EP1576019A1 - Graft polymers based on ethylene-alpha-olefin rubbers and method for the production thereof - Google Patents

Graft polymers based on ethylene-alpha-olefin rubbers and method for the production thereof

Info

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
Authority
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.)
Withdrawn
Application number
EP03789156A
Other languages
German (de)
French (fr)
Inventor
Gisbert Michels
Holger Warth
Pierre Vanhoorne
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.)
Lanxess Deutschland GmbH
Original Assignee
Lanxess Deutschland GmbH
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Lanxess Deutschland GmbH filed Critical Lanxess Deutschland GmbH
Publication of EP1576019A1 publication Critical patent/EP1576019A1/en
Withdrawn legal-status Critical Current

Links

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.

Landscapes

  • 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)

Abstract

The invention relates to graft polymers based on ethylene-alpha-olefin rubbers, a method for the production thereof, and rubber-modified molded thermoplastic materials which are provided with improved weathering resistance and contain the inventive graft polymers.

Description

Pfropfpolymerisate auf Basis von Ethylen-α-Olefin-Kautschuken und Verfahren zu ihrer HerstellungGraft polymers based on ethylene-α-olefin rubbers and process for their preparation
Die vorliegende Erfindung betrifft Pfropfpolymerisate auf Basis von Ethylen-α-The present invention relates to graft polymers based on ethylene-α-
Olefin-Kautschuken und ein Verfahren zu ihrer Herstellung sowie kautschukmodifizierte thermoplastische Formmassen mit verbesserter Witterungsbeständigkeit enthaltend diese Pfropfpolymerisate.Olefin rubbers and a process for their preparation, and rubber-modified thermoplastic molding compositions with improved weather resistance, comprising these graft polymers.
Pfropfpolymerisate, die durch Pfropφolymerisation von vinylaromatischen Monomeren und Vinylnitrilen auf Ethylen-α-Olefin-Kautschuke oder Ethylen-α-Olefm- Dien-Kautschuke erhältlich sind, sind im Prinzip bekannt und werden in der Regel als Pfropfpolymerisate vom AES-Typ bezeichnet. Pfropfpolymerisate vom AES-Typ werden beispielsweise beschrieben 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 und US 3,876,727.Graft polymers which are obtainable by graft polymerization of vinylaromatic monomers and vinyl nitriles on ethylene-α-olefin rubbers or ethylene-α-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.
Im Vergleich zu Pfropfpolymerisaten vom ABS-Typ zeichnen sie sich durch eine verbesserte Bewitterungsstabilität aus.Compared to graft polymers of the ABS type, they are characterized by improved weathering stability.
Die aus dem Stand der Technik bekannten Pfropfpolymerisate vom AES-Typ weisen jedoch sämtlich Defizite in mindestens einer Kategorie von Oberflächeneigen- schaften, mechanischen und polymerphysikalischen Eigenschaften auf.The graft polymers of the AES type known from the prior art, however, all have deficits in at least one category of surface properties, mechanical and polymer-physical properties.
Es bestand also nach wie vor die Aufgabe, Pfropfpolymerisate auf Basis von Ethylen- α-Olefin-Kautschuk bereitzustellen, die ein ausgewogenes Verhältnis von Oberflächeneigenschaften, mechanischen und polymerphysikalischen Eigenschaften aufweisen.It was therefore still the task to provide graft polymers based on ethylene-α-olefin rubber which have a balanced ratio of surface properties, mechanical and polymer-physical properties.
Es ist weiterhin bekannt, dass Blends, welche Pfropfpolymerisate vom AES-Typ ent- halten, witterungsbeständig sind, während deren mechanische Eigenschaften imIt is also known that blends which contain graft polymers of the AES type are weather-resistant, while their mechanical properties in the
Tieftemperaturbereich jedoch unbefriedigend sind. Bei Temperaturen unter 0°C wer- den diese Blends spröde und weisen unbefriedigende Zähigkeiten auf. Dadurch wird ein Einsatz dieser Formmassen bei tieferen Temperaturen behindert. Insbesondere die Kerbschlagzähigkeit von AES-Blends im Tieftemperaturbereich ist insbesondere im Vergleich zu Acrylnitril/Butadien/Styrol (ABS)-Blends schlecht.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. In particular, 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 betrifft die Herstellung von AES -Pfropfpolymerisaten und einem Copolymer, wobei das Copolymer aus 60 bis 76 Gew.-% eines aromatischen Monomers vom Vinyltyp und 40 bis 24 % eines aliphatischen Copolymers enthält. Aufgepfropft werden Vinylaromaten und/oder kernsubstituierte Vinylaromaten und Vinyl- cyanide und/oder (Meth)acrylsäure-(Cι-Cg)-alkylester. Diese thermoplastischen Co- polymere sollen neben den gewünschten guten Eigenschaften bezüglich Oberflächenglanz, Wetterfestigkeit und Gleiteigenschaften unter anderem eine gute Schlagfestigkeit aufweisen.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.
In JP-A 50 109 247 werden Polycarbonatblends mit AES, das 0,1 bis 10 Gew.-%JP-A 50 109 247 describes polycarbonate blends with AES which contain 0.1 to 10% by weight
Paraffϊnöl enthält, beschrieben. In der JP-A 58 098 354 werden Polycarbonatblends mit AES und 0,5 bis 20 Gew.-% Weichmachern für Vinylpolymere beschrieben. Es ist nicht bekannt, dass der Einsatz spezieller Additive, die sich gezielt in der Weichphase des Blends konzentrieren, bei Polycarbonat-AES-Blends zu einer deutlichen Verbesserung der Tieftemperatureigenschaften führt.Contains paraffin oil. 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.
Der Erfindung liegt daher auch die Aufgabe zugrunde, AES-Blends so zu modifizieren, dass sie unter Erhalt der Witterungsbeständigkeit im Tieftemperaturbereich ein verbessertes Eigenschaftsprofil, insbesondere auch verbesserte Kerbschlagzähig- keiten, aufweisen.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.
Es wurde nun überraschend gefunden, dass die oben genannten Aufgaben durch die erfindungsgemäßen AES -Pfropfpolymerisate beziehungsweise Formmassen enthaltend diese erfindungsgemäßen AES -Pfropfpolymerisate gelöst wird. Gegenstand der vorliegenden Erfindung sind Pfropfpolymerisate enthaltendIt has now surprisingly been found that the above-mentioned objects are achieved by the AES graft polymers according to the invention or molding compositions containing these AES graft polymers according to the invention. The present invention relates to graft polymers
a) eine kontinuierliche Phase aus polymerisierten vinylaromatischen Monomeren und efhylenisch ungesättigten Nitril-Monomeren unda) a continuous phase of polymerized vinyl aromatic monomers and efhylenically unsaturated nitrile monomers and
b) eine disperse Phase aus Ethylen-α-Olefin-Kautschuk, der mit vinylaromatischen Monomeren und ethylenisch ungesättigten Nitril-Monomeren bepfropft ist,b) a disperse phase composed of ethylene-α-olefin rubber which is grafted with vinyl aromatic monomers and ethylenically unsaturated nitrile monomers,
wobei die kontinuierliche Phase a) ein gewichtsmittleres Molekulargewicht Mw von größer 130.000, vorzugsweise größer 145.000, besonders bevorzugt größer 160.000 g/mol bis 275.000, bevorzugt bis 250.000 aufweist und die disperse Phase b) eine bepfropfte Kautschukphase ist, die eine gewichtsmittlere Teilchengröße Dw von kleiner 0,90 μm, vorzugsweise kleiner 0,80 μm, einen Pfropfgrad (gemessen durch Gelwertmessung in Aceton als Lösungsmittel) von mindestens 0,25 und höchstenswherein 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, and the disperse phase b) is a grafted rubber phase which has a weight-average particle size Dw of less 0.90 μm, preferably less than 0.80 μm, a degree of grafting (measured by measuring the gel value in acetone as solvent) of at least 0.25 and at most
