WO2015140016A1 - Polyamides réticulés - Google Patents

Polyamides réticulés Download PDF

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Publication number
WO2015140016A1
WO2015140016A1 PCT/EP2015/055018 EP2015055018W WO2015140016A1 WO 2015140016 A1 WO2015140016 A1 WO 2015140016A1 EP 2015055018 W EP2015055018 W EP 2015055018W WO 2015140016 A1 WO2015140016 A1 WO 2015140016A1
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weight
polyamide
molding compositions
thermoplastic molding
polyamides
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PCT/EP2015/055018
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German (de)
English (en)
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Manoranjan Prusty
Florian Richter
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Basf Se
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Publication of WO2015140016A1 publication Critical patent/WO2015140016A1/fr

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    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3415—Five-membered rings
    • C08K5/3417—Five-membered rings condensed with carbocyclic rings
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • 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
    • C08K2003/0856—Iron

Definitions

  • the invention relates to thermoplastic molding compositions containing
  • Ak is independently hydrogen, an alkyl radical having 1 to 10 C atoms, a C 0-1
  • Q is an alkylene radical having 2 to 12 C atoms, a phenylene radical, a C 1 -4 alkylene-phenyl-C 1 -4 alkylene radical or a C 0-4 alkylene-cyclohexanediyl-C 0-4 alkylene radical,
  • G 0 to 2% by weight of a polyethyleneimine homopolymer or copolymer
  • the present invention relates to the use of such molding compositions for the production of moldings of any kind and the moldings obtainable in this case, preferably automotive interior parts of any kind.
  • Thermoplastic polyamides such as PA6 and PA66 are often used in the form of glass fiber-reinforced molding compositions as construction materials for components that are exposed to elevated temperatures during their life, resulting in thermo-oxidative damage.
  • Polyamides typically have high resistance to wear, a low coefficient of friction, good heat resistance and high impact strength.
  • polyamides absorb water, which in particular affects the tensile strength, rigidity and impact strength.
  • Despite their excellent physical and chemical properties there has long been a need to further modify or improve the property profile of polyamides in terms of, for example, higher service temperatures, better chemical resistance, and improved mechanical properties. For this purpose, attempts have already been made to improve the properties of the polyamides by crosslinking.
  • crosslinked polyamides are used in which case an additive is added during the polymerization or the compounding. After injection of the polyamide part, via an external stimulus e.g. this additive is excited by radiation or heat to react with the polyamide chain.
  • this additive is excited by radiation or heat to react with the polyamide chain.
  • this additive is from Charlesby, A, 1953, Nature 171, 167 and Deeley, C.W., Woodward, AE., Sauer, J.A, 1957, J. Appl. Phys. 28, 1 124-1 130 irradiation for crosslinking of injection-molded thermoplastics known as polyamides.
  • DE-A 2010028062 describes a process for preparing crosslinked organic polymers by reacting a polymer with a crosslinking agent selected from the group consisting of substituted cyanurates and isocyanurates.
  • the crosslinking is carried out either by addition of a suitable peroxide at 160 to 190 ° C or by electron beam crosslinking.
  • An improved property is called increased heat resistance for crosslinked PA66.
  • the crosslinking can also be thermally excited: "Angew. Makromol.
  • Chem., 1983, 1111, 17-27 "describes the synthesis of aromatic polyamides having imide side groups from 4,4'-diaminodiphenyl ether and imide-diacid chlorides by solution polycondensation.
  • the polyamide-imides thus prepared can be crosslinked and heated by heating to 220.degree insoluble materials with improved mechanical strength.
  • Ethynyl-modified polymers can also be thermally crosslinked.
  • US5493002 describes the crosslinking of oligoimides which have been capped by PEPA (phenylethynylphthalic acid anhydride) (also referred to as capping end groups of a polymer) .
  • PEPA phenylethynylphthalic acid anhydride
  • the PEPA-modified oligomers / polymers are crosslinked by annealing at 400 ° C.
  • EP-A 2 444 387 discloses the modification of polyamides with ethynyl-modified phthalic anhydrides.
  • PA66 is melt modified by MEPA (5- (prop-1 -yn-1-yl) isobenzofuran-1,3-dione) by endcapping
  • MEPA 2- (prop-1 -yn-1-yl) isobenzofuran-1,3-dione
  • the thermally activated crosslinking of the resulting ethynyl-modified PA66 is determined by measuring the Melt viscosity at different temperatures shown.
  • the addition of, inter alia, ethynyl-modified phthalic anhydrides or imides can markedly improve the property profile of glass-fiber-reinforced PA.
  • the additives are compounded into the polyamide at the lowest possible temperatures, as a result of which they "endcap" the amino end groups of the polymer in the melt, but crosslinking does not take place or only on a very small scale, so that the polymer can still be processed Triple bonds of the additives are then thermally activated in a further step, for example by introducing large shear forces during injection molding or by annealing below the melting point of the polymer
  • the crosslinked polyamides thus obtained have an improved property profile.
  • the molding compositions of the invention contain 10 to 99, preferably 10 to 94 and in particular 10 to 90 wt .-%, most preferably 30 to 88 wt .-% of at least one polyamide.
  • the polyamides of the molding compositions according to the invention generally have a viscosity number of 90 to 350, preferably 1 10 to 240 ml / g, determined in a 0.5 wt .-% solution in 96 wt .-% sulfuric acid at 25 ° C according to ISO 307. Particularly preferred are polyamides having a VZ of 130-165 ml / g.
