Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
  • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
• • 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
  • C08K3/08—Metals
• • 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
  • C08K3/16—Halogen-containing compounds
• • 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
  • C08K3/32—Phosphorus-containing compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/04—Homopolymers or copolymers of ethene
  • C08L23/08—Copolymers of ethene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/04—Homopolymers or copolymers of ethene
  • C08L23/08—Copolymers of ethene
  • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
• • 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
• • 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
  • C08L25/16—Homopolymers or copolymers of alkyl-substituted styrenes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L35/00—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 carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L35/06—Copolymers with vinyl aromatic monomers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
  • C08L79/02—Polyamines
• • 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
  • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

Definitions

• thermoplastic molding compositions comprising
• G from 0 to 2% by weight of a polyethyleneimine homo- or copolymer
• the present invention further relates to the use of molding compositions of this type for producing moldings of any type and to the moldings thus obtainable, preferably interior parts of any type for motor vehicles.
• Thermoplastic polyamides such as PA6 and PA66
• PA6 and PA66 are often used in the form of glassfiber-reinforced molding compositions as structural materials for components which during their lifetime have exposure to elevated temperatures, and this results in thermooxidative degradation phenomena.
• Addition of known heat stabilizers can delay the occurrence of the thermooxidative degradation but cannot prevent it in the long term, and an example of this is seen in deterioration of mechanical properties.
• improved HAR can also permit the use of the components at higher temperatures.
• WO 2011/051123, WO 2011/051121 and WO 2010/076145 disclose further combinations of specific iron powders with other stabilizers.
• the surface of the moldings is not entirely satisfactory since the heat-ageing process produces porosity and causes blistering.
• the known molding compositions are not suitable for producing blow moldings since in particular melt stability is inadequate.
• Blow-moldable polyamide molding compositions have been disclosed in U.S. Pat. No. 4,966,941, ERA 295 906, CA 1,323,953, and DE-A 10042176.
• thermoplastic, blow-moldable polyamide molding compositions which have improved HAR and good surface after heat ageing, and also good mechanical properties.
• a particular intention was to improve melt stability during blow molding and to improve the surface of blow moldings.
• melt stability means not only melt strength but also thermal stability (molar mass alteration over defined periods).
• the molding compositions of the invention comprise, as component A), from 10 to 99.7% by weight, preferably from 20 to 99.5% by weight, and in particular from 30 to 94% by weight, very particularly preferably from 30 to 88% by weight, of at least one polyamide.
• the intrinsic viscosity of the polyamides of the molding compositions of the invention is generally from 90 to 350 ml/g, preferably from 110 to 240 ml/g, determined in 0.5% by weight solution in 96% by weight sulfuric acid at 25° C. in accordance with ISO 307. Particular preference is given to polyamides with IV greater than 150 ml/g, preferably greater than 165 ml/g.
• polyamides which derive from lactams having from 7 to 13 ring members, e.g. polycaprolactam, polycaprylolactam and polylaurolactam, and also polyamides obtained via reaction of dicarboxylic acids with diamines.
• Dicarboxylic acids which may be used are alkanedicarboxylic acids having from 6 to 12, in particular from 6 to 10, carbon atoms, and aromatic dicarboxylic acids. Acids which may be mentioned here merely as examples are adipic acid, azelaic acid, sebacic acid, dodecanedioic acid and terephthalic and/or isophthalic acid.
• Particularly suitable diamines are alkanediamines having from 6 to 12, in particular from 6 to 8, carbon atoms, and also m-xylylenediamine (e.g. Ultramid® X17 from BASF SE, 1:1 molar ratio of MXDA to adipic acid), di(4-aminophenyl)methane, di(4-aminocyclohexyl)methane, 2,2-di(4-aminophenyl)propane, 2,2-di(4-aminocyclohexyl)propane or 1,5-diamino-2-methylpentane.
• m-xylylenediamine e.g. Ultramid® X17 from BASF SE, 1:1 molar ratio of MXDA to adipic acid
• Preferred polyamides are polyhexamethyleneadipamide, polyhexamethylenesebacamide and polycaprolactam, and also nylon-6/6,6 copolyamides, in particular having a proportion of from 5 to 95% by weight of caprolactam units (e.g. Ultramid® C33 from BASF SE).
• Ultramid® C33 from BASF SE
• polystyrene resin e.g. polystyrene resin
• PA 6 aminocapronitrile
• PA 66 adiponitrile with hexamethylenediamine
• polyamides obtainable, by way of example, via condensation of 1,4-diaminobutane with adipic acid at an elevated temperature (nylon-4,6). Preparation processes for polyamides of this structure are described by way of example in EP-A 38 094, EP-A 38 582, and EP-A 39 524.
