EP1117737A1 - Matieres moulables thermoplastiques a resistance elevee aux chocs constituees de polystyrene syndiotactique et d'un modificateur acrylate - Google Patents

Matieres moulables thermoplastiques a resistance elevee aux chocs constituees de polystyrene syndiotactique et d'un modificateur acrylate

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Publication number
EP1117737A1
EP1117737A1 EP99938297A EP99938297A EP1117737A1 EP 1117737 A1 EP1117737 A1 EP 1117737A1 EP 99938297 A EP99938297 A EP 99938297A EP 99938297 A EP99938297 A EP 99938297A EP 1117737 A1 EP1117737 A1 EP 1117737A1
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EP
European Patent Office
Prior art keywords
weight
component
molding compositions
polymers
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Withdrawn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
EP99938297A
Other languages
German (de)
English (en)
Inventor
Graham Edmund Mckee
Josef WÜNSCH
Falko Ramsteiner
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 EP1117737A1 publication Critical patent/EP1117737A1/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Withdrawn legal-status Critical Current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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions 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
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/06—Polystyrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2300/00—Characterised by the use of unspecified polymers
    • C08J2300/22—Thermoplastic resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/24—Graft or block copolymers according to groups C08L51/00, C08L53/00 or C08L55/02; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes

Definitions

  • thermoplastic molding compositions made from syndiotactic polystyrene and acrylate modifier
  • the invention relates to thermoplastic molding compositions containing
  • the invention further 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.
  • syndiotactic polystyrene Due to its crystallinity, syndiotactic polystyrene has a very high melting point of approx. 270 ° C, high rigidity and tensile strength, dimensional stability, a low dielectric constant and a high chemical resistance. The mechanical property profile is maintained even at temperatures above the glass temperature.
  • the production of syndiotactic polystyrene in the presence of metallocene catalyst systems is known and z. B. described in detail in EP-A 0 535 582.
  • EP-A 755 972 describes SPS, which is impact modified with a mixture of a block copolymer of styrene and hydrogenated butadiene on the one hand and a core shell polymer with a butadiene polymer core on the other.
  • such modifiers are not heat or weather resistant and still have an un- sufficient impact strength and are therefore, among other things, not the optimal solution to the problem.
  • thermoplastic molding composition based on SPS which combines high impact strength, high rigidity (modulus of elasticity) and good flowability (MVR, processability) and is still weather-resistant.
  • 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), 30 to 99.9% by weight, preferably 40 to 99% by weight, in particular 50 to 95% by weight, of a vinylaromatic polymer with a syndiotactic structure.
  • the term "with syndiotactic structure” means here that the polymers are essentially syndiotactic, ie the syndiotactic fraction determined according to 13 C-MR is greater than 50, preferably greater than 60%, pimmad.
  • Component A) is preferably composed of compounds of the general formula I.
  • R 1 is hydrogen or C ⁇ ⁇ to C alkyl
  • R 2 to R 6 independently of one another are hydrogen, Ci to C ⁇ alkyl , C 6 to Ci 8 "aryl, halogen or two adjacent radicals together for 4 to 15 C atoms having cyclic groups, for example C 4 -C 8 -Cycloalkyl or fused ring systems.
  • Vinylaromatic compounds of the formula I are preferably used, in which
  • R 1 means hydrogen
  • Suitable substituents R 2 to R 6 are in particular hydrogen, C 1 -C 4 -alkyl, chlorine, phenyl, biphenyl, naphthalene or anthracene.
  • Two adjacent radicals can also together represent cyclic groups having 4 to 12 carbon atoms, so that naphthalene derivatives or anthracene derivatives, for example, result as the compound of the general formula I.
  • 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.
  • SPS syndiotactic polystyrene
  • Vinylaromatic polymers (A) 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.
