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
  • C08L67/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the carboxyl- and the hydroxy groups directly linked to aromatic rings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
  • C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • 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
  • 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
  • C08L51/04—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 rubbers
• • 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
  • 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
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • 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
  • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
  • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
• • 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 polymer blends containing modified polyesters, in particular with improved optical properties, and their use.
• EP-A 0603664 e.g. Describing polymer blends consisting of polycarbonates and ABS polymers. Further examples of polymer blends containing polycarbonates can be found in JP-Al 0245481 and EP-A 846729.
• WO 9824844 also describes the transesterification control in polyethylene terephthalates / polyethylene naphthalate blends.
• the UV properties of bottles are also described in JP-A 09302205.
• the optical properties in particular the raw tone and the color effects, are in need of improvement.
• the object of the present invention is accordingly to provide polymer blends which provide color improvement, raw tone improvement (raw tone brightening) and have improved processing behavior, for example in the production of thin-walled parts.
• polymer blends comprising a component selected from the group consisting of poly (ester) carbonate A, graft polymer B or mixtures thereof, polyalkylene naphthalate C and, if appropriate, a further component D selected from vinyl (co) polymer Dl, polyalkylene terephthalate D2 or mixtures of these, mixtures of polycarbonate, polyalkylene naphthalate and optionally polyalkylene terephthalate containing no tetrafluoroethylene polymer.
• polymer blends containing in particular are preferred:
• polycarbonate polyalkylene terephthalate, preferably polybutylene terephthalate, and polyalkylene naphthalate
• All or part of the graft polymers can be replaced by vinyl (co) polymers.
• the polymer blends mentioned preferably contain 0.2 to 99 parts by weight of polyalkylene naphthalate. 0.4 to 85 parts by weight are particularly preferred, and 0.6 to 75 parts by weight of polyalkylene naphthalate are very particularly preferred.
• the polymer blends can contain 1 to 99.8 parts by weight of polycarbonate A, graft polymer B or mixtures thereof. 15 to 99.6 parts by weight are preferred, and 25 to 99.4 parts by weight are particularly preferred.
• Vinyl (co) polymer and polyalkylene terephthalate as well as mixtures thereof can be contained in the polymer blends with up to 85 parts by weight. 3 to 80 parts by weight are preferred, in particular 5 to 75 parts by weight. The sum of components A to D used is 100 parts by weight.
• polycarbonate / polyalkylene naphthalate mixtures contain> 0 parts by weight of polyalkylene terephthalate, this is preferably contained in amounts of 5 to 75 parts by weight.
• Vinyl (co) polymer 0-60 1-40 2-30 The following amounts are preferred for group 3 (parts by weight):
• the present invention also relates to the use of the polymer blends for the production of moldings.
• Aromatic polycarbonates and / or aromatic polyester carbonates 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 production of aromatic polycarbonates 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, for example DE-A 3 077 934).
• Aromatic polycarbonates are produced e.g. by reacting diphenols with carbonic acid halides, preferably phosgene and / or with aromatic dicarboxylic acid dihalides, preferably benzenedicarboxylic acid dihalogenides, according to the phase interface method, optionally using chain terminators, for example monophenols and optionally using trifunctional or more than trifunctional branching agents or triphenols, for example triphenols.
• Polyester carbonates are preferably those of the formula (I)
• A is a single bond, C 1 -C 5 alkylene, C2-C 5 alkylidene, C 5 -C 6 cycloalkylidene, -O-, -SO-, -CO-, -S-, -SO2-, Cg -C ⁇ aryls, to which further aromatic rings optionally containing heteroatoms can be condensed,
• B in each case hydrogen, preferably methyl, halogen, preferably chlorine and / or bromine,
• R 5 and R 6 can be selected individually for each X ⁇ , independently of one another hydrogen or Ci-Cg-alky !, preferably hydrogen, methyl or ethyl, Kohlenstoffl carbon and
• 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 (hydroxyphenyl) -C i -C 5 alkanes, bis (hydroxyphenyl) -C 5 -C 6 cycloalkanes, bis (hydroxyphenyl) ether, bis - (Hydroxylphenyl) 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, 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.
• 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.