• suitable materials are polyamides obtainable via copolymerization of two or more of the abovementioned monomers, and mixtures of two or more polyamides in any desired mixing ratio. Particular preference is given to mixtures of nylon-6,6 with other polyamides, and in particular to nylon-6/6,6 copolyamides.
• polyamides which have proven particularly advantageous are semiaromatic copolyamides, such as PA 6/6T and PA 66/6T, where the triamine content of these is less than 0.5% by weight, preferably less than 0.3% by weight (see EP-A 299 444).
• EP-A 19 94 075 discloses other polyamides resistant to high temperature (PA 6T/6I/MXD6).
• the following list which is not comprehensive, comprises the polyamides A) mentioned and other polyamides A) for the purposes of the invention, and the monomers comprised.
• PA 46 Tetramethylenediamine, adipic acid
• PA 66 Hexamethylenediamine, adipic acid
• PA 69 Hexamethylenediamine, azelaic acid
• PA 610 Hexamethylenediamine, sebacic acid
• PA 612 Hexamethylenediamine, decanedicarboxylic acid
• PA 613 Hexamethylenediamine, undecanedicarboxylic acid
• PA 1212 1,12-Dodecanediamine, decanedicarboxylic acid
• PA 1313 1,13-Diaminotridecane, undecanedicarboxylic acid
• PA 6T Hexamethylenediamine, terephthalic acid
• PA 9T 1,9-Nonanediamine, terephthalic acid
• PA MXD6 m-Xylylenediamine, adipic acid
• PA 6I Hexamethylenediamine, isophthalic acid
• PA 6-3-T Trimethylhexamethylenediamine, terephthalic acid
• PA 6/6T (see PA 6 and PA 6T)
• PA 6/66 (see PA 6 and PA 66)
• PA 6/12 (see PA 6 and PA 12)
• PA 66/6/610 (see PA 66, PA 6 and PA 610)
• PA 6I/6T (see PA 6I and PA 6T)
• PA PACM 12 Diaminodicyclohexylmethane, laurolactam
• PA 6I/6T/PACM As PA 6I/6T + diaminodicyclohexylmethane
• PA 12/MACMI Laurolactam, dimethyldiaminodicyclohexylmethane, isophthalic acid
• PA 12/MACMT Laurolactam, dimethyldiaminodicyclohexylmethane, terephthalic acid
• PA PDA-T Ph
• the molding compositions of the invention comprise, as component B), from 1 to 30% by weight, preferably from 5 to 25% by weight, and in particular from 10 to 25% by weight, of an impact modifier (often also termed rubber, or elastomeric polymer).
• an impact modifier also termed rubber, or elastomeric polymer.
• the proportion of the functional groups B 3 ) is from 0.05 to 5% by weight, preferably from 0.2 to 4% by weight, and in particular from 0.3 to 3.5% by weight, based on 100% by weight of B).
• Particularly preferred components B3) are composed of an ethylenically unsaturated mono- or dicarboxylic acid or of a functional derivative of this type of acid.
• Suitable compounds are in principle any of the primary, secondary, and tertiary C 1 -C 18 -alkyl esters of acrylic acid or methacrylic acid, but preference is given to esters having from 1 to 12 carbon atoms, in particular having from 2 to 10 carbon atoms.
• Examples here are methyl, ethyl, propyl, n-butyl, isobutyl, tert-butyl, 2-ethylhexyl, octyl, and decyl acrylates and the corresponding methacrylates.
• n-butyl acrylate and 2-ethylhexyl acrylate are particularly preferred.
• the olefin polymers comprise, instead of the esters or in addition thereto, acid-functional and/or latent acid-functional monomers of ethylenically unsaturated mono- or dicarboxylic acids, or monomers having epoxy groups.
• monomers B 3 are acrylic acid, methacrylic acid, tertiary alkyl esters of these acids, in particular tert-butyl acrylate, and dicarboxylic acids, such as maleic acid and fumaric acid, and derivatives of these acids, and also monoesters thereof.
• latent acid-functional monomers means compounds which form free acid groups under the conditions of polymerization or during incorporation of the olefin polymers into the molding compositions. Examples that may be mentioned of these are anhydrides of dicarboxylic acids having up to 20 carbon atoms, in particular maleic anhydride, and tertiary C 1 -C 12 -alkyl esters of the abovementioned acids, in particular Cert-butyl acrylate and tert-butyl methacrylate.
• the acid-functional or latent acid-functional monomers and the monomers comprising epoxy groups are preferably incorporated into the olefin polymers via addition of compounds of the general formulae I-IV to the monomer mixture.