0,65, bevorzugt mindestens 0,30 und höchstens 0,60, ein Verhältnis des Gelwertes gemessen in Tetrahydrofuran (THF) zu dem Gelwert gemessen in Aceton von kleiner als 0,1, vorzugsweise kleiner als 0,05 hat, und eine Glastemperatur (Tg, ermittelt durch Messung des komplexen Schubmoduls in Abhängigkeit von der Temperatur) der Kautschuk- bzw. Weichphase von kleiner als -50°C aufweist.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.
Geeignete vinylaromatische Monomere, die zusammen mit ethylenisch ungesättigten Nitril-Monomeren radikalisch polymerisieren und dadurch die kontinuierliche Phase (Matrixphase) a) der Formmassen bilden, sind Styrol, α-Methylstyrol, , p-Methyl- styrol, Divinylbenzol und/oder anderen Alkylstyrolen, vorzugsweise mit 2 bisSuitable 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, α-methylstyrene,, p-methylstyrene, divinylbenzene and / or other alkylstyrenes, preferably with 2 to
6 C-Atomen im Alkylrest. Weiterhin können in Mischung mit diesen kernsubstituierte Chlorstyrole eingesetzt werden.6 carbon atoms in the alkyl radical. Core-substituted chlorostyrenes can also be used in a mixture with these.
Besonders bevorzugte vinylaromatische Monomere sind Styrol, α-Methylstyrol, und/oder p-Methylstyrol. Ganz besonders bevorzugt sind Styrol, α-Methylstyrol sowie deren Mischungen. Geeignete ethylenisch ungesättigte Nitril-Monomere sind beispielsweise und bevorzugt Acrylnitril und Methacrylnitril sowie deren Mischungen, besonders bevorzugt Acrylnitril.Particularly preferred vinyl aromatic monomers are styrene, α-methylstyrene and / or p-methylstyrene. Styrene, α-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.
Das Verhältms von vinylaromatischen Monomeren zu ethylenisch ungesättigten Nitril-Monomeren beträgt bei den erfindungsgemäßen thermoplastischen Formmassen 60-90 Gew.-% zu 40-10 Gew.-% bezogen auf die Matrixphase a).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).
Weiterhin können bis zu 30 Gew.-%, bevorzugt bis zu 20 Gew.-% der Gesamt- monomermenge Acrylmonomere oder Maleinsäurederivate eingesetzt werden wie beispielsweise Methyl(meth)acrylat, Ethyl(meth)acrylat, tert.-Butyl(meth)acrylat, n- Butyl(meth)acrylat, Ester der Fumar-, Itaconsäure, Maleinsäureanhydrid, Maleinsäureester, N-substituierte Maleinimide wie vorteilhaft N-Cycohexyl- oder N-Phenyl- maleinimid, N-Alkyl-phenyl-maleinimd, weiter Acrylsäure, Methacrylsäure, Fumar- säure, Itaconsäure, oder deren Amide.It is also possible to use up to 30% by weight, preferably up to 20% by weight, of the total monomer amount of 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.
Als Pfropfgrundlage für die disperse Phase b) geeignete Ethylen-α-Olefin- Kautschuke enthalten in polymerisierter Form Ethylen, ein α-Olefin und optional ein nicht konjugiertes Dien.As a graft base for the disperse phase b), suitable ethylene-α-olefin rubbers contain, in polymerized form, ethylene, an α-olefin and optionally a non-conjugated diene.
Geeignete α-Olefϊne sind Propen, 1 -Buten, 1 -Hexen, 1-Octen und deren Mischungen. Bevorzugte α-Olefine sind Propen, 1 -Hexen und 1-Octen.Suitable α-olefins are propene, 1-butene, 1-hexene, 1-octene and mixtures thereof. Preferred α-olefins are propene, 1-hexene and 1-octene.
Als nicht konjugierte Diene, die der besseren Bepfropfbarkeit des Kautschuks dienen, können beispielsweise Norbornene wie Alkenylnorbornene und Alkylidennor- bornene, cyclische Diene wie Dicyclopentadien sowie aliphatische Diene wie Hexa- dien oder Octadien eingesetzt werden. Bevorzugte Diene sind Ethylidennorbornen, Dicyclopentadien, 1,4-Hexadien nd 1,6-Octadien. Das Verhältms von Ethylen zu α-Olefin beträgt 30:70 bis 70:30 Gew.-%, mit der Vorgabe, dass die Kautschuke völlig amorph oder überwiegend amorph sind. Es konnte gezeigt werden, dass teilkristalline Kautschuke deutlich schlechtere Ergebnisse ergeben. Der Gehalt an nicht konjugierten Dienen beträgt 0 bis 15 Gew.-%, vorzugsweise 0 bis 10 Gew.-%.Examples of 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 α-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.
Geeignete Kautschuke weisen eine Mooney- Viskosität ML (1+4) 125°C (ohne Vorbehandlung, DLN 53523; ASTM D1646) von 3 bis 50, bevorzugt 3 bis 30 auf.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.
Geeignete Ethylen-α-Olefin-Kautschuke können eine lineare oder verzweigte Struktur besitzen. Es ist auch möglich eine Mischung aus linearen und verzweigten Ethy- len-α-Olefin-Kautschuken zu verwenden.Suitable ethylene-α-olefin rubbers can have a linear or branched structure. It is also possible to use a mixture of linear and branched ethylene-α-olefin rubbers.
Der Kautschukgehalt der erfindungsgemäßen thermoplastischen Formmassen beträgt 10-70 Gew.-%, bevorzugt 15-50 Gew.-%, besonders bevorzugt 17-35 Gew.-%, ganz besonders bevorzugt 18-23 Gew.-%, bezogen auf die Formmassen.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.
Die erfindungsgemäßen Pfiopfpolymerisate haben einen Glanz bei einem Messwinkel von 20° von größer als 65, vorzugsweise 70 und einen Glanz bei einem Messwinkel von 60° von größer als 85, vorzugsweise 90, eine KerbschlagzähigkeitThe 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
(ak-Izod) von größer 20 vorzugsweise größer 25, besonders bevorzugt größer 30 kJ/m2 und einen Schmelzindex von kleiner 14, vorzugsweise von kleiner 12, besonders bevorzugt kleiner 10 g/10' (220°C/10 kg). Aufgrund des geringeren Anteils an Doppelbindungen der Ethylen-α-Olefin-Kautschuke besitzen die erfindungsgemäßen Pfropfpolymerisate eine gegenüber ABS-Pfropfpolymerisaten verbesserte Bewitterungsstabilität.(ak-Izod) of greater than 20, preferably greater than 25, particularly preferably greater than 30 kJ / m 2 and a melt index of less than 14, preferably less than 12, particularly preferably less than 10 g / 10 '(220 ° C / 10 kg). Because of the lower proportion of double bonds in the ethylene-α-olefin rubbers, the graft polymers according to the invention have improved weathering stability compared to ABS graft polymers.
Die erfindungsgemäßen kautschukmodifizierten thermoplastischen Pfropfpolymerisate werden durch radikalische Polymerisation vinylaromatischer Monomerer und ethylenisch ungesättigter Nitril-Monomerer in Gegenwart eines Eτhylen-α-Olefm-The rubber-modified 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-α-olefin.
Kautschuks i Gegenwart von Lösungsmitteln nach im Prinzip bekannten Verfahren der Masse- oder Lösungspolymerisation in vorzugsweise kontinuierlicher Fahrweise hergestellt.Rubbers in the presence of solvents by methods known in principle bulk or solution polymerization, preferably in a continuous procedure.
Für die radikalische Polymerisation in Lösungsmitteln kommen als Lösungsmittel aromatische Kohlenwasserstoffe wie Toluol, Ethylbenzol und Xylole und derenAromatic hydrocarbons such as toluene, ethylbenzene and xylenes and the like are used as solvents for radical polymerization in solvents
Mischungen in Frage. Bevorzugt sind Toluol und Xylole sowie deren Mischungen, besonders bevorzugt ist Toluol.Mixtures in question. Toluene and xylenes and mixtures thereof are preferred, and toluene is particularly preferred.
Die Polymerisation wird vorteilhaft durch Radikalstarter ausgelöst. Geeignete Initia- toren für die radikalische Polymerisation sind pfropfaktive, in Radikale zerfallendeThe polymerization is advantageously triggered by radical initiators. Suitable initiators for radical polymerization are graft-active radicals which disintegrate
Peroxide wie Peroxycarbonate, Peroxydicarbonate, Diacylperoxide, Perketale, oder Dialkylperoxide und/oder Azoverbindungen oder Mischungen hieraus. Beispiele sind Azodiisobuttersäuredinitril, Azoisobuttersäurealkylester, tert.-Butylperpivalat, tert- Butylperoctoat, tert.-Butylperbenzoat, tert.-Butylperneodekanoat, tert.-Butylper-(2- ethylhexyl)carbonat. Diese Initiatoren werden in Mengen von 0,005 bis 1 Gew.-% bezogen auf die Monomeren eingesetzt.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.