  • Semicrystalline or amorphous resins having a weight average molecular weight of at least 5,000 such as e.g. U.S. Patents 2,071,250, 2,071,251, 2,130,523, 2,130,948, 2,241,322, 2,312,966, 2,512,606 and 3,393,210 are preferred.
  • Examples include polyamides derived from lactams having 7 to 13 ring members, such as polycaprolactam, polycapryllactam and polylaurolactam and polyamides obtained by reacting dicarboxylic acids with diamines.
  • alkanedicarboxylic acids having 6 to 12, in particular 6 to 10 carbon atoms and aromatic dicarboxylic acids can be used.
  • adipic acid, azelaic acid, sebacic acid, dodecanedioic acid and terephthalic and / or isophthalic acid may be mentioned as acids.
  • Suitable diamines are, in particular, alkanediamines having 6 to 12, in particular 6 to
  • Preferred polyamides are polyhexamethylene adipamide, polyhexamethylene sebacamide and polycaprolactam and copolyamides 6/66, in particular with an on part of Figure 5 to 95 wt .-% of caprolactam units (for example Ultramid ® C33 BASF SE).
  • polyamides are obtainable from ⁇ -aminoalkyl nitriles such as aminocapronitrile (PA 6) and adiponitrile with hexamethylenediamine (PA 66) by so-called direct polymerization in the presence of water, as for example in DE-A 10313681, EP-A 1 198491 and EP 922065.
  • PA 6 aminocapronitrile
  • PA 66 adiponitrile with hexamethylenediamine
  • polyamides may also be mentioned which are obtainable, for example, by condensation of 1,4-diaminobutane with adipic acid at elevated temperature (polyamide 4,6). Production processes for polyamides of this structure are described, for example, in EP-A 38 094, EP-A 38 582 and EP-A 39 524.
  • polyamides which are obtainable by copolymerization of two or more of the abovementioned monomers or mixtures of a plurality of polyamides are suitable, the mixing ratio being arbitrary. Particular preference is given to mixtures of polyamide 66 with other polyamides, in particular copolyamides 6/66.
  • the triamine content is less than 0.5, preferably less than 0.3 wt .-% (see EP-A 299 444).
  • Further high-temperature-resistant polyamides are known from EP-A 19 94 075 (PA 6T / 6I / MXD6).
  • the production of the preferred partly aromatic copolyamides with a low triamine content can be carried out by the processes described in EP-A 129 195 and 129 196.
  • PA 46 tetramethylenediamine, adipic acid
  • PA 66 hexamethylenediamine, adipic 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 61 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 61 and PA 6T
  • PA PA PACM 12 diaminodicyclohexylmethane, laurolactam
  • PA 6I / 6T / PACM Like PA 6I / 6T + diaminodicyclohexylmethane
  • PA PDA-T phenylenediamine, terephthalic acid
  • Preferred polyamides have a number of primary amino end groups of> 75 mmol / kg, in particular equal to 90 mmol / kg.
  • the number of primary amino end groups of the inventively employable polyamides can be adjusted in their preparation by an appropriate ratio of present in the monomers amino to carboxylic acid end groups. The presence of this particular number of primary amino end groups helps to increase the crosslinkability of the thermoplastic molding compositions of the invention.
  • the determination of the amino end groups can be carried out for example by means of titration of a solution of the polyamide in the presence of an indicator.
  • the polyamide is dissolved in a mixture of phenol and methanol (e.g., 75% by weight of phenol and 25% by weight of methanol) with heating.
  • the mixture may be refluxed at the boiling point until the polymer is dissolved.
  • the cooled solution is mixed with a suitable indicator mixture (for example, methanol solution of benzyl orange and methylene blue) and titrated with a methanol-containing perchloric acid solution in glycol until the color changes. From the perchloric acid consumption, the amino end group concentration is calculated.
  • the titration without indicator can also be carried out potentiometrically with a hydrochloric acid solution in a phenol / methanol mixture.
  • the determination of the carboxyl end groups can also be carried out, for example, by titration of a solution of the polyamide using an indicator.
  • the polyamide is dissolved in benzyl alcohol (phenylmethanol) with heating, for example until boiling, wherein a riser is placed and nitrogen gas is introduced.
  • a suitable indicator eg propanolic solution of cresol red
  • an alcoholic potassium hydroxide solution KOH dissolved in a mixture of methanol, 1-propanol and 1 -hexanol
  • the titration without indicator can also be carried out potentiometrically with a NaOH solution in benzyl alcohol, as described in WO 02/26865 on pages 1-12.
  • the polyamide has a molar fraction of diamine-controlled chains of> 30 mol%, preferably> 40 mol%, particularly preferably 50 mol%.
  • the presence of at least 30 mol% of polymer chains, which are controlled with a diamine, helps to significantly increase the stability against thermo-oxidative degradation and hydrolysis resistance.
  • the diamine is added to the monomer mixture at the beginning of the polymerization.
  • the diamine is metered in the preparation of the polyamide subsequently to the polymer melt.
  • Suitable polyamides are e.g. in U.S. Patents 2,071,250, 2,071,251, 2,130,523, 2,130,948, 2,241, 322, 2,312,966, 2,512,606 and 3,393,210.
  • Aliphatic, partially aromatic or aromatic polyamides may be used, with aliphatic polyamides being preferred.