  • a metallocene complex and a cocatalyst.
  • pentamethylcyclopentadienyltitanium trichloride, pentamethylcyclopentadienyltitanium trimethyl and pentamethylcyclopentadienyltitanium trimethylate are used 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 of 10,000 to 2,000,000 g / mol.
  • the molecular weight distributions M w / M n are generally in the range from 1.1 to 30, preferably from 1.4 to 10.
  • syntiotactic star polymers based on vinyl aromatic monomers are described, for example, in the older German patent application 196 34 375.5-44, in particular on pages 2, line 21 to page 6, line 25, and in the examples.
  • the graft polymers B whose core polymers are not polymerized by butadiene monomer - except in small amounts as crosslinkers - but preferably by polymerizing ⁇ - ⁇ -unsaturated carboxylic acids, ⁇ - ⁇ -unsaturated carboxylic acids - esters or ⁇ - ⁇ -unsaturated nitriles, such as acrylic acid, methacrylic acid, acrylic acid ester, methacrylic acid ester, acrylonitrile, methacrylonitrile or their mixtures, if appropriate also with the addition of crosslinking agents, are preferably obtained as follows:
  • the liquid monomers or liquid monomer mixture M ⁇ which for Core polymers P ⁇ to be polymerized is mixed with water and a protective colloid.
  • the polymerization initiator is either also added now or only after the monomer has been dispersed or after the dispersion has been heated.
  • the heterogeneous mixture is used to prepare a dispersion of the smallest monomer droplets in water by intensive stirring at high speed, for which intensive mixers of any design are suitable.
  • the desired particle size within the defined range can be determined, for example, by taking light microscopic images and counting the number of particles that have a specific diameter.
  • the polymerization is started by heating the dispersion.
  • the reaction which is now carried out with moderate stirring, in which the droplets are no longer divided, is continued until the conversion based on M ⁇ is above 50%, preferably above 85%.
  • Suitable monomers M s are styrene or its derivatives, acrylates, methacrylates, ⁇ -methylstyroi, acrylonitrile and methacrylonitrile. 100% of the vinyl aromatic monomers, preferably styrene or mixtures of more than 80% by weight, preferably 85 to 95% by weight, styrene and up to 20% by weight, preferably 5 to 15% by weight, of acrylonitrile are preferably used as monomers M 3 .
  • the grafting can also begin when the polymerization conversion of the monomer M ⁇ is still incomplete and is above 50%, preferably above 85%. In this case, form Shell and core a more smooth transition compared to the sharper demarcation of core and shell polymer in the case of the complete conversion of the core monomers.
  • the graft polymer has only one shell, which is generally sufficient, it consists of the material P s .
  • the graft cores are relatively small and if you want to incorporate a larger amount of the core polymer P into the particles, it is advisable to use grafted polymers with the structure P -P s ⁇ P ⁇ " p s ', the inner shells also being used other polymers Px can exist in order to modify and thereby improve the properties of the graft polymers.
  • the monomers M K are generally dispersed at a temperature of 0 to 100 ° C., preferably at room temperature, and generally 0.4 to 10 kg of water are used per kilogram of the monomers.
  • the protective colloids suitable for stabilizing the dispersion are water-soluble polymers which coat the monomer droplets and the polymer particles formed therefrom and in this way protect them from coagulation.
  • Suitable protective colloids are cellulose derivatives such as carboxymethyl cellulose and hydroxymethyl cellulose, poly-N-vinyl pyrrolidone, polyvinyl alcohol and polyethylene oxide, anionic polymers such as polyacrylic acid and cationic polymers such as poly-N-vinyl imidazole.
  • the amount of these protective colloids is preferably 0.1 to 5% by weight, based on the total mass of the monomers M ⁇ .
  • Low molecular weight surface-active compounds for example those of the anionic and cationic soap type, are generally not suitable alone for the preparation of the graft polymers according to the invention, since they lead to polymer particles with smaller diameters, such as those obtained in emulsion polymerization.
  • the use of a mixture of protective colloid and soap can, however, be advantageous in order to achieve a smaller particle size than is usually possible when using protective colloids alone.