Das erfindungsgemäße Verfahren wird vorzugsweise kontinuierlich durchgeführt. Bei der kontinuierlichen Ausfuhrungsform kann man vorteilhaft die Kautschuk- lösung, bestehend aus Kautschuk, Lösungsmittel, Monomeren und ggf. Additiven,The process according to the invention is preferably carried out continuously. In the continuous embodiment, the rubber solution consisting of rubber, solvents, monomers and, if appropriate, additives can advantageously be used.
Monomere und Lösungsmitteln in einen kontinuierlich beschickten, durchmischten und gerührten Tankreaktor bei einem stationären, nach der Phaseninversion liegenden Monomerenumsatz in der ersten Stufe von über 30 % polymerisieren und die radikalisch ausgelöste Polymerisation in mindestens einer weiteren Stufe bis zu einem Monomerenumsatz von 70-99 % unter Durchmischen in einem oder mehreren weiter kontinuierlich betriebenen Rührkesseln in Kaskade fortfuhren. In den jeweilig nachgeschalteten Reaktor können neben dem Polymerisationssirup aus dem vorgeschalteten Reaktor auch zusätzlich Monomere, Lösungsmittel, Radikalstarter und weitere Additive, wie z.B. Stabilisatoren, dosiert werden. Vorzugsweise werden für die kontinuierliche Polymerisation zwei gerührte Tankreaktoren eingesetzt. Restmonomere und Lösungsmittel können nach herkömmlichen Techniken (z.B. in Wärmetauscherverdampfer, Entspannungsverdampfer, Strangverdampfer, Dünnfilmoder Dünnschichtverdampfer, Schneckenverdampfer, gerührte Mehrphasen- Verdampfer mit Knet- und Abstreifvorrichtungen) entfernt werden, wobei auch der Ein- satz von Treib- und Schleppmitteln, z.B. Wasserdampf oder Stickstoff, möglich ist, und in den Prozeß, d.h. zur Herstellung der Kautschuklösung und/oder in die Polymerisationsreaktoren, zurückgeführt werden. Bevorzugt werden Wärmetauscherverdampfer eingesetzt.Polymerize monomers and solvents in a continuously charged, mixed and stirred tank reactor with a stationary monomer conversion after phase inversion in the first stage of over 30% and the radical-triggered polymerization in at least one further stage up to a monomer conversion of 70-99% Continue mixing in one or more continuously operated stirred tanks in a cascade. In addition to the polymerization syrup from the upstream reactor, monomers, solvents, radical initiators and other additives, such as stabilizers, can also be metered into the respective downstream reactor. Two stirred tank reactors are preferably used for the continuous polymerization. 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.
Während der Polymerisation und vor oder während der Polymerisolierung kömienDuring polymerization and before or during polymer isolation
Additive, z.B. Stabilisatoren, Alterungsschutzmittel, Füllstoffe, Gleitmittel zugesetzt werden. Wesentlich und wichtig ist, dass auf die üblichen Molekulargewichtsregler wie Mercaptane, Olefine, z.B. tert.-Dodecylmercaptan, n-Dodecylmercaptan, Cyclo- hexen, Terpinolen, α-Methylstyrol-Dimer verzichtet wird, um ein ausreichend hohes Molekulargewicht bzw. einen ausreichend niedrigen Schmelzindex zu erzielen.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, α-methylstyrene dimer is dispensed with in order to achieve a sufficiently high molecular weight or a sufficiently low melt index.
Weiterhin ist es erforderlich, die Reaktionsbedingungen derart zu wählen, dass eine Vernetzung der Kautschukphase unterbleibt, um das erfindungsgemäße Verhältnis des Gelwertes gemessen in THF zu dem Gelwert gemessen in Aceton von kleiner als 0,1, vorzugsweise kleiner als 0,05 zu erhalten. Beispielsweise dürfen die üblichen peroxidischen oder schwefelhaltigen Vernetzer nicht zugegen sein.Furthermore, it is necessary to select the reaction conditions in such a way that the rubber phase does not crosslink in order to obtain the ratio according to the invention of the gel value measured in THF to the gel value measured in acetone of less than 0.1, preferably less than 0.05. For example, the usual peroxidic or sulfur-containing crosslinkers must not be present.
Zur besseren Durchmischung und Zerteilung der eingespeisten Kautschuklösung in den ersten Reaktor kann der Sirup bei kontinuierlicher Fahrweise im Kreis über durchmischende und scherende Organe gepumpt werden. Solche Loopreaktoren sind aus dem Stand der Technik bekannt und können bei der Einstellung der Teilchengröße des Kautschuks hilfreich sein. Möglich ist auch die Anordnung von Scherorganen zwischen zwei separaten Reaktoren, um Rückvermischung, die zu einer Verbreiterung der Teilchengrößeverteilung führt, zu vermeiden. Eine weitere Möglichkeit zur besseren Durchmischung und Zerteilung der Kautschukphase stellt der Ein- satz von Rührorganen dar, die besonders hohe Scherraten aufbringen können. Die mittlere Verweilzeit beträgt 1 bis 10 Stunden, bevorzugt 2 bis 8 Stunden. Die Polymerisationstemperatur beträgt 50 bis 180°C, bevorzugt 100 bis 160°C. Die Reaktionstemperatur im ersten Reaktor beträgt vorzugsweise 100 bis 130°C, besonders bevorzugt 110 bis 130°C. Die Reaktionstemperatur im zweiten Reaktor beträgt vorzugsweise 120 bis 160°C, besonders bevorzugt 130 bis 160°C.For better mixing and division of the rubber solution fed into the first reactor, 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.
Die erfindungsgemäßen Pfropfpolymerisate können durch Extrudieren, Spritzgießen, Kalandrieren, Hohlkörperblasen, Pressen und Sintern zu Formteilen thermoplastisch verarbeitet werden. Ein weiterer Gegenstand der vorliegenden Erfindung sind daher Formmassen enthaltend mindestens ein erfindungsgemäßes Pfropfpolymerisat.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.
Die erfindungsgemäßen Pfropfpolymerisate können in Zusammensetzungen mit mindestens einem Polymeren ausgewählt aus der Gruppe bestehend aus Polycarbonaten, Polyamiden, Polyalkylentherephthalten, Copolymerisaten enthaltend vinylaroma- tische Monomere und ethylenisch ungesättigten Nitril-Monomere eingesetzt werden.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.
Die erfindungsgemäßen Formmassen können insbesondere aromatische Polycarbo- nate und/oder aromatische Polyestercarbonate, enthalten. Diese sind literaturbekannt und nach literaturbekannten Verfahren herstellbar. Zur Herstellung aromatischer Polyestercarbonate siehe beispielsweise Schnell, "Chemistry and Physics of Poly- carbonates", Interscience Publishers, 1964 sowie die 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; zur Herstellung aromatischer Polyestercarbonate z. B. DE-A 3 077 934) oder WO 00/26275.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.
Die Herstellung aromatischer Polycarbonate kann erfolgen durch Umsetzung vonAromatic polycarbonates can be prepared by reacting
Diphenolen mit Kohlensäurehalogeniden, vorzugsweise Phosgen, und/oder mit aromatischen Dicarbonsäuredihalogeniden, vorzugsweise Benzoldicarbonsäuredihalo- geniden, nach dem Phasengrenzflächenverfahren, gegebenenfalls unter Verwendung von Kettenabbrechern, beispielsweise Monophenolen und gegebenenfalls unter Ver- Wendung von ttifunktionellen oder mehr als tiifunktionellen Verzweigern, beispielsweise Triphenolen oder Tetraphenolen. Diphenole zur Herstellung der aromatischen Polycarbonate und/oder aromatischen Polyestercarbonate sind vorzugsweise solche der Formel (I)Diphenols with carbonic acid halides, preferably phosgene, and / or with aromatic dicarboxylic acid dihalides, preferably benzenedicarboxylic acid dihalogenides, by the phase interface method, optionally using chain terminators, for example monophenols and optionally using tifunctional or more than tiifunctional branching agents or triphenols, for example triphenols. Diphenols for the preparation of the aromatic polycarbonates and / or aromatic polyester carbonates are preferably those of the formula (I)
wobeiin which