• Suitable chain terminators 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-OS 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 have average weight-average molecular weights (M w , measured, for example, by means of an ultracentrifuge or scattered light measurement) of 10,000 to 200,000, preferably 20,000 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.
• 1 to 25% by weight, preferably 2.5 to 25% by weight (based on the total amount of diphenols to be used) of polydiorganosiloxanes with hydroxy-aryloxy end groups can also be used. These are known (see, for example, US Pat. No. 3,419,634) or can be produced by processes known from the literature.
• the production of polydiorganosiloxane-containing copolycarbonates is e.g. in DE-OS 3 334 782.
• preferred polycarbonates are polystyrene-co-styrene-co-styrene-co-styrene-co-styrene-co-styrene-co-styrene-co-styrene-co-styrene-co-styrene-co-styrene-co-styrene-co-styrene-co-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene
• 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 a bifunctional acid derivative.
• the amount of chain terminators is in each case 0.1 to 10 mol%, based on moles of diphenols in the case of the phenolic chain terminators and on moles 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 also DE-A 2 940 024 and DE-A 3 007 934).
• branching agents which can be used are 3- or polyfunctional carboxylic acid chlorides, such as trimesic acid trichloride, cyanuric acid trichloride, 3,3 ', 4,4'-benzophenonetetracarboxylic acid tetrachloride, 1,4,5, 8-naphthalenetetracarboxylic acid tetrachloride or pyromellitic acid tetrachloride, in amounts of 0.01 to 1.1.
• carboxylic acid chlorides such as trimesic acid trichloride, cyanuric acid trichloride, 3,3 ', 4,4'-benzophenonetetracarboxylic acid tetrachloride, 1,4,5, 8-naphthalenetetracarboxylic acid tetrachloride or pyromellitic acid tetrachloride, in amounts of 0.01 to 1.1.
• 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.
• the relative solution viscosity ( ⁇ re -) of the aromatic polycarbonates and aromatic polyester carbonates is in the range from 1.18 to 1.4, preferably from 1.22 to 1.3 (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 with one another.
• Component B is
• the rubber-modified graft polymer B comprises a statistical (co) polymer made from monomers according to B1 and / or B.1.2, and a rubber B.2 grafted with the statistical (co) polymer made from B1 and / or B.1.2, the production being B is carried out in a known manner by a bulk or solution or bulk suspension polymerization process, such as in U.S. Patent Nos. 3,243,481, 3,509,237, 3,660,535, 4,221,833, and 4,239,863.
• Examples of monomers B1 are styrene, ⁇ -methylstyrene, halogen- or alkyl core-substituted styrenes such as p-methylstyrene, p-chlorostyrene, (metal acrylic acid-Ci-Cg-alkyl esters such as methyl methacrylate, n-butyl acrylate and t-butyl acrylate.
• Examples of monomers B.1.2 are unsaturated nitriles such as acrylonitrile, methacrylonitrile, (meth) - C 1 -C 6 -alkyl acrylates such as methyl methacrylate, n-butyl acrylate, t-butyl acrylate,
• Preferred monomers B.l.l are styrene, ⁇ -methylstyrene and / or methyl methacrylate
• preferred monomers B.1.2 are acrylonitrile, maleic anhydride and / or
• Particularly preferred monomers are B.l.l styrene and B.1.2 acrylonitrile.
• Rubbers B.2 suitable for the rubber-modified graft polymers B are, for example, diene rubbers, EP (D) M rubbers, that is to say those based on ethylene / propylene and, if appropriate, diene, acrylate, polyurethane, silicone, chloroprene and ethylene / vinyl acetate rubbers.
• Preferred rubbers B.2 are diene rubbers (for example based on butadiene, isoprene etc.) or mixtures of diene rubbers or copolymers of diene rubbers. ken or their mixtures with other copolymerizable monomers (for example according to B1 and B.1.2), with the proviso that the glass transition temperature of component B.2 is below 10 ° C., preferably below -10 ° C. Pure polybutadiene rubber is particularly preferred.
• component B can additionally contain small amounts, usually less than 5% by weight, preferably less than 2% by weight, based on B.2, contain crosslinking ethylenically unsaturated monomers.
• crosslinking monomers are alkylene diol di
• (meth) acrylates polyester di (meth) acrylates, divinylbenzene, trivinylbenzene, tri-allyl cyanurate, allyl (meth) acrylate, diallyl maleate and diallyl fumarate.
• the rubber-modified graft polymer B is obtained by graft polymerization from 50 to 99, preferably 65 to 98, particularly preferably 75 to 95% by weight.
• the statistical copolymer of B1 and B.1.2 is usually present in the polymer B in part on or grafted onto the rubber B.2, this graft copolymer forming discrete particles in the polymer B.
• the proportion of the grafted or grafted copolymer from B1 and B.1.2 on the total copolymer from B1 and B.1.2 - i.e. the grafting yield (• weight ratio of the grafting monomers actually grafted to the total grafting monomers used x 100, stated in%) should be the same 2 to 40%, preferably 3 to 30%, particularly preferably 4 to 20%.
• the average particle diameter of the resulting grafted rubber particles is in the range from 0.5 to 5 ⁇ m, preferably 0.8 to 2.5 ⁇ m.
