Classifications

• • 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
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/20—Compounding polymers with additives, e.g. colouring
  • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
  • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
  • B29C48/25—Component parts, details or accessories; Auxiliary operations
  • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
  • B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
  • B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B82—NANOTECHNOLOGY
  • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
  • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
• • 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
  • C08J5/005—Reinforced macromolecular compounds with nanosized materials, e.g. nanoparticles, nanofibres, nanotubes, nanowires, nanorods or nanolayered materials
• • 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
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/02—Elements
  • C08K3/04—Carbon
  • C08K3/041—Carbon nanotubes
• • 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
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
• • 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
  • C08J2425/00—Characterised by the use 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; Derivatives of such polymers
• • 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
  • C08J2425/00—Characterised by the use 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; Derivatives of such polymers
  • C08J2425/02—Homopolymers or copolymers of hydrocarbons
  • C08J2425/04—Homopolymers or copolymers of styrene
  • C08J2425/08—Copolymers of styrene
  • C08J2425/12—Copolymers of styrene with unsaturated nitriles
• • 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
  • C08J2455/00—Characterised by the use of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08J2423/00 - C08J2453/00
• • 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
  • C08J2455/00—Characterised by the use of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08J2423/00 - C08J2453/00
  • C08J2455/02—Acrylonitrile-Butadiene-Styrene [ABS] polymers
• • 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 a process for producing impact modified carbon nanotube filled polycarbonate compositions and molding compositions, wherein the degradation of the molecular weight of the polycarbonate during compounding is improved over methods known in the art.
• WO-A 2001/92381 describes a process for incorporation of CNT agglomerates into a polymer matrix by hydrodynamic stress. In this way, a break up of the agglomerates is achieved.
• WO-A 2003/079375 claims polymeric material which exhibits mechanically and electrically improved properties by the addition of carbon nanotubes.
• the carbon nanotubes are cleaned of catalyst residues as well as of catalyst carriers by a wash. It also claims a process for producing such reinforced materials by incorporation in the melt.
• WO-A 2005/015574 discloses compositions containing organic polymer and carbon nanotubes (hereinafter also referred to as “carbon nanotubes” or “CNTs”) which form rope-like agglomerates and contain at least 0.1% impurities.
• the compositions are characterized by a reduced electrical resistance and a minimum of notched impact strength.
• US 5591382 A discloses polymer compositions containing carbon fibrils which are at least partly in the form of agglomerates.
• the agglomerates do not exceed a size of 35 ⁇ m.
• the compositions are characterized by reduced electrical resistance in combination with a minimum of impact strength. It also discloses a polymer composition in which agglomerates of the carbon fibrils are broken by a process of incorporation with the aid of shearing forces.
• US 6265466 Bl discloses a polymer composition of polymeric material and CNT which provides electromagnetic shielding and a method for its production. The method involves the use of shear forces, for example during extrusion, to orient the CNT.
• JP-A 2006-083195 discloses polycarbonate compositions containing CNT and polyolefins. It also claims a process for their preparation in which first the polyolefin is mixed with the CNT and then the polycarbonate is added.
• CNT impact modified carbon nanotubes
• fibrous graphite materials a process for producing impact modified carbon nanotubes (hereinafter also referred to as "CNT” or “fibrous graphite materials”) filled polycarbonate compositions and molding compositions, wherein the degradation of the molecular weight of the polycarbonate during compounding opposite the prior art method is improved.
• Polycarbonate and / or aromatic polyester carbonate (component A) and optionally further proportions B and D and optionally additives (component E) is mixed on a twin-screw extruder.
• the first step is carried out at a temperature of 240 to 300 ° C., more preferably 260 to 290 ° C.
• the ratio of the parts by weight of component C to the sum of parts by weight of components B and D is 2: 98 to 25: 75, more preferably 5:95 to 20:80.
• Components C, B and / or D are simultaneously or sequentially particularly preferably introduced simultaneously into the twin-screw extruder.
• the resulting material is granulated after the first step.
• the second step at a temperature of 240 - 300 0 C, particularly preferably from 250th
• the components CNT masterbatch, A and optionally further fractions B and D and, if appropriate, E are metered simultaneously or sequentially, more preferably at the same time.