A eine Einfachbindung, C1-C5-Alkylen, C -C5-Alkyliden, C5-C6-Cycloalky- liden, -O-, -SO-, -CO-, -S-, -SO2-, C6-C12-Arylen, an das weitere aromatische gegebenenfalls Heteroatome enthaltende Ringe kondensiert sein können,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,
oder ein Rest der Formel (II) oder (TU)or a radical of the formula (II) or (TU)
FT FTFT FT
B jeweils C^C^Alkyl, vorzugsweise Methyl, Halogen, vorzugsweise Chlor und/oder Brom x jeweils unabhängig voneinander 0, 1 oder 2,B each C ^ C ^ alkyl, preferably methyl, halogen, preferably chlorine and / or bromine x each independently of the other 0, 1 or 2,
p 1 oder 0 sind, undp are 1 or 0, and
R5 und R6 für jedes X1 individuell wählbar, unabhängig voneinander Wasserstoff oder C^-Cg-Alkyl, vorzugsweise Wasserstoff, Methyl oder Ethyl,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,
X1 Kohlenstoff undX 1 carbon and
m eine ganze Zahl von 4 bis 7, bevorzugt 4 oder 5 bedeuten, mit der Maßgabe, dass an mindestens einem Atom X1, R5 und R6 gleichzeitig Alkyl sind.m 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.
Bevorzugte Diphenole sind Hydrochinon, Resorcin, Dihydroxydiphenole, Bis-(hy- droxyphenyι)-Cι-C5-alkane, Bis-(hydroxyphenyl)-C5-C6-cycloalkane, Bis-(hydroxy- phenyl)-ether, Bis-(hydroxyphenyl)-sulfoxide, Bis-(hydroxyphenyl)-ketone, Bis- (hydroxyphenyl)-sulfone und α,α-Bis-(hydroxyphenyl)-diisopropyl-benzole sowie deren kernbromierte und/oder kernchlorierte Derivate.Preferred diphenols are hydroquinone, resorcinol, dihydroxydiphenols, bis- (hydroxyphenyι) -Cι-C5-alkanes, bis- (hydroxyphenyl) -C5-C6-cycloalkanes, bis- (hydroxyphenyl) ethers, bis- (hydroxyphenyl) sulfoxides, bis (hydroxyphenyl) ketones, bis (hydroxyphenyl) sulfones and α, α-bis (hydroxyphenyl) diisopropyl benzenes and their core-brominated and / or core-chlorinated derivatives.
Besonders bevorzugte Diphenole sind 4,4'-Dihydroxydiphenyl, Bisphenol- A, 2,4-Particularly preferred diphenols are 4,4'-dihydroxydiphenyl, bisphenol-A, 2,4-
Bis(4-hydroxyphenyl)-2-mefhylbutan, 1 , 1 -Bis-(4-hydroxyphenyl)-cyclohexan, 1,1- Bis-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexan, 4,4'-Dihydroxydiphenylsulfid, 4,4'-Dihydroxydiphenyl-sulfon sowie deren di- und tetrabromierten oder chlorierten Derivate wie 2,2-Bis(3-Chlor-4-hydroxyphenyl)-propan, 2,2-Bis-(3,5-dichlor-4-hy- droxyphenyl)-propan oder 2,2-Bis-(3,5-dibrom-4-hydroxyphenyl)-propan. Insbesondere bevorzugt ist 2,2-Bis-(4-hydroxyphenyl)-propan (Bisphenol- A).Bis (4-hydroxyphenyl) -2-methylbutane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 4,4'- Dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfone and their di- and tetrabrominated or chlorinated derivatives such as 2,2-bis (3-chloro-4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro- 4-hydroxyphenyl) propane or 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane. 2,2-bis (4-hydroxyphenyl) propane (bisphenol-A) is particularly preferred.
Die Diphenole können einzeln oder als beliebige Mischungen eingesetzt werden. Die Diphenole sind literaturbekannt oder nach üteraturbekannten Verfahren erhältlich. Für die Herstellung der thermoplastischen, aromatischen Polycarbonate oder Polyestercarbonate geeignete Kettenabbrecher sind beispielsweise Phenol, p-Chlorphenol, p-tert.-Butylphenol oder 2,4,6-Tribromphenol, aber auch langkettige Alkylphenole wie 4-(l,3-Tetramethylbutyl)-phenol gemäß DE-A 2 842 005 oder Monoalkylphenol. Die Menge des Kettenabbrechers beträgt im allgemeinen 0,5 bis 10 mol-%, bezogen auf die Molsumme der jeweils eingesetzten Diphenole.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.
Die thermoplastischen, aromatischen Polycarbonate haben mittlere Gewichtsmittel- molekulargewichte (M ), gemessen durch Ultrazentrifuge oder Streulichtmessung, von 10.000 bis 200.000, vorzugsweise 15.000 bis 80.000. Es können auch Mischungen aus Polycarbonaten mit verschiedenen Molekulargewichten eingesetzt werden.The 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.
Die thermoplastischen, aromatischen Polycarbonate oder Polyestercarbonate können in bekannter Weise verzweigt sein, und zwar vorzugsweise durch den Einbau von 0,05 bis 2,0 mol-%, bezogen auf die Summe der eingesetzten Diphenole, an drei- funktionellen oder mehr als dreifunktionellen Verbindungen, beispielsweise solchen mit drei und mehr phenolischen Gruppen. Als Verzweigungsmittel können beispielsweise 3- oder mekrfuriktionelle Carbonsäurechloride, wie Trimesinsäuretrichlo- rid, Cyanursäuretrichlorid oder 3- oder merirfunktionelle Phenole wie Phloroglucin in Mengen von 0,01 bis 1,0 mol-% bezogen auf eingesetzte Diphenole verwendet werden. Phenolische Verzweigungsmittel können mit den Diphenolen vorgelegt, Säurechlorid-Verzweigungsmittel können zusammen mit den Säuredichloriden eingetragen werden.The 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. For example, 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.
Geeignet sind sowohl Homopolycarbonate als auch Copolycarbonate. BevorzugteBoth homopolycarbonates and copolycarbonates are suitable. preferred
Polycarbonate sind neben den Bisphenol-A-Homopolycarbonaten die Copolycarbonate von Bisphenol-A mit bis zu 15 mol-%, bezogen auf die Molsummen an Diphenolen, anderen als bevorzugt oder besonders bevorzugt genannten Diphenolen, insbesondere 2,2-Bis(3,5-dibrom-4-hydroxyphenyl)-propan. Aromatische Dicarbonsäuredihalogenide zur Herstellung von aromatischen Poly- estercarbonaten sind vorzugsweise die Disäuredichloride der Isophthalsäure, Tere- phthalsäure, Diphenylether-4,4'-dicarbonsäure und der Naphthalin-2,6-dicarbonsäure.In addition to the bisphenol A homopolycarbonates, 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.
Besonders bevorzugt sind Gemische der Disäuredichloride der Isophthalsäure und der Terephfhalsäure im Verhältnis zwischen 1:20 und 20:1.Mixtures of the diacid dichlorides of isophthalic acid and terephthalic acid in a ratio between 1:20 and 20: 1 are particularly preferred.
Bei der Herstellung von Polyestercarbonaten wird zusätzlich ein Kohlensäurehalo- genid, vorzugsweise Phosgen, als bifunktionelles Säurederivat mitverwendet.In the production of polyester carbonates, a carbonic acid halide, preferably phosgene, is additionally used as the bifunctional acid derivative.
Die aromatischen Polyestercarbonate können auch aromatische Hydroxycarbon- säuren eingebaut enthalten.The aromatic polyester carbonates can also contain built-in aromatic hydroxycarboxylic acids.
In den thermoplastischen, aromatischen Polyestercarbonaten kann der Anteil an Car- bonatstraktureinheiten beliebig variieren. Vorzugsweise 'beträgt der Anteil an Carbo- natgruppen bis zu 100 mol-%, insbesondere bis zu 80 mol-%, besonders bevorzugt bis zu 50 mol-%, bezogen auf die Summe an Estergruppen und Carbonatgruppen. Sowohl der Ester- als auch der Carbonatanteil der aromatischen Polyestercarbonate kann in Form von Blöcken oder statistisch verteilt im Polykondensat vorliegen.The proportion of carbonate fracture units in the thermoplastic, aromatic polyester carbonates can vary as desired. Preferably, '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 Estergruppen 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.
Die relative Lösungsviskosität (ηreι) der aromatischen Polycarbonate und Polyestercarbonate liegt im Bereich 1,18 bis 1,4, vorzugsweise 1,20 bis 1,32, gemessen an Lösungen von 0,5 g Polycarbonat oder Polyestercarbonat in 100 ml Methylenchlorid- Lösung bei 25°C.The relative solution viscosity (η re ι) 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.
Die thermoplastischen, aromatischen Polycarbonate und Polyestercarbonate können allein oder im beliebigen Gemisch eingesetzt werden.The thermoplastic, aromatic polycarbonates and polyester carbonates can be used alone or in any mixture.
