EP1576019A1 - Pfropfpolymerisate auf basis von athylen-alpha-olefin-kautschuken und verfahren zu ihrer herstellung - Google Patents

Pfropfpolymerisate auf basis von athylen-alpha-olefin-kautschuken und verfahren zu ihrer herstellung

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Publication number
EP1576019A1
EP1576019A1 EP03789156A EP03789156A EP1576019A1 EP 1576019 A1 EP1576019 A1 EP 1576019A1 EP 03789156 A EP03789156 A EP 03789156A EP 03789156 A EP03789156 A EP 03789156A EP 1576019 A1 EP1576019 A1 EP 1576019A1
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EP
European Patent Office
Prior art keywords
ethylene
monomers
rubber
graft polymers
molding compositions
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.)
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Application number
EP03789156A
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German (de)
English (en)
French (fr)
Inventor
Gisbert Michels
Holger Warth
Pierre Vanhoorne
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Lanxess Deutschland GmbH
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Lanxess Deutschland GmbH
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Publication date
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Publication of EP1576019A1 publication Critical patent/EP1576019A1/de
Withdrawn legal-status Critical Current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
    • 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
    • C08L51/06—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 homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
    • C08F255/04—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms on to ethene-propene copolymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
    • C08F255/06—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms on to ethene-propene-diene terpolymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates

Definitions

  • the present invention relates to graft polymers based on ethylene- ⁇ -
  • Graft polymers which are obtainable by graft polymerization of vinylaromatic monomers and vinyl nitriles on ethylene- ⁇ -olefin rubbers or ethylene- ⁇ -olefin-diene rubbers are known in principle and are generally referred to as AES-type graft polymers. Graft polymers of the AES type are described, for example, in GB 2 059 427 A, DE 30 36 921 AI, EP 0 286 071 A2, EP 0 096 527 A2, WO 86/06733, EP 0 054 148 and US 3,876,727.
  • the graft polymers of the AES type known from the prior art all have deficits in at least one category of surface properties, mechanical and polymer-physical properties.
  • blends which contain graft polymers of the AES type are weather-resistant, while their mechanical properties in the
  • Low temperature range are unsatisfactory. At temperatures below 0 ° C because these blends are brittle and have unsatisfactory toughness. This hinders the use of these molding compositions at lower temperatures.
  • the notched impact strength of AES blends in the low temperature range is poor, in particular in comparison to acrylonitrile / butadiene / styrene (ABS) blends.
  • EP-A 0 502 367 relates to the preparation of AES graft polymers and a copolymer, the copolymer comprising from 60 to 76% by weight of a vinyl-type aromatic monomer and 40 to 24% of an aliphatic copolymer. Grafted vinyl aromatics and / or nucleus-substituted vinyl aromatics and vinyl cyanides and / or (meth) acrylic acid (-C-Cg) alkyl esters. In addition to the desired good properties with regard to surface gloss, weather resistance and sliding properties, these thermoplastic copolymers are said to have, among other things, good impact resistance.
  • JP-A 50 109 247 describes polycarbonate blends with AES which contain 0.1 to 10% by weight
  • JP-A 58 098 354 describes polycarbonate blends with AES and 0.5 to 20% by weight plasticizers for vinyl polymers. It is not known that the use of special additives, which concentrate specifically in the soft phase of the blend, leads to a significant improvement in the low-temperature properties in polycarbonate AES blends.
  • the invention is therefore also based on the object of modifying AES blends such that they have an improved property profile, in particular also improved notched impact strengths, while maintaining weather resistance in the low temperature range.
  • a disperse phase composed of ethylene- ⁇ -olefin rubber which is grafted with vinyl aromatic monomers and ethylenically unsaturated nitrile monomers
  • the continuous phase a) has a weight-average molecular weight Mw of greater than 130,000, preferably greater than 145,000, particularly preferably greater than 160,000 g / mol to 275,000, preferably up to 250,000
  • the disperse phase b) is a grafted rubber phase which has a weight-average particle size Dw of less 0.90 ⁇ m, preferably less than 0.80 ⁇ m, a degree of grafting (measured by measuring the gel value in acetone as solvent) of at least 0.25 and at most
  • 0.65 preferably at least 0.30 and at most 0.60, has a ratio of the gel value measured in tetrahydrofuran (THF) to the gel value measured in acetone of less than 0.1, preferably less than 0.05, and a glass transition temperature ( T g , determined by measuring the complex shear modulus as a function of the temperature) of the rubber or soft phase of less than -50 ° C.