• radicals R 1 -R 9 are hydrogen or alkyl groups having from 1 to 6 carbon atoms and m is an integer from 0 to 20 and n is an integer from 0 to 10.
• Hydrogen is preferred for R 1 -R 7 , the value 0 or 1 is preferred for m, and the value 1 is preferred for n.
• the corresponding compounds are maleic acid, fumaric acid, maleic anhydride and, respectively, alkenyl glycidyl ether or vinyl glycidyl ether.
• Preferred compounds of the formulae I, II, III and IV are maleic acid and maleic anhydride as component B 3 ) and epoxidized esters of acrylic acid and/or methacrylic acid, particular preference being given to glycidyl acrylate and glycidyl methacrylate (as component B 3 ).
• the ethylene copolymers described above can be produced by processes known per se, preferably via random copolymerization at high pressure and elevated temperature.
• the melt index of the ethylene copolymers is generally in the range from 1 to 80 g/10 min (measured at 190° C. with 2.16 kg load).
• the molar mass of these ethylene- ⁇ -olefin copolymers is from 10 000 to 500 000 g/mol, preferably from 15 000 to 400 000 g/mol (Mn, determined by means of GPC in 1,2,4-trichlorobenzene with PS calibration).
• One particular embodiment uses ethylene-a-olefin copolymers produced by means of what are known as single-site catalysts. Further details can be found in U.S. Pat. No. 5,272,236.
• the ethylene- ⁇ -olefin copolymers here have a molecular weight polydispersity which is narrow for polyolefins: smaller than 4, preferably smaller than 3.5.
• copolymers II composed of
• esters of acrylic and/or methacrylic acid are the methyl, ethyl, propyl, and isobutyl or tert-butyl esters.
• the ethylene copolymers described above can be produced by processes known per se, preferably via random copolymerization at high pressure and elevated temperature. Appropriate processes are well known.
• elastomers are emulsion polymers, production of which is described, for example, by Blackley in the monograph “Emulsion Polymerization”.
• the emulsifiers and catalysts that can be used are known per se.
• copolymers II which comprise no units B 5 ), where the acid component B 4 ) has however been neutralized with Zn.
• the molding compositions of the invention comprise, as component C), from 0.1 to 10% by weight, preferably from 0.25 to 5% by weight, and in particular from 0.5 to 3% by weight, of a copolymer of:
• Preferred radicals R are methyl, ethyl, and hydrogen.
• Preferred radicals R 1 are methyl and ethyl.
• Preferred components C 1 are styrene, a-methylstyrene, and mixtures of these.
• any of the dicarboxylic anhydrides known to the person skilled in the art and described in the prior art can be used as component C 2 ); it is preferable to use maleic anhydride, methylmaleic anhydride, itaconic anhydride, or a mixture of these; it is particularly preferable to use maleic anhydride.
• component C a copolymer of styrene (C 1 ) and maleic anhydride (C 2 ).
• copolymers C) with a ratio of from 1:1 to 8:1, preferably from 2:1 to 5:1, for the units C 1 :C 2 .
• Copolymers of this type are usually obtainable via free-radical polymerization.
• N,N-dimethylformamide/DMF N,N-dimethylformamide/DMF
• 2,2′-azobisiso-butyronitrile as initiator
• toluene e.g. Vora R. A. et al., Synthesis and characterization of styrene-maleic anhydride copolymers, J. Polym. Mater. 12 (1995), 111-120).
• Suitable materials are commercial high-molecular-weight copolymers C) with molar masses (M w ) between about 65 000 and 180 000 g/mol and with maleic anhydride contents of from 15 to 28% (Polyscope).
• copolymers C) with molar masses (M w ) of from 5000 to 25 000 g/mol, preferably from 8000 to 15 000 g/mol.
• M w molar masses
• Products of this type are obtainable with trademark SMA® from Cray Valley or Joncryl® ADR 3229 from BASF SE.
• the molding compositions of the invention comprise, as component D), from 0.001 to 20% by weight, preferably from 0.05 to 10% by weight, and in particular from 0.1 to 5% by weight, of iron powder, preferably with a particle size of at most 10 ⁇ m (d 50 value).
• Preferred Fe powders are obtainable via thermal decomposition of pentacarbonyl iron.
• Metallic iron is generally silver-white, density 7.874 g/cm 3 (heavy metal), m.p. 1539° C., boiling point 2880° C.; specific heat (from 18 to 100° C.) about 0.5 g ⁇ 1 K ⁇ 1 , tensile strength from 220 to 280 N/mm 2 . The values apply to chemically pure iron.