Die erfindungsgemäßen Formmassen können weiterlrin auch Polyalkylenterephtha- late, wie sie beispielsweise in WO 00/29 476 beschrieben sind, enthalten. Bevorzugt sindPolyethylen- oder Polybutylenterephthalate oder Mischungen hieraus. Die erfindungsgemäßen Formmassen können weiterhin auch kautschukfreie Copolymerisate enthalten. Als kautschukfreie Copolymerisate werden vorzugsweise Copolymerisate des Styrols und Acrylnitrils im Gewichtsverhältnis 95:5 bis 50:50 verwendet, wobei Styrol und/oder Acrylnitril ganz oder teilweise durch α-Mefhyl- styrol, Methylmethacrylat oder N-Phenylmaleinimid ersetzt werden kann.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 α-methylstyrene, methyl methacrylate or N-phenylmaleimide.
Besonders bevorzugt sind solche Copolymerisate, deren Acrylmtril-Anteil weniger als 30 Gew.-% beträgt.Copolymers whose acrylic content is less than 30% by weight are particularly preferred.
Die Copolymerisate besitzen vorzugsweise mittlere Molekulargewichte Mw von 20 000 bis 200 000 bzw. Grenzviskositäten [η] von 20 bis 110 ml/g (gemessen in Di- methylformamid bei 25°C).The copolymers preferably have average molecular weights M w of 20,000 to 200,000 or intrinsic viscosities [η] of 20 to 110 ml / g (measured in dimethylformamide at 25 ° C.).
Einzelheiten zur Herstellung dieser Harze sind beispielsweise in DE-A 2420 358 und DE-A 27 24 360 beschrieben. Durch Masse- bzw. Lösungspolymerisation hergestellte Vinylharze haben sich besonders bewährt. Die Copolymerisate können allein oder in beliebiger Mischung zugesetzt werden.Details of the production of these resins are described, for example, in DE-A 2420 358 and DE-A 27 24 360. Vinyl resins produced by bulk or solution polymerization have proven particularly useful. The copolymers can be added alone or in any mixture.
Die erfindungsgemäßen Formmassen enthalten in einer bevorzugten Ausfuhrungsform 10 bis 80 Gew.-% , vorzugsweise 20-70 Gew.-% , besonders bevorzugt 25 bis 60 Gew.-% des erfindungsgemäßen Pfropfpolymerisats und 20 bis 90 Gew.-%, vorzugsweise 30-80 Gew.-% , besonders bevorzugt 40 bis 75 Gew.-% Polycarbonat, bezogen jeweils auf die Summe Pfropfpolymerisat und Polycarbonat.In a preferred embodiment, 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.
Sofern kautschukfreie Copolymerisate eingesetzt werden, beträgt ihr Anteil bis 50 Gew.-% , vorzugsweise bis 30 Gew.-% , besonders bevorzugt bis 20 Gew.-%, bezogen auf die Summe Pfropfpolymerisat, Polycarbonat und kautschukfreies Copolyrnerisat. Die erfindungsgemäßen Formmassen können weiterhin für Blends sowie aromatische Polycarbonate bekannte Zusätze wie wenigstens eines der üblichen Additive, wie Gleit- und Entformungsmittel, beispielsweise Pentaerythrittetrastearat, Nukleier- mittel, Flammschutzmittel, Antistatika, Stabilisatoren, Füll- und Verstärkungsstoffe sowie Farbstoffe und Pigmente sowie elektrisch leitfähige Additive, z.B. Polyanilin oder Nanotubes, enthalten.If rubber-free copolymers are used, their proportion is up to 50% by weight, preferably up to 30% by weight, particularly preferably up to 20% by weight, based on the total of graft polymer, polycarbonate and rubber-free copolymer. 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.
Phosphorhaltige Flammschutzmittel im erfindungsgemäßen Sinne sind besonders bevorzugt ausgewählt aus den Gruppen der Mono- und oligomeren Phosphor- und Phosphonsäureester, Phosphonatamine und Phosphazene, wobei auch Mischungen von mehreren Komponenten ausgewählt aus einer oder verschiedenen dieser Gruppen als Flammschutzmittel zum Einsatz kommen können. Auch andere hier nicht speziell erwähnte halogenfreie Phosphorverbindungen können alleine oder in beliebiger Kombination mit anderen halogenfreien Phosphorverbindungen eingesetzt werden.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.
Die gefüllten bzw. verstärkten Formmassen können bis zu 60 Gew.-%, vorzugsweise 5 bis 40 Gew.-%, bezogen auf die gefüllte bzw. verstärkte Formmasse, Füll- und/oder Verstärkungsstoffe enthalten. Bevorzugte Verstärkungsstoffe sind Glasfasern. Bevor- zugte Füllstoffe, die auch verstärkend wirken können, sind Glaskugeln, Glimmer,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,
Silikate, Quarz, Talkum, Titandioxid, Wollastonit.Silicates, quartz, talc, titanium dioxide, wollastonite.
Die erfindungsgemäßen Formmassen können bis zu 35 Gew.-%, bezogen auf die Zusammensetzung, eines weiteren, gegebenenfalls synergistisch wirkenden Flamm- Schutzmittels enthalten. Beispielhaft werden als weitere Flammschut-zmittel organische Halogenverbindungen wie Decabrombisphenylether, Tetrabrombisphenol, anorganische Halogenverbindungen wie Ammoniumbromid, Stickstoffverbindungen wie Melamin genannt.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.
Die erfindungsgemäßen Zusammensetzungen können hergestellt werden, indem man die Bestandteile in bekannter Weise vermischt und bei erhöhten Temperaturen, vorzugsweise bei 200 bis 350°C, in den üblichen Vorrichtungen, wie Innenknetern, Extrudern oder Doppelwellenschnecken schmelzkompoundiert oder schmelzextru- diert. Die einzelnen Komponenten können nacheinander oder gleichzeitig zugemischt werden. Die erfindungsgemäßen Formkörper können durch Extrusion oder Spritz- guss hergestellt werden.The 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.
Erfindungsgemäße Formkörper sind beispielsweise Anwendungen im Außeneinsatz, z.B. Fensterteile, Klimaanlagen, Wassertanks, Automobilaußenteile, Gartengeräte, Gehäuseteile für Haushaltsgeräte, wie Saftpressen, Kaffeemaschinen, Mixer, für Büromaschinen, wie Monitore, Drucker, Kopierer oder Abdeckplatten für den Bausektor und Kfz-Teile. Sie sind außerdem auf dem Gebiet der Elekfrotechnik einsetzbar, weil sie sehr gute elektrische Eigenschaften haben. Die erfindungsgemäßen Formmassen sind ferner geeignet zur Herstellung von Formkörpern durch Tiefziehen aus zuvor hergestellten Platten oder Folien.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.
Weitere Anwendungen sind möglichFurther applications are possible
als Dateitechnikgeräte: Telekommunikationsgeräte wie Telefongeräte und Telefaxe, Computer, Drucker, Scanner, Plotter, Monitor, Tastatur, Schreibmaschine, Diktier- gerate, usw.,as file technology devices: telecommunication devices such as telephone devices and faxes, computers, printers, scanners, plotters, monitors, keyboards, typewriters, dictation machines, etc.,
als Elektrogeräte: Netzteile, Ladegeräte, Kleintransformatoren für Computer und Unterhaltungselektronik, Niederspannungstransformatoren, usw.,as electrical devices: power supplies, chargers, small transformers for computers and consumer electronics, low-voltage transformers, etc.,
als Gartengeräte: Gartenmöbel, Rasenmähergehäuse, Rohre und Gehäuse für Gartenbewässerung, Gartenhäuser, Laubsauger, Schredder, Häcksler, Spritzgeräte usw.,as garden tools: garden furniture, lawn mower housings, pipes and housings for garden irrigation, garden houses, leaf vacuums, shredders, shredders, sprayers etc.,
im Möbelbereich: Arbeitsplatten, Möbellaminate, Rolladenelemente, Büromöbel, Tische, Stühle, Sessel, Schränke, Regale, Türelemente, Fensterelemente, Bettkästen usw., als Spor Spielgeräte: Spielfahrzeuge, Sitzflächen, Pedale, Sportgeräte, Fahrräder, Tischtennisplatte, Heimtrainer, Golf-Caddys, Snowboards,. Bootsaußenteile, Campingartikel, Strandkörbe usw.,in the furniture sector: worktops, furniture laminates, roller shutter elements, office furniture, tables, chairs, armchairs, cupboards, shelves, door elements, window elements, bed frames etc., as Spor play equipment: toy vehicles, seats, pedals, sports equipment, bicycles, table tennis, exercise bikes, golf caddies, snowboards ,. Boat exterior parts, camping articles, beach chairs etc.,
im Bausektor innen/außen: Hausverkleidung, Profilleiste, Rohre, Kabel, Rolladenelemente, Briefkästen, Lampengehäuse, Dachziegel, Fliesen, Trennwände, Kabelkanäle, Fußbodenleiste, Steckdosen usw.,in the construction sector inside / outside: house cladding, profile strips, pipes, cables, roller shutter elements, letter boxes, lamp housings, roof tiles, tiles, partitions, cable ducts, floor strips, sockets etc.,