• the molding compositions according to the invention can also contain graft polymers prepared by emulsion polymerization.
• the description of the graft polymers preferably corresponds to that of the bulk polymerization, but is made by means of emulsion polymerization.
• the average particle diameter (d 50 value) of the graft base in the emulsion graft polymer is generally 0.05 to 5 ⁇ m, preferably 0.10 to 0.5 ⁇ m, particularly preferably 0.20 to 0.40 ⁇ m.
• the gel content of the graft base is at least 30% by weight, preferably at least 40% by weight.
• ABS graft polymer is a particularly preferred “emulsion graft polymer”.
• the weight ratio of graft polymer according to component B of the present invention produced by bulk polymerization to the graft polymer produced by emulsion polymerization is 100: 0 to 50:50, preferably 80:20 to 60:40.
• Component C is 100: 0 to 50:50, preferably 80:20 to 60:40.
• Polyalkylene naphthalates are used as component C (see e.g. EP-A-0846729). This is a polyester, the properties of which are similar to those of polyalkylene terephthalates.
• the polyalkylene naphthalates of component C can be both homopolymers and copolymers.
• the polyalkylene naphthalates of component C are reaction products of the optionally substituted naphthalene dicarboxylic acid or its reactive derivatives, such as dimethyl esters or anhydrides, with aliphatic, cycloaliphatic or araliphatic diols and mixtures of these reaction products.
• substituents on the naphthalene dicarboxylic acid are alkyl groups with 1 to 4 carbon atoms, alkylaryl groups and halogens.
• the polyalkylene naphthalates can contain up to 98 mol%, preferably up to 70 mol%, 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, e.g. Residues of phthalic acid, isophthalic acid, terephthalic acid, 4,4'-diphenyldicarboxylic acid, succinic acid, adipic acid, sebacic acid,
• the preferred polyalkylene naphthalates can contain up to 20 mol%, preferably up to 10 mol%, other aliphatic diols with 2 to 12 carbon atoms or cycloaliphatic diols with 6 to 21 Contain carbon atoms, e.g.
• the polyalkylene naphthalates can be prepared by incorporating relatively small amounts of trihydric or tetravalent alcohols or 3- or 4-basic carboxylic acids e.g. according to DE-A
• branching agents are trimesic acid, trimellitic acid, trimethylolethane and -propane and pentaerythritol.
• polyalkylene naphthalates which have been produced solely from naphthalenedicarboxylic acid and its reactive derivatives (e.g. its dialkyl esters) and ethylene glycol and / or 1,4-butanediol, and mixtures of these polyalkylene naphthalates.
• Mixtures of polyalkylene naphthalates contain 1 to 50% by weight, preferably
• polyethylene naphthalate 1 to 30% by weight, polyethylene naphthalate and 50 to 99% by weight, preferably 70 to 99% by weight, polybutylene naphthalate.
• the polyalkylene naphthalates 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 an Ubbelohde viscometer.
• the polyalkylene naphthalates can be prepared by known methods.
• vinyl polymers (co) according to component Dl are those of at least one monomer from the series styrene, ⁇ -methylstyrene and / or ring-substituted styrenes, C r C 8 alkyl methacrylate, C ⁇ -C 8 alkyl acrylate (D.1.1) with at least one monomer from the series: acrylonitrile, methacrylonitrile, Ci-Cg-alkyl methacrylate, Cj-Cg-alkyl acrylate, maleic anhydride and / or N-substituted maleimides (D.1.2).
• Ci-Cg alkyl acrylates or Ci-Cg alkyl methacrylates are esters of acrylic acid or methacrylic acid and monohydric alcohols with 1 to 8 carbon atoms. Methacrylic acid methyl esters, ethyl esters and propyl esters are particularly preferred. Methyl methacrylate is mentioned as a particularly preferred methacrylic acid ester.
• Thermoplastic (co) polymers with a composition according to component Dl can be used in the graft polymerization to produce component B as
• a by-product is created, especially when large amounts of monomers are combined with small ones
• Amounts of rubber are grafted.
• the amount to be used according to the invention is the amount to be used according to the invention.
• (Co) polymer Dl does not include these by-products of graft polymerization.
• the (co) polymers according to component Dl are resin-like, thermoplastic and rubber-free.
• thermoplastic (co) polymers Dl contain 50 to 99, preferably 60 to 95 parts by weight of D.I.l and 50 to 2, preferably 40 to 5 parts by weight of D.I.2.
• Particularly preferred (co) polymers D1 are those made from styrene with acrylonitrile and optionally with methyl methacrylate, from ⁇ -methylstyrene with acrylonitrile and optionally with methyl methacrylate, or from styrene and ⁇ -methylstyrene with acrylonitrile and optionally with methyl methacrylate.
• styrene-acrylonitrile copolymers according to component Dl are known and can be obtained by free-radical polymerization, in particular by emulsion
• the copolymers according to component Dl preferably have molecular weights M w (weight medium, determined by light scattering or sedimentation) between 15,000 and 200,000.