• mixing in steps 1 and 2 of the process according to the invention is carried out at speeds and throughputs customary according to the prior art, wherein these characteristics speed and throughput do not limit the present invention.
• the present invention also relates to compositions containing
• component A aromatic polycarbonate and / or aromatic polyestercarbonate
• component C carbon nanotubes
• compositions contain A) 30 to 94 parts by weight, preferably 49 to 73 parts by weight of component A,
• component B 5 to 30 parts by weight, preferably 10 to 20 parts by weight of component B,
• component C 1 to 10 parts by weight, preferably 2 to 6 parts by weight of component C and
• 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 example, see 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 preparation of aromatic polyester carbonates, eg DE-A 3 077 934) ,
• Diphenols for the preparation of the aromatic polycarbonates and / or aromatic polyester carbonates are preferably those of the formula (I)
• A denotes a single bond, C 1 to C 3 -alkylene, C 2 to C 5 -alkylidene, C 5 to C 6 -cycloalkylidene,
• Heteroatom-containing rings may be condensed, or a radical of the formula (II) or (EI)
• B are each C to C alkyl, preferably methyl, halogen, preferably chlorine and / or bromine x are each independently 0, 1 or 2, p is 1 or 0, and
• R 5 and R 6 are individually selectable for each X 1 independently of one another hydrogen or C to C -
• Alkyl preferably hydrogen, methyl or ethyl, X 1 carbon and 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.
• Preferred diphenols are hydroquinone, resorcinol, dihydroxydiphenols, bis (hydroxyphenyl) -C 1 -C 5 -alkanes, bis (hydroxyphenyl) -C 5 -C 6 -cycloalkanes, bis (hydroxyphenyl) ethers, bis (hydroxy-) phenyl) -sulfoxides, bis (hydroxyphenyl) -ketones, bis (hydroxyphenyl) -sulfones and ⁇ , ⁇ -bis (hydroxyphenyl) -diisopropyl-benzenes and their camemborated and / or ring-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'-dihydroxydiphenylsulfide, 4,4'-dihydroxydiphenylsulfone 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
• the diphenols can be used individually or as any mixtures. The diphenols are known from
• Chain terminators suitable for the preparation 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- [2- (2,4,4 -Trimethylpentyl)] - phenol, 4- (l, 3-tetramethyl-butyl) -phenol according to DE-A 2,842,005 or monoalkylphenol or dialkylphenols having a total of 8 to 20 carbon atoms in the alkyl substituents such as 3,5-di-tert.
• alkylphenols such as 4- [2- (2,4,4 -Trimethylpentyl)] - phenol, 4- (l, 3-tetramethyl-butyl) -phenol according to DE-A 2,842,005 or monoalkylphenol or dialkylphenols having a total of 8 to 20 carbon atoms in the alkyl substituents such as 3,5-di-
• 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 weight average molecular weights (M w , measured, for example, by GPC, ultracentrifuge or scattered light measurement) of 10,000 to 200,000 g / mol, preferably 15,000 to 80,000 g / mol, particularly preferably 24,000 to 32,000 g / mol.
• thermoplastic, aromatic polycarbonates may be branched in a known manner, preferably by the incorporation of 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 it is also possible to use 1 to 25% by weight, preferably 2.5 to 25 wt.%.
• polydiorganosiloxanes with hydroxyaryloxy end groups are used. These are known (US 3 419 634) and can be prepared by literature methods. The preparation of polydiorganosiloxane-containing copolycarbonates is described in DE-A 3 334 782.
• Preferred polycarbonates in addition to the bisphenol A homopolycarbonates, are the copolycarbonates of bisphenol A with up to 15 mol%, based on the molar sums of diphenols, of other than preferred or particularly preferred diphenols, in particular 2,2-bis (3,5-bis). dibromo-4-hydroxyphenyl) -propane.
• Aromatic dicarboxylic acid dihalides for the preparation 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.
• a carbonyl halide preferably phosgene, is additionally used as the bifunctional acid derivative.
• the amount of chain terminators is in each case 0.1 to 10 mol%, based on moles of diphenol in the case of the phenolic chain terminators and on moles of dicarboxylic acid dichloride in the case of monocarboxylic acid chloride chain terminators.