• Iron is produced industrially by smelting of iron ores, iron slag, burnt ores, or blast-furnace-flue dust, and by resmelting of scrap and alloys.
• the iron powder of the invention is preferably produced via thermal decomposition of pentacarbonyl iron, preferably at temperatures of from 150° C. to 350° C.
• the particles thus obtainable are preferably of spherical shape or almost spherical shape (another term used being spherolitic).
• the particle size distribution of preferred iron powder is as described below, and the particle size distribution here is determined by means of laser scattering in a highly dilute aqueous suspension (e.g. by using Beckmann LS13320 equipment). Grinding and/or sieving can optionally be used for adjustment to the particle size (and distribution) described below.
• d xx is that XX % of the total volume of the particles are smaller than the value.
• the iron content of component D) is preferably from 97 to 99.8 g/100 g, with preference from 97.5 to 99.6 g/100 g.
• the content of other metals is preferably below 1000 ppm, in particular below 100 ppm, and very particularly below 10 ppm.
• Fe content is usually determined by infrared spectroscopy.
• C content is preferably from 0.01 to 1.2 g/100 g, preferably from 0.05 to 1.1 g/100 g, and in particular from 0.4 to 1.1 g/100g.
• This C content in the preferred iron powders is appropriate for iron powders which are not reduced with hydrogen after the thermal decomposition process.
• C content is usually determined by a method based on ASTM E1019 via combustion of the specimen in a stream of oxygen followed by IR detection of the CO 2 gas produced (by means of a Leco CS230 or CS-mat 6250 from Juwe).
• Nitrogen content is preferably at most 1.5 g/100 g, preferably from 0.01 to 1.2 g/100 g.
• Oxygen content is preferably at most 1.3 g/100 g, with preference from 0.3 to 0.65 g/100 g.
• N and O are determined via heating of the specimen in a graphite oven to about 2100° C.
• the oxygen comprised in the specimen here is converted to CO and measured by way of an IR detector.
• the N liberated from the N-containing compounds under the reaction conditions is discharged with the carrier gas and detected by means of a thermal conductivity (TC) detector and recorded (both methods being based on ASTM E1019).
• TC thermal conductivity
• Tap density is preferably from 2.5 to 5 g/cm 3 , in particular from 2.7 to 4.4 g/cm 3 . This generally means the density after the powder has been compacted by, for example, charging to, and vibrating in, a container.
• Iron powders to which preference is further given can have a surface coating of iron phosphate, iron phosphite, or SiO 2 .
• BET surface area in accordance with DIN ISO 9277 is preferably from 0.1 to 10 m 2 /g, in particular from 0.1 to 5 m 2 /g, with preference from 0.2 to 1 m 2 /g, and in particular from 0.4 to 11 m 2 /g.
• a masterbatch with a polymer can be used.
• Suitable polymers for this purpose are those such as polyolefins, polyesters, or polyamides, and it is preferable here that the masterbatch polymer is the same as component A).
• the proportion by mass of the iron in the polymer is generally from 15 to 80% by mass, preferably from 20 to 40% by mass.
• the molding compositions of the invention comprise, as component E), from 0.05 to 3% by weight, preferably from 0.1 to 1,5% by weight, and in particular from 0.1 to 1% by weight, of a Cu stabilizer, preferably of a Cu(I) halide, in particular in a mixture with an alkali metal halide, preferably KI, in particular in a ratio of 1:4.
• a Cu stabilizer preferably of a Cu(I) halide, in particular in a mixture with an alkali metal halide, preferably KI, in particular in a ratio of 1:4.
• Preferred salts of monovalent copper used are cuprous acetate, cuprous chloride, cuprous bromide, and cuprous iodide.
• the materials comprise these in amounts of from 5 to 500 ppm of copper, preferably from 10 to 250 ppm, based on polyamide.
• the advantageous properties are in particular obtained if the copper is present with molecular distribution in the polyamide.
• a concentrate comprising polyamide, and comprising a salt of monovalent copper, and comprising an alkali metal halide in the form of a solid, homogeneous solution, is added to the molding composition.
• a typical concentrate is composed of from 79 to 95% by weight of polyamide and from 21 to 5% by weight of a mixture composed of copper iodide or copper bromide and potassium iodide.
• the copper concentration in the solid homogenous solution is preferably from 0.3 to 3% by weight, in particular from 0.5 to 2% by weight, based on the total weight of the solution, and the molar ratio of cuprous iodide to potassium iodide is from 1 to 11.5, preferably from 1 to 5.
• Particularly suitable concentrates are those using PA6 and/or PA66.
