EP0851895A1 - Matieres moulables thermoplastiques a base de polymeres aromatiques vinyliques a structure syndiotactique, de polyamides thermoplastiques et d'ethers de polyphenylene modifies avec des groupes polaires - Google Patents

Matieres moulables thermoplastiques a base de polymeres aromatiques vinyliques a structure syndiotactique, de polyamides thermoplastiques et d'ethers de polyphenylene modifies avec des groupes polaires

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Publication number
EP0851895A1
EP0851895A1 EP96932526A EP96932526A EP0851895A1 EP 0851895 A1 EP0851895 A1 EP 0851895A1 EP 96932526 A EP96932526 A EP 96932526A EP 96932526 A EP96932526 A EP 96932526A EP 0851895 A1 EP0851895 A1 EP 0851895A1
Authority
EP
European Patent Office
Prior art keywords
weight
thermoplastic
molding compositions
component
thermoplastic molding
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Withdrawn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
EP96932526A
Other languages
German (de)
English (en)
Inventor
Josef WÜNSCH
Martin Weber
Volker ALTSTÄDT
Axel Gottschalk
Herbert Fisch
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 EP0851895A1 publication Critical patent/EP0851895A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00Compositions of, homopolymers or 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; Compositions of derivatives of such polymers
    • C08L25/02Homopolymers or copolymers of hydrocarbons
    • C08L25/04Homopolymers or copolymers of styrene
    • C08L25/06Polystyrene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12Polyphenylene oxides
    • C08L71/126Polyphenylene oxides modified by chemical after-treatment
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12Polyphenylene oxides