  • aliphatic polyamides means that the polyamides are exclusively composed of aliphatic monomers
  • partially aromatic polyamides means that the polyamides are composed of both aliphatic and aromatic monomers.
  • aromatic polyamides means that the polyamides are composed exclusively of aromatic monomers.
  • polyamides selected from the group consisting of polyhexamethylene adipamide (nylon 66, polyamide 66), a mixture of polyamides having a polyamide 66 content of at least 80% by weight or a copolyamide whose components are at least 80% % By weight of adipic acid and hexamethylenediamine, polyhexamethyleneazelaic acid amide (nylon 69, polyamide 69), polyhexamethylenesebacamide (nylon 610, polyamide 610), polyhexamethylenedodecanediamide (nylon 612, polyamide 612), the polyamides obtained by ring opening of lactams, such as polycaprolactam ( Nylon 6, polyamide 6), polylauric acid lactam, poly-1 1 - aminoundecanoic acid and a polyamide of di (p-aminocyclohexyl) methane and dodecanedioic acid, polyamides,
  • thermoplastic molding composition polyamides selected from the group consisting of polyhexamethylene adipamide (nylon 66, nylon 66), a mixture of polyamides having a nylon 66 content of at least 80% by weight or a copolyamide, the components of which at least 80% by weight of adipic acid and hexamethylenediamine are derivable, polyhexamethyleneazelaic acid amide (nylon 69, polyamide 69), polyhexamethylenesebacamide (nylon 610, polyamide 610), polyhexamethylenedodecanediamide (nylon 612, polyamide 612), the polyamides obtained by ring opening of lactams, such as Polycaprolactam (nylon 6, polyamide 6), polylauri
  • Polycaprolactam (nylon 6, polyamide 6) can also be obtained by a polycondensation reaction of 6-aminohexanoic acid.
  • thermoplastic molding compositions which are selected from the group consisting of polyhexamethylene adipamide (nylon 66, nylon 66), a mixture of polyamides having a polyamide 66 content of at least 80% by weight or a copolyamide , whose building blocks are derivable to at least 80 wt .-% of adipic acid and hexamethylenediamine, polycaprolactam (nylon 6, polyamide 6) or mixtures thereof.
  • the novel thermoplastic molding compositions may contain, as component B), 0 to 50% by weight, preferably 5 to 45% by weight, in particular 10 to 40% by weight, of glass fibers.
  • thermoplastic molding compositions all glass fibers known to the person skilled in the art and suitable for use in thermoplastic molding compositions can be present. These glass fibers can be prepared by methods known to the person skilled in the art and, if appropriate, surface-treated. The glass fibers may be provided with a size for better compatibility with the matrix material, as e.g. in DE 101 17715.
  • E-glass fibers are used according to the invention. But it can also all other types of glass fiber, such. A, C, D, M, S, R glass fibers or any mixtures thereof or mixtures with E glass fibers are used.
  • glass fibers having a diameter of 5 to 15 ⁇ m, preferably 7 to 13 ⁇ m, particularly preferably 9 to 11 ⁇ m are used.
  • the incorporation of the glass fibers can take place both in the form of chopped glass fibers and in the form of endless strands (rovings).
  • the length of the usable glass fibers is in the Usually before incorporation as chopped glass fibers in the thermoplastic molding compositions typically 4 to 5 mm.
  • the glass fibers are usually in a mean length of 100 to 400 ⁇ , preferably 200 to 350 ⁇ ago.
  • the molding compositions according to the invention contain 0.1 to 20, preferably 0.2 to 20, in particular 1 to 15 wt .-% of a compound of general formula I or II or their Mischun s
  • Ak is independently hydrogen, an alkyl radical having 1 to 10 C atoms, a C 0-1
  • Q is an alkylene radical having 2 to 12 C atoms, a phenylene radical, a C 1 -4 alkylene-phenyl-C-1 -4 alkylene radical or a C 0-4 alkylene-cyclohexanediyl-C 0-4 alkylene radical.
  • Preferred crosslinkers as component C) are
  • the molding compositions of the invention contain from 0.001 to 20, preferably from 0.05 to 10, and in particular from 0.1 to 5,% by weight of iron powder, preferably with a particle size (also referred to as particle size) of not more than 10 ⁇ m (d 50 value).
  • Preferred Fe powders are obtainable by thermal decomposition of iron pentacarbonyl.
  • Iron occurs in several allotropic modifications: 1. ⁇ -Fe (ferrite) forms space-centered cubic lattice, is magnetisable, dissolves little carbon, occurs in pure iron up to 928 ° C. At 770 ° C (Curie temperature) it loses its ferromagnetic properties and becomes paramagnetic; Iron in the temperature range of 770 to 928 ° C is also referred to as ⁇ -Fe. At ordinary temperature and a pressure of at least 13000 MPa, ⁇ -Fe passes into so-called ⁇ -Fe under a vol. Reduction of about 0.20 cm 3 / mol, the density increasing from 7.85 to 9.1 (at
  • ⁇ -Fe (austenite) forms face-centered cubic lattice, is non-magnetic, dissolves a lot of carbon and can only be observed in the temperature range of 928 to 1398 ° C.
  • the iron powder of the invention is preferably prepared by thermal decomposition of iron pentacarbonyl, preferably at temperatures of 150 ° C to 350 ° C.