• copolymers Dl according to the invention are also random copolymers of styrene and maleic anhydride, which can be prepared from the corresponding monomer by continuous mass or solution polymerization with incomplete conversions.
• the preferred content of maleic anhydride is 5 to 25% by weight.
• the molecular weights (number average M n ) of the randomly constructed styrene-maleic anhydride copolymers according to component B which are suitable according to the invention can vary over a wide range. The range from 60,000 to 200,000 is preferred. An intrinsic viscosity of 0.3 to 0.9 (measured in dimethylformamide at 25 ° C.) is preferred for these products; see Hoffmann, Krömer, Kuhn, Polymeranalytik I, Stuttgart 1977, page 316 ff).
• the vinyl (co) polymers Dl can also contain nucleus-substituted styrenes such as p-methylstyrene, vinyltoluene, 2,4-dimethylstyrene and other substituted styrenes such as ⁇ -methylstyrene, which may or may not be substituted.
• nucleus-substituted styrenes such as p-methylstyrene, vinyltoluene, 2,4-dimethylstyrene and other substituted styrenes such as ⁇ -methylstyrene, which may or may not be substituted.
• the polyalkylene terephthalates of component D2 are reaction products made from aromatic dicarboxylic acids or their reactive derivatives, such as dimethyl esters or anhydrides, and ahphatic, 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% by weight, based on the diol component of ethylene glycol and / or butane-l, 4-residues.
• the preferred polyalkylene terephthalates can contain up to 20 mol%, preferably up to 10 mol%, 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, e.g. Residues of phthalic acid, isophthalic acid, 4,4'-diphenyldicarboxylic acid, succinic acid, adipic acid, sebacic acid,
• Azelaic acid cyclohexane-diacetic acid.
• the preferred polyalkylene terephthalates can contain up to 20 mol%, preferably up to 10 mol%, other aliphatic diols with 3 to 12 carbon atoms or cycloaliphatic diols with 6 to 21 Contain carbon atoms, e.g.
• the polyalkylene terephthalates can be prepared by incorporating relatively small amounts of trihydric or tetravalent alcohols or 3- or 4-basic carboxylic acids, e.g. according to DE-A
• branching agents are trimesic acid, trimellitic acid, trimethylolethane and -propane and pentaerythritol.
• Polyalkylene terephthalates which consist solely of terephthalic acid and its reactive derivatives (for example its dialkyl esters) and ethylene glycol are particularly preferred and / or 1,4-butanediol, and mixtures of these polyalkylene terephthalates.
• 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 (see e.g. Kunststoff-Handbuch, Volume VIII, p. 695 ff, Carl-Hanser-Verlag, Kunststoff 1973).
• the polymer blends according to the invention can contain conventional additives, such as flame retardants, anti-dripping agents, very finely divided inorganic compounds, lubricants and mold release agents, nucleating agents, antistatic agents, stabilizers, fillers and reinforcing materials, as well as dyes and pigments.
• conventional additives such as flame retardants, anti-dripping agents, very finely divided inorganic compounds, lubricants and mold release agents, nucleating agents, antistatic agents, stabilizers, fillers and reinforcing materials, as well as dyes and pigments.
• the polymer blends according to the invention can generally contain 0.01 to 20% by weight, based on the total mass, of flame retardants.
• flame retardants are organic halogen compounds such as decabromobisphenyl ether, tetrabromobisphenol, inorganic halogen compounds such as ammonium bromide, nitrogen compounds such as melamine, melamine formaldehyde resins, inorganic hydroxide compounds such as Mg-Al hydroxide, inorganic compounds such as aluminum oxides, titanium dioxide, antimony oxides, barium oxides.
• Metaborate hydroxo-antimonate, zirconium oxide, zirconium hydroxide, molybdenum oxide, ammonium molybdate, tin borate, ammonium borate, barium metaborate and tin oxide as well as siloxane compounds.
• Phosphorus compounds as described in EP-A 0363608, EP-A 0345522 or EP-A 0640655 can also be used as flame retardant compounds.
• Such phosphorus compounds are, for example, phosphorus compounds of the formula (IN)
• R 5 , R 6 , R 7 and R 8 independently of one another in each case optionally halogenated Ci-Cg-alkyl, in each case optionally substituted by alkyl, preferably C1-C4-alkyl, and / or halogen, preferably chlorine, bromine, C5-C6- Cycloalkyl, Cö-C Q aryl or C -C ⁇ aralkyl mean.
• R 5 , R 6 , R 7 and R 8 are preferably independently of one another Phenyl, ⁇ aphthyl or phenyl-C - [- C 4 -alkyl.
• the aromatic groups R 5 , R 6 , R 7 and R 8 can in turn be substituted with halogen and / or alkyl groups, preferably chlorine, bromine and / or C1-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 (IN) means a mono- or polynuclear aromatic radical having 6 to 30 C atoms. This is derived from diphenols such as diphenylphenol, bisphenol A, resorcinol or hydroquinone or their chlorinated or brominated derivatives.
• k 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 for 0 or an average value of 0.3 to 20, particularly preferably 0.5 to 10, in particular 0.5 to 6.