Definitions

  • thermoplastic molding compositions based on vinyl aromatic polymers with a syndiotic structure, thermoplastic polyamides and polyphenylene ethers modified with polar groups
  • the present invention relates to
  • thermoplastic polyamide B) 2 to 94.8% by weight of a thermoplastic polyamide
  • G 0 to 50% by weight of fibrous or particulate fillers or mixtures thereof.
  • the present invention relates to the use of the thermoplastic molding compositions for the production of fibers, films and moldings and the fibers, films and moldings obtainable therefrom.
  • compositions consist of syndiotactic polystyrene (s-PS) and polyphenylene ethers (PPE). This results in multiphase polymer systems, which are very brittle and have poorer heat resistance than s-PS.
  • s-PS syndiotactic polystyrene
  • PPE polyphenylene ethers
  • EP-A 546 497 describes a composition of s-PS, inorganic fillers and modified PPE. Here, however, the material is also brittle. It was therefore an object of the present invention to remedy the disadvantages mentioned and to provide thermoplastic molding compositions which are resistant to high temperatures, are dimensionally stable, have high rigidity and have low electrical conductivity.
  • thermoplastic molding compositions defined at the outset are thermoplastic molding compositions defined at the outset.
  • thermoplastic molding compositions for the production of fibers, films and moldings and the fibers, films and moldings obtainable therefrom were found.
  • thermoplastic molding compositions according to the invention contain, as component A), 5 to 97.8% by weight, preferably 15 to 96.3% by weight, in particular 25 to 93.7% by weight, of a vinylaromatic polymer with a syndiotactic structure.
  • component A a vinylaromatic polymer with a syndiotactic structure.
  • with syndiotactic structure means here that the polymers are essentially syndiotactic, ie the syndiotactic fraction determined by 13 C-NMR is greater than 50, preferably greater than 60%.
  • Component A) is preferably composed of compounds of the general formula I.
  • R 1 is hydrogen or C 1 -C 4 -alkyl
  • R 2 to R 6 are independently hydrogen, C. , - to C ⁇ 2 -alkyl ( C ⁇ - to Ci ⁇ 'Aryl, halogen or where two adjacent radicals together stand for 4 to 15 carbon atoms having cyclic groups.
  • Vinylaromatic compounds of the formula I are preferably used in which
  • R 1 means hydrogen
  • R 2 to R 6 are hydrogen, Ci to C alkyl, chlorine, phenyl,
  • Naphthalene derivatives or anthracene derivatives result.
  • Styrene p-methylstyrene, p-chlorostyrene, 2,4-dimethylstyrene, 4-vinylbiphenyl, vinylnaphthalene or vinylanthracene.
  • Mixtures of different vinyl aromatic compounds can also be used, but preferably only one vinyl aromatic compound is used.
  • Particularly preferred vinyl aromatic compounds are styrene and p-methylstyrene.
  • Mixtures of various vinylaromatic polymers with a syndiotactic structure can also be used as component A), but preferably only one vinylaromatic polymer is used, in particular s-PS.
  • Vinyl aromatic polymers with a syndiotactic structure and processes for their preparation are known per se and are described, for example, in EP-A 535 582.
  • the preparation is preferably carried out by reacting compounds of the general formula I in the presence of a metallocene complex and a cocatalyst.
  • Pentamethylcyclopentadienyltitanium trichloride, pentethylcyclopentadienyltitanium trimethyl and pentamethylcyclopentadienyltitanium triethylate are used in particular as metallocene complexes.
  • the vinyl aromatic polymers with a syndiotactic structure generally have a molecular weight M w (weight average) of 5,000 to 10,000,000, in particular 10,000 to 2,000,000.
  • the molecular weight distributions M w / M n (M n ... number average) are generally in the range from 1.1 to 30, preferably from 1.4 to 10.
  • thermoplastic molding compositions contain 2 to 94.8% by weight, preferably 3 to 84.3% by weight, in particular 5 to 40% by weight, of a thermoplastic polyamide.
  • polyamides are known per se and comprise the partially crystalline and amorphous resins with molecular weights (weight averages) of at least 5000, which are usually known as nylon be drawn.
  • Such polyamides are described, for example, in American Patents 2,071,250, 2,071,251, 2,130,523, 2,130,948, 2,241,322, 2,312,966, 2,512,606 and 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, with a saturated or aromatic diamine which has up to 14 carbon atoms or by condensation of ⁇ -aminocarboxylic acids or polymerization of 10 lacta enes.
  • polyamides examples include polyhexamethylene adipic acid amide (nylon 66), polyhexamethylene azelaic acid amide (nylon 69), poly hexamethylene sebacic acid amide (nylon 610), polyhexamethylene-15 dodecanedioic acid amide (nylon 612), the polyamides obtained by ring opening of lactams such as polycaprolactam (nylon 6), polylaur Poly-11-aminoundecanoic acid and a polyamide made from di (p-aminocyclohexyl) methane and dodecanedioic acid.
  • polyamides which have been prepared by copolycondensation of two or more of the above-mentioned monomers or their components, e.g. Copoly ere from adipic acid, isophthalic acid or terephthalic acid and hexamethylene diamine (polyamide 66 / 6T) or copolymers
  • Polyamide 6 / 6T Such partially aromatic copolyamides contain 40 to 90% by weight of units which are derived from terephthalic acid and hexamethylandiamine. A small proportion of the terephthalic acid, preferably not more than 20% by weight of the total
  • Aromatic dicarboxylic acids can be substituted by isophthalic acid or other aromatic dicarboxylic acids, preferably those in which the carboxyl groups are in the para position.
  • the partially aromatic copolyamides contain units which are derived from e-caprolactam and / or units which are derived from adipic acid and hexamethylene diamine.
  • the proportion of units derived from e-caprolactam is up to 50% by weight, preferably 20 to 50% by weight, in particular 25 to 40% by weight, while the proportion of units which are derived from adipic acid and hexymethylene diamine, up to
  • copolyamides can also contain units of e-caprolactam as well as units of adipic acid and hexamethylenediamine; in this case care must be taken to ensure that the proportion of units which are free from aromatic groups is at least 10% by weight, preferably at least 20% by weight.