  • Suitable polymerization initiators are free radical formers, in particular those which are noticeably soluble in the monomers and which preferably have a half-life of 10 hours when the temperature is between 25 and 150 ° C ("ten-hour half-life at 25 to 150 ° C").
  • Peroxides such as lauroyl peroxide, peroxosulfates, t-butyl perpivalate and azo compounds such as azodiisobutyronitrile are suitable, for example.
  • the amount of initiators is generally 0.1 to 2.5% by weight, based on the amount of monomers.
  • reaction mixture preferably contains buffers - substances such as Na 2 HP0 4 / NaH 2 P0 or Na citrate / citric acid, in order to set an essentially constant pH.
  • buffers - substances such as Na 2 HP0 4 / NaH 2 P0 or Na citrate / citric acid
  • molecular weight regulators such as ethylhexylthioglycolate or t-dedecyl mercaptan are generally added during the polymerization, in particular of the shell-building monomers M s .
  • the polymerization temperature of the monomers M R to the core consisting of P is generally 25 to 150 ° C., preferably 40 to 120 ° C.
  • the shells are grafted onto the core in general at 25 to 150 ° C., preferably 50 to 120 ° C.
  • the lower limit values of these ranges correspond to the decomposition temperatures of the polymerization initiators used in each case.
  • the graft polymers B) contain a phase with a glass temperature of less than 0 ° C., preferably less than -10 ° C., and in particular less than -20 ° C.
  • Suitable polymers with such glass transition temperatures are primarily those containing 50 to 100% by weight of (C 2 -C 3 g-alkyl) acrylates such as ethyl acrylate, n-propyl, iso-propyl acrylate, preferably n-butyl acrylate and / or 2-ethylhexyl acrylate are built up.
  • so-called “soft” monomers amounts of up to 50% by weight of so-called “hard” monomers such as methyl acrylate, the (C 1 -C 12 -alkyl) methacrylates, styrene and ⁇ -methylstyrene, acrylonitrile and are also suitable Methacrylonitrile.
  • hard monomers such as methyl acrylate, the (C 1 -C 12 -alkyl) methacrylates, styrene and ⁇ -methylstyrene, acrylonitrile and are also suitable Methacrylonitrile.
  • bifunctional or polyfunctional comonomers e.g. Butadiene and isoprene, divinyl esters of dicarboxylic acids such as succinic acid and adipic acid, diallyl and divinyl ethers of bifunctional alcohols such as ethylene glycol and butane-1,4-diol, diesters of acrylic acid and methacrylic acid with the bifunctional alcohols mentioned, 1,4 -Divinylbenzene and triallyl cyanurate.
  • the acrylic acid ester of tricyciodecenyl alcohol (dihydrodicyclopentadienyl acrylate) of the formula I is particularly preferred
  • the mass ratio of the sum of all shells to the core is approximately 0.05: 1 to 2.5: 1.
  • the average diameter of the particles - which are preferably produced using the microsuspension polymerization method, as described in DE 19702733.4, in particular on page 9, line 25 to page 18, line 6 - is approximately 0.1 to approximately 10 ⁇ m, preferably 0, 2 to 9 ⁇ m, particularly preferably 0.3 to 7 ⁇ m.
  • the mean diameter corresponds to the D 50 value, according to which 50% by weight of all particles have a smaller diameter and 50% by weight have a larger diameter than the diameter which corresponds to the D 50 value.
  • the Dio and D 90 values are often given. 10% by weight of all particles are smaller and 90% by weight larger than the D ⁇ o diameter. Analogously, 90% by weight of all particles have a smaller and 10% by weight larger diameter than that which corresponds to the Dgo value.
  • Component B) preferably has a shell which is compatible or partially compatible with the base polymer, that is to say the SPS (derivative).
  • the amount of component B) in the molding compositions according to the invention is in the range from 0.1 to 70% by weight, preferably 1 to 60
  • the rubber-elastic component C) from a styrene / diene block copolymer, the diene portion of which can be completely or partially hydrogenated is known, for example, from EP-A 755 972 and can be purchased, for example, from Shell under the name Kraton® G 1651, further examples being Cariflex® "TR types (Shell), Finaprene®-ypen (Fina) and Europrene® types (Enichen).
  • Additives or processing aids or mixtures thereof can be added to the thermoplastic molding compositions according to the invention in customary amounts.