• the aromatic polyester carbonates may also contain incorporated aromatic hydroxycarboxylic acids.
• the aromatic polyester carbonates can be branched both linearly and in a known manner (see DE-A 2 940 024 and DE-A 3 007 934).
• branching agents which may be used are trifunctional or polyfunctional carboxylic acid chlorides, such as trimesic acid trichloride, cyanuric trichloride, 3,3 ', 4,4'-benzophenone tetracarboxylic acid tetracarboxylic acid.
• the proportion of carbonate structural units 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 portion of the aromatic polyester carbonates may be present in the form of blocks or randomly distributed in the polycondensate.
• the relative solution viscosity ( ⁇ rel ) of the aromatic polycarbonates and polyester carbonates is in the range of 1.18 to 1.4, preferably 1.20 to 1.32 (measured on solutions of 0.5 g of polycarbonate or polyester carbonate in 100 ml of methylene chloride solution 25 ° C).
• thermoplastic, aromatic polycarbonates and polyester carbonates can be used alone or in any desired mixture.
• Component B comprises one or more graft polymers of
• the graft base B.2 generally has an average particle size (d 50 value) of 0.05 to 10 .mu.m, preferably 0.1 to 5 .mu.m, particularly preferably 0.2 to 1 .mu.m.
• Monomeric Bl are preferably mixtures of
• B.1.2 1 to 50 parts by weight of vinyl cyanides (unsaturated nitriles such as acrylonitrile and methacrylonitrile) and / or (meth) acrylic acid (Ci-C 8 ) alkyl esters, such as methyl methacrylate, n-butyl acrylate, t-butyl acrylate, and / or Derivatives (such as anhydrides and imides) of unsaturated carboxylic acids, for example maleic anhydride and N-phenylmaleimide.
• vinyl cyanides unsaturated nitriles such as acrylonitrile and methacrylonitrile
• Ci-C 8 alkyl esters such as methyl methacrylate, n-butyl acrylate, t-butyl acrylate, and / or Derivatives (such as anhydrides and imides) of unsaturated carboxylic acids, for example maleic anhydride and N-phenylmaleimide.
• Preferred monomers B.1.1 are selected from at least one of the monomers styrene, ⁇ -methylstyrene and methyl methacrylate
• preferred monomers B.1.2 are selected from at least one of the monomers acrylonitrile, maleic anhydride and methyl methacrylate.
• Particularly preferred monomers are B.1.1 styrene and B.1.2 acrylonitrile.
• Suitable graft bases B.2 for the graft polymers B are diene rubbers, EP (D) M rubbers, ie those based on ethylene / propylene and optionally diene, acrylate, polyurethane, silicone, chloroprene and ethylene / vinyl acetate rubbers.
• Other suitable bases are mixtures of silicone rubber and Acrylatkautscb.uk, for example, these two types of rubber are present as a physical mixture or where, for example, the silicone rubber and acrylate rubber forming an interpenetrating network form or, for example, the silicone rubber and acrylate rubber form a graft, which is a core-shell structure having.
• Preferred grafting bases B.2 are diene rubbers, for example based on butadiene and isoprene, or mixtures of diene rubbers or copolymers of diene rubbers or mixtures thereof with other copolymerizable monomers (for example according to B.1.1 and B.1.2), with the proviso that the glass transition temperature of Component B.2 below ⁇ 10 0 C, preferably ⁇ 0 0 C, particularly preferably ⁇ -10 0 C.
• Especially preferred is pure polybutadiene rubber.
• the gel content of the graft base B.2 is at least 30% by weight, preferably at least 40% by weight (measured in toluene).
• the graft copolymers B are prepared by free-radical polymerization, e.g. by emulsion, suspension, solution or bulk polymerization, preferably by emulsion or bulk polymerization.
• Particularly suitable graft rubbers are also ABS polymers which are prepared in the emulsion polymerization process by redox initiation with an initiator system of organic hydroperoxide and ascorbic acid according to US Pat. No. 4,937,285.
• graft polymers B according to the invention are also those products which are obtained by (co) polymerization of the graft monomers in the presence of the graft base and are obtained during the workup.
