrical components.
  • thermoplastic molding compositions according to the invention were mixed on a twin-screw extruder (ZSK 53 from Werner & Pfleiderer) at temperatures in the range from 270 to 310 ° C., melted, extruded, then granulated and dried.
  • the extruder consists of A total of 9 zones with the following temperature profile (zone 0-8): Cold-280-300-290-290-280-270-200-310 ° C.
  • Components B), b) and D) were metered into zone 0, components A) and C) as a masterbatch (produced on a ZSK 40 extruder at 280 ° C.) into zone 5 of the 5 twin-screw extruder.
  • the dried granules were processed into the corresponding shaped articles by means of injection molding.
  • the thermal expansion coefficient (CTE) was determined according to DIN 53 752 (method A) with continuous heating on two test specimens (10 mm x 10 mm x 4 mm) in the longitudinal and transverse directions. In order to rule out orientation effects, two measuring cycles were carried out.
  • the following table shows the mean CTE (longitudinal direction) of the test specimens in the second measurement run at a temperature in the range from 140 to 180 ° C. 5
  • the damage work W-T was determined according to DIN 53443 at -30 ° C.
  • the elongation at break was determined in a tensile test according to ISO 527.
  • Component A is a compound having Component A:
  • Component B is a compound having Component B:
  • Component b 35 citric acid (anhydrous)
  • Wollastonite with aminosilane size a bulk density (DIN 53 468) of 0.58 g / ml, an upper grain size d 95% of 13 ⁇ m and an average grain size d 50% of 3.5 ⁇ m (Tremin 283/600 AST, 5 Quartz movements)
  • Component D1 hydrogenated styrene-butadiene three-block copolymer (SEBS) with a styrene content of 32% by weight, a Shore A hardness of 75 and a glass transition temperature of -42 ° C (Kraton 1651, Shell).
  • SEBS hydrogenated styrene-butadiene three-block copolymer
  • Component D2 hydrogenated styrene-isoprene two-block copolymer (SEP) with a styrene content of 37% by weight, a Shore A hardness of 72 and a glass transition temperature of 20 ° C. of -42 ° C. (Kraton 1701, Shell).
  • SEP hydrogenated styrene-isoprene two-block copolymer
  • compositions of the molding compositions in parts by weight
  • results of the tests can be found in the tables below.

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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne des matières moulables thermoplastiques contenant comme constituants essentiels: A) 15 à 84,5 % en poids d'un polyamide thermoplastique, B) 15 à 84,5 % en poids d'un polyphénylènéther, C) 0,5 à 10 % en poids de kaolinite, dickite, nacrite, halloysiste, wollastonite, enstatite, diopsite ou spodumen, D) 0 à 20 % en poids d'au moins un polymère modifiant la résistance aux chocs de la phase polyphénylènéther, E) 0 à 10 % en poids d'au moins un polymère modifiant la résistance aux chocs de la phase polyamide, F) 0 à 20 % en poids d'un agent ignifuge, G) 0 à 30 % en poids de fibres de verre ou de carbone, fibrilles de carbone, noir de carbone, billes de verre ou fils de base coupés et H) 0 à 10 % en poids d'autres additifs ou produits auxiliaires.
PCT/EP1998/005056 1998-03-05 1998-08-10 Matieres moulables en polyamide-polyphenylenether comportant des charges minerales WO1999045069A1 (fr)

Priority Applications (1)