  • nucleating agents such as salts of carboxylic, organic sulfonic or phosphoric acids, preferably sodium benzoate, aluminum tris (p-tert-butylbenzoate), aluminum trisbenzoate, aluminum tris (p-carboxymethylbenzoate) and aluminum triscaproate;
  • Antioxidants like 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.
  • 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 are particularly preferably used,
  • Tris (n-octyl) phosphine oxide or tris (cyanoethyl) phosphine oxide Tris (n-octyl) phosphine oxide or tris (cyanoethyl) phosphine oxide.
  • Particularly suitable phosphates are alkyl and aryl-substituted phosphates.
  • Examples are phenyl bisdodecyl phosphate, phenyl bis neopentyl phosphate, phenyl ethyl hydrogen phosphate, phenyl bis (3, 5, 5-trimethyl hexyl phosphate), ethyl diphenyl phosphate, bis (2-ethyl hexyl) p-tolyl phosphate, tritolyl phosphate, trixylyl bis-phosphate, trixylyl bis-phosphate ) -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. Triphenyl 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.
  • Mixtures of different phosphorus compounds can also be used.
  • thermoplastic molding compositions according to the invention can contain fibrous or particulate fillers or mixtures thereof.
  • Glass fibers can be equipped with a size and an adhesion promoter. The incorporation of these glass fibers can take the form of both short glass fibers as well as in the form of endless strands (rovings). Preferred glass fibers contain an aminosilane size.
  • Amorphous silica, magnesium carbonate, powdered quartz, mica, talc, feldspar, calcium silicates or layered silicates can also be used.
  • thermoplastic molding compositions according to the invention can generally be obtained by mixing the individual components at temperatures of from 270 to 330 ° C. in customary mixing devices, such as kneaders, Banbury mixers and single-screw extruders, but preferably using a twin-screw extruder. Intensive mixing is necessary to obtain the most homogeneous molding compound possible.
  • the mixing order of the components can be varied, so two or, if necessary, several components can be premixed, but all components can also be mixed together.
  • thermoplastic molding compositions according to the invention can also be mixed with other polymers, such as atactic or isotactic homopolystyrene, styrene copolymers with, for example, acrylonitrile, methacrylates and / or diphenylethylene as comonomers, or with polyamides, polyesters or polyphenylene ethers or mixtures of the polymers, generally as described above .
  • other polymers such as atactic or isotactic homopolystyrene, styrene copolymers with, for example, acrylonitrile, methacrylates and / or diphenylethylene as comonomers, or with polyamides, polyesters or polyphenylene ethers or mixtures of the polymers, generally as described above .
  • thermoplastic molding compositions according to the invention are notable for high impact strength, high rigidity and good flowability (processability). They are suitable for the production of fibers, foils or molded articles.
  • the polymer obtained was washed with methanol and at 50 ° C in Vacuum dried.
  • 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 determined by 13 C-NMR was> 96%.
  • the conversion was 84% based on the monomer styrene used.
  • Styrene (St), acrylonitrile (AN), butyl acrylate (BA) and dihydrodicyclopentadienylacylate (DCPA) are from BASF and were used without further purification.
  • Mowiol 8/88 from Hoechst is a polyvinyl alcohol, the viscosity of which as a 4% solution in water at 20 ° C is 8 mPa / s (first digit) measured according to DIN 53015. The degree of hydrolysis of the Mowiol is 88 mol% ( last two digits).
  • Composition of the graft monomers changed accordingly.
  • the following batch was stirred under nitrogen with a Dispermat at 7000 rpm for 20 minutes.
  • the Dipermat was manufactured by VMA-Getzman and was provided with a 5 cm tooth lock washer.
  • the particle size distributions of the dispersions were determined using a Microtac UPA 150 laser scattered light device, manufacturer Leeds and Northrup.
  • Rubber MS-1 cover made of 100% styrene
  • Rubber MS-2 cover made of 95 styrene and 5% acrylonitrile
  • Kraton G 1651 is a block copolymer from Shell with the following structure:
  • Styrene-hydrogenated butadiene-styrene block copolymer The styrene: rubber ratio is 32:68
  • MSP rubber (MS-1, MS-2) brings a better combination of properties such as impact strength, MVI, E modulus and tensile strength and breaking stress than Kraton alone.

