EP1567562A1 - Melanges a proprietes ameliorees - Google Patents

Melanges a proprietes ameliorees

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Publication number
EP1567562A1
EP1567562A1 EP03779943A EP03779943A EP1567562A1 EP 1567562 A1 EP1567562 A1 EP 1567562A1 EP 03779943 A EP03779943 A EP 03779943A EP 03779943 A EP03779943 A EP 03779943A EP 1567562 A1 EP1567562 A1 EP 1567562A1
Authority
EP
European Patent Office
Prior art keywords
weight
vinyl
polymer
composition according
parts
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Withdrawn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
EP03779943A
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German (de)
English (en)
Inventor
Eckhard Wenz
Thomas König
Thomas Eckel
Herbert Eichenauer
Holger Warth
Bernd Urbanneck
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.)
Covestro Deutschland AG
Original Assignee
Bayer MaterialScience AG
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Filing date
Publication date
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Publication of EP1567562A1 publication Critical patent/EP1567562A1/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • 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
    • 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
    • C08F6/00—Post-polymerisation treatments
    • C08F6/14—Treatment of polymer emulsions
    • C08F6/22—Coagulation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/10—Reinforcing macromolecular compounds with loose or coherent fibrous material characterised by the additives used in the polymer mixture
    • 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
    • C08L69/005—Polyester-carbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • C08K5/523—Esters of phosphoric acids, e.g. of H3PO4 with hydroxyaryl compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/12—Copolymers of styrene with unsaturated nitriles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers

Definitions

  • the present invention relates to thermoplastic blends modified with special cofall products, a ner process for their production and molded parts produced therefrom.
  • Thermoplastic molding compositions made from polycarbonates and ABS polymers have been known for a long time.
  • DE-A 1 170 141 describes readily processable molding compositions composed of polycarbonates and graft polymers of monomer mixtures composed of acrylonitrile and an aromatic vinyl hydrocarbon on polybutadiene.
  • DE-A 1 810 993 emphasizes the improved heat resistance of polycarbonate when mixed with ABS graft polymers or copolymers based on ⁇ -methylstyrene.
  • DE-A 2 259 565 and DE-A 2 329 548 The subject of DE-A 2 259 565 and DE-A 2 329 548 is the improved flow seam strength of PC / ABS molding compositions, graft polymers of a certain particle size being used in both documents as part of the ABS component.
  • PC / AB S mixtures have particularly high low-temperature toughness when the ABS polymer contains two graft copolymers with different degrees of graft.
  • Thermoplastic molding compositions with a particle diameter of 0.20 to 0.35 ⁇ m are known from EP-A-0 704 488.
  • the object of the present invention is to provide impact-modified blend compositions with an optimized combination of properties from very good surface quality (in particular a very low number of defects, so-called "specks"), good flow behavior and very good toughness without negative influences on the stress crack resistance (ESC-V obtained ).
  • the compositions can also be flame retardant with flame retardants. Flame-retardant, impact-modified compositions are particularly suitable for thin-wall applications such as notebooks.
  • impact-modified polycarbonate compositions which contain a special mixture of at least one graft polymer and at least one thermoplastic vinyl (co) polymer obtained by co-precipitation have the desired properties.
  • compositions comprising
  • thermoplastic or a mixture of thermoplastics selected from at least one from the group of polycarbonates, polyester carbonates, polyamides,
  • thermoplastic vinyl (co) polymer prepared by solution, bulk or suspension polymerization.
  • compositions are preferred.
  • thermoplastic 10 to 99, preferably 20 to 98.5, in particular 30 to 98 parts by weight of thermoplastic or a mixture of thermoplastics selected from at least one of the
  • thermoplastic vinyl (co) polymer prepared by solution, bulk or suspension polymerization
  • Aromatic polycarbonates and aromatic polyestercarbonates according to component A which are suitable according to the invention are known from the literature or can be prepared by processes known from the literature (for the preparation of aromatic polycarbonates, see for example Schnell, "Chemistry and Physics of Polycarbonates", Interscience Publishers, 1964 and DE-AS 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, for example DE-A 3 077 934).
  • Aromatic polycarbonates are produced e.g. by melt processes or by reaction of diphenols with carbonic acid halides, preferably phosgene and / or with aromatic dicarboxylic acid dihalides, preferably benzene dicarboxylic acid dihalides, according to the phase interface method, optionally using chain terminators, for example monophenols and optionally using trifunctional or more than trifunctional branching agents or tetraphenols.
  • 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 ⁇ to C5 alkylene, C2 to Cs alkylidene, C5 to Cg cycloalkylidene, -O-, -SO-, -CO-, -S-, -SO2-, Cg to C ⁇ - Arylene, to which further aromatic rings optionally containing heteroatoms can be condensed, or a radical of the formula (II) or (DI)
  • R5 and R ⁇ can be selected individually for each X ', independently of one another hydrogen or C j to Cg-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 ⁇ l, R ⁇ and R ⁇ are simultaneously alkyl.