• the molding compositions of the invention comprise, as component F), from 100 ppm to 5% by weight, preferably from 500 ppm to 1% by weight, and in particular from 0.01 to 0.3% by weight, of a phosphorus-containing inorganic acid or salts thereof or ester derivatives thereof or a mixture thereof.
• Preferred acids are the oxo acids of phosphorus, e.g. hypophosphorous acid (phosphinic acid), phosphorous acid, phosphoric acid, and mixtures of these.
• Suitable metal cations for these salts are transition metal cations or alkali metal cations or alkaline earth metal cations, particular preference being given here to calcium, barium, magnesium, sodium, potassium, manganese, aluminum, and mixtures of these.
• Particularly preferred salts are Na hypophosphite, manganese(II) hypophosphite Mn(H 2 P0 2 ) 2 , aluminum hypophosphite, and mixtures of these.
• Suitable preferred ester derivatives (phosphonates or salts thereof) of the oxo acids of phosphorus are those bearing identical or different alkyl radicals having from 1 to 4 carbon atoms or aryl radicals having from 6 to 14 carbon atoms as substituents.
• Examples of preferred compounds are the Ca phosphonate obtainable as Irgamod® 195 from BASF SE and the diethyl phosphonate obtainable as Irgamod® 295 from BASF SE.
• the thermoplastic molding compositions can comprise, as component G), from 0 to 2% by weight of at least one polyethyleneimine homo- or copolymer.
• the proportion of G) is preferably from 0.01 to 2% by weight and in particular from 0.1 to 1% by weight, and very particularly preferably from 0.1 to 0.5% by weight, based on A) to H), and preference is given here to branched polyethyleneimines.
• polyethyleneimines means homo- or copolymers which are obtainable by way of example by the processes in Ullmann Electronic Release under keyword “Aziridines” or in accordance with WO-A 94/12560.
• the homopolymers are generally obtainable via polymerization of ethyleneimine (aziridine) in aqueous or organic solution in the presence of compounds which cleave to give acids, or of Lewis acids or of other acids.
• These homopolymers are branched polymers which generally comprise primary, secondary, and tertiary amino groups in a ratio of about 30%:40%:30%.
• the distribution of the amino groups can generally be determined by means of 13 C NMR spectroscopy. It is preferably from 1/0.7-1.4/0.3-1.1 to 1/0.8-1.3/0.5-0.9.
• Comonomers used are preferably compounds which have at least two amino functions.
• suitable comonomers are alkylenediamines having from 2 to 10 carbon atoms in the alkylene radical, preference being given here to ethylenediamine and propylenediamine.
• Comonomers having further suitability are diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenetriamine, tripropylenetetramine, dihexamethylenetriamine, aminopropylethylenediamine, and bisaminopropylethylenediamine.
• the average molecular weight (weight average) of polyethyleneimines is usually from 100 to 3 000 000, preferably from 500 to 2 000 000 (determined by light scattering).
• the preferred molecular weight M w is from 700 to 1 500 000, in particular from 1000 to 500 000.
• crosslinked polyethyleneimines obtainable via reaction of polyethyleneimines with bi- or polyfunctional crosslinking agents which have, as functional group, at least one halohydrin unit, glycidyl unit, aziridine unit, isocyanate unit, or one halogen atom.
• examples that may be mentioned are epichlorohydrin or bischlorohydrin ethers of polyalkylene glycols having from 2 to 100 ethylene oxide units and/or propylene oxide units, and also the compounds listed in DE-A 19 93 17 20 and U.S. Pat. No. 4,144,123.
• Processes for the production of crosslinked polyethyleneimines are known inter alia from the abovementioned specifications, and also EP-A 895 521 and EP-A 25 515.
• Grafted polyethyleneimines are also suitable, and the grafting agents that can be used comprise any of the compounds which can react with the amino or imino groups of the polyethyleneimines. Suitable grafting agents and processes for the production of grafted polyethyleneimines are found by way of example in EP-A 675 914.
• Polyethyleneimines likewise suitable for the purposes of the invention are amidated polymers, which are usually obtainable via reaction of polyethyleneimines with carboxylic acids, their esters or anhydrides, or carboxamides, or carbonyl halides.
• the amidated polymers can be subsequently crosslinked using the crosslinking agents mentioned. It is preferable that up to 30% of the amino functions are amidated here, in order that there are sufficient primary and/or secondary nitrogen atoms available for a subsequent crosslinking reaction.
• alkoxylated polyethyleneimines which are by way of example obtainable via reaction of polyethyleneimine with ethylene oxide and/or with propylene oxide.