• Mixtures of phosphorus compounds of the formula (IN) preferably contain 10 to 90% by weight, preferably 12 to 40% by weight, of at least one monophosphorus compound of the formula (IN) and at least one oligomeric phosphorus compound or a mixture of oligomeric phosphorus compounds in amounts from 10 to 90% by weight, preferably 60 to 88% by weight, based on the total amount of phosphorus compounds.
• Monophosphorus compounds of the formula (IN) are in particular tributyl phosphate,
• the mixtures of monomers and oligomeric phosphorus compounds of the formula (IN) have average ⁇ values of 0.3 to 20, preferably 0.5 to 10, in particular 0.5 to 6.
• the phosphorus compounds according to formula (IN) are known (cf., for example, EP-A 0363608, EP-A 0640655, EP-A 0542522) or can be prepared in an analogous manner by known methods (for example Ullmann's Encyclopedia of Industrial Chemistry, Vol. 18, Pp. 301 ff. 1979; Houben-Weyl, Methods of Organic Chemistry, Vol. 12/1,
• the polymer blends according to the invention can optionally contain flame retardants different from compounds of the formula (IV) in an amount of up to 20 parts by weight. Synergistic flame retardants are preferred. Organic halogen compounds such as decabromobisphenyl ether, tetrabromobisphenol, inorganic halogen compounds such as ammonium bromide, nitrogen compounds such as melamine, melamine formaldehyde resins or siloxane compounds are mentioned as examples of further flame retardants.
• Synergistic flame retardants are preferred.
• Organic halogen compounds such as decabromobisphenyl ether, tetrabromobisphenol, inorganic halogen compounds such as ammonium bromide, nitrogen compounds such as melamine, melamine formaldehyde resins or siloxane compounds are mentioned as examples of further flame retardants.
• the polymer blends according to the invention can optionally contain inorganic substances which differ from the inorganic compounds, such as, for example, inorganic hydroxide compounds such as Mg, Al hydroxide, inorganic compounds such as aluminum oxide, antimony oxides, barium metaborate, hydroxoantimonate, zirconium oxide, zirconium hydroxide, molybdenum oxide, ammonium molybdate, zinc borate, ammonium borate, Barium metaborate and tin oxide.
• inorganic hydroxide compounds such as Mg, Al hydroxide
• inorganic compounds such as aluminum oxide, antimony oxides, barium metaborate, hydroxoantimonate, zirconium oxide, zirconium hydroxide, molybdenum oxide, ammonium molybdate, zinc borate, ammonium borate, Barium metaborate and tin oxide.
• thermoplastic polymer blends according to the invention can contain very finely divided inorganic compounds which have a favorable effect on the flame retardant properties of the polymer blends according to the invention.
• inorganic compounds include compounds of one or more metals of the 1st to 5th main group or the 1st to 8th subgroup of the periodic table, preferably the
• 2nd to 5th main group or the 4th to 8th subgroup particularly preferably the 3rd to 5th main group or the 4th to 8th subgroup with the elements oxygen, sulfur, boron, phosphorus, carbon, nitrogen, hydrogen and / or silicon.
• Preferred compounds are, for example, oxides, hydroxides, water-containing
• Preferred very finely divided inorganic compounds are, for example, TiN, ⁇ O2, SnO 2 , WC, ZnO, Al 2 O 3 , AIO (OH), ZrO 2 , Sb 2 O 3 , SiO 2 , iron oxides, NaSO 4j BaSÜ4,
• Vanadium oxides, zinc borate, silicates such as Al silicates, Mg silicates, one, two, three dimensional silicates, mixtures and doped compounds can also be used.
• these nanoscale particles can be surface-modified with organic molecules in order to achieve better compatibility with the polymers. In this way, hydrophobic or hydrophilic surfaces can be created.
• the average particle diameters are less than or equal to 200 nm, preferably less than or equal to 150 nm, in particular 1 to 100 nm.
• Particle size and particle diameter always means the average particle diameter d5o, determined by ultracentrifuge measurements according to W. Scholtan et al. Colloid-Z. and Z. Polymers 250 (1972), pp. 782 to 796.
• the inorganic compounds can be present as powders, pastes, brine, dispersions or suspensions. Precipitation can result from dispersions, brine or
• the powders can be incorporated into the thermoplastic materials by customary methods, for example by direct kneading or extruding the constituents of the molding composition and the very finely divided inorganic powders.
• Preferred methods are the preparation of a master batch, e.g. in flame retardant additives, other additives, monomers, solvents, in component A or the co-precipitation of dispersions of components B or C with dispersions, suspensions, pastes or sols of the very finely divided inorganic materials.
• the thermoplastic polymer blends can contain inorganic fillers and reinforcing materials such as glass fibers, optionally cut or ground, glass beads, glass balls, flake-like reinforcing materials such as kaolin, talc, mica, silicates, quartz, talc, titanium dioxide, wollastonite, mica, carbon fibers or a mixture thereof. Cut or ground glass fibers are preferably used as the reinforcing material. Preferred fillers that are also reinforcing Glass balls, mica, silicates, quartz, talc, titanium dioxide, wollastonite can act