• Suitable acrylate rubbers according to B.2 of the polymers B are preferably polymers of alkyl acrylates, optionally with up to 40 wt .-%, based on B.2 other polymerizable, ethylenically unsaturated monomers.
• the preferred polymerisable acrylic acid esters include C 1 to C 6 alkyl esters, for example methyl, ethyl, butyl, n-octyl and 2-ethylhexyl esters; Haloalkyl esters, preferably halo-C 1 -C 8 -alkyl esters, such as chloroethyl acrylate and mixtures of these monomers.
• crosslinking monomers having more than one polymerizable double bond can be copolymerized.
• Preferred examples of crosslinking monomers are esters of unsaturated ones
• Monocarboxylic acids having 3 to 8 carbon atoms and unsaturated monohydric alcohols having 3 to 12 carbon atoms
• Monomers are allyl methacrylate, ethylene glycol dimethacrylate, diallyl phthalate and heterocyclic
• crosslinking monomers are the cyclic monomers triallyl cyanurate,
• the amount of the crosslinked monomers is preferably 0.02 to 5, especially 0.05 to 2 wt .-%, based on the
• Grafting B.2 For cyclic crosslinking monomers having at least three ethylenic unsaturated groups, it is advantageous to limit the amount to less than 1 wt .-% of the graft B.2.
• Preferred "other" polymerizable, ethylenically unsaturated monomers which may optionally be used for preparing the graft B.2 addition to Acrylklareestern are, for example acrylonitrile, styrene, ⁇ -methyl styrene, acrylamides, vinyl-Ci-C ö -alkyl ethers, methyl methacrylate, butadiene.
• Preferred acrylate rubbers as the graft base B.2 are emulsion polymers which have a gel content of at least 60% by weight.
• graft bases according to B.2 are silicone rubbers with graft-active sites, as 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 B.2 is determined at 25 ° C. in a suitable solvent (M. Hoffmann, H. Krömer, R. Kuhn, Polymeranalytik I and ⁇ , Georg Thieme Verlag, Stuttgart 1977).
• the average particle size dso is the diameter, above and below which each 50 wt .-% of the particles are. It can be determined by ultracentrifuge measurement (W. Scholtan, H. Lange, Kolloid, Z. and Z. Polymere 250 (1972), 782-1796).
• Carbon nanotubes are preferably understood as meaning cylindrical carbon tubes with a carbon content of> 95%, which contain no amorphous carbon.
• the carbon nanotubes preferably have an outer diameter between 3 and 80 nm, more preferably 5 to 20 nm.
• the mean value of the outer diameter is preferably 13 to 16 nm.
• the length of the cylindrical carbon nanotubes is preferably 0.1 to 20 .mu.m, more preferably 1 to 10 microns.
• the carbon nanotubes preferably consist of 2 to 50, more preferably 3 to 15 graphitic layers (also referred to as "layers" or “walls”) having a minimum inside diameter of 2 to 6 nm.
• These carbon nanotubes are also referred to as "carbon fibrils” or “hollow carbon fibers", for example.
• the preparation of the CNT used according to the invention is generally known (cf., for example, US Pat. No. 5,643,502 and DE-A 10 2006 017 695), preferably the preparation is carried out according to the method described in DE-A 10 2006 017 695, particularly preferably according to the method disclosed in Example 3 of DE-A 10 2006 017 695.
• Component D comprises one or more thermoplastic vinyl (co) polymers D.l and / or polyalkylene terephthalates D.2.
• Suitable vinyl (co) polymers D1 are polymers of at least one monomer from the group of vinylaromatics, vinyl cyanides (unsaturated nitriles), (meth) acrylic acid (Ci-Cg) - alkyl esters, unsaturated carboxylic acids and derivatives (such as anhydrides and imides) unsaturated carboxylic acids. Particularly suitable are (co) polymers of
• Methyl methacrylate, n-butyl acrylate, t-butyl acrylate, and / or unsaturated carboxylic acids such as maleic acid, and / or derivatives such as anhydrides and imides, unsaturated carboxylic acids such as maleic anhydride and N-phenylmaleimide).
• the vinyl (co) polymers D.l are resinous, thermoplastic and rubber-free. Particularly preferred is the copolymer of D.1.1 styrene and F.1.2 acrylonitrile.