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DE19809157 1998-03-05

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WO2001090241A1 (fr) * 2000-05-19 2001-11-29 Bayer Aktiengesellschaft Compositions polymeres a resilience modifiee
WO2004048474A1 (fr) * 2002-11-25 2004-06-10 Lanxess Deutschland Gmbh Compositions a base de polymeres presentant une resilience modifiee
EP1736512A1 (fr) * 2004-04-14 2006-12-27 Asahi Kasei Chemicals Corporation Composition de resine conductrice
DE10305558B4 (de) * 2003-02-10 2007-05-16 Benefit Gmbh Zusammensetzung zur Verstärkung von Thermoplasten und deren Herstellungsverfahren und Verwendung
CN100354370C (zh) * 2002-11-25 2007-12-12 兰爱克谢斯德国有限责任公司 冲击强度改进的聚合物组合物
WO2009125315A1 (fr) 2008-04-09 2009-10-15 Sabic Innovative Plastics Ip B.V. Compositions chargées et son procédé de préparation
EP2192156A1 (fr) * 1999-11-12 2010-06-02 Sabic Innovative Plastics IP B.V. mélange conducteur de polyphénylene éther - polyamide
DE102009016214A1 (de) * 2009-04-03 2010-10-14 Volkswagen Ag Verfahren zur Herstellung eines Teilchenverbundwerkstoffes sowie Verfahren zur Herstellung von Folien aus den Teilchenverbundwerkstoff und Bauteil, welches den Verbundwerkstoff umfasst
WO2015002650A1 (fr) * 2013-07-03 2015-01-08 Sabic Innovative Plastics Ip B.V. Composition de polyamide conductrice et article
CN104845351A (zh) * 2014-02-14 2015-08-19 国乔石油化学股份有限公司 聚氧二甲苯/聚酰胺66塑料的改质方法

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EP0183195A2 (fr) * 1984-11-27 1986-06-04 BASF Aktiengesellschaft Matières à mouler auto-extinguibles à base de polyamides thermoplastiques
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DE3929590A1 (de) * 1989-09-06 1991-03-07 Basf Ag Thermoplastische formmasse mit erhoehter waermeformbestaendigkeit
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Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2192156A1 (fr) * 1999-11-12 2010-06-02 Sabic Innovative Plastics IP B.V. mélange conducteur de polyphénylene éther - polyamide
WO2001090241A1 (fr) * 2000-05-19 2001-11-29 Bayer Aktiengesellschaft Compositions polymeres a resilience modifiee
CN100354370C (zh) * 2002-11-25 2007-12-12 兰爱克谢斯德国有限责任公司 冲击强度改进的聚合物组合物
WO2004048474A1 (fr) * 2002-11-25 2004-06-10 Lanxess Deutschland Gmbh Compositions a base de polymeres presentant une resilience modifiee
DE10305558B4 (de) * 2003-02-10 2007-05-16 Benefit Gmbh Zusammensetzung zur Verstärkung von Thermoplasten und deren Herstellungsverfahren und Verwendung
EP1736512A1 (fr) * 2004-04-14 2006-12-27 Asahi Kasei Chemicals Corporation Composition de resine conductrice
EP1736512A4 (fr) * 2004-04-14 2008-07-02 Asahi Kasel Chemicals Corp Composition de resine conductrice
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WO2009125315A1 (fr) 2008-04-09 2009-10-15 Sabic Innovative Plastics Ip B.V. Compositions chargées et son procédé de préparation
CN102056989A (zh) * 2008-04-09 2011-05-11 沙伯基础创新塑料知识产权有限公司 填充组合物和制备方法
DE102009016214A1 (de) * 2009-04-03 2010-10-14 Volkswagen Ag Verfahren zur Herstellung eines Teilchenverbundwerkstoffes sowie Verfahren zur Herstellung von Folien aus den Teilchenverbundwerkstoff und Bauteil, welches den Verbundwerkstoff umfasst
WO2015002650A1 (fr) * 2013-07-03 2015-01-08 Sabic Innovative Plastics Ip B.V. Composition de polyamide conductrice et article
CN105358626A (zh) * 2013-07-03 2016-02-24 沙特基础全球技术有限公司 导电聚酰胺组合物以及制品
US9650084B2 (en) 2013-07-03 2017-05-16 Sabic Global Technologies B.V. Conductive polyamide composition and article
CN104845351A (zh) * 2014-02-14 2015-08-19 国乔石油化学股份有限公司 聚氧二甲苯/聚酰胺66塑料的改质方法

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