  • THF tetrahydrofuran
  • Suitable vinyl aromatic monomers which polymerize radically together with ethylenically unsaturated nitrile monomers and thereby form the continuous phase (matrix phase) a) of the molding compositions, styrene, ⁇ -methylstyrene,, p-methylstyrene, divinylbenzene and / or other alkylstyrenes, preferably with 2 to
  • Core-substituted chlorostyrenes can also be used in a mixture with these.
  • Particularly preferred vinyl aromatic monomers are styrene, ⁇ -methylstyrene and / or p-methylstyrene. Styrene, ⁇ -methylstyrene and mixtures thereof are very particularly preferred.
  • Suitable ethylenically unsaturated nitrile monomers are, for example and preferably, acrylonitrile and methacrylonitrile and mixtures thereof, particularly preferably acrylonitrile.
  • the ratio of vinyl aromatic monomers to ethylenically unsaturated nitrile monomers in the thermoplastic molding compositions according to the invention is 60-90% by weight to 40-10% by weight, based on the matrix phase a).
  • acrylic monomers or maleic acid derivatives such as, for example, methyl (meth) acrylate, ethyl (meth) acrylate, tert-butyl (meth) acrylate, n-Butyl (meth) acrylate, esters of fumaric acid, itaconic acid, maleic anhydride, maleic acid esters, N-substituted maleimides such as advantageously N-cycohexyl- or N-phenyl-maleimide, N-alkylphenyl-maleimide, further acrylic acid, methacrylic acid, fumarate - acid, itaconic acid, or their amides.
  • acrylic monomers or maleic acid derivatives such as, for example, methyl (meth) acrylate, ethyl (meth) acrylate, tert-butyl (meth) acrylate, n-Butyl (meth) acrylate, esters of fumaric acid, itaconic acid, male
  • suitable ethylene- ⁇ -olefin rubbers contain, in polymerized form, ethylene, an ⁇ -olefin and optionally a non-conjugated diene.
  • Suitable ⁇ -olefins are propene, 1-butene, 1-hexene, 1-octene and mixtures thereof.
  • Preferred ⁇ -olefins are propene, 1-hexene and 1-octene.
  • non-conjugated dienes which serve to improve the graftability of the rubber are norbornenes such as alkenylnorbornenes and alkylidene norbornenes, cyclic dienes such as dicyclopentadiene and aliphatic dienes such as hexadiene or octadiene.
  • Preferred dienes are ethylidene norbornene, dicyclopentadiene, 1,4-hexadiene and 1,6-octadiene.
  • the ratio of ethylene to ⁇ -olefin is 30:70 to 70:30% by weight, with the stipulation that the rubbers are completely amorphous or predominantly amorphous. It could be shown that partially crystalline rubbers give significantly worse results.
  • the content of non-conjugated dienes is 0 to 15% by weight, preferably 0 to 10% by weight.
  • Suitable rubbers have a Mooney viscosity ML (1 + 4) 125 ° C (without pretreatment, DLN 53523; ASTM D1646) of 3 to 50, preferably 3 to 30.
  • Suitable ethylene- ⁇ -olefin rubbers can have a linear or branched structure. It is also possible to use a mixture of linear and branched ethylene- ⁇ -olefin rubbers.
  • the rubber content of the thermoplastic molding compositions according to the invention is 10-70% by weight, preferably 15-50% by weight, particularly preferably 17-35% by weight, very particularly preferably 18-23% by weight, based on the molding compositions.
  • the graft polymers according to the invention have a gloss at a measurement angle of 20 ° of greater than 65, preferably 70 and a gloss at a measurement angle of 60 ° of greater than 85, preferably 90, a notched impact strength
  • the graft polymers according to the invention have improved weathering stability compared to ABS graft polymers.
  • thermoplastic graft polymers according to the invention are obtained by radical polymerization of vinylaromatic monomers and ethylenically unsaturated nitrile monomers in the presence of an ethylene- ⁇ -olefin.
  • Rubbers in the presence of solvents by methods known in principle bulk or solution polymerization, preferably in a continuous procedure.