• the (co) polymers according to D.1 are known and can be prepared by free-radical polymerization, in particular by emulsion, suspension, solution or bulk polymerization.
• the (co) polymers preferably have average molecular weights Mw (weight average, determined by light scattering or sedimentation) of between 15,000 and 200,000.
• the polyalkylene terephthalates of component D.2 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 wt .-%, preferably at least 90 mol%, based on the diol component of ethylene glycol and / or 1,4-butanediol radicals.
• the preferred polyalkylene terephthalates may contain, in addition to terephthalic acid residues, up to 20 mole%, preferably up to 10 mole%, of other aromatic or cycloaliphatic dicarboxylic acids having 8 to 14 carbon atoms or aliphatic dicarboxylic acids having 4 to 12 carbon atoms, e.g. 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 may contain up to 20 mol%, preferably up to 10 mol%, of other aliphatic diols having 3 to 12 carbon atoms or cycloaliphatic diols having 6 to 21 carbon atoms.
• Contain atoms eg Residues of 1,3-propanediol, 2-ethylpropane-1,3-diol, 3-neopentyl glycol, pentanediol-1,5, 1,6-hexanediol, cyclohexane-dimethanol-1,4, 3-ethyl-pentanediol-2,4, 2- Methylpentanediol-2,4, 2,2,4-trimethylpentanediol-1,3, 2-ethylhexanediol-1,3,3,2-diethylpropanediol-1,3-hexanediol-2,5,1,4-di- ( ⁇ -hydroxyethoxy) benzene, 2,2-bis- (4-hydroxycyclohexyl) -propane, 2,4-dihydroxy-1,1,3,3-tetramethyl-cyclobutane, 2,2-bis- (4-.
• the polyalkylene terephthalates can be prepared by incorporation of relatively small amounts of trihydric or trihydric alcohols or 3- or 4-basic carboxylic acids, e.g. according to DE-A 1 900 270 and US-PS
• branching agents are trimesic acid, trimellitic acid, trimethylolethane and -propane and pentaerythritol.
• polyalkylene terephthalates prepared from terephthalic acid alone and their reactive derivatives (e.g., their dialkyl esters) and ethylene glycol and / or butane-1,4-diol, and mixtures of these polyalkylene terephthalates.
• Mixtures of polyalkylene terephthalates contain from 1 to 50% by weight, preferably from 1 to 30% by weight, of polyethylene terephthalate and from 50 to 99% by weight, preferably from 70 to 99% by weight, of polybutylene terephthalate.
• the polyalkylene terephthalates preferably used have an intrinsic viscosity of 0.4 to 1.5 dl / g, preferably 0.5 to 1.2 dl / g, as 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, for example, Kunststoff-Handbuch, Volume Vm, p. 695 ff, Carl Hanser Verlag, Kunststoff 1973).
• the composition may contain further additives as component E.
• Further additives according to component E are in particular customary polymer additives, such as flame retardants (for example organic phosphorus or halogen compounds, especially bisphenol A-based oligophosphate), antidripping agents (for example compounds of the substance classes of fluorinated polyolefins, silicones and aramid fibers), lubricants and mold release agents, for example Pentaerythritol tetrastearate, nucleating agents, antistatic agents, stabilizers, CNT different fillers and reinforcing agents (for example, talc, glass fibers, mica, kaolin, CaCO 3 and glass flakes) and dyes and pigments (for example, titanium dioxide or iron oxide) in question.
• flame retardants for example organic phosphorus or halogen compounds, especially bisphenol A-based oligophosphate
• antidripping agents for example compounds of the substance classes of fluorinated polyolefins, silicones and aramid fibers
• the invention also relates to the compositions which are obtainable by the process according to the invention.
• molding compositions can be used for the production of moldings of any kind. These can be produced by injection molding, extrusion and blow molding. Another form of processing is the production of moldings by deep drawing from previously prepared plates or films.
• moldings are films, profiles, housing parts of any kind, e.g. for household appliances such as juice presses, coffee machines, blenders; for office machines such as monitors, flat screens, notebooks, printers, copiers; Panels, pipes, electrical installation ducts, windows, doors and other profiles for the construction sector (interior and exterior applications) and electrical and electronic parts such as switches, plugs and sockets, as well as body and interior components for commercial vehicles, in particular for the automotive sector.