  • Preferred diphenols are hydroquinone, resorcinol, dihydroxydiphenols, bis (hydroxyphenyl) -C j -C5-alkanes, bis (hydroxyphenyl) -C5-C6-cycloalkanes, bis (hydroxyphenyl) ether, 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-bis (4-hydroxyphenyl) -2-methylbutane, l, l-bis (4-hydroxyphenyl) cyclohexane, l, l-bis- (4-hydroxyphenyl) -3.3.5-trimethylcyclohexane, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfone and its 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.
  • 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 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 or dialkylphenols with a total of 8 to 20 carbon atoms in the alkyl substituents, such as 3,5-di-tert-butylphenol, p-iso-octylphenol, p-tert-octylphenol, p-dodecylphenol and 2- (3,5-dimethylheptyl) phenol and 4- (3,5-dimethylheptyl) phenol.
  • the amount of chain terminators to be used is generally between 0.5 mol% and 10 mol%, based on the molar sum of the diphenols used in each case.
  • thermoplastic, aromatic polycarbonates and polyester carbonates have average weight-average molecular weights (Mw, measured, for example, by means of an ultracentrifuge or scattered light measurement) of 10,000 to 200,000, preferably 15,000 to 80,000.
  • thermoplastic, aromatic polycarbonates 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 and more phenolic groups.
  • copolycarbonates Both homopolycarbonates and copolycarbonates are suitable.
  • copolycarbonates according to the invention according to component A 1 to 25% by weight, preferably 2.5 to 25% by weight, based on the total amount of diphenols to be used, polydiorganosiloxanes with hydroxyaryloxy end groups can also be used. These are known (US Pat. No. 3,419,634) and can be prepared by processes known from the literature. The preparation of polydiorganosiloxane-containing copolycarbonates is described in DE-A 3 334 782.
  • preferred polycarbonates are the copolycarbonates of bisphenol A with up to 15 mol%, based on the molar sum of di- phenols, 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 also used as a bifunctional acid derivative.
  • the amount of chain terminators is in each case 0.1 to 10 mol%, based on mol of diphenol in the case of the phenolic chain terminators and on mol of dicarboxylic acid dichlorides in the case of monocarboxylic acid chloride chain terminators.
  • the aromatic polyester carbonates can also contain aromatic hydroxycarboxylic acids.
  • the aromatic polyester carbonates can be linear or branched in a known manner (see DE-A 2 940 024 and DE-A 3 007 934).
  • three or more functional carboxylic acid chlorides such as trimesic acid trichloride, cyanuric acid trichloride, 3,3 '-, 4,4'-benzophenone-tetracarboxylic acid tetrachloride, 1,4,5,8-naphthalenetetracarbonate acid tetrachloride or pyromellitic acid tetrachloride
  • branching agents in quantities from 0.01 to 1.0 mol% (based on the dicarboxylic acid dichlorides used) or trifunctional or multifunctional phenols, such as phloroglucin, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -hepten-2 , 4,4-dimethyl-2,4-6-tri- (4-hydroxyphenyl) heptane, 1,3,5-tri- (4-hydroxyphenyl) benzene, 1,1,1-tri- (4- hydroxyphenyl) ethane, tri- (4-
  • the proportion of carbonate structural units in the thermoplastic, aromatic polyester carbonates can vary as desired.
  • the proportion of carbonate groups is preferably up to 100 mol%, in particular up to 80 mol%, particularly preferably up to 50 mol%, based on the sum of ester groups 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.
  • thermoplastic, aromatic polycarbonates and polyester carbonates can be used alone or in any mixture.
  • Polyamides suitable according to the invention are known or can be prepared by processes known from the literature.
  • Polyamides suitable according to the invention are known homopolyamides, copolyamides and mixtures of these polyamides. These can be partially crystalline and / or amorphous polyamides. Polyamide-6, polyamide-6,6, mixtures and corresponding copolymers of these components are suitable as partially crystalline polyamides.
  • partially crystalline polyamides the acid components of which are wholly or partly composed of terephthalic acid and / or isophthalic acid and / or suberic acid and / or sebacic acid and / or azelaic acid and / or adipic acid and / or cyclohexanedicarboxylic acid, the diamine component of which consists entirely or partly of m- and / or p-xylylenediamine and / or hexamethylenediamine and / or 2,2,4-trirnethylhexa-methylenediamine and / or 2,4,4-trimethylhexamethylenediamine and / or isophoronedia and the composition of which is known in principle.
  • polyamides which are wholly or partly prepared from lactams with 7 to 12 carbon atoms in the ring, optionally with the use of one or more of the above-mentioned starting components.