  • Aromatic hydrocarbons such as toluene, ethylbenzene and xylenes and the like are used as solvents for radical polymerization in solvents
  • the polymerization is advantageously triggered by radical initiators.
  • Suitable initiators for radical polymerization are graft-active radicals which disintegrate
  • Peroxides such as peroxycarbonates, peroxydicarbonates, diacyl peroxides, perketals, or dialkyl peroxides and / or azo compounds or mixtures thereof.
  • Examples are azodiisobutyronitrile, azoisobutyric acid alkyl ester, tert-butyl perpivalate, tert-butyl peroctoate, tert-butyl perbenzoate, tert-butyl perneodecanoate, tert-butyl per- (2-ethylhexyl) carbonate.
  • These initiators are used in amounts of 0.005 to 1% by weight, based on the monomers.
  • the process according to the invention is preferably carried out continuously.
  • the rubber solution consisting of rubber, solvents, monomers and, if appropriate, additives can advantageously be used.
  • Residual monomers and solvents can be removed using conventional techniques (eg in heat exchanger evaporators, flash evaporators, strand evaporators, thin-film or thin-film evaporators, screw evaporators, stirred multi-phase evaporators with kneading and stripping devices), including the use of propellants and entraining agents, eg water vapor or nitrogen , is possible, and in the process, ie for the production of the rubber solution and / or in the polymerization reactors.
  • Heat exchanger evaporators are preferably used.
  • Additives e.g. Stabilizers, anti-aging agents, fillers, lubricants are added. It is essential and important that conventional molecular weight regulators such as mercaptans, olefins, e.g. tert-dodecyl mercaptan, n-dodecyl mercaptan, cyclohexene, terpinolene, ⁇ -methylstyrene dimer is dispensed with in order to achieve a sufficiently high molecular weight or a sufficiently low melt index.
  • molecular weight regulators such as mercaptans, olefins, e.g. tert-dodecyl mercaptan, n-dodecyl mercaptan, cyclohexene, terpinolene, ⁇ -methylstyrene dimer is dispensed with in order to achieve a sufficiently high molecular weight or a sufficiently low melt index.
  • the syrup can be pumped in a circle in a continuous manner over mixing and shearing organs.
  • Such loop reactors are known from the prior art and can be helpful in adjusting the particle size of the rubber. It is also possible to arrange shear members between two separate reactors in order to avoid back-mixing, which leads to a broadening of the particle size distribution.
  • Another option for better mixing and dividing the rubber phase is the use of stirring elements that can apply particularly high shear rates.
  • the average residence time is 1 to 10 hours, preferably 2 to 8 hours.
  • the polymerization temperature is 50 to 180 ° C, preferably 100 to 160 ° C.
  • the reaction temperature in the first reactor is preferably 100 to 130 ° C, particularly preferably 110 to 130 ° C.
  • the reaction temperature in the second reactor is preferably 120 to 160 ° C, particularly preferably 130 to 160 ° C.
  • the graft polymers according to the invention can be processed into molded parts by extrusion, injection molding, calendering, blow molding, pressing and sintering.
  • the present invention therefore furthermore relates to molding compositions comprising at least one graft polymer according to the invention.
  • the graft polymers according to the invention can be used in compositions with at least one polymer selected from the group consisting of polycarbonates, polyamides, polyalkylene terephthalates, copolymers containing vinyl aromatic monomers and ethylenically unsaturated nitrile monomers.
  • the molding compositions according to the invention can in particular contain aromatic polycarbonates and / or aromatic polyester carbonates. These are known from the literature and can be produced by processes known from the literature. For the production of aromatic polyester carbonates, see for example Schnell, "Chemistry and Physics of Polycarbonates", Interscience Publishers, 1964 and DE-A 1 495 626, DE-A 2 232 877, DE-A 2 703 376, DE-A 2 714 544, DE-A 3,000 610, DE-A 3 832 396; for the production of aromatic polyester carbonates e.g. B. DE-A 3 077 934) or WO 00/26275.