• alkoxylated polymers can also be subsequently crosslinked.
• polyethyleneimines of the invention are polyethyleneimines containing hydroxy groups and amphoteric polyethyleneimines (incorporation of anionic groups), and also lipophilic polyethyleneimines, which are generally obtained via incorporation of long-chain hydrocarbon radicals into the polymer chain. Processes for the production of these polyethyleneimines are known to the person skilled in the art, and further details in this connection would therefore be superfluous.
• the molding compositions of the invention can comprise, as component H), up to 60% by weight, preferably up to 50% by weight, of further additives.
• Fibrous or particulate fillers H are carbon fibers, glass fibers, glass beads, amorphous silica, calcium silicate, calcium metasilicate, magnesium carbonate, kaolin, chalk, powdered quartz, mica, barium sulfate and feldspar, used in amounts of from 1 to 50% by weight, in particular from 5 to 40% by weight, preferably from 10 to 40% by weight.
• Preferred fibrous fillers which may be mentioned are carbon fibers, aramid fibers and potassium titanate fibers, and particular preference is given to glass fibers in the form of E glass. These may be used as rovings or in the commercially available forms of chopped glass.
• the fibrous fillers may have been surface-pretreated with a silane compound to improve compatibility with the thermoplastic.
• Suitable silane compounds have the general formula:
• n is an integer from 2 to 10, preferably from 3 to 4,
• n is an integer from 1 to 5, preferably from 1 to 2
• k is an integer from 1 to 3, preferably 1.
• Preferred silane compounds are aminopropyltrimethoxysilane, aminobutyltrimethoxysilane, aminopropyltriethoxysilane and aminobutyltriethoxysilane, and also the corresponding silanes which comprise a glycidyl group as substituent X.
• Long glass fibers are also suitable as component H) and these can be used as rovings.
• the diameter of the glass fibers used as rovings in the invention is from 6 to 20 ⁇ m, preferably from 10 to 18 ⁇ m, and the cross section of the glass fibers here is round, oval, or polygonal.
• E glass fibers are used in the invention.
• the L/D (length/diameter) ratio is from 100 to 4000, in particular from 350 to 2000, and very particularly from 350 to 700.
• acicular mineral fillers are mineral fillers with strongly developed acicular character.
• An example is acicular wollastonite.
• the mineral preferably has an L/D (length to diameter) ratio of from 8:1 to 35:1, preferably from 8:1 to 11:1.
• the mineral filler may, if appropriate, have been pretreated with the abovementioned silane compounds, but the pretreatment is not essential.
• fillers which may be mentioned are kaolin, calcined kaolin, wollastonite, talc and chalk, and also lamellar or acicular nanofillers, the amounts of these preferably being from 0.1 to 10%.
• lamellar nanofillers are organically modified by prior-art methods, to give them good compatibility with the organic binder. Addition of the lamellar or acicular nanofillers to the inventive nanocomposites gives a further increase in mechanical strength.
• the inventive molding compositions can comprise, as component H), from 0.05 to 3% by weight, preferably from 0.1 to 1.5% by weight, and in particular from 0.1 to 1% by weight, of a lubricant.
• the metal ions are preferably alkaline earth metal and Al, particular preference being given to Ca or Mg.
• Preferred metal salts are Ca stearate and Ca montanate, and also Al stearate.
• the carboxylic acids can be monobasic or dibasic. Examples which may be mentioned are pelargonic acid, palmitic acid, lauric acid, margaric acid, dodecanedioic acid, behenic acid, and particularly preferably stearic acid, capric acid, and also montanic acid (a mixture of fatty acids having from 30 to 40 carbon atoms).
• the aliphatic alcohols can be monohydric to tetrahydric.
• examples of alcohols are n-butanol or n-octanol, stearyl alcohol, ethylene glycol, propylene glycol, neopentyl glycol, pentaerythritol, preference being given to glycerol and pentaerythritol.
• the aliphatic amines can be mono- to tribasic. Examples of these are stearylamine, ethylenediamine, propylenediamine, hexamethylenediamine, di(6-aminohexyl)amine, particular preference being given to ethylenediamine and hexamethylenediamine.
• Preferred esters or amides are correspondingly glycerol distearate, glycerol tristearate, ethylenediamine distearate, glycerol monopalmitate, glycerol trilaurate, glycerol monobehenate, and pentaerythritol tetrastearate.
• Suitable sterically hindered phenols H are in principle any of the compounds having a phenolic structure and having at least one bulky group on the phenolic ring.
• R 1 and R 2 are an alkyl group, a substituted alkyl group, or a substituted triazole group, where the radicals R 1 and R 2 can be identical or different, and R 3 is an alkyl group, a substituted alkyl group, an alkoxy group, or a substituted amino group.