  • the particles (particles) obtainable in this case have a preferably spherical shape, i. spherical or nearly spherical shape (also referred to as spherulitic).
  • Preferred iron powder has a particle size distribution as described below, the particle size distribution being determined by laser diffraction in a highly diluted aqueous suspension (e.g.
  • the particle size (and distribution) described below can be adjusted by milling and / or sieving.
  • dxx XX% of the total volume of the particles is smaller than the value.
  • 3.4 to 5.2 ⁇ dio values preferably 1 to 5 ⁇ , in particular 1 to 3 and very particularly 1, 4 to 2.7 ⁇ dgo values: preferably 3 to 35 ⁇ , in particular 3 to 12 and very particularly 6.4 to
  • the component D) has an iron content of 97 to 99.8 g / 100 g, preferably from 97.5 to 99.6 g / 100 g.
  • the content of further metals is preferably below 1000 ppm, in particular below 100 ppm and very particularly below 10 ppm.
  • the Fe content is usually determined by infrared spectroscopy.
  • the C content is preferably 0.01 to 1.2, preferably 0.05 to 1.1, g / 100 g, more preferably 0.4 to 1.1 g / 100 g. In the case of the preferred iron powders, this C content corresponds to those which are not reduced with hydrogen following the thermal decomposition.
  • the C content is usually determined by burning the sample amount in the oxygen stream and subsequent IR detection of the resulting CO 2 gas (using Leco CS230 or CS-mat 6250 from Juwe) based on ASTM E1019.
  • the nitrogen content is preferably max. 1.5 g / 100 g, preferably from 0.01 to 1.2 g / 100 g.
  • the oxygen content is preferably max. 1.3 g / 100 g, preferably 0.3 to 0.65 g / 100 g.
  • the determinations of N and O are made by heating the sample in the graphite furnace to ca.
  • the oxygen obtained in the sample is converted to CO and measured by an IR detector.
  • the N released from the N-containing compounds under the reaction conditions is discharged with the carrier gas and detected and recorded by means of WLD (Thermal Conductivity Detector / TC) (both methods in accordance with ASTM E1019).
  • the tap density is preferably 2.5 to 5 g / cm 3 , in particular 2.7 to 4.4 g / cm 3 . This is generally understood to mean density when, for example, the powder is filled into the container and shaken to achieve compaction.
  • iron powders may be surface-coated with iron phosphate, iron phosphite or S1O2.
  • the 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, preferably from 0.2 to 1 m 2 / g and in particular from 0.4 to 1 m 2 / g.
  • the iron particles can be used as a batch with a polymer.
  • Polymers such as polyolefins, polyesters or polyamides are suitable for this, wherein preferably the batch polymer is equal to component A).
  • the mass fraction of the iron in the polymer is usually 15 to 80, preferably 20 to 40% by mass.
  • the molding compositions according to the invention contain from 0.05 to 3, preferably 0.1 to 1, 5 and in particular 0.1 to 1 wt .-% of a Cu stabilizer, preferably a Cu (I) halide, in particular Mixture with an alkali halide, preferably KJ, in particular in the ratio 1: 4.
  • a Cu stabilizer preferably a Cu (I) halide, in particular Mixture with an alkali halide, preferably KJ, in particular in the ratio 1: 4.
  • Suitable salts of monovalent copper are preferably copper (I) acetate, copper (I) chloride, bromide and iodide. These are contained in amounts of 5 to 500 ppm of copper, preferably 10 to 250 ppm, based on polyamide.
  • the advantageous properties are obtained in particular when the copper is present in molecular distribution in the polyamide. This is achieved by adding to the molding compound a concentrate containing polyamide, a salt of monovalent copper and an alkali halide in the form of a solid, homogeneous solution.
  • a typical concentrate is e.g. from 79 to
  • the concentration of the solid homogeneous solution of copper is preferably between 0.3 and 3, in particular between 0.5 and 2 wt .-%, based on the total weight of the solution and the molar ratio of copper (I) iodide to potassium iodide is between 1 and 1 are 1, 5, preferably between 1 and 5.
  • Suitable concentrates are in particular those with PA6 and / or PA66.
  • molding compositions of the invention can be from 0 to 5, preferably 100 ppm to 5 wt .-%, preferably from 500 ppm to 1 wt .-% and in particular from 0.01 to 0.3 wt .-% of a phosphorus-containing inorganic Acid or its salts or their ester derivatives or mixtures thereof.
  • Preferred acids are the oxygen acids of phosphorus such as hypophosphorous acid (phosphinic acid), phosphorous acid, phosphoric acid or mixtures thereof.
  • Suitable metal cations for such salts are transition metal cations or alkali metal or alkaline earth metal cations, with calcium, barium, magnesium, sodium, potassium, manganese, aluminum or mixtures thereof being particularly preferred.
  • Particularly preferred salts are Na hypophosphite, manganese (II) hypophosphite Mn (H2PO 2) 2, aluminum hypophosphite or mixtures thereof.
  • Suitable preferred ester derivatives (phosphonates or salts thereof) of the oxygen acids of phosphorus are those which carry the same or different alkyl radicals having 1 to 4 C atoms, A- rylreste having 6 to 14 C atoms as substituents.
  • Preferred compounds are, for example, the Ca salt of a phosphonate (available as Irgamol® 195 from BASF SE) or the diethyl ester of a phosphonate (available as
  • the thermoplastic molding compositions may contain as component G) according to the invention 0 to 2 wt .-% of at least one polyethyleneimine homopolymer or copolymer.