im Bereich der Kfz/S c enenfahrzeuge: Wand-, Decken- Verkleidungen, Sitzschalen, Sitze, Bänke, Tische, Gepäckablagen, Radkappen, Heckspoiler, Kotflügel, Heckklappen, Motorhauben, Seitenteile usw.. in the field of motor vehicles / cen t vehicles: wall, ceiling cladding, seat shells, seats, benches, tables, luggage racks, hubcaps, rear spoilers, fenders, tailgates, bonnets, side panels, etc.
BeispieleExamples
Messmethodenmeasurement methods
Die Umsatzbestimmung erfolgte durch Feststoffbestimmung durch Eindampfen beiThe sales were determined by determining the solids by evaporation
200°C. Der Kautschukgehalt im Endprodukt wurde aus der Massenbilanz bestimmt. Gelgehalte wurden in Aceton als Dispergiermedium bestimmt. Die Molekulargewichte des löslichen Anteils wurde durch GPC mit THF oder Methylenchlorid als Lösungsmittel gegenüber Polystyrolstandard bestimmt. Die Teilchengröße und -Verteilung der Kautschukpartikel wurde durch Zonalzentrifugation gemessen; es wird das Gewichtsmittel (Dw), das Flächenmittel (Da) und das Zahlmittel (Dn) angegeben. Die Kerbschlagzähigkeit (aκ-Izod) wurde bei 23°C nach ISO 180/1A, der Schmelzvolumenindex (MFI 220°C/10 kg) nach DIN 53735 gemessen. Die Untersuchung der Phasenstruktur erfolgte durch Messung des komplexen Schubmoduls in Abhängigkeit von der Temperatur (dynamisch-mechanische Messung der Schubmodulcharakteristik G*(T)) an den Probekörpern bei einer Frequenz von ca. 1 Hz im Temperaturbereich von -150 bis 200°C mit dem RDA II der Fa. Rheometrics. Es wurde die Glastemperatur (Tg) der Weichphase und der Matrix bestimmt. Weiterhin wurde der korrigierte Schubmodul bei 23 °C (G'k0rr.(RT)) bestimmt. Die Messwerte wurden an spritzgegossenen Formkörpern bei einer Massetemperatur von 240°C und einer Werkzeugtemperatur von 70°C gemessen. Die Bestimmung des Glanzes wurde an 60*75*1 mm-Prüfkörpern mit einem Messgerät BYK-Gardner bei 20 und 60° nach DLN 67530 durchgeführt. Beispiele 1-5200 ° C. 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 (aκ-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. Furthermore, 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
Herstellung der erfindungs gemäßen PfropfpolymerisatePreparation of the graft polymers according to the invention
Die Pfropfpolymerisate wurden durch kontinuierliche Lösungspolymerisation in zwei hintereinandergeschalteten Reaktoren mit Wendelrührern hergestellt. Die Eindampfung der Polymerlösung erfolgte koninuierlich in einem Einwellen-Extruder bei einem Vakuum von ca. 100 mbar. In den 1. Reaktor wurde die Kautschuklösung, Monomere und eine Initiatorlösung, in den 2. Reaktor eine Initiatorlösung dosiert. In die Transferleitung vom 2. Reaktor zur Eindampfungsapparatur wurde ggf. eineThe 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
Stabilisatorlösung dosiert.Stabilizer solution dosed.
In den Beispielen 1 und 2 wurde als Kautschuk ein amorphes EPDM (Buna EP G 3850 der Bayer AG) mit einer Mooney- Viskosität ML (1+4) 125°C von 28, einem Ethylidennorbornen-Gehalt von 8 % und einem Ethylen-Gehalt von 48 % eingesetzt.In Examples 1 and 2, an amorphous EPDM (Buna EP G 3850 from Bayer AG) with a Mooney viscosity ML (1 + 4) of 125 ° C. of 28, an ethylidene norbornene content of 8% and an ethylene content was used as the rubber used by 48%.
In den Beispielen 3 und 4 wurde als Kautschuk ein weitestgehend amorphes Ethylen- 1-Octen (Engage 8842 von DuPont Dow Elastomers) mit einer Mooney- Viskosität ML (1+4) 121 °C von 26 und einem Ethylen-Gehalt von 45 % eingesetzt.In Examples 3 and 4, a largely amorphous ethylene-1-octene (Engage 8842 from DuPont Dow Elastomers) with a Mooney viscosity ML (1 + 4) of 121 ° C. of 26 and an ethylene content of 45% was used as the rubber ,
In Beispiel 5 wurde der Stabilisator in den 2. Reaktor dosiert. Die Eindampfung erfolgte kontinuierlich über einen zwei hintereinander geschaltete Wärmetauscher. Das Vakuum in der 1. Eindampfstufe betrug 200 mbar und in der 2. Eindampfstufe 5 mbar.In example 5, 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.
Nergleichsbeispiele 1-3Comparative examples 1-3
Im Vergleichsbeispiel 1 wurde als Kautschuk ein teilkristallines EPDM (Bezeichnung EPDM 2) mit einem Mooney- Viskosität ML (1+4) 125°C von 20, einem EΝB- Gehalt von 4,2 % und einem Ethylen-Gehalt von 70 % eingesetzt. In den Vergleichsbeispielen 2 und 3 wurde als Kautschuk Buna EP G 3850 eingesetzt.In Comparative Example 1, a partially crystalline EPDM (name EPDM 2) with a Mooney viscosity ML (1 + 4) 125 ° C. of 20, an EΝB 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.
Die Zusammensetzungen der Rezepturen, Ergebnisse der Polymerisation und Charakterisierung der Formmassen sind in den nachfolgenden Tabellen 1 bis 3 zusammengefasst; alle Mengenangaben erfolgen in [Tle.], Durchflüsse in [Tle./h]. The compositions of the formulations, results of the polymerization and characterization of the molding compositions are summarized in Tables 1 to 3 below; all quantities are given in [Tle.], flows in [Tle./h].
Tabelle 1; Mengenangaben und DosierströmeTable 1; Quantities and dosing flows
t ot o
Tabelle 1 (Fortsetzung)Table 1 (continued)
Is-iIs-i
Tabelle 2: ReaktionsbedingungenTable 2: Reaction conditions
tt
Tabelle 3: EigenschaftenTable 3: Properties
t t
Beispiele zur Herstellung von Blends:Examples for the production of blends:
Es wurden PC /AES-Blends der folgenden Zusammensetzung als Basismaterial zur Durchführung von Prüfungen hergestellt:PC / AES blends of the following composition were produced as the base material for carrying out tests:
Das Mischen der Komponenten erfolgt auf einem 3-1-Innenkneter. Die Formkörper werden auf einer Spritzgießmaschine Typ Arburg 270 E bei 260°C hergestellt.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.
Die erfindungsgemäßen Blends 6 bis 10 und die Vergleichsbeispiele 6 bis 8 wurden nach folgender Rezeptur hergestellt:Blends 6 to 10 according to the invention and comparative examples 6 to 8 were produced according to the following recipe:
58 Gew.-Teile Polycarbonat (Macrolon® 2600) 0 bzw. 3 (Bsp. 6) Gew.-Teile StyiOlacrylnitril (SAN M 60) 42 bzw. 41 (Bsp. 6) Gew.-Teile erfindungsgemäßes AES-Blend 0,9 Gew.-Teile übliche Additive, wie z. B.Entformungsmittel, Antioxidantien58 parts by weight of polycarbonate (Macrolon® 2600) 0 or 3 (Example 6) parts by weight of StyiOlacrylonitrile (SAN M 60) 42 or 41 (Example 6) parts by weight of the AES blend according to the invention 0.9 Parts by weight of conventional additives, such as. B. mold release agents, antioxidants
Die Vergleichsbeispiele 4 (9 % Kautschukgehalt) und 5 (8 % Kautschukgehalt) wurden nach folgender Rezeptur hergestellt:Comparative Examples 4 (9% rubber content) and 5 (8% rubber content) were produced according to the following recipe:
58 Gew.-Teile Polycarbonat (Macrolon® 2600) 58 parts by weight of polycarbonate (Macrolon® 2600)
30,5 bzw. 29,1 Gew.-Teile Styrolacrylnitril (SAN M 60) 30.5 or 29.1 parts by weight of styrene acrylonitrile (SAN M 60)
Bestimmung des E-Moduls erfolgte nach ISO 527 mit 1 mm/min. Die Schmelzvolumenfließrate (MVR) wurde nach ISO 1133 bei 260°C und 5kg Auflagegewicht bestimmt.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.
In Tabelle 4 sind die Prüfergebnisse für die Blends wiedergegeben. Diese Ergebnisse zeigen eine deutliche Senkung der kritischen Temperatur (Zäh/Sprödübergang), ohne mechanische Eigenschaften wie die Kerbschlagzähigkeit zu beeinträchtigen. Dies ist ein eindeutiges Maß für die gesteigerte Effizienz der erfindungsgemäßen Formmassen gegenüber dem Stand der Technik, wie in den beiden Vergleichspielen auf Basis kommerziell erhältlicher AES Pfroppolymerisate ersichtlich. 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.