  • Particularly preferred partially crystalline polyamides are polyamide 6 and polyamide 6,6 and their mixtures.
  • Known products can be used as amorphous polyamides. she are obtained by polycondensation of diamines such as ethylenediamine, hexamethylenediamine, decamethylenediamine, 2,2,4- and / or 2,4,4-trimethylhexamethylenediamine, m- and / or p-xylylenediamine, bis- (4-aminocyclohexyl) methane , Bis (4-aminocyclohexyl) propane, 3,3'-dimethyl-4,4'-diamino-dicyclohexyl-methane, 3-aminomethyl-3,5,5-trimethyl-cyclohexylamine, 2,5- and / or 2,6-bis (aminomethyl) norbornane and / or 1,4-diamino-methylcyclohexane with dicarboxylic acids such as o
  • Copolymers which are obtained by polycondensation of several monomers are also suitable, furthermore copolymers which are prepared with the addition of aminocarboxylic acids such as ⁇ -aminocaproic acid, ⁇ -aminoundecanoic acid or ⁇ -aminolauric acid or their lactams.
  • aminocarboxylic acids such as ⁇ -aminocaproic acid, ⁇ -aminoundecanoic acid or ⁇ -aminolauric acid or their lactams.
  • Particularly suitable amorphous polyamides are the polyamides made from isophthalic acid, hexamethylene diamine and other diamines such as 4,4-diaminodicyclohexyl methane, isophore diamine, 2,2,4- and / or 2,4,4-trimethylhexamethylene diamine, 2,5- and / or 2,6-bis (aminomethyl) norbornene; or from isophthalic acid, 4,4'-diamino-dicyclohexylmethane and ⁇ -caprolactam; or from isophthalic acid, 3,3'-dimethyl-4,4'-diamino-dicyclohexylmethane and laurolactam; or from terephthalic acid and the isomer mixture of 2,2,4- and / or 2,4,4-trimethylhexamethylene diamine.
  • the polyamides preferably have a relative viscosity (measured on a 1% strength by weight solution in m-cresol at 25 ° C.) from 2.0 to 5.0, particularly preferably from 2.5 to 4.0.
  • the polyamides can be contained in component A alone or in any mixture with one another.
  • Suitable polyalkylene terephthalates are reaction products of aromatic dicarboxylic acids or their reactive derivatives, such as dimethyl esters or anhydrides, and aliphatic, cycloaliphatic or araliphatic diols and mixtures of these reaction products.
  • Preferred polyalkylene terephthalates contain at least 80% by weight, preferably at least 90% by weight, based on the dicarboxylic acid component of terephthalic acid residues and at least 80% by weight, preferably at least 90 mol%, based on the diol component of ethylene glycol and / or butanediol - 1,4 residues.
  • the preferred polyalkylene terephthalates can contain up to 20 mol%, preferably up to 10 mmol%, of residues of other aromatic or cycloaliphatic dicarboxylic acids with 8 to 14 C atoms or aliphatic dicarboxylic acids with 4 to 12 C atoms, such as residues of phthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, 4,4'-diphenyldicarboxylic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, cyclohexanediacetic acid.
  • the preferred polyalkylene terephthalates can contain up to 20 mol%, preferably up to 10 mol%, other aliphatic diols with 3 to 12 C atoms or cycloaliphatic diols with 6 to 21 C atoms included, e.g.
  • the polyalkylene terephthalates can be made by incorporating relatively small amounts of trihydric or tetravalent alcohols or 3- or 4-basic carboxylic acids, e.g. according to DE-A 1 900 270 and US Pat. No. 3,692,744.
  • preferred branching agents are trimesic acid, trimellitic acid, trimethylol ethane and propane and pentaerythritol.
  • polyalkylene terephthalates which have been prepared solely from terephthalic acid and its reactive derivatives (for example its dialkyl esters) and ethylene glycol and / or 1,4-butanediol, and mixtures of these polyalkylene terephthalates.
  • Mixtures of polyalkylene terephthalates contain 1 to 50% by weight, preferably 1 to 30% by weight, polyethylene terephthalate and 50 to 99% by weight, preferably 70 to 99% by weight, polybutylene terephthalate.
  • the polyalkylene terephthalates preferably used generally have an intrinsic viscosity of 0.4 to 1.5 dl / g, preferably 0.5 to 1.2 dl / g, measured in phenol / o-dichlorobenzene (1: 1 parts by weight) at 25 ° C. in the Ubbelohde viscometer.
  • the polyalkylene terephthalates can be prepared by known methods (e.g. Kunststoff-Handbuch, Volume VIII, p. 695 ff., Carl-Hanser-Verlag, Kunststoff 1973).
  • polyoxymethylenes are also suitable as component A).