  • the ratio of the units which are derived from e-caprolactam and from adipic acid and hexamethylene diamine is not subject to any particular restriction.
  • compositions composed of 50 to 70% by weight units derived from terephthalic acid and hexamethylene diamine and 10 to 20% by weight units derived from adipic acid and hexamethylene diamine and 20 to 30 units have proven particularly advantageous for ternary copolyamides % By weight units derived from isophthalic acid and hexamethylenediamine have been found.
  • the production of the partially aromatic copolyamides can e.g. by the method described in EP-A 129 195 and EP-A 129 196.
  • polyamides which are essentially composed of units which are derived from terephthalic acid, isophthalic acid, hexamethylenediamine and aliphatic cyclic diamines having 6 to 30 carbon atoms.
  • Preferred polyamides are polyhexamethylene adipic acid amide, polyhexamethylene sebacic acid amide and polycaprolactam as well as polyamide 6 / 6T and polyamide 66 / 6T.
  • the polyamides generally have a relative viscosity of 2.0 to 5, determined on one
  • Polyamides which can be obtained, for example, by condensing 1,4-diaminobutane with adipic acid at elevated temperature (polyamide-4,6) may also be mentioned. Production processes for polyamides of this structure are described, for example, in EP-A 38 094, EP-A 38 582 and EP-A 39 524. Mixtures of the abovementioned polyamides can also be used.
  • thermoplastic molding compositions according to the invention contain, as component C), 0.1 to 50% by weight, preferably 0.2 to 20% by weight, in particular 0.5 to 10% by weight, of a polyphenylene ether modified with polar groups .
  • polyphenylene ethers modified with polar groups and processes for their preparation are known per se and are described, for example, in DE-A 41 29 499.
  • Polyphenylene ethers which are modified with polar groups and are composed of are preferably used as component C)
  • c 3 0.05 to 5% by weight of at least one compound which contains at least one double or triple bond and at least one functional group selected from the group of carboxylic acids, carboxylic esters, carboxylic anhydrides, carboxamides, epoxides, oxazolines or urethanes .
  • polyphenylene ether c .. examples are
  • Poly (2-ethyl-6-propyl-1, -phenylene) ether examples of preferred vinylaromatic polymers c 2 ) can be found in the monograph by Olabisi, pp. 224 to 230 and 245. Vinyl aromatic polymers made from styrene, chlorostyrene, ⁇ -methylstyrene and p-methylstyrene are only representative here; In minor proportions (preferably not more than 20%, in particular not more than 8% by weight), comonomers such as (meth) acrylonitrile or (meth) acrylic acid esters can also be involved in the structure. Particularly preferred vinylaromatic polymers are polystyrene and impact modified polystyrene It is understood that mixtures of these polymers can also be used
  • Production is preferably carried out by the method described in EP-A 302 485.
  • Suitable modifiers c 3 are, for example, maleic acid, methyl maleic acid, itaconic acid, tetrahydrophthalic acid, their anhydrides and imides, fumaric acid, the mono- and diesters of these acids, for example C __- and C - to Cs-alkanols, the mono- or diamides of these acids such as N-phenyl maleimide, maleic hydrazide.
  • N-vinylpyrrolidone and (meth) acryloylcaprolactam may also be mentioned, for example.
  • modifiers includes, for example, the acid chloride of trimellitic anhydride, benzene-1,2-dicarboxylic acid anhydride-4-carboxylic acid acetic anhydride, pyromellitic acid dianhydride, chloroethanoylsuccinaldehyde, chloroformylsuccinic aldehyde, citric acid and hydroxysuccinic acid.
  • Particularly preferred polyphenylene ethers C) modified with polar groups in the molding compositions according to the invention are obtained by modification with maleic acid, maleic anhydride or fumaric acid.
  • Such polyphenylene ethers preferably have a molecular weight (weight average M w ) in the range from 10,000 to 80,000, preferably from 20,000 to 60,000.
  • thermoplastic molding compositions according to the invention contain 0.1 to 50% by weight, preferably 0.5 to 15% by weight, in particular 0.8 to 12% by weight, of additives or processing aids or mixtures thereof.
  • nucleating agents such as salts of carboxylic, organic sulfonic or phosphoric acids, preferably sodium benzoate, aluminum tris (p-tert-butyl benzoate), aluminum trisbenzoate, aluminum tris (p-carboxymethylbenzoate) and aluminum triscaproat;
  • Antioxidants such as phenolic antioxidants, phosphites or phosphonites, especially trisnornylphenyl phosphite; Stabilizers such as sterically hindered phenols and hydroquinones.
  • Lubricants and mold release agents, dyes, pigments and plasticizers can also be used as component D).
  • component D preference is given to adding 0.3 to 5% by weight of nucleating agents, 0.3 to 5% by weight of antioxidants and 0.2 to 2% by weight of stabilizers.
  • thermoplastic molding compositions according to the invention can contain 0 to 20% by weight, preferably 0 to 18% by weight, in particular 0 to 15% by weight, of a flame retardant.
  • Organophosphorus compounds such as phosphates or phosphine oxides, can be used as flame retardants.
  • phosphine oxides are triphenylphosphine oxide, tritolylphosphine oxide, trisnonylphenylphosphine oxide, tricyclohexylphosphine oxide, tris (n-butyl) phosphine oxide, tris (n-hexyl) phosphine oxide, tris (n-octyl) phosphine oxide, tris (cyanoethyl) ) -phosphine oxide, benzylbis (cyclohexyl) -phosphine oxide, benzylbisphenylphosphine oxide, phenylbis- (n-hexyl) -phosphine oxide. Triphenylphosphine oxide, tricyclohexylphosphine oxide, tris (n-octyl) phosphine oxide or tris (cyanoethyl) phosphine oxide are particularly preferably used.
  • Particularly suitable phosphates are alkyl and aryl-substituted phosphates.
  • Examples are phenylbisdodecyl phosphate, phenylbisneopentyl phosphate, phenylethyl hydrogen phosphate, phenyl bis (3,5,5-trimethylhexyl phosphate), ethyl diphenyl phosphate, bis (2-ethyl hexyl) p-tolyl phosphate, tritolyl phosphate, trixylyl phosphate, tri-esyl phosphate 2-ethylhexyl) phenyl phosphate, tris (nonylphenyl) phosphate, bis (dodecyl) p- (tolyl) phosphate, tricresyl phosphate, triphenyl phosphate, di-butylphenyl phosphate, p-tolyl-bis- (2.5, 5- trimethylhe