  • aromatic polyester carbonates see for example Schnell, "Chemistry and Physics of Polycarbonates", Interscience Publishers, 1964 and DE-A 1 495 626, DE-A 2 232 877, DE-A 2 703 376, DE-A 2 714 544, DE-A 3,000 610, DE-A 3 832 396; for the production of aromatic polyester carbonates e.g
  • Aromatic polycarbonates can be prepared by reacting
  • Diphenols for the preparation of the aromatic polycarbonates and / or aromatic polyester carbonates are preferably those of the formula (I)
  • A is a single bond, C 1 -C 5 alkylene, C -C 5 alkylidene, C 5 -C 6 cycloalkylidene, -O-, -SO-, -CO-, -S-, -SO 2 -, C6-C 12 arylene, can be fused to which further aromatic rings optionally containing hetero atoms,
  • each C ⁇ C ⁇ alkyl preferably methyl, halogen, preferably chlorine and / or bromine x each independently of the other 0, 1 or 2,
  • R 5 and R 6 can be selected individually for each X 1 , independently of one another hydrogen or C 1 -C 6 -alkyl, preferably hydrogen, methyl or ethyl,
  • n is an integer from 4 to 7, preferably 4 or 5, with the proviso that at least one atom X 1 , R 5 and R 6 are simultaneously alkyl.
  • Preferred diphenols are hydroquinone, resorcinol, dihydroxydiphenols, bis- (hydroxypheny ⁇ ) -C ⁇ -C5-alkanes, bis- (hydroxyphenyl) -C5-C6-cycloalkanes, bis- (hydroxyphenyl) ethers, bis- (hydroxyphenyl) sulfoxides, bis (hydroxyphenyl) ketones, bis (hydroxyphenyl) sulfones and ⁇ , ⁇ -bis (hydroxyphenyl) diisopropyl benzenes and their core-brominated and / or core-chlorinated derivatives.
  • diphenols are 4,4'-dihydroxydiphenyl, bisphenol-A, 2,4-
  • 2,2-bis (4-hydroxyphenyl) propane bisphenol-A is particularly preferred.
  • the diphenols can be used individually or as any mixtures.
  • the diphenols are known from the literature or can be obtained by processes known from the literature.
  • Chain terminators suitable for the production of the thermoplastic, aromatic polycarbonates or polyester carbonates are, for example, phenol, p-chlorophenol, p-tert-butylphenol or 2,4,6-tribromophenol, but also long-chain alkylphenols such as 4- (1,3-tetramethylbutyl) - phenol according to DE-A 2 842 005 or monoalkylphenol.
  • the amount of chain terminator is generally 0.5 to 10 mol%, based on the molar sum of the diphenols used in each case.
  • thermoplastic, aromatic polycarbonates have average weight-average molecular weights (M), measured by ultracentrifuge or scattered light measurement, of 10,000 to 200,000, preferably 15,000 to 80,000. Mixtures of polycarbonates with different molecular weights can also be used.
  • thermoplastic, aromatic polycarbonates or polyester carbonates can be branched in a known manner, preferably by incorporating 0.05 to 2.0 mol%, based on the sum of the diphenols used, of trifunctional or more than trifunctional compounds, for example those with three or more phenolic groups.
  • 3- or mechanical carboxylic acid chlorides such as trimesic acid trichloride, cyanuric trichloride or 3- or merir-functional phenols such as phloroglucin in amounts of 0.01 to 1.0 mol% based on the diphenols used can be used as branching agents.
  • Phenolic branching agents can be introduced with the diphenols
  • acid chloride branching agents can be introduced together with the acid dichlorides.
  • polycarbonates are the copolycarbonates of bisphenol A with up to 15 mol%, based on the molar sum of diphenols, of other diphenols mentioned as preferred or particularly preferred, in particular 2,2-bis (3,5- dibromo-4-hydroxyphenyl) propane.
  • Aromatic dicarboxylic acid dihalides for the production of aromatic polyester carbonates are preferably the diacid dichlorides of isophthalic acid, terephthalic acid, diphenyl ether-4,4'-dicarboxylic acid and naphthalene-2,6-dicarboxylic acid.
  • Mixtures of the diacid dichlorides of isophthalic acid and terephthalic acid in a ratio between 1:20 and 20: 1 are particularly preferred.
  • a carbonic acid halide preferably phosgene, is additionally used as the bifunctional acid derivative.
  • the aromatic polyester carbonates can also contain built-in aromatic hydroxycarboxylic acids.
  • the proportion of carbonate fracture units in the thermoplastic, aromatic polyester carbonates can vary as desired.
  • the proportion of carbonate groups is up to 100% by mol, in particular up to 80 mol%, particularly preferably up to 50 mol%, based on the sum of Ester weakness and carbonate groups.