  • Component B comprises a mixture obtained by co-precipitation from at least one graft polymer B.l prepared by emulsion polymerization
  • thermoplastic vinyl (co) polymer B.2 produced by emulsion polymerization, built up from monomers i).
  • the graft base ii) generally has an average particle size (d50 value) of 0.05 to 5 ⁇ m, preferably 0.10 to 0.5 ⁇ m, particularly preferably 0.20 to 0.40 ⁇ m.
  • Monomers i) are preferably mixtures of
  • vinyl aromatics and / or core-substituted vinyl aromatics such as styrene, ⁇ -methylstyrene, p-methylstyrene, p-chlorostyrene
  • acrylic acid (Cl-C8) alkyl esters such as Methyl methacrylate, ethyl methacrylate
  • vinyl cyanides unsaturated nitriles such as acrylonitrile and methacrylonitrile
  • acrylic acid Cl-C8 alkyl esters (such as methyl meth- acrylate, n-butyl acrylate, t-butyl acrylate) and / or derivatives (such as anhydrides and imides) of unsaturated carboxylic acids (for example maleic anhydride and N phenyl-maleimide).
  • Preferred monomers il) are selected from at least one of the monomers styrene, ⁇ -methylstyrene and methyl methacrylate
  • preferred monomers i2) are selected from at least one of the monomers acrylonitrile, maleic anhydride and methyl methacrylate.
  • Particularly preferred monomers are il) styrene and i2) acrylonitrile.
  • Graft bases ii) suitable for the graft polymer B1 are, for example, diene rubbers, EP (D) M rubbers, that is to say those based on ethylene / propylene and, if appropriate, diene monomers, and also acrylate, polyurethane, silicone, chloroprene and ethylene / Ninylacetat rubbers.
  • Preferred graft bases ii) are diene rubbers.
  • Diene rubbers for the purposes of the present invention include diene rubbers (for example based on butadiene, isoprene, etc.) or mixtures of diene rubbers or copolymers of diene rubbers or their mixtures with other copolymerizable monomers (for example according to II) and i2)), preferably butadiene Styrene copolymers with preferably up to 30% by weight of styrene, understood with the proviso that the glass transition temperature of component ii) is ⁇ 10 ° C., preferably ⁇ 0 ° C., particularly preferably ⁇ -20 ° C.
  • Pure polybutadiene rubber is particularly preferred.
  • Suitable acrylate rubbers according to ii) of the polymer B. 1 are preferably polymers of alkyl acrylates, optionally with up to 40% by weight, based on ii) of other polymerizable, ethylenically unsaturated monomers.
  • the preferred polymerizable acrylic acid esters include C 1 -C 4 -alkyl esters, for example methyl, ethyl, butyl, n-octyl and 2-ethylhexyl esters; Halogen alkyl esters, preferably halogen C 1 -C 6 alkyl esters, such as chloroethyl acrylate and mixtures of these monomers.
  • Monomers with more than one polymerizable double bond can be copolymerized for crosslinking.
  • Preferred examples of crosslinking monomers are esters of unsaturated monocarboxylic acids with 3 to 8 C atoms and unsaturated monohydric alcohols with 3 to 12 C atoms, or saturated polyols with 2 to 4 OH groups and 2 to 20 C atoms, such as, for example, ethylene glycol dimethacrylate, allyl methacrylate; polyunsaturated heterocyclic compounds, such as, for example, trivinyl and triallyl cyanurate; polyfunctional Vinyl compounds such as di- and trivinylbenzenes; but also triallyl phosphate and diallyl phthalate.
  • Preferred crosslinking monomers are allyl methacrylate, ethylene glycol dimethacrylate, diallyl phthalate and heterocyclic compounds which have at least 3 ethylenically unsaturated groups.
  • crosslinking monomers are the cyclic monomers triallyl cyanurate, triallyl isocyanurate, triacryloylhexahydro-s-triazine, triallylbenzenes.
  • the amount of the crosslinked monomers is preferably 0.02 to 5, in particular 0.05 to 2% by weight, based on the graft base ii).
  • Preferred "other" polymerizable, ethylenically unsaturated monomers which, in addition to the acrylic acid esters, can optionally be used to prepare the graft base ii), are e.g. Acrylonitrile, styrene, ⁇ -methylstyrene, acrylamides, vinyl-Cl-C6-alkyl ethers, methyl methacrylate, butadiene.
  • Preferred acrylate rubbers as the graft base ii) are emulsion polymers which have a gel content of at least 60% by weight.
  • graft bases according to ii) are silicone rubbers with graft-active sites, as are described in DE-OS 3 704 657, DE-OS 3 704 655, DE-OS 3 631 540 and DE-OS 3 631 539.
  • the gel content of the graft base ii) is determined at 25 ° C. in a suitable solvent (M. Hoffmann, H. Krömer, R. Kuhn, Polymeranalytik I and II, Georg Thieme-Verlag, Stuttgart 1977).