Claims

Patentansprüche claims
1. Pfropfpolymerisate enthaltend1. Containing graft polymers
a) eine kontinuierliche Phase aus polymerisierten vinylaromatischen Monomeren und ethylenisch ungesättigten Nitril-Monomeren unda) a continuous phase of polymerized vinyl aromatic monomers and ethylenically unsaturated nitrile monomers and
b) eine disperse Phase aus Ethylen-α-Olefin-Kautschuk, der mit vinylaromatischen Monomeren und ethylenisch ungesättigten Nitril-Monomeren be- pfropft ist,b) a disperse phase composed of ethylene-α-olefin rubber, which is grafted with vinyl aromatic monomers and ethylenically unsaturated nitrile monomers,
wobei die kontinuierliche Phase a) ein gewichtsmittleres Molekulargewicht Mw von größer 130.000 bis 275.000 g/mol aufweist und die disperse Phase b) eine bepfropfte Kautschukphase ist, die eine gewichtsmittlere Teilchengröße Dw von kleiner 0,90 μm, einen Pfropfgrad (gemessen durch Gelwertmessung in Aceton als Lösungsmittel) von mindestens 0,25 und höchstens 0,65, ein Verhältnis des Gelwertes gemessen in THF zu dem Gelwert gemessen in Aceton von kleiner als 0,1 hat und eine Glastemperatur (Tg, ermittelt durch Messung des komplexen Schubmoduls in Abhängigkeit von der Temperatur) der Kautschuk- bzw. Weichphase von kleiner als -50°C aufweist.wherein the continuous phase a) has a weight-average molecular weight Mw of greater than 130,000 to 275,000 g / mol and the disperse phase b) is a grafted rubber phase which has a weight-average particle size Dw of less than 0.90 μm, a degree of grafting (measured by measuring the gel value in acetone as solvent) of at least 0.25 and at most 0.65, has a ratio of the gel value measured in THF to the gel value measured in acetone of less than 0.1 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.
2. Pfropfpolymerisate gemäß Anspruch 1, wobei die vinylaromatischen Monomere mindestens eines ausgewählt aus Styrol, α-Methylstyrol, p-Methylstyrol, Divinylbenzol, anderen Alkylstyrolen mit 2 bis 6 C-Atomen im Alkylrest und kernsubstituierten Chlorstyrolen sind.2. Graft polymers according to claim 1, wherein the vinyl aromatic monomers are at least one selected from styrene, α-methylstyrene, p-methylstyrene, divinylbenzene, other alkylstyrenes having 2 to 6 carbon atoms in the alkyl radical and nucleus-substituted chlorostyrenes.
3. Pfropfpolymerisate gemäß Anspruch 1, wobei die ethylenisch ungesättigten Nitril-Monomeren ausgewählt sind aus Acrylnitril und Methacrylnitril sowie derenMischungen. Graft polymers according to claim 1, wherein the ethylenically unsaturated nitrile monomers are selected from acrylonitrile and methacrylonitrile and mixtures thereof.
4. Pfropfpolymerisate gemäß Anspruch 1, wobei der Ethylen-α-Olefin-Kau- tschuk in polymerisierter Form Ethylen und ein α-Olefin ausgewählt aus Propen, 1 -Buten, 1 -Hexen, 1-Octen und deren Mischungen enthält.4. Graft polymers according to claim 1, wherein the ethylene-α-olefin rubber contains in polymerized form ethylene and an α-olefin selected from propene, 1-butene, 1-hexene, 1-octene and mixtures thereof.
5. Pfropfpolymerisate gemäß Anspruch 1, wobei der Ethylen-α-Olefin-Kau- tschuk in polymerisierter Form Ethylen, ein α-Olefin ausgewählt aus Propen, 1 -Buten, 1 -Hexen, 1-Octen und deren Mischungen und zusätzlich mindestens ein nicht konjugiertes Dien enthält.5. Graft polymers according to claim 1, wherein the ethylene-α-olefin rubber in polymerized form ethylene, an α-olefin selected from propene, 1-butene, 1-hexene, 1-octene and mixtures thereof and additionally at least one contains conjugated diene.
6. Verfahren zur Herstellung der Formmassen gemäß Anspruch 1, worin6. A method for producing the molding compositions according to claim 1, wherein
Monomere, Lösungsmittel sowie eine Kautschuklösung, bestehend aus Ethy- len-α-Olefin-Kautschuk, Lösungsmittel, Monomeren und ggf. Additiven in einem kontinuierlich beschickten, durchmischten und gerührten Tankreaktor bei einem stationären, nach der Phaseninversion liegenden Monomeren- umsatz in der ersten Stufe von über 30 % radikalisch polymerisiert werden und die Polymerisation in mindestens einer weiteren Stufe bis zu einem Monomerenumsatz von 70-99 % unter Durchmischen in einem oder mehreren weiter kontinuierlich betriebenen Rührkesseln in Kaskade fortgeführt wird, dadurch gekennzeichnet, dass keine Molekulargewichtsregler zugesetzt wer- den.Monomers, solvents and a rubber solution consisting of ethylene-α-olefin rubber, solvents, monomers and possibly additives in a continuously charged, mixed and stirred tank reactor in a stationary monomer conversion after the phase inversion in the first stage of over 30% are polymerized by free radicals and the polymerization is continued in a cascade in at least one further stage up to a monomer conversion of 70-99% with mixing in one or more continuously operated stirred kettles, characterized in that no molecular weight regulators are added.
7. Verfahren gemäß Anspruch 6, wobei die Verweilzeit 1 bis 10 Stunden und die Reaktionstemperatur im ersten Reaktor 100 bis 130°C beträgt.7. The method according to claim 6, wherein the residence time is 1 to 10 hours and the reaction temperature in the first reactor is 100 to 130 ° C.
8. Formassen enthaltend mindestens ein Pfropfpolymerisat gemäß Anspruch 1.8. Molding compositions containing at least one graft polymer according to claim 1.
9. Formmassen enthaltend mindestens ein Pfropfpolymerisat gemäß Anspruch lund mindestens ein Polymer ausgewählt aus der Gruppe bestehend aus Poly- carbonaten, Polyamiden, Polyalkylentherephthalten, Copolymerisaten enthal- tend vinylaromatische Monomere und ethylenisch ungesättigten Nitril-9. Molding compositions comprising at least one graft polymer according to claim 1 and at least one polymer selected from the group consisting of polycarbonates, polyamides, polyalkylene terephthalates, copolymers containing vinyl aromatic monomers and ethylenically unsaturated nitrile
Monomere. Monomers.
10. Formmassen enthaltend 10 bis 80 Gew.-% mindestens ein Pfropfpolymerisat gemäß Anspruch 1 und 20 bis 90 Gew.-% Polycarbonat, bezogen jeweils auf die Summe Pfropfpolymerisat und Polycarbonat.10. Molding compositions containing 10 to 80 wt .-% at least one graft polymer according to claim 1 and 20 to 90 wt .-% polycarbonate, based in each case on the sum of graft polymer and polycarbonate.
11. Verwendung von Formmassen gemäß Anspruch 1 oder von Zusammensetzungen gemäß Anspruch 8 für die Herstellung von Formteilen.11. Use of molding compositions according to claim 1 or of compositions according to claim 8 for the production of moldings.
12. Formteile erhältlich aus Formmassen gemäß Anspruch 1 oder Zusammensetzungen gemäß Anspruch 8. 12. Moldings obtainable from molding compositions according to claim 1 or compositions according to claim 8.
EP03789156A 2002-12-19 2003-12-06 Graft polymers based on ethylene-alpha-olefin rubbers and method for the production thereof Withdrawn EP1576019A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10259500A DE10259500A1 (en) 2002-12-19 2002-12-19 Graft polymers based on ethylene-α-olefin rubbers and process for their preparation
DE10259500 2002-12-19
PCT/EP2003/013835 WO2004056891A1 (en) 2002-12-19 2003-12-06 GRAFT POLYMERS BASED ON ETHYLENE-α-OLEFIN RUBBERS AND METHOD FOR THE PRODUCTION THEREOF