  • the proportion of G) is preferably from 0.01 to 2% by weight and in particular from 0.1 to 1 and very particularly preferably from 0.1 to 0.5% by weight, based on A) to H), branched polyisocyanate being lyethylenimines are preferred.
  • polyethyleneimines are to be understood as meaning both homopolymers and copolymers which are obtainable, for example, by the processes in Ullmann Electronic Release under the heading "aziridines" or according to WO-A 94/12560.
  • the homopolymers are generally obtainable by polymerization of ethyleneimine (aziridine) in aqueous or organic solution in the presence of acid-releasing compounds, acids or Lewis acids.
  • Such homopolymers are branched polymers, which usually contain primary, secondary and tertiary amino groups in the ratio of about 30% to 40% to 30%.
  • the distribution of the amino groups can be determined in general by means of 13 C-NMR spectroscopy. This is preferably 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 with 2 to 10 carbon atoms in the alkylene radical, with ethylenediamine and propylenediamine being preferred.
  • Further suitable comonomers are diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenetriamine, tripropylenetetramine, dihexamethylenetriamine, aminopropylethylenediamine and bisaminopropylethylenediamine.
  • Polyethyleneimines typically have a weight average molecular weight of from 100 to 3,000,000, preferably from 500 to 2,000,000 (as determined by light scattering).
  • the preferred M w is from 700 to 1,500,000, especially from 1,000 to 500,000.
  • crosslinked polyethyleneimines which are obtainable by reaction of polyethyleneimines with bifunctional or polyfunctional crosslinkers which have as a functional group at least one halohydrin, glycidyl, aziridine, isocyanate unit or a halogen atom are suitable. Examples thereof include its epichlorohydrin or bischlorohydrin ether of polyalkylene glycols having 2 to 100 ethylene oxide and / or propylene oxide units and the compounds listed in DE-A 19 93 17 20 and US Pat. No. 4,144,123. Processes for the preparation of crosslinked polyethyleneimines are known inter alia from the abovementioned publications and EP-A 895 521 and EP-A 25 515.
  • grafted polyethyleneimines are suitable, it being possible for all compounds which can react with the amino or imino groups of the polyethyleneimines to be used as the grafting agent.
  • Suitable grafting agents and processes for the preparation of grafted polyethyleneimines can be found, for example, in EP-A 675 914.
  • suitable polyethyleneimines according to the invention are amidated polymers which are usually obtainable by reacting polyethyleneimines with carboxylic acids, their esters or anhydrides, carboxamides or carbonyl halides.
  • carboxylic acids their esters or anhydrides, carboxamides or carbonyl halides.
  • the amidated polymers can be subsequently crosslinked with said crosslinkers.
  • up to 30% of the amino functions are amidated, so that sufficient primary and / or secondary nitrogen atoms are available for a subsequent crosslinking reaction.
  • alkoxylated polyethyleneimines which are obtainable, for example, by reacting polyethyleneimine with ethylene oxide and / or propylene oxide. Such alkoxylated polymers are also crosslinkable.
  • polyethyleneimines according to the invention are hydroxyl-containing polyethyleneimines and amphoteric polyethyleneimines (incorporation of anionic groups) and also lipophilic polyethyleneimines, which are generally obtained by incorporation of long-chain hydrocarbon radicals into the polymer chain. Processes for the preparation of such polyethyleneimines are known to the person skilled in the art, so that further details are unnecessary.
  • molding compositions of the invention may contain up to 60, preferably up to 50 wt .-% of other additives.
  • fibrous or particulate fillers H) (different from component B)), carbon fibers, glass spheres, amorphous silica, calcium silicate, calcium metasilicate, magnesium carbonate, kaolin, chalk, powdered quartz, mica, barium sulfate and feldspar, which are used in quantities of 1 to 50 wt .-%, in particular 5 to 40, preferably 10 to 40 wt .-% are used.
  • Preferred fibrous fillers are carbon fibers, aramid fibers and potassium titanate fibers.
  • the fibrous fillers can be surface-pretreated for better compatibility with the thermoplastic with a silane compound.
  • Suitable silane compounds are those of the general formula (X- (CH 2 ) n) k -Si (O-C m H 2 m + 1) 4-k in which the substituents have the following meanings: n is an integer from 2 to 10, preferably 3 to 4
  • n is an integer from 1 to 5, preferably 1 to 2
  • k is an integer from 1 to 3, preferably 1 Preferred silane compounds are aminopropyltrimethoxysilane, aminobutyltrimethoxysilane, aminopropyltriethoxysilane, aminobutyltriethoxysilane and the corresponding silanes which contain a glycidyl group as substituent X.
  • the silane compounds are generally used in amounts of 0.01 to 2, preferably 0.025 to 1, 0 and in particular 0.05 to 0.5 wt .-% (based on H)) for surface coating.
  • acicular mineral fillers are also suitable.
  • the term "needle-shaped mineral fillers” is understood to mean a mineral filler with a pronounced, needle-like character.
  • An example is acicular wollastonite.
  • the mineral has an L / D (length: diameter ratio of 8: 1 to 35: 1, preferably 8: 1 to 1: 1: 1)
  • the mineral filler may optionally be pretreated with the silane compounds mentioned above, the pretreatment however, is not essential.