• Antioxidants of the type mentioned are described by way of example in DE-A 27 02 661 (U.S. Pat. No. 4,360,617).
• Another group of preferred sterically hindered phenols is those derived from substituted benzenecarboxylic acids, in particular from substituted benzenepropionic acids.
• Particularly preferred compounds from this class are compounds of the formula
• R 4 , R 5 , R 7 , and R 8 independently of one another, are C 1 -C 8 -alkyl groups which themselves may have substitution (at least one of these being a bulky group), and R 6 is a divalent aliphatic radical which has from 1 to 10 carbon atoms and whose main chain may also have C—O bonds.
• the amount comprised of the antioxidants H), which may be used individually or as a mixture, is from 0.05 up to 3% by weight, preferably from 0.1 up to 1.5% by weight, in particular from 0.1 to 1% by weight, based on the total weight of the molding compositions A) to G).
• sterically hindered phenols having no more than one sterically hindered group in ortho-position with respect to the phenolic hydroxy group have proven particularly advantageous, in particular when assessing colorfastness on storage in diffuse light over relatively long periods.
• Preferred components H) have not only a P-containing substituent but also a sterically hindered phenol system and are available commercially by way of example as Irgafos®168, Irgafos® TPP, Irgafos® TNPP, or Irgafos® P-EPQ (phosphonite) from BASF SE.
• the molding compositions of the invention can comprise, as component H), from 0.05 to 5% by weight, preferably from 0.1 to 2% by weight, and in particular from 0.25 to 1.5% by weight, of a nigrosin.
• Nigrosins are generally various embodiments (water-soluble, fat-soluble, petroleum-soluble) of a group of black or gray phenazine dyes (azine dyes) related to the indulins and used in wool dyeing, wool printing, black dyeing of silk, for the coloring of leather, of shoe polishes, of varnishes, of plastics, of stoving lacquers, of inks, and the like, and also as microscopy dyes.
• azine dyes phenazine dyes
• Component H can be used in the form of free base or else in the form of salt (e.g. hydrochloride).
• thermoplastic molding compositions of the invention can comprise, as component H), conventional processing aids, such as stabilizers, oxidation retarders, agents to counteract decomposition by heat and decomposition by ultraviolet light, lubricants and mold-release agents, colorants, such as dyes and pigments, nucleating agents, plasticizers, etc.
• processing aids such as stabilizers, oxidation retarders, agents to counteract decomposition by heat and decomposition by ultraviolet light
• lubricants and mold-release agents colorants, such as dyes and pigments, nucleating agents, plasticizers, etc.
• oxidation retarders and heat stabilizers examples include sterically hindered phosphites and amines (e.g. TAD), hydroquinones, aromatic secondary amines, such as diphenylamines, various substituted representatives of these groups, and mixtures of these, in concentrations up to 1% by weight, based on the weight of the thermoplastic molding compositions.
• TAD sterically hindered phosphites and amines
• hydroquinones such as diphenylamines
• aromatic secondary amines such as diphenylamines
• various substituted representatives of these groups such as diphenylamines
• mixtures of these in concentrations up to 1% by weight, based on the weight of the thermoplastic molding compositions.
• UV stabilizers that may be mentioned, these generally being used in amounts of up to 2% by weight, based on the molding composition, are various substituted resorcinols, salicylates, benzotriazoles, and benzophenones.
• Colorants that may be added are inorganic pigments, such as titanium dioxide, ultramarine blue, iron oxide and carbon black, and also organic pigments, such as phthalocyanines, quinacridones, perylenes, and also dyes, such as anthraquinones.
• inorganic pigments such as titanium dioxide, ultramarine blue, iron oxide and carbon black
• organic pigments such as phthalocyanines, quinacridones, perylenes, and also dyes, such as anthraquinones.
• Flame retardants that may be mentioned are phosphorus and P- and N-containing compounds.
• Nucleating agents that can be used are sodium phenylphosphinate, aluminum oxide, silicon dioxide, and also preferably talc powder.
• thermoplastic molding compositions of the invention can be produced by processes known per se, by mixing the starting components in conventional mixing apparatuses, such as screw-based extruders, Brabender mixers, or Banbury mixers, and then extruding them.
• the extrudate can be cooled and comminuted. It is also possible to premix individual components and then to add the remaining starting materials individually and/or likewise in mixed form.
• the mixing temperatures are generally from 230 to 320° C.
• components B) to G), and also, if appropriate, H) can be mixed, compounded, and pelletized with a prepolymer.