• the filled or reinforced polymer blends can contain up to 60, preferably 10 to 40,% by weight, based on the filled or reinforced molding composition, filler and / or
• Fluorinated polyolefins can also be added.
• the fluorinated polyolefins are high molecular weight and have glass transition temperatures of above -30 ° C., generally above 100 ° C., fluorine contents, preferably from 65 to 76, in particular from 70 to 76% by weight, average particle diameter d5 Q of 0.05 to 1,000 ⁇ m, preferably 0.08 to 20 ⁇ m.
• the fluorinated polyolefins E have a density of 1.2 to 2.3 g cm ⁇ .
• Preferred fluorinated polyolefins are polytetrafluoroethylene, polyvinylidene fluoride,
• Tetrafluoroethylene / hexafluoropropylene and ethylene / tetrafluoroethylene copolymers Tetrafluoroethylene / hexafluoropropylene and ethylene / tetrafluoroethylene copolymers.
• the fluorinated polyolefins are known (cf. EP-A 0640655).
• the fluorinated polyolefins E are used in the form of special preparations:
• the fluorinated polyolefins E as a powder with a powder or granules at least one of components A to C is mixed and compounded in the melt, generally at temperatures from 208 ° C. to 330 ° C. in conventional units such as internal kneaders, extruders or twin-screw screws.
• Suitable tetrafluoroethylene polymer emulsions are commercially available products and are offered, for example, by DuPont as Teflon® 30 N.
• the invention also includes a method for producing the polymer blends.
• the polymer blends according to the invention containing components A to E, are produced by mixing the respective constituents in a known manner and melt-compounding or melt-extruding at temperatures from 200 ° C. to 300 ° C. in conventional units such as internal kneaders, extruders and twin-screw screws, the fluorinated polyolefins are preferably used in the form of the coagulated mixture already mentioned.
• 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 polymer blends of the present invention can be used to make any type of molded article.
• shaped bodies can be produced by injection molding.
• moldings that can be produced are: Housing parts of all types, e.g. for household appliances, such as juicers, coffee machines, mixers, for office machines, such as computers, printers, monitors or cover plates for the
• Construction sector and parts for the automotive sector are also used in the field of electrical engineering because they have very good electrical properties.
• the polymer blends are particularly suitable for the production of thin-walled molded parts (eg data technology housing parts) where particularly high demands are made Notched impact strength and stress crack resistance of the plastics used.
• Another form of processing is the production of moldings by blow molding or by deep drawing from previously produced sheets or foils.
• Ratio of 72:28 and an intrinsic viscosity of 0.55 dl g (measurement in dimethylformamide at 20 ° C)
• the tensile strength is determined in accordance with ISO 527.
• the elongation at break is determined in accordance with ISO 527.
• the melt volume rate is determined in accordance with ISO 1133.
• the raw tone was assessed visually. Starting from the comparative example as a control (value "0"), the brightening (+, ++) of the examples according to the invention was assessed.
• the molding compositions according to the invention are notable for a favorable combination of properties comprising improved flowability, mechanical properties and raw clay.
• the raw tone is significantly improved by the components C1 and C2 added compared to the prior art, the mechanical properties additionally improving in contrast to color pigments.
• the flowability here in the form of the melt volume rate, also increases.
• the molding compositions according to the invention are distinguished by a favorable combination of properties of mechanical and thermal properties and of the raw clay.
• the raw clay is significantly improved by the components C1 and C2 added compared to the prior art, while maintaining or improving the mechanical properties, such as notched impact strength and elongation at break.
• the mechanical properties such as notched impact strength and elongation at break.
• an increase in the Vicat temperature which is advantageous for many applications can be achieved.
• the molding compositions according to the invention are distinguished by a favorable combination of properties of improved raw clay and flowability or mechanical properties.
• the raw clay is significantly improved (+) by the components C1 and C2 added compared to the prior art while maintaining the mechanical and theological properties, such as notched impact strength or melt volume rate.
• the molding compositions according to the invention have a very beautiful pearlescent effect. While maintaining the notched impact strength and improving the elongation at break, housings for mobile phones were successfully produced from the material.