  • further fillers are kaolin, calcined kaolin, wollastonite, talc and chalk called and additionally platelet or needle-shaped nanofillers preferably in amounts between 0.1 and 10%.
  • the molding compositions according to the invention may contain 0.05 to 3, preferably 0.1 to 1, 5 and in particular 0.1 to 1 wt .-% of a lubricant.
  • the metal ions are preferably alkaline earth and Al, with Ca or Mg being particularly preferred.
  • Preferred metal salts are Ca-stearate and Ca-montanate as well as Al-stearate.
  • the carboxylic acids can be 1- or 2-valent. 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 montanic acid (mixture of fatty acids having 30 to 40 carbon atoms).
  • the aliphatic alcohols can be 1 - to 4-valent.
  • examples of alcohols are n-butanol, n-octanol, stearyl alcohol, ethylene glycol, propylene glycol, neopentyl glycol, pentaerythritol, with glycerol and pentaerythritol being preferred.
  • the aliphatic amines can be 1 - to 3-valent. Examples of these are stearylamine, ethylenediamine, propylenediamine, hexamethylenediamine, di (6-aminohexyl) amine, with ethylenediamine and hexamethylenediamine being particularly preferred. Accordingly, preferred esters or amides are glycerin distearate, glycerol tristearate, ethylenediamine distearate, glycerin monopalmitate, glycerol trilaurate, glycerin monobehenate and pentaerythritol tetrastearate.
  • R 1 and R 2 are an alkyl group, a substituted alkyl group or a substituted triazole group, wherein the radicals R 1 and R 2 may be the same 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, for example, in DE-A 27 02 661 (US Pat. No. 4,360,617).
  • Another group of preferred sterically hindered phenols are derived from substituted benzenecarboxylic acids, especially substituted benzenepropionic acids.
  • Particularly preferred compounds of 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 in turn may be substituted (at least one of which is a sterically demanding group) and R 6 is a bivalent aliphatic radical having 1 to 10 C atoms means that may also have CO bonds in the main chain.
  • the antioxidants H which can be used individually or as mixtures, are in an amount of 0.05 to 3 wt .-%, preferably from 0.1 to 1, 5 wt .-%, in particular 0.1 to 1 Wt .-%, based on the total weight of the molding compositions A) to H).
  • sterically hindered phenols having no more than one sterically hindered group ortho to the phenolic hydroxy group have been found to be particularly advantageous; especially when assessing color stability when stored in diffused light for extended periods of time.
  • Preferred components H) have both a P-containing substituent and a hindered phenol moiety and are e.g. as lrgafos®168, lrgafos® TPP, Irgafos® TNPP, Irgafos® P-EPQ (phosphonite) from BASF SE are commercially available.
  • the molding compositions according to the invention may contain 0.05 to 5, preferably 0.1 to 2 and in particular 0.25 to 1, 5 wt .-% of a nigrosine.
  • Nigrosines are generally understood to mean a group of black or gray indulene-related phenazine dyes (azine dyes) in various embodiments (water-soluble, fat-soluble, gas-soluble) used in wool dyeing and printing, in black dyeing of silks, for dyeing of leather, shoe creams, varnishes, plastics, stoving lacquers, inks and the like, as well as being used as microscopy dyes.
  • the nigrosine is technically obtained by heating nitrobenzene, aniline and aniline with anhydrous metal.
  • Component H can be used as the free base or else as the salt (for example hydrochloride).
  • nigrosines can be found, for example, in the electronic lexicon Rompp Online, Version 2.8, Thieme-Verlag Stuttgart, 2006, keyword "nigrosine".
  • thermoplastic molding compositions according to the invention may contain conventional processing aids such as stabilizers, antioxidants, agents against thermal decomposition 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, antioxidants, agents against thermal decomposition and decomposition by ultraviolet light, lubricants and mold release agents, colorants such as dyes and pigments, nucleating agents, plasticizers, etc.
  • oxidation inhibitors and heat stabilizers are sterically hindered phosphites and amines (eg TAD), hydroquinones, aromatic secondary amines such as diphenylamines, various substituted representatives of these groups and mixtures thereof in concentrations up to 1 wt .-%, based on the weight of called thermoplastic molding compositions.
  • TAD sterically hindered phosphites and amines
  • hydroquinones such as diphenylamines
  • aromatic secondary amines such as diphenylamines
  • UV stabilizers which are generally used in amounts of up to 2 wt .-%, based on the molding composition, various substituted resorcinols, salicylates, Benzotriazo- le and benzophenones may be mentioned. It is possible to add inorganic pigments such as titanium dioxide, ultramarine blue, iron oxide and carbon black, furthermore organic pigments such as phthalocyanines, quinacridones, perylenes and also dyes such as anthraquinones as colorants.
  • 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 as colorants.
  • Flame retardants which may be mentioned are phosphorus, P- and N-containing compounds.
  • sodium phenylphosphinate, alumina, silica and preferably talc may be used as nucleating agents.
  • thermoplastic molding compositions according to the invention can be prepared by processes known per se by mixing the starting components in customary mixing devices such as screw extruders, Brabender mills or Banbury mills and then extruding. After extrusion, the extrudate can be cooled and comminuted. It It is also possible to premix individual components and then to add the remaining starting materials individually and / or likewise mixed.
  • the mixing temperatures are usually 230 to 320 ° C.