  • Phosphorus compounds in which each R is an aryl radical are particularly suitable. Tri-phenyl phosphate, trixylyl phosphate and trimesityl phosphate are very particularly suitable. Cyclic phosphates can also be used. Diphenylpentaerythritol diphosphate is particularly suitable. Resorcinol diphosphate is also preferred.
  • thermoplastic molding compositions according to the invention can contain 0 to 50% by weight, preferably 0 to 30% by weight, in particular 0 to 20% by weight, of rubber-elastic polymers.
  • Graft rubbers with a crosslinked, elastomeric core and a graft cover made of polystyrene, EP and EPDM rubbers, block copolymers and thermoplastic polyester elastomers are only examples here.
  • a polyoctylene the name Vestenamer ® (Hüls AG), and a variety of suitable block copolymers with at least one vinylaromatic and an elastomeric block.
  • suitable block copolymers with at least one vinylaromatic and an elastomeric block.
  • Examples include the Cariflex ® -T types (Shell), the Kraton ® -G types (Shell), the Finaprene ® types (Fina) and the Europrene ® -SOL types (Enichem).
  • Block copolymers are preferably used.
  • thermoplastic molding compositions according to the invention can contain 0 to 50% by weight, preferably 0 to 40% by weight, in particular 0 to 35% by weight of fibrous or particulate fillers or mixtures thereof.
  • Glass fibers can be equipped with a size and an adhesion promoter. These glass fibers can be incorporated both in the form of short glass fibers and in the form of endless strands (rovings). Preferred glass fibers contain a _ ⁇ minosilane size.
  • Amorphous silica, magnesium carbonate, powdered quartz, mica, talc, feldspar or calcium silicates can also be used as component G).
  • the sum of the% by weight of the components used is always 100.
  • thermoplastic molding compositions according to the invention can be mixed by mixing the individual components at temperatures of 270 to 350 ° C in conventional mixing devices such as kneaders, Banbury mixers and Single-screw extruders, but preferably with a twin-screw extruder.
  • conventional mixing devices such as kneaders, Banbury mixers and Single-screw extruders, but preferably with a twin-screw extruder.
  • intensive mixing is necessary.
  • the mixing order of the components can be varied, so two or, if necessary, also several components can be premixed, but all components can also be mixed together.
  • thermoplastic molding compositions according to the invention are notable for high heat resistance, high rigidity and toughness. They are suitable for the production of fibers, foils or molded articles.
  • a polycaprolactam (PA 6) having a relative viscosity of 2.7 (measured by weight as 1 -.% Solution in 96 wt -.% H 2 S0 at 25 ° C) (Ultramid B3 ® from BASF Aktiengesellschaft)
  • a modified polyphenylene ether produced at 300 ° C in a twin-screw extruder by reacting
  • the melt was degassed, extruded, extruded through a water bath and pelletized.
  • TNPP Trisnornylphenylphosph.it
  • Component D3 A with tert. -Butyl groups sterically hindered phenol (Irganox ® 3052 from Ciba Geigy) as a stabilizer Components E
  • Component E2 resorcinol diphosphate
  • the components were mixed in a twin-screw extruder (ZSK 30 from Werner & Pfleiderer) at a temperature of 285 ° C., discharged as a strand, cooled and granulated.
  • ZSK 30 from Werner & Pfleiderer
  • the dried granules were then at 290 ° C. into round disks (thickness 2 mm, diameter 60 mm), flat bars (127 mm x 12.7 mm x 1.6 mm) and standard small bars (50 mm x 6 mm x 4 mm) processed and examined.
  • the heat resistance was carried out by Vicat softening temperatures according to DIN 53460.
  • the injection temperature was 290 ° C and the mold temperature 150 ° C.
  • the flat bars were flame-treated according to UL-4294.
  • Flame-retardant thermoplastics are classified in UL94 V0 fire class if the following criteria are met: In the case of a set of 5 samples with the dimensions 127 x 12.7 x 1.6 mm, after two flames of 10 s duration each time, all samples must not continue to burn for longer than 10 s with an open flame (height 19 mm). The sum of the afterburning times for 10 flame treatments of 5 samples must not exceed 50 s. There must be no burning dripping, complete separation or afterglow for longer than 30 s. The classification in the fire class UL-94 VI requires that the afterburning times are not longer than 30 s and that the sum of the afterburning times of 10 flames of 5 samples is not greater than 250 s. The afterglow must not last longer than 60 s. The other criteria are identical to those mentioned above. A classification in the fire class UL 94 V2 follows if there is burning dripping if the other criteria for UL-94 VI are met.
  • thermoplastic molding compositions are summarized 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)
  • General Chemical & Material Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne des matières moulables thermoplastiques contenant: A) 5 à 97,8 % en poids d'un polymère aromatique vinylique à structure syndiotactique, B) 2 à 94,8 % en poids d'un polyamide thermoplastique, C) 0,1 à 50 % en poids d'un éther de polyphènylène modifié avec des groupes polaires, D) 0,1 à 25 % en poids d'additifs ou d'auxiliaires de transformation ou leurs mélanges, E) 0 à 20 % en poids d'un agent ignifugeant, F) 0 à 50 % en poids d'un polymère présentant l'élasticité du caoutchouc et G) 0 à 50 % en poids de charges fibreuses ou particulaires ou leurs mélanges.
EP96932526A 1995-09-23 1996-09-13 Matieres moulables thermoplastiques a base de polymeres aromatiques vinyliques a structure syndiotactique, de polyamides thermoplastiques et d'ethers de polyphenylene modifies avec des groupes polaires Withdrawn EP0851895A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE1995135400 DE19535400A1 (de) 1995-09-23 1995-09-23 Thermoplastische Formmassen auf der Basis von vinylaromatischen Polymeren mit syndiotaktischer Struktur, thermoplastischen Polyamiden und mit polaren Gruppen modifizierten Polyphenylenethern
DE19535400 1995-09-23
PCT/EP1996/004033 WO1997011124A1 (fr) 1995-09-23 1996-09-13 Matieres moulables thermoplastiques a base de polymeres aromatiques vinyliques a structure syndiotactique, de polyamides thermoplastiques et d'ethers de polyphenylene modifies avec des groupes polaires