  • the average particle size d50 is the diameter above and below which 50% by weight of the particles lie. It can be determined by means of ultracentrifuge measurement (W. Scholtan, H. Lange, Kolloid-Z. And Z. Polymer 250 (1972), 782-796).
  • Particularly preferred polymers B.l are e.g. ABS polymers (preferably through
  • the gel percentage of the graft Basis ii) is generally at least 30% by weight, preferably at least 40% by weight (measured in toluene).
  • the graft copolymer B.l to be used according to the invention is preferably prepared by redox initiation.
  • Redox initiator systems suitable according to the invention generally consist of an organic oxidizing agent and a reducing agent, it being possible for heavy metal ions to additionally be present in the reaction medium; it is preferred to work without heavy metal ions.
  • Organic oxidizing agents which are suitable according to the invention are, for example and preferably, di-tert-butyl peroxide, cumene hydroperoxide, dicyclohexyl percarbonate, tert-butyl hydroperoxide, p-menthane hydroperoxide or mixtures thereof, cumene hydroperoxide and tert-butyl hydroperoxide are particularly preferred.
  • H2O2 can also be used.
  • Reducing agents which can be used according to the invention are preferably water-soluble compounds having a reducing action, preferably selected from the group consisting of the salts of sulfinic acid, salts of sulphurous acid, sodium dithionite, sodium sulfite, sodium hyposulfite, sodium hydrogen sulfite, ascorbic acid and their salts, Rongalit®C (sodium formaldehyde sulfoxylate), mono- and dihydroxyacetone, sugar (e.g. glucose or dextrose).
  • a reducing action preferably selected from the group consisting of the salts of sulfinic acid, salts of sulphurous acid, sodium dithionite, sodium sulfite, sodium hyposulfite, sodium hydrogen sulfite, ascorbic acid and their salts, Rongalit®C (sodium formaldehyde sulfoxylate), mono- and dihydroxyacetone, sugar (e.g. glucose or dextrose).
  • Iron (II) salts such as Iron (IT) sulfate, tin (II) salts such as Tin (IT) chloride, titanium (HI) salts such as titanium (III) sulfate; however, such metal salts are preferably not used.
  • reducing agents are dextrose, ascorbic acid (salts) or sodium formaldehyde sulfoxylate (Rongalit®C).
  • Persulfate compounds suitable according to the invention are ammonium peroxodisulfate, potassium peroxodisulfate, sodium peroxodisulfate or mixtures thereof.
  • the vinyl monomers listed under i) are usually used for the production of the vinyl (co) polymer component B.2.
  • monomers i) are preferably mixtures of
  • vinyl aromatics and / or core-substituted vinyl aromatics such as styrene, ⁇ -methylstyrene, p-methylstyrene, p-chlorostyrene
  • acrylic acid (Cl-C8) alkyl esters such as Methyl methacrylate, ethyl methacrylate
  • vinyl cyanides unsaturated nitriles such as acrylonitrile and methacrylonitrile
  • acrylic acid Cl-C8 alkyl esters (such as methyl methacrylate, n-butyl acrylate, t-butyl acrylate) and / or derivatives (such as anhydrides and imides) of unsaturated carboxylic acids (e.g. maleic anhydride and N-pheny 1-maleimide).
  • Preferred monomers il) are selected from at least one of the monomers styrene, ⁇ -methylstyrene and methyl methacrylate
  • preferred monomers i2) are selected from at least one of the monomers acrylonitrile, maleic anhydride and methyl methacrylate.
  • Particularly preferred monomers are il) styrene and i2) acrylonitrile.
  • the vinyl (co) polymer component B.2 is produced by emulsion polymerization.
  • the procedure to be used is state of the art.
  • the graft polymers B.l and the vinyl (co) polymer B.2 can be co-precipitated in any mixing ratio.
  • the weight ratio B.1 -.B.2 is preferably 95: 5 to 5:95, particularly preferably 90:10 to 25:75 and very particularly preferably 85:15 to 50:50.
  • the co-precipitation products to be used according to the invention are produced by mixing at least one graft polymer B. 1 in latex form with at least one vinyl (co) polymer B.2 in latex form, homogeneously mixing the latices and working up the resulting graft polymer / vinyl (co) polymer mixed product using known methods.
  • Suitable processing methods are, for example, the precipitation of the mixed product by the action of aqueous electrolyte solutions such as, for example, solutions of salts (for example magnesium sulfate, calcium chloride, sodium chloride), solutions of acids (for example sulfuric acid, acetic acid) or mixtures thereof, precipitation by the action of Cold (freeze coagulation) or direct extraction of the co-precipitation product from the latex by spray drying.