  • Both the ester and the carbonate content of the aromatic polyester carbonates can be present in the form of blocks or randomly distributed in the polycondensate.
  • the relative solution viscosity ( ⁇ re ⁇ ) of the aromatic polycarbonates and polyester carbonates is in the range from 1.18 to 1.4, preferably from 1.20 to 1.32, measured on solutions of 0.5 g of polycarbonate or polyester carbonate in 100 ml of methylene chloride solution at 25 ° C.
  • thermoplastic, aromatic polycarbonates and polyester carbonates can be used alone or in any mixture.
  • the molding compositions according to the invention can also contain polyalkylene terephthalates, as described, for example, in WO 00/29 476. Polyethylene or polybutylene terephthalates or mixtures thereof are preferred.
  • the molding compositions according to the invention can also contain rubber-free copolymers.
  • the rubber-free copolymers used are preferably copolymers of styrene and acrylonitrile in a weight ratio of 95: 5 to 50:50, it being possible for styrene and / or acrylonitrile to be replaced in whole or in part by ⁇ -methylstyrene, methyl methacrylate or N-phenylmaleimide.
  • Copolymers whose acrylic content is less than 30% by weight are particularly preferred.
  • the copolymers preferably have average molecular weights M w of 20,000 to 200,000 or intrinsic viscosities [ ⁇ ] of 20 to 110 ml / g (measured in dimethylformamide at 25 ° C.).
  • the molding compositions according to the invention contain 10 to 80% by weight, preferably 20-70% by weight, particularly preferably 25 to 60% by weight of the graft polymer according to the invention and 20 to 90% by weight, preferably 30-80 % By weight, particularly preferably 40 to 75% by weight, of polycarbonate, based in each case on the sum of graft polymer and polycarbonate.
  • the molding compositions according to the invention can also contain additives known for blends and aromatic polycarbonates, such as at least one of the customary additives, such as lubricants and mold release agents, for example pentaerythritol tetrastearate, nucleating agents, flame retardants, antistatic agents, stabilizers, fillers and reinforcing materials, and also dyes and pigments and electrically conductive additives , for example polyaniline or nanotubes.
  • the customary additives such as lubricants and mold release agents, for example pentaerythritol tetrastearate, nucleating agents, flame retardants, antistatic agents, stabilizers, fillers and reinforcing materials, and also dyes and pigments and electrically conductive additives , for example polyaniline or nanotubes.
  • Phosphorus-containing flame retardants in the sense of the invention are particularly preferably selected from the groups of the mono- and oligomeric phosphorus and phosphonic acid esters, phosphonatamines and phosphazenes, mixtures of several components selected from one or different of these groups also being able to be used as flame retardants.
  • Other halogen-free phosphorus compounds not specifically mentioned here can also be used alone or in any combination with other halogen-free phosphorus compounds.
  • the filled or reinforced molding compositions can contain up to 60% by weight, preferably 5 to 40% by weight, based on the filled or reinforced molding composition, fillers and / or reinforcing materials.
  • Preferred reinforcing materials are glass fibers.
  • Preferred fillers, which can also have a reinforcing effect, are glass balls, mica,
  • Silicates, quartz, talc, titanium dioxide, wollastonite Silicates, quartz, talc, titanium dioxide, wollastonite.
  • the molding compositions according to the invention can contain up to 35% by weight, based on the composition, of a further, optionally synergistic flame retardant.
  • Organic halogen compounds such as decabromobisphenyl ether, tetrabromobisphenol, inorganic halogen compounds such as ammonium bromide and nitrogen compounds such as melamine are mentioned as examples of further flame retardants.
  • compositions according to the invention can be prepared by mixing the constituents in a known manner and at elevated temperatures, preferably at 200 to 350 ° C., melt-compounded or melt-extruded in the usual devices, such as internal kneaders, extruders or twin-screw screws.
  • the individual components can be mixed in one after the other or simultaneously.
  • the moldings according to the invention can be produced by extrusion or injection molding.
  • Shaped bodies according to the invention are, for example, outdoor applications, e.g. Window parts, air conditioners, water tanks, automotive exterior parts, garden tools, housing parts for household appliances, such as juicers, coffee machines, mixers, for office machines, such as monitors, printers, copiers or cover plates for the construction sector and automotive parts. They can also be used in the field of electrical engineering because they have very good electrical properties.