  • the crosslinking of the molding compositions is preferably carried out not or only in minimal form in the packaging itself, but in particular in the subsequent processing, for example by injection molding, carried out here in particular a) by increasing the shear rate or
  • the shear rates are increased compared to the usual packaging and are generally from 10 000 1 / s to 200 000 1 / s, preferably from 75 000 1 / s to 125 000 1 / s.
  • the temperature can also be increased, depending on the speed of the crosslinking, in order to achieve an optimal degree of crosslinking. Suitable temperatures are in glass fiber reinforced polyamides in the range of 200 to 340, preferably from 240 to 320 ° C.
  • the molding compositions according to the invention can be prepared in advance without significant branching and in the subsequent processing, e.g. by injection molding by tempering the shaped bodies, e.g. be carried out in the form of the component itself (tool) or by annealing the moldings in the oven.
  • the heat treatment is usually carried out over a period of 1 to 100 hours, preferably from 4 to 48 hours, preferably at temperatures of 150 to 300, in particular from 180 to 240 ° C.
  • the gel content measured by GPC is usually stated.
  • the gel fraction in the polymer was determined indirectly by GPC.
  • the samples were dissolved in hexafluoroisopropanol + 0.05% trifluoroacetic acid potassium salt and filtered through a filter (Millipore Millex FG) having a pore size of 0.2 ⁇ m. Subsequently, the concentration of the polymer eluted from the GPC was determined.
  • the shaped bodies preferably have a gel content of at least 20, preferably at least 40 to 80, in particular greater than 80%.
  • the molding compositions and moldings of the invention are distinguished by good heat resistance, chemical resistance, lower water absorption, better mechanical properties in the conditioned state, scratch resistance, dimensional stability and creep behavior.
  • the molding compositions are suitable for the production of moldings of any kind, especially in the automotive sector.
  • Cylinder head covers motorcycle covers, intake pipes, intercooler caps, connectors, gears, fan wheels, cooling water boxes.
  • dashboards In the car interior is a use for dashboards, steering column switches, seat parts, headrests, center consoles, gear components and door modules, in the car exterior door handles, exterior mirror components, windscreen wiper components, windscreen wiper housing, grille, roof rails, sunroof frames, engine covers, cylinder head covers, intake pipes (in particular Intake manifold), windscreen wipers and exterior body parts possible.
  • PA 6 with a VZ of 145 ml / g (Ultramid® B27 from BASF SE).
  • NEXAMITE® A32 (Nexam Chem.) (4- (methylethynyl) phthalic anhydride (CAS: 1240685-26-0)
  • Iron powder CAS-No. 7439-89-6 Determination of the Fe, C, N and O content (see description pages 10 and 11), used as a 25% batch in PA 66.
  • Lupasol ® registered trademark of BASF SE
  • the ratio of primary / secondary / tertiary amines was determined by 13 C NMR spectroscopy.
  • the molding compositions were prepared on a ZSK 25 at a throughput of 8 kg / h and about 280 ° C flat temperature profile.
  • Carboxyl end groups (CEG): The polyamide granules are dissolved in benzyl alcohol at 220 ° C and titrated with 0.05 mol / l Kalilauge standard solution against cresol red as an indicator in the heat to the end point.
  • Amino end groups (AEG):
  • the polyamide granules are dissolved at 100 ° C. in a phenol / methanol mixture (weight ratio 75: 25% by weight) and titrated potentiographically with 0.02 mol / l hydrochloric acid standard solution at RT against inflection point.
  • HDT HDT / A according to ISO 75-2: 2004; Load 1.8 MPa
  • Creep behavior according to DIN EN ISO 899-1; applied voltage: 40 MPa at 150 ° C
  • Heat storage The storage was carried out at the indicated temperatures in a convection oven up to 3000h.
  • composition of the molding compositions can be found in Table 1.
  • Tool Plate 120-120x3 mm; tensile bars were sawn from the plate according to ISO 572-2 IBA; Melt temperature: 290 ° C; Tool temperature 100 ° C
  • the gel content in the polymer was determined indirectly by GPC.
  • the samples were dissolved in hexafluoroisopropanol + 0.05% trifluoroacetic acid potassium salt and filtered through a filter (Millipore Millex FG) with a pore size of 0.2 ⁇ .
  • concentration of the polymer eluted from the GPC was determined.
  • Injection pressure 500 bar gel content after annealing at 200 ° C
  • bMV and 2 were first annealed at 240 ° C for 24 h in air and then annealed for 1000h at 200 ° C in air
  • Composition 1V unannealed
  • Composition 2 annealed at 240 ° C for 24 h

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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne des masses moulées thermoplastiques contenant : A) 10 à 99 % en poids d'un polyamide ; B) 0 à 50 % en poids de fibres de verre ; C) 0,1 à 20 % en poids d'un composé de formule générale I ou II ou leurs mélanges, Ak représentant, indépendamment les uns des autres, l'hydrogène, un radical alkyle ayant de 1 à 10 atomes de C, un radical alkylène(en C0-1 )cyclohexyle, Q représentant un radical alkylène ayant de 2 à 12 atomes de C, un radical phényle, un radical alkylène (en C1-4)-phénylalkylène (en C1-4) ou un radical alkylène (en C0-4)-cyclohexanediyl-alkylène (en C0-4) ; D) 0,001 à 20 % en poids de poudre de fer ; E) 0,05 à 3 % en poids d'un stabilisateur contenant du cuivre ; F) 0 ppm à 5 % en poids d'un acide inorganique contenant du phosphore ou ses sels ou ses dérivés d'ester ou leurs mélanges ; G) 0 à 2 % en poids d'un homopolymère ou copolymère de polyéthylène-imine ; H) 0 à 60 % en poids d'autres additifs, la somme en pourcentage en poids de A) à H) donnant 100 %.