Landscapes

• 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)
• Manufacture Of Macromolecular Shaped Articles (AREA)

Priority Applications (8)

Applications Claiming Priority (2)

Related Child Applications (2)

Publications (2)

Family

ID=7923497

Family Applications (1)

Country Status (14)

Cited By (1)

Families Citing this family (13)

Family Cites Families (16)

• 1999
  • 1999-09-28 DE DE19946323A patent/DE19946323A1/de not_active Withdrawn
• 2000
  • 2000-09-15 AU AU75189/00A patent/AU7518900A/en not_active Abandoned
  • 2000-09-15 BR BR0014371-5A patent/BR0014371A/pt not_active IP Right Cessation
  • 2000-09-15 JP JP2001526617A patent/JP2004508425A/ja active Pending
  • 2000-09-15 MX MXPA02003196A patent/MXPA02003196A/es unknown
  • 2000-09-15 EP EP00964175A patent/EP1230302B1/de not_active Expired - Lifetime
  • 2000-09-15 DE DE50012137T patent/DE50012137D1/de not_active Expired - Lifetime
  • 2000-09-15 CN CNB008135509A patent/CN1192059C/zh not_active Expired - Fee Related
  • 2000-09-15 AT AT00964175T patent/ATE316549T1/de not_active IP Right Cessation
  • 2000-09-15 CA CA002385818A patent/CA2385818A1/en not_active Abandoned
  • 2000-09-15 RU RU2002111409/04A patent/RU2002111409A/ru not_active Application Discontinuation
  • 2000-09-15 WO PCT/EP2000/009015 patent/WO2001023474A2/de not_active Ceased
  • 2000-09-15 KR KR1020027003968A patent/KR100667148B1/ko not_active Expired - Fee Related
  • 2000-09-26 AR ARP000105031A patent/AR025778A1/es unknown
• 2004
  • 2004-06-10 US US10/776,819 patent/US7081490B2/en not_active Expired - Fee Related

Also Published As

Similar Documents

Legal Events