• the resultant pellets are then solid-phase condensed continuously or batchwise under an inert gas at a temperature below the melting point of component A) until the desired viscosity has been reached.
• the long-glassfiber-reinforced polyamide molding compositions of the invention can be produced by the known processes for producing elongate long-fiber-reinforced pellets, in particular by pultrusion processes, in which the continuous fiber strand (roving) is completely saturated with the polymer melt and then is cooled and chopped.
• the elongate long-fiber-reinforced pellets obtained in this manner preferably with pellet length of from 3 to 25 mm, in particular from 5 to 14 mm, can be further processed by the usual processing methods (e.g. injection molding, compression molding) to give moldings.
• the preferred L/D ratio of the pellets after pultrusion is preferably from 2 to 8, in particular from 3 to 4.5.
• non-aggressive processing methods particularly means substantial avoidance of excessive fiber breakage and of the attendant severe reduction of fiber length.
• high cylinder temperatures are used that rapidly melt the elongate pellets (contact heating) and that the fibers are not excessively comminuted through excessive exposure to shear.
• moldings are obtained which have higher average fiber length than comparable moldings produced from short-fiber-reinforced molding compositions. This gives an additional improvement in properties, in particular in relation to tensile modulus and modulus of elasticity, ultimate tensile strength, and notched impact resistance.
• Fiber length after processing of the molding, e.g. via injection molding, is usually from 0.5 to 10 mm, in particular from 1 to 3 mm.
• thermoplastic molding compositions of the invention feature good melt strength and good processability, in particular in the extrusion blow molding process (3D suction blow molding or 3D application processes) or injection stretch blow molding, together with good mechanical properties, and also markedly improved weld line strength and surface, and also thermal stability (in particular HAR).
• Nylon-6,6 with intrinsic viscosity IV 205 ml/g, measured on a 0.5% by weight solution in 96% by weight sulfuric acid at 25° C. in accordance with ISO 307. (Ultramid® A34 from BASF SE was used.)
• PA 6 with IV 250 ml/g (Ultramid® B40 from BASF SE).
• Ethylene-methacrylic acid copolymer (90/10), neutralized to an extent of about 70% with zinc (Surlyn® 9520 from DuPont)
• Styrene-maleic anhydride copolymer (3:1) (SMA® 3000P from Cray Valley)
• Iron powder CAS No. 7439-89-6 (see page 11) of description for determination of Fe, C, N, and O content used in the form of 25% masterbatch in PA 66.
• Lupasol ® WF M w 25 000 Prim./sec./tert. amines 1/1.2/0.76 Lupasol ® registered trademark of BASF SE 13 C NMR spectroscopy was used to determine the primary/secondary/tertiary amines ratio.
• Glass fibers (chopped glass fiber with thickness about 10 ⁇ m).
• the molding compositions (predrying to ⁇ 0.05%) were produced in a (ZSK) MC26 with throughput 10 kg/h and flat temperature profile at about 280° C.
• Rz is what is known as maximum roughness profile height in accordance with DIN EN ISO 4287
• Rz is determined as arithmetic average from the maximum profile heights from 5 individual measurements.
• the traverse speed vt is 0.5 mm/s.
• the TK300 sensor Hommelwerke is used, the sensor tip radius r SP max is 5 ⁇ m, and the digitization spacing ⁇ x max is 1.5 ⁇ m.
• An annular die was used for this purpose (dimensions: length L within cylindrical gap 10 mm, internal diameter 8 mm, external diameter 9 mm) in conjunction with a capillary rheometer from Göttfert.
• the specimen was compressed with the aid of the ram after melting.
• the ram was moved downward until the scale indicator was at 17.2 cm.
• the die outlet was then cleaned and the ram was moved downward to 17 cm.
• the machine After the melting time of 5 minutes, the machine initiated the ram advance at 20 mm/s for 5 seconds. The strand discharged from the die was filmed with a video camera.
• the resultant tube was removed after cooling.
• the weight, length, and diameter of the specimen strand were determined.
• a caliber gage is used to measure the maximum diameter about 2 cm below the bead on the specimen.
• SR involves calculating a ratio of the lengths of the extruded tube once ram advance has ended after 5 s of extrusion time (L1) to the length of the tube after complete cooling (L2):
• the tensile test was carried out in accordance with ISO 527-2 prior to and after heat-aging at 200° C. for 500 and 1000 hours, and also at 220° C. for 500 and 1000 hours.
• the table will show the constitiutions of the molding compositions and the results of the tests.

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• 2012
  • 2012-11-14 CN CN201280057770.9A patent/CN103958609B/zh active Active
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