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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017006212A1 (fr) * 2015-07-06 2017-01-12 Sabic Global Technologies B.V. Formulations thermoplastiques à résistance élevée à la fatigue
WO2017098181A1 (fr) * 2015-12-10 2017-06-15 Arkema France Compositions reactives a base de prepolymere thermoplastique amine et d'allongeur insature pour materiaux composites thermoplastiques
WO2017098179A1 (fr) * 2015-12-10 2017-06-15 Arkema France Compositions reactives a base de prepolymere semi-cristallin polyamide amine et d'allongeur insature pour materiaux composites thermoplastiques
US10202498B2 (en) 2013-08-21 2019-02-12 Basf Se Composite plastic part with improved adhesion between the plastic components contained in the composite plastic part
US10583595B2 (en) 2013-08-21 2020-03-10 Basf Se Method for producing a composite plastic part (CK)
EP3725773A1 (fr) * 2019-04-16 2020-10-21 Shin-Etsu Chemical Co., Ltd. Composés et matériaux pour la formation de film organique, substrat pour la fabrication de dispositif semiconducteur, procédé de formation de film organique, et procédé de formation de motifs
US11078362B2 (en) 2016-02-19 2021-08-03 Basf Se Polyamide composition containing a polyamide and an additive
US11692066B2 (en) 2019-04-16 2023-07-04 Shin-Etsu Chemical Co., Ltd. Material for forming organic film, substrate for manufacturing semiconductor device, method for forming organic film, patterning process, and compound for forming organic film

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WO2011051121A1 (fr) * 2009-10-27 2011-05-05 Basf Se Polyamides ignifuges résistant au vieillissement thermique
EP2444387A1 (fr) * 2010-10-22 2012-04-25 Nexam Chemical AB Groupe terminal réticulable pour des fonctions amino primaires

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Publication number Priority date Publication date Assignee Title
WO2011051121A1 (fr) * 2009-10-27 2011-05-05 Basf Se Polyamides ignifuges résistant au vieillissement thermique
EP2444387A1 (fr) * 2010-10-22 2012-04-25 Nexam Chemical AB Groupe terminal réticulable pour des fonctions amino primaires

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10583595B2 (en) 2013-08-21 2020-03-10 Basf Se Method for producing a composite plastic part (CK)
US10202498B2 (en) 2013-08-21 2019-02-12 Basf Se Composite plastic part with improved adhesion between the plastic components contained in the composite plastic part
WO2017006212A1 (fr) * 2015-07-06 2017-01-12 Sabic Global Technologies B.V. Formulations thermoplastiques à résistance élevée à la fatigue
FR3045060A1 (fr) * 2015-12-10 2017-06-16 Arkema France Compositions reactives a base de prepolymere thermoplastique amine et d'allongeur insature pour materiaux composites thermoplastiques
FR3045061A1 (fr) * 2015-12-10 2017-06-16 Arkema France Compositions reactives a base de prepolymere semi-cristallin polyamide amine et d'allongeur insature pour materiaux composites thermoplastiques
WO2017098179A1 (fr) * 2015-12-10 2017-06-15 Arkema France Compositions reactives a base de prepolymere semi-cristallin polyamide amine et d'allongeur insature pour materiaux composites thermoplastiques
WO2017098181A1 (fr) * 2015-12-10 2017-06-15 Arkema France Compositions reactives a base de prepolymere thermoplastique amine et d'allongeur insature pour materiaux composites thermoplastiques
US11078362B2 (en) 2016-02-19 2021-08-03 Basf Se Polyamide composition containing a polyamide and an additive
EP3725773A1 (fr) * 2019-04-16 2020-10-21 Shin-Etsu Chemical Co., Ltd. Composés et matériaux pour la formation de film organique, substrat pour la fabrication de dispositif semiconducteur, procédé de formation de film organique, et procédé de formation de motifs
JP2020177226A (ja) * 2019-04-16 2020-10-29 信越化学工業株式会社 有機膜形成用材料、半導体装置製造用基板、有機膜の形成方法、パターン形成方法、及び有機膜形成用化合物
TWI751525B (zh) * 2019-04-16 2022-01-01 日商信越化學工業股份有限公司 有機膜形成用材料、半導體裝置製造用基板、有機膜之形成方法、圖案形成方法、以及有機膜形成用化合物
US11500292B2 (en) 2019-04-16 2022-11-15 Shin-Etsu Chemical Co., Ltd. Material for forming organic film, substrate for manufacturing semiconductor device, method for forming organic film, patterning process, and compound for forming organic film
US11692066B2 (en) 2019-04-16 2023-07-04 Shin-Etsu Chemical Co., Ltd. Material for forming organic film, substrate for manufacturing semiconductor device, method for forming organic film, patterning process, and compound for forming organic film
JP7308168B2 (ja) 2019-04-16 2023-07-13 信越化学工業株式会社 有機膜形成用材料、半導体装置製造用基板、有機膜の形成方法、パターン形成方法、及び有機膜形成用化合物

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