Publications (1)

Publication Number Publication Date
EP1576019A1 true EP1576019A1 (en) 2005-09-21

Family

ID=32403962

Family Applications (1)

Application Number Title Priority Date Filing Date
EP03789156A Withdrawn EP1576019A1 (en) 2002-12-19 2003-12-06 Graft polymers based on ethylene-alpha-olefin rubbers and method for the production thereof

Country Status (8)

Country Link
US (1) US7060751B2 (en)
EP (1) EP1576019A1 (en)
JP (1) JP2006510764A (en)
CN (1) CN100448903C (en)
AU (1) AU2003293785A1 (en)
DE (1) DE10259500A1 (en)
TW (1) TWI275599B (en)
WO (1) WO2004056891A1 (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6146890B2 (en) * 2010-08-27 2017-06-14 テクノポリマー株式会社 Contact parts made of thermoplastic resin composition with reduced squeaking noise
CN102898759B (en) * 2012-09-27 2015-05-13 上海锦湖日丽塑料有限公司 Acrylonitrile-ethylene-styrene (AES) resin composition and preparation method thereof
CN105008420B (en) * 2013-02-15 2017-05-24 Umg Abs株式会社 Graft copolymer, thermoplastic resin composition, and moulded article of said resin composition
JP6087330B2 (en) * 2014-09-24 2017-03-01 テクノポリマー株式会社 Thermoplastic resin composition and molded product with reduced squeaking noise

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 (en) 1974-02-04 1975-08-28 Sumitomo Chemical Co NETSUKASOSEIJUSHISOSEIBUTSU
DE2616375A1 (en) * 1976-04-14 1977-10-27 Bayer Ag Tough, ageing resistant thermoplastic materials - consisting of vinyl chloride (co) polymer, and graft copolymer of styrene acrylonitrile on EPDM elastomer
CH606243A5 (en) * 1975-07-30 1978-10-31 Bayer Ag
JPS5598214A (en) * 1979-01-19 1980-07-26 Japan Synthetic Rubber Co Ltd Production of rubber-modified thermoplastic resin
JPS5918408B2 (en) 1979-10-01 1984-04-27 ジェイエスアール株式会社 Continuous production method of rubber-modified thermoplastic resin
DE3047295A1 (en) 1980-12-16 1982-07-29 Basf Ag, 6700 Ludwigshafen METHOD FOR THE CONTINUOUS PRODUCTION OF AGING-RESISTANT AES POLYMERISATES
JPS5898354A (en) 1981-12-07 1983-06-11 Sumitomo Naugatuck Co Ltd Thermoplastic resin composition
JPS58208307A (en) 1982-05-29 1983-12-05 Japan Synthetic Rubber Co Ltd Production of rubber-modified thermoplastic resin
US4485212A (en) * 1983-05-27 1984-11-27 Uniroyal, Inc. Impact resistant blend of polybutylene terephthalate resin and OSA graft copolymer
JPS62501156A (en) 1985-05-06 1987-05-07 ザ・ダウ・ケミカル・カンパニ− Method for manufacturing reinforced weather-resistant thermoplastics
US4656225A (en) * 1985-12-23 1987-04-07 General Electric Company Polycarbonate resin blends exhibiting improved resistance to stress crazing and cracking
IT1218559B (en) * 1987-04-07 1990-04-19 Montedipe Spa PROCESS FOR THE SOLUTION AND CONTINUOUS PRODUCTION OF STYRENIC THERMOPLASTIC RESINS
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 (en) * 1990-07-12 1994-12-12 Montedipe Srl THERMOPLASTIC COMPOSITIONS BASED ON A SCRATCHED AROMATIC VINYL COPOLYMER AND A POLYAMIDE
JP3147392B2 (en) 1991-03-04 2001-03-19 宇部サイコン株式会社 Thermoplastic resin composition
WO1993020142A1 (en) * 1992-03-31 1993-10-14 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 *

Also Published As

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

Similar Documents

Publication Publication Date Title
EP0315868B1 (en) Use of redox graft polymers for improving the resistance against petrol of thermoplastic, aromatic polycarbonate and/or polyester carbonate moulding compositions
DE69516552T2 (en) Impact-resistant copolycarbonate mixture
US5290859A (en) Thermoplastic molding materials based on polycarbonates, styrene/acrylonitrile polymers and polyolefins
EP0158931B1 (en) Thermoplastic moulding compositions based on polycarbonate-graft polymer mixtures
EP2125952B1 (en) Impact resistant-modified polycarbonate compositions
DE69920200T2 (en) COMPATIBILIZED ABS POLYCARBONATE MOLD
US4868235A (en) Thermoplastic molding materials
EP2556114B1 (en) Flame-protected polycarbonate compositions
EP0704488A2 (en) Polycarbonate moulding compositions with improved toughness
EP0199193B1 (en) Thermoplastic moulding compounds consisting of polycarbonates, grafted polymers and copolymers
EP0210510A1 (en) Moulding compositions having an improved processability
WO2002036684A1 (en) Thermoplastic blends exhibiting an improved low-temperature strength
EP2283074A1 (en) Polycarbonate blends of low-temperature toughness
EP1910469B2 (en) Production methods of polycarbonate compositions with modified resilience
EP1576019A1 (en) Graft polymers based on ethylene-alpha-olefin rubbers and method for the production thereof
EP0372336B1 (en) High impact polycarbonate moulding compositions
EP0456030A2 (en) Polycarbonate-ABS moulding compositions
EP3562882B1 (en) Composition and thermoplastic moulding composition with good degree of toughness at a low temperature, high degree of gloss and high processing stability
EP3562883B1 (en) Composition and thermoplastic molding compound having reduced gloss and good chemical resistance
EP0499927B1 (en) Gasoline resistant polycarbonate mouldings
EP3662017B1 (en) Polycarbonate composition and polycarbonate moulding with improved flowability

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20050719

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL LT LV MK

DAX Request for extension of the european patent (deleted)
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20100701