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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)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Graft Or Block Polymers (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Polymerisation Methods In General (AREA)
  • Artificial Filaments (AREA)

Abstract

Matières moulables thermoplastiques contenant (A) de 30 à 99,9 % en poids d'un polymère vinylaromatique à structure syndiotactique, (B) de 0,1 à 70 % en poids d'un polymère caoutchouteux greffé particulaire et (C) de 0 à 69,9 % en poids d'un copolymère séquencé diène/styrène caoutchouteux particulaire dont la partie diène peut être totalement ou partiellement hydrogénée, les particules du constituant (B) ayant une valeur D(50) de l'ordre de 0,1 à 10 νm et le constituant (B) étant différent du constituant (C).
EP99938297A 1998-08-13 1999-07-20 Matieres moulables thermoplastiques a resistance elevee aux chocs constituees de polystyrene syndiotactique et d'un modificateur acrylate Withdrawn EP1117737A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19836621 1998-08-13
DE19836621A DE19836621A1 (de) 1998-08-13 1998-08-13 Schlagzähe thermoplastische Formmassen aus syndiotaktischem Polystyrol und Acrylatmodifier
PCT/EP1999/005163 WO2000009608A1 (fr) 1998-08-13 1999-07-20 Matieres moulables thermoplastiques a resistance elevee aux chocs constituees de polystyrene syndiotactique et d'un modificateur acrylate

Publications (1)

Publication Number Publication Date
EP1117737A1 true EP1117737A1 (fr) 2001-07-25

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EP99938297A Withdrawn EP1117737A1 (fr) 1998-08-13 1999-07-20 Matieres moulables thermoplastiques a resistance elevee aux chocs constituees de polystyrene syndiotactique et d'un modificateur acrylate

Country Status (11)

Country Link
EP (1) EP1117737A1 (fr)
JP (1) JP2002522615A (fr)
KR (1) KR20010072434A (fr)
CN (1) CN1131278C (fr)
AU (1) AU5285499A (fr)
BR (1) BR9912886A (fr)
CA (1) CA2340231A1 (fr)
CZ (1) CZ2001540A3 (fr)
DE (1) DE19836621A1 (fr)
TR (1) TR200100480T2 (fr)
WO (1) WO2000009608A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10016280A1 (de) 2000-04-03 2001-10-04 Basf Ag Schlagzähe thermoplastische Formmassen aus syndiotaktischem Polystyrol, Glasfasern und Acrylat-Schlagzähmodifier
JP7512504B1 (ja) 2023-11-16 2024-07-08 デンカ株式会社 熱可塑性離型フィルムの製造方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5395890A (en) * 1987-09-14 1995-03-07 Idemitsu Kosan Co., Ltd. Styrene-based resin composition
JPH05271501A (ja) * 1992-03-24 1993-10-19 Mitsubishi Rayon Co Ltd 耐衝撃性、耐熱性及び耐候性に優れたポリスチレン系樹脂組成物
DE69604250T2 (de) * 1995-07-24 2000-05-31 Rohm And Haas Co., Philadelphia Styrolpolymerzusammensetzung
DE19702733A1 (de) * 1997-01-27 1998-07-30 Basf Ag Thermoplastische Formmassen mit hoher Zähigkeit

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0009608A1 *

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Publication number Publication date
TR200100480T2 (tr) 2001-07-23
AU5285499A (en) 2000-03-06
JP2002522615A (ja) 2002-07-23
WO2000009608A1 (fr) 2000-02-24
BR9912886A (pt) 2001-05-08
CA2340231A1 (fr) 2000-02-24
KR20010072434A (ko) 2001-07-31
DE19836621A1 (de) 2000-02-17
CN1131278C (zh) 2003-12-17
CN1312834A (zh) 2001-09-12
CZ2001540A3 (cs) 2001-11-14

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