  • aqueous electrolyte solutions such as, for example, solutions of salts (for example magnesium sulfate, calcium chloride, sodium chloride), solutions of acids (for example sulfuric acid, acetic acid) or mixtures thereof, precipitation by the action of Cold (freeze coagulation) or direct extraction of the co-precipitation product from the latex by spray drying.
  • a washing step preferably with water
  • a drying step for example in a fluidized bed dryer or a stream dryer
  • a preferred work-up process after the precipitation is the mixing of the moist graft polymer / vinyl (co) polymer mixture described in EP-A 867 463 with a thermoplastic resin melt in a kneading reactor. Details of this work-up process are also described in EP-A 867 463 , The mixtures of graft polymer / ninyl (co) polymer mixture and obtained after this work-up process.
  • Thermoplastic resin C (in particular styrene / acrylonitrile copolymer) are preferably used to produce the molding compositions according to the invention.
  • Suitable thermoplastic resins according to component C are vinyl (co) polymers. They are resinous, thermoplastic and rubber-free. These are polymers of at least one monomer from the group of the vinyl aromatics, vinyl cyanides (unsaturated nitriles), (meth) acrylic acid (C j -Cg) alkyl esters, unsaturated carboxylic acids and derivatives (such as anhydrides and imides) of unsaturated carboxylic acids. (Co) polymers of are particularly suitable
  • the copolymer of styrene and acrylonitrile is particularly preferred.
  • the co-precipitation product B is particularly preferably in dispersed form in a matrix of vinyl (co) polymer C, preferably in a styrene / acrylonitrile copolymer matrix.
  • the weight ratio B: C is 90:10 to 10:90, preferably 80:20 to 30:70 and particularly preferably 70:30 to 40:60.
  • thermoplastic resin component A thermoplastic resin component
  • graft polymer / vinyl (co) polymer mixture obtained by co-precipitation of B1 and B.2 and the vinyl (co) polymer component C) and, if appropriate, additives
  • B1 and B.2 graft polymer / vinyl (co) polymer mixture obtained by co-precipitation of B1 and B.2 and the vinyl (co) polymer component C) and, if appropriate, additives
  • styrene / acrylonitrile copolymers are used both as component B.2 and as component C.
  • the styrene / acrylonitrile copolymers differ in acrylonitrile content by 1 to 15% by weight, preferably by 2 to 10% by weight and particularly preferably by 2.5 to 7.5% by weight, where component C preferably has a higher acrylonitrile content than component B.2.
  • compositions can be made flame-retardant by adding suitable additives.
  • Halogen compounds for example based on chlorine and bromine, compounds containing phosphorus and silicon compounds, in particular silicone compounds, may be mentioned as examples of flame retardants.
  • Flame retardants are preferably used in an amount of 1 to 18, particularly preferably 2 to 16 parts by weight.
  • compositions preferably contain phosphorus-containing flame retardants from the groups of the monomeric and oligomeric phosphorus and phosphonic acid esters, phosphonate amines and phosphazenes, mixtures of several components selected from one or different of these groups also being able to be used as flame retardants.
  • Other phosphorus compounds not specifically mentioned here can also be used alone or in any combination with other flame retardants.
  • Preferred mono- and oligomeric phosphoric or phosphonic acid esters are phosphorus compounds of the general formula (IN)
  • R 1 , R 2 , R 3 and R 4 independently of one another in each case optionally halogenated C j to C alkyl, each optionally substituted by alkyl, preferably C j to C ⁇ alkyl, and / or halogen, preferably chlorine, bromine, C5 bis C 6 -cycloalkyl, C to C2o-aryl or C7 to Ci2-aralkyl,
  • n independently of one another, 0 or 1
  • X is a mono- or polynuclear aromatic radical with 6 to 30 C atoms, or a linear or branched aliphatic radical with 2 to 30 C atoms, which can be OH-substituted and can contain up to 8 ether bonds.
  • R 1, R 2, R 3 and R 4 are each independently C] to C j alkyl, phenyl, naphthyl or phenyl-C ⁇ -C4-alkyl.
  • the aromatic groups R 1 , R 2 , R 3 and R 4 can in turn be substituted with halogen and / or alkyl groups, preferably chlorine, bromine and / or C j to C4-alkyl.
  • Particularly preferred aryl radicals are cresyl, phenyl, xylenyl, propylphenyl or butylphenyl and the corresponding brominated and chlorinated derivatives thereof.
  • X in the formula (IV) preferably denotes a mono- or polynuclear aromatic
  • n in the formula (IN), independently of one another, can be 0 or 1, preferably n is 1. stands for values from 0 to 30, preferably 0.3 to 20, particularly preferably 0.5 to 10, in particular 0.5 to 6, very particularly preferably 0.6 to 2.
  • X is derived from resorcinol, hydroquinone, bisphenol A or diphenylphenol.
  • X is particularly preferably derived from bisphenol A.