Publications (1)

Publication Number Publication Date
EP0851895A1 true EP0851895A1 (fr) 1998-07-08

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EP96932526A Withdrawn EP0851895A1 (fr) 1995-09-23 1996-09-13 Matieres moulables thermoplastiques a base de polymeres aromatiques vinyliques a structure syndiotactique, de polyamides thermoplastiques et d'ethers de polyphenylene modifies avec des groupes polaires

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EP (1) EP0851895A1 (fr)
DE (1) DE19535400A1 (fr)
WO (1) WO1997011124A1 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19616075A1 (de) * 1996-04-23 1997-10-30 Basf Ag Thermoplastische Formmassen auf der Basis von vinylaromatischen Polymeren mit syndiotaktischer Struktur, niederviskosen Polyamiden und mit polaren Gruppen modifizierten Polyphenylenethern
EP0810263B1 (fr) * 1996-05-29 2001-01-10 Shell Internationale Researchmaatschappij B.V. Composition élastomère à base de copolymères-blocs
DE19737959A1 (de) * 1997-08-30 1999-03-04 Basf Ag Thermoplastische Formmassen auf Basis von Polyamid und Styrol/Diphenylethylen-Copolymeren
CA2301701A1 (fr) * 1997-09-12 1999-03-25 John M. Warakomski Melanges de polymeres durcis
US6894102B2 (en) 2002-05-20 2005-05-17 General Electric Syndiotactic polystyrene blends

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU628651B2 (en) * 1989-10-13 1992-09-17 Idemitsu Kosan Co. Ltd Styrene polymer composition
EP0546497A3 (en) * 1991-12-10 1993-11-18 Idemitsu Kosan Co Thermoplastic resin composition
JPH08143729A (ja) * 1994-11-25 1996-06-04 Idemitsu Kosan Co Ltd ポリスチレン系樹脂組成物

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9711124A1 *

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WO1997011124A1 (fr) 1997-03-27
DE19535400A1 (de) 1997-03-27

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