  • the molding compositions according to the invention are also suitable for the production of moldings by deep drawing from previously produced plates or films.
  • telecommunication devices such as telephone devices and faxes, computers, printers, scanners, plotters, monitors, keyboards, typewriters, dictation machines, etc.
  • garden tools garden furniture, lawn mower housings, pipes and housings for garden irrigation, garden houses, leaf vacuums, shredders, shredders, sprayers etc.,
  • the rubber content in the end product was determined from the mass balance. Gel contents were determined in acetone as the dispersing medium. The molecular weights of the soluble fraction were determined by GPC with THF or methylene chloride as solvent against the polystyrene standard. The particle size and distribution of the rubber particles were measured by zonal centrifugation; the weight average (Dw), the area average (Da) and the number average (Dn) are given. The notched impact strength (a ⁇ -Izod) was measured at 23 ° C according to ISO 180 / 1A, the melt volume index (MFI 220 ° C / 10 kg) according to DIN 53735.
  • the phase structure was examined by measuring the complex shear modulus depending on the temperature (dynamic mechanical measurement of the shear modulus characteristic G * (T)) on the test specimens at a frequency of approx. 1 Hz in the temperature range from -150 to 200 ° C with the RDA II from Rheometrics.
  • the glass transition temperature (Tg) of the soft phase and the matrix was determined.
  • the corrected shear modulus at 23 ° C (G ' k0rr . (RT)) was determined.
  • the measured values were measured on injection molded articles at a melt temperature of 240 ° C and a mold temperature of 70 ° C.
  • the gloss was determined on 60 * 75 * 1 mm test specimens using a BYK-Gardner measuring device at 20 and 60 ° in accordance with DLN 67530. Examples 1-5
  • the graft polymers were prepared by continuous solution polymerization in two reactors connected in series with spiral stirrers. The evaporation of the polymer solution was carried out continuously in a single-screw extruder under a vacuum of approx. 100 mbar. The rubber solution, monomers and an initiator solution were metered into the first reactor and an initiator solution into the second reactor. In the transfer line from the 2nd reactor to the evaporation apparatus, a
  • the stabilizer was metered into the second reactor.
  • the evaporation was carried out continuously via a two heat exchanger connected in series.
  • the vacuum in the 1st evaporation stage was 200 mbar and in the 2nd evaporation stage 5 mbar.
  • Comparative Example 1 a partially crystalline EPDM (name EPDM 2) with a Mooney viscosity ML (1 + 4) 125 ° C. of 20, an E ⁇ B content of 4.2% and an ethylene content of 70% was used as the rubber. In Comparative Examples 2 and 3, Buna EP G 3850 was used as the rubber.
  • PC / AES blends of the following composition were produced as the base material for carrying out tests:
  • the components are mixed on a 3-1 internal mixer.
  • the moldings are produced on an Arburg 270 E injection molding machine at 260 ° C.
  • Blends 6 to 10 according to the invention and comparative examples 6 to 8 were produced according to the following recipe:
  • Comparative Examples 4 (9% rubber content) and 5 (8% rubber content) were produced according to the following recipe:
  • the modulus of elasticity was determined according to ISO 527 at 1 mm / min.
  • the melt volume flow rate (MVR) was determined according to ISO 1133 at 260 ° C and 5kg coating weight.