  • Phosphorus compounds of the formula (IV) are, in particular, tributyl phosphate, triphenyl phosphate, tricresyl phosphate, diphenyl cresyl phosphate, diphenyl octyl phosphate, diphenyl 2-ethyl cresyl phosphate, tri (isopropylphenyl) phosphate, resorcinol-bridged diphosphate and bisphosphate diphosphate and bisphosphate.
  • the phosphorus compounds according to component D are known (cf. for example EP-A 0 363 608, EP-A 0 640 655) or can be prepared in an analogous manner by known methods (for example Ulimann's Encyclopedia of Industrial Chemistry, vol. 18, p. 301 ff. 1979; Houben-Weyl, Methods of Organic Chemistry, Vol. 12/1, p. 43; Beilstein Vol. 6, p. 177).
  • the mean q values can be determined by using a suitable method (gas chromatography (GC), high pressure liquid chromatography (HPLC), gel permeation chromatography (GPC)) to determine the composition of the phosphate mixture (molecular weight distribution) and from this the mean values for q be calculated. Furthermore, phosphonate amines and phosphazenes, as described in WO 00/00541 and WO 01/18105, can be used as flame retardants.
  • GC gas chromatography
  • HPLC high pressure liquid chromatography
  • GPC gel permeation chromatography
  • the flame retardants can be used alone or in any mixture with one another or in a mixture with other flame retardants.
  • the flame retardants according to component D are often used in combination with so-called anti-dripping agents, which reduce the tendency of the material to burn when dripping.
  • anti-dripping agents Compounds of the substance classes of fluorinated polyolefins, silicones and aramid fibers may be mentioned here as examples. These can also be used in the compositions according to the invention. Fluorinated polyolefins are preferably used as anti-dripping agents.
  • Fluorinated polyolefins are known and are described, for example, in EP-A 0 640 655. For example, they are marketed by DuPont under the Teflon® 30N brand.
  • the fluorinated polyolefins can be used both in pure form and in the form of a coagulated mixture of emulsions of the fluorinated polyolefins with emulsions of graft polymers (for example component B1) or with an emulsion of a copolymer (for example component B.2), preferably on styrene / acrylonitrile -Base are used, the fluorinated polyolefin being mixed as an emulsion with an emulsion of the graft polymer or the copolymer and then coagulated.
  • a coagulated mixture of emulsions of the fluorinated polyolefins with emulsions of graft polymers (for example component B1) or with an emulsion of a copolymer (for example component B.2), preferably on styrene / acrylonitrile -Base are used, the fluorinated polyolefin being mixed
  • the fluorinated polyolefins can be used as a precompound with the graft polymer (component B.l) or a copolymer according to C, preferably based on styrene / acrylonitrile.
  • the fluorinated polyolefins are mixed as a powder with a powder or granules of the graft polymer or copolymer and compounded in the melt generally at temperatures from 200 to 330 ° C. in conventional units such as internal kneaders, extruders or twin-screw screws.
  • the fluorinated polyolefins can also be used in the form of a masterbatch which is prepared by emulsion polymerization of at least one monoethylenically unsaturated monomer in the presence of an aqueous dispersion of the fluorinated polyolefin.
  • Preferred monomer components are styrene, acrylonitrile and mixtures thereof. After acidic precipitation and subsequent drying, the polymer is used as a free-flowing powder.
  • the coagulates, pre-compounds or masterbatches usually have solids contents of fluorinated polyolefin of 5 to 95% by weight, preferably 7 to 60% by weight.
  • the antidripping agents can be used in the composition according to the invention in an amount of preferably 0.01 to 3 parts by weight, particularly preferably 0.05 to 2 parts by weight and most preferably 0.1 to 0.8 parts by weight. Parts.
  • compositions according to the invention can furthermore contain at least one of the customary additives, such as lubricants and mold release agents, for example pentaerythritol tetra stearate, nucleating agents, antistatic agents, stabilizers, fillers and reinforcing materials, and also dyes and pigments.
  • customary additives such as lubricants and mold release agents, for example pentaerythritol tetra stearate, nucleating agents, antistatic agents, stabilizers, fillers and reinforcing materials, and also dyes and pigments.
  • compositions according to the invention are produced by mixing the respective constituents in a known manner and melt-compounding and melt-extruding at temperatures from 200 ° C. to 300 ° C. in conventional units such as internal kneaders, extruders and twin-screw screws.
  • the individual constituents can be mixed in a known manner both successively and simultaneously, both at about 20 ° C. (room temperature) and at a higher temperature.
  • the molding compositions according to the invention can be used for the production of moldings of any kind. These can be made by injection molding, extrusion and blow molding. Another form of processing is the production of molded parts by deep drawing from previously produced plates or films and the process of film back injection (IMD).