• household appliances such as juice presses, coffee machines, blenders
• office machines such as monitors, flat screens, notebooks, printers, copiers
• Panels, pipes, electrical installation ducts, windows, doors and other profiles for the construction sector (interior and exterior applications) and electrical and electronic parts such as switches, plugs and sockets, as well as body and interior components for commercial vehicles, in particular for the automotive sector.
• the molding compositions according to the invention can also be used, for example, for the production of the following moldings or moldings: Interior fittings for Rolling stock, ships, aircraft, buses and other automobiles, electrical equipment housings for small transformers, information processing and transmission equipment housings, medical equipment housings and cladding, massagers and housings therefor, toy vehicles for children, flat wall elements, safety enclosures, thermally insulated ones Transport containers, fittings for sanitary and bath equipment, grilles for fan openings and housings for garden tools.
• Component B is a mixture of 50% by weight of components B-I and 50
• 500 mg of a catalyst consisting of the active components manganese (37 wt .-%) and cobalt (43 wt .-%) and the support materials magnesium oxide (10 wt .-%) and alumina (10 wt .-%) are in a quartz glass Fluidized bed reactor with an internal diameter of 49 mm given.
• the catalyst particles have a diameter between 100 ⁇ m and 125 ⁇ m.
• the reactor is heated from the outside to a temperature of 650 0 C, after inerting a gas mixture consisting of 40 vol .-% of ethylene, 40 vol .-% hydrogen and 20 vol .-% nitrogen at a temperature of 25 0 C by a Glass frit at the bottom of the reactor fed into the apparatus; the gas empty tube speed under operating conditions is 31.64 cm / s. Carbon nanotubes form on the catalyst, as a result of which the catalyst particles are broken up and agglomerate particles of carbon nanotubes and catalyst residues are formed.
• the temperatures in the reactor at positions 1 cm, 5 cm and 15 cm above the glass frit are observed. After about 15 minutes, a significant drop in temperature is observed 1 cm above the frit.
• the removed product is agglomerates of cylindrical carbon tubes with a carbon content of> 95%, which contain no amorphous carbon.
• the carbon nanotubes have an outer diameter between 5 to 20 nm and an average outer diameter of 13 to 16 nm.
• the length of the cylindrical carbon nanotubes is 0.1 to 20 microns.
• the carbon nanotubes consist of 3 to 15 graphitic layers, which have a smallest inner diameter of 2 to 6 nm.
• EI pentaerythritol tetrastearate as lubricant / mold release agent
• E-2 anhydrous citric acid: phosphite stabilizer, Irganox ® B 900, Ciba Specialty Chemicals E-3.
• twin-screw extruder ZSK-25 (Werner and Pfleiderer) (Werner and Pfleiderer) components A, B, D and E in the respective weight ratio shown in Table 1 at a speed of 225 rpm and a throughput of 20 kg / h at a temperature of 260 0 C mixed and then granulated. All components are simultaneously introduced into the twin-screw extruder.
• the CNT masterbatch CI is used on a twin-screw extruder (ZSK-25) (Werner and Pfleiderer) with the other components A, B, D and E in the weight ratio shown in Table 1 at a speed of 225 rpm and a throughput of 20 kg / h mixed at a temperature of 260 0 C and then granulated. All components are simultaneously introduced into the twin-screw extruder.
• ZSK-25 twin-screw extruder
• the CNT masterbatch C-2 is on a twin-screw extruder (ZSK-25) (Werner and Pfleiderer) with the other components A, B, D and E in the respective weight ratio shown in Table 1 at a speed of 225 rpm and a Throughput of 20 kg / h mixed at a temperature of 260 0 C and then granulated. All components are simultaneously introduced into the twin-screw extruder.
• ZSK-25 twin-screw extruder
• the respective average molecular weight (Mw) of the polycarbonate portion of the resulting molding compositions is determined by means of GPC (compared to standards of bisphenol A polycarbonate).
• Polycarbonateanteils only low (i.e., small value for ⁇ Mw), while in the

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