  • Table 4 shows the test results for the blends. These results show a significant reduction in the critical temperature (toughness / brittleness transition) without impairing mechanical properties such as notched impact strength. This is a clear measure of the increased efficiency of the molding compositions according to the invention compared to the prior art, as can be seen in the two comparison games based on commercially available AES graft polymers.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Graft Or Block Polymers (AREA)
EP03789156A 2002-12-19 2003-12-06 Pfropfpolymerisate auf basis von athylen-alpha-olefin-kautschuken und verfahren zu ihrer herstellung Withdrawn EP1576019A1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10259500 2002-12-19
DE10259500A DE10259500A1 (de) 2002-12-19 2002-12-19 Pfropfpolymerisate auf Basis von Ethylen-α-Olefin-Kautschuken und Verfahren zu ihrer Herstellung
PCT/EP2003/013835 WO2004056891A1 (de) 2002-12-19 2003-12-06 PFROPFPOLYMERISATE AUF BASIS VON ATHYLEN-α-OLEFIN-KAUTSCHUKEN UND VERFAHREN ZU IHRER HERSTELLUNG

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EP1576019A1 true EP1576019A1 (de) 2005-09-21

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JP6146890B2 (ja) 2010-08-27 2017-06-14 テクノポリマー株式会社 軋み音を低減した熱可塑性樹脂組成物製接触用部品
CN102898759B (zh) * 2012-09-27 2015-05-13 上海锦湖日丽塑料有限公司 Aes树脂组合物及其制备方法
HUE046407T2 (hu) 2013-02-15 2020-02-28 Techno Umg Co Ltd Ojtott kopolimer, hõre lágyuló gyantakészítmény, valamint a gyantakészítmény formázott gyártmánya
JP6087330B2 (ja) * 2014-09-24 2017-03-01 テクノポリマー株式会社 軋み音を低減した熱可塑性樹脂組成物及び成形品

Family Cites Families (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3683050A (en) * 1969-04-24 1972-08-08 Copolymer Rubber & Chem Corp Process for preparing improved plastic compositions and the resulting products
US3876727A (en) 1969-11-21 1975-04-08 Curtis L Meredith Plastic composition and method of preparing same
JPS50109247A (ja) 1974-02-04 1975-08-28 Sumitomo Chemical Co Netsukasoseijushisoseibutsu
CH606243A5 (enExample) * 1975-07-30 1978-10-31 Bayer Ag
DE2616375A1 (de) * 1976-04-14 1977-10-27 Bayer Ag Thermoplastische formmassen
JPS5598214A (en) * 1979-01-19 1980-07-26 Japan Synthetic Rubber Co Ltd Production of rubber-modified thermoplastic resin
JPS5918408B2 (ja) * 1979-10-01 1984-04-27 ジェイエスアール株式会社 ゴム変性熱可塑性樹脂の連続的製造方法
DE3047295A1 (de) 1980-12-16 1982-07-29 Basf Ag, 6700 Ludwigshafen Verfahren zur kontinuierlichen herstellung alterungsbestaendiger aes-polymerisate
JPS5898354A (ja) 1981-12-07 1983-06-11 Sumitomo Naugatuck Co Ltd 熱可塑性樹脂組成物
JPS58208307A (ja) 1982-05-29 1983-12-05 Japan Synthetic Rubber Co Ltd ゴム変性熱可塑性樹脂の製造方法
US4485212A (en) * 1983-05-27 1984-11-27 Uniroyal, Inc. Impact resistant blend of polybutylene terephthalate resin and OSA graft copolymer
CA1274635A (en) 1985-05-06 1990-09-25 Li C. Tien Reinforced weatherable thermoplastic manufacturing process
US4656225A (en) * 1985-12-23 1987-04-07 General Electric Company Polycarbonate resin blends exhibiting improved resistance to stress crazing and cracking
IT1218559B (it) * 1987-04-07 1990-04-19 Montedipe Spa Processo per la produzione in soluzione e in continuo di resine termoplastiche stireniche
US4895907A (en) * 1988-08-15 1990-01-23 The Dow Chemical Company Polymerization process using bisquinone peroxide catalyst
US5306778A (en) * 1988-08-24 1994-04-26 Japan Synthetic Rubber Co., Ltd. Process for producing rubber-modified thermoplastic resin
IT1246980B (it) * 1990-07-12 1994-12-12 Montedipe Srl Composizioni termoplastiche a base di un copolimero graffato vinil aromatico e di una poliammide
JP3147392B2 (ja) 1991-03-04 2001-03-19 宇部サイコン株式会社 熱可塑性樹脂組成物
EP0587907B1 (en) * 1992-03-31 1997-06-04 Sumitomo Dow Limited Thermoplastic resin composition containing glass fiber

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2004056891A1 *

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JP2006510764A (ja) 2006-03-30
AU2003293785A1 (en) 2004-07-14
TWI275599B (en) 2007-03-11
US7060751B2 (en) 2006-06-13
US20040127642A1 (en) 2004-07-01
DE10259500A1 (de) 2004-07-01
CN1751074A (zh) 2006-03-22
TW200427709A (en) 2004-12-16
WO2004056891A1 (de) 2004-07-08
CN100448903C (zh) 2009-01-07

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