  • IMD film back injection
  • molded parts are foils, profiles, housing parts of all kinds, for example for household appliances such as juicers, coffee machines, mixers; for office machines such as monitors, printers, copiers; Automotive exterior and interior parts; Panels, pipes, electrical installation ducts, windows, doors and other profiles for the construction sector (interior and exterior applications) as well as electrical and electronic parts such as switches, plugs and sockets.
  • the molding compositions according to the invention can also be used, for example, to produce the following moldings:
  • housings for small transformers-containing electrical appliances housings for devices for information processing and transmission, housings and cladding for medical devices, massagers and housings therefor, toy vehicles for Children, flat wall elements, housings for safety devices, heat-insulated transport containers, devices for keeping or caring for small animals, molded parts for sanitary and bathroom equipment, cover grilles for ventilation openings, molded parts for garden and tool sheds, housings for garden tools.
  • the invention therefore also relates to a process for the preparation of the compositions and their use for the production of moldings and the moldings themselves.
  • Component Bl.l (comparison material)
  • Component B2.2 (comparison material)
  • Pentaerythritol tetrastearate Pentaerythritol tetrastearate.
  • the components used are mixed with the usual processing aids on a ZSK 25 twin-screw extruder.
  • the moldings are produced on an Arburg 270E injection molding machine at 260 ° C.
  • the impact strength is determined at room temperature (akRT) and at -20 ° C (ak-20 ° C) according to ISO 180 / 1A (unit: kJ / m 2 ).
  • thermoplastic flowability MNR (melt volume flow rate) is determined according to ISO 1133 (unit: cm 3/10 min).
  • FIGS. 1 and 2 show a surface that represents the assessment ++
  • Fig. 2 shows the assessment -.
  • Defects in the sense of the present inventions are any deviations from a flat and smooth surface, for example depressions (holes) or elevations, rough surface.
  • the molding compositions according to the invention lead to very greatly improved surface qualities while maintaining the other properties, such as toughness and thermoplastic flowability.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

L'invention concerne des mélanges thermoplastiques modifiés par des produits de co-précipitation spéciaux, leur procédé de production, ainsi que des pièces moulées produites à partir de ces mélanges.
EP03779943A 2002-11-29 2003-11-17 Melanges a proprietes ameliorees Withdrawn EP1567562A1 (fr)

Applications Claiming Priority (3)

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DE10255825A DE10255825A1 (de) 2002-11-29 2002-11-29 Blends mit verbesserten Eigenschaften
DE10255825 2002-11-29
PCT/EP2003/012806 WO2004050720A1 (fr) 2002-11-29 2003-11-17 Melanges a proprietes ameliorees

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KR (1) KR20050085186A (fr)
CN (1) CN1717422A (fr)
AU (1) AU2003288075A1 (fr)
BR (1) BR0316711A (fr)
CA (1) CA2507622A1 (fr)
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DE102005018472A1 (de) 2005-04-21 2006-10-26 Bayer Materialscience Ag Polycarbonat-Formmassen
WO2009129962A1 (fr) * 2008-04-24 2009-10-29 Bayer Materialscience Ag Compositions polycarbonate à résilience modifiée, à haute résistance hydrolytique et à couleur naturelle claire
TW201014758A (en) * 2008-10-07 2010-04-16 Chia-Hao Chiang Goods protecting bag
CN102449061B (zh) * 2008-12-22 2014-08-20 美国圣戈班性能塑料公司 改性的全氟聚合物片材料以及制造它的方法
JP5860239B2 (ja) * 2011-07-28 2016-02-16 丸菱油化工業株式会社 難燃性樹脂組成物
US11352487B2 (en) 2015-05-18 2022-06-07 Ineos Styrolution Group Gmbh ABS molding compound having a good property combination of processability and surface quality
WO2018081006A1 (fr) 2016-10-24 2018-05-03 Saint-Gobain Performance Plastics Corporation Compositions polymères, matériaux et procédés de fabrication
US20200079956A1 (en) 2016-12-28 2020-03-12 Covestro Ag Polycarbonate compositions having good mechanical properties
CN112457645B (zh) * 2020-11-06 2022-03-22 金发科技股份有限公司 一种聚碳酸酯合金组合物及其制备方法和应用
CN112646342B (zh) * 2020-12-21 2022-11-04 安徽卡洛塑业科技有限公司 静电耗散聚碳酸酯合金及其应用

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WO2004050720A1 (fr) 2004-06-17
CN1717422A (zh) 2006-01-04
MXPA05005654A (es) 2005-07-27
AU2003288075A1 (en) 2004-06-23
KR20050085186A (ko) 2005-08-29
JP2006508218A (ja) 2006-03-09
BR0316711A (pt) 2005-10-18
CA2507622A1 (fr) 2004-06-17
US20060122325A1 (en) 2006-06-08

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